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WO2015076172A1 - Metal-air battery and metal-air battery unit - Google Patents

Metal-air battery and metal-air battery unit Download PDF

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Publication number
WO2015076172A1
WO2015076172A1 PCT/JP2014/080033 JP2014080033W WO2015076172A1 WO 2015076172 A1 WO2015076172 A1 WO 2015076172A1 JP 2014080033 W JP2014080033 W JP 2014080033W WO 2015076172 A1 WO2015076172 A1 WO 2015076172A1
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WO
WIPO (PCT)
Prior art keywords
metal
electrode
air
air battery
sheet
Prior art date
Application number
PCT/JP2014/080033
Other languages
French (fr)
Japanese (ja)
Inventor
昌明 久保田
彩乃 伊藤
芳延 平
阿部　英俊
小野　眞一
陽洋 小野
努 高原
博幸 飯塚
勲 阿部
渡邉　晃
集平 宮嶋
Original Assignee
古河電池株式会社
凸版印刷株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2014009265A external-priority patent/JP5687782B1/en
Priority claimed from JP2014017122A external-priority patent/JP5684929B1/en
Priority claimed from JP2014185154A external-priority patent/JP5687795B1/en
Priority claimed from JP2014229002A external-priority patent/JP5690443B1/en
Application filed by 古河電池株式会社, 凸版印刷株式会社 filed Critical 古河電池株式会社
Publication of WO2015076172A1 publication Critical patent/WO2015076172A1/en

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/138—Primary casings; Jackets or wrappings adapted for specific cells, e.g. electrochemical cells operating at high temperature
    • H01M50/1385—Hybrid cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
    • H01M12/065—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode with plate-like electrodes or stacks of plate-like electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a metal-air battery including an exterior body having an air electrode and containing a metal electrode, and a metal-air battery unit.
  • Metal-air batteries are known that can generate electric power by injecting an electrolyte solution such as saline in natural disasters, storms and floods, and in environments where AC power is difficult to obtain.
  • a metal can or a resin container is used for the exterior of the metal-air battery.
  • this type of exterior body requires a packing and a sealing material to prevent leakage of the electrolyte, so the number of members increases and the number of assembly steps and costs increase.
  • the electrolyte may leak due to a defect or deterioration of the packing or the sealing material.
  • the outer casing of the metal can or the resin container is heavy.
  • a laminated film in which a resin and an aluminum foil are laminated as a package (a packaging material for a Li battery) (for example, see Patent Document 1).
  • the present invention has been made in view of the above-mentioned circumstances, and it is an object of the present invention to provide a metal-air battery which is low in cost, light in weight and advantageous in discardability, and a metal-air battery unit accommodating a plurality of metal-air batteries.
  • the purpose is.
  • the present invention provides a metal-air battery having an air electrode and having an outer body for accommodating a metal electrode facing the air electrode, wherein the outer body is formed of a sheet material containing paper. It is characterized by According to this configuration, it is possible to provide a metal-air battery that is low in cost, light in weight, and advantageous in discardability.
  • the sheet material is preferably a paper laminated with a heat fusible resin. According to this configuration, it is possible to prevent the electrolyte from leaking to the outside even when the battery is discharged and then used for a long time, for example, after rest and re-discharge. In addition, by making the proportion of paper 50%, it is easy to separate and discard as paper waste according to the rules of each local government, and easy to obtain.
  • the sheet material preferably covers the metal electrode while leaving a gap, bends a part of the sheet material, traverses the gap, and integrally includes a support bending portion for supporting the metal electrode.
  • the metal electrode can be supported with a simple configuration in which a part of the exterior body formed of a sheet material containing paper is bent, and it is advantageous for securing the amount of the electrolyte and reducing the weight.
  • the support bending portion preferably holds the metal electrode at a position spaced apart from the air electrode. According to this configuration, since the metal electrode and the air electrode can be reliably separated, the electrolytic solution can be sufficiently held between the electrodes.
  • the supporting bent portion may be a first bent portion from a wall portion on the air electrode side with respect to the metal electrode in the sheet material and a wall portion on the opposite side to the air electrode toward the metal electrode. A bent portion may be provided, and a second bent portion bent from the tip of the first bent portion and in contact with the metal electrode. According to this configuration, the metal electrode can be supported by a simple bending structure.
  • the first bent portion may be provided above the liquid surface of the electrolytic solution in the outer package, and may be inclined obliquely downward toward the metal electrode. According to this configuration, the electrolytic solution can not be easily discharged to the outside by the first bent portion, and the electrolytic solution attached to the lower surface of the first bent portion can be efficiently returned.
  • the metal pole has a tab portion projecting upward, and the support bending portion extends over the width of the metal pole, and the support bending portion is in the width direction of the metal pole. It is divided on the basis of the boundary of a tab part and a non-tab part without the tab part, and any one of the divided part by the side of the tab part and the divided part by the side of the non-tab part is the air pole of the metal pole.
  • the movement to the side may be restricted, and the other may restrict the movement to the opposite side of the cathode of the metal electrode. According to this configuration, it is possible to restrict both the movement of the metal electrode to the air electrode side and the movement to the opposite side by each divided portion of the support bending portion while avoiding the tab portion.
  • the exterior body may have a bottom plate portion bent in a downward convex shape in which the lower end of the metal electrode is fitted. According to this configuration, it is possible to position the lower end of the metal pole with a simple bending structure and to prevent misalignment. Further, the support bending portion is bent from the wall portion on the air electrode side and the wall portion on the opposite side of the air electrode along the metal electrode to the inside of the outer package, and is folded back to the opposite side. While having a folded back portion that protrudes to the outside of the exterior body than the metal electrode, sandwiching the metal electrode with a part of each folded back portion, joining the remaining protruding portions to the outside of the exterior body together It may be sealed. According to this configuration, evaporation and leakage of the electrolytic solution can be suppressed, deformation of the outer package can be prevented, and displacement of the metal electrode can be suppressed.
  • the exterior body may include a sheet piece connected to a lid covering the upper side of the metal electrode and joined to a side wall covering the side of the metal electrode. According to this configuration, evaporation and leakage of the electrolytic solution can be suppressed with a simple configuration, and deformation of the exterior body can be further prevented.
  • the sheet material is a sheet material containing paper, and is provided with a bottom plate sheet portion bent in a downward convex shape into which the lower end of the metal electrode fits, and the bottom plate sheet portion is a pair of front and back sheets At least one of the ends may be joined. According to this configuration, it is possible to suppress the positional deviation of the metal electrode and to suppress the damage of the exterior body by the metal electrode.
  • the sheet material forming the exterior body is bent in a concave shape that opens upward to form a bottom plate portion of the exterior body, and the bottom plate sheet portion is a state in which the sheet material forming the exterior body is expanded in a planar shape.
  • at least one of a pair of front and rear end portions is joined to the sheet material so as to straddle the bottom plate portion, and when the sheet material is bent in the concave shape opening upward, the sheathing is separated from the bottom plate portion
  • the lower end of the metal pole may be fitted between the pair of upright portions by having a pair of upright portions standing upright inside the body. According to this configuration, the bottom plate sheet portion can be easily assembled.
  • an electrolyte container which contains an electrolyte for operating as a battery by pouring water into the outer package.
  • the electrolyte container is a sheet material containing paper, and is attached to an electrode plate attachment sheet attached to the surface of the metal electrode opposite to the air electrode, and the electrolyte is joined to the electrode plate attachment sheet.
  • a bag body for containing the According to this configuration, it is possible to suppress the corrosion of the metal electrode due to the influence of the electrolyte by the sheet material, and it is not necessary to attach the bag containing the electrolyte to the outer package, and the configuration of the outer package can be simplified The attachment work of the bag is easy.
  • the electrode plate mounting sheet may be crimped and fixed to the metal electrode, and the bag body may be fused to the electrode plate mounting sheet. According to this configuration, attachment of the electrode plate attachment sheet and the bag body is easy. Further, the electrode plate mounting sheet has a restricting portion that bends a part of the sheet to restrict the movement of the metal electrode with respect to the sheet, and the metal plate mounting sheet is held by the exterior body. The pole may be held by the outer package. According to this configuration, a structure for directly holding the metal electrode on the exterior body side is unnecessary, and the exterior body can be easily structured.
  • the sheet material covers the metal electrode with a gap formed, and at least the inner surface side is formed to be liquid impermeable, and the exterior body is provided with an opening where the air electrode is mounted from the outer surface side
  • the end face of the opening may be subjected to an end face treatment for preventing the permeation of the electrolytic solution poured therein.
  • the edge of the sheet material may be folded outward as the end face treatment of the end face of the opening. According to this configuration, it is possible to suppress the influence of the electrolytic solution on the opening by a simple method of bending the sheet material.
  • the end face of the opening may be covered with a sheet-like liquid impermeable material as the end face treatment. According to this configuration, it is possible to obtain coating performance according to the film performance. For example, by using a widely distributed film, cost reduction can be easily achieved, and desired coating performance can be selected by film selection.
  • non-liquid-permeable material may be attached to both surfaces of the sheet material, and the non-liquid-permeable materials may be joined to cover the end surface. According to this structure, when laminating both sides of a sheet material, it can coat using the lamination film.
  • the end surface may be covered by covering the end surface with the liquid impermeable material. According to this configuration, it is possible to obtain a coated form in which the end face of the opening is enclosed, and it is easy to prevent the electrolyte from permeating the end face.
  • the end face of the opening may be impregnated with a hydrophobic agent as the end face treatment. According to this configuration, the penetration of the electrolytic solution from the end face of the opening can be prevented by the method using a drug.
  • a hot melt may be applied from the sheet material to the air electrode, and the end surface of the opening may be covered with the hot melt. According to this configuration, it is possible to efficiently increase the bonding strength of the hot melt that functions as a coating by utilizing the surface asperity shape of the air electrode.
  • a sheet-like impermeable material may be attached from the sheet material to the air electrode, and the end surface of the opening may be covered with the impermeable material. According to this configuration, it is possible to efficiently increase the bonding strength of the film functioning as a coating by utilizing the surface asperity shape of the air electrode.
  • the liquid impermeable material may be in the form of an integral frame extending across the edge of the opening. According to this configuration, the number of components can be reduced and the number of attaching operations can be reduced to one, as compared with the case where the liquid impermeable material is attached to each edge of the opening.
  • non-liquid-permeable material may be connected with a plurality of strip-like non-liquid-permeable materials so as to form a frame extending over the edge of the opening. According to this configuration, when cutting out from the film material of the liquid-impervious material, it is easy to reduce the excess of the material, and it becomes easy to correspond to various shapes.
  • a passive film is not formed on the surface of the metal electrode before injection of the electrolytic solution, and a passive film is formed on the surface by an oxide generated by a battery reaction after the injection of the electrolytic solution.
  • the metal-air battery which is a metal electrode and has the metal electrode and the air electrode, selectively selects a closed circuit including the metal electrode and the air electrode in a state where no load is connected to remove the passive film. And a circuit formed on the circuit. According to this configuration, a closed circuit including the negative electrode and the positive electrode is formed to remove the passivation film formed on the surface of the negative electrode (metal electrode) of the metal-air battery, thereby refreshing the surface of the negative electrode (metal electrode). It becomes easy to restart the battery reaction.
  • the circuit may be a switchable short circuit provided between the negative electrode and the positive electrode. According to this configuration, the battery reaction can be easily resumed with a simple configuration.
  • the circuit may be a switchable resistance discharge circuit provided between the negative electrode and the positive electrode. According to this configuration, the battery reaction can be easily resumed with a simple configuration.
  • the resistive discharge circuit may be a circuit protector switch which opens when the value of the current flowing through the circuit exceeds a predetermined value. According to this configuration, protection of the circuit can be facilitated, and the switch opening operation can be made unnecessary. In addition, the loss of discharge power can also be reduced.
  • a plurality of unit cells including the negative electrode and the positive electrode may be connected in series, and the circuit may be provided between the negative electrode and the positive electrode at both ends of a battery pack including the plurality of unit cells.
  • a current detection unit that detects a current value flowing through the closed circuit may be provided. According to this configuration, it is possible to remove the passivation film formed on the surface of the negative electrode (metal electrode) of the metal-air battery, and obtain information that can be used to determine whether the surface of the negative electrode (metal electrode) can be refreshed. In this case, the current detection unit may open the circuit according to the detected current value. According to this configuration, it is possible to eliminate the need for user operation for switching to the open circuit, and to reduce the loss of discharge power.
  • an integrated current detection unit may be provided which detects an integrated current value flowing through the closed circuit. According to this configuration, it is possible to remove the passivation film formed on the surface of the negative electrode (metal electrode) of the metal-air battery, and obtain information that can be used to determine whether the surface of the negative electrode (metal electrode) can be refreshed. In this case, the integrated current detection unit may open the circuit according to the detected integrated current value. According to this configuration, it is possible to eliminate the need for user operation for switching to the open circuit, and to reduce the loss of discharge power.
  • a time detection unit may be provided to detect an elapsed time after the closed circuit. According to this configuration, it is possible to remove the passivation film formed on the surface of the negative electrode (metal electrode) of the metal-air battery, and obtain information that can be used to determine whether the surface of the negative electrode (metal electrode) can be refreshed. In this case, the time detection unit may open the circuit according to the detected elapsed time. According to this configuration, it is possible to eliminate the need for user operation for switching to the open circuit, and to reduce the loss of discharge power.
  • the negative electrode may be formed of a magnesium alloy containing at least zinc. According to this configuration, when it becomes difficult to restart the battery reaction after the battery is stopped due to the influence of zinc, it becomes easy to restart the battery reaction.
  • the plurality of metal air batteries are housed in the outer case with a gap for air to be accumulated therein, and are projected into the gap in the side portion of the outer case and the outer case It is characterized in that it has a projecting piece for supporting the body. According to this configuration, the projection provided on the side surface of the outer case protrudes into the gap to support the outer package, thereby suppressing the expansion of the outer package of the metal-air battery and preventing the decrease in the output of the battery.
  • a plurality of the projecting pieces may be provided at intervals in the vertical direction on the side surface portion of the outer case.
  • a spacer may be disposed between the metal-air batteries, and the protrusion may be engaged with the spacer.
  • the spacer is a three-dimensional spacer, and includes a retention portion in which air is retained at a central portion, and a pocket in which an air electrode is opposed and a metal air battery is disposed on both sides You may
  • the spacer may be formed three-dimensionally by bending a sheet of sheet cardboard.
  • a frame member may be arrange
  • the outer box may be made of paper or resin. Further, the projecting piece may be connected to the side surface of the outer box through a part to be separated, and the part to be separated may be separated to protrude into the gap to support the air electrode.
  • the exterior body which has an air electrode and accommodates the metal electrode facing the air electrode is characterized by being formed of a sheet material containing paper. According to this configuration, it is low in cost, light in weight, and advantageous in discardability. Also, by providing a switchable short circuit provided between the metal electrode and the air electrode, the passive film (sometimes referred to as "protective film” in the following description) formed on the metal electrode surface is easily removed. It is possible to return to a state in which the battery reaction can be easily resumed.
  • FIG. 1 is a view showing a magnesium-air battery according to a first embodiment of the metal-air battery.
  • FIG. 2 is a view of a magnesium-air battery, FIG. 2 (A) is a view from the rear, FIG. 2 (B) is a view from the top, and FIG. 2 (C) is a view from the right.
  • FIG. 3: is the figure which expand
  • FIG. 4 is a cross-sectional view taken along line IV-IV of FIG.
  • FIG. 5 is a sectional view taken along the line V--V of FIG.
  • FIG. 6 is a cross-sectional view schematically showing a first embodiment of end face treatment of the opening.
  • FIG. 4 is a cross-sectional view taken along line IV-IV of FIG.
  • FIG. 5 is a sectional view taken along the line V--V of FIG.
  • FIG. 6 is a cross-sectional view schematically showing a first embodiment of end face treatment of the
  • FIG. 7 is a view showing a second embodiment of the end face treatment of the opening
  • FIG. 7 (A) is a sectional view schematically showing the second embodiment
  • FIG. 7 (B) is an outer surface of the outer package. Is a view showing a case where is laminated.
  • FIG. 8 is a cross-sectional view schematically showing a third embodiment of the end face treatment of the opening.
  • FIGS. 9A to 9D are cross sectional views schematically showing, in chronological order, the fourth embodiment of the end face treatment of the opening.
  • FIG. 10 is a cross-sectional view schematically showing a fifth example of the end face treatment of the opening.
  • FIG. 11 is a cross-sectional view schematically showing a sixth example of the end face treatment of the opening.
  • FIG. 12 is a cross-sectional view schematically showing a seventh embodiment of the end face treatment of the opening.
  • FIG. 13 is a cross-sectional view schematically showing an eighth embodiment of end face treatment of an opening.
  • FIG. 14 is a view for explaining a film used in the eighth embodiment, FIG. 14 (A) is a view showing an integral type film, and FIG. 14 (B) is a view showing a separate type film.
  • FIG. 15 is a perspective view of the exterior body of the second embodiment.
  • FIG. 16 is a developed view of the exterior body of the second embodiment.
  • FIG. 17 is a view of the second embodiment, FIG. 17 (A) is a front view of the exterior body, and FIG. 17 (B) is an AA cross-sectional view of FIG. 17 (A).
  • FIG. 14 is a view for explaining a film used in the eighth embodiment
  • FIG. 14 (A) is a view showing an integral type film
  • FIG. 14 (B) is a view showing a separate type film.
  • FIG. 18 is a partially developed view of a modification of the second embodiment, and FIG. 18 (A) is a view in which the upper plate portion is formed long and one handle is provided, and FIG. It is a figure which formed and provided two handles.
  • FIG. 19 is a view of the exterior body of the third embodiment, FIG. 19 (A) is a front view of the exterior body, and FIG. 19 (B) is a cross-sectional view taken along the line BB in FIG.
  • FIG. 20 is a perspective view of the bottom plate sheet portion of the third embodiment.
  • FIG. 21 is a perspective view of a magnesium-air battery according to a fourth embodiment.
  • FIG. 22 is a side sectional view of the magnesium-air battery of the fourth embodiment.
  • FIG. 23 is a view of the fourth embodiment, and FIG.
  • FIG. 23 (A) is a perspective view of the electrolyte container as viewed from the air electrode side together with the magnesium electrode
  • FIG. 23 (B) is a perspective view from the opposite side of the air electrode.
  • FIG. 24 is a side sectional view of a magnesium-air battery according to a modification of the fourth embodiment.
  • FIG. 25 is a view of a modification of the fourth embodiment
  • FIG. 25 (A) is a perspective view of the electrolyte containing body as viewed from the air electrode side together with the magnesium electrode
  • FIG. 25 (B) is seen from the opposite side to the air electrode.
  • FIG. FIG. 26 is a side sectional view of a magnesium-air battery according to a fifth embodiment.
  • FIG. 27 is a perspective view of the exterior body of the fifth embodiment.
  • FIG. 28 is a view of the fifth embodiment
  • FIG. 28 (A) is a developed view of the outer package
  • FIG. 28 (B) is a view corresponding to the X region of FIG.
  • FIG. 28D is a diagram corresponding to the Z region of FIG.
  • FIG. 29 is a perspective view showing an embodiment of a metal-air battery unit.
  • FIG. 30 is a perspective view showing an embodiment of the metal-air battery unit.
  • FIG. 31 is a perspective view showing a spacer of the metal-air battery unit together with its peripheral configuration.
  • FIG. 32 is a perspective view of a single spacer.
  • FIG. 33 is a top view of the spacer alone.
  • FIG. 34 is a side view of the spacer alone.
  • FIG. 35 is a cross-sectional view corresponding to the II line shown in FIG. 36 of the magnesium-air battery.
  • FIG. 36 is a top partial perspective view of the upper part of the exterior of the magnesium-air battery before being folded.
  • FIG. 37 is a developed view of the spacer.
  • FIG. 38 is a development view of the outer case.
  • FIG. 39 is a perspective view showing another embodiment of the metal-air battery unit.
  • FIG. 40 is a perspective view showing another embodiment of the metal-air battery unit.
  • FIG. 41 is a view showing the configuration of the first embodiment of the metal-air battery system.
  • FIG. 42 is a view showing a modification of the metal-air battery system according to the first embodiment.
  • FIG. 43 is a view of a metal-air battery system, FIG.
  • FIG. 43 (A) is a view showing a configuration of a second embodiment of the metal-air battery system
  • FIG. 43 (B) is a modification of the second embodiment.
  • FIG. FIG. 44 is a view showing another modified example of the metal-air battery system according to the second embodiment.
  • FIG. 45 is a diagram of a metal-air battery system
  • FIG. 45 (A) is a diagram showing the configuration of a third embodiment of the metal-air battery system
  • FIG. 45 (B) is a fourth embodiment of the metal-air battery system It is the figure which showed the structure of the form.
  • FIG. 46 is a view showing the configuration of the fifth embodiment of the metal-air battery system.
  • FIG. 47 is a view showing the configuration of the sixth embodiment of the metal-air battery system.
  • FIG. 1 is a view showing a magnesium-air battery according to a first embodiment of the metal-air battery of the present invention.
  • the magnesium-air battery 10 is provided with a hollow box-shaped exterior body (also referred to as a housing) 11 formed of a foldable sheet material (shown by reference numeral 101 in FIG. 6 in the latter stage and the like).
  • the air electrode 13 is attached to the exterior body 11, and a magnesium electrode (metal electrode) 15 is accommodated so as to face the air electrode 13.
  • the magnesium-air battery 10 is a primary battery in which the air electrode 13 acts as a positive electrode and the magnesium electrode 15 acts as a negative electrode.
  • Each direction such as top, bottom, left, and right shown in FIG. 1 and each drawing described later corresponds to each direction when the magnesium air battery 10 is used as a battery, and is the same as each direction used in the following description.
  • FIG. 2 is a view showing the magnesium-air battery 10
  • FIG. 2 (A) is a view from the rear
  • FIG. 2 (B) is a view from the top
  • FIG. 2 (C) is a view from the right.
  • the exterior body 11 is formed in a thin rectangular parallelepiped shape, and a bottom plate portion 21 configuring a bottom surface of the exterior body 11, a front wall portion 22 configuring a front surface, and a rear wall portion 23 configuring a rear surface (FIG. 2)
  • the left and right side wall portions (left wall portion, right wall portion) 24 constituting the left and right side surfaces and the upper plate portion 25 constituting the upper surface are integrally formed.
  • the front wall portion 22 and the rear wall portion 23 are surfaces of the same shape, arranged in parallel to each other, and form the largest surface of the exterior body 11.
  • the front wall portion 22 is provided with an opening 22K (see FIG. 3 described later) to which the air electrode 13 is attached (adhered).
  • the air electrode 13 is made of a rectangular (not including the tab portion 13T) copper mesh (copper mesh) made of a mixture of carbon and Teflon (registered trademark) in a sheet shape having a predetermined thickness using a roller press machine or the like. Then, it is dried and fired at a predetermined temperature for a predetermined time, and the sheet cut into approximately the same size as the copper mesh is pressed (pressed) from both sides and held between them, heat is applied to the opening 22K of the exterior body It has a structure bonded by fusion bonding or an adhesive, and has air permeability and water impermeable property (corresponding to liquid impermeable property).
  • each air pole 13 and magnesium pole 15 are arranged in the vertical direction.
  • the air electrode 13 is provided with a tab portion 13T projecting upward, and a positive electrode wiring (not shown) is connected to the tab portion 13T.
  • a plate member made of Ni or copper is used as the tab portion 13T, and is joined to the copper mesh of the air electrode 13 by welding or the like.
  • the tab portion 13T protrudes above the upper plate portion 25 of the exterior body 11, and can easily connect the positive electrode wiring from above.
  • a tab portion 15T projecting upward is also provided in the magnesium electrode 15, and a negative electrode wiring (not shown) is connected to the tab portion 15T.
  • the tab portion 15T of the magnesium electrode 15 is integrally provided on the magnesium electrode 15, and protrudes upward beyond the exterior body 11. That is, the magnesium electrode 15 includes a rectangular plate-shaped magnesium electrode main body (metal electrode main body) 15A (see FIG. 4 described later) and a tab 15T projecting upward from the magnesium electrode main body 15A by the same thickness. It is equipped with one.
  • the tab part 15T of the magnesium pole 15 is offset and provided in the width direction one end side (left end side) in the magnesium pole 15.
  • the tab portion 13T of the air electrode 13 is provided at a position offset to the other end side (right end side in FIG. 1) in the width direction than the tab portion 15T of the magnesium electrode 15.
  • the tab portions 15T and 13T are arranged so as not to overlap in a front view (FIG. 1).
  • the upper plate portion 25 functions as a covering member that covers the upper side of the internal space formed between the front wall portion 22, the rear wall portion 23 and the left and right side wall portions 24.
  • the upper plate 25 covers the upper surface of the magnesium electrode main body 15A, and the tab 15T is exposed to the outside.
  • the upper plate portion 25 is provided with a pair of left and right holes 25H serving as an inlet for an electrolytic solution (in the present configuration, a saline solution).
  • Each hole 25H corresponds to the inner circumferential portion of the cut along the arc, and when the tip of the injection bottle for injecting the electrolyte is abutted against the inside of the cut, each hole 25H is opened, and the electrolyte is internally contained. Can be injected.
  • the pair of left and right holes 25H serving as the electrolyte injection port may be more than two in number, and the shape of the holes 25H is not limited to a circular arc, but is particularly limited such as triangular or square. is not.
  • at least one portion may be configured as an air hole.
  • three holes 25H are provided, two are a liquid inlet and one is an air.
  • the other when injecting the electrolyte solution from one side, the other can be functioned as an air hole for extracting the air in the exterior body 11 to the outside. .
  • the gas generated inside at the time of the cell reaction can also be extracted outside efficiently. That is, one of the holes 25H functions as an electrolyte injection port, and the other functions as an air hole and a gas release hole.
  • the hole 25H selectively opened by the cut is provided, the battery can be kept closed before using the battery, and foreign matter such as dust can be prevented from entering.
  • the exterior body 11 of this configuration can support the magnesium electrode 15 with a simple configuration, and is advantageously configured to secure the amount of the electrolyte and to reduce the weight.
  • the exterior body 11 is made of a sheet material containing paper (indicated by reference numeral 101 in FIG. 6 and the like in the subsequent stage). More specifically, for this sheet material, a paper having at least the inner surface laminated with a heat fusible resin (for example, polyethylene (PE)), that is, a laminated paper is used. For this reason, the inner surface side is formed to be impervious to liquid so that the electrolytic solution does not exude (leak) to the outside, and it is lightweight and inexpensive as compared with the case of using a metal can or a resin container. In addition, you may use the double-sided lamination paper which laminated-processed both the front and back 2nd of a sheet material.
  • PE polyethylene
  • the sheet material containing paper in the present construction is a composite of paper and a heat fusible resin by lamination or the like.
  • the proportion of paper in the sheet material is preferably greater than 50%.
  • the exterior body 11 of this configuration can be discarded, for example, as paper waste by setting the ratio of paper to be 50% or more.
  • the exterior body 11 is made of a punched sheet 100 in which a sheet material is punched into a predetermined shape.
  • the punched sheet 100 satisfies the strength required for the outer package 11 after assembly by the so-called strength of paper (corresponding to the strength of paper). In other words, it is manufactured to have a desired strength by adjusting the thickness of the punched sheet 100, the length of the contained paper fiber, the material of the paper fiber, and the like. Further, by adjusting the strength of the paper, it can be held in a bent state, and the strength necessary for holding the magnesium electrode 15 by the pair of front and rear upper plate parts 25F and 25R described later is also obtained.
  • paper those having relatively thick strength, such as coated balls, uncoated balls, paperboard, card paper, etc. can be suitably used.
  • cup base paper, paper pack base paper, etc. in which paper and heat fusible resin are complexed in advance, can also be suitably used.
  • the heat fusible resin a sheet material is joined by heat fusible to be able to be formed in a liquid-tight box shape, and any resin may be used as long as heat fusible is possible
  • a polyolefin-based resin such as polyethylene, polypropylene, ethylene-vinyl acetate copolymer and the like.
  • the thickness of the heat-fusible resin is at least 10 ⁇ m, preferably 20 ⁇ m or more, in order to obtain a sufficient heat-fused state.
  • the surface on the inner surface side of the exterior body 11 have a thickness of 40 ⁇ m or more in order to make the sealing performance more reliable.
  • polyethylene terephthalate (PET), polyamide (Ny), and oriented polypropylene (OPP) films can be laminated.
  • PET polyethylene terephthalate
  • Polyamide films are films excellent in puncture resistance, and are preferably used.
  • these films can provide the sheet material with excellent printability by laminating on the outer surface side of the sheet material. That is, when printing patterns or characters on a sheet material, printing may be directly performed on paper, but by printing on PET or OPP in advance and laminating it on paper, a beautiful pattern on the sheet material may be printed. And letters can be given.
  • the heat fusible resin and other films may be laminated to paper, respectively, or the heat fusible resin and the other film may be laminated in advance and then laminated to paper. And co-extrusion films obtained by co-extrusion of other resins may be laminated and laminated.
  • the sheet material containing the paper of the present invention needs to have a predetermined strength.
  • the stiffness (taber) can be adjusted by changing the thickness and density of the paper, the type and thickness of the heat fusible resin and other films to be laminated.
  • the lamination of the paper and the heat fusible resin is preferably a simple method of extruding and laminating the heat fusible resin on the paper, but other known lamination methods such as a dry lamination method using an adhesive for dry lamination are preferable. A method can also be adopted.
  • the lamination of PET, Ny, and OPP can also be performed using a known lamination method, and a dry lamination method using an adhesive, a sand lamination method using a heat fusible resin, and the like are generally used. Specific examples of the layer configuration of the sheet material are shown below. (1) PE / paper / PE (2) PE / paper / PE / (PE / Ny / PE) Note: () is co-extrusion film (3) PET / PE / paper / PE
  • the exterior body 11 When manufacturing the exterior body 11, it manufactures by producing the punching sheet 100 which pierce
  • the end surface treatment a method of coating the end surface with a hot melt or an adhesive to cover the end surface, a method of attaching a separate film, or the like can be adopted.
  • FIG. 3 is a view showing the punching sheet 100, which corresponds to a developed view of the exterior body 11. As shown in FIG. In FIG. 3, the folds are indicated by alternate long and short dash lines in order to make the description easy to understand. 4 is a cross-sectional view taken along the line IV-IV of FIG. 1, and FIG. 5 is a cross-sectional view taken along the line V-V of FIG. As shown in FIG.
  • the punched sheet 100 has a rectangular bottom plate 21, a rectangular front wall 22 connected to a front edge 21 A (corresponding to a fold line) of the bottom plate 21, and a rear edge 21 B of the bottom plate 21 (fold And the rectangular rear wall portion 23 continuous with the By bending the front wall portion 22 and the rear wall portion 23 with reference to the front edge 21A and the rear edge 21B of the bottom plate portion 21, as shown in FIGS. 4 and 5, from the bottom plate portion 21 to the front wall portion 22 and the back wall 23 stand.
  • an opening 22 K to which the air electrode 13 is attached is formed in the front wall 22, and the opening 22 K is punched at the same time when, for example, punching is performed to form the punching sheet 100.
  • the bottom plate portion 21 is bent on the basis of a fold line 21C (FIG. 3) which divides the bottom plate portion 21 back and forth (the present configuration is equally divided), and as shown in FIG. 4 and FIG. It is formed in a letter shape.
  • the magnesium electrode 15 is placed on the bottom plate portion 21. Thereby, the lower end of the magnesium electrode 15 is guided by the inclination of the bottom plate portion 21 and fitted in the downward convex portion 21T, and the lower end of the magnesium electrode 15 can be easily positioned. Further, it is possible to maintain an appropriate separation distance between the magnesium electrode 15 and the air electrode 13 by the downward convex portion 21T and the first bent parts 25F1 and 25R1 described later, and the separation distance is the crease 21C, 22C and 23C. It can be easily adjusted by changing the distance.
  • the punched sheet 100 includes a pair of left and right side wall portion constituting pieces 24F connected to the left and right side edges 22S (corresponding to the fold) of the front wall 22 and the left and right side edges 23S of the rear wall 23
  • a pair of left and right side wall portion constituting pieces 24R connected to (corresponding to a fold) are integrally provided.
  • the left and right side wall portions 24 are formed by the side wall portion configuration pieces 24F and 24R. More specifically, each side wall component piece 24F, 24R is formed in a vertically-long rectangular shape extending over the front wall 22 and the rear wall 23, respectively. It is bent inward (corresponding to the inside of the exterior body 11) with reference to the left and right side edges 22S, 23S.
  • each side wall portion constituting piece 24F, 24R is bent outward (outside of the exterior body 11) on the basis of the folds 24C, 24D which divides each constituting piece 24F, 24R into two right and left parts (this part is equally divided).
  • the outside bent pieces 24FS and 24RS which are bent outward are joined by heat fusion.
  • the outer bent pieces 24FS and 24RS are bent so as to be in close contact with the inner bent pieces 24FU and 24RU bent inward, thereby forming the side wall portion 24.
  • the outer bent pieces 24FS and 24RS may be joined to the inner bent pieces 24FU and 24RU by heat fusion, or the outer bent pieces 24FS and 24RS may be joined to the inner bent pieces 24FU using an adhesive material such as a tape.
  • reference numeral 24L is a downward projecting portion formed at both ends of the bottom plate portion 21 of the exterior body 11, and the downward projecting portion 24L corresponds to the lower portion of the inner bent piece 24FU of the side wall portion constituting piece 24F. .
  • the punched sheet 100 includes an upper plate portion constituting piece 25F connected to the upper edge 22A (corresponding to the fold) of the front wall portion 22, and an upper edge 23A (corresponding to the fold And the upper plate portion constituting piece 25R connected to the.
  • the upper plate portion 25 is formed by the pair of upper plate portion configuration pieces 25F, 25R. More specifically, each upper plate portion constituting piece 25F, 25R is formed in a horizontally long rectangular shape (a plate shape extending in the width direction) extending over the entire width of the front wall portion 22 and the rear wall portion 23, respectively. . And each upper-plate part structure piece 25F, 25R is based on upper edge 22A, 23A of the front wall part 22 and the rear wall part 23, as shown to FIG.
  • each upper plate portion constituting piece 25F, 25R is a first bent portion 25F1, 25R1 which is bent from both of the front wall portion 22 and the rear wall portion 23 toward the magnesium electrode 15. And second bent portions 25F2 and 25R2 which are bent from the tips of the first bent portions 25F1 and 25R1 (corresponding to the folds 22C and 23C) and abut on the magnesium electrode 15, thereby supporting the upper portion of the magnesium electrode 15 Be done.
  • the upper plate portion constituting piece 25R of the rear wall portion 23 has a cut K (see FIG. 3) at a position corresponding to both side edges of the tab portion 15T of the magnesium electrode 15 in the width direction of the magnesium electrode 15. It is divided into a divided portion 25X on the tab portion side and a divided portion 25Y on the non-tab portion side on the basis of the boundary between the tab portion 15T and the non-tab portion without the tab portion 15T. In the divided portion 25X on the tab portion side, as shown in FIG.
  • the first bent portion 25R1 is formed to have a length extending from the rear wall portion 23 to the rear surface MR of the magnesium electrode 15, and the second bent portion 25R2 is By being bent downward, it abuts on the rear surface MR of the magnesium electrode 15.
  • the upper plate portion constituting piece 25R bridges between the rear surface MR of the magnesium electrode 15 and the rear wall portion 23, and the movement of the magnesium electrode 15 to the rear wall portion 23 side by the upper plate portion constituting piece 25R (air electrode 13) and movement to the opposite side is regulated.
  • the first bent portion 25R1 passes over the magnesium electrode main portion 15A and the second bent portion 25R2 abuts on the front surface MF of the magnesium electrode 15. It is bent to Thereby, the upper plate portion constituting piece 25R bridges between the front surface MF and the rear wall portion 23 of the magnesium electrode 15, and the movement of the magnesium electrode 15 to the front wall portion 22 side by the upper plate portion constituting piece 25R (air electrode 13) movement is restricted. In this manner, the upper plate portion configuration piece 25R of the rear wall portion 23 restricts the movement of the magnesium electrode 15 to both the front and back.
  • the first bent portion 25F1 is formed to have a length extending from the front wall portion 22 to the front surface MF of the magnesium electrode 15. Ru. Then, by bending the second bent portion 25F2 downward, the second bent portion 25F2 abuts on the front surface MF of the magnesium electrode 15 through the second bent portion 25R2 of the upper plate portion constituting piece 25F of the rear wall portion 23. As a result, the front face MF of the magnesium electrode 15 and the front wall 22 are bridged, and the movement of the magnesium electrode 15 to the front wall 22 side (movement to the air electrode 13) by the upper plate portion constituting piece 25F It is regulated. In this manner, both of the upper plate portion constituting pieces 25F and 25R of the front wall portion 22 and the rear wall portion 23 function as support bending portions for supporting the magnesium electrode 15 by bending a part of the sheet material.
  • a punching sheet 100 made of a sheet material containing paper is prepared.
  • the punched sheet 100 is folded in half on the basis of the front edge 21A and the rear edge 21B of the bottom plate 21 to erect the front wall 22 and the rear wall 23, and the front wall 22 and the rear wall 23
  • the left and right side wall portion construction pieces 24F and 24R are bent and joined by heat fusion to form the left and right side wall portions 24 (first assembling step).
  • the exterior body 11 is assembled in a state in which the internal space is opened upward.
  • the bottom plate portion 21 is bent in a V-shape in a downward convex shape in a side view (see FIGS.
  • the magnesium electrode 15 is inserted into the outer package 11 from above, and the lower end of the magnesium electrode 15 is abutted against the downward convex portion 21T (FIG. 4, FIG. 5) of the bottom plate 21 to position the lower end of the magnesium electrode 15 (2nd assembly process).
  • the upper plate portion constituting piece 25R connected to the rear wall portion 23 is bent toward the magnesium electrode 15 to form a first bent portion 25R1, and the first bent portion 25R1.
  • the second bent portion 25R2 which is bent downward at a fold line 23C (FIG. 3) corresponding to the tip of the second contact portion to abut on the magnesium electrode 15 is formed (third assembling step).
  • the divided portion 25X on the tab portion side is bent downward on the rear surface MR side of the magnesium electrode 15, as shown in FIG. It contacts and controls movement to the rear wall 23 side of magnesium pole 15.
  • the divided portion 25Y on the non-tab portion side is bent downward on the front surface MF side of the magnesium electrode 15 over the magnesium electrode body 15A and abuts on the front surface MF. It regulates movement to the front wall 22 side.
  • the upper plate portion constituting piece 25F connected to the front wall portion 22 is bent toward the magnesium electrode 15 to form a first bent portion 25F1, and the first bent portion 25F1 is formed.
  • a second bent portion 25F2 is formed by bending downward at a fold line 22C (FIG. 3) corresponding to the front end (fourth assembly step).
  • the second bent portion 25F2 bridges between the front surface MF of the magnesium electrode 15 and the front wall portion 22. Therefore, the movement of the magnesium electrode 15 to the front wall portion 22 side (movement to the air electrode 13 side) is restricted. Do. In this manner, the magnesium electrode 15 can be positioned by supporting the magnesium electrode 15 from the front and back by the pair of front and rear upper plate parts 25F and 25R, and the displacement of the magnesium electrode 15 can be prevented.
  • a pair of upper plate portion configuration pieces 25F, 25R are not shown members that connect the upper plate portion configuration pieces 25F, 25R from above (a lid (lid They are connected to each other by attaching a member or a patch such as a tape.
  • the air electrode 13 may be attached to the exterior body 11 before the first assembly process, or attached (adhered) after assembly of the exterior body 11 (for example, after the fourth assembly process). It is good.
  • the magnesium-air battery 10 is assembled, and the electrolytic solution is injected into the exterior body 11 when used as a battery.
  • the magnesium air battery 10 after assembly will be described.
  • the exterior body 11 made of a sheet material containing paper covers the clearances SF and SR with the magnesium electrode 15 at the front and back, and covers these clearances SF , SR from above and has a configuration in which the pair of upper plate portion configuration pieces 25F, 25R are bent so as to cross the gaps SF, SR. Therefore, the amount of the electrolytic solution in the exterior body 11 can be sufficiently secured, and the magnesium electrode 15 can be held at a position separated from the air electrode 13 with a simple configuration. And since exterior body 11 is formed from a sheet material containing paper, weight reduction of exterior body 11 and reduction of processing cost are also possible.
  • the main parts constituting the magnesium-air battery 10 are only three parts: the exterior body 11, the magnesium electrode 15, and the air electrode 13 (including the tab portion 13T), the number of parts is small, and the number of assembling steps is reduced. The weight of the entire battery 10 can be reduced.
  • the upper portion of the magnesium electrode 15 is supported by the pair of upper and lower upper plate portions 25F and 25R, and the lower end is positioned by the downward convex portion 21T of the bottom plate portion 21.
  • the positional deviation can be efficiently suppressed.
  • (OH) 2 Magnesium hydroxide is gradually pushed out from the gap SF between the air electrode 13 and the magnesium electrode 15 to the side opposite to the air electrode 13, and the electrolyte on the opposite side to the air electrode is magnesium and the air electrode.
  • the symbol UL indicates the liquid level of the electrolytic solution.
  • the front and rear pair of upper plate component pieces 25F and 25R are located above the liquid surface UL of the electrolytic solution, and the first bent portions 25F1 and 25R1 of the upper plate component pieces 25F and 25R face the magnesium electrode 15, respectively. And slant downward. Therefore, when the electrolyte is scattered upward due to the generation of hydrogen due to the discharge reaction, the electrolyte flows along the lower surface of the first bent portions 25F1 and 25R1, and the electrolyte stored in the lower part is quickly and smoothly. It can be returned. Further, the first bent portions 25F1 and 25R1 of the upper plate portion configuration pieces 25F and 25R are butted against each other.
  • first bent portions 25F1 and 25R1 are held between the front wall portion 22 and the rear wall portion 23, and the front wall portion 22 and the rear wall portion 23 are separated and easily held parallel to each other. Further, since the upper surfaces of the first bent portions 25F1 and 25R1 are continuous, it is easy to connect the first bent portions 25F1 and 25R1 with an adhesive material such as a tape.
  • the exterior body 11 of the magnesium-air battery 10 of the present embodiment is formed of a sheet material containing paper, it is possible to reduce the cost and weight. Moreover, since this sheet material is a heat-fusion resin-made paper composited by laminating etc., the electrolytic solution leaks out (leaks) even when used for a long time such as stopping the battery after discharging and re-discharging. ) Can be prevented. Furthermore, by making the ratio of paper 50% over, it is easy to separate and discard as paper waste according to the rules of each local government, and there is also an advantage that it is easy to obtain easily. As a result, it is possible to provide a magnesium air battery 10 which is low in cost, light in weight, and excellent in discardability.
  • the negative electrode material consisting of the positive electrode, the separator and the gel-like metal is wrapped in an outer package molded by a laminate sheet containing a heat-fusible resin layer, Has been proposed (for example, Japanese Patent Laid-Open No. 2004-288571).
  • an air diffusion sheet, an air electrode sheet, a separator, a gelled negative electrode metal, and a negative electrode assembly are laminated to form a thick power generating element.
  • the exterior body 11 of the magnesium-air battery 10 of the present embodiment is formed of a sheet material containing paper, and the sheet material covers the magnesium electrode (metal electrode) 15 with gaps SF and SR open. And a pair of upper plate portion constituting pieces 25F and 25R functioning as a support bending portion for bending the part of the sheet material to cross the gaps SF and SR and support the magnesium electrode 15, so that paper is contained
  • the magnesium electrode 15 can be supported with a simple configuration such as bending a part of the exterior body 11 formed of a sheet material, and it is advantageous for securing the amount of the electrolyte and reducing the weight. Further, the weight reduction of the exterior body 11 makes it possible to obtain a high weight energy density.
  • the number of parts can be reduced, and it is easy to add a configuration of power generation elements other than the magnesium electrode 15. Therefore, the cost can be easily reduced, and the degree of freedom in changing the configuration is also high.
  • each upper plate portion constituting piece 25F, 25R is a wall portion (front wall portion 22) on the air electrode 13 side with respect to the magnesium electrode 15 in the sheet material (punched sheet 100), and on the opposite side to the air electrode 13.
  • the first bent portions 25F1 and 25R1 are provided above the liquid level UL of the electrolytic solution in the exterior body 11 and inclined obliquely downward toward the magnesium electrode 15, the first bent portions 25F1 and 25R1 While becoming difficult to take out electrolyte solution outside, the electrolyte solution adhering to the lower surface of 1st bending part 25F1, 25R1 can be returned efficiently.
  • the upper plate constituting piece 25R connected to the rear wall 23 is divided on the basis of the boundary between the tab portion 15T and the non-tab portion without the tab portion 15T in the width direction of the magnesium electrode 15, and the tab portion side One of the divided portion 25X (FIG. 3) and the divided portion 25Y (FIG.
  • the exterior body 11 has the bottom plate portion 21 bent in a downward convex shape in which the lower end of the magnesium electrode 15 is fitted, the lower end of the magnesium electrode 15 can be positioned with a simple bending structure to prevent displacement.
  • a conventional metal-air battery has been proposed in which an anode material made of a positive electrode, a separator and a gel-like metal is wrapped in an outer package formed of a laminate sheet containing a heat-fusible resin layer (e.g. 2004-288571), as batteries other than metal-air batteries, those having a composite paper container in which an exterior body is combined with paper are proposed (for example, Japanese Patent No. 4296771).
  • an air diffusion sheet, an air electrode sheet, a separator, a gelled negative electrode metal, and a negative electrode assembly are stacked to form a thick power generating element. Since the element is housed and held in the recess formed between the negative electrode side laminate sheet and the positive electrode side laminate sheet, the number of parts is large, the structure is complicated, and the cost reduction is disadvantageous. On the other hand, if the outer casing of the metal-air battery is formed of a sheet material containing paper, it is low in cost, light in weight, and advantageous in discardability.
  • the metal-air battery case has an opening for taking in air through the air electrode
  • the electrolyte penetrates from the end of the opening and the strength decreases and the appearance is deteriorated.
  • the exterior body 11 is formed of a sheet material (punched sheet 100) containing paper, and the purpose is to suppress the influence of the electrolyte penetration from the end face of the opening 22K for taking in air. I have one.
  • the end face processing of the opening 22K will be described below.
  • the end face of the opening 22K is subjected to end face treatment for preventing the permeation of the electrolytic solution injected into the inside, whereby the electrolyte permeates from the end face and the strength of the exterior body 11 decreases and the appearance It avoids the situation that causes deterioration.
  • end surface treatment when roughly classified, a structure (end surface covering structure) covering the end surface of the sheet material (hereinafter referred to as sheet material 101) itself and a structure covering the sheet material 101 and the air electrode 13 (Cover structure of air electrode utilization type), and an embodiment of end face processing will be described below.
  • FIG. 6 is a cross-sectional view schematically showing the first embodiment.
  • the sheet material 101 constituting the exterior body 11 is formed in a two-layer structure including a paper layer 102 containing paper and an inner layer 103 constituting a laminate layer.
  • the inner layer 103 is a layer that makes the inner surface side of the outer package 11 impervious to liquid, and in the present embodiment, a film made of a synthetic resin having waterproofness (corresponding to liquid resistance to the electrolytic solution) and heat fusion. It is formed of
  • a polyolefin resin, a polyester resin, or the like is used, and a film made of polyethylene is particularly preferable.
  • the air electrode 13 is attached to the opening 22K of the exterior body 11 from the outside, and the tab portion 13T can be disposed outside without being processed into the exterior body 11.
  • the air electrode 13 is formed in a three-layer structure including a base layer 111 made of copper mesh, and an inner layer 112 and an outer layer 113 provided on the inner and outer surfaces of the base layer 111.
  • the inner layer 112 and the outer layer 113 are layers having air permeability and non-water permeability (non-liquid permeability), and in this embodiment, polytetrafluoroethylene (PTFE) and carbon black are mixed to form a large number of fine pores. It is formed in the provided porous structure.
  • PTFE polytetrafluoroethylene
  • the edge portion 101A of the sheet material 101 is folded outward.
  • This turning angle is 180 degrees.
  • the edge portion 101A overlaps the outside of the portion 101B other than the edge portion 101A, and the inner circumferential layer of the edge portion 101A is exposed outward.
  • the air electrode 13 is superimposed on the area of the outwardly exposed inner layer 103 so as to bring the inner layer 112 into contact, and is joined by heat fusion. Thereby, the gap between the air electrode 13 and the edge 101A is closed.
  • the end face of the edge portion 101A of the sheet material 101 can be exposed outward so as not to be in contact with the electrolytic solution inside, and the air electrode 13 is utilized by using the inner layer 103 of the sheet material 101. Can be joined. Therefore, penetration of the electrolytic solution from the end face of the opening 22K can be prevented by a simple method of bending the sheet material 101, and the strength reduction of the exterior body 11 and the deterioration of the appearance can be avoided. Moreover, this coating process also has the merit that it can be applied even when the outer surface (the outer surface of the sheet material 101) of the exterior body 11 is not laminated.
  • FIG. 7A is a cross-sectional view schematically showing the second embodiment.
  • the edge portion 101A located at the peripheral portion of the opening 22K is folded outward.
  • the outer surface of the sheet material 101 is a flat continuous surface.
  • the air electrode 13 can be joined by heat fusion, and the amount of protrusion of the air electrode 13 from the sheet material 101 (exterior body 11) can be reduced.
  • the magnesium air battery 10 thinner than the first embodiment.
  • FIG. 7B shows the case where the outer surface of the exterior body 11 is laminated.
  • the outer layer 104 constituting the laminate layer is formed of a film made of a heat fusible resin (for example, polyethylene (PE)).
  • PE polyethylene
  • FIG. 8 is a sectional view schematically showing a third embodiment.
  • the films 121 and 122 which are sheet-like impermeable materials are attached to both the front and back sides of the paper layer 102, and the respective films 121 and 122 are joined by heat fusion or the like to form the opening 22K.
  • Cover the end face of the The film 121 on the inner layer side also serves as the inner layer 103 (see FIG. 8) constituting the laminate layer of the sheet material 101, and the film 122 on the outer layer side constitutes the outer layer 104 (FIG. 8) constituting the laminate layer of the sheet material 101. See also).
  • a single layer film or a laminated film may be applied to the films 121 and 122, and various films used for known end face protection members and the like can be applied.
  • a material having heat resistance and mechanical strength may be applied to the films 121 and 122 (or the base of each of the films 121 and 122).
  • a stretched film of stretched polyethylene terephthalate, stretched nylon, stretched polypropylene, stretched vinyl alcohol or the like may be used.
  • laminated films described in JP-A-8-337238 are preferable.
  • a laminated film is described in which a front or back layer is an adhesive layer made of a heat fusible resin, and an intermediate layer having a melting point higher than that of the adhesive layer is provided adjacent to the adhesive layer.
  • FIGS. 9A to 9D are sectional views schematically showing the fourth embodiment in chronological order.
  • the sheet 22 is provided with an opening 22K (FIG. 9A), and a sheet-like liquid-impervious material is formed on both the front and back sides so as to be a window (final lamination configuration) covering the opening 22K.
  • An inner layer 103 and an outer layer 104 are provided by laminating a film (for example, a polyethylene film), which is a material, or by an extruder process, and the inner layer 103 and the outer layer 104 are laminated together at the opening 22K (FIG. 9). (B)).
  • a film for example, a polyethylene film
  • the bonded and integrated part is punched out.
  • a part of the bonded and integrated part (in FIG. 9, symbol FX) remains around the opening 22K, and the end face of the opening 22K is covered.
  • the air electrode 13 is joined by heat fusion (see FIG. 9D).
  • the end face of the opening 22K can be covered by a relatively simple operation such as bonding and punching, and a coated form in which the end face of the opening 22K is wrapped with a film can be obtained. Thereby, the permeation of the electrolytic solution from the end face of the opening 22K can be prevented, and the strength reduction of the exterior body 11 and the deterioration of the appearance can be avoided.
  • the air electrode 13 can be easily joined by heat fusion using the outer layer 104 of the sheet material 101.
  • the covering process of this embodiment can be performed simultaneously with the lamination when laminating both sides of the paper layer 102.
  • the step of forming the window covering the opening 22K (FIG. 9B, FIG. 9C) is not limited to bonding the films from both sides of the opening 22K, but may be performed on one side of the opening 22K.
  • a piece of film may be stacked and bonded to a film (for example, the inner layer of the sheet material 101) provided in advance in the opening 22K, and a part of the bonded films may be punched out.
  • the structure of the mouthpiece is simplified while using a window-sticking film, and the inner peripheral end face of the base material through hole is properly covered, and the contents on the inner peripheral end face of the base material through hole
  • the technique described in Japanese Patent No. 3047755 may be applied, which is said to prevent soaking.
  • FIG. 10 is a cross-sectional view schematically showing the fifth embodiment.
  • the film 125 which is a sheet-like non-liquid-permeable material covering the end face of the opening 22K, is formed in a three-layer structure in which the adhesive layers 127 and 128 are provided on both sides of the support layer 126 made of stretched film It is done. Then, as shown in FIG. 10, the end face of the opening 22K of the sheet material is wrapped by the film 125, and in this state, it is joined by heat fusion.
  • the end face of the opening 22K can be wrapped and covered with the film 125, and an effect such as the permeation of the electrolytic solution from the end face of the opening 22K can be prevented.
  • the air electrode 13 can be easily bonded by using the adhesive layer 128 of the film 125.
  • the heat resistance is improved by applying the laminated film described in JP-A-8-337238, and generation of pinholes and the like due to heat fusion is realized. It becomes possible to avoid and to improve adhesion stability.
  • FIG. 11 is a cross-sectional view schematically showing a sixth embodiment.
  • the end face of the opening 22K is impregnated with the hydrophobic agent MX, thereby preventing the electrolyte from permeating the end face, thereby lowering the strength of the exterior body 11 or Avoid the deterioration of the appearance.
  • a urethane adhesive or liquid paraffin may be applied to the hydrophobic agent MX.
  • the agent MX an organic solvent is used, and one having a low viscosity is preferable.
  • the medicine MX can be easily held in the gaps of the paper fibers from the end face of the sheet material 101, and the effect of preventing the permeation of the electrolytic solution can be obtained for a long time.
  • FIG. 12 is a cross-sectional view schematically showing the seventh embodiment.
  • a hot melt also referred to as a hot melt adhesive
  • the hot melt HX known materials such as thermoplastics such as ethylene vinyl acetate (EVA) and urethane-based reaction curing type hot melt resins are applicable. Thereby, the effect that the penetration of the electrolyte solution from the end face of the opening 22K can be prevented can be obtained by the hot melt HX.
  • the hot melt HX bites into the inner layer 112 of the air electrode 13, ie, the porous surface, the bonding strength between the hot melt HX and the air electrode 13 can be maintained high. Therefore, the bonding strength of the hot melt HX is efficiently enhanced by utilizing the surface structure of the air electrode 13, which is advantageous for improving the durability of the coating.
  • a coating agent for example, a curable adhesive in the form of jelly which has high viscosity and is hardened after processing, instead of the hot melt HX.
  • this covering process has an advantage that it can be applied even when the outer surface of the exterior body 11 is not laminated.
  • hot melt, tape attachment, or adhesive attachment may be used.
  • FIG. 13 is a cross sectional view schematically showing an eighth embodiment.
  • a film 131 which is a sheet-like impermeable material is attached to one surface (inner surface) of the sheet material 101, and the end 131A of the film 131 is bonded to the air electrode 13.
  • the film 131 is attached from the sheet material 101 to the air electrode 13, and the end face of the opening 22 ⁇ / b> K is covered with the film 131.
  • a known material such as a heat fusible resin (for example, polyethylene (PE)) can be applied to the film 131, and the film 131 is bonded to the air electrode 13 by heat fusible or the like.
  • PE polyethylene
  • the film 131 can prevent the electrolyte from permeating the end face of the opening 22K.
  • the film 131 is bonded to the inner layer 112 of the air electrode 13, that is, in a state of being bitten into the porous surface, and the bonding strength between the film 131 and the air electrode 13 can be maintained high.
  • the surface structure of the air electrode 13 is used to efficiently increase the bonding strength of the film 131, which is advantageous for improving the durability of the coating.
  • this covering process has an advantage that it can be applied even when the outer surface of the exterior body 11 is not laminated.
  • FIG. 14A and 14B show an example of the film 131.
  • FIG. FIG. 14A shows the case where the film 131 is formed integrally.
  • a four-way frame in which four rectangular portions (upper side covering portion 132, left and right side covering portions 133 and 134, lower side covering portion 135) covering each side of rectangular opening 22K of air electrode 13 are integrated. Film is produced.
  • the integral frame shape extending over the edge of the opening 22K can reduce the number of parts and facilitate the covering operation.
  • FIG. 14B shows the case where four covering portions 132 to 135 are formed separately. That is, strip portions corresponding to the four covering portions 132 to 135 are separately prepared, and each strip portion is joined by heat fusion or the like to form a frame-shaped film extending over the edge of the opening 22K. It is made. In this case, the remainder of the film material can be reduced when it is cut out from the film material as compared to the case of FIG. In addition, it becomes easy to produce films of various shapes, and it becomes easy to cope with design changes and size changes.
  • the exterior body 11 of this configuration is formed of the sheet material 101 containing paper, and the sheet material 101 covers the magnesium electrode (metal electrode) 15 with the gaps SF and SR open and at least the inner surface side
  • the case body 11 is provided with an opening 22K to which the air electrode 13 is attached from the outer surface side, and the end face of the opening 22K prevents permeation of the electrolytic solution injected therein. Since the end face processing is performed, the configuration in which the exterior body 11 is formed of the sheet material 101 containing paper can suppress the influence of the electrolyte penetration from the end face of the opening 22K for taking in air, etc. .
  • the end surface of the opening 22K is a sheet material. It is possible to suppress the influence of the electrolytic solution on the opening 22K by a simple method such as bending 101. In this case, members other than the sheet material 101 are unnecessary, which is advantageous for cost reduction. Further, if the end face of the opening 22K is covered with the film 121, 122, 125, 131 which is a sheet-like non-liquid-permeable material as the end face treatment (third to eighth embodiments, FIG. 8 to 13), coating performance according to film performance can be obtained. In this case, by using a widely distributed film, cost reduction can be easily achieved, and desired coating performance can be selected by selecting a film.
  • the films 121 and 122 which are sheet-like non-liquid permeable materials are attached to both surfaces of the sheet material 101 and the films 121 and 122 are joined to cover the end surface (third embodiment, FIG. And) when laminating both sides of the sheet material 101, it can coat using the lamination film.
  • a film (non-liquid-permeable material) or a film (non-liquid-permeable material) 125 constituting the inner layer 103 and the outer layer 104 is attached to the surface of the sheet material 101, and the end face of the opening 22K is wrapped by these films. If the end face is covered (fourth and fifth embodiments, FIG. 9, FIG. 10), and as shown in FIGS. 9 and 10, a covering form in which the end face of the opening 22K is wrapped can be obtained. It becomes easy to prevent the penetration of the electrolytic solution.
  • the end face of the opening 22K is impregnated with a hydrophobic drug MX as the end face treatment (sixth embodiment, FIG. 11), the end face of the opening 22K is obtained by a method using this agent MX. Penetration of the electrolyte from the In this case, it is advantageous to improve the durability of the coating by using a drug of low viscosity which can be held in the fiber gap of the end face of the opening 22K for the drug MX. Further, as the end face treatment, when the hot melt HX is applied from the sheet material 101 to the air electrode 13 and the end face of the opening 22K is covered with the hot melt HX (seventh embodiment, FIG. 12) The bonding strength of the hot melt HX functioning as a coating can be efficiently enhanced by utilizing the surface asperity shape of the pole 13.
  • a film (non-liquid-permeable material) 131 is pasted from the sheet material 101 to the air electrode 13 and the end face of the opening 22 K is covered with the film 131 (Eighth Embodiment)
  • the surface asperity shape of the air electrode 13 can be utilized to efficiently increase the bonding strength of the film 131 functioning as a coating.
  • the film 131 is made into an integral frame extending over the edge of the opening 22K (FIG. 14A), the film is attached to each edge of the opening 22K and In comparison, the number of parts can be reduced, and only one pasting operation is required.
  • a plurality of strip-like films are connected so as to form a frame shape extending over the edge of the opening 22K (FIG. 14 (B)). It becomes easy to reduce the remainder of material when it cuts out from the film material of the sex material, and it becomes easy to correspond to various shapes.
  • the present invention is not limited to the above configuration, and various modifications and changes are possible.
  • two or more of the end face treatments described above may be combined.
  • an impregnation method in which the end face of the opening 22K is impregnated may be combined with the embodiment except the impregnation method of the sixth embodiment.
  • the folding method described in the first and second embodiments may be combined with the film bonding method described in the other embodiments. It becomes easy to improve coating performance (durability) etc. by combining.
  • the above-mentioned embodiment demonstrated the case where each member was joined by heat sealing, you may apply the joining method of other than that. For example, impulse sealing, ultrasonic sealing, pressure bonding after heating with hot air, hot melt, tape application, an adhesive, or the like may be applied to a film for covering.
  • FIG. 15 is a perspective view of the exterior body 11 according to the second embodiment
  • FIG. 16 is a view in which the exterior body 11 according to the second embodiment is developed (a view corresponding to the punching sheet 100).
  • the same components as those described above are denoted by the same reference numerals, and redundant description will be omitted, and different parts will be described in detail.
  • an upper plate portion constituting piece 25F continuous with the upper edge 22A (FIG. 16) of the front wall portion 22 is formed longer in the vertical direction than the upper plate portion constituting piece 25F (FIG. 3) of the first embodiment. It is done.
  • the upper plate portion constituting piece 25F has the first bent portion 25F1, the second bent portion 25F2, and the first bent portion 25F1 in order from the front wall portion 22 with reference to the folds 22C and 22D (FIG. 16) which are divided into three vertically. Three bent portions 25F3 are provided.
  • the upper plate portion constituting piece 25R connected to the upper edge 23A (FIG. 16) of the rear wall portion 23 is also formed longer than the upper plate portion constituting piece 25R (FIG. 3) of the first embodiment,
  • the first bent portion 25R1, the second bent portion 25R2, and the third bent portion 25R3 are provided in order from the back wall 23 side with reference to the fold lines 23C and 23D (FIG. 16) divided into three.
  • FIG. 17 is a view showing the exterior body 11 of the second embodiment
  • FIG. 17 (A) is a front view
  • FIG. 17 (B) is a cross-sectional view taken along the line AA of FIG. 17 (A).
  • FIG. As shown in FIGS. 17A and 17B, the second bent portions 25F2 and 25R2 are bent to the inside of the exterior body 11, and the third bent portions 25F3 and 25R3 are bent to the outside of the exterior body 11.
  • the tips of the third bent portions 25F3 and 25R3 are longer than the second bent portions 25F2 and 25R2 It projects upward and the third bent portions 25F3 and 25R3 come in contact with each other.
  • the upper plate portion constituting pieces 25F, 25R are bent along the magnesium electrode 15 to the inside of the outer package 11 and are folded back to the opposite side so that they are folded back parts that project beyond the magnesium electrode 15 to the outer surface of the outer package 11
  • the second bent portion 25F2, 25R2 and the third bent portion 25F3, 25R3 are formed.
  • the upper portion of the magnesium electrode 15 is sandwiched between the lower portions of the pair of front and rear folded portions (lower portions of the third bent portions 25F3 and 25R3), and the state is maintained.
  • the folded-back portions that project to the outside of the outer package 11 are joined together by heat fusion.
  • the magnesium electrode 15 can be held at the lower portion of the folded portion, and the upper plate portion constituting pieces 25F and 25R, that is, the upper portion of the exterior body 11 can be sealed. Therefore, both of the upper plate portion constituting pieces 25F, 25R function as a support bending portion supporting the magnesium electrode 15, and also function as a sealing portion sealing the upper portion of the exterior body 11.
  • the sealing of the upper portion can be made reliable, and evaporation and leakage of the electrolytic solution can be suppressed.
  • the upper plate portion constituting pieces 25F, 25R are not divided into right and left, it becomes difficult to form wrinkles at the time of folding.
  • the rigidity of the upper plate portion constituting pieces 25F, 25R itself is improved, so that wrinkles and deformation can be prevented, rigidity improvement of the exterior body 11, and support capacity of the magnesium electrode 15 are improved. It is possible.
  • the tab portion 15T protruding upward is not formed on the magnesium electrode 15, but instead, a wire 15H (FIG. 21 described later) is connected to the top of the magnesium electrode 15 and It has become.
  • sheet pieces 26F are integrally provided on the left and right of the first bent portion 25F1 which is a lid that is bent at the upper edge 22A of the front wall 22 and covers the upper side of the magnesium electrode 15. ing. As shown in FIG. 15, these sheet pieces 26F are bent downward (along the inner bent pieces 24FU) on the basis of the left and right side edges of the first bent portion 25F1, and then the outer bent pieces 24FS of the side wall portion constituting pieces 24F. The sheet pieces 26F which are vertically folded are sandwiched by a heat fusion machine and joined by heat fusion. By fixing the upper ends of the exterior body 11 with the sheet piece 26F as described above, the upper portions of the bent pieces 24FU and 24FS can be reinforced.
  • the gap between the first bent portion 25F1 serving as the lid and the side wall portion constituting piece 24F serving as the side wall can be sealed by the sheet piece 26F, and the evaporation and leakage of the electrolytic solution are suppressed. can do. Further, the connection strength between the first bent portion 25F1 and the side wall portion constituting piece 24F is improved, and the upward spread of the first bent portion 25F1 and the spread of the side wall portion constituting piece 24F in the lateral direction can be suppressed.
  • the above-described also applies to the left and right of the first bent portion 25R1 which is a lid portion which is bent at the upper edge 23A of the rear wall portion 23 and covers the upper side of the magnesium electrode 15.
  • a sheet piece 26R similar to the sheet piece 26F is integrally provided (see FIG. 16). As shown in FIG. 15, these sheet pieces 26R are bent downward (along the inner bent pieces 24RU) based on the left and right side edges of the first bent portion 25R1, and then the outer bent pieces 24RS of the side wall portion constituting pieces 24R. After bending the sheet 26 R vertically, the vertically bent sheet piece 26 R is sandwiched by a heat fusion machine and joined by heat fusion.
  • the upper portions of the bent pieces 24RU and 24RS can be reinforced.
  • the space between the first bent portion 25R1 serving as the lid and the side wall portion constituting piece 24R serving as the side wall portion can be sealed to suppress evaporation and leakage of the electrolytic solution, and the first bent portion 25R1 and the side wall portion
  • the connection strength with the component piece 24R is improved, and the upward extension of the first bent portion 25R1 and the lateral extension of the side wall component piece 24R can be suppressed.
  • the heat fusion between the sheet piece 26F and the sheet piece 26R which are bent vertically is not only heat uniforming but also heat fusion only once, so it is preferable to heat fuse both at the same time.
  • notches 28 are provided in advance between the left and right sheet pieces 26F and 26R and the upper plate portion constituting pieces 25F and 25R, and the exterior body 11 is assembled as shown in FIG. As shown, a space 28K through which a wire 15H (see FIG. 21 described later) from the magnesium electrode 15 can pass is secured between the sheet pieces 26F and 26R and the upper plate component pieces 25F and 25R.
  • the upper plate portion constituting pieces 25F and 25R (support bending portions) It is bent from the wall 22 and the rear wall 23 along the magnesium electrode 15 to the inside of the exterior body 11 and has a folded back portion that is folded back to the opposite side and overhangs the exterior of the exterior body 11 more than the magnesium electrode 15 Since the magnesium electrode 15 is held at the lower part of the folded back portion and the remaining portions protruding to the outside of the exterior body 11 are joined to each other to seal the upper plate portion constituting pieces 25F and 25R, evaporation and leakage of the electrolyte It is possible to suppress deformation of the exterior body 11 while suppressing the displacement of the magnesium electrode 15 and keep the separation distance between the magnesium electrode 15 and the air electrode 13 appropriately. .
  • the upper plate portion configuration pieces 25F, 25R protrudes upward, it can be used as a gripping portion when carrying the exterior body 11. Further, since the parts of the upper plate component pieces 25F, 25R are joined by fusion bonding, they can be easily joined utilizing the heat fusion property of the sheet material laminated and the like with the heat fusion resin. it can.
  • upper-plate part structure piece 25F, 25R is not limited to the said shape.
  • the upper plate portion 25 may be elongated to change the shape of the third bent portions 25F3 and 25R3 to the shape of a handle to further facilitate gripping.
  • the third bent portions 25F3 and 25R3 are enlarged in the vertical direction, and elongated holes 29 extending in the lateral direction are provided, and a finger such as a user is passed through each elongated hole 29 to make the exterior body 11
  • the aspect which formed one handle easy to hold is shown.
  • each long hole 29 of one third bent portion 25R3, a bent portion 29A which is bent toward each long hole 29 of the other third bent portion 25F3 is provided. It is also possible to ease the hit of the finger.
  • segments each of 3rd bending part 25F3, 25R3 into right and left is further provided, and it is the aspect which formed two handles. By providing this notch 30, it is possible to avoid interference with internal members.
  • FIG. 19A is a front view of the exterior body 11 of the third embodiment.
  • FIG. 19B is a cross-sectional view taken along the line BB in FIG. 19A.
  • the exterior body 11 is provided with a pair of left and right bottom plate sheets 35 into which the lower end of the magnesium electrode 15 is fitted.
  • the lower end of the magnesium electrode 15 is fitted with the same sheet material as the sheet material constituting the exterior body 11, that is, the sheet material in which the paper and the heat fusible resin are compounded by laminating or the like. It is bent and formed in a downward convex shape.
  • FIG. 20 is a perspective view of the bottom plate sheet portion 35 of the third embodiment.
  • the bottom plate sheet portion 35 is substantially horizontal inward from the lower end of each of the end portions 35AF and 35AR and a pair of front and rear end portions 35AF and 35AR joined to lower portions of the front wall portion 22 and the rear wall portion 23 respectively.
  • a pair of front and rear first bent portions 35B (35BF, 35BR) which are bent into two, a pair of front and rear second bent portions 35C which are bent downward from one end of each first bent portion 35B, and each second bent portion 35C (35CF, 35CF, And a bridge portion 35D for connecting the lower ends of the 35 CR) integrally.
  • the distance between the second bent portions 35C is formed to have substantially the same length as the thickness of the magnesium electrode 15. Thereby, as shown in FIG. 19B, the lower end of the magnesium electrode 15 is held by arranging the magnesium electrode 15 between the second bent portions 35C.
  • the end portions 35AF and 35AR are thermally fused to the sheet material so as to straddle the bottom plate portion 21 of the exterior body 11 in a state in which the sheet material forming the exterior body 11 is spread in a planar shape. It is joined. Then, when the sheet material is bent in a concave shape that opens upward to form the exterior body 11, the first bent portion 35A and the second bent portion 35B stand up inside the exterior body 11 so as to be separated from the bottom plate portion 21.
  • the bottom sheet portion 35 is formed.
  • the sheet length between the end portions 35AF and 35AR in the bottom plate sheet portion 35 is the bottom plate of the exterior body 11 It is formed equal to the distance between the joining portion with the sheet portion 35 (the distance shown by symbol LX in FIG. 19B), and can be foldable into a shape shown by the portions 35B to 35D. A fold is provided in advance.
  • the bottom plate sheet portion 35 developed flat can be easily joined, and then, the sheet material of the exterior body 11 is concaved to form the bottom plate portion 21 If it bends, the rising part which consists of the 1st bent part 35B and the 2nd bending part 35C of bottom plate sheet part 35 will stand up so that it may estrange from bottom plate part 21, bottom plate sheet part 35 can be assembled easily.
  • the bottom plate sheet portion 35 it is possible to suppress positional deviation of the magnesium electrode 15 before and after, and to properly maintain the distance (separation distance) between the magnesium electrode 15 and the air electrode 13. Moreover, the effect that it becomes possible to suppress the damage of the exterior body 11 by the magnesium electrode 15 is also acquired. Further, the bridge portion 35D of the bottom plate portion 35 is positioned on the bottom plate portion 21 by being fitted to the downward convex portion 21T of the bottom plate portion 21. This also makes it easy to suppress the displacement of the magnesium electrode 15.
  • the bridge portion 35D of the bottom plate sheet portion 35 is disposed at the center of the exterior body 11 in the front-rear direction, but the front and rear of the first bent portion 35B (35BF and 35BR) of the bottom plate sheet portion 35
  • the ratio of the length of the direction is adjusted, and the ratio of the length of the first bent portions 25F1 and 25R1 of the upper folded plate members 25F and 25R in the front-rear direction is adjusted to correspond to it. It is possible to appropriately adjust the position in the front-rear direction (the distance between the electrodes).
  • the end portions 35AF and 35AR of the bottom plate portion 35 are joined to the sheet member by heat fusion, but at least one of the front and rear end portions 35AF and 35AR is a thermal fusion. It should be worn.
  • FIG. 21 is a perspective view of a magnesium-air battery 10 according to a fourth embodiment
  • FIG. 22 is a side cross-sectional view of the magnesium-air battery 10 of the fourth embodiment.
  • the magnesium-air battery 10 is provided with an electrolyte container 41 for containing the electrolyte contained in the electrolytic solution, and when used as a battery, the electrolyte is dissolved out by pouring in water so as to be an electrolytic solution. ing.
  • water is easier to obtain than an electrolytic solution (for example, saline solution). Therefore, if water can be prepared, the advantage of being able to use a battery and being able to be used anywhere is obtained.
  • the electrolyte container 41 includes an electrode plate mounting sheet 42 mounted on the surface of the magnesium electrode 15 opposite to the air electrode 13, and a bag 43 provided on the electrode plate mounting sheet 42. As shown in FIG. 22, the electrode plate mounting sheet 42 is held between the front and rear pair of upper plate portion constituting pieces 25 F and 25 R of the exterior body 11 so as to be held. More specifically, as shown in FIG.
  • the second bent portions 25F2 and 25R2 of the upper plate portion constituting pieces 25F and 25R are bent to the outside (corresponding to the upper side) of the exterior body 11, and these second bent portions
  • the upper portion of the electrode plate mounting sheet 42 is sandwiched between 25F2 and 25R2, and in that state, the second bent portions 25F2 and 25R2 and the electrode plate mounting sheet 42 are joined together by heat fusion.
  • the upper portion of the electrode plate mounting sheet 42 is suspended and held by the exterior body 11.
  • FIG. 23A is a perspective view of the electrolyte containing body 41 as viewed from the air electrode 13 side together with the magnesium electrode 15, and FIG. 23B is a perspective view of the electrolyte container 41 as viewed from the opposite side to the air electrode 13.
  • the electrode plate attachment sheet 42 is formed of the same sheet material as the sheet material constituting the exterior body 11, that is, a sheet material in which paper and a thermally fusible resin are composited by laminating or the like.
  • the electrode plate mounting sheet 42 includes a sheet body 42A covering the back of the magnesium electrode 15, a pair of left and right lower fitting portions 42B which are bent from the lower portion of the sheet body 42A and into which the lower portion of the magnesium electrode 15 is fitted.
  • an upper fitting portion 42C which is cut and raised at a part of the upper center of the upper part and fitted in a recess 15D provided in the upper part of the magnesium electrode 15.
  • the movement of the magnesium electrode 15 in the vertical direction and the front-rear direction with respect to the electrode plate mounting sheet 42 is restricted by the three fitting portions 42B and 42C.
  • the electrode plate mounting sheet 42 and the magnesium electrode 15 are crimped and fixed to each other by a pair of left and right crimp fittings 45. More specifically, as the crimp fitting 45, an edge fitting (a fitting also referred to as an eyelet or a hatch) for rounding a round hole is used, and the crimp fitting 45 is used as the electrode plate mounting sheet 42 and the magnesium electrode 15 The electrode plate mounting sheet 42 and the magnesium electrode 15 are fixed by mounting the pair of left and right round holes.
  • a metal fitting provided at the tip of the wiring 15H is fixed to one of the crimp fittings 45. Thereby, the magnesium electrode 15 and the wiring 15H can be easily connected.
  • This wire 15H is drawn out of the case 11 through the space 28K (FIG. 21) provided in the case 11 and used as a part of the negative electrode wire instead of the tab portion 15T shown in FIG. .
  • a connection terminal (in the present configuration, a terminal for connection) 15J used for wire connection is attached to facilitate connection with other wires.
  • the wire 13H is connected to the upper portion of the air electrode 13 using the same crimp fitting 46 as the crimp fitting 45, and the same connection terminal 13J is attached to the other end of the wire 13H. It shows.
  • the lower fitting portion 42B formed by bending the lower portion of the electrode plate mounting sheet 42 is, as shown in FIG. 22, the same distance as the separation distance (corresponding to the gap SF) between the magnesium electrode 15 and the front wall 22 It projects to the wall 22 side and abuts on the back of the front wall 22.
  • the lower fitting portion 42B also functions as a restricting member that restricts the distance between the magnesium electrode 15 and the air electrode 13 to a certain distance.
  • the electrode plate mounting sheet 42 is provided with a pair of left and right lower bent portions 42D formed by bending the lower portion to the opposite side of the air electrode 13. As shown in FIG.
  • these lower bent portions 42D project toward the rear wall portion 23 by the same length as the separation distance between the magnesium electrode 15 and the rear wall portion 23 (corresponding to the clearance SR). It abuts on the back surface, and functions as a restricting member that restricts the distance between the magnesium electrode 15 and the rear wall 23 to a constant value.
  • the positional deviation in the front-rear direction of the lower part of the magnesium electrode 15 can be effectively suppressed, and the separation distance between the magnesium electrode 15 and the air electrode 13 can be properly maintained.
  • the bag 43 is formed of a water-permeable material such as paper, nonwoven fabric, water-permeable material such as woven fabric, starch-based film such as a wafer, polyvinyl alcohol-based film, and the like.
  • a water-permeable material such as paper, nonwoven fabric, water-permeable material such as woven fabric, starch-based film such as a wafer, polyvinyl alcohol-based film, and the like.
  • sodium chloride as an electrolyte is put in the inside of the bag 43, and then the upper part of the bag 43 is joined to the electrode plate mounting sheet 42 by heat fusion. By heat-sealing the upper portion of the bag body 43, the electrolyte is not exposed to the outside or leaked out even if the posture is upside down.
  • the joining between the electrode plate mounting sheet 42 and the bag body 43 is not limited to heat fusion, and a stapler, a tape or the like may be used.
  • the mounting position of the bag body 43 is the back surface (surface opposite to the magnesium electrode 15) of the electrode plate mounting sheet 42 and is set below the hole 25H (see FIG. 16) serving as a water injection port. .
  • the electrolyte can be rapidly dissolved by the injected water, and a suitable electrolyte can be rapidly generated.
  • the bag 43 that wraps the electrolyte is attached to the electrode plate mounting sheet 42, the situation in which the electrolyte adheres to the magnesium electrode 15 and is corroded can be avoided.
  • the bag 43 has a gap smaller than the particle diameter of sodium chloride, and does not allow passage of solid sodium chloride, but has water permeability for passing water.
  • the average pore diameter of the bag 43 is preferably 0.05 mm to 0.3 mm, which is smaller than the particle diameter of sodium chloride.
  • the mass is preferably in the range of 4% to 18% with respect to the mass of water poured.
  • the inventors verified that if it is less than 4%, the resistance of the electrolyte increases and the voltage drop increases, so that the voltage is low and the power that can be taken out is reduced.
  • the content was more than 18%, it was confirmed that sodium chloride was saturated and precipitated at the end of discharge, and was accumulated between the electrodes inside the cell to inhibit the discharge reaction and to be unable to discharge.
  • you may also contain except sodium chloride.
  • the main component of the electrolyte may be sodium chloride, and other components may be included.
  • the electrode plate mounting sheet 42 is provided with a cut and raised portion 51 which is formed by cutting and raising a part of the sheet 42 and positioned above the bag body 43.
  • the cut-and-raised portion 51 is a horizontal plate portion 51A bent horizontally from the sheet main body 42A of the electrode plate attachment sheet 42 and a rear wall bent downward from the tip of the horizontal plate portion 51A and abutting on the rear wall portion 23 It is formed in an L-shaped cross section integrally provided with the contact portion 51B.
  • the horizontal plate portion 51A is disposed below the hole 25H serving as a water injection port and above the bag body 43, and functions as a diffusion member that applies the injected water to the horizontal plate portion 51A and diffuses it around Do.
  • the horizontal plate portion 51A a plurality of small holes are formed at intervals, and a part of the water is dropped downward through the small holes and the rest of the water is diffused to the surroundings. .
  • the injected water is diffused and supplied to the bag 43, so that the electrolyte in the bag 43 can be efficiently dissolved, and the timing of the discharge start can be advanced to facilitate extraction of electricity.
  • the horizontal plate portion 51A also functions as a measure of the insertion depth of the water injection jig when water is injected using the water injection jig or the like. Thereby, it is possible to prevent damage to the bag 43 due to the water injection jig or the like.
  • a pair of cut and raised portions 51 is provided on the left and right sides, and either or both of the cut and raised portions can be bent depending on the size of the bag 43. ing.
  • the bag body 43 is disposed only under the one cut and raised portion 51, only the one cut and raised portion 51 may be bent.
  • the both cut and raised portions 51 are bent and the electrolyte is made by putting water from both holes 25H. It can be melted efficiently.
  • an electrolyte container for containing an electrolyte for operating as a battery by pouring water into the exterior body 11 on the surface of the magnesium electrode 15 opposite to the air electrode 13.
  • the provision of the reference numeral 41 makes it possible to use the battery as a battery only by adding the solvent of the electrolytic solution, and to suppress the corrosion of the magnesium electrode 15 due to the influence of the electrolyte.
  • the electrolyte container 41 is a sheet material containing paper, and is attached to the electrode plate mounting sheet 42 mounted on the surface of the magnesium electrode 15 opposite to the air electrode 13 and the electrode plate mounting sheet 42 for electrolyte Since the bag body 43 for containing the above is provided, the sheet material intervenes between the magnesium electrode 15 and the electrolyte, and the corrosion of the magnesium electrode 15 due to the influence of the electrolyte can be suppressed. Moreover, since it is not necessary to attach the bag 43 containing an electrolyte to the package 11, the structure of the package 11 can be simplified easily, and the attachment of the bag 43 is also easy.
  • the electrode plate mounting sheet 42 is crimped and fixed to the magnesium electrode 15 and the bag 43 is fused to the electrode plate mounting sheet 42, the electrode plate mounting sheet 42 and the bag 43 can be easily attached.
  • the electrode plate mounting sheet 42 has a fitting portion 42B and an upper fitting portion 42C (regulating portion) for bending a part of the sheet 42 to restrict the movement of the magnesium electrode 15 with respect to the sheet, and the electrode plate mounting Since the sheet 42 is held by the case 11 and the magnesium electrode 15 is held by the case 11, the structure for directly holding the magnesium electrode 15 on the side of the case 11 is unnecessary, and the case 11 can be easily structured.
  • the magnesium electrode 15 supported by the electrode plate mounting sheet 42 is mounted on the bottom plate portion 21 of the exterior body 11. There is no need to put it. Therefore, the degree of freedom of the lower end position of the magnesium electrode 15 is improved, and as shown in FIG. 22, the lower end of the magnesium electrode 15 can be aligned to almost the same height as the lower end of the air electrode 13. Thereby, the part which hardly contributes to the battery reaction of magnesium electrode 15 can be reduced, and miniaturization of magnesium electrode 15 is attained.
  • the case where the electrode plate mounting sheet 42 is fixed by floating above the bottom plate portion 21 of the exterior body 11 has been described.
  • the lower portion of the electrode plate mounting sheet 42 may be placed on the bottom plate portion 21 by extending downward until reaching the bottom plate portion 21 of the body 11.
  • the relatively heavy magnesium electrode 15 can be supported using the bottom plate portion 21 of the exterior body 11.
  • FIGS. 25 (A) and 25 (B) An example of the electrolyte container 41 in this case is shown in FIGS. 25 (A) and 25 (B).
  • the lower portion of the electrode plate mounting sheet 42 is bent so as to form a flat plate portion 42G having the same shape as the opening in the exterior body 11. This makes it possible to secure a wide contact area between the lower portion (flat plate portion 42G) of the electrode plate mounting sheet 42 and the bottom plate portion 21 of the exterior body 11 and secure a supporting force of the electrode plate mounting sheet 42 It becomes easy to suppress the deformation of 21.
  • the lower portion (flat plate portion 42G) of the electrode plate mounting sheet 42 is fitted in the exterior body 11 and the front, rear, left, and right movement is regulated, the positional deviation of the electrode plate mounting sheet 42 can be effectively restricted. it can.
  • the electrode plate attachment sheet 42 is provided with projecting portions 42H projecting outward to the left and right at positions above the flat plate portion 42G, and each projecting portion 42H is
  • the left and right lower fitting portions 42B into which the lower portion of the magnesium electrode 15 is fitted are formed by bending the center side and inserting a part thereof into the flat plate portion 42G.
  • the shape of each portion such as the lower fitting portion 42B and the flat plate portion 42G is not limited to the above shape, and can be appropriately changed.
  • the cut-and-raised part 51 (refer FIG. 23 (B)) is not formed in the electrode plate mounting sheet 42. As shown in FIG. That is, the presence or absence of the cut and raised portion 51 can be changed as appropriate.
  • the shape of each part of the electrode plate mounting sheet 42 may be appropriately changed as long as the above-described functions can be realized.
  • FIG. 26 is a side sectional view of a magnesium-air battery 10 according to the fifth embodiment.
  • the magnesium-air battery 10 is the same as the fourth embodiment in that the magnesium-air battery 10 has an electrolyte container 41 consisting of an electrode plate mounting sheet 42 and a bag 43, but the electrode plate mounting sheet 42 forms the outer package 11
  • the fourth embodiment differs from the fourth embodiment in that it is provided integrally with the sheet material.
  • 28B is a diagram corresponding to the X region of FIG. 27,
  • FIG. 28C shows a diagram corresponding to the Y region of FIG. 27, and
  • FIG. 28D is a diagram corresponding to the Z region of FIG. It is a figure which corresponds.
  • the exterior body 11 is bent at the upper edge 23A of the rear wall 23 to form a lid (upper plate 25) that covers the top of the magnesium electrode 15.
  • the electrode plate mounting sheet 42 is connected to the bent portion 25R1 via the fold line 23C.
  • the electrode plate mounting sheet 42 has a rectangular sheet main body 42A which is bent into the outer package 11 through the fold line 23C, and the magnesium electrode 15 is crimped to the sheet main body 42A by a pair of left and right crimp fittings 45 (FIG. 17) It is fixed.
  • the first bent portion 25F1 serving as a lid portion which is bent at the upper edge 23A (corresponding to the fold) of the front wall portion 22 and which covers the upper side of the magnesium electrode 15 includes the first bent portion 25R1 and the electrode plate mounting sheet 42.
  • the insertion part 62 inserted in the opening part 61 (FIG. 28 (A)) provided in the boundary part of these, and the left-right paired tab part 63 located in the right and left of the insertion part 62 are provided integrally.
  • 1st bending part 25F1 and 25R1 comrades are connected by inserting the insertion part 62 in the opening part 61.
  • the pair of left and right tab portions 63 are bent to the inside of the exterior body 11.
  • a pair of left and right side pieces 42J connected to the left and right side edges of the sheet body 42A and a lower piece 42K connected to the lower edge of the sheet body 42A are integrated.
  • the pair of left and right side pieces 42J are respectively divided up and down to constitute an upper side piece 42JA and a lower side piece 42JB.
  • the upper side piece 42JA is, as shown in FIG. 28C, in a state where the sheet main body 42A is bent 90 degrees with respect to the lid (first folded portion 25R1), the upper side piece 42JA is the lid (first folded portion 25R1). It is bent almost at a right angle to get into the bottom.
  • the upper side piece 42JA abuts on the lower surface of the lid (first bent portion 25R1), so that movement of the sheet main body 42A to the lid (first bent portion 25R1) can be restricted.
  • the sheet main body 42A and the lid (the first bent portion 25R1) can be easily held at a right-angled positional relationship.
  • the lower side pieces 42JB fold the outer edges 42N of the inner folded portions 42JU by folding the inner side bent portions 42JU that are folded toward the rear wall 23 side of the exterior body 11 by folding the left and right side edges 42M of the sheet main body 42A. It has integrally with the outer side bending part 42JS bend
  • the lower piece 42K connected to the lower edge of the sheet body 42A is bent upward based on the lower edge of the sheet body 42A and joined to the sheet body 42A by heat fusion as shown in FIG.
  • moisture content (electrolyte solution) to a sheet end surface can be suppressed, and the strength reduction of a sheet
  • seat can be suppressed.
  • the lower edge of the sheet body 42A may be covered with a tape-shaped plastic film instead of providing the lower piece 42K and bending so as to prevent the infiltration of moisture to the end face of the sheet. In this configuration, as shown in FIG.
  • the lower end of the electrode plate mounting sheet 42 is positioned above the bottom plate portion 21 of the exterior body 11. That is, the electrode plate mounting sheet 42 is suspended and supported by the lid (the first bent portion 25R1) of the exterior body 11. As a result, the magnesium electrode 15 supported by the electrode plate mounting sheet 42 does not have to be placed on the bottom plate portion 21 of the exterior body 11, and the degree of freedom of the lower end position of the magnesium electrode 15 is improved.
  • the lower end of the magnesium electrode 15 by setting the lower end of the magnesium electrode 15 at a position higher than the lower end of the air electrode 13, a wide space between the magnesium electrode 15 and the bottom plate portion 21 of the exterior body 11 can be secured. Thereby, the part which hardly contributes to the battery reaction of magnesium electrode 15 can be reduced, and miniaturization of magnesium electrode 15 is attained.
  • the lower end of the magnesium electrode 15 may be aligned with the lower end of the air electrode 13 at substantially the same height.
  • a sheet piece 71R is integrally provided on the upper edge of a pair of left and right side wall part constituting pieces 24R (more specifically, inner bent pieces 24RU) connected to the left and right of the rear wall 23.
  • these sheet pieces 71R are joined by heat fusion to the lower surface of the first bent portion 25R1 which is the lid portion of the exterior body 11.
  • the bonding strength between the side wall portion constituting piece 24R and the first bent portion 25R1 is improved, and the bent shape of the rear wall portion 23, the side wall portion (side wall portion constituting piece 24R), and the lid portion (first bent portion 25R1) Can be held well.
  • a sheet piece 71F (FIG.
  • the electrode plate mounting sheet 42 mounted on the surface of the magnesium electrode 15 (metal electrode) opposite to the air electrode 13 is integrated with the sheet material forming the exterior body 11. Since it is provided, in addition to the various effects of the fourth embodiment, the number of parts can be reduced. Moreover, since the electrode plate mounting sheet 42 is provided in the lid (the first bent portion 25R1), the electrode plate mounting sheet 42 is suspended above the bottom plate portion 21 of the exterior body 11 as shown in FIG. It can be fixed. For this reason, it is not necessary to place the magnesium electrode 15 supported by the electrode plate mounting sheet 42 on the bottom plate portion 21 of the exterior body 11, and the flexibility of the lower end position of the magnesium electrode 15 is improved. Therefore, it is possible to secure a wide space that does not affect the cell reaction even if a space for pouring in water and mixing with the electrolyte and a product (magnesium hydroxide in this configuration) generated by the discharge reaction are accumulated.
  • the right and left sides of the electrode plate mounting sheet 42 are bent and joined to the rear wall 23 of the exterior body 11, positioning and holding of the electrode plate mounting sheet 42 can be performed, and the support of the magnesium electrode 15 (metal electrode) The strength can be easily secured, and the separation distance between the magnesium electrode 15 and the air electrode 13 can be maintained constant.
  • the metal-air battery of the present invention is not limited to the embodiments described above, and various modifications and changes are possible based on the technical concept of the present invention.
  • the shape of the exterior body 11 may be changed as appropriate, and the shapes of the air electrode 13 and the magnesium electrode 15 may also be changed as appropriate.
  • the sheet material used for the exterior body 11 is a sheet material other than laminated paper, and a sheet material containing paper may be used.
  • the upper plate portion constituting piece 25R connected to the rear wall portion 23 is divided based on the tab portion 15T, and the movement of the magnesium electrode 15 to the air electrode 13 side is performed by the upper plate portion constituting piece 25R.
  • the upper plate portion constituting piece 25F of the front wall portion 22 is divided on the basis of the tab portion 15T, and the movement of the magnesium electrode 15 to the air electrode 13 side is reversed by the upper plate portion constituting piece 25F. You may restrict both of them.
  • the case where the movement of the magnesium electrode 15 is restricted by bending the pair of upper plate part configuration pieces 25F and 25R in an L shape has been described, but the movement of the magnesium electrode 15 can be restricted.
  • the bending method of the pair of upper plate portion configuration pieces 25F and 25R may be changed.
  • any one of the support of the magnesium electrode 15 by the upper plate portion configuration pieces 25F and 25R may be omitted as long as the movement of the magnesium electrode 15 can be appropriately regulated.
  • the bottom plate portion 21 is bent in the downward convex shape in which the lower end of the magnesium electrode 15 is fitted as the exterior body 11, but the bottom plate portion 21 may be bent upward.
  • the magnesium electrode 15 is not parallel to the air electrode 13, the movement prevention of the magnesium electrode 15 can be made stronger.
  • the bonding is not limited thereto, and other bonding methods such as ultrasonic sealing may be used. It may be adopted.
  • the magnesium-air battery 10 is not limited to the use, and a plurality of magnesium-air batteries 10 are connected in series according to the voltage and current of the load used. It is possible to connect and use in parallel.
  • a plurality of magnesium air batteries 10 may be fastened with a binding band or the like, or may be stored and used in a plastic case or an iron box made of resin. It is also possible.
  • this invention was applied to the magnesium air battery 10 was demonstrated in the above-mentioned each embodiment, it can apply widely not only to this but to a well-known metal air battery.
  • a metal such as zinc, iron, aluminum or an alloy thereof for the metal electrode.
  • a potassium hydroxide aqueous solution may be used for the electrolytic solution
  • iron when used for the metal electrode, an alkaline aqueous solution may be used for the electrolytic solution.
  • an electrolyte containing sodium hydroxide or potassium hydroxide may be used.
  • Metal-air battery unit Next, the metal air battery unit will be described.
  • Some conventional metal-air batteries are used in layers (see, for example, Japanese Utility Model Publication No. 58-46535).
  • this type of metal-air battery When using this type of metal-air battery in a stacked manner, it is general to provide a large gap in front of the air electrode of the metal-air battery.
  • this type of metal-air battery has a problem that the product generated by the cell reaction between the electrodes floats between the electrodes and causes the outer package to expand. When the outer package expands, the gap in front of the air electrode may be narrowed or the gap may be lost, which causes a problem of reducing the battery output.
  • the metal-air battery unit 1 is provided with an outer case 210 for containing a plurality of magnesium air batteries 10, and two spacers 230 are provided in the outer case 210 so as to prevent the magnesium air batteries 10 contained from being inadvertently moved. It is arranged side by side.
  • the outer case 210 and the spacer 230 are made of a sheet material containing paper, more specifically, a cardboard having a multilayer structure of paperboard to increase its strength.
  • FIG. 31 and 32 are perspective views of the spacer 230
  • FIG. 33 is a top view of the spacer 230
  • FIG. 34 is a side view of the spacer 230.
  • the spacer 230 is formed by bending a sheet of cardboard paper, and two pockets (battery storage units) 250 are provided on both sides.
  • the magnesium air battery 10 is accommodated in the pocket 250, respectively.
  • the magnesium-air battery unit 1 is provided with a total of four magnesium-air batteries 10, and the four magnesium-air batteries 10 are connected in series by a wire 90 and connected to the DC-DC converter 300 as shown in FIG. It is done.
  • the two wires 90 are insulated from each other and integrated into one immediately before being connected to the DC-DC converter 300.
  • the location corresponding to the location as stated above about the magnesium air battery 10 attaches and shows the same code
  • the magnesium-air battery 10 is a hollow box-shaped exterior body 11 formed by folding and folding one foldable sheet material in two, bonding the side edges of the sheet material, and bending it. Have.
  • the air electrode 13 is attached to the exterior body 11, and the magnesium electrode (metal electrode) 15 is accommodated to face the air electrode 13, and an electrolytic solution such as a saline solution is filled up to the liquid level UL.
  • the magnesium-air battery 10 is a primary battery, and the air electrode 13 acts as a positive electrode, and the magnesium electrode 15 acts as a negative electrode.
  • the exterior body 11 integrally has a rectangular bottom plate 21, a rectangular front wall 22, a rectangular rear wall 23, and left and right side walls 24.
  • the front wall portion 22 is provided with a rectangular opening 22K, and the air pole 13 is disposed in the opening 22K.
  • the bottom plate portion 21 is formed in a downward convex V shape in a side view.
  • the lower end of the magnesium pole 15 is guided by the inclination of the bottom plate portion 21 and fitted in the downward convex portion 21T, and the lower end of the magnesium pole 15 is easily positioned.
  • the upper ends of the front wall 22 and the rear wall 23 are bent.
  • the first bent portions 25F1 and 25R1 maintain an appropriate distance between the magnesium electrode 15 and the air electrode 13, and the second bent portions 25F2 and 25R2 support the upper portion of the magnesium electrode 15. Clearances SF and SR of the same width are provided on both sides of the magnesium electrode 15.
  • FIG. 36 is a top partial perspective view of the upper part of the exterior body 11 of the magnesium-air battery 10 before being folded.
  • the magnesium electrode 15 (including the tab portion 15T not shown) is completely accommodated in the exterior body 11, and the second bent portions 25F2 and 25R2 are respectively formed by the two notches 25C. It is divided into three.
  • both end portions 25F2-1 of the second bent portion 25F2 are inserted in front of the upper portion of the magnesium electrode 15 housed in the exterior body 11, and the central portion 25F2-2 is the upper end of the magnesium electrode 15. It is inserted in the back beyond.
  • both end portions 25R2-1 are inserted into the back beyond the upper portion of the magnesium electrode 15, and both end portions 25F2-1 of the second bent portion 25F2 of the front wall portion 22.
  • the central portion 25R2-2 is inserted in front of the upper portion of the magnesium pole 15, and contacts the central portion 25F2-2 of the second bent portion 25F2 of the front wall portion 22.
  • the bent portion 24U at the upper end of the side wall portion 24 is bent in an L shape.
  • the tip of the bent portion 24U is inserted into the slit 25S provided in the first bent portions 25F1 and 25R1 when the exterior body 11 is assembled. Thereby, restoration of the first bent portions 25F1, 25R1 and the like to be bent and processed is prevented, and the upper surface of the exterior body 11 is sealed.
  • a portion indicated by an alternate long and short dash line is a mountain fold. Further, the wire connected to the magnesium electrode 15 is guided to the outside of the exterior body 11 through a gap that is open at the bent portion of the exterior body 11.
  • FIG. 37 is a developed view of the spacer 230.
  • the spacer 230 is formed by bending a sheet of cardboard paper 270.
  • the cardboard 270 is cut with a die by a press.
  • the spacer 230 is not limited to the cardboard 300, and may be formed of, for example, cardboard, or may be formed of a resin sheet.
  • An upper surface connection portion 234 is disposed at a central portion of the cardboard 270.
  • the inner side portions 232, 232 are disposed at both ends of the upper surface connecting portion 234 via the folding lines 271, 271, respectively, and the folding lines 271, 271 are mountain-folded.
  • Bottom portions 233, 233 are connected to the inner side portions 232, 232 via fold lines 273, 273, and outer side portions 231 are formed on the bottom portions 233, 233 via fold lines 275, 275. , 231 are connected. Fold lines 273, 273 and fold lines 275, 275 are valley folded.
  • claw holding parts 237 and 237 are provided in the both sides of the inner side surface parts 232 and 232 via the folding lines 237a and 237a.
  • the claw holding portions 237, 237 are provided with upper claws 236, 236 via the fold lines 236a, 236a.
  • lower claws 235, 235 are provided on both sides of the inner side surface portions 232, 232 via fold lines 235a, 235a.
  • a nail hole holding portion 238 is provided on both sides of the outer side surface portions 231, 231 via fold lines 238a, 238a.
  • the claw holes 239 and 239 are cut in the claw hole holding portion 238.
  • the upper surface connection portion 234 is formed with a pair of circular air ports 246, 246, and a rectangular groove 245 is formed in the middle of the air ports 246, 246.
  • An air electrode opening 232K is formed in the inner side surface parts 232, 232 except for the frame member 244, and a rectangular groove 232M is formed in the air electrode opening 232K.
  • a pair of floating support portions 251, 251 is disposed across the inner side surface portions 232, 232.
  • the floating support portions 251, 251 respectively have notches 251a, 251a on both sides.
  • Three fold lines 251b, 251c, 251d are disposed between the notches 251a, 251a.
  • the folding procedure of the spacer 230 will be described.
  • the fold lines 271 and 271 at both ends of the upper surface connection portion 234 are mountain-folded, and the fold lines 273 and 273 at the both sides and the fold lines 275 and 275 are valley-folded.
  • FIG. 32 in a side view, it is bent in a substantially W-like shape.
  • the lower claws 235, 235 are bent and the lower claws are fitted.
  • the pair of inner side surface portions 232, 232 are held in parallel.
  • the part enclosed by the inner side surface parts 232 and 232 comprises the retention part 260 as a gap
  • the claw holding portions 237, 237 and the claw hole holding portion 238 are bent, and the upper claws 236, 236 of the claw holding portions 237, 237 fit into the claw holes 239, 239 of the claw hole holding portion 238. United.
  • the outer side surface portions 231, 231 and the inner side surface portions 232, 232 are held in parallel.
  • the portion surrounded by the outer side surface portions 231, 231 and the inner side surface portions 232, 232 constitutes a pocket 250.
  • the magnesium air battery 10 is accommodated in the pocket 250, respectively.
  • the magnesium-air battery 10 is accommodated with the air electrode 13 directed toward the air electrode opening 232 K of the inner side surface portions 232, 232.
  • the pair of floating support portions 251, 251 are disposed.
  • the floating support portions 251, 251 have notches 251a, 251a, and three fold lines 251b, 251c, 251d between the notches 251a, 251a. Therefore, when the floating support portion 251 is pushed into the pockets 250, 250, the fold line 251b is valley-folded, the fold line 251c is mountain-folded, and the fold line 251d is valley-folded, as shown in FIG. 251 is bent into an L shape.
  • the floating support portion 251 supports the bottom plate portion 21 (FIG.
  • the cardboard used as the spacer 230 may have its surface laminated with PE or the like on one side or both sides. In this case, absorption of moisture in the air can be suppressed, and deterioration in long-term storage can be prevented.
  • FIG. 38 is a developed view of the outer case 210.
  • the outer case 210 is formed by bending a sheet of cardboard 220.
  • the cardboard 220 is cut with a die by a press.
  • the outer box 210 is not limited to the cardboard 220, and may be formed of, for example, a cardboard, or may be formed of a resin sheet.
  • the corrugated paper sheet 220 has side portions 211 with protrusions (211A, 211B) and side portions 212 without protrusions (212A, 212B) alternately in the center along the fold lines 311, 313, 315. Prepare.
  • the short lid 221 is disposed on the upper side of the side surface portion 211A via the folding line 321, and the fitting lid 222 is disposed on the upper side of the side surface portion 211B via the folding line 323, and on the upper side of the side surface portion 212B.
  • the upper lid 223 is disposed via the folding line 327.
  • a piece 224 is disposed on the fitting lid 222 via a fold line 325, and a claw member 225 is disposed on the piece 224.
  • a piece 226 is disposed on the upper lid 223 via a fold line 328.
  • the short lid 221, the fitting lid 222, and the upper lid 223 constitute a lid member.
  • the bottoms 215 and 215 are disposed on the lower side of the protrusion-formed side portions 211 (211A and 211B) via the fold line 319, and the lower sides of the side portions 212 (212A and 212B) on which the protrusions do not exist via the fold line 320.
  • the bottom portion 216, 216 with a bottom portion is disposed.
  • the bottoms 215, 215 and the bottoms 216, 216 with the inset form bottoms.
  • a sheet of cardboard 220 is folded at the folding lines 311, 313, 315, and the piece 213 connected to the side portion 212B without a protrusion is glued with the side portion 211A with a protrusion, and the side portion of the outer case 210 is formed. Be done. Then, the bottom portions 215, 215 and the bottom portions 216, 216 with fitting portions are fitted to form a bottom member. Furthermore, as shown in FIG. 30, the short cover 221, the fitting cover 222, and the upper cover 223 form a cover member.
  • the protrusion 81 includes a pair of upper protrusions 81A and 81A and a pair of lower protrusions 81B and 81B.
  • Each projecting piece 81 has the same form, and is connected to the side surface portion 211 via a portion to be separated 82 such as a perforation or a cut.
  • Each protrusion 81 has a claw 81C formed at the tip.
  • Each projecting piece 81 is connected to the side surface portion 211 at the connecting portion 83 when it is separated from the side surface portion 211 at the portion 82 to be separated.
  • each protrusion 81 (81A, 81B) is equal to the internal dimension W2 (FIG. 32) of the inner side surface portions 232, 232 of the spacer 230.
  • the length L3 (FIG. 38) of each protrusion 81 is formed equal to the length L4 from the claw holding portions 237, 237 of the spacer 230 shown in FIG. 31 to the groove 232M.
  • the width W of each protrusion 81 provided on the outer case 210 is formed equal to the internal dimension W2 (FIG. 32) of the inner side surface portions 232, 232 of the spacer 230.
  • the rigidity of each of the protrusions 81 regulates the dimension W2 between the inner side surface portions 32, 32.
  • a product is produced by a battery reaction between the air electrode 13 and the magnesium electrode 15, and this product floats in the space between the air electrode 13 and the magnesium electrode 15 to form the front wall 22
  • the cathode 13 is expanded by the expansion.
  • each protrusion 81 can suppress the expansion of the exterior body 11 and ensure the width W2 of the staying portion 260 in front of the air electrode 13 as specified. Therefore, a drop in battery output can be prevented. Furthermore, since the expansion of the exterior body 11 is suppressed, the distance between the air electrode 13 and the magnesium electrode (metal electrode) 15 is maintained at a specified distance, which also prevents the reduction of the battery output.
  • the length L3 (FIG. 38) of each protrusion 81 is formed equal to the length L4 from the claw holding portions 237 and 237 of the spacer 230 shown in FIG. 31 to the groove 232M. The frame member 244 on the outside of the air pole opening 232 K is to be suppressed.
  • a restricting member 85 for restricting the gap between the inner surface of the claw hole holding portion 238 and the magnesium air battery 10 may be disposed.
  • the gaps in the width direction of the magnesium-air battery 10 can be maintained by the respective projecting pieces 81 described above, and the gaps in the longitudinal direction of the magnesium-air battery 10 can be maintained by the regulating member 85.
  • the cardboard 220 used as the outer box 210 may have its surface laminated with PE or the like on one side or both sides. In this case, absorption of moisture in the air can be suppressed, and deterioration in long-term storage can be prevented.
  • a retention portion 260 surrounded by the inner side surface portions 232, 232 is formed at the central portion of the spacer 230, and the retention portion 260 is a portion of the outer case 210 after each projection 81 is pushed. It communicates with the outside of the outer case 210 through the opening (air passage hole). Therefore, air outside the outer case 210 can always be taken into the air electrode 72 of the magnesium-air battery 10 through the stagnation portion 260 and the air electrode opening 232 K of the spacer 230. Since the air ports 246 and 246 are formed in the upper surface connecting portion 234 of the spacer 230, the air that has entered the retention portion 260 flows back through the outer case 210 through the air ports 246 and 246.
  • the spacer 30 and the outer box 210 are both manufactured by assembling one sheet of cardboard 270, 220. Therefore, weight reduction can be achieved as compared to the case of manufacturing the spacer 230 and the outer case 210 with metal.
  • the lid member is configured of a short lid 221, a fitting lid 222, and an upper lid 223.
  • the upper lid 223 is opened, as shown in FIG. 30, the short lid 221 and the fitting lid 222 are exposed.
  • the piece 224 is bent at the folding line 325 shown in FIG. 38, and as shown in FIG. 30, the claw member 225 provided on the piece 224 fits in the groove portion 245 of the upper surface connecting portion 234 of the spacer 230. It is done.
  • the fitting lid 222 hides the wire 90 and can prevent an accident or the like from being caught by the wire 90 in a state where the upper lid 223 is opened.
  • the DC-DC conversion device 300 is housed under the short lid 221, and when the unit is used, the upper lid 223 and the fitting lid 222 are opened and taken out, and after injecting the electrolytic solution into the magnesium air battery 10, Used for charging.
  • the present invention is not limited to this.
  • the protruding pieces 81 are provided at two locations with respect to the retaining portion 260 formed in the spacer 230, the number may be one, three or more.
  • the projecting piece 81 may be pressed immediately before use of the unit 1, in which case the air pole is closed because the opening of the outer case 210 formed by pushing the projecting piece 81 is blocked during storage until use. 13 is preferable because it can be protected.
  • the frame member 244 may be formed separately from the spacer 230, and the presence of the frame member 244 makes it possible to suppress the expansion by the projecting piece 81 over the entire circumference of the wall portion of the exterior body 11.
  • the spacer 230 may be formed in an inverted U-shape, and the spacer 230 may be interposed between the magnesium-air batteries 10, or a plurality of plate-like members may be stacked and used.
  • the gap formed facing the air electrode 13 is not limited to the gap formed by utilizing the spacer 230, and a plate in which a hole through which the magnesium-air battery 10 passes is formed in the outer case 210.
  • the magnesium air battery 10 may be vertically disposed and the magnesium air battery 10 may be inserted into the hole to form a gap, or only the protrusion 81 may be formed by pushing the magnesium air battery 10 between the holes. What is shown in the form is desirable.
  • FIG. 39 and 40 show an embodiment of the metal-air battery unit 1 without the projecting piece 81.
  • FIG. 39 it is the metal air unit 1 using the outer case 210 in which the air flow holes 92 are provided substantially in the entire side portions 211A and 211B intersecting perpendicularly with the magnesium air battery 10, more specifically In each side surface portion 211A, 211B, seven air circulation holes 92 are provided at equal intervals in the vertical and horizontal directions.
  • the empty space in the outer case 210 (the space in the spacer 230 and the space above the spacer 230, etc.) is provided via the air flow holes 92. It can communicate with the outside. Therefore, the internal air whose temperature has been raised by the reaction of the magnesium-air battery 10 can be discharged to the outside through the air flow holes 92, and the magnesium-air battery 10 can be cooled by the external air. Therefore, the magnesium-air batteries 10 in the outer case 210 can be maintained at an appropriate temperature, and the temperatures can be easily equalized.
  • FIG. 40 The embodiment shown in FIG. 40 is the same as the case of FIG. 39 in that the air flow holes 92 are provided in the pair of side surface portions 211A and 211B, but the air flow holes 92 This embodiment is different from the case of FIG. 39 in that it is limited to a region communicating with the retaining portion 260 and the space above the spacer 230). Also with this configuration, the internal air whose temperature has been raised by the reaction of the magnesium-air battery 10 can be discharged to the outside through the air flow holes 92, and the magnesium-air battery 10 can be cooled by the external air. That is, the air flow holes 92 are provided only in the area that contributes to the cooling of the magnesium-air battery 10, and the air flow holes 92 are not provided in the area that does not contribute to the cooling.
  • a hole 90H through which the wire 90 passes is provided in the piece 224 which is folded back below the lid member (the fitting lid 222) of the outer case 210.
  • the protective film may inhibit the battery reaction, and there was a risk that the battery reaction would be difficult to resume when trying to use the battery again after stopping and pausing the battery. . Therefore, an embodiment of a system configuration of the magnesium-air battery 10 (hereinafter, referred to as a metal-air battery system 10S) in which the battery reaction is easily restarted will be described below.
  • the metal air battery system 10S is applied to the metal air battery unit 1 described above.
  • the parts corresponding to the parts described above are shown with the same reference numerals.
  • FIG. 41 is a view showing the configuration of the metal-air battery system 10S according to the first embodiment of the present invention.
  • the metal-air battery system 10S includes a plurality of (four in the present configuration) magnesium-air batteries 10 that constitute a unit battery (a single-cell battery).
  • Each magnesium-air battery 10 is a primary battery that includes a pair of magnesium electrodes (metal electrodes) 15 and an air electrode 13 and generates electric power by utilizing oxygen in air for an electrochemical reaction.
  • the magnesium electrode 15 acts as a negative electrode
  • the air electrode 13 acts as a positive electrode.
  • the plurality of magnesium-air cells 10 are connected in series, and a DC-DC converter (power converter) 300 is connected to the magnesium electrode 15 and the air electrode 13 at both ends.
  • a DC-DC converter (power converter) 300 is connected to the magnesium electrode 15 and the air electrode 13 at both ends.
  • the DC-DC converter 300 includes a converter circuit 301 that converts DC power into different DC power.
  • the DC power output from the battery pack 10A is converted into DC power suitable for charging the mobile phone and the like, and is output from the metal air battery system 10S.
  • the DC-DC conversion device 300 functions as a power conversion device that converts the power to the power of the user's device. Therefore, for example, in the case where the device on the use side requires a higher current value or voltage value than the mobile phone, it can be easily coped with by changing the DC-DC conversion device 300. Further, the DC-DC converter 300 may be configured to have a switching function of switching the output power to various powers. In addition, a DC-AC conversion device for converting into AC power may be provided.
  • an electrolytic solution in which magnesium ions can be eluted from the magnesium electrode 15 is filled between the magnesium electrode 15 and the air electrode 13.
  • the electrolyte contains chloride ions as anions, alkali metal ions (Li, Na, K, Rb, Cs, Fr) as cations, alkaline earth metal ions (Be, Mg, Ca, Sr, An aqueous solution containing at least one of Ba, Ra) is used.
  • a sodium chloride aqueous solution containing sodium ions is used as the electrolytic solution in terms of high safety and conductivity.
  • the magnesium electrode 15 is made of, for example, AZ31 or AZ61, AZ91 or the like of ASTM standard of 96% of magnesium, 3% of aluminum, and 1% of zinc. In addition, you may use not only what is based on ASTM specification but a well-known Mg-Al-Zn type alloy. In addition, elements other than aluminum and zinc may be added, and for example, other elements such as Si, Cu, Li, Na, K, Fe, Ni, Ti, and Zr may be added.
  • magnesium is a highly reactive material, and thus self-discharge tends to occur as described above.
  • a protective film is formed on the surface of the magnesium electrode 15 to inhibit self-discharge and suppress the generation of hydrogen by the oxide (for example, zinc oxide) generated by the battery reaction. , Self-discharge reaction can be suppressed.
  • the protective film may also inhibit the battery reaction (power generation reaction), and when the battery is stopped and stopped after the battery is stopped, the battery reaction is sufficient. It has been found that the required current can not be extracted. In particular, when zinc was added, it was easy to occur a situation where current could not be extracted.
  • the open / close short circuit 331 is provided between the magnesium electrode 15 and the air electrode 13 of the magnesium-air battery 10.
  • the switchable short circuit 331 is connected between the magnesium electrode 15 and the air electrode 13 at both ends of the magnesium air battery 10 connected in series, and a manual switch (so-called manual switch) that can be manually opened and closed by the user. Is configured. Then, by switching the open / close short circuit 331 from the open state to the closed state, the closed circuit including the air electrode 13 and the magnesium electrode 15 of all the magnesium-air batteries 10, that is, all the magnesium-air batteries 10 are shorted. A closed circuit is formed.
  • a protective film also referred to as passive film or passive film layer
  • a protective film formed on the surface of the magnesium electrode 15 is contained in the electrolyte. It can be dissolved to expose a fresh metal surface.
  • the magnesium air battery 10 can be easily refreshed by temporarily switching the open / close short circuit 331 from the open state to the closed state after the battery is stopped, so that the cell reaction can be easily resumed. be able to. Therefore, by returning the short circuit 331 from the closed state to the open state after the refresh, the cell reaction can be restarted, and a sufficient current can be output immediately. As a result, when the use-side device is connected to the output side of the metal air battery system 10S, it becomes possible to immediately supply power suitable for driving and charging the use-side device.
  • the open / close short circuit 331 is provided in the DC-DC converter 300.
  • the short circuit 331 can be accommodated using the exterior body of the DC-DC conversion device 300 and the like, and the exterior body dedicated to the short circuit 331 can be eliminated.
  • the short circuit 331 is configured to be inserted between the magnesium electrode 15 and the air electrode 13 of the battery pack 10A, the short circuit 331 can be easily made to the conventional metal-air battery system not provided with the short circuit 331. It is possible to add.
  • the short circuit 331 is provided on the input side (the magnesium air battery 10 side) of the conversion circuit 301, conversion to a closed circuit which can be performed when the short circuit 331 is closed. There is no circuit, and the resistance in the closed circuit can be reduced accordingly. Therefore, a large current (short circuit current) can be efficiently flowed, and the magnesium-air battery 10 can be easily refreshed.
  • the short circuit 331 is provided in the DC-DC conversion device 300, if the DC-DC conversion device 300 is removed, the short circuit 331 can also be removed, and the short circuit 331 can be easily attached and detached. Therefore, maintenance work such as replacement / inspection of the short circuit 331 can be easily performed.
  • the metal air battery system 10S of the present embodiment is a circuit that selectively forms a closed circuit including the magnesium electrode 15 forming the negative electrode and the air electrode 13 forming the positive electrode. Since the circuit 331 is provided, the battery reaction can be easily resumed even when it is difficult to resume the battery reaction after the battery is stopped due to the influence of the protective film (passive film) of the magnesium electrode 15 or the like.
  • the short circuit 331 may be provided simply between the magnesium electrode 15 and the air electrode 13 of the battery assembly 10A. Therefore, an increase in the number of parts and an increase in the size of the apparatus can be suppressed, and the cost increase can be easily suppressed. Further, since the open / close short circuit 331 is formed of a manual switch, it can be simply configured and is easy for the user to operate.
  • the short circuit 331 is provided on the side of the battery pack 10A of the DC-DC converter 300.
  • the short circuit 331 is connected to the output side of the DC-DC converter 300.
  • Or may be provided outside the DC-DC conversion device 300. That is, the position of the short circuit 331 may be changed as appropriate.
  • FIG. 43 (A) is a view showing the configuration of a metal-air battery system 10S according to the second embodiment.
  • a switchable resistance discharge circuit 333 is provided between the magnesium electrode 15 and the air electrode 13 of the battery assembly 10A.
  • the resistive discharge circuit 333 is composed of a resistor and a switch.
  • the resistive discharge circuit 333 can also form a closed circuit including the battery pack 10A by temporarily switching the switch from open to closed.
  • FIG. 43B shows a specific example in which the circuit protector switch 333 S is applied to the resistive discharge circuit 333.
  • the circuit protector switch 333S is a switch that opens when the current value flowing through the closed circuit, which can be switched from opening to closing the switch 333S, exceeds a predetermined threshold, and is also referred to as a circuit protector.
  • the switch can be automatically opened before the current value exceeds a predetermined value set to the allowable current or less, which facilitates protection of the circuit. Further, the switch opening operation can be made unnecessary, and since it is not necessary to discharge without permission, the loss of discharge power can also be reduced.
  • the circuit protector switch 333S is a widely distributed part, it is also advantageous for cost increase reduction.
  • FIGS. 43A and 43B illustrate the case where the resistive discharge circuit 333 (including the circuit protector switch 333S) is provided on the battery pack 10A side of the DC-DC conversion device 300
  • the resistive discharge circuit 333 may be provided on the output side of the DC-DC converter 300 or may be provided outside the DC-DC converter 300. That is, the position of the resistive discharge circuit 333 may be changed as appropriate.
  • FIG. 45 (A) is a view showing the configuration of a metal-air battery system 10S according to the third embodiment.
  • the third embodiment shows a metal air battery system 10S not provided with the DC-DC converter 300. Also in the metal-air battery system 10S, the battery reaction can be easily resumed by providing the open / close short circuit 331 between the magnesium electrode 15 and the air electrode 13 of the battery pack 10A. Similar various effects can be obtained.
  • FIG. 45 (B) is a view showing the configuration of a metal-air battery system 10S according to the fourth embodiment.
  • the fourth embodiment has a configuration in which a resistive discharge circuit 333 is provided instead of the short circuit circuit 331 of FIG. 45 (A). With this configuration, various effects similar to those of the metal-air battery system 10S of the second embodiment can be obtained.
  • the circuit protector switch 333 S may be applied to the resistive discharge circuit 333.
  • FIG. 46 is a view showing the configuration of a metal-air battery system 10S according to the fifth embodiment.
  • an integrated current detection unit 335 is provided.
  • the integrated current detection unit 335 integrates the current flowing through the closed circuit including the magnesium air battery 10 to detect the integrated current value, and the automatic switch function to switch the short circuit 331 to the open state according to the integrated current value. And have.
  • a threshold value is set in advance so that the short circuit 331 is switched to open when the integrated current value sufficient to refresh the magnesium-air battery 10 is reached.
  • the circuit is automatically switched to the open circuit, and the refresh operation can be ended. Therefore, the user operation for switching to the open circuit can be made unnecessary, and the loss of discharge power can be reduced.
  • the integration current detection unit 335 A wide range of known configurations can be applied to the integration current detection unit 335. Also, as a modification, the automatic switch function may be omitted. In this case, preferably, when the detected integrated current value reaches a predetermined value, the integrated current detection unit 335 notifies the user to that effect. This allows the user to be notified of the switch operation timing. Therefore, the user can operate the switch at an appropriate timing.
  • a known notification device such as a display device for transmitting information by lighting or display, an audio output device for transmitting information by sound, or the like can be widely applied.
  • a resistive discharge circuit 333 instead of the short circuit 331, a resistive discharge circuit 333 may be provided instead of the short circuit 331, a resistive discharge circuit 333 may be provided.
  • the integrated current value is detected, and the switching operation of the switch of the short circuit 331 is performed according to the value.
  • the current value is detected, and the short circuit is detected according to the value.
  • the switching operation of the switch 331 may be performed.
  • FIG. 47 is a view showing the configuration of a metal-air battery system 10S according to the sixth embodiment.
  • a time detection unit 337 is provided.
  • the time detection unit 337 has a function of detecting (measuring) an elapsed time after the circuit is closed and an automatic switch function of switching the short circuit 331 to the open state in accordance with the detected elapsed time.
  • a threshold value is set in advance so that the short circuit 331 is switched to open when an elapsed time sufficient to refresh the magnesium-air battery 10 is reached.
  • the circuit is automatically switched to the open circuit, and the refresh operation can be ended at an appropriate timing. Therefore, the user operation for switching to the open circuit can be made unnecessary, and the loss of discharge power can be reduced.
  • a well-known configuration can be widely applied to the time detection unit 337.
  • the automatic switch function may be omitted.
  • the time detection unit 337 notify the user of that when the detected elapsed time reaches a predetermined value.
  • the user can be notified of the switch operation timing, and the user can perform switch operation at an appropriate timing.
  • a resistive discharge circuit 333 may be provided instead of the short circuit 331.
  • the metal air battery system 10S is not limited to the above-mentioned embodiment, Based on the technical thought of this invention, various deformation
  • the above-mentioned embodiment explained the case where the present invention was applied to magnesium air battery 10 provided with magnesium electrode 15 which added aluminum and zinc, it is not restricted to this, but Mg-Zn system alloy which added zinc at least
  • the present invention may be applied to a metal-air battery.
  • the present invention may be applied to a metal-air battery provided with a magnesium electrode not containing zinc, or a metal-air battery provided with a metal electrode other than magnesium. The point is that the present invention can be widely applied to a metal-air battery in which reactivation of the battery reaction may become difficult after a pause due to the material of the metal electrode or the like.

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Abstract

Provided are: a low-cost lightweight metal-air battery which is advantageous in terms of disposability; and a metal-air battery unit. An outer package (11), which has an air electrode (13) and contains a magnesium electrode (15) that constitutes a metal electrode facing the air electrode (13), is formed of a sheet material that contains paper. Paper complexed by lamination using a thermally adhesive resin is used for the sheet material.

Description

金属空気電池、および金属空気電池ユニットMetal air battery and metal air battery unit
　本発明は、空気極を有するとともに金属極を収容する外装体を備える金属空気電池、および金属空気電池ユニットに関する。 BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to a metal-air battery including an exterior body having an air electrode and containing a metal electrode, and a metal-air battery unit.
　天災時や風水害時およびＡＣ電源の入手困難な環境で、食塩水などの電解液を注入すると発電可能な金属空気電池が知られている。金属空気電池の外装体には、一般的に金属缶や樹脂製容器が使用されている。しかし、この種の外装体は、電解液の漏れを防ぐためのパッキンやシール材が必要となるため、部材数が多くなり、組立工数やコストの増加が生じる。さらにパッキンやシール材の不良や劣化により電解液が漏れるおそれもある。また、金属缶や樹脂製容器の外装体は、重くなってしまう。
　また、金属空気電池以外の電池には、樹脂とアルミニウム箔とを積層した積層フィルムを包装体（Ｌｉ電池用包材）として使用することが提案されている（例えば、特許文献１参照）。 Metal-air batteries are known that can generate electric power by injecting an electrolyte solution such as saline in natural disasters, storms and floods, and in environments where AC power is difficult to obtain. Generally, a metal can or a resin container is used for the exterior of the metal-air battery. However, this type of exterior body requires a packing and a sealing material to prevent leakage of the electrolyte, so the number of members increases and the number of assembly steps and costs increase. Furthermore, there is also a possibility that the electrolyte may leak due to a defect or deterioration of the packing or the sealing material. In addition, the outer casing of the metal can or the resin container is heavy.
Further, for batteries other than metal-air batteries, it has been proposed to use a laminated film in which a resin and an aluminum foil are laminated as a package (a packaging material for a Li battery) (for example, see Patent Document 1).
特許第４２９６７７１号公報Patent No. 4296771
　本発明は、上述した事情を鑑みてなされたものであり、低コスト且つ軽量で、廃棄性にも有利な金属空気電池、および複数の金属空気電池を収容する金属空気電池ユニットを提供することを目的としている。 The present invention has been made in view of the above-mentioned circumstances, and it is an object of the present invention to provide a metal-air battery which is low in cost, light in weight and advantageous in discardability, and a metal-air battery unit accommodating a plurality of metal-air batteries. The purpose is.
　この明細書には、日本国特許出願の特願２０１３－２３８６２８、特願２０１４－００９２６５、特願２０１４－０１７１２２、特願２０１４－０１７６０６、特願２０１４－１８５１５４の全ての内容が含まれる。
　上記課題を解決するため、本発明は、空気極を有するとともに前記空気極と対向する金属極を収容する外装体を備える金属空気電池において、前記外装体は、紙を含有するシート材で形成されることを特徴とする。この構成によれば、低コスト且つ軽量で、廃棄性にも有利な金属空気電池を提供することが可能になる。 This specification includes all the contents of Japanese Patent Application Nos. 2013-238628, 2014-009265, 2014-017122, 2014-017606, and 2014-185154.
In order to solve the above problems, the present invention provides a metal-air battery having an air electrode and having an outer body for accommodating a metal electrode facing the air electrode, wherein the outer body is formed of a sheet material containing paper. It is characterized by According to this configuration, it is possible to provide a metal-air battery that is low in cost, light in weight, and advantageous in discardability.
　前記シート材は、熱融着性樹脂でラミネート加工された紙であることが好ましい。この構成によれば、電池を放電後休止し再放電するなどの長時間使用時にも電解液が外部に染み出すことを防止できる。また、紙の比率を５０％超過にすることで、各自治体の決まりによるものの紙ゴミなどとして分別・廃棄し易く、且つ、容易に手に入れ易い。 The sheet material is preferably a paper laminated with a heat fusible resin. According to this configuration, it is possible to prevent the electrolyte from leaking to the outside even when the battery is discharged and then used for a long time, for example, after rest and re-discharge. In addition, by making the proportion of paper 50%, it is easy to separate and discard as paper waste according to the rules of each local government, and easy to obtain.
　前記シート材は、隙間を空けて前記金属極を覆うとともに、前記シート材の一部を折り曲げて前記隙間を横断し、前記金属極を支える支持用折り曲げ部を一体に備えることが好ましい。この構成によれば、紙を含有するシート材で形成された外装体の一部を折り曲げる、といった簡易な構成で金属極を支持できるとともに、電解液の量の確保や軽量化に有利である。 The sheet material preferably covers the metal electrode while leaving a gap, bends a part of the sheet material, traverses the gap, and integrally includes a support bending portion for supporting the metal electrode. According to this configuration, the metal electrode can be supported with a simple configuration in which a part of the exterior body formed of a sheet material containing paper is bent, and it is advantageous for securing the amount of the electrolyte and reducing the weight.
　前記支持用折り曲げ部は、前記金属極を前記空気極から離間させた位置に保持するようにすることが好ましい。この構成によれば、金属極と空気極とを確実に離すことができるため、極間に電解液を十分に保持することができる。
　また、前記支持用折り曲げ部は、前記シート材における前記金属極に対して前記空気極側の壁部、および、前記空気極と反対側の壁部から前記金属極に向けて折り曲げられた第１折り曲げ部と、前記第１折り曲げ部の先端から折り曲げられて前記金属極に当接する第２折り曲げ部とを有するようにしても良い。この構成によれば、簡易な折り曲げ構造で、金属極を支持することができる。 The support bending portion preferably holds the metal electrode at a position spaced apart from the air electrode. According to this configuration, since the metal electrode and the air electrode can be reliably separated, the electrolytic solution can be sufficiently held between the electrodes.
In addition, the supporting bent portion may be a first bent portion from a wall portion on the air electrode side with respect to the metal electrode in the sheet material and a wall portion on the opposite side to the air electrode toward the metal electrode. A bent portion may be provided, and a second bent portion bent from the tip of the first bent portion and in contact with the metal electrode. According to this configuration, the metal electrode can be supported by a simple bending structure.
　また、前記第１折り曲げ部は、前記外装体内の電解液の液面よりも上方に設けられるとともに、前記金属極に向かって斜め下方に傾斜するようにしても良い。この構成によれば、第１折り曲げ部により電解液が外部に出難くなるとともに、第１折り曲げ部の下面に付着した電解液を効率良く戻すことができる。 Further, the first bent portion may be provided above the liquid surface of the electrolytic solution in the outer package, and may be inclined obliquely downward toward the metal electrode. According to this configuration, the electrolytic solution can not be easily discharged to the outside by the first bent portion, and the electrolytic solution attached to the lower surface of the first bent portion can be efficiently returned.
　また、前記金属極が上方に突出するタブ部を有するとともに、前記支持用折り曲げ部が前記金属極の幅に渡って延在し、前記支持用折り曲げ部は、前記金属極の幅方向で、前記タブ部と、前記タブ部のない非タブ部との境を基準にして分割され、前記タブ部側の分割部と前記非タブ部側の分割部のいずれか一方が、前記金属極の空気極側への移動を規制し、他方が前記金属極の空気極の反対側への移動を規制するようにしても良い。この構成によれば、タブ部を避けつつ、支持用折り曲げ部の各分割部によって、金属極の空気極側への移動と反対側への移動の両方を規制することができる。 Further, the metal pole has a tab portion projecting upward, and the support bending portion extends over the width of the metal pole, and the support bending portion is in the width direction of the metal pole. It is divided on the basis of the boundary of a tab part and a non-tab part without the tab part, and any one of the divided part by the side of the tab part and the divided part by the side of the non-tab part is the air pole of the metal pole The movement to the side may be restricted, and the other may restrict the movement to the opposite side of the cathode of the metal electrode. According to this configuration, it is possible to restrict both the movement of the metal electrode to the air electrode side and the movement to the opposite side by each divided portion of the support bending portion while avoiding the tab portion.
　また、前記外装体は、前記金属極の下端が嵌る下方凸形状に折り曲げられた底板部を有するようにしても良い。この構成によれば、金属極の下端を簡易な折り曲げ構造で位置決めし、ズレを防止することができる。
　また、前記支持用折り曲げ部は、前記空気極側の壁部、および、前記空気極の反対側の壁部から前記金属極に沿って外装体内側に折り曲げられるとともに、その反対側に折り返されて前記金属極よりも外装体外側に張り出す折り返し部を有し、各折り返し部の一部で前記金属極を挟持するとともに、残りの外装体外側に突出した部分を互いに接合して折り返し部間を封止するようにしても良い。この構成によれば、電解液の蒸発や漏出を抑制するとともに外装体の変形を防止し、且つ、金属極の位置ずれを抑えることができる。 Further, the exterior body may have a bottom plate portion bent in a downward convex shape in which the lower end of the metal electrode is fitted. According to this configuration, it is possible to position the lower end of the metal pole with a simple bending structure and to prevent misalignment.
Further, the support bending portion is bent from the wall portion on the air electrode side and the wall portion on the opposite side of the air electrode along the metal electrode to the inside of the outer package, and is folded back to the opposite side. While having a folded back portion that protrudes to the outside of the exterior body than the metal electrode, sandwiching the metal electrode with a part of each folded back portion, joining the remaining protruding portions to the outside of the exterior body together It may be sealed. According to this configuration, evaporation and leakage of the electrolytic solution can be suppressed, deformation of the outer package can be prevented, and displacement of the metal electrode can be suppressed.
　また、前記外装体は、前記金属極の上方を覆う蓋部に連なって前記金属極の側方を覆う側壁部に接合されるシート片を備えるようにしても良い。この構成によれば、簡易な構成で、電解液の蒸発や漏出を抑制することができるとともに、外装体の変形をより防止することができる。
　また、紙を含有するシート材であって、前記金属極の下端が嵌る下方凸形状に折り曲げられた底板シート部を備え、前記底板シート部は、前記外装体を形成するシート材に前後一対の端部の少なくとも一方が接合されるようにしても良い。この構成によれば、金属極の位置ずれを抑えるとともに、金属極による外装体の傷つきを抑制することが可能になる。 The exterior body may include a sheet piece connected to a lid covering the upper side of the metal electrode and joined to a side wall covering the side of the metal electrode. According to this configuration, evaporation and leakage of the electrolytic solution can be suppressed with a simple configuration, and deformation of the exterior body can be further prevented.
The sheet material is a sheet material containing paper, and is provided with a bottom plate sheet portion bent in a downward convex shape into which the lower end of the metal electrode fits, and the bottom plate sheet portion is a pair of front and back sheets At least one of the ends may be joined. According to this configuration, it is possible to suppress the positional deviation of the metal electrode and to suppress the damage of the exterior body by the metal electrode.
　また、前記外装体を形成するシート材を上方に開口する凹状に折り曲げて前記外装体の底板部を形成し、前記底板シート部は、前記外装体を形成するシート材を平面状に展開した状態で、前記底板部を跨ぐように該シート材に前後一対の端部の少なくとも一方が接合され、該シート材を上方に開口する前記凹状に折り曲げた際に、前記底板部から離間するように外装体内側に起立する一対の起立部を有し、前記一対の起立部間に前記金属極の下端が嵌まるようにしても良い。この構成によれば、底板シート部を容易に組み立てることができる。 Further, the sheet material forming the exterior body is bent in a concave shape that opens upward to form a bottom plate portion of the exterior body, and the bottom plate sheet portion is a state in which the sheet material forming the exterior body is expanded in a planar shape. And at least one of a pair of front and rear end portions is joined to the sheet material so as to straddle the bottom plate portion, and when the sheet material is bent in the concave shape opening upward, the sheathing is separated from the bottom plate portion The lower end of the metal pole may be fitted between the pair of upright portions by having a pair of upright portions standing upright inside the body. According to this configuration, the bottom plate sheet portion can be easily assembled.
　また、前記金属極における前記空気極と反対側の面に、前記外装体内に水を注ぎ入れることによって電池として作動させるための電解質を収容する電解質収容体を設けるようにしても良い。この構成によれば、電解液の溶媒を入れるだけで電池として利用できる構成にするとともに、電解質の影響による金属極の腐食を抑制することができる。
　また、前記電解質収容体は、紙を含有するシート材であって前記金属極における前記空気極と反対側の面に装着される極板装着シートと、前記極板装着シートに接合されて前記電解質を収容する袋体とを備えるようにしても良い。この構成によれば、シート材により電解質の影響による金属極の腐食を抑制することができるとともに、電解質を収容する袋体を外装体に取り付ける必要がなく、外装体の構成を簡易化し易く、また、袋体の取付作業も容易である。 Further, on the surface of the metal electrode on the opposite side to the air electrode, an electrolyte container may be provided which contains an electrolyte for operating as a battery by pouring water into the outer package. According to this configuration, it is possible to use the battery as the battery only by adding the solvent of the electrolytic solution, and to suppress the corrosion of the metal electrode due to the influence of the electrolyte.
The electrolyte container is a sheet material containing paper, and is attached to an electrode plate attachment sheet attached to the surface of the metal electrode opposite to the air electrode, and the electrolyte is joined to the electrode plate attachment sheet. And a bag body for containing the According to this configuration, it is possible to suppress the corrosion of the metal electrode due to the influence of the electrolyte by the sheet material, and it is not necessary to attach the bag containing the electrolyte to the outer package, and the configuration of the outer package can be simplified The attachment work of the bag is easy.
　また、前記極板装着シートは前記金属極に圧着固定され、前記袋体は前記極板装着シートに融着されるようにしても良い。この構成によれば、極板装着シートおよび袋体の取付が容易である。
　また、前記極板装着シートは、当該シートの一部を折り曲げて当該シートに対する前記金属極の移動を規制する規制部を有し、前記極板装着シートを前記外装体に保持させることによって前記金属極を前記外装体に保持するようにしても良い。この構成によれば、外装体側に金属極を直接保持する構造が不要となり、外装体を簡易な構造にし易くなる。 The electrode plate mounting sheet may be crimped and fixed to the metal electrode, and the bag body may be fused to the electrode plate mounting sheet. According to this configuration, attachment of the electrode plate attachment sheet and the bag body is easy.
Further, the electrode plate mounting sheet has a restricting portion that bends a part of the sheet to restrict the movement of the metal electrode with respect to the sheet, and the metal plate mounting sheet is held by the exterior body. The pole may be held by the outer package. According to this configuration, a structure for directly holding the metal electrode on the exterior body side is unnecessary, and the exterior body can be easily structured.
　また、前記シート材は、隙間を空けて前記金属極を覆うとともに、少なくとも内面側が非透液性に形成され、前記外装体には、前記空気極が外面側から装着される開口部が設けられ、前記開口部の端面には、内部に注液した電解液の浸透を防止する端面処理が施されていることを特徴とする。この構成によれば、紙を含有するシート材で外装体を形成した構成で、開口部の端面からの電解液の浸透を防止し、外装体の強度低下や外観の劣化を回避することができる。 Further, the sheet material covers the metal electrode with a gap formed, and at least the inner surface side is formed to be liquid impermeable, and the exterior body is provided with an opening where the air electrode is mounted from the outer surface side The end face of the opening may be subjected to an end face treatment for preventing the permeation of the electrolytic solution poured therein. According to this configuration, in the configuration in which the exterior body is formed of the sheet material containing paper, the permeation of the electrolytic solution from the end face of the opening can be prevented, and the strength reduction of the exterior body and the deterioration of the appearance can be avoided. .
　前記開口部の端面は、前記端面処理として、前記シート材の縁部が外方に向かって折り返されるようにしても良い。この構成によれば、シート材を折り曲げる、といった簡易な方法で、開口部への電解液の影響を抑えることが可能になる。 The edge of the sheet material may be folded outward as the end face treatment of the end face of the opening. According to this configuration, it is possible to suppress the influence of the electrolytic solution on the opening by a simple method of bending the sheet material.
　また、前記開口部の端面は、前記端面処理として、シート状の非透液性材料により被覆されるようにしても良い。この構成によれば、フィルム性能に応じた被覆性能を得ることができる。例えば、広く流通するフィルムを用いることにより、コスト低減を図りやすくなり、且つ、フィルムの選定により所望の被覆性能を選択可能になる。 The end face of the opening may be covered with a sheet-like liquid impermeable material as the end face treatment. According to this configuration, it is possible to obtain coating performance according to the film performance. For example, by using a widely distributed film, cost reduction can be easily achieved, and desired coating performance can be selected by film selection.
　また、前記シート材の両面に前記非透液性材料を貼り付け、前記非透液性材料同士を接合して前記端面を被覆しても良い。この構成によれば、シート材の両面をラミネートする場合に、そのラミネートフィルムを利用して被覆することができる。 Further, the non-liquid-permeable material may be attached to both surfaces of the sheet material, and the non-liquid-permeable materials may be joined to cover the end surface. According to this structure, when laminating both sides of a sheet material, it can coat using the lamination film.
　また、前記非透液性材料により前記端面を包み込んで前記端面を被覆しても良い。この構成によれば、開口部の端面を包み込んだ被覆形態を得ることができ、端面からの電解液の浸透を防止し易くなる。 In addition, the end surface may be covered by covering the end surface with the liquid impermeable material. According to this configuration, it is possible to obtain a coated form in which the end face of the opening is enclosed, and it is easy to prevent the electrolyte from permeating the end face.
　また、前記開口部の端面は、前記端面処理として、疎水性の薬剤が含浸されるようにしても良い。この構成によれば、薬剤を用いる方法により開口部の端面からの電解液の浸透を防止できる。 The end face of the opening may be impregnated with a hydrophobic agent as the end face treatment. According to this configuration, the penetration of the electrolytic solution from the end face of the opening can be prevented by the method using a drug.
　また、前記端面処理として、前記シート材から前記空気極に渡ってホットメルトを塗布し、前記ホットメルトにより前記開口部の端面を覆うようにしても良い。この構成によれば、空気極の表面凹凸形状を利用して被覆として機能するホットメルトの接合強度を効率よく高めることができる。 Further, as the end surface treatment, a hot melt may be applied from the sheet material to the air electrode, and the end surface of the opening may be covered with the hot melt. According to this configuration, it is possible to efficiently increase the bonding strength of the hot melt that functions as a coating by utilizing the surface asperity shape of the air electrode.
　また、前記端面処理として、前記シート材から前記空気極に渡ってシート状の非透液性材料を貼り付け、前記非透液性材料により前記開口部の端面を覆うようにしても良い。この構成によれば、空気極の表面凹凸形状を利用して被覆として機能するフィルムの接合強度を効率よく高めることができる。 Further, as the end surface treatment, a sheet-like impermeable material may be attached from the sheet material to the air electrode, and the end surface of the opening may be covered with the impermeable material. According to this configuration, it is possible to efficiently increase the bonding strength of the film functioning as a coating by utilizing the surface asperity shape of the air electrode.
　また、前記非透液性材料は、前記開口部の縁部に渡って延出する一体型の枠状にしても良い。この構成によれば、開口部の縁部毎に非透液性材料を貼り付ける場合と比べて、部品点数を低減でき、且つ、貼り付け作業が一回で済む。 The liquid impermeable material may be in the form of an integral frame extending across the edge of the opening. According to this configuration, the number of components can be reduced and the number of attaching operations can be reduced to one, as compared with the case where the liquid impermeable material is attached to each edge of the opening.
　また、前記非透液性材料は、前記開口部の縁部に渡って延出する枠状となるように複数の短冊状の非透液材料を接続しても良い。この構成によれば、非透液性材料のフィルム素材から切り出す際に材料の余りを低減し易くなり、また、様々な形状に対応し易くなる。 Further, the non-liquid-permeable material may be connected with a plurality of strip-like non-liquid-permeable materials so as to form a frame extending over the edge of the opening. According to this configuration, when cutting out from the film material of the liquid-impervious material, it is easy to reduce the excess of the material, and it becomes easy to correspond to various shapes.
　また、前記金属極は、電解液の注入前には、表面に不動態被膜が形成されておらず、電解液の注入後に電池反応で発生する酸化物により、表面に不動態被膜が形成される金属極であり、前記金属極と前記空気極とを有する前記金属空気電池は、前記不動態被膜を除去するため負荷を接続しない状態で前記金属極と前記空気極とを含む閉回路を選択的に形成する回路を備えることを特徴とする。この構成によれば、負極と正極とを含む閉回路を形成して金属空気電池の負極（金属極）表面に形成された不動態被膜を除去し、負極（金属極）表面をリフレッシュさせることができ、電池反応を再開させ易くなる。 In addition, a passive film is not formed on the surface of the metal electrode before injection of the electrolytic solution, and a passive film is formed on the surface by an oxide generated by a battery reaction after the injection of the electrolytic solution. The metal-air battery, which is a metal electrode and has the metal electrode and the air electrode, selectively selects a closed circuit including the metal electrode and the air electrode in a state where no load is connected to remove the passive film. And a circuit formed on the circuit. According to this configuration, a closed circuit including the negative electrode and the positive electrode is formed to remove the passivation film formed on the surface of the negative electrode (metal electrode) of the metal-air battery, thereby refreshing the surface of the negative electrode (metal electrode). It becomes easy to restart the battery reaction.
　前記回路は、前記負極と前記正極との間に設けられる開閉式の短絡回路であっても良い。この構成によれば、簡易な構成で、電池反応を再開させ易くなる。 The circuit may be a switchable short circuit provided between the negative electrode and the positive electrode. According to this configuration, the battery reaction can be easily resumed with a simple configuration.
　また、前記回路は、前記負極と前記正極との間に設けられる開閉式の抵抗放電回路であっても良い。この構成によれば、簡易な構成で、電池反応を再開させ易くなる。
　この場合、前記抵抗放電回路は、当該回路を流れる電流値が所定値を超えるとスイッチ開となるサーキットプロテクタスイッチであっても良い。この構成によれば、回路の保護などを図り易くなるとともに、スイッチ開にする操作を不要にすることができる。また、放電電力のロスも低減することもできる。 The circuit may be a switchable resistance discharge circuit provided between the negative electrode and the positive electrode. According to this configuration, the battery reaction can be easily resumed with a simple configuration.
In this case, the resistive discharge circuit may be a circuit protector switch which opens when the value of the current flowing through the circuit exceeds a predetermined value. According to this configuration, protection of the circuit can be facilitated, and the switch opening operation can be made unnecessary. In addition, the loss of discharge power can also be reduced.
　また、前記負極と前記正極とを備える複数の単位電池が直列接続され、前記複数の単位電池からなる組電池の両端の前記負極と前記正極との間に、前記回路を設けるようにしても良い。この構成によれば、単位電池毎に開閉式の短絡回路を設ける場合に比して、大電流を流し易くなるとともに、部品点数を削減可能である。 In addition, a plurality of unit cells including the negative electrode and the positive electrode may be connected in series, and the circuit may be provided between the negative electrode and the positive electrode at both ends of a battery pack including the plurality of unit cells. . According to this configuration, large current can easily flow and the number of parts can be reduced, as compared with the case where the switchable short circuit is provided for each unit battery.
　また、前記閉回路を流れる電流値を検出する電流検出部を設けるようにしても良い。この構成によれば、金属空気電池の負極（金属極）表面に形成された不動態被膜を除去し、負極（金属極）表面をリフレッシュできたか否かを判断可能な情報を得ることができる。
　この場合、前記電流検出部は、検出した電流値に応じて回路を開回路にするようにしても良い。この構成によれば、開回路に切り替えるためのユーザー操作を不要にすることができ、且つ、放電電力のロスを低減することができる。 In addition, a current detection unit that detects a current value flowing through the closed circuit may be provided. According to this configuration, it is possible to remove the passivation film formed on the surface of the negative electrode (metal electrode) of the metal-air battery, and obtain information that can be used to determine whether the surface of the negative electrode (metal electrode) can be refreshed.
In this case, the current detection unit may open the circuit according to the detected current value. According to this configuration, it is possible to eliminate the need for user operation for switching to the open circuit, and to reduce the loss of discharge power.
　また、前記閉回路を流れる積算電流値を検出する積算電流検出部を設けるようにしても良い。この構成によれば、金属空気電池の負極（金属極）表面に形成された不動態被膜を除去し、負極（金属極）表面をリフレッシュできたか否かを判断可能な情報を得ることができる。
　この場合、前記積算電流検出部は、検出した積算電流値に応じて回路を開回路にするようにしても良い。この構成によれば、開回路に切り替えるためのユーザー操作を不要にすることができ、且つ、放電電力のロスを低減することができる。 Further, an integrated current detection unit may be provided which detects an integrated current value flowing through the closed circuit. According to this configuration, it is possible to remove the passivation film formed on the surface of the negative electrode (metal electrode) of the metal-air battery, and obtain information that can be used to determine whether the surface of the negative electrode (metal electrode) can be refreshed.
In this case, the integrated current detection unit may open the circuit according to the detected integrated current value. According to this configuration, it is possible to eliminate the need for user operation for switching to the open circuit, and to reduce the loss of discharge power.
　また、前記閉回路にしてからの経過時間を検出する時間検出部を設けるようにしても良い。この構成によれば、金属空気電池の負極（金属極）表面に形成された不動態被膜を除去し、負極（金属極）表面をリフレッシュできたか否かを判断可能な情報を得ることができる。
　この場合、前記時間検出部は、検出した経過時間に応じて回路を開回路にするようにしても良い。この構成によれば、開回路に切り替えるためのユーザー操作を不要にすることができ、且つ、放電電力のロスを低減することができる。 Further, a time detection unit may be provided to detect an elapsed time after the closed circuit. According to this configuration, it is possible to remove the passivation film formed on the surface of the negative electrode (metal electrode) of the metal-air battery, and obtain information that can be used to determine whether the surface of the negative electrode (metal electrode) can be refreshed.
In this case, the time detection unit may open the circuit according to the detected elapsed time. According to this configuration, it is possible to eliminate the need for user operation for switching to the open circuit, and to reduce the loss of discharge power.
　また、前記負極は、少なくとも亜鉛を含むマグネシウム合金で形成されるようにしても良い。この構成によれば、亜鉛の影響により電池を休止後に電池反応を再開し難くなる場合に、電池反応を再開させ易くなる。 The negative electrode may be formed of a magnesium alloy containing at least zinc. According to this configuration, when it becomes difficult to restart the battery reaction after the battery is stopped due to the influence of zinc, it becomes easy to restart the battery reaction.
　また、本発明の金属空気電池ユニットは、複数の前記金属空気電池が、空気が滞留する間隙をあけて外箱内に収納され、前記外箱の側面部に、前記間隙内に突出して前記外装体を支える突片を備えたことを特徴とする。この構成によれば、外箱の側面部に設けた突片が、前記間隙内に突出して前記外装体を支えるため、金属空気電池の外装体の膨張を抑え、電池の出力低下を防止できる。 Further, in the metal air battery unit of the present invention, the plurality of metal air batteries are housed in the outer case with a gap for air to be accumulated therein, and are projected into the gap in the side portion of the outer case and the outer case It is characterized in that it has a projecting piece for supporting the body. According to this configuration, the projection provided on the side surface of the outer case protrudes into the gap to support the outer package, thereby suppressing the expansion of the outer package of the metal-air battery and preventing the decrease in the output of the battery.
　また、前記突片が前記外箱の側面部に上下方向に間隔をあけて複数設けられていても良い。
　また、前記金属空気電池間にスペーサが配置され、前記スペーサに前記突片が係止されていても良い。
　また、前記スペーサは立体的なスペーサであって、中央部に空気が滞留する滞留部を備え、この滞留部の両側部に、空気極を対向させて金属空気電池が配置されるポケットを備えるようにしても良い。 Further, a plurality of the projecting pieces may be provided at intervals in the vertical direction on the side surface portion of the outer case.
Further, a spacer may be disposed between the metal-air batteries, and the protrusion may be engaged with the spacer.
In addition, the spacer is a three-dimensional spacer, and includes a retention portion in which air is retained at a central portion, and a pocket in which an air electrode is opposed and a metal air battery is disposed on both sides You may
　また、前記スペーサは一枚のシート状のダンボールを折り曲げて立体的に形成されるようにしても良い。
　また、前記外装体の側面に枠部材が配置され、この枠部材の開口部に前記空気極が配置され、前記突片が前記枠部材を支えても良い。この外箱は紙製であってもよく、或いは樹脂製であってもよい。
　また、前記突片が前記外箱の側面部に一部の切り離し予定部を介して連結され、前記切り離し予定部が切り離されて前記間隙内に突出し前記空気極を支えるようにしても良い。 The spacer may be formed three-dimensionally by bending a sheet of sheet cardboard.
Moreover, a frame member may be arrange | positioned at the side surface of the said exterior body, the said air electrode may be arrange | positioned at the opening part of this frame member, and the said projection piece may support the said frame member. The outer box may be made of paper or resin.
Further, the projecting piece may be connected to the side surface of the outer box through a part to be separated, and the part to be separated may be separated to protrude into the gap to support the air electrode.
　本発明では、空気極を有するとともに前記空気極と対向する金属極を収容する外装体は、紙を含有するシート材で形成されることを特徴とする。この構成によれば、低コスト且つ軽量で、廃棄性にも有利である。
　また、金属極と空気極の間に設けられる開閉式の短絡回路を設けることで、金属極表面に形成された不動態被膜（後述する説明では「保護被膜」という場合がある）を容易に除去することができ、電池反応を再開させ易い状態に戻すことが可能である。 In the present invention, the exterior body which has an air electrode and accommodates the metal electrode facing the air electrode is characterized by being formed of a sheet material containing paper. According to this configuration, it is low in cost, light in weight, and advantageous in discardability.
Also, by providing a switchable short circuit provided between the metal electrode and the air electrode, the passive film (sometimes referred to as "protective film" in the following description) formed on the metal electrode surface is easily removed. It is possible to return to a state in which the battery reaction can be easily resumed.
図１は金属空気電池の第１実施形態に係るマグネシウム空気電池を示した図である。FIG. 1 is a view showing a magnesium-air battery according to a first embodiment of the metal-air battery. 図２はマグネシウム空気電池の図であり、図２（Ａ）は後方から見た図、図２（Ｂ）は上方から見た図、図２（Ｃ）は右から見た図である。FIG. 2 is a view of a magnesium-air battery, FIG. 2 (A) is a view from the rear, FIG. 2 (B) is a view from the top, and FIG. 2 (C) is a view from the right. 図３は第１実施形態の外装体を展開した図である。FIG. 3: is the figure which expand | deployed the exterior body of 1st Embodiment. 図４は図１のＩＶ-ＩＶ断面図である。FIG. 4 is a cross-sectional view taken along line IV-IV of FIG. 図５は図１のＶ-Ｖ断面図である。FIG. 5 is a sectional view taken along the line V--V of FIG. 図６は開口部の端面処理の第１実施例を模式的に示した断面図である。FIG. 6 is a cross-sectional view schematically showing a first embodiment of end face treatment of the opening. 図７は開口部の端面処理の第２実施例を示す図であり、図７（Ａ）は第２実施例を模式的に示した断面図であり、図７（Ｂ）は外装体の外面がラミネートされている場合を示した図である。FIG. 7 is a view showing a second embodiment of the end face treatment of the opening, FIG. 7 (A) is a sectional view schematically showing the second embodiment, and FIG. 7 (B) is an outer surface of the outer package. Is a view showing a case where is laminated. 図８は開口部の端面処理の第３実施例を模式的に示した断面図である。FIG. 8 is a cross-sectional view schematically showing a third embodiment of the end face treatment of the opening. 図９（Ａ）～図９（Ｄ）は開口部の端面処理の第４実施例を時系列順で模式的に示した断面図である。FIGS. 9A to 9D are cross sectional views schematically showing, in chronological order, the fourth embodiment of the end face treatment of the opening. 図１０は開口部の端面処理の第５実施例を模式的に示した断面図である。FIG. 10 is a cross-sectional view schematically showing a fifth example of the end face treatment of the opening. 図１１は開口部の端面処理の第６実施例を模式的に示した断面図である。FIG. 11 is a cross-sectional view schematically showing a sixth example of the end face treatment of the opening. 図１２は開口部の端面処理の第７実施例を模式的に示した断面図である。FIG. 12 is a cross-sectional view schematically showing a seventh embodiment of the end face treatment of the opening. 図１３は開口部の端面処理の第８実施例を模式的に示した断面図である。FIG. 13 is a cross-sectional view schematically showing an eighth embodiment of end face treatment of an opening. 図１４は第８実施例に用いるフィルムを説明する図であり、図１４（Ａ）は一体型のフィルムを示した図であり、図１４（Ｂ）は別体型のフィルムを示した図である。FIG. 14 is a view for explaining a film used in the eighth embodiment, FIG. 14 (A) is a view showing an integral type film, and FIG. 14 (B) is a view showing a separate type film. . 図１５は第２実施形態の外装体の斜視図である。FIG. 15 is a perspective view of the exterior body of the second embodiment. 図１６は第２実施形態の外装体を展開した図である。FIG. 16 is a developed view of the exterior body of the second embodiment. 図１７は第２実施形態の図であり、図１７（Ａ）は外装体を正面から見た図、図１７（Ｂ）は図１７（Ａ）のＡ－Ａ断面図である。FIG. 17 is a view of the second embodiment, FIG. 17 (A) is a front view of the exterior body, and FIG. 17 (B) is an AA cross-sectional view of FIG. 17 (A). 図１８は第２実施形態の変形例の一部展開図であり、図１８（Ａ）は上板部を長く形成し取っ手を１つ設けた図、図１８（Ｂ）は上板部を長く形成し取っ手を２つ設けた図である。FIG. 18 is a partially developed view of a modification of the second embodiment, and FIG. 18 (A) is a view in which the upper plate portion is formed long and one handle is provided, and FIG. It is a figure which formed and provided two handles. 図１９は第３実施形態の外装体の図であり、図１９（Ａ）は外装体を正面から見た図、図１９（Ｂ）は図１９（Ａ）のＢ－Ｂ断面図である。FIG. 19 is a view of the exterior body of the third embodiment, FIG. 19 (A) is a front view of the exterior body, and FIG. 19 (B) is a cross-sectional view taken along the line BB in FIG. 図２０は第３実施形態の底板シート部の斜視図である。FIG. 20 is a perspective view of the bottom plate sheet portion of the third embodiment. 図２１は第４実施形態に係るマグネシウム空気電池の斜視図である。FIG. 21 is a perspective view of a magnesium-air battery according to a fourth embodiment. 図２２は第４実施形態のマグネシウム空気電池の側断面図である。FIG. 22 is a side sectional view of the magnesium-air battery of the fourth embodiment. 図２３は第４実施形態の図であり、図２３（Ａ）は電解質収容体をマグネシウム極と共に空気極側から見た斜視図、図２３（Ｂ）は空気極と反対側から見た斜視図である。FIG. 23 is a view of the fourth embodiment, and FIG. 23 (A) is a perspective view of the electrolyte container as viewed from the air electrode side together with the magnesium electrode, and FIG. 23 (B) is a perspective view from the opposite side of the air electrode. It is. 図２４は第４実施形態の変形例に係るマグネシウム空気電池の側断面図である。FIG. 24 is a side sectional view of a magnesium-air battery according to a modification of the fourth embodiment. 図２５は第４実施形態の変形例の図であり、図２５（Ａ）は電解質収容体をマグネシウム極と共に空気極側から見た斜視図、図２５（Ｂ）は空気極と反対側から見た斜視図である。FIG. 25 is a view of a modification of the fourth embodiment, and FIG. 25 (A) is a perspective view of the electrolyte containing body as viewed from the air electrode side together with the magnesium electrode, and FIG. 25 (B) is seen from the opposite side to the air electrode. FIG. 図２６は第５実施形態に係るマグネシウム空気電池の側断面図である。FIG. 26 is a side sectional view of a magnesium-air battery according to a fifth embodiment. 図２７は第５実施形態の外装体の斜視図である。FIG. 27 is a perspective view of the exterior body of the fifth embodiment. 図２８は第５実施形態の図であり、図２８（Ａ）は外装体を展開した図、図２８（Ｂ）は図２７のＸ領域に相当する図、図２８（Ｃ）は図２７のＹ領域に相当する図、図２８（Ｄ）は図２７のＺ領域に相当する図である。FIG. 28 is a view of the fifth embodiment, FIG. 28 (A) is a developed view of the outer package, FIG. 28 (B) is a view corresponding to the X region of FIG. FIG. 28D is a diagram corresponding to the Z region of FIG. 図２９は金属空気電池ユニットの実施形態を示した斜視図である。FIG. 29 is a perspective view showing an embodiment of a metal-air battery unit. 図３０は金属空気電池ユニットの実施形態を示した斜視図である。FIG. 30 is a perspective view showing an embodiment of the metal-air battery unit. 図３１は金属空気電池ユニットのスペーサを周辺構成と共に示した斜視図である。FIG. 31 is a perspective view showing a spacer of the metal-air battery unit together with its peripheral configuration. 図３２はスペーサ単体の斜視図である。FIG. 32 is a perspective view of a single spacer. 図３３はスペーサ単体の上面図である。FIG. 33 is a top view of the spacer alone. 図３４はスペーサ単体の側面図である。FIG. 34 is a side view of the spacer alone. 図３５はマグネシウム空気電池の図３６に示すＩ―Ｉ線相当断面図である。FIG. 35 is a cross-sectional view corresponding to the II line shown in FIG. 36 of the magnesium-air battery. 図３６はマグネシウム空気電池の外装体上部の折り曲げ前の上部部分斜視図である。FIG. 36 is a top partial perspective view of the upper part of the exterior of the magnesium-air battery before being folded. 図３７はスペーサの展開図である。FIG. 37 is a developed view of the spacer. 図３８は外箱の展開図である。FIG. 38 is a development view of the outer case. 図３９は金属空気電池ユニットの他の実施例を示した斜視図である。FIG. 39 is a perspective view showing another embodiment of the metal-air battery unit. 図４０は金属空気電池ユニットの他の実施例を示した斜視図である。FIG. 40 is a perspective view showing another embodiment of the metal-air battery unit. 図４１は金属空気電池システムの第１実施形態の構成を示した図である。FIG. 41 is a view showing the configuration of the first embodiment of the metal-air battery system. 図４２は第１実施形態に係る金属空気電池システムの変形例を示した図である。FIG. 42 is a view showing a modification of the metal-air battery system according to the first embodiment. 図４３は金属空気電池システムの図であり、図４３（Ａ）は金属空気電池システムの第２実施形態の構成を示した図であり、図４３（Ｂ）は第２実施形態の変形例を示した図である。FIG. 43 is a view of a metal-air battery system, FIG. 43 (A) is a view showing a configuration of a second embodiment of the metal-air battery system, and FIG. 43 (B) is a modification of the second embodiment. FIG. 図４４は第２実施形態に係る金属空気電池システムの別の変形例を示した図である。FIG. 44 is a view showing another modified example of the metal-air battery system according to the second embodiment. 図４５は金属空気電池システムの図であり、図４５（Ａ）は金属空気電池システムの第３実施形態の構成を示した図であり、図４５（Ｂ）は金属空気電池システムの第４実施形態の構成を示した図である。FIG. 45 is a diagram of a metal-air battery system, and FIG. 45 (A) is a diagram showing the configuration of a third embodiment of the metal-air battery system, and FIG. 45 (B) is a fourth embodiment of the metal-air battery system It is the figure which showed the structure of the form. 図４６は金属空気電池システムの第５実施形態の構成を示した図である。FIG. 46 is a view showing the configuration of the fifth embodiment of the metal-air battery system. 図４７は金属空気電池システムの第６実施形態の構成を示した図である。FIG. 47 is a view showing the configuration of the sixth embodiment of the metal-air battery system.
　以下、図面を参照して本発明の一実施形態について説明する。
（第１実施形態）
　図１は本発明の金属空気電池の第１実施形態に係るマグネシウム空気電池を示した図である。
　マグネシウム空気電池１０は、折り曲げ自在なシート材（後段の図６などに符号１０１を付して示す）で形成された中空箱形状の外装体（筐体とも言う）１１を備えている。外装体１１には、空気極１３が装着されるとともに、空気極１３と対向するようにマグネシウム極（金属極）１５が収容される。このマグネシウム空気電池１０は、空気極１３が正極として作用し、マグネシウム極１５が負極として作用する一次電池である。
　図１および後述する各図に示す上下左右などの各方向は、マグネシウム空気電池１０を電池として使用するときの各方向に対応し、以下の説明で使用する各方向と同じである。 Hereinafter, an embodiment of the present invention will be described with reference to the drawings.
First Embodiment
FIG. 1 is a view showing a magnesium-air battery according to a first embodiment of the metal-air battery of the present invention.
The magnesium-air battery 10 is provided with a hollow box-shaped exterior body (also referred to as a housing) 11 formed of a foldable sheet material (shown by reference numeral 101 in FIG. 6 in the latter stage and the like). The air electrode 13 is attached to the exterior body 11, and a magnesium electrode (metal electrode) 15 is accommodated so as to face the air electrode 13. The magnesium-air battery 10 is a primary battery in which the air electrode 13 acts as a positive electrode and the magnesium electrode 15 acts as a negative electrode.
Each direction such as top, bottom, left, and right shown in FIG. 1 and each drawing described later corresponds to each direction when the magnesium air battery 10 is used as a battery, and is the same as each direction used in the following description.
　図２はマグネシウム空気電池１０を示す図であり、図２（Ａ）は後方から見た図、図２（Ｂ）は上方から見た図、図２（Ｃ）は右から見た図である。外装体１１は、薄型の直方体形状に形成されており、外装体１１の底面を構成する底板部２１と、前面を構成する前壁部２２と、後面を構成する後壁部２３（図２）と、左右側面を構成する左右の側壁部（左壁部、右壁部）２４と、上面を構成する上板部２５とを一体に有している。
　前壁部２２および後壁部２３は、同一形状の面であって、互いに平行に配置され、外装体１１の中で最も大きい面を形成する。前壁部２２には、空気極１３が装着（接着）される開口部２２Ｋ（後述する図３参照）が設けられている。 FIG. 2 is a view showing the magnesium-air battery 10, FIG. 2 (A) is a view from the rear, FIG. 2 (B) is a view from the top, and FIG. 2 (C) is a view from the right. . The exterior body 11 is formed in a thin rectangular parallelepiped shape, and a bottom plate portion 21 configuring a bottom surface of the exterior body 11, a front wall portion 22 configuring a front surface, and a rear wall portion 23 configuring a rear surface (FIG. 2) The left and right side wall portions (left wall portion, right wall portion) 24 constituting the left and right side surfaces and the upper plate portion 25 constituting the upper surface are integrally formed.
The front wall portion 22 and the rear wall portion 23 are surfaces of the same shape, arranged in parallel to each other, and form the largest surface of the exterior body 11. The front wall portion 22 is provided with an opening 22K (see FIG. 3 described later) to which the air electrode 13 is attached (adhered).
　空気極１３は、矩形状（タブ部１３Ｔを除く）の銅メッシュ（銅製の金網）に、カーボンとテフロン（登録商標）を混合した素材を、ローラープレス機などを用い所定厚さのシート状とした後、所定時間、所定温度で乾燥、焼成させ、前記銅メッシュと略同等の大きさに裁断したシートを両面から圧迫（プレス）し狭持したものを、外装体１１の開口部２２Ｋに熱融着や接着剤などにより接着した構造であり、通気性と非透水性（非透液性に相当）とを有している。即ち、前記シート状とした素材は、外部の空気は外装体の内部に通気可能であり、外装体１１内部の電解液は外部に透過不能な非透水性を有するものである。なお、空気極１３には公知の構成を広く適用可能である。
　マグネシウム極１５は、前壁部２２と後壁部２３との間であって、各壁部２２、２３から離間した位置にて空気極１３と平行に配置される。また、空気極１３およびマグネシウム極１５は、前壁部２２および後壁部２３に対しても平行である。図１に示す電池使用状態では、各空気極１３、マグネシウム極１５は鉛直方向に配置される。 The air electrode 13 is made of a rectangular (not including the tab portion 13T) copper mesh (copper mesh) made of a mixture of carbon and Teflon (registered trademark) in a sheet shape having a predetermined thickness using a roller press machine or the like. Then, it is dried and fired at a predetermined temperature for a predetermined time, and the sheet cut into approximately the same size as the copper mesh is pressed (pressed) from both sides and held between them, heat is applied to the opening 22K of the exterior body It has a structure bonded by fusion bonding or an adhesive, and has air permeability and water impermeable property (corresponding to liquid impermeable property). That is, in the sheet-like material, external air can be ventilated to the inside of the exterior body, and the electrolyte solution inside the exterior body 11 has impermeability to the outside. A wide range of known configurations can be applied to the air electrode 13.
The magnesium electrode 15 is disposed parallel to the air electrode 13 at a position between the front wall 22 and the rear wall 23 and apart from each of the walls 22 and 23. The air electrode 13 and the magnesium electrode 15 are also parallel to the front wall 22 and the rear wall 23. In the battery used state shown in FIG. 1, each air pole 13 and magnesium pole 15 are arranged in the vertical direction.
　空気極１３には、上方に突出するタブ部１３Ｔが設けられ、このタブ部１３Ｔに不図示の正極配線が接続される。タブ部１３Ｔとしては、Ｎｉ製や銅製の板部材が用いられ、空気極１３の銅メッシュに溶接などによって接合される。このタブ部１３Ｔは、外装体１１の上板部２５よりも上方に突出し、上方から正極配線を容易に接続可能である。
　また、マグネシウム極１５にも、上方に突出するタブ部１５Ｔが設けられ、このタブ部１５Ｔに不図示の負極配線が接続される。 The air electrode 13 is provided with a tab portion 13T projecting upward, and a positive electrode wiring (not shown) is connected to the tab portion 13T. A plate member made of Ni or copper is used as the tab portion 13T, and is joined to the copper mesh of the air electrode 13 by welding or the like. The tab portion 13T protrudes above the upper plate portion 25 of the exterior body 11, and can easily connect the positive electrode wiring from above.
Further, a tab portion 15T projecting upward is also provided in the magnesium electrode 15, and a negative electrode wiring (not shown) is connected to the tab portion 15T.
　マグネシウム極１５のタブ部１５Ｔは、マグネシウム極１５に一体に設けられ、外装体１１よりも上方に突出する。すなわち、マグネシウム極１５は、矩形板状のマグネシウム極本体部（金属極本体部）１５Ａ（後述する図４参照）と、マグネシウム極本体部１５Ａから同じ厚さで上方に突出するタブ部１５Ｔとを一体に備えている。
　なお、図１に示すように、マグネシウム極１５のタブ部１５Ｔは、マグネシウム極１５における幅方向一端側（左端側）にオフセットして設けられる。また、空気極１３のタブ部１３Ｔは、マグネシウム極１５のタブ部１５Ｔよりも幅方向他端側（図１中、右端側）にオフセットした位置に設けられる。これによって、正面視（図１）で各タブ部１５Ｔ、１３Ｔが重ならないように配置されている。 The tab portion 15T of the magnesium electrode 15 is integrally provided on the magnesium electrode 15, and protrudes upward beyond the exterior body 11. That is, the magnesium electrode 15 includes a rectangular plate-shaped magnesium electrode main body (metal electrode main body) 15A (see FIG. 4 described later) and a tab 15T projecting upward from the magnesium electrode main body 15A by the same thickness. It is equipped with one.
In addition, as shown in FIG. 1, the tab part 15T of the magnesium pole 15 is offset and provided in the width direction one end side (left end side) in the magnesium pole 15. As shown in FIG. Further, the tab portion 13T of the air electrode 13 is provided at a position offset to the other end side (right end side in FIG. 1) in the width direction than the tab portion 15T of the magnesium electrode 15. As a result, the tab portions 15T and 13T are arranged so as not to overlap in a front view (FIG. 1).
　上板部２５は、前壁部２２と後壁部２３と左右の側壁部２４との間に形成された内部空間の上方を覆う覆い部材として機能する。この上板部２５は、マグネシウム極本体部１５Ａの上面を覆う一方で、タブ部１５Ｔは外部に露出させる。また、上板部２５には、電解液（本構成では食塩水）の注入口となる左右一対の孔部２５Ｈが設けられる。各孔部２５Ｈは、円弧に沿った切れ目の内周部分に相当し、電解液を注入する注入ボトルの先端が切れ目の内側に突き当てられることによって各孔部２５Ｈが開口し、電解液を内部に注入させることができる。このとき、電解液はいずれか一つの孔部から注入され、それ以外の孔部は空気孔となる。なお、前記電解液の注入口となる左右一対の孔部２５Ｈは２個を超える複数でも良く、また、孔部２５Ｈの形状は円弧のみならず、三角形状や四角形状など、特に限定されるものではない。なお、孔部２５Ｈを複数個設ける場合には、少なくとも一箇所を空気孔として構成していれば良く、例えば孔部２５Ｈを３個設ける場合には、２個を注液口、１個を空気孔とすることで、注液時間を短縮することが可能である。 The upper plate portion 25 functions as a covering member that covers the upper side of the internal space formed between the front wall portion 22, the rear wall portion 23 and the left and right side wall portions 24. The upper plate 25 covers the upper surface of the magnesium electrode main body 15A, and the tab 15T is exposed to the outside. Further, the upper plate portion 25 is provided with a pair of left and right holes 25H serving as an inlet for an electrolytic solution (in the present configuration, a saline solution). Each hole 25H corresponds to the inner circumferential portion of the cut along the arc, and when the tip of the injection bottle for injecting the electrolyte is abutted against the inside of the cut, each hole 25H is opened, and the electrolyte is internally contained. Can be injected. At this time, the electrolytic solution is injected from any one of the holes, and the other holes become air holes. The pair of left and right holes 25H serving as the electrolyte injection port may be more than two in number, and the shape of the holes 25H is not limited to a circular arc, but is particularly limited such as triangular or square. is not. In the case where a plurality of holes 25H are provided, at least one portion may be configured as an air hole. For example, in the case where three holes 25H are provided, two are a liquid inlet and one is an air. By making the holes, it is possible to shorten the liquid injection time.
　本構成では、前記するように複数の孔部２５Ｈを設けているため、一方から電解液を注入する際に、他方を、外装体１１内の空気を外部に抜く空気孔として機能させることができる。また、単一の孔部２５Ｈを設けた場合に比して、電池反応時に内部に発生したガスを効率良く外に抜くこともできる。つまり、上記孔部２５Ｈは、一方は電解液注入口、他方は空気孔およびガス抜き孔として機能する。
　このように、切れ目によって選択的に開口する孔部２５Ｈを設けたので、電池使用前は閉じた状態に保持でき、塵などの異物が入ることを防止することができる。 In this configuration, since the plurality of holes 25H are provided as described above, when injecting the electrolyte solution from one side, the other can be functioned as an air hole for extracting the air in the exterior body 11 to the outside. . In addition, compared with the case where a single hole 25H is provided, the gas generated inside at the time of the cell reaction can also be extracted outside efficiently. That is, one of the holes 25H functions as an electrolyte injection port, and the other functions as an air hole and a gas release hole.
Thus, since the hole 25H selectively opened by the cut is provided, the battery can be kept closed before using the battery, and foreign matter such as dust can be prevented from entering.
　さらに、本構成の外装体１１は、簡易な構成でマグネシウム極１５を支持可能で、且つ、電解液の量の確保や軽量化に有利に構成されている。
　まず、この外装体１１は、紙を含有したシート材（後段の図６などに符号１０１を付して示す）によって製作されている。より具体的には、このシート材には、熱融着性樹脂（例えば、ポリエチレン（ＰＥ））により少なくとも内面がラミネート加工された紙、つまり、ラミネート紙が用いられる。このため、内面側が非透液性に形成され、電解液が外部に染み出す（漏れる）ことがなく、また、金属缶や樹脂製容器を使用する場合に比して、軽量かつ安価である。なお、シート材の表裏両面をラミネート加工した両面ラミネート紙を用いても良い。 Furthermore, the exterior body 11 of this configuration can support the magnesium electrode 15 with a simple configuration, and is advantageously configured to secure the amount of the electrolyte and to reduce the weight.
First, the exterior body 11 is made of a sheet material containing paper (indicated by reference numeral 101 in FIG. 6 and the like in the subsequent stage). More specifically, for this sheet material, a paper having at least the inner surface laminated with a heat fusible resin (for example, polyethylene (PE)), that is, a laminated paper is used. For this reason, the inner surface side is formed to be impervious to liquid so that the electrolytic solution does not exude (leak) to the outside, and it is lightweight and inexpensive as compared with the case of using a metal can or a resin container. In addition, you may use the double-sided lamination paper which laminated-processed both the front and back 2nd of a sheet material.
　なお、本構成における紙を含有したシート材とは、紙と熱融着性樹脂とをラミネート加工などにより複合化したものである。シート材中の紙の比率としては、好ましくは５０％を超えるようにする。本構成の外装体１１は、紙の比率を５０％超過とすることで、例えば紙ゴミとして廃棄可能である。
　後述するように、外装体１１は、シート材を所定形状に打ち抜いた打ち抜きシート１００で作成される。前記打ち抜きシート１００は、いわゆる紙のコシの強さ（紙の強度に相当）によって、組立後に外装体１１に必要とされる強度を満足する。言い換えれば、打ち抜きシート１００の厚さ、含有する紙繊維の長さ、および、紙繊維の材料などを調整することによって所望の強度を有するように製作される。また、紙のコシの強さの調整により、折り曲げた状態に保持させることができ、後述する前後一対の上板部構成片２５Ｆ、２５Ｒによるマグネシウム極１５の保持に必要な強度も得ている。 The sheet material containing paper in the present construction is a composite of paper and a heat fusible resin by lamination or the like. The proportion of paper in the sheet material is preferably greater than 50%. The exterior body 11 of this configuration can be discarded, for example, as paper waste by setting the ratio of paper to be 50% or more.
As described later, the exterior body 11 is made of a punched sheet 100 in which a sheet material is punched into a predetermined shape. The punched sheet 100 satisfies the strength required for the outer package 11 after assembly by the so-called strength of paper (corresponding to the strength of paper). In other words, it is manufactured to have a desired strength by adjusting the thickness of the punched sheet 100, the length of the contained paper fiber, the material of the paper fiber, and the like. Further, by adjusting the strength of the paper, it can be held in a bent state, and the strength necessary for holding the magnesium electrode 15 by the pair of front and rear upper plate parts 25F and 25R described later is also obtained.
　より具体的には、紙としては、コートボール、ノーコートボール、板紙、カード紙などの、比較的厚手の強度を有するものが好適に使用できる。また、紙と熱融着性樹脂が予め複合化された、カップ原紙や紙パック原紙なども好適に使用できる。
　また、熱融着性樹脂としては、シート材を熱融着により接合して、液密な箱形状に形成可能とするものであり、熱融着が可能なものであれば任意の樹脂が使用可能であるが、ポリエチレン、ポリプロピレン、エチレン－酢酸ビニル共重合体などのポリオレフィン系樹脂を用いることが好ましい。熱融着性樹脂の厚さは、十分な熱融着状態を得るために、少なくとも１０μｍ、好ましくは２０μｍ以上とする。特に外装体１１の内面側となる面は、密封性をより確実なものとするために、４０μｍ以上の厚さとすることが、より好ましい。 More specifically, as paper, those having relatively thick strength, such as coated balls, uncoated balls, paperboard, card paper, etc. can be suitably used. In addition, cup base paper, paper pack base paper, etc., in which paper and heat fusible resin are complexed in advance, can also be suitably used.
Further, as the heat fusible resin, a sheet material is joined by heat fusible to be able to be formed in a liquid-tight box shape, and any resin may be used as long as heat fusible is possible Although possible, it is preferable to use a polyolefin-based resin such as polyethylene, polypropylene, ethylene-vinyl acetate copolymer and the like. The thickness of the heat-fusible resin is at least 10 μm, preferably 20 μm or more, in order to obtain a sufficient heat-fused state. In particular, it is more preferable that the surface on the inner surface side of the exterior body 11 have a thickness of 40 μm or more in order to make the sealing performance more reliable.
　また、シート材としては、さらに必要に応じて他のフィルムなどを積層することができる。例えばシート材に強度を付与する目的で、ポリエチレンテレフタレート（ＰＥＴ）やポリアミド（Ｎｙ）、延伸ポリプロピレン（ＯＰＰ）フィルムを積層することができる。ポリアミドフィルムは突き刺し耐性に優れるフィルムであり、好ましく使用される。またこれらのフィルムは、シート材の外面側に積層することにより、シート材に優れた印刷適性を付与することができる。すなわち、シート材に絵柄や文字などを印刷する場合は、紙に直接印刷を施してもよいが、ＰＥＴやＯＰＰにあらかじめ印刷を施し、これを紙に積層することで、シート材に美麗な絵柄や文字などを付与することができる。 Moreover, as a sheet material, another film etc. can be laminated | stacked as needed. For example, for the purpose of imparting strength to a sheet material, polyethylene terephthalate (PET), polyamide (Ny), and oriented polypropylene (OPP) films can be laminated. Polyamide films are films excellent in puncture resistance, and are preferably used. Moreover, these films can provide the sheet material with excellent printability by laminating on the outer surface side of the sheet material. That is, when printing patterns or characters on a sheet material, printing may be directly performed on paper, but by printing on PET or OPP in advance and laminating it on paper, a beautiful pattern on the sheet material may be printed. And letters can be given.
　熱融着性樹脂、他のフィルムはそれぞれ紙に貼り合わせるようにしてもよく、熱融着性樹脂と他のフィルムをあらかじめ積層した後に紙に積層してもよく、また、熱融着性樹脂と他の樹脂を共押し出しした共押し出しフィルムを貼り合わせて積層しても良い。 The heat fusible resin and other films may be laminated to paper, respectively, or the heat fusible resin and the other film may be laminated in advance and then laminated to paper. And co-extrusion films obtained by co-extrusion of other resins may be laminated and laminated.
　本発明の紙を含むシート材は、所定の強度を有する必要がある。具体的には、こわさ（テーバー）（ＪＩＳ－Ｐ　８１２５「紙及び板紙－こわさ試験方法－」準拠）」がＭＤ方向（抄紙機の進行方向に並行な紙の方向；ＭＤ＝ｍａｃｈｉｎｅ　ｄｉｒｅｃｔｉｏｎ）において５～３０ｍＮ・ｍ、ＣＤ方向（抄紙機の進行方向に直角な紙の方向；ＣＤ＝ｃｒｏｓｓ　ｄｉｒｅｃｔｉｏｎ）において２～１５ｍＮ・ｍのものを用いることが好ましい。こわさ（テーバー）は、紙の厚さや密度、積層する熱融着性樹脂や他のフィルムの種類、厚さを変更することにより調整が可能である。
　なお、こわさ（テーバー）が前記値よりも小さい場合、強度が不足して電池外装体としての形状維持が難しい。また、前記値よりも大きい場合、強度が強すぎて折り曲げ加工などの作業が困難となる。 The sheet material containing the paper of the present invention needs to have a predetermined strength. Specifically, in the MD direction (the paper direction parallel to the traveling direction of the paper machine; MD = machine direction), the stiffness (taber) (based on JIS-P 8125 "paper and paperboard-stiffness test method") is 5 It is preferable to use one having a size of 2 to 15 mN · m in the direction of ̃30 mN · m, CD (direction of paper perpendicular to the direction of travel of the paper machine; CD = cross direction). The stiffness (taber) can be adjusted by changing the thickness and density of the paper, the type and thickness of the heat fusible resin and other films to be laminated.
In addition, when stiffness (taber) is smaller than the said value, intensity | strength runs short and shape maintenance as a battery exterior body is difficult. Moreover, when it is larger than the said value, intensity | strength is too strong and operation | works, such as a bending process, become difficult.
　前記する紙と熱融着性樹脂の積層は、熱融着性樹脂を紙に押し出しラミネートする方法が簡便であり好ましいが、ドライラミネート用接着剤を用いたドライラミネート法など、他の公知の積層方法も採用できる。ＰＥＴやＮｙ，ＯＰＰの積層も、公知の積層方法が採用可能であり、接着剤を用いたドライラミネート法や、熱融着性樹脂を介在させたサンドラミネーション法などが一般的に用いられる。
　前記シート材の層構成の具体例は以下に示す。
　（１）ＰＥ／紙／ＰＥ
　（２）ＰＥ／紙／ＰＥ／（ＰＥ／Ｎｙ／ＰＥ）　注：（）内は共押し出しフィルム
　（３）ＰＥＴ／ＰＥ／紙／ＰＥ The lamination of the paper and the heat fusible resin is preferably a simple method of extruding and laminating the heat fusible resin on the paper, but other known lamination methods such as a dry lamination method using an adhesive for dry lamination are preferable. A method can also be adopted. The lamination of PET, Ny, and OPP can also be performed using a known lamination method, and a dry lamination method using an adhesive, a sand lamination method using a heat fusible resin, and the like are generally used.
Specific examples of the layer configuration of the sheet material are shown below.
(1) PE / paper / PE
(2) PE / paper / PE / (PE / Ny / PE) Note: () is co-extrusion film (3) PET / PE / paper / PE
　外装体１１を製作する場合には、上記シート材を所定形状に打ち抜いた打ち抜きシート１００を作成し、この打ち抜きシート１００を折り曲げることによって製作される。この際、切断した端面のうち、後述する電解液に触れる可能性のある箇所については、電解液のシート材への浸み込みを防止するための端面処理を施すことが好ましい。端面処理としては、端面にホットメルトや接着剤を塗布して端面を覆う方法や、別体のフィルムを貼り付ける方法などが採用可能である。 When manufacturing the exterior body 11, it manufactures by producing the punching sheet 100 which pierce | punched the said sheet material in predetermined shape, and bend | folding this punching sheet 100. As shown in FIG. Under the present circumstances, it is preferable to perform the end surface process for preventing the penetration to the sheet material of electrolyte solution about the location which may contact the electrolyte solution mentioned later among the cut-off end surfaces. As the end surface treatment, a method of coating the end surface with a hot melt or an adhesive to cover the end surface, a method of attaching a separate film, or the like can be adopted.
　図３は打ち抜きシート１００を示した図であり、外装体１１を展開した図に相当している。なお、図３には、説明を判りやすくするため、折り目を一点鎖線で示している。また、図４は図１のＩＶ-ＩＶ断面図であり、図５は図１のＶ-Ｖ断面図である。
　図３に示すように、打ち抜きシート１００は、矩形の底板部２１と、底板部２１の前縁２１Ａ（折り目に相当）に連なる矩形の前壁部２２と、底板部２１の後縁２１Ｂ（折り目に相当）に連なる矩形の後壁部２３とを一体に有している。この底板部２１の前縁２１Ａと後縁２１Ｂとを基準にして、前壁部２２と後壁部２３とを折り曲げることによって、図４および図５に示すように、底板部２１から前壁部２２と後壁部２３とが立設する。図３に示すように、前壁部２２には、空気極１３が装着される開口部２２Ｋが形成されており、この開口部２２Ｋは、例えば、打ち抜いて打ち抜きシート１００を作成する際に同時に打ち抜かれる。 FIG. 3 is a view showing the punching sheet 100, which corresponds to a developed view of the exterior body 11. As shown in FIG. In FIG. 3, the folds are indicated by alternate long and short dash lines in order to make the description easy to understand. 4 is a cross-sectional view taken along the line IV-IV of FIG. 1, and FIG. 5 is a cross-sectional view taken along the line V-V of FIG.
As shown in FIG. 3, the punched sheet 100 has a rectangular bottom plate 21, a rectangular front wall 22 connected to a front edge 21 A (corresponding to a fold line) of the bottom plate 21, and a rear edge 21 B of the bottom plate 21 (fold And the rectangular rear wall portion 23 continuous with the By bending the front wall portion 22 and the rear wall portion 23 with reference to the front edge 21A and the rear edge 21B of the bottom plate portion 21, as shown in FIGS. 4 and 5, from the bottom plate portion 21 to the front wall portion 22 and the back wall 23 stand. As shown in FIG. 3, an opening 22 K to which the air electrode 13 is attached is formed in the front wall 22, and the opening 22 K is punched at the same time when, for example, punching is performed to form the punching sheet 100. Be
　底板部２１は、底板部２１を前後に二分割（本構成は等分割）する折り目２１Ｃ（図３）を基準に折り曲げられ、図４および図５に示すように、側面視で下方凸のＶ字形状に形成される。この底板部２１の上にはマグネシウム極１５が載置される。これによって、マグネシウム極１５の下端が底板部２１の傾斜に案内されて下方凸の部分２１Ｔに嵌り、マグネシウム極１５の下端を容易に位置決めすることができる。また、下方凸の部分２１Ｔと後述する第１折り曲げ部２５Ｆ１、２５Ｒ１によってマグネシウム極１５と空気極１３との離間距離を適正に保つことが可能であり、前記離間距離は折り目２１Ｃ、２２Ｃ、２３Ｃの距離を変化させることで容易に調整可能である。 The bottom plate portion 21 is bent on the basis of a fold line 21C (FIG. 3) which divides the bottom plate portion 21 back and forth (the present configuration is equally divided), and as shown in FIG. 4 and FIG. It is formed in a letter shape. The magnesium electrode 15 is placed on the bottom plate portion 21. Thereby, the lower end of the magnesium electrode 15 is guided by the inclination of the bottom plate portion 21 and fitted in the downward convex portion 21T, and the lower end of the magnesium electrode 15 can be easily positioned. Further, it is possible to maintain an appropriate separation distance between the magnesium electrode 15 and the air electrode 13 by the downward convex portion 21T and the first bent parts 25F1 and 25R1 described later, and the separation distance is the crease 21C, 22C and 23C. It can be easily adjusted by changing the distance.
　同図３に示すように、打ち抜きシート１００は、前壁部２２の左右の側縁２２Ｓ（折り目に相当）に連なる左右一対の側壁部構成片２４Ｆと、後壁部２３の左右の側縁２３Ｓ（折り目に相当）に連なる左右一対の側壁部構成片２４Ｒとを一体に有する。そして、これらの側壁部構成片２４Ｆ、２４Ｒによって、左右の側壁部２４が形成される。
　詳述すると、各側壁部構成片２４Ｆ、２４Ｒは、前壁部２２および後壁部２３の上下に渡って各々延在する縦長の矩形形状に形成され、前壁部２２および後壁部２３の左右の側縁２２Ｓ、２３Ｓを基準にして内側（外装体１１の内側に相当）に折り曲げられる。また、各側壁部構成片２４Ｆ、２４Ｒは、各構成片２４Ｆ、２４Ｒを左右に二分割（本構成は等分割）する折り目２４Ｃ、２４Ｄを基準にして、外側（外装体１１の外側）に折り曲げられ、外側に折り曲げられた外側折り曲げ片２４ＦＳ、２４ＲＳ同士が熱融着により接合される。接合された後は、外側折り曲げ片２４ＦＳ、２４ＲＳは、内側に折り曲げられた内側折り曲げ片２４ＦＵ、２４ＲＵに密着するように折り曲げられ、これによって、側壁部２４が形成される。
　この場合、熱融着により、外側折り曲げ片２４ＦＳ、２４ＲＳを内側折り曲げ片２４ＦＵ、２４ＲＵに接合しても良いし、テープなどの貼付材を用いて、外側折り曲げ片２４ＦＳ、２４ＲＳを内側折り曲げ片２４ＦＵ、２４ＲＵに密着させても良い。これによって、底板部２１と前壁部２２と後壁部２３と左右の側壁部２４とが組み立てられる。なお、図４中、符号２４Ｌは外装体１１の底板部２１の両端に形成される下方突出部であり、この下方突出部２４Ｌは、側壁部構成片２４Ｆの内側折り曲げ片２４ＦＵの下部に相当する。 As shown in FIG. 3, the punched sheet 100 includes a pair of left and right side wall portion constituting pieces 24F connected to the left and right side edges 22S (corresponding to the fold) of the front wall 22 and the left and right side edges 23S of the rear wall 23 A pair of left and right side wall portion constituting pieces 24R connected to (corresponding to a fold) are integrally provided. The left and right side wall portions 24 are formed by the side wall portion configuration pieces 24F and 24R.
More specifically, each side wall component piece 24F, 24R is formed in a vertically-long rectangular shape extending over the front wall 22 and the rear wall 23, respectively. It is bent inward (corresponding to the inside of the exterior body 11) with reference to the left and right side edges 22S, 23S. Further, each side wall portion constituting piece 24F, 24R is bent outward (outside of the exterior body 11) on the basis of the folds 24C, 24D which divides each constituting piece 24F, 24R into two right and left parts (this part is equally divided). The outside bent pieces 24FS and 24RS which are bent outward are joined by heat fusion. After being joined, the outer bent pieces 24FS and 24RS are bent so as to be in close contact with the inner bent pieces 24FU and 24RU bent inward, thereby forming the side wall portion 24.
In this case, the outer bent pieces 24FS and 24RS may be joined to the inner bent pieces 24FU and 24RU by heat fusion, or the outer bent pieces 24FS and 24RS may be joined to the inner bent pieces 24FU using an adhesive material such as a tape. You may make it adhere to 24 RU. Thus, the bottom plate 21, the front wall 22, the rear wall 23, and the left and right side walls 24 are assembled. In FIG. 4, reference numeral 24L is a downward projecting portion formed at both ends of the bottom plate portion 21 of the exterior body 11, and the downward projecting portion 24L corresponds to the lower portion of the inner bent piece 24FU of the side wall portion constituting piece 24F. .
　また、打ち抜きシート１００は、同図３に示すように、前壁部２２の上縁２２Ａ（折り目に相当）に連なる上板部構成片２５Ｆと、後壁部２３の上縁２３Ａ（折り目に相当）に連なる上板部構成片２５Ｒとを一体に有する。そして、これら一対の上板部構成片２５Ｆ、２５Ｒによって、上板部２５が形成される。
　詳述すると、各上板部構成片２５Ｆ、２５Ｒは、前壁部２２および後壁部２３の全幅に渡って各々延在する横長の矩形形状（幅方向に延びた板形状）に形成される。そして、各上板部構成片２５Ｆ、２５Ｒは、図４および図５に示すように、前壁部２２および後壁部２３の上縁２２Ａ、２３Ａを基準にして内側（外装体１１の内側に相当）に折り曲げられるとともに、各構成片２５Ｆ、２５Ｒを上下に二分割する折り目２２Ｃ、２３Ｃ（図３）を基準にして、さらに内側（外装体１１の内側）に折り曲げられ、側面視（図４、図５）で略Ｌ字状に屈曲する。 In addition, as shown in FIG. 3, the punched sheet 100 includes an upper plate portion constituting piece 25F connected to the upper edge 22A (corresponding to the fold) of the front wall portion 22, and an upper edge 23A (corresponding to the fold And the upper plate portion constituting piece 25R connected to the. Then, the upper plate portion 25 is formed by the pair of upper plate portion configuration pieces 25F, 25R.
More specifically, each upper plate portion constituting piece 25F, 25R is formed in a horizontally long rectangular shape (a plate shape extending in the width direction) extending over the entire width of the front wall portion 22 and the rear wall portion 23, respectively. . And each upper-plate part structure piece 25F, 25R is based on upper edge 22A, 23A of the front wall part 22 and the rear wall part 23, as shown to FIG. 4 and FIG. And the inner side of the exterior body 11 with reference to the folds 22C and 23C (FIG. 3) that divides each of the component pieces 25F and 25R into upper and lower parts, and the side view (FIG. 4) , Bend in a substantially L shape in FIG.
　図４および図５に示すように、各上板部構成片２５Ｆ、２５Ｒは、前壁部２２および後壁部２３の双方からマグネシウム極１５に向かうように折り曲げられた第１折り曲げ部２５Ｆ１、２５Ｒ１と、第１折り曲げ部２５Ｆ１、２５Ｒ１の先端（折り目２２Ｃ、２３Ｃに相当）から折り曲げられてマグネシウム極１５に当接する第２折り曲げ部２５Ｆ２、２５Ｒ２とを有し、これらによってマグネシウム極１５の上部が支持される。 As shown in FIGS. 4 and 5, each upper plate portion constituting piece 25F, 25R is a first bent portion 25F1, 25R1 which is bent from both of the front wall portion 22 and the rear wall portion 23 toward the magnesium electrode 15. And second bent portions 25F2 and 25R2 which are bent from the tips of the first bent portions 25F1 and 25R1 (corresponding to the folds 22C and 23C) and abut on the magnesium electrode 15, thereby supporting the upper portion of the magnesium electrode 15 Be done.
　より具体的には、後壁部２３の上板部構成片２５Ｒは、マグネシウム極１５の幅方向において、マグネシウム極１５のタブ部１５Ｔの両側縁に対応する位置に切れ目Ｋ（図３参照）を有し、これによって、タブ部１５Ｔと、タブ部１５Ｔのない非タブ部の境を基準にして、タブ部側の分割部２５Ｘと、非タブ部側の分割部２５Ｙとに分割される。そして、タブ部側の分割部２５Ｘでは、図４に示すように、第１折り曲げ部２５Ｒ１が、後壁部２３からマグネシウム極１５の後面ＭＲまで延びる長さに形成され、第２折り曲げ部２５Ｒ２が下方に折り曲げられることによってマグネシウム極１５の後面ＭＲに当接する。これによって、マグネシウム極１５の後面ＭＲと後壁部２３との間を上板部構成片２５Ｒが架橋し、上板部構成片２５Ｒによりマグネシウム極１５の後壁部２３側への移動（空気極１３と反対側への移動）が規制される。 More specifically, the upper plate portion constituting piece 25R of the rear wall portion 23 has a cut K (see FIG. 3) at a position corresponding to both side edges of the tab portion 15T of the magnesium electrode 15 in the width direction of the magnesium electrode 15. It is divided into a divided portion 25X on the tab portion side and a divided portion 25Y on the non-tab portion side on the basis of the boundary between the tab portion 15T and the non-tab portion without the tab portion 15T. In the divided portion 25X on the tab portion side, as shown in FIG. 4, the first bent portion 25R1 is formed to have a length extending from the rear wall portion 23 to the rear surface MR of the magnesium electrode 15, and the second bent portion 25R2 is By being bent downward, it abuts on the rear surface MR of the magnesium electrode 15. Thereby, the upper plate portion constituting piece 25R bridges between the rear surface MR of the magnesium electrode 15 and the rear wall portion 23, and the movement of the magnesium electrode 15 to the rear wall portion 23 side by the upper plate portion constituting piece 25R (air electrode 13) and movement to the opposite side is regulated.
　また、非タブ部側の分割部２５Ｙにおいては、図５に示すように、第１折り曲げ部２５Ｒ１がマグネシウム極本体部１５Ａを乗り越え、第２折り曲げ部２５Ｒ２がマグネシウム極１５の前面ＭＦに当接するように折り曲げられる。これによって、マグネシウム極１５の前面ＭＦと後壁部２３との間を上板部構成片２５Ｒが架橋し、上板部構成片２５Ｒによりマグネシウム極１５の前壁部２２側への移動（空気極１３側への移動）が規制される。このようにして、後壁部２３の上板部構成片２５Ｒは、マグネシウム極１５の前後両方への移動を規制する。 Further, in the non-tab-side divided portion 25Y, as shown in FIG. 5, the first bent portion 25R1 passes over the magnesium electrode main portion 15A and the second bent portion 25R2 abuts on the front surface MF of the magnesium electrode 15. It is bent to Thereby, the upper plate portion constituting piece 25R bridges between the front surface MF and the rear wall portion 23 of the magnesium electrode 15, and the movement of the magnesium electrode 15 to the front wall portion 22 side by the upper plate portion constituting piece 25R (air electrode 13) movement is restricted. In this manner, the upper plate portion configuration piece 25R of the rear wall portion 23 restricts the movement of the magnesium electrode 15 to both the front and back.
　一方、前壁部２２の上板部構成片２５Ｆでは、図４および図５に示すように、第１折り曲げ部２５Ｆ１が、前壁部２２からマグネシウム極１５の前面ＭＦまで延びる長さに形成される。そして、第２折り曲げ部２５Ｆ２が下方に折り曲げられることによって、後壁部２３の上板部構成片２５Ｆの第２折り曲げ部２５Ｒ２を介してマグネシウム極１５の前面ＭＦに当接する。これによって、マグネシウム極１５の前面ＭＦと前壁部２２との間を架橋し、上板部構成片２５Ｆによりマグネシウム極１５の前壁部２２側への移動（空気極１３側への移動）が規制される。
　このようにして、前壁部２２および後壁部２３の上板部構成片２５Ｆ、２５Ｒの双方は、シート材の一部を折り曲げることによってマグネシウム極１５を支える支持用折り曲げ部として機能する。 On the other hand, in the upper plate portion constituting piece 25F of the front wall portion 22, as shown in FIGS. 4 and 5, the first bent portion 25F1 is formed to have a length extending from the front wall portion 22 to the front surface MF of the magnesium electrode 15. Ru. Then, by bending the second bent portion 25F2 downward, the second bent portion 25F2 abuts on the front surface MF of the magnesium electrode 15 through the second bent portion 25R2 of the upper plate portion constituting piece 25F of the rear wall portion 23. As a result, the front face MF of the magnesium electrode 15 and the front wall 22 are bridged, and the movement of the magnesium electrode 15 to the front wall 22 side (movement to the air electrode 13) by the upper plate portion constituting piece 25F It is regulated.
In this manner, both of the upper plate portion constituting pieces 25F and 25R of the front wall portion 22 and the rear wall portion 23 function as support bending portions for supporting the magnesium electrode 15 by bending a part of the sheet material.
　次に、マグネシウム空気電池１０の組み立て手順を説明する。
　まず、紙を含有するシート材からなる打ち抜きシート１００を用意する。そして、この打ち抜きシート１００を、底板部２１の前縁２１Ａおよび後縁２１Ｂを基準に二つ折りして前壁部２２と後壁部２３を立設させるとともに、前壁部２２および後壁部２３の左右の側壁部構成片２４Ｆ、２４Ｒを折り曲げ、熱融着により接合して左右の側壁部２４を形成する（第１組立工程）。これによって、外装体１１が、内部空間を上方に開口させた状態に組み立てられる。なお、この第１組立工程において、底板部２１は、側面視で下方凸のＶ字形状に折り曲げられる（図４、図５参照）。
　次いで、外装体１１内に、上方からマグネシウム極１５を挿入し、マグネシウム極１５の下端を底板部２１の下方凸の部分２１Ｔ（図４、図５）に突き当て、マグネシウム極１５の下端を位置決めさせる（第２組立工程）。 Next, an assembly procedure of the magnesium air battery 10 will be described.
First, a punching sheet 100 made of a sheet material containing paper is prepared. Then, the punched sheet 100 is folded in half on the basis of the front edge 21A and the rear edge 21B of the bottom plate 21 to erect the front wall 22 and the rear wall 23, and the front wall 22 and the rear wall 23 The left and right side wall portion construction pieces 24F and 24R are bent and joined by heat fusion to form the left and right side wall portions 24 (first assembling step). Thereby, the exterior body 11 is assembled in a state in which the internal space is opened upward. In the first assembly step, the bottom plate portion 21 is bent in a V-shape in a downward convex shape in a side view (see FIGS. 4 and 5).
Then, the magnesium electrode 15 is inserted into the outer package 11 from above, and the lower end of the magnesium electrode 15 is abutted against the downward convex portion 21T (FIG. 4, FIG. 5) of the bottom plate 21 to position the lower end of the magnesium electrode 15 (2nd assembly process).
　続いて、図４および図５に示すように、後壁部２３に連なる上板部構成片２５Ｒを、マグネシウム極１５に向けて折り曲げて第１折り曲げ部２５Ｒ１を形成するとともに、第１折り曲げ部２５Ｒ１の先端に相当する折り目２３Ｃ（図３）で下方に折り曲げ、マグネシウム極１５に当接する第２折り曲げ部２５Ｒ２を形成する（第３組立工程）。
　このとき、後壁部２３の上板部構成片２５Ｒのうち、タブ部側の分割部２５Ｘは、図４に示すように、マグネシウム極１５の後面ＭＲ側で下方に折り曲げられて後面ＭＲに当接し、マグネシウム極１５の後壁部２３側への移動を規制する。また、非タブ部側の分割部２５Ｙは、図５に示すように、マグネシウム極本体部１５Ａを乗り越えてマグネシウム極１５の前面ＭＦ側で下方に折り曲げられて前面ＭＦに当接し、マグネシウム極１５の前壁部２２側への移動を規制する。 Subsequently, as shown in FIGS. 4 and 5, the upper plate portion constituting piece 25R connected to the rear wall portion 23 is bent toward the magnesium electrode 15 to form a first bent portion 25R1, and the first bent portion 25R1. The second bent portion 25R2 which is bent downward at a fold line 23C (FIG. 3) corresponding to the tip of the second contact portion to abut on the magnesium electrode 15 is formed (third assembling step).
At this time, among the upper plate portion constituting pieces 25R of the rear wall portion 23, the divided portion 25X on the tab portion side is bent downward on the rear surface MR side of the magnesium electrode 15, as shown in FIG. It contacts and controls movement to the rear wall 23 side of magnesium pole 15. Further, as shown in FIG. 5, the divided portion 25Y on the non-tab portion side is bent downward on the front surface MF side of the magnesium electrode 15 over the magnesium electrode body 15A and abuts on the front surface MF. It regulates movement to the front wall 22 side.
　その後、図４および図５に示すように、前壁部２２に連なる上板部構成片２５Ｆを、マグネシウム極１５に向けて折り曲げて第１折り曲げ部２５Ｆ１を形成するとともに、第１折り曲げ部２５Ｆ１の先端に相当する折り目２２Ｃ（図３）で下方に折り曲げて、第２折り曲げ部２５Ｆ２を形成する（第４組立工程）。この第２折り曲げ部２５Ｆ２は、マグネシウム極１５の前面ＭＦと前壁部２２との間を架橋するので、マグネシウム極１５の前壁部２２側への移動（空気極１３側への移動）を規制する。
　このようにして、前後一対の上板部構成片２５Ｆ、２５Ｒによって、マグネシウム極１５を前後から支えてマグネシウム極１５を位置決めすることができ、マグネシウム極１５ズレを防止することができる。 Thereafter, as shown in FIGS. 4 and 5, the upper plate portion constituting piece 25F connected to the front wall portion 22 is bent toward the magnesium electrode 15 to form a first bent portion 25F1, and the first bent portion 25F1 is formed. A second bent portion 25F2 is formed by bending downward at a fold line 22C (FIG. 3) corresponding to the front end (fourth assembly step). The second bent portion 25F2 bridges between the front surface MF of the magnesium electrode 15 and the front wall portion 22. Therefore, the movement of the magnesium electrode 15 to the front wall portion 22 side (movement to the air electrode 13 side) is restricted. Do.
In this manner, the magnesium electrode 15 can be positioned by supporting the magnesium electrode 15 from the front and back by the pair of front and rear upper plate parts 25F and 25R, and the displacement of the magnesium electrode 15 can be prevented.
　なお、外装体１１は熱融着により封止されるとともに、前後一対の上板部構成片２５Ｆ、２５Ｒ同士は、上方から上板部構成片２５Ｆ、２５Ｒ同士を接合する不図示の部材（蓋部材、或いは、テープなどの貼付材）を装着することによって互いに連結される。また、空気極１３については、第１組立工程の前に外装体１１に装着しても良いし、外装体１１の組立後（例えば、第４組立工程の後）に装着（接着）するようにしても良い。以上により、マグネシウム空気電池１０が組み立てられ、電池として使用する場合に外装体１１内に電解液が注入される。 In addition, while the exterior body 11 is sealed by heat sealing, a pair of upper plate portion configuration pieces 25F, 25R are not shown members that connect the upper plate portion configuration pieces 25F, 25R from above (a lid (lid They are connected to each other by attaching a member or a patch such as a tape. The air electrode 13 may be attached to the exterior body 11 before the first assembly process, or attached (adhered) after assembly of the exterior body 11 (for example, after the fourth assembly process). It is good. Thus, the magnesium-air battery 10 is assembled, and the electrolytic solution is injected into the exterior body 11 when used as a battery.
　続いて、組立後のマグネシウム空気電池１０について説明する。
　図４および図５に示すように、マグネシウム空気電池１０は、紙を含有するシート材からなる外装体１１がマグネシウム極１５との間に前後に隙間ＳＦ、ＳＲを空けて覆うとともに、これら隙間ＳＦ、ＳＲを上方から覆って該隙間ＳＦ、ＳＲを横断するように前後一対の上板部構成片２５Ｆ、２５Ｒが折り曲げられた構成を具備する。
　このため、外装体１１内の電解液の量を十分に確保できるとともに、簡易な構成でマグネシウム極１５を空気極１３から離間させた位置に保持できる。しかも、外装体１１が紙を含有するシート材から形成されるため、外装体１１の軽量化や加工コストの低減も可能である。
　さらに、マグネシウム空気電池１０を構成する主要部品が、外装体１１、マグネシウム極１５、空気極１３（タブ部１３Ｔを含む）の３部品で済むので、部品点数が少なく、組立工数の低減およびマグネシウム空気電池１０全体の軽量化が可能になる。 Subsequently, the magnesium air battery 10 after assembly will be described.
As shown in FIGS. 4 and 5, in the magnesium-air battery 10, the exterior body 11 made of a sheet material containing paper covers the clearances SF and SR with the magnesium electrode 15 at the front and back, and covers these clearances SF , SR from above and has a configuration in which the pair of upper plate portion configuration pieces 25F, 25R are bent so as to cross the gaps SF, SR.
Therefore, the amount of the electrolytic solution in the exterior body 11 can be sufficiently secured, and the magnesium electrode 15 can be held at a position separated from the air electrode 13 with a simple configuration. And since exterior body 11 is formed from a sheet material containing paper, weight reduction of exterior body 11 and reduction of processing cost are also possible.
Furthermore, since the main parts constituting the magnesium-air battery 10 are only three parts: the exterior body 11, the magnesium electrode 15, and the air electrode 13 (including the tab portion 13T), the number of parts is small, and the number of assembling steps is reduced. The weight of the entire battery 10 can be reduced.
　また、マグネシウム極１５は、上部が前後一対の上板部構成片２５Ｆ、２５Ｒによって支持されるとともに、下端が底板部２１の下方凸の部分２１Ｔで位置決めされるので、マグネシウム極１５の支持力が向上し、位置ずれを効率良く抑えることができる。
　また、マグネシウム極１５に対し、空気極１３と反対側にも電解液が入る隙間ＳＲが設けられるので、放電反応によりマグネシウム極１５と空気極１３の間に生成される生成物（本構成ではＭｇ（ＯＨ）2：水酸化マグネシウム）は、次第に空気極１３とマグネシウム極１５との間の隙間ＳＦから空気極１３と反対側に押し出されて、空気極と反対側の電解液がマグネシウムと空気極の間に回り込むため、放電反応を継続し易くなる、というメリットも得られる。 The upper portion of the magnesium electrode 15 is supported by the pair of upper and lower upper plate portions 25F and 25R, and the lower end is positioned by the downward convex portion 21T of the bottom plate portion 21. Thus, the positional deviation can be efficiently suppressed.
In addition, since the gap SR where the electrolytic solution enters on the opposite side to the air electrode 13 with respect to the magnesium electrode 15 is provided, a product (Mg in this configuration) generated between the magnesium electrode 15 and the air electrode 13 by the discharge reaction. (OH) 2 : Magnesium hydroxide is gradually pushed out from the gap SF between the air electrode 13 and the magnesium electrode 15 to the side opposite to the air electrode 13, and the electrolyte on the opposite side to the air electrode is magnesium and the air electrode. In addition, there is a merit that the discharge reaction can be easily continued.
　図４および図５中、符号ＵＬは、電解液の液面を示している。
　前後一対の上板部構成片２５Ｆ、２５Ｒは、電解液の液面ＵＬよりも上方に位置し、各上板部構成片２５Ｆ、２５Ｒの第１折り曲げ部２５Ｆ１、２５Ｒ１は、マグネシウム極１５に向かって斜め下方に傾斜している。このため、放電反応による水素の発生によって電解液が上方に飛散した際に、第１折り曲げ部２５Ｆ１、２５Ｒ１の下面に沿って電解液が流れ、下方に貯留される電解液内に迅速かつ円滑に戻すことができる。
　また、各上板部構成片２５Ｆ、２５Ｒの第１折り曲げ部２５Ｆ１、２５Ｒ１同士は突き当てられている。このため、前壁部２２と後壁部２３との間で第１折り曲げ部２５Ｆ１、２５Ｒ１同士が突っ張り、前壁部２２と後壁部２３とを離間させるとともに互いに平行に保持し易くなる。また、第１折り曲げ部２５Ｆ１、２５Ｒ１の上面が連続するので、テープなどの貼付材によって第１折り曲げ部２５Ｆ１、２５Ｒ１同士を連結し易くなる。 In FIG. 4 and FIG. 5, the symbol UL indicates the liquid level of the electrolytic solution.
The front and rear pair of upper plate component pieces 25F and 25R are located above the liquid surface UL of the electrolytic solution, and the first bent portions 25F1 and 25R1 of the upper plate component pieces 25F and 25R face the magnesium electrode 15, respectively. And slant downward. Therefore, when the electrolyte is scattered upward due to the generation of hydrogen due to the discharge reaction, the electrolyte flows along the lower surface of the first bent portions 25F1 and 25R1, and the electrolyte stored in the lower part is quickly and smoothly. It can be returned.
Further, the first bent portions 25F1 and 25R1 of the upper plate portion configuration pieces 25F and 25R are butted against each other. Therefore, the first bent portions 25F1 and 25R1 are held between the front wall portion 22 and the rear wall portion 23, and the front wall portion 22 and the rear wall portion 23 are separated and easily held parallel to each other. Further, since the upper surfaces of the first bent portions 25F1 and 25R1 are continuous, it is easy to connect the first bent portions 25F1 and 25R1 with an adhesive material such as a tape.
（外装体１１の素材について）
　上述したように、本実施形態のマグネシウム空気電池１０の外装体１１は、紙を含有するシート材で形成されるので、低コスト且つ軽量にすることができる。しかも、このシート材は熱融着性樹脂でラミネート加工などにより複合化された紙であるため、電池を放電後休止し再放電するなどの長時間使用時でも電解液が外部に染み出す（漏れる）ことを防止することができる。さらに、紙の比率を５０％超過にすることで、各自治体の決まりによるものの紙ゴミなどとして分別・廃棄し易くなり、且つ、容易に手に入れ易い、というメリットも得られる。これらによって、低コスト且つ軽量で、廃棄性などに優れたマグネシウム空気電池１０を提供することが可能になる。 (About the material of exterior body 11)
As described above, since the exterior body 11 of the magnesium-air battery 10 of the present embodiment is formed of a sheet material containing paper, it is possible to reduce the cost and weight. Moreover, since this sheet material is a heat-fusion resin-made paper composited by laminating etc., the electrolytic solution leaks out (leaks) even when used for a long time such as stopping the battery after discharging and re-discharging. ) Can be prevented. Furthermore, by making the ratio of paper 50% over, it is easy to separate and discard as paper waste according to the rules of each local government, and there is also an advantage that it is easy to obtain easily. As a result, it is possible to provide a magnesium air battery 10 which is low in cost, light in weight, and excellent in discardability.
（金属極（マグネシウム極１５）の支持構造について）
　ところで、従来の金属空気電池には、正極、セパレータおよびゲル状金属からなる負極材料を、熱融着性樹脂層を含むラミネートシートによって成形された外装体で包み、負極材料の電池内体積占有率を４０％以上９０％以下にした構成が提案されている（例えば、特開２００４－２８８５７１号公報）。
　しかし、上記特許文献に記載の構成は、空気拡散紙、空気極シート、セパレータ、ゲル状負極金属、負極集合体を積層して厚みのある発電要素を構成し、この発電要素を、負極側ラミネートシートと正極側ラミネートシートとの間に形成した凹部内に収納して保持する構成であるため、部品点数が多く、電解液の量が少なくなってしまう。
　電解液の量が少ないと、放電反応で電解液を消費する電池では十分な容量を得られなくなってしまう。また、部品点数を低減するために、いずれかの発電要素部品（例えば、セパレータ）を省略すると、金属極（負極）を支持することができず、部品点数の低減が困難である。また、部品点数が多いと、組立工数の増大や重量の増大を招き、コスト低減に不利である。
　上述した事情を考慮すると、簡易な構成で金属極を支持できるとともに、電解液の量の確保や軽量化に有利な金属空気電池を提供することが望まれる。 (About the support structure of the metal electrode (magnesium electrode 15))
By the way, in the conventional metal-air battery, the negative electrode material consisting of the positive electrode, the separator and the gel-like metal is wrapped in an outer package molded by a laminate sheet containing a heat-fusible resin layer, Has been proposed (for example, Japanese Patent Laid-Open No. 2004-288571).
However, in the configuration described in the above patent document, an air diffusion sheet, an air electrode sheet, a separator, a gelled negative electrode metal, and a negative electrode assembly are laminated to form a thick power generating element. Since it is a structure accommodated and hold | maintained in the recessed part formed between the sheet | seat and the positive electrode side lamination sheet, a number of parts will increase and the quantity of electrolyte solution will decrease.
If the amount of the electrolytic solution is small, a battery that consumes the electrolytic solution by the discharge reaction can not obtain a sufficient capacity. In addition, if any of the power generation component parts (for example, a separator) is omitted in order to reduce the number of parts, the metal electrode (negative electrode) can not be supported, which makes it difficult to reduce the number of parts. In addition, when the number of parts is large, the number of assembling steps and the weight are increased, which is disadvantageous for cost reduction.
In consideration of the above-described circumstances, it is desirable to provide a metal-air battery that can support a metal electrode with a simple configuration and that is advantageous for securing the amount of electrolyte solution and reducing weight.
　上述したように、本実施形態のマグネシウム空気電池１０の外装体１１は、紙を含有するシート材で形成され、このシート材は、隙間ＳＦ、ＳＲを空けてマグネシウム極（金属極）１５を覆うとともに、シート材の一部を折り曲げて隙間ＳＦ、ＳＲを横断し、マグネシウム極１５を支える支持用折り曲げ部として機能する一対の上板部構成片２５Ｆ、２５Ｒを一体に備えるので、紙を含有するシート材で形成された外装体１１の一部を折り曲げる、といった簡易な構成でマグネシウム極１５を支持できるとともに、電解液の量の確保や軽量化に有利である。また、外装体１１の軽量化により高い重量エネルギー密度を得ることが可能になる。
　さらに、マグネシウム極１５を支えるための専用部品が不要になるので、部品点数の削減が可能であり、また、マグネシウム極１５以外の発電要素の構成を追加することも容易な構成である。従って、コストを低減し易く、且つ、構成の変更自由度も高い。 As described above, the exterior body 11 of the magnesium-air battery 10 of the present embodiment is formed of a sheet material containing paper, and the sheet material covers the magnesium electrode (metal electrode) 15 with gaps SF and SR open. And a pair of upper plate portion constituting pieces 25F and 25R functioning as a support bending portion for bending the part of the sheet material to cross the gaps SF and SR and support the magnesium electrode 15, so that paper is contained The magnesium electrode 15 can be supported with a simple configuration such as bending a part of the exterior body 11 formed of a sheet material, and it is advantageous for securing the amount of the electrolyte and reducing the weight. Further, the weight reduction of the exterior body 11 makes it possible to obtain a high weight energy density.
Furthermore, since a dedicated part for supporting the magnesium electrode 15 is not required, the number of parts can be reduced, and it is easy to add a configuration of power generation elements other than the magnesium electrode 15. Therefore, the cost can be easily reduced, and the degree of freedom in changing the configuration is also high.
　また、一対の上板部構成片２５Ｆ、２５Ｒは、マグネシウム極１５を空気極１３から離間させた位置に保持するので、マグネシウム極１５と空気極１３とを確実に離すことができる。このため、極間に電解液を十分に保持することができる。また、マグネシウム極１５と空気極１３との間の距離（離間距離）を適正に保ち易くなる。
　また、各上板部構成片２５Ｆ、２５Ｒは、シート材（打ち抜きシート１００）におけるマグネシウム極１５に対して空気極１３側の壁部（前壁部２２）、および、空気極１３と反対側の壁部（後壁部２３）からマグネシウム極１５に向けて折り曲げられた第１折り曲げ部２５Ｆ１、２５Ｒ１と、第１折り曲げ部２５Ｆ１、２５Ｒ１の先端から折り曲げられてマグネシウム極１５極に当接する第２折り曲げ部２５Ｆ２、２５Ｒ２とを有するので、簡易な折り曲げ構造で、マグネシウム極１５を支持することができる。 Further, since the pair of upper plate portion constituting pieces 25F, 25R holds the magnesium electrode 15 at a position separated from the air electrode 13, the magnesium electrode 15 and the air electrode 13 can be reliably separated. Therefore, the electrolytic solution can be sufficiently held between the electrodes. In addition, the distance (separation distance) between the magnesium electrode 15 and the air electrode 13 can be easily maintained properly.
Further, each upper plate portion constituting piece 25F, 25R is a wall portion (front wall portion 22) on the air electrode 13 side with respect to the magnesium electrode 15 in the sheet material (punched sheet 100), and on the opposite side to the air electrode 13. The second bent part 25F1 and 25R1 bent from the wall part (rear wall part 23) toward the magnesium electrode 15 and the tip of the first bent parts 25F1 and 25R1 to abut on the magnesium electrode 15 pole Since the portions 25F2 and 25R2 are provided, the magnesium electrode 15 can be supported with a simple bending structure.
　さらに、第１折り曲げ部２５Ｆ１、２５Ｒ１は、外装体１１内の電解液の液面ＵＬよりも上方に設けられるとともにマグネシウム極１５に向かって斜め下方に傾斜するので、第１折り曲げ部２５Ｆ１、２５Ｒ１により電解液が外部に出難くなるとともに、第１折り曲げ部２５Ｆ１、２５Ｒ１の下面に付着した電解液を効率良く戻すことができる。
　また、後壁部２３に連なる上板部構成片２５Ｒは、マグネシウム極１５の幅方向において、タブ部１５Ｔと、タブ部１５Ｔのない非タブ部との境を基準にして分割され、タブ部側の分割部２５Ｘ（図３）と非タブ部側の分割部２５Ｙ（図３）のいずれか一方が、マグネシウム極１５の空気極１３側への移動を規制し、他方がマグネシウム極１５の空気極１３の反対側への移動を規制するので、タブ部１５Ｔを避けつつ、後壁部２３に連なる上板部構成片２５Ｒの各分割部２５Ｘ、２５Ｙによって、マグネシウム極１５の空気極１３側への移動と反対側への移動の両方を規制することができる。 Furthermore, since the first bent portions 25F1 and 25R1 are provided above the liquid level UL of the electrolytic solution in the exterior body 11 and inclined obliquely downward toward the magnesium electrode 15, the first bent portions 25F1 and 25R1 While becoming difficult to take out electrolyte solution outside, the electrolyte solution adhering to the lower surface of 1st bending part 25F1, 25R1 can be returned efficiently.
The upper plate constituting piece 25R connected to the rear wall 23 is divided on the basis of the boundary between the tab portion 15T and the non-tab portion without the tab portion 15T in the width direction of the magnesium electrode 15, and the tab portion side One of the divided portion 25X (FIG. 3) and the divided portion 25Y (FIG. 3) on the non-tab portion side restricts the movement of the magnesium electrode 15 toward the air electrode 13, and the other is the air electrode of the magnesium electrode 15. Since movement to the opposite side of 13 is restricted, the magnesium pole 15 is moved to the air pole 13 side by the divided portions 25X and 25Y of the upper plate portion configuration piece 25R connected to the rear wall 23 while avoiding the tab portion 15T. Both movement and movement to the opposite side can be regulated.
　また、外装体１１は、マグネシウム極１５の下端が嵌る下方凸形状に折り曲げられた底板部２１を有するので、マグネシウム極１５の下端を簡易な折り曲げ構造で位置決めし、ズレを防止することができる。 Further, since the exterior body 11 has the bottom plate portion 21 bent in a downward convex shape in which the lower end of the magnesium electrode 15 is fitted, the lower end of the magnesium electrode 15 can be positioned with a simple bending structure to prevent displacement.
（外装体の開口部について）
　一般に、従来の金属空気電池の外装体には、金属缶や樹脂製容器が使用されている。この種の外装体は、電解液の漏れを防ぐためのパッキンやシール材が必要となるため、部材数が多くなり、組立工数やコストの増加が生じ、さらにパッキンやシール材の不良や劣化により電解液が漏れるおそれもあり、外装体自体が重くなってしまう。
　従来の金属空気電池には、正極、セパレータおよびゲル状金属からなる負極材料を、熱融着性樹脂層を含むラミネートシートによって成形された外装体で包むものが提案されており（例えば、特開２００４－２８８５７１号公報）、金属空気電池以外の電池には、外装体を紙と複合した複合紙容器で構成したものが提案されている（例えば、特許第４２９６７７１号公報）。 (About the opening of the exterior body)
Generally, metal cans and resin containers are used for the exterior body of the conventional metal air battery. Since this type of exterior body requires packing and sealing material to prevent leakage of the electrolyte, the number of members increases, assembly man-hours and costs increase, and the packing and sealing material become defective or deteriorated. There is a possibility that the electrolyte may leak, and the outer package itself becomes heavy.
A conventional metal-air battery has been proposed in which an anode material made of a positive electrode, a separator and a gel-like metal is wrapped in an outer package formed of a laminate sheet containing a heat-fusible resin layer (e.g. 2004-288571), as batteries other than metal-air batteries, those having a composite paper container in which an exterior body is combined with paper are proposed (for example, Japanese Patent No. 4296771).
　しかし、特開２００４－２８８５７１号公報に記載の金属空気電池は、空気拡散紙、空気極シート、セパレータ、ゲル状負極金属、負極集合体を積層して厚みのある発電要素を構成し、この発電要素を、負極側ラミネートシートと正極側ラミネートシートとの間に形成した凹部内に収納して保持する構成であるため、部品点数が多く、構造が複雑化してしまい、コスト低減に不利である。
　一方、金属空気電池の外装体を、紙を含有するシート材で形成すれば、低コスト且つ軽量で、廃棄性にも有利になる。しかしながら、金属空気電池の外装体は、空気極を介して空気を取り込む開口部を有するため、紙製の外装体の場合、開口部の端部から電解液が浸透し、強度低下や外観の劣化を招いてしまうおそれが生じる。
　そこで、本構成では、紙を含有するシート材（打ち抜きシート１００）で外装体１１を形成した構成で、空気を取り込む開口部２２Ｋの端面からの電解液の浸透などの影響を抑えることを目的の一つとしている。 However, in the metal-air battery described in JP-A-2004-288571, an air diffusion sheet, an air electrode sheet, a separator, a gelled negative electrode metal, and a negative electrode assembly are stacked to form a thick power generating element. Since the element is housed and held in the recess formed between the negative electrode side laminate sheet and the positive electrode side laminate sheet, the number of parts is large, the structure is complicated, and the cost reduction is disadvantageous.
On the other hand, if the outer casing of the metal-air battery is formed of a sheet material containing paper, it is low in cost, light in weight, and advantageous in discardability. However, since the metal-air battery case has an opening for taking in air through the air electrode, in the case of a paper case, the electrolyte penetrates from the end of the opening and the strength decreases and the appearance is deteriorated. There is a risk of causing
Therefore, in the present configuration, the exterior body 11 is formed of a sheet material (punched sheet 100) containing paper, and the purpose is to suppress the influence of the electrolyte penetration from the end face of the opening 22K for taking in air. I have one.
　以下、開口部２２Ｋの端面処理を説明する。
　本構成では、開口部２２Ｋの端面には、内部に注液した電解液の浸透を防止する端面処理が施され、これによって、端面から電解液が浸透し、外装体１１の強度低下や外観の劣化を招いてしまう事態を回避している。
　この端面処理には、大別すると、シート材（以下、シート材１０１と表記する）そのものの端面を被覆する構造（端面被覆構造）と、シート材１０１と空気極１３とにまたがって被覆する構造（空気極利用型の被覆構造）とがあり、以下、端面処理の実施例について説明する。 The end face processing of the opening 22K will be described below.
In this configuration, the end face of the opening 22K is subjected to end face treatment for preventing the permeation of the electrolytic solution injected into the inside, whereby the electrolyte permeates from the end face and the strength of the exterior body 11 decreases and the appearance It avoids the situation that causes deterioration.
In this end surface treatment, when roughly classified, a structure (end surface covering structure) covering the end surface of the sheet material (hereinafter referred to as sheet material 101) itself and a structure covering the sheet material 101 and the air electrode 13 (Cover structure of air electrode utilization type), and an embodiment of end face processing will be described below.
（第１実施例；端面被覆構造・折り返し方式）
　図６は第１実施例を模式的に示した断面図である。
　まず、外装体１１を構成するシート材１０１は、紙を含有する紙層１０２と、ラミネート層を構成する内層１０３とを備えた二層構造に形成されている。内層１０３は、外装体１１の内面側を非透液性にする層であり、本実施例では、防水性（電解液に対する耐液性に相当）と熱融着性を有する合成樹脂製のフィルムで形成されている。この内層１０３には、ポリオレフィン系樹脂、ポリエステル系樹脂などが使用され、特にポリエチレン製のフィルムが好適である。 (First embodiment; end surface covering structure / folding method)
FIG. 6 is a cross-sectional view schematically showing the first embodiment.
First, the sheet material 101 constituting the exterior body 11 is formed in a two-layer structure including a paper layer 102 containing paper and an inner layer 103 constituting a laminate layer. The inner layer 103 is a layer that makes the inner surface side of the outer package 11 impervious to liquid, and in the present embodiment, a film made of a synthetic resin having waterproofness (corresponding to liquid resistance to the electrolytic solution) and heat fusion. It is formed of For the inner layer 103, a polyolefin resin, a polyester resin, or the like is used, and a film made of polyethylene is particularly preferable.
　空気極１３は、外装体１１の開口部２２Ｋに外側から装着され、タブ部１３Ｔを外装体１１に加工せずに外に配置可能にしている。この空気極１３は、銅メッシュからなる基材層１１１と、基材層１１１の内面および外面に設けられる内層１１２および外層１１３とを備えた三層構造に形成されている。内層１１２および外層１１３は、通気性と非透水性（非透液性）を有する層であり、本実施例では、ポリテトラフルオロエチレン（ＰＴＦＥ）とカーボンブラックとを混在させ、微細な孔を多数備えた多孔構造に形成されている。 The air electrode 13 is attached to the opening 22K of the exterior body 11 from the outside, and the tab portion 13T can be disposed outside without being processed into the exterior body 11. The air electrode 13 is formed in a three-layer structure including a base layer 111 made of copper mesh, and an inner layer 112 and an outer layer 113 provided on the inner and outer surfaces of the base layer 111. The inner layer 112 and the outer layer 113 are layers having air permeability and non-water permeability (non-liquid permeability), and in this embodiment, polytetrafluoroethylene (PTFE) and carbon black are mixed to form a large number of fine pores. It is formed in the provided porous structure.
　図６に示すように、シート材１０１の縁部１０１Ａ、より具体的には、開口部２２Ｋの周縁部分に位置する縁部１０１Ａは、外方に向かって折り返される。この折り返し角度は１８０度である。これによって、縁部１０１Ａが、縁部１０１Ａ以外の部分１０１Ｂの外方に重なり、縁部１０１Ａの内周層が外方に露出する。この外方に露出した内層１０３の領域に、空気極１３が内層１１２を接触させるように重ねられ、熱融着により接合される。これにより、空気極１３と縁部１０１Ａとの間の隙間が閉塞される。 As shown in FIG. 6, the edge portion 101A of the sheet material 101, more specifically, the edge portion 101A located at the peripheral portion of the opening 22K is folded outward. This turning angle is 180 degrees. Thus, the edge portion 101A overlaps the outside of the portion 101B other than the edge portion 101A, and the inner circumferential layer of the edge portion 101A is exposed outward. The air electrode 13 is superimposed on the area of the outwardly exposed inner layer 103 so as to bring the inner layer 112 into contact, and is joined by heat fusion. Thereby, the gap between the air electrode 13 and the edge 101A is closed.
　この構成によれば、シート材１０１の縁部１０１Ａの端面を外方に露出させて内部の電解液に接触させないようにすることができるとともに、シート材１０１の内層１０３を利用して空気極１３を接合できる。従って、シート材１０１を折り曲げる、といった簡易な方法で、開口部２２Ｋの端面からの電解液の浸透を防止でき、外装体１１の強度低下や外観の劣化を回避することができる。また、この被覆処理は、外装体１１の外面（シート材１０１の外面）がラミネートされていない場合でも適用できる、というメリットもある。 According to this configuration, the end face of the edge portion 101A of the sheet material 101 can be exposed outward so as not to be in contact with the electrolytic solution inside, and the air electrode 13 is utilized by using the inner layer 103 of the sheet material 101. Can be joined. Therefore, penetration of the electrolytic solution from the end face of the opening 22K can be prevented by a simple method of bending the sheet material 101, and the strength reduction of the exterior body 11 and the deterioration of the appearance can be avoided. Moreover, this coating process also has the merit that it can be applied even when the outer surface (the outer surface of the sheet material 101) of the exterior body 11 is not laminated.
（第２実施例；端面被覆構造・折り返し方式）
　図７（Ａ）は第２実施例を模式的に示した断面図である。
　第２実施例でも、第１実施例と同様に、開口部２２Ｋの周縁部分に位置する縁部１０１Ａは、外方に向かって折り返される。但し、第２実施例では、シート材１０１の縁部１０１Ａおよび縁部１０１Ａと重なる部分１０１Ｂの紙層１０２を予め削ることによって、厚さを半分にしている（図７中、厚さｔ＝０．５×Ｔ）。
　この構成により、図７（Ａ）に示すように、シート材１０１の縁部１０１Ａを折り返した際に、縁部１０１Ａと部分１０１Ｂとが重なった部分と、重ならない部分１０１Ｃとの厚さを揃えることができる。この場合、シート材１０１の外面が面一に連続する平面となる。これにより、空気極１３を熱融着により接合できるとともに、空気極１３のシート材１０１（外装体１１）からの出っ張り量を低減することができる。この第２実施例によれば、第１実施例と同様の効果に加え、第１実施例よりもマグネシウム空気電池１０の薄型化が可能になる。 (2nd embodiment; end surface covering structure / folding method)
FIG. 7A is a cross-sectional view schematically showing the second embodiment.
In the second embodiment, as in the first embodiment, the edge portion 101A located at the peripheral portion of the opening 22K is folded outward. However, in the second embodiment, the thickness is halved by scraping in advance the paper layer 102 of the portion 101B overlapping the edge portion 101A and the edge portion 101A of the sheet material 101 (in FIG. 7, thickness t = 0 .5 x T).
With this configuration, as shown in FIG. 7A, when the edge 101A of the sheet material 101 is folded back, the thicknesses of the overlapping portion of the edge 101A and the portion 101B and the non-overlapping portion 101C are equalized. be able to. In this case, the outer surface of the sheet material 101 is a flat continuous surface. Thus, the air electrode 13 can be joined by heat fusion, and the amount of protrusion of the air electrode 13 from the sheet material 101 (exterior body 11) can be reduced. According to the second embodiment, in addition to the same effect as that of the first embodiment, it is possible to make the magnesium air battery 10 thinner than the first embodiment.
　また、この被覆処理は、外装体１１の外面（シート材１０１の外面）がラミネートされていない場合、および、ラミネートされている場合のいずれも適用可能である。
　図７（Ｂ）は外装体１１の外面がラミネートされている場合を示す。ここで、ラミネート層を構成する外層１０４は、内層１０３と同様に、熱融着性樹脂（例えば、ポリエチレン（ＰＥ））製のフィルムで形成されている。この構成によれば、図７（Ｂ）に示すように、空気極１３の内層１１２を、シート材１０１の外層１０４にも熱融着により接合することができる。このため、外装体１１の外面のラミネートを利用して、接合面積を広く確保することができる。従って、空気極１３の接合強度を高めたい場合に有利である。 Moreover, this coating process is applicable also when the outer surface (the outer surface of the sheet material 101) of the exterior body 11 is not laminated, and when it is laminated.
FIG. 7B shows the case where the outer surface of the exterior body 11 is laminated. Here, like the inner layer 103, the outer layer 104 constituting the laminate layer is formed of a film made of a heat fusible resin (for example, polyethylene (PE)). According to this configuration, as shown in FIG. 7B, the inner layer 112 of the air electrode 13 can be joined to the outer layer 104 of the sheet material 101 by heat fusion. For this reason, using the laminate of the outer surface of the exterior body 11, a wide bonding area can be secured. Therefore, it is advantageous to increase the bonding strength of the air electrode 13.
（第３実施例；端面被覆構造・フィルム貼り方式）
　図８は第３実施例を模式的に示した断面図である。
　第３実施例では、紙層１０２の表裏両面に、シート状の非透液性材料であるフィルム１２１、１２２を貼り付け、各フィルム１２１、１２２同士を熱融着などにより接合して開口部２２Ｋの端面を被覆させる。なお、内層側のフィルム１２１は、シート材１０１のラミネート層を構成する内層１０３（図８参照）を兼用し、外層側のフィルム１２２は、シート材１０１のラミネート層を構成する外層１０４（図８参照）を兼用する。 (Third embodiment: end surface covering structure / film sticking method)
FIG. 8 is a sectional view schematically showing a third embodiment.
In the third embodiment, the films 121 and 122 which are sheet-like impermeable materials are attached to both the front and back sides of the paper layer 102, and the respective films 121 and 122 are joined by heat fusion or the like to form the opening 22K. Cover the end face of the The film 121 on the inner layer side also serves as the inner layer 103 (see FIG. 8) constituting the laminate layer of the sheet material 101, and the film 122 on the outer layer side constitutes the outer layer 104 (FIG. 8) constituting the laminate layer of the sheet material 101. See also).
　これらフィルム１２１、１２２については、単層フィルム、積層フィルムのいずれを適用しても良く、公知の端面保護部材などに使用される様々なフィルムを適用可能である。例えば、フィルム１２１、１２２（或いは各フィルム１２１、１２２の基材）には、耐熱性および機械的強度を有する素材を適用すれば良い。具体的には、延伸ポリエチレンテレフタレート、延伸ナイロン、延伸ポリプロピレン、延伸ビニルアルコールなどの延伸フィルムを使用すれば良い。なお、後述する各フィルムについても、同様の素材を用いることが可能である。
　この構成によれば、シート状の非透液性材料により簡易に開口部２２Ｋを被覆することができ、開口部２２Ｋの端面からの電解液の浸透を防止し、外装体１１の強度低下や外観の劣化を回避することができる。 A single layer film or a laminated film may be applied to the films 121 and 122, and various films used for known end face protection members and the like can be applied. For example, a material having heat resistance and mechanical strength may be applied to the films 121 and 122 (or the base of each of the films 121 and 122). Specifically, a stretched film of stretched polyethylene terephthalate, stretched nylon, stretched polypropylene, stretched vinyl alcohol or the like may be used. In addition, it is possible to use the same raw material also about each film mentioned later.
According to this configuration, the opening 22K can be easily covered with a sheet-like liquid impermeable material, and the permeation of the electrolytic solution from the end face of the opening 22K is prevented, and the strength reduction and appearance of the exterior body 11 Can be avoided.
　また、これらフィルム１２１、１２２の具体例として、特開平８－３３７２３８号公報に記載される積層フィルムが好適である。
　この特許公報には、表面または裏面層を、熱融着性樹脂からなる接着層とし、その接着層に隣接して、接着層よりも融点の高い中間層を備える積層フィルムが記載される。このフィルムを使用することにより、単層フィルムを使用した場合と比べて耐熱性を向上させ、熱融着によるピンホールなどの発生を回避し、接着安定性の向上を図ることが可能になる。 As a specific example of these films 121 and 122, laminated films described in JP-A-8-337238 are preferable.
In this patent publication, a laminated film is described in which a front or back layer is an adhesive layer made of a heat fusible resin, and an intermediate layer having a melting point higher than that of the adhesive layer is provided adjacent to the adhesive layer. By using this film, heat resistance can be improved as compared to the case of using a single layer film, generation of pinholes and the like due to heat fusion can be avoided, and adhesion stability can be improved.
（第４実施例；端面被覆構造・窓貼り方式）
　図９（Ａ）～図９（Ｄ）は第４実施例を時系列順で模式的に示した断面図である。
　第４実施例では、シート材１０１に開口部２２Ｋを設け（図９（Ａ））、開口部２２Ｋを覆う窓（最終積層構成）となるように、表裏両面に、シート状の非透液性材料であるフィルム（例えばポリエチレンフィルム）を貼り合わせるか、または、エキストルーダー加工により内層１０３と外層１０４を設け、開口部２２Ｋの部分で、内層１０３と外層１０４を貼り合わせて一体としている（図９（Ｂ））。 (Fourth embodiment: end surface covering structure / window pasting method)
FIGS. 9A to 9D are sectional views schematically showing the fourth embodiment in chronological order.
In the fourth embodiment, the sheet 22 is provided with an opening 22K (FIG. 9A), and a sheet-like liquid-impervious material is formed on both the front and back sides so as to be a window (final lamination configuration) covering the opening 22K. An inner layer 103 and an outer layer 104 are provided by laminating a film (for example, a polyethylene film), which is a material, or by an extruder process, and the inner layer 103 and the outer layer 104 are laminated together at the opening 22K (FIG. 9). (B)).
　次いで、図９（Ｃ）に示すように、貼り合わせて一体とした部分を打ち抜く。これにより、開口部２２Ｋの周囲に、貼り合わせて一体とした部分の一部（図９中、符号ＦＸ）が残り、開口部２２Ｋの端面が被覆される。その後、空気極１３を熱融着により接合する（図９（Ｄ）参照）。
　この構成によれば、貼り合わせ、打ち抜きといった比較的簡易な作業により開口部２２Ｋの端面を被覆することができ、また、フィルムにより開口部２２Ｋの端面を包み込んだ被覆形態を得ることができる。これにより、開口部２２Ｋの端面からの電解液の浸透を防止でき、外装体１１の強度低下や外観の劣化を回避することができる。 Next, as shown in FIG. 9C, the bonded and integrated part is punched out. As a result, a part of the bonded and integrated part (in FIG. 9, symbol FX) remains around the opening 22K, and the end face of the opening 22K is covered. Thereafter, the air electrode 13 is joined by heat fusion (see FIG. 9D).
According to this configuration, the end face of the opening 22K can be covered by a relatively simple operation such as bonding and punching, and a coated form in which the end face of the opening 22K is wrapped with a film can be obtained. Thereby, the permeation of the electrolytic solution from the end face of the opening 22K can be prevented, and the strength reduction of the exterior body 11 and the deterioration of the appearance can be avoided.
　また、図９（Ｄ）に示すように、シート材１０１の外層１０４を利用して、空気極１３を熱融着により容易に接合することもできる。また、本実施例の被覆処理は、紙層１０２の両面をラミネートする場合に、ラミネートと同時に行うことも可能である。
　なお、開口部２２Ｋを覆う窓を形成する工程（図９（Ｂ）、図９（Ｃ））は、上記の開口部２２Ｋの両面からフィルムを貼り合わせるものに限らず、開口部２２Ｋの片面にフィルム片を重ね、開口部２２Ｋ内に予め設けたフィルム（例えば、シート材１０１の内層）に接合し、接合したフィルム同士の一部を打ち抜くようにしても良い。この場合、例えば、窓貼りフィルムを用いながら飲口部の構造を簡単なものとするとともに、基材透孔の内周端面を適正に覆うようにし、基材透孔の内周端面に内容物が染み込まないようにする、と言った、特許第３０４７７５５号に記載の技術を適用すれば良い。 Further, as shown in FIG. 9D, the air electrode 13 can be easily joined by heat fusion using the outer layer 104 of the sheet material 101. Further, the covering process of this embodiment can be performed simultaneously with the lamination when laminating both sides of the paper layer 102.
Note that the step of forming the window covering the opening 22K (FIG. 9B, FIG. 9C) is not limited to bonding the films from both sides of the opening 22K, but may be performed on one side of the opening 22K. A piece of film may be stacked and bonded to a film (for example, the inner layer of the sheet material 101) provided in advance in the opening 22K, and a part of the bonded films may be punched out. In this case, for example, the structure of the mouthpiece is simplified while using a window-sticking film, and the inner peripheral end face of the base material through hole is properly covered, and the contents on the inner peripheral end face of the base material through hole The technique described in Japanese Patent No. 3047755 may be applied, which is said to prevent soaking.
（第５実施例；端面被覆構造・フィルム貼り方式）
　図１０は第５実施例を模式的に示した断面図である。
　第５実施例では、開口部２２Ｋの端面を覆うシート状の非透液性材料であるフィルム１２５が、延伸フィルムからなる支持層１２６の両面に接着層１２７、１２８を備えた三層構造に形成されている。そして、図１０に示すように、シート材の開口部２２Ｋの端面を上記フィルム１２５で包み込み、その状態で熱融着により接合している。
　これにより、フィルム１２５により開口部２２Ｋの端面を包み込んで被覆することができ、開口部２２Ｋの端面からの電解液の浸透を防止できるなどの効果を得ることができる。また、フィルム１２５の接着層１２８を利用して、空気極１３を容易に接合することができる。
　この場合も、上記第３実施例に記載したように、特開平８－３３７２３８号公報に記載される積層フィルムを適用することにより、耐熱性を向上させ、熱融着によるピンホールなどの発生を回避し、接着安定性の向上を図ることが可能になる。 (Fifth embodiment: end surface covering structure / film sticking method)
FIG. 10 is a cross-sectional view schematically showing the fifth embodiment.
In the fifth embodiment, the film 125, which is a sheet-like non-liquid-permeable material covering the end face of the opening 22K, is formed in a three-layer structure in which the adhesive layers 127 and 128 are provided on both sides of the support layer 126 made of stretched film It is done. Then, as shown in FIG. 10, the end face of the opening 22K of the sheet material is wrapped by the film 125, and in this state, it is joined by heat fusion.
Thus, the end face of the opening 22K can be wrapped and covered with the film 125, and an effect such as the permeation of the electrolytic solution from the end face of the opening 22K can be prevented. In addition, the air electrode 13 can be easily bonded by using the adhesive layer 128 of the film 125.
Also in this case, as described in the third embodiment, the heat resistance is improved by applying the laminated film described in JP-A-8-337238, and generation of pinholes and the like due to heat fusion is realized. It becomes possible to avoid and to improve adhesion stability.
（第６実施例；端面被覆構造・含浸方式）
　図１１は第６実施例を模式的に示した断面図である。
　第６実施例では、図１１に示すように、開口部２２Ｋの端面に、疎水性の薬剤ＭＸを含浸させ、これによって、端面からの電解液の浸透を防止し、外装体１１の強度低下や外観の劣化を回避する。この疎水性の薬剤ＭＸには、ウレタン系の接着剤や流動パラフィンなどを適用すれば良い。この薬剤ＭＸには、有機溶剤を使い、且つ、低粘度のものが好ましい。この構成によれば、薬剤ＭＸがシート材１０１の端面から紙繊維の隙間に保持され易くなり、電解液の浸透などの防止効果を長期に渡って得ることができる。
　また、この被覆処理は、図１１に示すように、外装体１１の内外両面がラミネートされていることが好ましい。この構成によれば、ラミネート層を構成する外層１０４と空気極１３とが接合されるので、シート材１０１（外装体１１）と空気極１３との間からの電解液の浸透を効果的に防止することができる。 (Sixth embodiment: end surface coating structure / impregnation method)
FIG. 11 is a cross-sectional view schematically showing a sixth embodiment.
In the sixth embodiment, as shown in FIG. 11, the end face of the opening 22K is impregnated with the hydrophobic agent MX, thereby preventing the electrolyte from permeating the end face, thereby lowering the strength of the exterior body 11 or Avoid the deterioration of the appearance. A urethane adhesive or liquid paraffin may be applied to the hydrophobic agent MX. As the agent MX, an organic solvent is used, and one having a low viscosity is preferable. According to this configuration, the medicine MX can be easily held in the gaps of the paper fibers from the end face of the sheet material 101, and the effect of preventing the permeation of the electrolytic solution can be obtained for a long time.
Further, as shown in FIG. 11, it is preferable that in this covering process, both the inside and outside of the exterior body 11 be laminated. According to this configuration, since the outer layer 104 constituting the laminate layer and the air electrode 13 are joined, the permeation of the electrolytic solution from between the sheet material 101 (exterior body 11) and the air electrode 13 is effectively prevented. can do.
（第７実施例；空気極利用型の被覆構造・ホットメルト）
　図１２は第７実施例を模式的に示した断面図である。
　第７実施例では、シート材１０１から空気極１３に渡ってホットメルト（ホットメルト接着剤とも言う）を塗布し、ホットメルトＨＸにより開口部２２Ｋの端面を被覆する。このホットメルトＨＸには、エチレン酢酸ビニル（ＥＶＡ）などの熱可塑性プラスチックや、ウレタン系の反応硬化型のホットメルト樹脂などの公知の素材を適用可能である。
　これにより、ホットメルトＨＸにより、開口部２２Ｋの端面からの電解液の浸透を防止できるなどの効果を得ることができる。また、ホットメルトＨＸは、空気極１３の内層１１２、つまり、多孔性の表面に食い込むので、ホットメルトＨＸと空気極１３との接合強度を高く維持することができる。従って、空気極１３の表面構造を利用してホットメルトＨＸの接合強度を効率よく高め、被覆の耐久性向上に有利となる。
　また、ホットメルトＨＸに代えて、高粘度で加工後に硬化する被覆剤（例えばゼリー状の硬化型接着剤）を用いて端面を被覆することも可能である。 (Seventh embodiment: coating structure using air electrode-hot melt)
FIG. 12 is a cross-sectional view schematically showing the seventh embodiment.
In the seventh embodiment, a hot melt (also referred to as a hot melt adhesive) is applied from the sheet material 101 to the air electrode 13, and the end face of the opening 22K is covered with the hot melt HX. For the hot melt HX, known materials such as thermoplastics such as ethylene vinyl acetate (EVA) and urethane-based reaction curing type hot melt resins are applicable.
Thereby, the effect that the penetration of the electrolyte solution from the end face of the opening 22K can be prevented can be obtained by the hot melt HX. In addition, since the hot melt HX bites into the inner layer 112 of the air electrode 13, ie, the porous surface, the bonding strength between the hot melt HX and the air electrode 13 can be maintained high. Therefore, the bonding strength of the hot melt HX is efficiently enhanced by utilizing the surface structure of the air electrode 13, which is advantageous for improving the durability of the coating.
Moreover, it is also possible to coat the end face with a coating agent (for example, a curable adhesive in the form of jelly) which has high viscosity and is hardened after processing, instead of the hot melt HX.
　また、この被覆処理は、図１２に示すように、外装体１１の外面がラミネートされていない場合でも適用できる、というメリットもある。
　なお、紙（紙層１０２）が剥き出しである外装体１１の外面に空気極１３を接着するには、ホットメルト、テープ貼り、接着剤貼りを使用すれば良い。 In addition, as shown in FIG. 12, this covering process has an advantage that it can be applied even when the outer surface of the exterior body 11 is not laminated.
In order to adhere the air electrode 13 to the outer surface of the exterior body 11 from which the paper (paper layer 102) is exposed, hot melt, tape attachment, or adhesive attachment may be used.
（第８実施例；空気極利用型の被覆構造・フィルム貼り方式）
　図１３は第８実施例を模式的に示した断面図である。
　第８実施例では、シート材１０１の片面(内面)に、シート状の非透液性材料であるフィルム１３１を貼り付け、このフィルム１３１の端部１３１Ａを空気極１３に接合する。これによって、シート材１０１から空気極１３に渡ってフィルム１３１が貼り付けられ、フィルム１３１により開口部２２Ｋの端面が被覆される。このフィルム１３１には、熱融着性樹脂（例えば、ポリエチレン（ＰＥ））などの公知の素材を適用可能であり、熱融着などにより空気極１３に接合される。
　この構成によれば、フィルム１３１により、開口部２２Ｋの端面からの電解液の浸透を防止できるなどの効果を得ることができる。また、フィルム１３１は、空気極１３の内層１１２、つまり、多孔性の表面に食い込んだ状態で接合され、フィルム１３１と空気極１３との接合強度を高く維持することができる。従って、空気極１３の表面構造を利用してフィルム１３１の接合強度を効率よく高め、被覆の耐久性向上に有利となる。
　また、この被覆処理についても、第７実施例と同様に、外装体１１の外面がラミネートされていない場合でも適用できる、というメリットがある。 (Eighth embodiment: Coating structure with air electrode and film sticking method)
FIG. 13 is a cross sectional view schematically showing an eighth embodiment.
In the eighth embodiment, a film 131 which is a sheet-like impermeable material is attached to one surface (inner surface) of the sheet material 101, and the end 131A of the film 131 is bonded to the air electrode 13. Thus, the film 131 is attached from the sheet material 101 to the air electrode 13, and the end face of the opening 22 </ b> K is covered with the film 131. A known material such as a heat fusible resin (for example, polyethylene (PE)) can be applied to the film 131, and the film 131 is bonded to the air electrode 13 by heat fusible or the like.
According to this configuration, it is possible to obtain the effect that the film 131 can prevent the electrolyte from permeating the end face of the opening 22K. In addition, the film 131 is bonded to the inner layer 112 of the air electrode 13, that is, in a state of being bitten into the porous surface, and the bonding strength between the film 131 and the air electrode 13 can be maintained high. Accordingly, the surface structure of the air electrode 13 is used to efficiently increase the bonding strength of the film 131, which is advantageous for improving the durability of the coating.
Also, as in the seventh embodiment, this covering process has an advantage that it can be applied even when the outer surface of the exterior body 11 is not laminated.
　図１４（Ａ）および図１４（Ｂ）はフィルム１３１の一例を示している。
　図１４（Ａ）はフィルム１３１を一体型に形成した場合を示している。つまり、空気極１３の矩形の開口部２２Ｋの各辺を被覆する４つの矩形状の部分（上辺被覆部１３２、左右の側辺被覆部１３３、１３４、下辺被覆部１３５）を一体にした四方枠状のフィルムを製作している。
　このように、開口部２２Ｋの縁部に渡って延出する一体型の枠状にすれば、部品点数を低減でき、被覆作業の簡易化を図りやすくなる。 14A and 14B show an example of the film 131. FIG.
FIG. 14A shows the case where the film 131 is formed integrally. In other words, a four-way frame in which four rectangular portions (upper side covering portion 132, left and right side covering portions 133 and 134, lower side covering portion 135) covering each side of rectangular opening 22K of air electrode 13 are integrated. Film is produced.
As described above, the integral frame shape extending over the edge of the opening 22K can reduce the number of parts and facilitate the covering operation.
　また、図１４（Ｂ）は４つの被覆部１３２～１３５を別々に形成した場合を示している。つまり、４つの被覆部１３２～１３５に相当する短冊部を別々に作製し、各短冊部を、熱融着などにより接合して開口部２２Ｋの縁部に渡って延出する枠状のフィルムを作製している。
　この場合、図１４（Ａ）の場合と比べて、フィルム素材から切り出す際にフィルム素材の余りを低減することができる。また、様々な形状のフィルムを作製し易くなり、設計変更やサイズ変更に対応し易くなる。 Further, FIG. 14B shows the case where four covering portions 132 to 135 are formed separately. That is, strip portions corresponding to the four covering portions 132 to 135 are separately prepared, and each strip portion is joined by heat fusion or the like to form a frame-shaped film extending over the edge of the opening 22K. It is made.
In this case, the remainder of the film material can be reduced when it is cut out from the film material as compared to the case of FIG. In addition, it becomes easy to produce films of various shapes, and it becomes easy to cope with design changes and size changes.
　上述したように、本構成の外装体１１は、紙を含有するシート材１０１で形成され、シート材１０１は、隙間ＳＦ、ＳＲを空けてマグネシウム極（金属極）１５を覆うとともに、少なくとも内面側が非透液性に形成され、外装体１１には、空気極１３が外面側から装着される開口部２２Ｋが設けられ、開口部２２Ｋの端面には、内部に注液した電解液の浸透を防止する端面処理が施されるので、紙を含有するシート材１０１で外装体１１を形成した構成で、空気を取り込む開口部２２Ｋの端面からの電解液の浸透などの影響を抑えることが可能になる。 As described above, the exterior body 11 of this configuration is formed of the sheet material 101 containing paper, and the sheet material 101 covers the magnesium electrode (metal electrode) 15 with the gaps SF and SR open and at least the inner surface side The case body 11 is provided with an opening 22K to which the air electrode 13 is attached from the outer surface side, and the end face of the opening 22K prevents permeation of the electrolytic solution injected therein. Since the end face processing is performed, the configuration in which the exterior body 11 is formed of the sheet material 101 containing paper can suppress the influence of the electrolyte penetration from the end face of the opening 22K for taking in air, etc. .
　また、開口部２２Ｋの端面は、上記端面処理として、シート材１０１の縁部が外方に向かって折り返されるようにすれば（第１、第２実施例、図６、図７）、シート材１０１を折り曲げる、といった簡易な方法で、開口部２２Ｋへの電解液の影響を抑えることが可能になる。この場合、シート材１０１以外の部材が不要であり、コスト低減に有利である。
　また、開口部２２Ｋの端面は、上記端面処理として、シート状の非透液性材料であるフィルム１２１、１２２、１２５、１３１により被覆されるようにすれば（第３～第８実施例、図８～図１３）、フィルム性能に応じた被覆性能を得ることができる。この場合、広く流通するフィルムを用いることにより、コスト低減を図りやすくなり、且つ、フィルムの選定により所望の被覆性能を選択可能になる。 Further, if the edge of the sheet material 101 is folded back outward as the end surface treatment (the first and second embodiments, FIGS. 6 and 7), the end surface of the opening 22K is a sheet material. It is possible to suppress the influence of the electrolytic solution on the opening 22K by a simple method such as bending 101. In this case, members other than the sheet material 101 are unnecessary, which is advantageous for cost reduction.
Further, if the end face of the opening 22K is covered with the film 121, 122, 125, 131 which is a sheet-like non-liquid-permeable material as the end face treatment (third to eighth embodiments, FIG. 8 to 13), coating performance according to film performance can be obtained. In this case, by using a widely distributed film, cost reduction can be easily achieved, and desired coating performance can be selected by selecting a film.
　この場合、シート材１０１の両面に、シート状の非透液性材料であるフィルム１２１、１２２を貼り付け、フィルム１２１、１２２同士を接合して端面を被覆すれば（第３実施例、図８）、シート材１０１の両面をラミネートする場合に、そのラミネートフィルムを利用して被覆することができる。
　また、シート材１０１の表面に、内層１０３、外層１０４を構成するフィルム（非透液性材料）やフィルム（非透液性材料）１２５を貼り付け、これらフィルムにより開口部２２Ｋの端面を包み込んで端面を被覆すれば（第４、第５実施例、図９、図１０）、図９および図１０に示すように、開口部２２Ｋの端面を包み込んだ被覆形態を得ることができ、端面からの電解液の浸透を防止し易くなる。 In this case, if the films 121 and 122 which are sheet-like non-liquid permeable materials are attached to both surfaces of the sheet material 101 and the films 121 and 122 are joined to cover the end surface (third embodiment, FIG. And) when laminating both sides of the sheet material 101, it can coat using the lamination film.
In addition, a film (non-liquid-permeable material) or a film (non-liquid-permeable material) 125 constituting the inner layer 103 and the outer layer 104 is attached to the surface of the sheet material 101, and the end face of the opening 22K is wrapped by these films. If the end face is covered (fourth and fifth embodiments, FIG. 9, FIG. 10), and as shown in FIGS. 9 and 10, a covering form in which the end face of the opening 22K is wrapped can be obtained. It becomes easy to prevent the penetration of the electrolytic solution.
　また、開口部２２Ｋの端面は、上記端面処理として、疎水性の薬剤ＭＸが含浸されるようにすれば（第６実施例、図１１）、この薬剤ＭＸを用いる方法により、開口部２２Ｋの端面からの電解液の浸透を防止できる。この場合、薬剤ＭＸに、開口部２２Ｋの端面の繊維の隙間に保持可能な低粘度の薬剤を用いることにより、被覆の耐久性向上に有利となる。
　また、上記端面処理として、シート材１０１から空気極１３に渡ってホットメルトＨＸを塗布し、ホットメルトＨＸにより開口部２２Ｋの端面を覆うようにすれば（第７実施例、図１２）、空気極１３の表面凹凸形状を利用して被覆として機能するホットメルトＨＸの接合強度を効率よく高めることができる。 Further, if the end face of the opening 22K is impregnated with a hydrophobic drug MX as the end face treatment (sixth embodiment, FIG. 11), the end face of the opening 22K is obtained by a method using this agent MX. Penetration of the electrolyte from the In this case, it is advantageous to improve the durability of the coating by using a drug of low viscosity which can be held in the fiber gap of the end face of the opening 22K for the drug MX.
Further, as the end face treatment, when the hot melt HX is applied from the sheet material 101 to the air electrode 13 and the end face of the opening 22K is covered with the hot melt HX (seventh embodiment, FIG. 12) The bonding strength of the hot melt HX functioning as a coating can be efficiently enhanced by utilizing the surface asperity shape of the pole 13.
　また、上記端面処理として、シート材１０１から空気極１３に渡ってフィルム（非透液性材料）１３１を貼り付け、このフィルム１３１により開口部２２Ｋの端面を覆うようにしても（第８実施例、図１３）、ホットメルトＨＸの場合と同様に、空気極１３の表面凹凸形状を利用して被覆として機能するフィルム１３１の接合強度を効率よく高めることができる。
　このとき、フィルム１３１を、開口部２２Ｋの縁部に渡って延出する一体型の枠状にすることにより（図１４（Ａ））、開口部２２Ｋの縁部毎にフィルムを貼り付ける場合と比べて、部品点数を低減でき、且つ、貼り付け作業が一回で済む。一方、このフィルム１３１を、開口部２２Ｋの縁部に渡って延出する枠状となるように複数の短冊状のフィルムを接続した構成にすることにより（図１４（Ｂ））、非透液性材料のフィルム素材から切り出す際に材料の余りを低減し易くなり、また、様々な形状に対応し易くなる。 Further, as the end face treatment, a film (non-liquid-permeable material) 131 is pasted from the sheet material 101 to the air electrode 13 and the end face of the opening 22 K is covered with the film 131 (Eighth Embodiment) As in the case of the hot melt HX, as shown in FIG. 13), the surface asperity shape of the air electrode 13 can be utilized to efficiently increase the bonding strength of the film 131 functioning as a coating.
At this time, by making the film 131 into an integral frame extending over the edge of the opening 22K (FIG. 14A), the film is attached to each edge of the opening 22K and In comparison, the number of parts can be reduced, and only one pasting operation is required. On the other hand, a plurality of strip-like films are connected so as to form a frame shape extending over the edge of the opening 22K (FIG. 14 (B)). It becomes easy to reduce the remainder of material when it cuts out from the film material of the sex material, and it becomes easy to correspond to various shapes.
　なお、本発明は上記構成に限定されず、各種の変形および変更が可能である。
　例えば、上記の端面処理を二つ以上組み合わせても良い。例えば、第６実施例の含浸方式を除く実施例に対し、開口部２２Ｋの端面に含浸させる含浸方式を組み合わせても良い。また、第１および第２実施例に記載した折り返し方式と、他の実施例に記載したフィルム貼り方式とを組み合わせても良い。組み合わせることで、被覆性能（耐久性）などを高め易くなる。
　また、上述の実施形態では、熱融着により各部材を接合する場合を説明したが、それ以外の接合方法を適用しても良い。例えば、被覆用のフィルムに、インパルスシール、超音波シール、ホットエアーで加熱後の圧着、ホットメルト、テープ貼り、接着剤などを適用しても良い。 The present invention is not limited to the above configuration, and various modifications and changes are possible.
For example, two or more of the end face treatments described above may be combined. For example, an impregnation method in which the end face of the opening 22K is impregnated may be combined with the embodiment except the impregnation method of the sixth embodiment. Also, the folding method described in the first and second embodiments may be combined with the film bonding method described in the other embodiments. It becomes easy to improve coating performance (durability) etc. by combining.
Moreover, although the above-mentioned embodiment demonstrated the case where each member was joined by heat sealing, you may apply the joining method of other than that. For example, impulse sealing, ultrasonic sealing, pressure bonding after heating with hot air, hot melt, tape application, an adhesive, or the like may be applied to a film for covering.
（第２実施形態）
　図１５は第２実施形態の外装体１１の斜視図であり、図１６は第２実施形態の外装体１１を展開した図（＝打ち抜きシート１００に相当する図）である。なお、以下の説明において、前述した構成と同様の構成は同一の符号を付して重複説明を省略し、異なる部分を詳述する。
　この外装体１１は、前壁部２２の上縁２２Ａ（図１６）に連なる上板部構成片２５Ｆが、第１実施形態の上板部構成片２５Ｆ（図３）よりも上下方向に長く形成されている。そして、この上板部構成片２５Ｆは、上下に三分割する折り目２２Ｃ、２２Ｄ（図１６）を基準にして、前壁部２２側から順に、第１折り曲げ部２５Ｆ１、第２折り曲げ部２５Ｆ２および第３折り曲げ部２５Ｆ３が設けられる。 Second Embodiment
FIG. 15 is a perspective view of the exterior body 11 according to the second embodiment, and FIG. 16 is a view in which the exterior body 11 according to the second embodiment is developed (a view corresponding to the punching sheet 100). In the following description, the same components as those described above are denoted by the same reference numerals, and redundant description will be omitted, and different parts will be described in detail.
In the exterior body 11, an upper plate portion constituting piece 25F continuous with the upper edge 22A (FIG. 16) of the front wall portion 22 is formed longer in the vertical direction than the upper plate portion constituting piece 25F (FIG. 3) of the first embodiment. It is done. Then, the upper plate portion constituting piece 25F has the first bent portion 25F1, the second bent portion 25F2, and the first bent portion 25F1 in order from the front wall portion 22 with reference to the folds 22C and 22D (FIG. 16) which are divided into three vertically. Three bent portions 25F3 are provided.
　また、後壁部２３の上縁２３Ａ（図１６）に連なる上板部構成片２５Ｒについても、第１実施形態の上板部構成片２５Ｒ（図３）よりも長く形成されるとともに、上下に三分割する折り目２３Ｃ、２３Ｄ（図１６）を基準にして、後壁部２３側から順に、第１折り曲げ部２５Ｒ１、第２折り曲げ部２５Ｒ２および第３折り曲げ部２５Ｒ３が設けられる。 Further, the upper plate portion constituting piece 25R connected to the upper edge 23A (FIG. 16) of the rear wall portion 23 is also formed longer than the upper plate portion constituting piece 25R (FIG. 3) of the first embodiment, The first bent portion 25R1, the second bent portion 25R2, and the third bent portion 25R3 are provided in order from the back wall 23 side with reference to the fold lines 23C and 23D (FIG. 16) divided into three.
　図１７は第２実施形態の外装体１１を示す図であり、図１７（Ａ）は正面から見た図であり、図１７（Ｂ）は図１７（Ａ）のＡ－Ａ断面を示した図である。
　図１７（Ａ）および図１７（Ｂ）に示すように、第２折り曲げ部２５Ｆ２、２５Ｒ２は外装体１１内側にそれぞれ折り曲げられ、第３折り曲げ部２５Ｆ３、２５Ｒ３は外装体１１外側にそれぞれ折り曲げられる。
　この場合、第３折り曲げ部２５Ｆ３、２５Ｒ３は、第２折り曲げ部２５Ｆ２、２５Ｒ２よりも上下方向に長く形成されているので、第３折り曲げ部２５Ｆ３、２５Ｒ３の先端は第２折り曲げ部２５Ｆ２、２５Ｒ２よりも上方に突出し、第３折り曲げ部２５Ｆ３、２５Ｒ３同士が互いに当接することになる。 FIG. 17 is a view showing the exterior body 11 of the second embodiment, FIG. 17 (A) is a front view, and FIG. 17 (B) is a cross-sectional view taken along the line AA of FIG. 17 (A). FIG.
As shown in FIGS. 17A and 17B, the second bent portions 25F2 and 25R2 are bent to the inside of the exterior body 11, and the third bent portions 25F3 and 25R3 are bent to the outside of the exterior body 11.
In this case, since the third bent portions 25F3 and 25R3 are formed longer in the vertical direction than the second bent portions 25F2 and 25R2, the tips of the third bent portions 25F3 and 25R3 are longer than the second bent portions 25F2 and 25R2 It projects upward and the third bent portions 25F3 and 25R3 come in contact with each other.
　つまり、上板部構成片２５Ｆ、２５Ｒは、マグネシウム極１５に沿って外装体１１内側に折り曲げられるとともに、その反対側に折り返されてマグネシウム極１５よりも外装体１１外側に張り出す折り返し部（第２折り曲げ部２５Ｆ２、２５Ｒ２、および第３折り曲げ部２５Ｆ３、２５Ｒ３からなる）を形成している。
　そして、図１７（Ｂ）に示すように、この前後一対の折り返し部の下部間（第３折り曲げ部２５Ｆ３、２５Ｒ３の下部間）に、マグネシウム極１５の上部が挟み込まれ、その状態を保持するように、外装体１１外側に突出した折り返し部が互いに熱融着により接合される。
　これによって、折り返し部の下部でマグネシウム極１５を挟持するとともに、上板部構成片２５Ｆ、２５Ｒ間、つまり、外装体１１の上部を封止することができる。従って、上板部構成片２５Ｆ、２５Ｒの双方が、マグネシウム極１５を支える支持用折り曲げ部として機能するとともに、外装体１１の上部を封止する封止部として機能する。 That is, the upper plate portion constituting pieces 25F, 25R are bent along the magnesium electrode 15 to the inside of the outer package 11 and are folded back to the opposite side so that they are folded back parts that project beyond the magnesium electrode 15 to the outer surface of the outer package 11 The second bent portion 25F2, 25R2 and the third bent portion 25F3, 25R3 are formed.
Then, as shown in FIG. 17B, the upper portion of the magnesium electrode 15 is sandwiched between the lower portions of the pair of front and rear folded portions (lower portions of the third bent portions 25F3 and 25R3), and the state is maintained. In addition, the folded-back portions that project to the outside of the outer package 11 are joined together by heat fusion.
Thus, the magnesium electrode 15 can be held at the lower portion of the folded portion, and the upper plate portion constituting pieces 25F and 25R, that is, the upper portion of the exterior body 11 can be sealed. Therefore, both of the upper plate portion constituting pieces 25F, 25R function as a support bending portion supporting the magnesium electrode 15, and also function as a sealing portion sealing the upper portion of the exterior body 11.
　この構成によれば、第１実施形態の図４などに示す折り込み型と比較して、上部の封止を確実なものにして、電解液の蒸発や漏出を抑制することができる。
　また、図５に示すように、上板部構成片２５Ｆ、２５Ｒを左右に分割しないため、折り込み時にしわが出来にくくなる。また、内側に折り返した後に外側に折り返すので、上板部構成片２５Ｆ、２５Ｒ自体の剛性が向上し、しわや変形を防止でき、外装体１１の剛性向上、およびマグネシウム極１５の支持力向上が可能である。
　なお、本実施形態では、マグネシウム極１５に上方に突出するタブ部１５Ｔ（図１参照）が形成されず、その代わりに、マグネシウム極１５上部に配線１５Ｈ（後述する図２１）を接続する構成となっている。 According to this configuration, as compared with the folding type shown in FIG. 4 and the like of the first embodiment, the sealing of the upper portion can be made reliable, and evaporation and leakage of the electrolytic solution can be suppressed.
Further, as shown in FIG. 5, since the upper plate portion constituting pieces 25F, 25R are not divided into right and left, it becomes difficult to form wrinkles at the time of folding. In addition, since it is folded back inside after being folded back inside, the rigidity of the upper plate portion constituting pieces 25F, 25R itself is improved, so that wrinkles and deformation can be prevented, rigidity improvement of the exterior body 11, and support capacity of the magnesium electrode 15 are improved. It is possible.
In the present embodiment, the tab portion 15T (see FIG. 1) protruding upward is not formed on the magnesium electrode 15, but instead, a wire 15H (FIG. 21 described later) is connected to the top of the magnesium electrode 15 and It has become.
　また、図１６に示すように、前壁部２２の上縁２２Ａで折り曲げられてマグネシウム極１５の上方を覆う蓋部となる第１折り曲げ部２５Ｆ１の左右には、シート片２６Ｆが一体に設けられている。これらシート片２６Ｆは、図１５に示すように、第１折り曲げ部２５Ｆ１の左右側縁を基準に下方（内側折り曲げ片２４ＦＵに沿って）に折り曲げられ、次いで側壁部構成片２４Ｆの外側折り曲げ片２４ＦＳに沿って垂直に折り曲げた後、垂直に折り曲げられたシート片２６Ｆを熱融着機で挟みこんで、熱融着によって接合する。
　このように外装体１１の上部両端をシート片２６Ｆで固定することで、各折り曲げ片２４ＦＵ、２４ＦＳの上部を補強することができる。
　この構成によれば、蓋部となる第１折り曲げ部２５Ｆ１と側壁部となる側壁部構成片２４Ｆとの間の隙間をシート片２６Ｆによって封止することができ、電解液の蒸発や漏出を抑制することができる。また、第１折り曲げ部２５Ｆ１と側壁部構成片２４Ｆとの連結強度が向上し、第１折り曲げ部２５Ｆ１の上方への拡がりや、側壁部構成片２４Ｆの左右方向への拡がりを抑えることができる。 Further, as shown in FIG. 16, sheet pieces 26F are integrally provided on the left and right of the first bent portion 25F1 which is a lid that is bent at the upper edge 22A of the front wall 22 and covers the upper side of the magnesium electrode 15. ing. As shown in FIG. 15, these sheet pieces 26F are bent downward (along the inner bent pieces 24FU) on the basis of the left and right side edges of the first bent portion 25F1, and then the outer bent pieces 24FS of the side wall portion constituting pieces 24F. The sheet pieces 26F which are vertically folded are sandwiched by a heat fusion machine and joined by heat fusion.
By fixing the upper ends of the exterior body 11 with the sheet piece 26F as described above, the upper portions of the bent pieces 24FU and 24FS can be reinforced.
According to this configuration, the gap between the first bent portion 25F1 serving as the lid and the side wall portion constituting piece 24F serving as the side wall can be sealed by the sheet piece 26F, and the evaporation and leakage of the electrolytic solution are suppressed. can do. Further, the connection strength between the first bent portion 25F1 and the side wall portion constituting piece 24F is improved, and the upward spread of the first bent portion 25F1 and the spread of the side wall portion constituting piece 24F in the lateral direction can be suppressed.
　また、本実施の形態では、前壁部２２と同様に、後壁部２３の上縁２３Ａで折り曲げられてマグネシウム極１５の上方を覆う蓋部となる第１折り曲げ部２５Ｒ１の左右にも、上記シート片２６Ｆと同様のシート片２６Ｒが一体に設けられている（図１６参照）。これらシート片２６Ｒは、図１５に示すように、第１折り曲げ部２５Ｒ１の左右側縁を基準に下方（内側折り曲げ片２４ＲＵに沿って）に折り曲げられ、次いで側壁部構成片２４Ｒの外側折り曲げ片２４ＲＳに沿って垂直に折り曲げた後、垂直に折り曲げられたシート片２６Ｒを熱融着機で挟みこんで、熱融着によって接合する。
　このように外装体１１の上部両端をシート片２６Ｒで固定することで、各折り曲げ片２４ＲＵ、２４ＲＳの上部を補強することができる。
　これによって、蓋部となる第１折り曲げ部２５Ｒ１と側壁部となる側壁部構成片２４Ｒとの間を封止して、電解液の蒸発や漏出を抑制できるとともに、第１折り曲げ部２５Ｒ１と側壁部構成片２４Ｒとの連結強度が向上し、第１折り曲げ部２５Ｒ１の上方への拡がりや、側壁部構成片２４Ｒの左右方向への拡がりを抑えることができる。
　なお、垂直に折り曲げられたシート片２６Ｆとシート片２６Ｒとの熱融着は、熱を均一にかけられる他、熱融着が一度で済むため、両者を同時に熱融着することが好ましい。 Further, in the present embodiment, similarly to the front wall portion 22, the above-described also applies to the left and right of the first bent portion 25R1 which is a lid portion which is bent at the upper edge 23A of the rear wall portion 23 and covers the upper side of the magnesium electrode 15. A sheet piece 26R similar to the sheet piece 26F is integrally provided (see FIG. 16). As shown in FIG. 15, these sheet pieces 26R are bent downward (along the inner bent pieces 24RU) based on the left and right side edges of the first bent portion 25R1, and then the outer bent pieces 24RS of the side wall portion constituting pieces 24R. After bending the sheet 26 R vertically, the vertically bent sheet piece 26 R is sandwiched by a heat fusion machine and joined by heat fusion.
By fixing the upper ends of the exterior body 11 with the sheet piece 26R as described above, the upper portions of the bent pieces 24RU and 24RS can be reinforced.
As a result, the space between the first bent portion 25R1 serving as the lid and the side wall portion constituting piece 24R serving as the side wall portion can be sealed to suppress evaporation and leakage of the electrolytic solution, and the first bent portion 25R1 and the side wall portion The connection strength with the component piece 24R is improved, and the upward extension of the first bent portion 25R1 and the lateral extension of the side wall component piece 24R can be suppressed.
The heat fusion between the sheet piece 26F and the sheet piece 26R which are bent vertically is not only heat uniforming but also heat fusion only once, so it is preferable to heat fuse both at the same time.
　これらにより、上記シート片２６Ｆ、２６Ｒによって、電解液の蒸発や漏出をより抑制するとともに、外装体１１の変形をより防止することができる。
　なお、本構成では、左右のシート片２６Ｆ、２６Ｒと上板部構成片２５Ｆ、２５Ｒとの間に切り欠き２８（図１６参照）を予め設け、外装体１１を組み立てた際に、図１５に示すように、シート片２６Ｆ、２６Ｒと上板部構成片２５Ｆ、２５Ｒとの間に、マグネシウム極１５からの配線１５Ｈ（後述する図２１）を通すことが可能なスペース２８Ｋを確保している。 By these, the evaporation and leakage of the electrolytic solution can be further suppressed by the sheet pieces 26F and 26R, and the deformation of the exterior body 11 can be further prevented.
In this configuration, notches 28 (see FIG. 16) are provided in advance between the left and right sheet pieces 26F and 26R and the upper plate portion constituting pieces 25F and 25R, and the exterior body 11 is assembled as shown in FIG. As shown, a space 28K through which a wire 15H (see FIG. 21 described later) from the magnesium electrode 15 can pass is secured between the sheet pieces 26F and 26R and the upper plate component pieces 25F and 25R.
　以上説明したように、本実施形態の金属極（マグネシウム極１５）の支持構造では、図１７（Ｂ）に示したように、上板部構成片２５Ｆ、２５Ｒ（支持用折り曲げ部）が、前壁部２２および後壁部２３からマグネシウム極１５に沿って外装体１１内側に折り曲げられるとともに、その反対側に折り返されてマグネシウム極１５よりも外装体１１外側に張り出す折り返し部を有し、各折り返し部の下部でマグネシウム極１５を挟持するとともに、残りの外装体１１外側に突出した部分を互いに接合して上板部構成片２５Ｆ、２５Ｒ間を封止するので、電解液の蒸発や漏出を抑制するとともに外装体１１の変形を防止し、且つ、マグネシウム極１５の位置ずれを抑えてマグネシウム極１５と空気極１３との離間距離を適正に保つことが可能になる。 As described above, in the support structure of the metal electrode (magnesium electrode 15) according to the present embodiment, as shown in FIG. 17B, the upper plate portion constituting pieces 25F and 25R (support bending portions) It is bent from the wall 22 and the rear wall 23 along the magnesium electrode 15 to the inside of the exterior body 11 and has a folded back portion that is folded back to the opposite side and overhangs the exterior of the exterior body 11 more than the magnesium electrode 15 Since the magnesium electrode 15 is held at the lower part of the folded back portion and the remaining portions protruding to the outside of the exterior body 11 are joined to each other to seal the upper plate portion constituting pieces 25F and 25R, evaporation and leakage of the electrolyte It is possible to suppress deformation of the exterior body 11 while suppressing the displacement of the magnesium electrode 15 and keep the separation distance between the magnesium electrode 15 and the air electrode 13 appropriately. .
　しかも、上板部構成片２５Ｆ、２５Ｒの一部が上方に突出するので、外装体１１を持ち運ぶ際の把持部として用いることができる。また、上板部構成片２５Ｆ、２５Ｒの各部の接合は融着により行われるので、熱融着性樹脂でラミネート加工などがされたシート材の熱融着性を活かして容易に接合することができる。 Moreover, since a part of the upper plate portion configuration pieces 25F, 25R protrudes upward, it can be used as a gripping portion when carrying the exterior body 11. Further, since the parts of the upper plate component pieces 25F, 25R are joined by fusion bonding, they can be easily joined utilizing the heat fusion property of the sheet material laminated and the like with the heat fusion resin. it can.
　また、蓋部を構成する上板部構成片２５Ｆ、２５Ｒに連なって側壁部を構成する側壁部構成片２４Ｆ、２４Ｒに接合されるシート片２６Ｆ、２６Ｒ（図１５）を備えるので、簡易な構成で、上板部構成片２５Ｆ、２５Ｒと側壁部構成片２４Ｆ、２４Ｒとの間を封止して電解液の蒸発や漏出を抑制することができる。しかも、上板部構成片２５Ｆ、２５Ｒと側壁部構成片２４Ｆ、２４Ｒとの連結強度が向上し、外装体１１の変形をより防止することができる。 In addition, since the sheet pieces 26F and 26R (FIG. 15) joined to the side wall portion constituting pieces 24F and 24R constituting the side wall portion are connected to the upper plate portion constituting pieces 25F and 25R constituting the lid portion, a simple structure is provided. Thus, it is possible to seal between the upper plate portion constituting pieces 25F and 25R and the side wall portion constituting pieces 24F and 24R to suppress evaporation and leakage of the electrolytic solution. In addition, the connection strength between the upper plate portion constituting pieces 25F and 25R and the side wall portion constituting pieces 24F and 24R is improved, and the deformation of the exterior body 11 can be further prevented.
　なお、上板部構成片２５Ｆ、２５Ｒは上記形状に限定されない。例えば、図１８（Ａ）および図１８（Ｂ）に示すように、上板部２５を長くして第３折り曲げ部２５Ｆ３、２５Ｒ３を取っ手の形状に変更し、更に把持しやすくしても良い。
　図１８（Ａ）では、第３折り曲げ部２５Ｆ３、２５Ｒ３を上下方向に大型化するとともに左右方向に延びる長孔２９を設け、各長孔２９にユーザーなどの指を通すことで外装体１１をより把持しやすい一つの取っ手を形成した態様を示している。また、一方の第３折り曲げ部２５Ｒ３の各長孔２９には、他方の第３折り曲げ部２５Ｆ３の各長孔２９に向けて折り曲げられる折り曲げ部２９Ａが設けられ、これによって、長孔２９に通した指の当たりを緩和することもできる。
　また、図１８（Ｂ）では、さらに、第３折り曲げ部２５Ｆ３、２５Ｒ３のそれぞれを左右に分割する切り欠き３０を設け、２つの取っ手を形成した態様である。この切り欠き３０を設けることで、内部の部材との干渉を避けることが可能である。 In addition, upper-plate part structure piece 25F, 25R is not limited to the said shape. For example, as shown in FIGS. 18 (A) and 18 (B), the upper plate portion 25 may be elongated to change the shape of the third bent portions 25F3 and 25R3 to the shape of a handle to further facilitate gripping.
In FIG. 18A, the third bent portions 25F3 and 25R3 are enlarged in the vertical direction, and elongated holes 29 extending in the lateral direction are provided, and a finger such as a user is passed through each elongated hole 29 to make the exterior body 11 The aspect which formed one handle easy to hold is shown. Further, in each long hole 29 of one third bent portion 25R3, a bent portion 29A which is bent toward each long hole 29 of the other third bent portion 25F3 is provided. It is also possible to ease the hit of the finger.
Moreover, in FIG. 18 (B), the notch 30 which divides | segments each of 3rd bending part 25F3, 25R3 into right and left is further provided, and it is the aspect which formed two handles. By providing this notch 30, it is possible to avoid interference with internal members.
（第３実施形態）
　図１９（Ａ）は第３実施形態の外装体１１を正面から見た図である。また、図１９（Ｂ）は図１９（Ａ）のＢ－Ｂ断面を示した図である。
　この外装体１１には、マグネシウム極１５の下端が嵌まる左右一対の底板シート部３５が設けられている。これらの底板シート部３５は、外装体１１を構成するシート材と同じシート材、つまり、紙と熱融着性樹脂とをラミネート加工などにより複合化したシート材を、マグネシウム極１５の下端が嵌まる下方凸形状に折り曲げて形成されている。 Third Embodiment
FIG. 19A is a front view of the exterior body 11 of the third embodiment. FIG. 19B is a cross-sectional view taken along the line BB in FIG. 19A.
The exterior body 11 is provided with a pair of left and right bottom plate sheets 35 into which the lower end of the magnesium electrode 15 is fitted. In the bottom plate portion 35, the lower end of the magnesium electrode 15 is fitted with the same sheet material as the sheet material constituting the exterior body 11, that is, the sheet material in which the paper and the heat fusible resin are compounded by laminating or the like. It is bent and formed in a downward convex shape.
　図２０は第３実施形態の底板シート部３５の斜視図である。
　底板シート部３５は、前壁部２２および後壁部２３の両端の下部にそれぞれに接合される前後一対の端部３５ＡＦ、３５ＡＲと、各端部３５ＡＦ、３５ＡＲの下端から内側に向けて略水平に折り曲げられる前後一対の第１折り曲げ部３５Ｂ（３５ＢＦ、３５ＢＲ）と、各第１折り曲げ部３５Ｂの一端から下方に折り曲げられる前後一対の第２折り曲げ部３５Ｃと、各第２折り曲げ部３５Ｃ（３５ＣＦ、３５ＣＲ）の下端間をつなぐ架橋部３５Ｄとを一体に備えている。
　第２折り曲げ部３５Ｃ間の間隔は、マグネシウム極１５の板厚とほぼ同じ長さに形成される。これにより、図１９（Ｂ）に示すように、第２折り曲げ部３５Ｃ間にマグネシウム極１５が配置されることによって、マグネシウム極１５の下端が保持される。 FIG. 20 is a perspective view of the bottom plate sheet portion 35 of the third embodiment.
The bottom plate sheet portion 35 is substantially horizontal inward from the lower end of each of the end portions 35AF and 35AR and a pair of front and rear end portions 35AF and 35AR joined to lower portions of the front wall portion 22 and the rear wall portion 23 respectively. A pair of front and rear first bent portions 35B (35BF, 35BR) which are bent into two, a pair of front and rear second bent portions 35C which are bent downward from one end of each first bent portion 35B, and each second bent portion 35C (35CF, 35CF, And a bridge portion 35D for connecting the lower ends of the 35 CR) integrally.
The distance between the second bent portions 35C is formed to have substantially the same length as the thickness of the magnesium electrode 15. Thereby, as shown in FIG. 19B, the lower end of the magnesium electrode 15 is held by arranging the magnesium electrode 15 between the second bent portions 35C.
　この底板シート部３５は、外装体１１を形成するシート材を平面状に展開した状態で、外装体１１の底板部２１を跨ぐように各端部３５ＡＦ、３５ＡＲが該シート材に熱融着によって接合される。そして、該シート材を上方に開口する凹状に折り曲げて外装体１１を形成した際に、底板部２１から離間するように第１折り曲げ部３５Ａ、および第２折り曲げ部３５Ｂが外装体１１内側に起立し、上記底板シート部３５が形成されるようになっている。
　言い換えると、この底板シート部３５における端部３５ＡＦ、３５ＡＲ間のシート長（一対の第１折り曲げ部３５Ｂ、一対の第２折り曲げ部３５Ｃおよび架橋部３５Ｄからなるシート長）が、外装体１１における底板シート部３５との接合部間の距離（図１９（Ｂ）中、符号ＬＸで示す距離）と等しく形成されるとともに、各部３５Ｂ～３５Ｄが図示される形状に折り曲げ可能に山折り又は谷折りの折り目が予め設けられている。 In the bottom plate sheet portion 35, the end portions 35AF and 35AR are thermally fused to the sheet material so as to straddle the bottom plate portion 21 of the exterior body 11 in a state in which the sheet material forming the exterior body 11 is spread in a planar shape. It is joined. Then, when the sheet material is bent in a concave shape that opens upward to form the exterior body 11, the first bent portion 35A and the second bent portion 35B stand up inside the exterior body 11 so as to be separated from the bottom plate portion 21. The bottom sheet portion 35 is formed.
In other words, the sheet length between the end portions 35AF and 35AR in the bottom plate sheet portion 35 (the sheet length including the pair of first bent portions 35B, the pair of second bent portions 35C and the bridge portion 35D) is the bottom plate of the exterior body 11 It is formed equal to the distance between the joining portion with the sheet portion 35 (the distance shown by symbol LX in FIG. 19B), and can be foldable into a shape shown by the portions 35B to 35D. A fold is provided in advance.
　これにより、外装体１１のシート材を展開した状態で、平面状に展開した底板シート部３５を容易に接合でき、その後、外装体１１のシート材を、底板部２１を形成するように凹状に折り曲げれば、底板シート部３５の第１折り曲げ部３５Ｂおよび第２折り曲げ部３５Ｃからなる起立部が、底板部２１から離間するように起立し、底板シート部３５を容易に組み立てることができる。
　この底板シート部３５を設けることによって、マグネシウム極１５の前後の位置ずれを抑え、マグネシウム極１５と空気極１３との間の距離（離間距離）を適正に保ち易くなる。また、マグネシウム極１５による外装体１１の傷つきを抑制することが可能になる、という効果も得られる。
　また、底板シート部３５の架橋部３５Ｄは、底板部２１の下方凸の部分２１Ｔに嵌ることで底板部２１に位置決めされ、これによってもマグネシウム極１５の位置ずれを抑え易くなる。 Thereby, in a state where the sheet material of the exterior body 11 is developed, the bottom plate sheet portion 35 developed flat can be easily joined, and then, the sheet material of the exterior body 11 is concaved to form the bottom plate portion 21 If it bends, the rising part which consists of the 1st bent part 35B and the 2nd bending part 35C of bottom plate sheet part 35 will stand up so that it may estrange from bottom plate part 21, bottom plate sheet part 35 can be assembled easily.
By providing the bottom plate sheet portion 35, it is possible to suppress positional deviation of the magnesium electrode 15 before and after, and to properly maintain the distance (separation distance) between the magnesium electrode 15 and the air electrode 13. Moreover, the effect that it becomes possible to suppress the damage of the exterior body 11 by the magnesium electrode 15 is also acquired.
Further, the bridge portion 35D of the bottom plate portion 35 is positioned on the bottom plate portion 21 by being fitted to the downward convex portion 21T of the bottom plate portion 21. This also makes it easy to suppress the displacement of the magnesium electrode 15.
　なお、本実施形態では、底板シート部３５の架橋部３５Ｄを外装体１１の前後方向の中央に位置するように設置したが、底板シート部３５の第１折り曲げ部３５Ｂ（３５ＢＦと３５ＢＲ）の前後方向の長さの比率を調整し、それに対応するように各上板部構成片２５Ｆ、２５Ｒの第１折り曲げ部２５Ｆ１と２５Ｒ１の前後方向の長さの比率を調整することで、マグネシウム極１５の前後方向の位置（電極間距離）を適宜調整することが可能である。
　また、本実施形態では、前記底板シート部３５の各端部３５ＡＦ、３５ＡＲを該シート材に熱融着によって接合した例を示したが、前後一対の端部３５ＡＦ、３５ＡＲの少なくとも一方が熱融着されていれば良い。 In the present embodiment, the bridge portion 35D of the bottom plate sheet portion 35 is disposed at the center of the exterior body 11 in the front-rear direction, but the front and rear of the first bent portion 35B (35BF and 35BR) of the bottom plate sheet portion 35 The ratio of the length of the direction is adjusted, and the ratio of the length of the first bent portions 25F1 and 25R1 of the upper folded plate members 25F and 25R in the front-rear direction is adjusted to correspond to it. It is possible to appropriately adjust the position in the front-rear direction (the distance between the electrodes).
In the embodiment, the end portions 35AF and 35AR of the bottom plate portion 35 are joined to the sheet member by heat fusion, but at least one of the front and rear end portions 35AF and 35AR is a thermal fusion. It should be worn.
（第４実施形態）
　図２１は第４実施形態に係るマグネシウム空気電池１０の斜視図であり、図２２は第４実施形態のマグネシウム空気電池１０の側断面図である。
　このマグネシウム空気電池１０は、電解液に含まれる電解質を収容する電解質収容体４１を備えており、電池として使用するときに水を注ぎ入れることによって電解質が溶け出して電解液となるように構成されている。一般に、電解液（例えば食塩水）よりも水の方が入手しやすいので、水を用意できれば電池を使用でき、場所を選ばずに使用できる、という優位性が得られる。 Fourth Embodiment
FIG. 21 is a perspective view of a magnesium-air battery 10 according to a fourth embodiment, and FIG. 22 is a side cross-sectional view of the magnesium-air battery 10 of the fourth embodiment.
The magnesium-air battery 10 is provided with an electrolyte container 41 for containing the electrolyte contained in the electrolytic solution, and when used as a battery, the electrolyte is dissolved out by pouring in water so as to be an electrolytic solution. ing. In general, water is easier to obtain than an electrolytic solution (for example, saline solution). Therefore, if water can be prepared, the advantage of being able to use a battery and being able to be used anywhere is obtained.
　電解質収容体４１は、マグネシウム極１５における空気極１３と反対側の面に装着される極板装着シート４２と、極板装着シート４２に設けられる袋体４３とを備えている。
　図２２に示すように、極板装着シート４２は、外装体１１の前後一対の上板部構成片２５Ｆ、２５Ｒ間に挟まれて保持される。より具体的には、図２２に示すように、上板部構成片２５Ｆ、２５Ｒの第２折り曲げ部２５Ｆ２、２５Ｒ２が、外装体１１の外側（上側に相当）に折り曲げられ、これら第２折り曲げ部２５Ｆ２、２５Ｒ２間に、極板装着シート４２の上部が挟み込まれ、その状態で、第２折り曲げ部２５Ｆ２、２５Ｒ２および極板装着シート４２が互いに熱融着によって接合される。これによって、極板装着シート４２の上部が外装体１１に宙づりで保持される。 The electrolyte container 41 includes an electrode plate mounting sheet 42 mounted on the surface of the magnesium electrode 15 opposite to the air electrode 13, and a bag 43 provided on the electrode plate mounting sheet 42.
As shown in FIG. 22, the electrode plate mounting sheet 42 is held between the front and rear pair of upper plate portion constituting pieces 25 F and 25 R of the exterior body 11 so as to be held. More specifically, as shown in FIG. 22, the second bent portions 25F2 and 25R2 of the upper plate portion constituting pieces 25F and 25R are bent to the outside (corresponding to the upper side) of the exterior body 11, and these second bent portions The upper portion of the electrode plate mounting sheet 42 is sandwiched between 25F2 and 25R2, and in that state, the second bent portions 25F2 and 25R2 and the electrode plate mounting sheet 42 are joined together by heat fusion. As a result, the upper portion of the electrode plate mounting sheet 42 is suspended and held by the exterior body 11.
　図２３（Ａ）は電解質収容体４１をマグネシウム極１５と共に空気極１３側から見た斜視図であり、図２３（Ｂ）は空気極１３と反対側から見た斜視図である。
　極板装着シート４２は、外装体１１を構成するシート材と同じシート材、つまり、紙と熱融着性樹脂とをラミネート加工などにより複合化したシート材で形成される。この極板装着シート４２は、マグネシウム極１５の背面を覆うシート本体４２Ａと、シート本体４２Ａの下部から折り曲げられてマグネシウム極１５の下部が嵌まる左右一対の下部嵌合部４２Ｂと、シート本体４２Ａの上部中央の一部を切り起こしてマグネシウム極１５の上部に設けた凹部１５Ｄに嵌まる上側嵌合部４２Ｃとを一体に備えている。これら３つの嵌合部４２Ｂ、４２Ｃにより、極板装着シート４２に対するマグネシウム極１５の上下方向と前後方向の移動が規制される。 FIG. 23A is a perspective view of the electrolyte containing body 41 as viewed from the air electrode 13 side together with the magnesium electrode 15, and FIG. 23B is a perspective view of the electrolyte container 41 as viewed from the opposite side to the air electrode 13.
The electrode plate attachment sheet 42 is formed of the same sheet material as the sheet material constituting the exterior body 11, that is, a sheet material in which paper and a thermally fusible resin are composited by laminating or the like. The electrode plate mounting sheet 42 includes a sheet body 42A covering the back of the magnesium electrode 15, a pair of left and right lower fitting portions 42B which are bent from the lower portion of the sheet body 42A and into which the lower portion of the magnesium electrode 15 is fitted. And an upper fitting portion 42C which is cut and raised at a part of the upper center of the upper part and fitted in a recess 15D provided in the upper part of the magnesium electrode 15. The movement of the magnesium electrode 15 in the vertical direction and the front-rear direction with respect to the electrode plate mounting sheet 42 is restricted by the three fitting portions 42B and 42C.
　この極板装着シート４２とマグネシウム極１５とは、左右一対の圧着金具４５によって互いに圧着固定される。より具体的には、圧着金具４５としては、丸孔を縁取る縁取り金具（鳩目、又は、ハトメとも称する金具）が用いられ、この圧着金具４５を、極板装着シート４２とマグネシウム極１５とを貫通する左右一対の丸孔に装着することにより、極板装着シート４２とマグネシウム極１５とが固定される。 The electrode plate mounting sheet 42 and the magnesium electrode 15 are crimped and fixed to each other by a pair of left and right crimp fittings 45. More specifically, as the crimp fitting 45, an edge fitting (a fitting also referred to as an eyelet or a hatch) for rounding a round hole is used, and the crimp fitting 45 is used as the electrode plate mounting sheet 42 and the magnesium electrode 15 The electrode plate mounting sheet 42 and the magnesium electrode 15 are fixed by mounting the pair of left and right round holes.
　このとき、一方の圧着金具４５には、配線１５Ｈの先端に設けた金具が固定される。これにより、マグネシウム極１５と配線１５Ｈとを容易に接続することができる。この配線１５Ｈは、外装体１１に設けられたスペース２８Ｋ（図２１）を通って外装体１１の外に引き出され、図１に示すタブ部１５Ｔの代わり、或いは、負極配線の一部として用いられる。なお、この配線１５Ｈの他端には、配線接続に用いられる接続端子（本構成ではギボシ端子）１５Ｊが取り付けられ、他の配線との接続を容易にしている。
　なお、図２１の例では、空気極１３の上部に上記圧着金具４５と同じ圧着金具４６を用いて配線１３Ｈを接続し、また、この配線１３Ｈの他端に同じ接続端子１３Ｊを取り付けた場合を示している。 At this time, a metal fitting provided at the tip of the wiring 15H is fixed to one of the crimp fittings 45. Thereby, the magnesium electrode 15 and the wiring 15H can be easily connected. This wire 15H is drawn out of the case 11 through the space 28K (FIG. 21) provided in the case 11 and used as a part of the negative electrode wire instead of the tab portion 15T shown in FIG. . At the other end of the wire 15H, a connection terminal (in the present configuration, a terminal for connection) 15J used for wire connection is attached to facilitate connection with other wires.
In the example of FIG. 21, the wire 13H is connected to the upper portion of the air electrode 13 using the same crimp fitting 46 as the crimp fitting 45, and the same connection terminal 13J is attached to the other end of the wire 13H. It shows.
　極板装着シート４２の下部を折り曲げて形成した下部嵌合部４２Ｂは、図２２に示すように、マグネシウム極１５と前壁部２２との離間距離（隙間ＳＦに相当）と同じ長さだけ前壁部２２側に出っ張って前壁部２２の裏面に当接する。これにより、下部嵌合部４２Ｂは、マグネシウム極１５と空気極１３との離間距離を一定に規制する規制部材としても機能する。
　また、図２３（Ｂ）に示すように、極板装着シート４２には、その下部を空気極１３の反対側に折り曲げて形成した左右一対の下部折り曲げ部４２Ｄが設けられる。これら下部折り曲げ部４２Ｄは、図２２に示すように、マグネシウム極１５と後壁部２３との離間距離（隙間ＳＲに相当）と同じ長さだけ後壁部２３側に出っ張って後壁部２３の裏面に当接し、マグネシウム極１５と後壁部２３との離間距離を一定に規制する規制部材として機能する。
　このようにして、マグネシウム極１５の下部の前後方向の位置ずれを効果的に抑えることができ、マグネシウム極１５と空気極１３との離間距離を適正に保つことができる。 The lower fitting portion 42B formed by bending the lower portion of the electrode plate mounting sheet 42 is, as shown in FIG. 22, the same distance as the separation distance (corresponding to the gap SF) between the magnesium electrode 15 and the front wall 22 It projects to the wall 22 side and abuts on the back of the front wall 22. Thus, the lower fitting portion 42B also functions as a restricting member that restricts the distance between the magnesium electrode 15 and the air electrode 13 to a certain distance.
Further, as shown in FIG. 23B, the electrode plate mounting sheet 42 is provided with a pair of left and right lower bent portions 42D formed by bending the lower portion to the opposite side of the air electrode 13. As shown in FIG. 22, these lower bent portions 42D project toward the rear wall portion 23 by the same length as the separation distance between the magnesium electrode 15 and the rear wall portion 23 (corresponding to the clearance SR). It abuts on the back surface, and functions as a restricting member that restricts the distance between the magnesium electrode 15 and the rear wall 23 to a constant value.
Thus, the positional deviation in the front-rear direction of the lower part of the magnesium electrode 15 can be effectively suppressed, and the separation distance between the magnesium electrode 15 and the air electrode 13 can be properly maintained.
　袋体４３は、紙、不織布、織布のような透水性材料、オブラートのような澱粉系のフィルムやポリビニルアルコール系フィルムなどのような水溶性材料で形成される。前記袋体４３の内部には、例えば電解質である塩化ナトリウムを入れた後、極板装着シート４２に袋体４３の上部を熱融着によって接合する。袋体４３の上部を熱融着することで、上下逆さま等の様々な姿勢となっても電解質が外部に露出したり、漏れ出したりしない構造となっている。なお、前記極板装着シート４２と袋体４３との接合は熱融着に限定することなく、ホッチキスやテープなどを用いても良い。
　この袋体４３の取付位置は、極板装着シート４２の背面（マグネシウム極１５と反対側の面）であって、水の注水口となる孔部２５Ｈ（図１６参照）の下方に設定される。このため、注水された水によって電解質を迅速に溶かし、適切な電解液を迅速に生成することができる。
　本構成では、電解質を包む袋体４３を極板装着シート４２に取り付けるため、電解質がマグネシウム極１５に付着して腐食させてしまう事態を避けることができる。なお、電解質として塩化ナトリウムを用いた場合、前記袋体４３は、塩化ナトリウムの粒径よりも小さい隙間を有し、固体の塩化ナトリウムは通さない一方、水を通す透水性を有している。具体的には、塩化ナトリウムの粒径は０．４ｍｍが最も出回っているため、袋体４３の平均孔径は、前記塩化ナトリウムの粒径よりも小さい０．０５ｍｍ～０．３ｍｍが好ましい。 The bag 43 is formed of a water-permeable material such as paper, nonwoven fabric, water-permeable material such as woven fabric, starch-based film such as a wafer, polyvinyl alcohol-based film, and the like. For example, sodium chloride as an electrolyte is put in the inside of the bag 43, and then the upper part of the bag 43 is joined to the electrode plate mounting sheet 42 by heat fusion. By heat-sealing the upper portion of the bag body 43, the electrolyte is not exposed to the outside or leaked out even if the posture is upside down. The joining between the electrode plate mounting sheet 42 and the bag body 43 is not limited to heat fusion, and a stapler, a tape or the like may be used.
The mounting position of the bag body 43 is the back surface (surface opposite to the magnesium electrode 15) of the electrode plate mounting sheet 42 and is set below the hole 25H (see FIG. 16) serving as a water injection port. . For this reason, the electrolyte can be rapidly dissolved by the injected water, and a suitable electrolyte can be rapidly generated.
In this configuration, since the bag 43 that wraps the electrolyte is attached to the electrode plate mounting sheet 42, the situation in which the electrolyte adheres to the magnesium electrode 15 and is corroded can be avoided. When sodium chloride is used as the electrolyte, the bag 43 has a gap smaller than the particle diameter of sodium chloride, and does not allow passage of solid sodium chloride, but has water permeability for passing water. Specifically, since the particle diameter of sodium chloride is 0.4 mm, the average pore diameter of the bag 43 is preferably 0.05 mm to 0.3 mm, which is smaller than the particle diameter of sodium chloride.
　なお、電解質として塩化ナトリウムを使用する場合の質量は、注ぎ入れる水の質量に対して４％～１８％の範囲内が好ましい。発明者等が検証したところ、４％未満だと、電解液の抵抗が大きくなり電圧降下が大きくなってしまうため、電圧が低く、取り出せる電力が少なくなってしまうことを確認した。一方、１８％より多いと、放電末期に塩化ナトリウムが飽和状態になって析出し、セル内部の極間などに溜まって放電反応を阻害し、放電できなくなることを確認した。
　また、上記の電解質として塩化ナトリウムを使用する場合は塩化ナトリウム以外を含んでも良い。要は、この場合は電解質の主成分が塩化ナトリウムであれば良く、他の成分を含んでも良い。 In the case of using sodium chloride as the electrolyte, the mass is preferably in the range of 4% to 18% with respect to the mass of water poured. The inventors verified that if it is less than 4%, the resistance of the electrolyte increases and the voltage drop increases, so that the voltage is low and the power that can be taken out is reduced. On the other hand, when the content was more than 18%, it was confirmed that sodium chloride was saturated and precipitated at the end of discharge, and was accumulated between the electrodes inside the cell to inhibit the discharge reaction and to be unable to discharge.
Moreover, when using sodium chloride as said electrolyte, you may also contain except sodium chloride. In short, in this case, the main component of the electrolyte may be sodium chloride, and other components may be included.
　図２３（Ｂ）に示すように、極板装着シート４２には、当該シート４２の一部を切り起こして袋体４３の上方に位置する切り起こし部５１が設けられている。この切り起こし部５１は、極板装着シート４２のシート本体４２Ａから折り曲げられて水平に延びる水平板部５１Ａと、水平板部５１Ａの先端から下方に折り曲げられて後壁部２３に当接する後壁当接部５１Ｂとを一体に備えるＬ字断面に形成される。
　水平板部５１Ａは、水の注水口となる孔部２５Ｈの下方、且つ、袋体４３の上方に配置され、注水された水を当該水平板部５１Ａに当てて周囲に拡散する拡散部材として機能する。より具体的には、水平板部５１Ａには、間隔を空けて複数の小孔が形成され、水の一部を、小孔を介して下方に落下させるとともに、水の残りを周囲に拡散する。これにより、注水された水を拡散して袋体４３に供給し、袋体４３内の電解質を効率良く溶かすことができ、放電開始のタイミングを早めて電気を取り出し易くなる。また、注水開始時の濃度勾配を低減して部分的な腐食を回避し易くなる。
　また、水平板部５１Ａは注水冶具などを用いて注水する際の注水冶具の差し込み深さの目安としても機能する。これにより、注水冶具などによる袋体４３の損傷を防止することが可能である。 As shown in FIG. 23B, the electrode plate mounting sheet 42 is provided with a cut and raised portion 51 which is formed by cutting and raising a part of the sheet 42 and positioned above the bag body 43. The cut-and-raised portion 51 is a horizontal plate portion 51A bent horizontally from the sheet main body 42A of the electrode plate attachment sheet 42 and a rear wall bent downward from the tip of the horizontal plate portion 51A and abutting on the rear wall portion 23 It is formed in an L-shaped cross section integrally provided with the contact portion 51B.
The horizontal plate portion 51A is disposed below the hole 25H serving as a water injection port and above the bag body 43, and functions as a diffusion member that applies the injected water to the horizontal plate portion 51A and diffuses it around Do. More specifically, in the horizontal plate portion 51A, a plurality of small holes are formed at intervals, and a part of the water is dropped downward through the small holes and the rest of the water is diffused to the surroundings. . As a result, the injected water is diffused and supplied to the bag 43, so that the electrolyte in the bag 43 can be efficiently dissolved, and the timing of the discharge start can be advanced to facilitate extraction of electricity. In addition, it is easy to avoid partial corrosion by reducing the concentration gradient at the start of water injection.
The horizontal plate portion 51A also functions as a measure of the insertion depth of the water injection jig when water is injected using the water injection jig or the like. Thereby, it is possible to prevent damage to the bag 43 due to the water injection jig or the like.
　なお、放電を開始した後はマグネシウムの自己放電反応により水素が発生するため、この水素の発生により電解液がかき混ぜられ、濃度勾配をより一層低減することが可能である。
　また、本実施形態では、図２３に示すように、切り起こし部５１を左右一対設けており、袋体４３の大きさに応じて、いずれか一方、或いは、両方の切り起こし部を折り曲げ可能にしている。例えば、図２３（Ｂ）の例では、袋体４３が一方の切り起こし部５１の下方だけに配置されるので、一方の切り起こし部５１だけを折り曲げれば良い。これに対し、袋体４３が両方の切り起こし部５１の下方に渡って配置される幅広の場合には、両方の切り起こし部５１を折り曲げ、両方の孔部２５Ｈから水を入れることによって電解質を効率良く溶かすことができる。 In addition, since hydrogen is generated by the self-discharge reaction of magnesium after the discharge is started, the electrolytic solution is stirred by the generation of hydrogen, and the concentration gradient can be further reduced.
Further, in the present embodiment, as shown in FIG. 23, a pair of cut and raised portions 51 is provided on the left and right sides, and either or both of the cut and raised portions can be bent depending on the size of the bag 43. ing. For example, in the example of FIG. 23B, since the bag body 43 is disposed only under the one cut and raised portion 51, only the one cut and raised portion 51 may be bent. On the other hand, in the case where the bag body 43 is wide disposed so as to extend below the both cut and raised portions 51, the both cut and raised portions 51 are bent and the electrolyte is made by putting water from both holes 25H. It can be melted efficiently.
　以上説明したように、本実施の形態では、マグネシウム極１５における空気極１３と反対側の面に、外装体１１内に水を注ぎ入れることによって電池として作動させるための電解質を収容する電解質収容体４１を設けているので、電解液の溶媒を入れるだけで電池として利用できる構成にするとともに、電解質の影響によるマグネシウム極１５の腐食を抑制することができる。
　しかも、電解質収容体４１は、紙を含有するシート材であってマグネシウム極１５における空気極１３と反対側の面に装着される極板装着シート４２と、極板装着シート４２に接合されて電解質を収容する袋体４３とを備えるので、マグネシウム極１５と電解質との間にシート材が介在し、電解質の影響によるマグネシウム極１５の腐食を抑制することができる。また、電解質を収容する袋体４３を外装体１１に取り付ける必要がないので、外装体１１の構成を簡易化し易く、また、袋体４３の取付作業も容易である。 As described above, in the present embodiment, an electrolyte container for containing an electrolyte for operating as a battery by pouring water into the exterior body 11 on the surface of the magnesium electrode 15 opposite to the air electrode 13. The provision of the reference numeral 41 makes it possible to use the battery as a battery only by adding the solvent of the electrolytic solution, and to suppress the corrosion of the magnesium electrode 15 due to the influence of the electrolyte.
In addition, the electrolyte container 41 is a sheet material containing paper, and is attached to the electrode plate mounting sheet 42 mounted on the surface of the magnesium electrode 15 opposite to the air electrode 13 and the electrode plate mounting sheet 42 for electrolyte Since the bag body 43 for containing the above is provided, the sheet material intervenes between the magnesium electrode 15 and the electrolyte, and the corrosion of the magnesium electrode 15 due to the influence of the electrolyte can be suppressed. Moreover, since it is not necessary to attach the bag 43 containing an electrolyte to the package 11, the structure of the package 11 can be simplified easily, and the attachment of the bag 43 is also easy.
　また、極板装着シート４２はマグネシウム極１５に圧着固定され、袋体４３は極板装着シート４２に融着されるので、極板装着シート４２および袋体４３の取付が容易である。
　また、極板装着シート４２は、当該シート４２の一部を折り曲げて当該シートに対するマグネシウム極１５の移動を規制する嵌合部４２Ｂおよび上側嵌合部４２Ｃ（規制部）を有し、極板装着シート４２を外装体１１に保持させてマグネシウム極１５を外装体１１に保持するので、外装体１１側にマグネシウム極１５を直接保持する構造が不要となり、外装体１１を簡易な構造にし易くなる。 Further, since the electrode plate mounting sheet 42 is crimped and fixed to the magnesium electrode 15 and the bag 43 is fused to the electrode plate mounting sheet 42, the electrode plate mounting sheet 42 and the bag 43 can be easily attached.
Further, the electrode plate mounting sheet 42 has a fitting portion 42B and an upper fitting portion 42C (regulating portion) for bending a part of the sheet 42 to restrict the movement of the magnesium electrode 15 with respect to the sheet, and the electrode plate mounting Since the sheet 42 is held by the case 11 and the magnesium electrode 15 is held by the case 11, the structure for directly holding the magnesium electrode 15 on the side of the case 11 is unnecessary, and the case 11 can be easily structured.
　また、極板装着シート４２を、外装体１１の底板部２１よりも上方に宙づりで固定するので、この極板装着シート４２に支持されるマグネシウム極１５を、外装体１１の底板部２１に載置する必要がない。このため、マグネシウム極１５の下端位置の自由度が向上し、図２２に示すように、マグネシウム極１５の下端を、空気極１３の下端とほぼ同じ高さに揃えることができる。これにより、マグネシウム極１５の電池反応に殆ど寄与しない部分を削減でき、マグネシウム極１５の小型化が可能になる。 Further, since the electrode plate mounting sheet 42 is fixed by floating above the bottom plate portion 21 of the exterior body 11, the magnesium electrode 15 supported by the electrode plate mounting sheet 42 is mounted on the bottom plate portion 21 of the exterior body 11. There is no need to put it. Therefore, the degree of freedom of the lower end position of the magnesium electrode 15 is improved, and as shown in FIG. 22, the lower end of the magnesium electrode 15 can be aligned to almost the same height as the lower end of the air electrode 13. Thereby, the part which hardly contributes to the battery reaction of magnesium electrode 15 can be reduced, and miniaturization of magnesium electrode 15 is attained.
　なお、第４実施形態では、極板装着シート４２を、外装体１１の底板部２１よりも上方に宙づりで固定する場合を説明したが、図２４に示すように、極板装着シート４２を外装体１１の底板部２１に到達するまで下方に延ばし、極板装着シート４２の下部を底板部２１に載置するようにしても良い。この場合、相対的に重量を有するマグネシウム極１５を、外装体１１の底板部２１を利用して支えることができる。 In the fourth embodiment, the case where the electrode plate mounting sheet 42 is fixed by floating above the bottom plate portion 21 of the exterior body 11 has been described. However, as shown in FIG. The lower portion of the electrode plate mounting sheet 42 may be placed on the bottom plate portion 21 by extending downward until reaching the bottom plate portion 21 of the body 11. In this case, the relatively heavy magnesium electrode 15 can be supported using the bottom plate portion 21 of the exterior body 11.
　この場合の電解質収容体４１の一例を、図２５（Ａ）および図２５（Ｂ）に示す。図２５（Ａ）および図２５（Ｂ）に示すように、極板装着シート４２の下部は、外装体１１内の開口形状と一致する平板状の平板部４２Ｇを形成するように折り曲げられる。これによって、極板装着シート４２の下部（平板部４２Ｇ）と外装体１１の底板部２１との当接面積を広く確保することができ、極板装着シート４２の支持力を確保するとともに底板部２１の変形を抑え易くなる。
　しかも、極板装着シート４２の下部（平板部４２Ｇ）が、外装体１１内に嵌まって前後左右の移動が規制されるので、極板装着シート４２の位置ずれを効果的に規制することができる。 An example of the electrolyte container 41 in this case is shown in FIGS. 25 (A) and 25 (B). As shown in FIGS. 25A and 25B, the lower portion of the electrode plate mounting sheet 42 is bent so as to form a flat plate portion 42G having the same shape as the opening in the exterior body 11. This makes it possible to secure a wide contact area between the lower portion (flat plate portion 42G) of the electrode plate mounting sheet 42 and the bottom plate portion 21 of the exterior body 11 and secure a supporting force of the electrode plate mounting sheet 42 It becomes easy to suppress the deformation of 21.
Moreover, since the lower portion (flat plate portion 42G) of the electrode plate mounting sheet 42 is fitted in the exterior body 11 and the front, rear, left, and right movement is regulated, the positional deviation of the electrode plate mounting sheet 42 can be effectively restricted. it can.
　なお、図２５（Ａ）および図２５（Ｂ）では、極板装着シート４２に対し、上記平板部４２Ｇよりも上方位置にて左右外側に張り出す張り出し部４２Ｈを設け、各張り出し部４２Ｈを左右中央側に折り曲げるとともに、その一部を平板部４２Ｇに差し込むことによって、マグネシウム極１５の下部が嵌まる左右の下部嵌合部４２Ｂを形成している。但し、下部嵌合部４２Ｂや平板部４２Ｇなどの各部の形状は上記形状に限定されず、適宜に変更が可能である。
　また、図２５（Ａ）および図２５（Ｂ）では、極板装着シート４２に、切り起こし部５１（図２３（Ｂ）参照）を形成していない。つまり、切り起こし部５１の有無についても適宜に変更が可能である。このように極板装着シート４２の各部の形状は、上記各機能を実現可能な範囲で適宜に変更しても良い。 In FIGS. 25 (A) and 25 (B), the electrode plate attachment sheet 42 is provided with projecting portions 42H projecting outward to the left and right at positions above the flat plate portion 42G, and each projecting portion 42H is The left and right lower fitting portions 42B into which the lower portion of the magnesium electrode 15 is fitted are formed by bending the center side and inserting a part thereof into the flat plate portion 42G. However, the shape of each portion such as the lower fitting portion 42B and the flat plate portion 42G is not limited to the above shape, and can be appropriately changed.
Moreover, in FIG. 25 (A) and FIG. 25 (B), the cut-and-raised part 51 (refer FIG. 23 (B)) is not formed in the electrode plate mounting sheet 42. As shown in FIG. That is, the presence or absence of the cut and raised portion 51 can be changed as appropriate. As described above, the shape of each part of the electrode plate mounting sheet 42 may be appropriately changed as long as the above-described functions can be realized.
（第５実施形態）
　図２６は第５実施形態に係るマグネシウム空気電池１０の側断面図である。このマグネシウム空気電池１０は、極板装着シート４２および袋体４３からなる電解質収容体４１を有する点で、上記第４実施形態と同様であるが、上記極板装着シート４２が外装体１１を形成するシート材に一体に設けられる点で第４実施形態と異なっている。 Fifth Embodiment
FIG. 26 is a side sectional view of a magnesium-air battery 10 according to the fifth embodiment. The magnesium-air battery 10 is the same as the fourth embodiment in that the magnesium-air battery 10 has an electrolyte container 41 consisting of an electrode plate mounting sheet 42 and a bag 43, but the electrode plate mounting sheet 42 forms the outer package 11 The fourth embodiment differs from the fourth embodiment in that it is provided integrally with the sheet material.
　図２７は外装体１１の斜視図であり、図２８（Ａ）は外装体１１を展開した図（＝打ち抜きシート１００に相当する図）である。また、図２８（Ｂ）は図２７のＸ領域に相当する図であり、図２８（Ｃ）は図２７のＹ領域に相当する図を示し、図２８（Ｄ）は図２７のＺ領域に相当する図である。
　図２７および図２８（Ａ）に示すように、この外装体１１は、後壁部２３の上縁２３Ａで折り曲げられてマグネシウム極１５の上方を覆う蓋部（上板部２５）となる第１折り曲げ部２５Ｒ１に、折り目２３Ｃを介して極板装着シート４２を連接している。極板装着シート４２は、折り目２３Ｃを介して外装体１１内に折り曲げられる矩形状のシート本体４２Ａを有し、このシート本体４２Ａにマグネシウム極１５が左右一対の圧着金具４５（図１７）によって圧着固定される。 FIG. 27 is a perspective view of the exterior body 11, and FIG. 28 (A) is a developed view of the exterior body 11 (= a view corresponding to the punching sheet 100). 28B is a diagram corresponding to the X region of FIG. 27, FIG. 28C shows a diagram corresponding to the Y region of FIG. 27, and FIG. 28D is a diagram corresponding to the Z region of FIG. It is a figure which corresponds.
As shown in FIGS. 27 and 28A, the exterior body 11 is bent at the upper edge 23A of the rear wall 23 to form a lid (upper plate 25) that covers the top of the magnesium electrode 15. The electrode plate mounting sheet 42 is connected to the bent portion 25R1 via the fold line 23C. The electrode plate mounting sheet 42 has a rectangular sheet main body 42A which is bent into the outer package 11 through the fold line 23C, and the magnesium electrode 15 is crimped to the sheet main body 42A by a pair of left and right crimp fittings 45 (FIG. 17) It is fixed.
　また、前壁部２２の上縁２３Ａ（折り目に相当）で折り曲げられてマグネシウム極１５の上方を覆う蓋部となる第１折り曲げ部２５Ｆ１には、第１折り曲げ部２５Ｒ１と極板装着シート４２との境界部分に設けられた開口部６１（図２８（Ａ））に差し込まれる差し込み部６２と、差し込み部６２の左右に位置する左右一対のタブ部６３とが一体に設けられている。
　外装体１１を組み立てる際に、図２８（Ｂ）に示すように、差し込み部６２を開口部６１に差し込むことによって、第１折り曲げ部２５Ｆ１、２５Ｒ１同士が連結される。また、図２７に示すように、左右一対のタブ部６３は外装体１１の内側に折り曲げられる。 In addition, the first bent portion 25F1 serving as a lid portion which is bent at the upper edge 23A (corresponding to the fold) of the front wall portion 22 and which covers the upper side of the magnesium electrode 15 includes the first bent portion 25R1 and the electrode plate mounting sheet 42. The insertion part 62 inserted in the opening part 61 (FIG. 28 (A)) provided in the boundary part of these, and the left-right paired tab part 63 located in the right and left of the insertion part 62 are provided integrally.
When assembling the exterior body 11, as shown to FIG. 28 (B), 1st bending part 25F1 and 25R1 comrades are connected by inserting the insertion part 62 in the opening part 61. As shown in FIG. Further, as shown in FIG. 27, the pair of left and right tab portions 63 are bent to the inside of the exterior body 11.
　図２８（Ａ）に示すように、極板装着シート４２は、シート本体４２Ａの左右の側縁に連なる左右一対の側片４２Ｊと、シート本体４２Ａの下縁に連なる下片４２Ｋとを一体に有している。
　左右一対の側片４２Ｊは、それぞれ上下に分割されて上側の側片４２ＪＡと下側の側片４２ＪＢとを構成する。上側の側片４２ＪＡは、図２８（Ｃ）に示すように、蓋部（第１折り曲げ部２５Ｒ１）に対してシート本体４２Ａを９０度折り曲げた状態で、蓋部（第１折り曲げ部２５Ｒ１）の下に入り込むように略直角に折り曲げられる。
　この場合、上側の側片４２ＪＡが蓋部（第１折り曲げ部２５Ｒ１）の下面に当接することで、シート本体４２Ａが蓋部（第１折り曲げ部２５Ｒ１）側へ移動することを規制できる。これにより、シート本体４２Ａと蓋部（第１折り曲げ部２５Ｒ１）とを直角の位置関係に保持し易くなる。 As shown in FIG. 28A, in the electrode plate mounting sheet 42, a pair of left and right side pieces 42J connected to the left and right side edges of the sheet body 42A and a lower piece 42K connected to the lower edge of the sheet body 42A are integrated. Have.
The pair of left and right side pieces 42J are respectively divided up and down to constitute an upper side piece 42JA and a lower side piece 42JB. The upper side piece 42JA is, as shown in FIG. 28C, in a state where the sheet main body 42A is bent 90 degrees with respect to the lid (first folded portion 25R1), the upper side piece 42JA is the lid (first folded portion 25R1). It is bent almost at a right angle to get into the bottom.
In this case, the upper side piece 42JA abuts on the lower surface of the lid (first bent portion 25R1), so that movement of the sheet main body 42A to the lid (first bent portion 25R1) can be restricted. As a result, the sheet main body 42A and the lid (the first bent portion 25R1) can be easily held at a right-angled positional relationship.
　下側の側片４２ＪＢは、シート本体４２Ａの左右の側縁４２Ｍを折り目にして外装体１１の後壁部２３側に折り曲げられる内側折り曲げ部４２ＪＵと、内側折り曲げ部４２ＪＵの外縁４２Ｎを折り目にして左右外側に折り曲げられる外側折り曲げ部４２ＪＳとを一体に有している。
　図２８（Ｃ）および図２８（Ｄ）に示すように、外側折り曲げ部４２ＪＳは、外装体１１の後壁部２３に熱融着により接合される。これにより、シート本体４２Ａが後壁部２３に連結される。この場合、図２７に示すように、シート本体４２Ａと後壁部２３との間を内側折り曲げ部４２ＪＵが架橋するので、シート本体４２Ａと後壁部２３との離間距離を一定に保つことができる。これにより、シート本体４２Ａの位置決め、および保持を行うことができ、比較的重量を有するマグネシウム極１５の支持強度を十分に確保でき、且つ、マグネシウム極１５と空気極１３との離間距離を一定に維持できる。 The lower side pieces 42JB fold the outer edges 42N of the inner folded portions 42JU by folding the inner side bent portions 42JU that are folded toward the rear wall 23 side of the exterior body 11 by folding the left and right side edges 42M of the sheet main body 42A. It has integrally with the outer side bending part 42JS bend | folded to the left-right outer side.
As shown in FIGS. 28C and 28D, the outer bent portion 42JS is joined to the rear wall portion 23 of the exterior body 11 by heat fusion. Thereby, the sheet main body 42A is connected to the rear wall portion 23. In this case, as shown in FIG. 27, since the inward bent portion 42JU bridges between the sheet main body 42A and the rear wall 23, the separation distance between the sheet main 42A and the rear wall 23 can be kept constant. . Thereby, positioning and holding of the sheet main body 42A can be performed, supporting strength of the relatively heavy magnesium electrode 15 can be sufficiently secured, and a separation distance between the magnesium electrode 15 and the air electrode 13 is made constant. It can be maintained.
　シート本体４２Ａの下縁に連なる下片４２Ｋは、図２７に示すように、シート本体４２Ａの下縁を基準に上方に折り曲げられてシート本体４２Ａに熱融着により接合される。これにより、上記下片４２Ｋを備えない構成と比べて、シート端面への水分（電解液）の浸入を抑えることができ、シートの強度低下を抑制できる。なお、下片４２Ｋを設けて折り曲げる代わりに、シート本体４２Ａの下縁を、テープ状のプラスチックフィルムで被覆し、シート端面への水分の浸入を防ぐようにしても良い。
　本構成では、図２６に示すように、極板装着シート４２の下端は、外装体１１の底板部２１よりも上方に位置する。つまり、極板装着シート４２は、外装体１１の蓋部（第１折り曲げ部２５Ｒ１）に宙づりで支持される。これによって、極板装着シート４２に支持されるマグネシウム極１５を、外装体１１の底板部２１に載置する必要がなく、マグネシウム極１５の下端位置の自由度が向上する。 The lower piece 42K connected to the lower edge of the sheet body 42A is bent upward based on the lower edge of the sheet body 42A and joined to the sheet body 42A by heat fusion as shown in FIG. Thereby, compared with the structure which is not equipped with the said lower piece 42K, permeation of the water | moisture content (electrolyte solution) to a sheet end surface can be suppressed, and the strength reduction of a sheet | seat can be suppressed. The lower edge of the sheet body 42A may be covered with a tape-shaped plastic film instead of providing the lower piece 42K and bending so as to prevent the infiltration of moisture to the end face of the sheet.
In this configuration, as shown in FIG. 26, the lower end of the electrode plate mounting sheet 42 is positioned above the bottom plate portion 21 of the exterior body 11. That is, the electrode plate mounting sheet 42 is suspended and supported by the lid (the first bent portion 25R1) of the exterior body 11. As a result, the magnesium electrode 15 supported by the electrode plate mounting sheet 42 does not have to be placed on the bottom plate portion 21 of the exterior body 11, and the degree of freedom of the lower end position of the magnesium electrode 15 is improved.
　このように、マグネシウム極１５の下端を、空気極１３の下端よりも高い位置にすることで、マグネシウム極１５と外装体１１の底板部２１との間のスペースを広く確保できる。これにより、マグネシウム極１５の電池反応に殆ど寄与しない部分を削減でき、マグネシウム極１５の小型化が可能になる。なお、マグネシウム極１５の下端を空気極１３の下端とほぼ同じ高さに揃えても良い。 Thus, by setting the lower end of the magnesium electrode 15 at a position higher than the lower end of the air electrode 13, a wide space between the magnesium electrode 15 and the bottom plate portion 21 of the exterior body 11 can be secured. Thereby, the part which hardly contributes to the battery reaction of magnesium electrode 15 can be reduced, and miniaturization of magnesium electrode 15 is attained. The lower end of the magnesium electrode 15 may be aligned with the lower end of the air electrode 13 at substantially the same height.
　図２８（Ａ）に示すように、後壁部２３の左右に連なる左右一対の側壁部構成片２４Ｒ（より具体的には内側折り曲げ片２４ＲＵ）の上縁には、シート片７１Ｒが一体に設けられる。これらシート片７１Ｒは、図２８（Ｃ）に示すように、外装体１１の蓋部となる第１折り曲げ部２５Ｒ１の下面に熱融着により接合される。これによって、側壁部構成片２４Ｒと第１折り曲げ部２５Ｒ１との接合強度を向上し、後壁部２３、側壁部（側壁部構成片２４Ｒ）、および蓋部（第１折り曲げ部２５Ｒ１）の折り曲げ形状を十分に保持することができる。
　同様に、前壁部２２の左右に連なる左右一対の側壁部構成片２４Ｆ（より具体的には内側折り曲げ片２４ＦＵ）の上縁にも、シート片７１Ｆ（図２８（Ａ））がそれぞれ一体に設けられる。これらシート片７１Ｆは、図２８（Ｃ）に示すように、外装体１１の蓋部となる第１折り曲げ部２５Ｆ１の下面に熱融着により接合される。これによって、側壁部構成片２４Ｆと第１折り曲げ部２５Ｆ１との接合強度を向上し、前壁部２２、側壁部（側壁部構成片２４Ｆ）、および蓋部（第１折り曲げ部２５Ｆ１）の折り曲げ形状を十分に保持することができる。 As shown in FIG. 28A, a sheet piece 71R is integrally provided on the upper edge of a pair of left and right side wall part constituting pieces 24R (more specifically, inner bent pieces 24RU) connected to the left and right of the rear wall 23. Be As shown in FIG. 28C, these sheet pieces 71R are joined by heat fusion to the lower surface of the first bent portion 25R1 which is the lid portion of the exterior body 11. As a result, the bonding strength between the side wall portion constituting piece 24R and the first bent portion 25R1 is improved, and the bent shape of the rear wall portion 23, the side wall portion (side wall portion constituting piece 24R), and the lid portion (first bent portion 25R1) Can be held well.
Similarly, a sheet piece 71F (FIG. 28A) is integrally formed on the upper edge of the pair of left and right side wall component pieces 24F (more specifically, the inner bent pieces 24FU) connected to the left and right of the front wall 22. Provided. As shown in FIG. 28C, these sheet pieces 71F are joined by heat fusion to the lower surface of the first bent portion 25F1 which is the lid of the exterior body 11. As a result, the bonding strength between the side wall portion constituting piece 24F and the first bent portion 25F1 is improved, and the bent shape of the front wall portion 22, the side wall portion (side wall portion constituting piece 24F), and the lid portion (first bent portion 25F1) Can be held well.
　以上説明したように、本実施の形態では、マグネシウム極１５（金属極）における空気極１３と反対側の面に装着される極板装着シート４２を、外装体１１を形成するシート材に一体に設けたので、上記第４実施形態の各種効果に加え、部品点数を低減することができる。
　しかも、極板装着シート４２を蓋部（第１折り曲げ部２５Ｒ１）に設けているので、図２６に示すように、極板装着シート４２を、外装体１１の底板部２１よりも上方に宙づりで固定することができる。このため、極板装着シート４２に支持されるマグネシウム極１５を外装体１１の底板部２１に載置する必要がなく、マグネシウム極１５の下端位置の自由度が向上する。従って、水を注ぎ入れて電解質と混合するスペースや放電反応により生成される生成物（本構成では水酸化マグネシウム）が溜まっても電池反応に影響を与えないスペースを広く確保できる。 As described above, in the present embodiment, the electrode plate mounting sheet 42 mounted on the surface of the magnesium electrode 15 (metal electrode) opposite to the air electrode 13 is integrated with the sheet material forming the exterior body 11. Since it is provided, in addition to the various effects of the fourth embodiment, the number of parts can be reduced.
Moreover, since the electrode plate mounting sheet 42 is provided in the lid (the first bent portion 25R1), the electrode plate mounting sheet 42 is suspended above the bottom plate portion 21 of the exterior body 11 as shown in FIG. It can be fixed. For this reason, it is not necessary to place the magnesium electrode 15 supported by the electrode plate mounting sheet 42 on the bottom plate portion 21 of the exterior body 11, and the flexibility of the lower end position of the magnesium electrode 15 is improved. Therefore, it is possible to secure a wide space that does not affect the cell reaction even if a space for pouring in water and mixing with the electrolyte and a product (magnesium hydroxide in this configuration) generated by the discharge reaction are accumulated.
　また、極板装着シート４２の左右を折り曲げて外装体１１の後壁部２３に接合するので、極板装着シート４２の位置決め、および保持を行うことができ、マグネシウム極１５（金属極）の支持強度を確保し易くなるとともに、マグネシウム極１５と空気極１３との離間距離を一定に維持することができる。 Further, since the right and left sides of the electrode plate mounting sheet 42 are bent and joined to the rear wall 23 of the exterior body 11, positioning and holding of the electrode plate mounting sheet 42 can be performed, and the support of the magnesium electrode 15 (metal electrode) The strength can be easily secured, and the separation distance between the magnesium electrode 15 and the air electrode 13 can be maintained constant.
　本発明の金属空気電池は既述の実施形態に限定されるものではなく、本発明の技術思想に基づいて各種の変形、および変更が可能である。
　例えば、外装体１１の形状は適宜に変更しても良く、空気極１３やマグネシウム極１５の形状も適宜に変更しても良い。また、外装体１１に用いるシート材は、ラミネート紙以外のシート材であって、紙を含有するシート材を用いても良い。 The metal-air battery of the present invention is not limited to the embodiments described above, and various modifications and changes are possible based on the technical concept of the present invention.
For example, the shape of the exterior body 11 may be changed as appropriate, and the shapes of the air electrode 13 and the magnesium electrode 15 may also be changed as appropriate. Further, the sheet material used for the exterior body 11 is a sheet material other than laminated paper, and a sheet material containing paper may be used.
　上記第１実施形態では、後壁部２３に連なる上板部構成片２５Ｒを、タブ部１５Ｔを基準に分割し、この上板部構成片２５Ｒによって、マグネシウム極１５の空気極１３側への移動と反対側への移動の両方を規制する場合を説明したが、これに限らない。例えば、前壁部２２の上板部構成片２５Ｆを、タブ部１５Ｔを基準に分割し、この上板部構成片２５Ｆによって、マグネシウム極１５の空気極１３側への移動と反対側への移動の両方を規制するようにしても良い。 In the first embodiment, the upper plate portion constituting piece 25R connected to the rear wall portion 23 is divided based on the tab portion 15T, and the movement of the magnesium electrode 15 to the air electrode 13 side is performed by the upper plate portion constituting piece 25R. Although the case of restricting both movement to the opposite side has been described, it is not limited thereto. For example, the upper plate portion constituting piece 25F of the front wall portion 22 is divided on the basis of the tab portion 15T, and the movement of the magnesium electrode 15 to the air electrode 13 side is reversed by the upper plate portion constituting piece 25F. You may restrict both of them.
　また、第１実施形態では、一対の上板部構成片２５Ｆ、２５ＲをＬ字状に折り曲げてマグネシウム極１５の移動を規制する場合を説明したが、マグネシウム極１５の移動を規制可能な範囲で、一対の上板部構成片２５Ｆ、２５Ｒの折り曲げ方は変更しても良い。また、マグネシウム極１５の移動を適切に規制できる範囲で、上板部構成片２５Ｆ、２５Ｒによるマグネシウム極１５の支持のいずれか一方を省略しても良い。
　また、上述の実施例では、外装体１１として、マグネシウム極１５の下端が嵌る下方凸形状に折り曲げられた底板部２１を有する例を説明したが、底板部２１を上方凸形状に折り曲げることによっても、マグネシウム極１５の下端を保持可能とすることができる。この場合には、マグネシウム極１５が空気極１３と平行にはならないものの、マグネシウム極１５の移動防止をより強いものとすることができる。
　また、本実施形態では各折り返し部やシート片２６Ｆ、２６Ｒ、７１Ｆ、７１Ｒの接合を熱融着により行なう場合を示したが、接合はこれに限らず、超音波シールなどの他の接合方法を採用しても良い。 Further, in the first embodiment, the case where the movement of the magnesium electrode 15 is restricted by bending the pair of upper plate part configuration pieces 25F and 25R in an L shape has been described, but the movement of the magnesium electrode 15 can be restricted. The bending method of the pair of upper plate portion configuration pieces 25F and 25R may be changed. In addition, any one of the support of the magnesium electrode 15 by the upper plate portion configuration pieces 25F and 25R may be omitted as long as the movement of the magnesium electrode 15 can be appropriately regulated.
In the above-described embodiment, an example is described in which the bottom plate portion 21 is bent in the downward convex shape in which the lower end of the magnesium electrode 15 is fitted as the exterior body 11, but the bottom plate portion 21 may be bent upward. , And the lower end of the magnesium electrode 15 can be held. In this case, although the magnesium electrode 15 is not parallel to the air electrode 13, the movement prevention of the magnesium electrode 15 can be made stronger.
Further, although the present embodiment shows the case where the bonding of the folded portions and the sheet pieces 26F, 26R, 71F, 71R is performed by heat fusion, the bonding is not limited thereto, and other bonding methods such as ultrasonic sealing may be used. It may be adopted.
　また、上述の各実施形態では、単セルのマグネシウム空気電池１０について説明したが、使用用途に限定されること無く、使用する負荷の電圧、電流などに応じて、マグネシウム空気電池１０を複数個直列、並列に接続し使用することが可能である。また、使用時の形態に付いても特に限定されること無く、例えば、複数個のマグネシウム空気電池１０を結束バンドなどで締結したり、樹脂製のプラスチックケース、鉄箱などに収納し使用したりすることも可能である。
　さらに、上述の各実施形態では、本発明をマグネシウム空気電池１０に適用する場合を説明したが、これに限らず、公知の金属空気電池に広く適用が可能である。例えば、金属極に亜鉛、鉄、アルミニウムなどの金属またはその合金を用いることが可能である。金属極に亜鉛を用いた場合は、電解液に水酸化カリウム水溶液を用いるようにすれば良く、金属極に鉄を用いた場合は、電解液にアルカリ性水溶液を用いるようにすれば良い。また、金属極にアルミニウムを用いた場合は、水酸化ナトリウム又は水酸化カリウムを含む電解液を用いるようにすれば良い。 Further, although the single-cell magnesium-air battery 10 has been described in each of the above-described embodiments, the magnesium-air battery 10 is not limited to the use, and a plurality of magnesium-air batteries 10 are connected in series according to the voltage and current of the load used. It is possible to connect and use in parallel. In addition, there is no particular limitation on the form in use, and for example, a plurality of magnesium air batteries 10 may be fastened with a binding band or the like, or may be stored and used in a plastic case or an iron box made of resin. It is also possible.
Furthermore, although the case where this invention was applied to the magnesium air battery 10 was demonstrated in the above-mentioned each embodiment, it can apply widely not only to this but to a well-known metal air battery. For example, it is possible to use a metal such as zinc, iron, aluminum or an alloy thereof for the metal electrode. When zinc is used for the metal electrode, a potassium hydroxide aqueous solution may be used for the electrolytic solution, and when iron is used for the metal electrode, an alkaline aqueous solution may be used for the electrolytic solution. When aluminum is used for the metal electrode, an electrolyte containing sodium hydroxide or potassium hydroxide may be used.
（金属空気電池ユニット）
　次いで、金属空気電池ユニットについて説明する。
　従来の金属空気電池には積層して用いられるものがある（例えば、実公昭５８－４６５３５号公報参照）。この種の金属空気電池を積層して用いる場合には、金属空気電池の空気極の前方に大きな間隙を設けるのが一般的である。
　しかし、この種の金属空気電池は、電極間の電池反応で生じた生成物が両極間に浮遊し外装体を膨張させるという問題があった。外装体が膨張すると、空気極の前方の間隙が狭まり、或いは、間隙がなくなる恐れがあり、電池出力を低下させるという問題があった。
　また、外装体が膨張すると、空気極と金属極間の距離が大きくなり、これによっても電池出力を低下させるという問題があった。
　さらに、複数個の金属空気電池を収容する金属空気電池ユニットを構成し、収容された金属空気電池を複数個接続して使用する場合には、金属空気電池ユニットの軽量化が望まれる。そこで、以下、金属空気電池の外装体の膨張を抑え、軽量化が図れる金属空気電池ユニットの実施形態を説明する。 (Metal-air battery unit)
Next, the metal air battery unit will be described.
Some conventional metal-air batteries are used in layers (see, for example, Japanese Utility Model Publication No. 58-46535). When using this type of metal-air battery in a stacked manner, it is general to provide a large gap in front of the air electrode of the metal-air battery.
However, this type of metal-air battery has a problem that the product generated by the cell reaction between the electrodes floats between the electrodes and causes the outer package to expand. When the outer package expands, the gap in front of the air electrode may be narrowed or the gap may be lost, which causes a problem of reducing the battery output.
In addition, when the outer package expands, the distance between the air electrode and the metal electrode increases, which also causes a problem of reducing the battery output.
Furthermore, in the case where a metal air battery unit accommodating a plurality of metal air batteries is configured and used by connecting a plurality of metal air batteries accommodated, weight reduction of the metal air battery unit is desired. Therefore, an embodiment of a metal-air battery unit capable of reducing the weight of the metal-air battery by suppressing expansion of the outer package is described below.
　図２９および図３０は本発明の実施形態に係る金属空気電池ユニット１の斜視図である。金属空気電池ユニット１は、複数のマグネシウム空気電池１０を収容する外箱２１０を備え、この外箱２１０内には、収納されるマグネシウム空気電池１０が不用意に移動しないようにスペーサ２３０が二個横並びに配置されている。これら外箱２１０およびスペーサ２３０は、紙を含有したシート材、より具体的には、板紙を多層構造にして強度を高めたダンボールで製作されている。 29 and 30 are perspective views of the metal-air battery unit 1 according to the embodiment of the present invention. The metal air battery unit 1 is provided with an outer case 210 for containing a plurality of magnesium air batteries 10, and two spacers 230 are provided in the outer case 210 so as to prevent the magnesium air batteries 10 contained from being inadvertently moved. It is arranged side by side. The outer case 210 and the spacer 230 are made of a sheet material containing paper, more specifically, a cardboard having a multilayer structure of paperboard to increase its strength.
　図３１および図３２はスペーサ２３０の斜視図、図３３はスペーサ２３０の上面図、図３４はスペーサ２３０の側面図である。このスペーサ２３０は、一枚のダンボール紙を折り曲げて構成され、両側に、ポケット（電池収容部）２５０が二ヶ所設けられている。ポケット２５０には、マグネシウム空気電池１０がそれぞれ収容されている。
　マグネシウム空気電池ユニット１は、合計４個のマグネシウム空気電池１０を備え、４個のマグネシウム空気電池１０は、図２９に示すように、配線９０により、直列につながれ、ＤＣ－ＤＣ変換装置３００に接続されている。なお、ＤＣ－ＤＣ変換装置３００に接続される直前で２本の配線９０は互いに絶縁されて１本に纏められている。なお、マグネシウム空気電池１０について既述の箇所に対応する箇所は同一の符号を付して示す。 31 and 32 are perspective views of the spacer 230, FIG. 33 is a top view of the spacer 230, and FIG. 34 is a side view of the spacer 230. The spacer 230 is formed by bending a sheet of cardboard paper, and two pockets (battery storage units) 250 are provided on both sides. The magnesium air battery 10 is accommodated in the pocket 250, respectively.
The magnesium-air battery unit 1 is provided with a total of four magnesium-air batteries 10, and the four magnesium-air batteries 10 are connected in series by a wire 90 and connected to the DC-DC converter 300 as shown in FIG. It is done. The two wires 90 are insulated from each other and integrated into one immediately before being connected to the DC-DC converter 300. In addition, the location corresponding to the location as stated above about the magnesium air battery 10 attaches and shows the same code | symbol.
　マグネシウム空気電池１０は、図３５に示すように、折り曲げ自在な１枚のシート材を２つ折りして重ね、その両側縁を接合し、折り曲げ加工して形成された中空箱形状の外装体１１を備えている。外装体１１には、空気極１３が装着されるとともに、空気極１３と対向するようにマグネシウム極（金属極）１５が収容され、液面ＵＬまで食塩水などの電解液が入れられる。マグネシウム空気電池１０は一次電池であり、空気極１３が正極として作用し、マグネシウム極１５が負極として作用する。 As shown in FIG. 35, the magnesium-air battery 10 is a hollow box-shaped exterior body 11 formed by folding and folding one foldable sheet material in two, bonding the side edges of the sheet material, and bending it. Have. The air electrode 13 is attached to the exterior body 11, and the magnesium electrode (metal electrode) 15 is accommodated to face the air electrode 13, and an electrolytic solution such as a saline solution is filled up to the liquid level UL. The magnesium-air battery 10 is a primary battery, and the air electrode 13 acts as a positive electrode, and the magnesium electrode 15 acts as a negative electrode.
　外装体１１は、矩形の底板部２１と、矩形の前壁部２２と、矩形の後壁部２３と、左右の側壁部２４とを一体に有している。前壁部２２には矩形の開口部２２Ｋが設けられ、開口部２２Ｋに空気極１３が配置されている。
　底板部２１は、側面視で下方凸のＶ字形に形成される。マグネシウム極１５の下端は、底板部２１の傾斜に案内されて下方凸の部分２１Ｔに嵌り、マグネシウム極１５の下端が容易に位置決めされる。
　前壁部２２、および後壁部２３の上端は折り曲げられる。第１折り曲げ部２５Ｆ１、２５Ｒ１は、マグネシウム極１５と空気極１３との離間距離を適正に保ち、第２折り曲げ２５Ｆ２、２５Ｒ２は、マグネシウム極１５の上部を支持する。マグネシウム極１５の両側には同一幅の隙間ＳＦ、ＳＲが設けられる。 The exterior body 11 integrally has a rectangular bottom plate 21, a rectangular front wall 22, a rectangular rear wall 23, and left and right side walls 24. The front wall portion 22 is provided with a rectangular opening 22K, and the air pole 13 is disposed in the opening 22K.
The bottom plate portion 21 is formed in a downward convex V shape in a side view. The lower end of the magnesium pole 15 is guided by the inclination of the bottom plate portion 21 and fitted in the downward convex portion 21T, and the lower end of the magnesium pole 15 is easily positioned.
The upper ends of the front wall 22 and the rear wall 23 are bent. The first bent portions 25F1 and 25R1 maintain an appropriate distance between the magnesium electrode 15 and the air electrode 13, and the second bent portions 25F2 and 25R2 support the upper portion of the magnesium electrode 15. Clearances SF and SR of the same width are provided on both sides of the magnesium electrode 15.
　図３６はマグネシウム空気電池１０の外装体１１上部の折り曲げ前の上部部分斜視図である。図３５および図３６に示すように、マグネシウム極１５（不図示のタブ部１５Ｔを含む）は、外装体１１内に完全に収容され、第２折り曲げ部２５Ｆ２、２５Ｒ２は、２つの切り込み２５Ｃによりそれぞれ３分割される。
　第２折り曲げ部２５Ｆ２の両端部分２５Ｆ２－１は、図３６に示すように、外装体１１内に収納されているマグネシウム極１５の上部手前に差し込まれ、中央部分２５Ｆ２－２はマグネシウム極１５の上端を超えて奥に差し込まれる。
　一方、後壁部２３の第２折り曲げ部２５Ｒ２は、両端部分２５Ｒ２－１が、マグネシウム極１５の上部を超えて奥に差し込まれ、前壁部２２の第２折り曲げ部２５Ｆ２の両端部分２５Ｆ２－１と接する。中央部分２５Ｒ２－２はマグネシウム極１５の上部の手前に差し込まれ、前壁部２２の第２折り曲げ部２５Ｆ２の中央部分２５Ｆ２－２に接する。この様にすることで、マグネシウム極１５の上部は挟み込む様にして支持され、その固定をより確実強固なものとする。 FIG. 36 is a top partial perspective view of the upper part of the exterior body 11 of the magnesium-air battery 10 before being folded. As shown in FIGS. 35 and 36, the magnesium electrode 15 (including the tab portion 15T not shown) is completely accommodated in the exterior body 11, and the second bent portions 25F2 and 25R2 are respectively formed by the two notches 25C. It is divided into three.
As shown in FIG. 36, both end portions 25F2-1 of the second bent portion 25F2 are inserted in front of the upper portion of the magnesium electrode 15 housed in the exterior body 11, and the central portion 25F2-2 is the upper end of the magnesium electrode 15. It is inserted in the back beyond.
On the other hand, in the second bent portion 25R2 of the back wall portion 23, both end portions 25R2-1 are inserted into the back beyond the upper portion of the magnesium electrode 15, and both end portions 25F2-1 of the second bent portion 25F2 of the front wall portion 22. I am in contact with The central portion 25R2-2 is inserted in front of the upper portion of the magnesium pole 15, and contacts the central portion 25F2-2 of the second bent portion 25F2 of the front wall portion 22. By doing this, the upper portion of the magnesium electrode 15 is supported in a sandwiching manner, and the fixation is made more secure and strong.
　側壁部２４上端の折り曲げ部２４Ｕは、Ｌ字状に折り曲げられる。折り曲げ部２４Ｕの先端は、外装体１１の組立時に、第１折り曲げ部２５Ｆ１、２５Ｒ１に設けたスリット２５Ｓへ挿入される。これにより、折り曲げ加工される第１折り曲げ部２５Ｆ１、２５Ｒ１などの復元が防止され、外装体１１の上面が封口される。なお、図３６中、一点鎖線で示される部分は山折り箇所である。また、マグネシウム極１５に接続された配線は外装体１１の折り曲げ箇所に空く隙間を通って外装体１１の外へ導引される。 The bent portion 24U at the upper end of the side wall portion 24 is bent in an L shape. The tip of the bent portion 24U is inserted into the slit 25S provided in the first bent portions 25F1 and 25R1 when the exterior body 11 is assembled. Thereby, restoration of the first bent portions 25F1, 25R1 and the like to be bent and processed is prevented, and the upper surface of the exterior body 11 is sealed. In FIG. 36, a portion indicated by an alternate long and short dash line is a mountain fold. Further, the wire connected to the magnesium electrode 15 is guided to the outside of the exterior body 11 through a gap that is open at the bent portion of the exterior body 11.
　図３７はスペーサ２３０の展開図である。
　スペーサ２３０は、一枚のシート状のダンボール紙２７０を折り曲げて形成される。ダンボール紙２７０はプレスにより金型で裁断される。
　スペーサ２３０は、ダンボール紙３００に限定されず、例えば厚紙で形成してもよく、或いは、樹脂製のシートで形成しても良い。
　ダンボール紙２７０の中央部には、上面接続部２３４が配置されている。上面接続部２３４の両端には、折り線２７１、２７１を介して、それぞれ内側側面部２３２、２３２が配置され、折り線２７１、２７１は山折りにされる。内側側面部２３２、２３２には、折り線２７３、２７３を介して、底面部２３３、２３３が接続されており、底面部２３３、２３３には、折り線２７５、２７５を介して、外側側面部２３１、２３１が接続されている。折り線２７３、２７３、および折り線２７５、２７５は谷折りにされる。 FIG. 37 is a developed view of the spacer 230. FIG.
The spacer 230 is formed by bending a sheet of cardboard paper 270. The cardboard 270 is cut with a die by a press.
The spacer 230 is not limited to the cardboard 300, and may be formed of, for example, cardboard, or may be formed of a resin sheet.
An upper surface connection portion 234 is disposed at a central portion of the cardboard 270. The inner side portions 232, 232 are disposed at both ends of the upper surface connecting portion 234 via the folding lines 271, 271, respectively, and the folding lines 271, 271 are mountain-folded. Bottom portions 233, 233 are connected to the inner side portions 232, 232 via fold lines 273, 273, and outer side portions 231 are formed on the bottom portions 233, 233 via fold lines 275, 275. , 231 are connected. Fold lines 273, 273 and fold lines 275, 275 are valley folded.
　内側側面部２３２、２３２の両辺には、折り線２３７ａ、２３７ａを介して、ツメ保持部２３７、２３７が備えられている。ツメ保持部２３７、２３７には、折り線２３６ａ、２３６ａを介して、上部ツメ２３６、２３６が備えられている。
　また、内側側面部２３２、２３２の両辺には、折り線２３５ａ、２３５ａを介して、下部ツメ２３５、２３５が備えられている。外側側面部２３１、２３１の両辺には、折り線２３８ａ、２３８ａを介して、ツメ孔保持部２３８が備えられている。ツメ孔保持部２３８には、ツメ孔２３９、２３９が切りかかれている。 The nail | claw holding parts 237 and 237 are provided in the both sides of the inner side surface parts 232 and 232 via the folding lines 237a and 237a. The claw holding portions 237, 237 are provided with upper claws 236, 236 via the fold lines 236a, 236a.
Further, lower claws 235, 235 are provided on both sides of the inner side surface portions 232, 232 via fold lines 235a, 235a. A nail hole holding portion 238 is provided on both sides of the outer side surface portions 231, 231 via fold lines 238a, 238a. The claw holes 239 and 239 are cut in the claw hole holding portion 238.
　上面接続部２３４には、一対の円形の空気口部２４６、２４６が形成され、これら空気口部２４６、２４６の中間部に長方形の溝部２４５が形成されている。
　内側側面部２３２、２３２には、枠部材２４４を残して空気極開口部２３２Ｋが形成され、空気極開口部２３２Ｋには、矩形の溝部２３２Ｍが形成されている。
　底面部２３３、２３３には、内側側面部２３２、２３２に跨って、一対のフローティング支持部２５１、２５１が配置されている。フローティング支持部２５１、２５１は、それぞれ両側に切り込み２５１ａ、２５１ａを備えている。それぞれの切り込み２５１ａ、２５１ａの間には、３つの折り線２５１ｂ、２５１ｃ、２５１ｄが配置される。 The upper surface connection portion 234 is formed with a pair of circular air ports 246, 246, and a rectangular groove 245 is formed in the middle of the air ports 246, 246.
An air electrode opening 232K is formed in the inner side surface parts 232, 232 except for the frame member 244, and a rectangular groove 232M is formed in the air electrode opening 232K.
In the bottom surface portion 233, 233, a pair of floating support portions 251, 251 is disposed across the inner side surface portions 232, 232. The floating support portions 251, 251 respectively have notches 251a, 251a on both sides. Three fold lines 251b, 251c, 251d are disposed between the notches 251a, 251a.
　このスペーサ２３０の折り手順を説明する。
　まず、上面接続部２３４の両端の折り線２７１、２７１を山折りし、その両側の折り線２７３、２７３、および折り線２７５、２７５を谷折りする。すると、図３２に示すように、側面部視で、略Ｗ字形態に折り曲げられる。
　ついで、下部ツメ２３５、２３５が折り曲げられ、下部ツメ同士が嵌合される。これによって、図３４に示すように、一対の内側側面部２３２、２３２が平行に保持される。そして、内側側面部２３２、２３２で囲われた部分が、空気が滞留する間隙としての滞留部２６０を構成する。
　図３２に示すように、ツメ保持部２３７、２３７とツメ孔保持部２３８が折り曲げられ、ツメ保持部２３７、２３７の上部ツメ２３６、２３６が、ツメ孔保持部２３８のツメ孔２３９、２３９に嵌合される。これによって、図３４に示すように、外側側面部２３１、２３１と内側側面部２３２、２３２が平行に保持される。外側側面部２３１、２３１と内側側面部２３２、２３２で囲われた部分が、ポケット２５０を構成する。ポケット２５０には、図３１に示すように、マグネシウム空気電池１０がそれぞれ収容される。マグネシウム空気電池１０は、空気極１３を、内側側面部２３２、２３２の空気極開口部２３２Ｋに向けて収容される。 The folding procedure of the spacer 230 will be described.
First, the fold lines 271 and 271 at both ends of the upper surface connection portion 234 are mountain-folded, and the fold lines 273 and 273 at the both sides and the fold lines 275 and 275 are valley-folded. Then, as shown in FIG. 32, in a side view, it is bent in a substantially W-like shape.
Then, the lower claws 235, 235 are bent and the lower claws are fitted. As a result, as shown in FIG. 34, the pair of inner side surface portions 232, 232 are held in parallel. And the part enclosed by the inner side surface parts 232 and 232 comprises the retention part 260 as a gap | interval which air retains.
As shown in FIG. 32, the claw holding portions 237, 237 and the claw hole holding portion 238 are bent, and the upper claws 236, 236 of the claw holding portions 237, 237 fit into the claw holes 239, 239 of the claw hole holding portion 238. United. As a result, as shown in FIG. 34, the outer side surface portions 231, 231 and the inner side surface portions 232, 232 are held in parallel. The portion surrounded by the outer side surface portions 231, 231 and the inner side surface portions 232, 232 constitutes a pocket 250. As shown in FIG. 31, the magnesium air battery 10 is accommodated in the pocket 250, respectively. The magnesium-air battery 10 is accommodated with the air electrode 13 directed toward the air electrode opening 232 K of the inner side surface portions 232, 232.
　また、図３７を参照し、底面部２３３、２３３には、上述のように、一対のフローティング支持部２５１、２５１が配置されている。このフローティング支持部２５１、２５１は、切り込み２５１ａ、２５１ａを備え、各切り込み２５１ａ、２５１ａ間に、３つの折り線２５１ｂ、２５１ｃ、２５１ｄを備える。そのため、フローティング支持部２５１を、ポケット２５０、２５０の内部に押し込むと、折り線２５１ｂが谷折り、折り線２５１ｃが山折り、折り線２５１ｄが谷折りされ、図３４に示すように、フローティング支持部２５１がＬ字の形状に折り曲げられる。このフローティング支持部２５１は、マグネシウム空気電池１０の外装体１１の底板部２１（図３５）をフローティング状態で支持する。したがって、シート材の折り込み加工により外装体１１の底板部２１の両端に形成される下方突出部２４Ｌ（図３５）を保護すると共に外箱２１０の底部に衝撃が作用しても、マグネシウム空気電池１０の破損を防止できる。
　なお、スペーサ２３０として用いたダンボール紙は、その表面をＰＥなどで片面或いは両面をラミネート加工しても良い。この場合は空気中の湿気の吸収を抑えることができ、長期保存した場合の劣化を防止できる。 Further, referring to FIG. 37, in the bottom surface portions 233, 233, as described above, the pair of floating support portions 251, 251 are disposed. The floating support portions 251, 251 have notches 251a, 251a, and three fold lines 251b, 251c, 251d between the notches 251a, 251a. Therefore, when the floating support portion 251 is pushed into the pockets 250, 250, the fold line 251b is valley-folded, the fold line 251c is mountain-folded, and the fold line 251d is valley-folded, as shown in FIG. 251 is bent into an L shape. The floating support portion 251 supports the bottom plate portion 21 (FIG. 35) of the exterior body 11 of the magnesium-air battery 10 in a floating state. Therefore, the magnesium air battery 10 is protected even if an impact acts on the bottom of the outer case 210 while protecting the lower projecting portions 24L (FIG. 35) formed on both ends of the bottom plate 21 of the exterior body 11 by folding the sheet material. Can prevent the damage.
The cardboard used as the spacer 230 may have its surface laminated with PE or the like on one side or both sides. In this case, absorption of moisture in the air can be suppressed, and deterioration in long-term storage can be prevented.
　図３８は外箱２１０の展開図である。
　外箱２１０は、一枚のシート状のダンボール紙２２０を折り曲げて形成される。ダンボール紙２２０はプレスにより金型で裁断される。
　外箱２１０は、ダンボール紙２２０に限定されず、例えば厚紙で形成してもよく、或いは、樹脂製のシートで形成しても良い。
　ダンボール紙２２０は、中央部に横並びに、折り線３１１、３１３、３１５を介して、突片付き側面部２１１（２１１Ａ、２１１Ｂ）と、突片の無い側面部２１２（２１２Ａ、２１２Ｂ）とを交互に備える。側面部２１１Ａの上辺には、折り線３２１を介して、短蓋２２１が配置され、側面部２１１Ｂの上辺には、折り線３２３を介して、嵌め込み蓋２２２が配置され、側面部２１２Ｂの上辺には、折り線３２７を介して、上蓋２２３が配置される。嵌め込み蓋２２２には折り線３２５を介して片２２４が配置され、片２２４には爪部材２２５が配置される。上蓋２２３には折り線３２８を介して片２２６が配置される。ここで短蓋２２１、嵌め込み蓋２２２、上蓋２２３は蓋部材を構成する。
　突片付き側面部２１１（２１１Ａ、２１１Ｂ）の下辺には折り線３１９を介して底面部２１５、２１５が配置され、突片の無い側面部２１２（２１２Ａ、２１２Ｂ）の下辺には折り線３２０を介して嵌め込み部付き底面部２１６、２１６が配置される。底面部２１５、２１５、および嵌め込み部付き底面部２１６、２１６は底部材を構成する。 FIG. 38 is a developed view of the outer case 210. FIG.
The outer case 210 is formed by bending a sheet of cardboard 220. The cardboard 220 is cut with a die by a press.
The outer box 210 is not limited to the cardboard 220, and may be formed of, for example, a cardboard, or may be formed of a resin sheet.
The corrugated paper sheet 220 has side portions 211 with protrusions (211A, 211B) and side portions 212 without protrusions (212A, 212B) alternately in the center along the fold lines 311, 313, 315. Prepare. The short lid 221 is disposed on the upper side of the side surface portion 211A via the folding line 321, and the fitting lid 222 is disposed on the upper side of the side surface portion 211B via the folding line 323, and on the upper side of the side surface portion 212B. The upper lid 223 is disposed via the folding line 327. A piece 224 is disposed on the fitting lid 222 via a fold line 325, and a claw member 225 is disposed on the piece 224. A piece 226 is disposed on the upper lid 223 via a fold line 328. Here, the short lid 221, the fitting lid 222, and the upper lid 223 constitute a lid member.
The bottoms 215 and 215 are disposed on the lower side of the protrusion-formed side portions 211 (211A and 211B) via the fold line 319, and the lower sides of the side portions 212 (212A and 212B) on which the protrusions do not exist via the fold line 320. The bottom portion 216, 216 with a bottom portion is disposed. The bottoms 215, 215 and the bottoms 216, 216 with the inset form bottoms.
　一枚のダンボール紙２２０は、折り線３１１、３１３、３１５で折り曲げられ、突片の無い側面部２１２Ｂに繋がる片２１３と、突片付き側面部２１１Ａとが糊付けされ、外箱２１０の側面部が形成される。ついで、底面部２１５、２１５と、嵌め込み部付き底面部２１６、２１６とが嵌合し、底部材が形成される。さらに、図３０に示すように、短蓋２２１、嵌め込み蓋２２２、上蓋２２３により蓋部材が形成される。 A sheet of cardboard 220 is folded at the folding lines 311, 313, 315, and the piece 213 connected to the side portion 212B without a protrusion is glued with the side portion 211A with a protrusion, and the side portion of the outer case 210 is formed. Be done. Then, the bottom portions 215, 215 and the bottom portions 216, 216 with fitting portions are fitted to form a bottom member. Furthermore, as shown in FIG. 30, the short cover 221, the fitting cover 222, and the upper cover 223 form a cover member.
　本実施の形態では、図３８に示すように、突片付き側面部２１１（２１１Ａ、２１１Ｂ）に、各４個の突片（間隙規制部材）８１が設けられている。突片８１は、一対の上突片８１Ａ、８１Ａと、一対の下突片８１Ｂ、８１Ｂを備えている。各突片８１は、同一の形態であり、側面部２１１に切り離し予定部８２、例えばミシン目や切り込みなどを介して接続されている。各突片８１は、先端に、爪部８１Ｃが形成されている。各突片８１は、切り離し予定部８２で側面部２１１から切り離されたときには、連結部８３で側面部２１１に連結される。各突片８１（８１Ａ、８１Ｂ）の幅Ｗは、スペーサ２３０の内側側面部２３２、２３２の内法寸法Ｗ２（図３２）と等しく形成される。各突片８１の長さＬ３（図３８）は、図３１に示すスペーサ２３０のツメ保持部２３７、２３７から溝部２３２Ｍに至るまでの長さＬ４と等しく形成される。 In the present embodiment, as shown in FIG. 38, four projecting pieces (gap regulating members) 81 are provided on the projecting side parts 211 (211A, 211B). The protrusion 81 includes a pair of upper protrusions 81A and 81A and a pair of lower protrusions 81B and 81B. Each projecting piece 81 has the same form, and is connected to the side surface portion 211 via a portion to be separated 82 such as a perforation or a cut. Each protrusion 81 has a claw 81C formed at the tip. Each projecting piece 81 is connected to the side surface portion 211 at the connecting portion 83 when it is separated from the side surface portion 211 at the portion 82 to be separated. The width W of each protrusion 81 (81A, 81B) is equal to the internal dimension W2 (FIG. 32) of the inner side surface portions 232, 232 of the spacer 230. The length L3 (FIG. 38) of each protrusion 81 is formed equal to the length L4 from the claw holding portions 237, 237 of the spacer 230 shown in FIG. 31 to the groove 232M.
　この外箱２１０には、図２９に示すように、マグネシウム空気電池１０を、互いに空気極１３が、滞留部２６０を介して向き合うように２個収容したスペーサ２３０（図３１）が、二個横並びに収容される。スペーサ２３０が収容された後、上突片８１Ａ、８１Ａと、下突片８１Ｂ、８１Ｂが、外箱２１０の内側に押し込まれる。すると、各突片８１が、外箱２１０の両側から外箱２１０内に突出する。
　各突片８１は、爪部８１Ｃ（図３８）が溝部２３２Ｍ（図３１）に嵌合し、溝部２３２Ｍの上辺または下辺に引っ掛かるまで、内側に押し込まれる。 As shown in FIG. 29, in the outer case 210, two spacers 230 (FIG. 31) in which two air electrodes 13 are accommodated so as to face each other with the air electrode 13 facing each other as shown in FIG. Housed in After the spacer 230 is accommodated, the upper protruding pieces 81A, 81A and the lower protruding pieces 81B, 81B are pushed into the inside of the outer case 210. Then, the respective projecting pieces 81 project into the outer case 210 from both sides of the outer case 210.
Each protrusion 81 is pushed inward until the claw portion 81C (FIG. 38) fits in the groove portion 232M (FIG. 31) and is caught on the upper side or the lower side of the groove portion 232M.
　本実施形態では、外箱２１０に設けた各突片８１の幅Ｗが、スペーサ２３０の内側側面部２３２、２３２の内法寸法Ｗ２（図３２）と等しく形成されるため、各突片８１が、外箱２１０の内側に押し込まれると、各突片８１の剛性によって、内側側面部３２、３２間の寸法Ｗ２が規制される。マグネシウム空気電池１０は、空気極１３、マグネシウム極１５間の電池反応で生成物が生じ、この生成物が空気極１３、マグネシウム極１５間の空いているスペースに浮遊して、前壁部２２を膨張させ、その結果により、空気極１３を膨張させるのが一般的である。
　本実施の形態では、各突片８１の剛性によって、外装体１１の膨張を抑え、空気極１３の前方の滞留部２６０の幅Ｗ２を規定通りに確保することができる。よって、電池出力の低下を防止できる。さらにまた、外装体１１の膨張が抑えられるため、空気極１３とマグネシウム極（金属極）１５間の距離が規定の距離に維持され、これによっても、電池出力の低下を防止できる。
　各突片８１の長さＬ３（図３８）は、図３１に示すスペーサ２３０のツメ保持部２３７、２３７から溝部２３２Ｍに至るまでの長さＬ４と等しく形成されるため、各突片８１は、空気極開口部２３２Ｋの外側の枠部材２４４を抑えることとなる。したがって、各突片８１によって、空気極開口部２３２Ｋが塞がれることがない。
　また、図３１に示すように、ツメ孔保持部２３８の内面と、マグネシウム空気電池１０との間に両者間の間隙を規制する規制部材８５を配置しても良い。上述した各突片８１によりマグネシウム空気電池１０の幅方向の間隙を維持でき、この規制部材８５によりマグネシウム空気電池１０の長さ方向の間隙を維持することができる。
　なお、外箱２１０として用いたダンボール紙２２０は、その表面をＰＥなどで片面或いは両面をラミネート加工しても良い。この場合は空気中の湿気の吸収を抑えることができ、長期保存した場合の劣化を防止できる。 In the present embodiment, the width W of each protrusion 81 provided on the outer case 210 is formed equal to the internal dimension W2 (FIG. 32) of the inner side surface portions 232, 232 of the spacer 230. When pushed into the inside of the outer case 210, the rigidity of each of the protrusions 81 regulates the dimension W2 between the inner side surface portions 32, 32. In the magnesium-air battery 10, a product is produced by a battery reaction between the air electrode 13 and the magnesium electrode 15, and this product floats in the space between the air electrode 13 and the magnesium electrode 15 to form the front wall 22 In general, the cathode 13 is expanded by the expansion.
In the present embodiment, the rigidity of each protrusion 81 can suppress the expansion of the exterior body 11 and ensure the width W2 of the staying portion 260 in front of the air electrode 13 as specified. Therefore, a drop in battery output can be prevented. Furthermore, since the expansion of the exterior body 11 is suppressed, the distance between the air electrode 13 and the magnesium electrode (metal electrode) 15 is maintained at a specified distance, which also prevents the reduction of the battery output.
The length L3 (FIG. 38) of each protrusion 81 is formed equal to the length L4 from the claw holding portions 237 and 237 of the spacer 230 shown in FIG. 31 to the groove 232M. The frame member 244 on the outside of the air pole opening 232 K is to be suppressed. Therefore, the air electrode opening 232K is not blocked by the protrusions 81.
Further, as shown in FIG. 31, a restricting member 85 for restricting the gap between the inner surface of the claw hole holding portion 238 and the magnesium air battery 10 may be disposed. The gaps in the width direction of the magnesium-air battery 10 can be maintained by the respective projecting pieces 81 described above, and the gaps in the longitudinal direction of the magnesium-air battery 10 can be maintained by the regulating member 85.
The cardboard 220 used as the outer box 210 may have its surface laminated with PE or the like on one side or both sides. In this case, absorption of moisture in the air can be suppressed, and deterioration in long-term storage can be prevented.
　本実施の形態では、スペーサ２３０の中央部に、内側側面部２３２、２３２により囲われた滞留部２６０が形成され、この滞留部２６０が、各突片８１が押し込まれた後の外箱２１０の開口（空気流通孔）を介して、外箱２１０の外側に連通する。したがって、外箱２１０の外の空気を、滞留部２６０、およびスペーサ２３０の空気極開口部２３２Ｋを介して、マグネシウム空気電池１０の空気極７２に常に取り入れることができる。
　スペーサ２３０の上面接続部２３４に、空気口部２４６、２４６が形成されているため、滞留部２６０に入った空気が、空気口部２４６、２４６を経て、外箱２１０内を還流する。したがって、マグネシウム空気電池１０の反応により、外箱２１０の内部が暖まった場合にも、空気により冷却されて、適温を保つことができる。
　この空気口部２４６、２４６は、マグネシウム空気電池１０と共にスペーサ２３０を外箱２１０に収容する際の指掛けとして利用できる。
　本実施の形態では、スペーサ３０、および外箱２１０が、共に、一枚のダンボール紙２７０、２２０を組み立てて制作されている。そのため、金属でスペーサ２３０や外箱２１０を作製する場合と比べ、軽量化が図れる。 In the present embodiment, a retention portion 260 surrounded by the inner side surface portions 232, 232 is formed at the central portion of the spacer 230, and the retention portion 260 is a portion of the outer case 210 after each projection 81 is pushed. It communicates with the outside of the outer case 210 through the opening (air passage hole). Therefore, air outside the outer case 210 can always be taken into the air electrode 72 of the magnesium-air battery 10 through the stagnation portion 260 and the air electrode opening 232 K of the spacer 230.
Since the air ports 246 and 246 are formed in the upper surface connecting portion 234 of the spacer 230, the air that has entered the retention portion 260 flows back through the outer case 210 through the air ports 246 and 246. Therefore, even if the inside of the outer case 210 is warmed up by the reaction of the magnesium-air battery 10, it can be cooled by the air to maintain an appropriate temperature.
The air ports 246, 246 can be used as finger hooks when the spacer 230 is housed in the outer case 210 together with the magnesium air battery 10.
In the present embodiment, the spacer 30 and the outer box 210 are both manufactured by assembling one sheet of cardboard 270, 220. Therefore, weight reduction can be achieved as compared to the case of manufacturing the spacer 230 and the outer case 210 with metal.
　本実施の形態では、図２９に示すように、蓋部材が、短蓋２２１、嵌め込み蓋２２２、上蓋２２３により構成されている。上蓋２２３を開けると、図３０に示すように、短蓋２２１と嵌め込み蓋２２２が露出する。
　この嵌め込み蓋２２２は、図３８に示す折り線３２５で片２２４が折り曲げられ、図３０に示すように、片２２４に設けた爪部材２２５が、スペーサ２３０の上面接続部２３４の溝部２４５に嵌合されている。この嵌め込み蓋２２２は、配線９０を隠しており、上蓋２２３を開けた状態での該配線９０に物を引っ掛けたりする事故などを防止できる。なお、ＤＣ－ＤＣ変換装置３００は、短蓋２２１の下に収納されて、ユニット使用時に上蓋２２３と嵌め込み蓋２２２を開けて取り出し、マグネシウム空気電池１０に電解液を注入した後、携帯電話などの充電に使用される。 In the present embodiment, as shown in FIG. 29, the lid member is configured of a short lid 221, a fitting lid 222, and an upper lid 223. When the upper lid 223 is opened, as shown in FIG. 30, the short lid 221 and the fitting lid 222 are exposed.
In this fitting lid 222, the piece 224 is bent at the folding line 325 shown in FIG. 38, and as shown in FIG. 30, the claw member 225 provided on the piece 224 fits in the groove portion 245 of the upper surface connecting portion 234 of the spacer 230. It is done. The fitting lid 222 hides the wire 90 and can prevent an accident or the like from being caught by the wire 90 in a state where the upper lid 223 is opened. The DC-DC conversion device 300 is housed under the short lid 221, and when the unit is used, the upper lid 223 and the fitting lid 222 are opened and taken out, and after injecting the electrolytic solution into the magnesium air battery 10, Used for charging.
　なお、本発明は、これに限定されるものではない。例えばスペーサ２３０に形成される滞留部２６０に対し、突片８１を二ヶ所設けたが、一ヶ所でもよく、三ヶ所以上でも良い。
　更に、突片８１は、ユニット１の使用直前に押し込んでも良く、その場合は、使用までの保管中は突片８１を押し込むことで形成される外箱２１０の開口を塞いでいるので、空気極１３を保護でき好ましい。
　更に、枠部材２４４はスペーサ２３０と別体で形成しても良く、この枠部材２４４があることで、突片８１による膨張抑制効果が外装体１１の壁部の全周に及び好ましい。
　更に、スペーサ２３０を逆Ｕ字状に形成し、このスペーサ２３０をマグネシウム空気電池１０間に介在させてもよく、板状のものを多数枚重ねて用いても良い。更に、空気極１３と対向して形成される空気が滞留する間隙は、スペーサ２３０を利用して形成するものに限らず、外箱２１０内にマグネシウム空気電池１０が貫通する穴を形成した板を上下に配置し、その穴内にマグネシウム空気電池１０を挿入して間隙を形成するようにしても良いし、突片８１のみをマグネシウム空気電池１０間に押し込んで形成するようにしても良いが、実施形態に示したものが望ましい。 The present invention is not limited to this. For example, although the protruding pieces 81 are provided at two locations with respect to the retaining portion 260 formed in the spacer 230, the number may be one, three or more.
Furthermore, the projecting piece 81 may be pressed immediately before use of the unit 1, in which case the air pole is closed because the opening of the outer case 210 formed by pushing the projecting piece 81 is blocked during storage until use. 13 is preferable because it can be protected.
Furthermore, the frame member 244 may be formed separately from the spacer 230, and the presence of the frame member 244 makes it possible to suppress the expansion by the projecting piece 81 over the entire circumference of the wall portion of the exterior body 11.
Furthermore, the spacer 230 may be formed in an inverted U-shape, and the spacer 230 may be interposed between the magnesium-air batteries 10, or a plurality of plate-like members may be stacked and used. Further, the gap formed facing the air electrode 13 is not limited to the gap formed by utilizing the spacer 230, and a plate in which a hole through which the magnesium-air battery 10 passes is formed in the outer case 210. The magnesium air battery 10 may be vertically disposed and the magnesium air battery 10 may be inserted into the hole to form a gap, or only the protrusion 81 may be formed by pushing the magnesium air battery 10 between the holes. What is shown in the form is desirable.
　更に、突片８１を省略しても良い。図３９および図４０は突片８１を備えない金属空気電池ユニット１の実施例を示している。図３９に示す実施例では、マグネシウム空気電池１０と垂直に交わる側面部２１１Ａ、２１１Ｂの略全体に空気流通孔９２を設けた外箱２１０を用いた金属空気ユニット１であり、より具体的には、各側面部２１１Ａ、２１１Ｂに縦横に等間隔で７個ずつの空気流通孔９２を設けている。
　側面部２１１Ａ、２１１Ｂの略全体に空気流通孔９２を設けることで、外箱２１０内の空き空間（スペーサ２３０内の滞留部２６０やスペーサ２３０上方の空間等）を、空気流通孔９２を介して外部に連通させることができる。
　このため、マグネシウム空気電池１０の反応により温度上昇した内部空気を、空気流通孔９２を介して外部に排出し、また、外部空気によりマグネシウム空気電池１０を冷却することができる。従って、外箱２１０内の各マグネシウム空気電池１０を適温に保つとともに、温度を均等化させ易くなる。 Furthermore, the protrusion 81 may be omitted. 39 and 40 show an embodiment of the metal-air battery unit 1 without the projecting piece 81. FIG. In the embodiment shown in FIG. 39, it is the metal air unit 1 using the outer case 210 in which the air flow holes 92 are provided substantially in the entire side portions 211A and 211B intersecting perpendicularly with the magnesium air battery 10, more specifically In each side surface portion 211A, 211B, seven air circulation holes 92 are provided at equal intervals in the vertical and horizontal directions.
By providing the air flow holes 92 in substantially the entire side surface portions 211A and 211B, the empty space in the outer case 210 (the space in the spacer 230 and the space above the spacer 230, etc.) is provided via the air flow holes 92. It can communicate with the outside.
Therefore, the internal air whose temperature has been raised by the reaction of the magnesium-air battery 10 can be discharged to the outside through the air flow holes 92, and the magnesium-air battery 10 can be cooled by the external air. Therefore, the magnesium-air batteries 10 in the outer case 210 can be maintained at an appropriate temperature, and the temperatures can be easily equalized.
　図４０に示す実施例は、一対の側面部２１１Ａ、２１１Ｂに空気流通孔９２を設ける点では図３９の場合と同じであるが、空気流通孔９２を外箱２１０内の空き空間（スペーサ２３０内の滞留部２６０やスペーサ２３０上方の空間等）に連通する領域に限定して設ける点が図３９の場合と異なっている。
　この構成によっても、マグネシウム空気電池１０の反応により温度上昇した内部空気を、空気流通孔９２を介して外部に排出し、また、外部空気によりマグネシウム空気電池１０を冷却することができる。つまり、マグネシウム空気電池１０の冷却に寄与する領域に限定して空気流通孔９２を設け、冷却に寄与しない領域に空気流通孔９２を設けないようにしている。
　このため、空気流通孔９２の数や、空気流通孔９２のトータル面積を低減することができ、その分、外箱２１０の強度向上を図り易くなる。なお、図３９および図４０では、外箱２１０の蓋部材（嵌め込み蓋２２２）の下方に折り返される片２２４に、配線９０を通す孔９０Ｈを設けている。 The embodiment shown in FIG. 40 is the same as the case of FIG. 39 in that the air flow holes 92 are provided in the pair of side surface portions 211A and 211B, but the air flow holes 92 This embodiment is different from the case of FIG. 39 in that it is limited to a region communicating with the retaining portion 260 and the space above the spacer 230).
Also with this configuration, the internal air whose temperature has been raised by the reaction of the magnesium-air battery 10 can be discharged to the outside through the air flow holes 92, and the magnesium-air battery 10 can be cooled by the external air. That is, the air flow holes 92 are provided only in the area that contributes to the cooling of the magnesium-air battery 10, and the air flow holes 92 are not provided in the area that does not contribute to the cooling.
Therefore, the number of air flow holes 92 and the total area of the air flow holes 92 can be reduced, and the strength of the outer case 210 can be easily improved. In FIG. 39 and FIG. 40, a hole 90H through which the wire 90 passes is provided in the piece 224 which is folded back below the lid member (the fitting lid 222) of the outer case 210.
（金属空気電池の電池反応を再開させ易くした構成）
　ところで、従来の金属空気電池には、金属極に、主反応物質である金属元素に加えて他の元素を調合した合金を使用したものがある（例えば、特開２０１２－２３４７９９号公報参照）。この特許文献には、金属極の自己放電反応による水素ガスの発生を抑制するために、金属極にアルミニウム（Ａｌ）や亜鉛（Ｚｎ）などを添加したマグネシウム合金を使用することが記載されている。
　上記の添加元素は、合金の表面に自己反応を阻害し水素の発生を抑制する保護被膜の形成に大きく関与することが知られている。発明者らが検討したところ、保護被膜は電池反応を阻害することがあり、電池を使用停止して休止させた後に再び電池を使用しようとしたときに電池反応が再開し難くなるおそれがあった。
　そこで、電池反応を再開させ易くしたマグネシウム空気電池１０のシステム構成（以下、金属空気電池システム１０Ｓと言う）の実施形態を以下に説明する。なお、金属空気空電池システム１０Ｓは、上記金属空気電池ユニット１に適用されるものである。また、上述した部分に対応する箇所は同一の符号を付して示している。 (Configuration to make it easy to restart the battery reaction of metal air battery)
By the way, there is a conventional metal-air battery that uses, in a metal electrode, an alloy prepared by blending other elements in addition to the metal element which is the main reactant (for example, see JP 2012-234799 A). This patent document describes the use of a magnesium alloy in which aluminum (Al), zinc (Zn) or the like is added to the metal electrode in order to suppress the generation of hydrogen gas due to the self-discharge reaction of the metal electrode. .
The above-mentioned additive elements are known to be greatly involved in the formation of a protective film on the surface of the alloy that inhibits self-reaction and suppresses the generation of hydrogen. As a result of investigations by the inventors, the protective film may inhibit the battery reaction, and there was a risk that the battery reaction would be difficult to resume when trying to use the battery again after stopping and pausing the battery. .
Therefore, an embodiment of a system configuration of the magnesium-air battery 10 (hereinafter, referred to as a metal-air battery system 10S) in which the battery reaction is easily restarted will be described below. The metal air battery system 10S is applied to the metal air battery unit 1 described above. The parts corresponding to the parts described above are shown with the same reference numerals.
（金属空気電池システムの第１実施形態）
　図４１は本発明の第１実施形態に係る金属空気電池システム１０Ｓの構成を示した図である。
　この金属空気電池システム１０Ｓは、単位電池（単セルの電池）を構成する複数（本構成では４個）のマグネシウム空気電池１０を備えている。各マグネシウム空気電池１０は、一対のマグネシウム極（金属極）１５と空気極１３とを備え、空気中の酸素を電気化学反応に利用して発電する一次電池である。この電気化学反応（電池反応）の際、マグネシウム極１５が負極として作用し、空気極１３が正極として作用する。 (First Embodiment of Metal-Air Battery System)
FIG. 41 is a view showing the configuration of the metal-air battery system 10S according to the first embodiment of the present invention.
The metal-air battery system 10S includes a plurality of (four in the present configuration) magnesium-air batteries 10 that constitute a unit battery (a single-cell battery). Each magnesium-air battery 10 is a primary battery that includes a pair of magnesium electrodes (metal electrodes) 15 and an air electrode 13 and generates electric power by utilizing oxygen in air for an electrochemical reaction. During the electrochemical reaction (battery reaction), the magnesium electrode 15 acts as a negative electrode, and the air electrode 13 acts as a positive electrode.
　複数のマグネシウム空気電池１０は、直列に接続され、両端のマグネシウム極１５と空気極１３とにＤＣ－ＤＣ変換装置（電力変換装置）３００が接続される。これら複数のマグネシウム空気電池１０を特に区別して説明する必要がない場合、組電池１０Ａと表記する。
　ＤＣ－ＤＣ変換装置３００は、直流電力を異なる直流電力に変換する変換回路３０１を備えている。これによって、組電池１０Ａから出力された直流電力は、携帯電話の充電などに適した直流電力に変換されて金属空気電池システム１０Ｓから出力される。 The plurality of magnesium-air cells 10 are connected in series, and a DC-DC converter (power converter) 300 is connected to the magnesium electrode 15 and the air electrode 13 at both ends. When it is not necessary to distinguish and describe the plurality of magnesium air batteries 10 in particular, they will be referred to as a battery pack 10A.
The DC-DC converter 300 includes a converter circuit 301 that converts DC power into different DC power. As a result, the DC power output from the battery pack 10A is converted into DC power suitable for charging the mobile phone and the like, and is output from the metal air battery system 10S.
　すなわち、ＤＣ－ＤＣ変換装置３００は、利用側の機器に合わせた電力に変換する電力変換装置として機能する。従って、例えば、利用側の機器が、携帯電話よりも高い電流値又は電圧値を要求する機器の場合には、ＤＣ－ＤＣ変換装置３００を変更することによって容易に対応可能である。また、このＤＣ－ＤＣ変換装置３００が、出力電力を様々な電力に切り替える切替機能を具備するように構成しても良い。また、交流電力に変換するＤＣ－ＡＣ変換装置を具備するように構成しても良い。 That is, the DC-DC conversion device 300 functions as a power conversion device that converts the power to the power of the user's device. Therefore, for example, in the case where the device on the use side requires a higher current value or voltage value than the mobile phone, it can be easily coped with by changing the DC-DC conversion device 300. Further, the DC-DC converter 300 may be configured to have a switching function of switching the output power to various powers. In addition, a DC-AC conversion device for converting into AC power may be provided.
　この金属空気電池システム１０Ｓを使用する場合には、マグネシウム極１５と空気極１３との間に、マグネシウム極１５からマグネシウムイオンが溶出可能な電解液が充填される。
　具体的には、電解液は、アニオンとして塩化物イオンを含み、カチオンとしてアルカリ金属イオン（Ｌｉ，Ｎａ，Ｋ，Ｒｂ，Ｃｓ，Ｆｒ）、アルカリ土類金属イオン（Ｂｅ，Ｍｇ，Ｃａ，Ｓｒ，Ｂａ，Ｒａ）の少なくとも１つを含む水溶液が用いられる。本実施形態では、電解液として、安全性および導電性の高い点からナトリウムイオンを含む塩化ナトリウム水溶液が用いられる。 When this metal-air battery system 10S is used, an electrolytic solution in which magnesium ions can be eluted from the magnesium electrode 15 is filled between the magnesium electrode 15 and the air electrode 13.
Specifically, the electrolyte contains chloride ions as anions, alkali metal ions (Li, Na, K, Rb, Cs, Fr) as cations, alkaline earth metal ions (Be, Mg, Ca, Sr, An aqueous solution containing at least one of Ba, Ra) is used. In the present embodiment, a sodium chloride aqueous solution containing sodium ions is used as the electrolytic solution in terms of high safety and conductivity.
　マグネシウム極１５は、マグネシウムが９６％、アルミニウムが３％、亜鉛が１％のＡＳＴＭ規格のＡＺ３１、又は、ＡＺ６１、ＡＺ９１などが用いられる。なお、ＡＳＴＭ規格によるものに限らず、公知のＭｇ－Ａｌ－Ｚｎ系合金を用いても良い。また、アルミニウムおよび亜鉛以外の元素を添加しても良く、例えば、Ｓｉ，Ｃｕ，Ｌｉ，Ｎａ，Ｋ，Ｆｅ，Ｎｉ，Ｔｉ，Ｚｒなどの他の元素を添加しても良い。 The magnesium electrode 15 is made of, for example, AZ31 or AZ61, AZ91 or the like of ASTM standard of 96% of magnesium, 3% of aluminum, and 1% of zinc. In addition, you may use not only what is based on ASTM specification but a well-known Mg-Al-Zn type alloy. In addition, elements other than aluminum and zinc may be added, and for example, other elements such as Si, Cu, Li, Na, K, Fe, Ni, Ti, and Zr may be added.
　本構成のマグネシウム空気電池１０において、空気極１３およびマグネシウム極１５のそれぞれの反応は以下の通りである。 In the magnesium-air battery 10 of this configuration, the respective reactions of the air electrode 13 and the magnesium electrode 15 are as follows.
　（空気極）Ｏ2＋２Ｈ2Ｏ＋４ｅ－→４ＯＨ－
　（マグネシウム極）
　　　マグネシウムの発電反応：Ｍｇ＋２ＯＨ－→Ｍｇ（ＯＨ）2＋２ｅ－
　　　マグネシウムの自己放電：Ｍｇ＋２Ｈ2Ｏ→Ｍｇ（ＯＨ）2＋Ｈ2
　　　亜鉛の発電反応：Ｚｎ＋４ＯＨ－→Ｚｎ（ＯＨ）4 2-＋２ｅ－
　　　電解液中：Ｚｎ（ＯＨ）4 2-→ＺｎＯ＋Ｈ2Ｏ＋２ＯＨ－
　　　アルミニウムの発電反応：Ａｌ＋３ＯＨ－→Ａｌ（ＯＨ）3＋３ｅ－ (Air electrode) O 2 + 2H 2 O + 4e- → 4OH-
(Magnesium pole)
Power generation reaction of magnesium: Mg + 2 OH-→ Mg (OH) 2 + 2 e-
Magnesium self-discharge: Mg + 2 H 2 O → Mg (OH) 2 + H 2
Zinc reaction reaction: Zn + 4 OH-→ Zn (OH) 4 2- + 2 e-
In the electrolyte: Zn (OH) 4 2- → ZnO + H 2 O + 2 OH-
Generation reaction of aluminum: Al + 3 OH-→ Al (OH) 3 + 3 e-
　一般に、マグネシウムは反応性が高い材質であるため、上記のように自己放電が生じやすい。
　本構成では、上記マグネシウム合金を用いることにより、電池反応で発生する酸化物（例えば、亜鉛酸化物）によって、マグネシウム極１５の表面に自己放電を阻害し水素の発生を抑制する保護被膜を形成し、自己放電反応を抑制することができる。 In general, magnesium is a highly reactive material, and thus self-discharge tends to occur as described above.
In this configuration, by using the above-mentioned magnesium alloy, a protective film is formed on the surface of the magnesium electrode 15 to inhibit self-discharge and suppress the generation of hydrogen by the oxide (for example, zinc oxide) generated by the battery reaction. , Self-discharge reaction can be suppressed.
　ところが、発明者等の検討によると、保護被膜が電池反応（発電反応）も阻害することがあり、電池を使用停止して休止させた後に再び電池を使用しようとしたときに、電池反応が十分に再開されず、必要な電流を取り出せないことがあることが判った。特に、亜鉛が添加されているときに、電流を取り出せない事態が生じ易かった。 However, according to studies by the inventors, the protective film may also inhibit the battery reaction (power generation reaction), and when the battery is stopped and stopped after the battery is stopped, the battery reaction is sufficient. It has been found that the required current can not be extracted. In particular, when zinc was added, it was easy to occur a situation where current could not be extracted.
　そこで、本実施形態では、マグネシウム空気電池１０のマグネシウム極１５と空気極１３との間に、開閉式の短絡回路３３１を設けている。この開閉式の短絡回路３３１は、直列接続されたマグネシウム空気電池１０の両端のマグネシウム極１５と空気極１３との間に接続され、ユーザーが手動で開閉可能な手動式のスイッチ（いわゆる手動スイッチ）に構成されている。
　そして、この開閉式の短絡回路３３１を開から閉へと切り替えることにより、全ての全てのマグネシウム空気電池１０の空気極１３、マグネシウム極１５を含む閉回路、つまり、全てのマグネシウム空気電池１０を短絡させる閉回路が形成される。これによって、各マグネシウム空気電池１０に一時的に比較的大きな電流を強制的に流し、マグネシウム極１５の表面に形成された保護被膜（不動態被膜、不動態膜層とも称する）を電解液中に溶解させ、フレッシュな金属表面を露出させることができる。 Therefore, in the present embodiment, the open / close short circuit 331 is provided between the magnesium electrode 15 and the air electrode 13 of the magnesium-air battery 10. The switchable short circuit 331 is connected between the magnesium electrode 15 and the air electrode 13 at both ends of the magnesium air battery 10 connected in series, and a manual switch (so-called manual switch) that can be manually opened and closed by the user. Is configured.
Then, by switching the open / close short circuit 331 from the open state to the closed state, the closed circuit including the air electrode 13 and the magnesium electrode 15 of all the magnesium-air batteries 10, that is, all the magnesium-air batteries 10 are shorted. A closed circuit is formed. As a result, a relatively large current is temporarily forced to flow to each magnesium-air battery 10, and a protective film (also referred to as passive film or passive film layer) formed on the surface of the magnesium electrode 15 is contained in the electrolyte. It can be dissolved to expose a fresh metal surface.
　従って、電池を休止させた後に、開閉式の短絡回路３３１を開から閉へと一時的に切り替えることにより、マグネシウム空気電池１０を簡単にリフレッシュさせることができ、電池反応を再開させ易い状態に戻すことができる。
　このため、リフレッシュ後に短絡回路３３１を閉から開へと戻すことにより、電池反応を再開させることができ、十分な電流を直ぐに出力可能となる。これによって、金属空気電池システム１０Ｓの出力側に利用側機器を接続すれば、その利用側機器の駆動や充電に適した電力を直ぐに供給することが可能になる。
　なお、全てのマグネシウム空気電池１０を直列接続させた状態で短絡させるため、個々のマグネシウム空気電池１０毎に開閉式の短絡回路３３１を設ける場合に比して、大電流を流し易くなるとともに、部品点数を削減可能である。 Therefore, the magnesium air battery 10 can be easily refreshed by temporarily switching the open / close short circuit 331 from the open state to the closed state after the battery is stopped, so that the cell reaction can be easily resumed. be able to.
Therefore, by returning the short circuit 331 from the closed state to the open state after the refresh, the cell reaction can be restarted, and a sufficient current can be output immediately. As a result, when the use-side device is connected to the output side of the metal air battery system 10S, it becomes possible to immediately supply power suitable for driving and charging the use-side device.
In addition, in order to make it short-circuit in the state which connected all the magnesium air cells 10 in series, while becoming easy to flow a large current compared with the case where the short circuit 331 of a switching type is provided for every magnesium air cell 10, The score can be reduced.
　さらに、開閉式の短絡回路３３１は、図４１に示すように、ＤＣ－ＤＣ変換装置３００内に設けられている。このため、ＤＣ－ＤＣ変換装置３００の外装体などを利用して短絡回路３３１を収容可能であり、短絡回路３３１専用の外装体などを不要にすることができる。また、短絡回路３３１は、組電池１０Ａのマグネシウム極１５と空気極１３との間に介挿される構成であるため、短絡回路３３１を備えない従来の金属空気電池システムに、短絡回路３３１を容易に追加可能である。
　しかも、同図４１に示すように、短絡回路３３１を、変換回路３０１の入力側（マグネシウム空気電池１０側）に設けているので、短絡回路３３１を閉に切り替えた場合にできる閉回路上に変換回路が存在せず、その分、閉回路中の抵抗を小さくすることができる。従って、効率良く大電流（短絡電流）を流すことができ、マグネシウム空気電池１０をリフレッシュさせ易くなる。 Further, as shown in FIG. 41, the open / close short circuit 331 is provided in the DC-DC converter 300. For this reason, the short circuit 331 can be accommodated using the exterior body of the DC-DC conversion device 300 and the like, and the exterior body dedicated to the short circuit 331 can be eliminated. Further, since the short circuit 331 is configured to be inserted between the magnesium electrode 15 and the air electrode 13 of the battery pack 10A, the short circuit 331 can be easily made to the conventional metal-air battery system not provided with the short circuit 331. It is possible to add.
Moreover, as shown in FIG. 41, since the short circuit 331 is provided on the input side (the magnesium air battery 10 side) of the conversion circuit 301, conversion to a closed circuit which can be performed when the short circuit 331 is closed. There is no circuit, and the resistance in the closed circuit can be reduced accordingly. Therefore, a large current (short circuit current) can be efficiently flowed, and the magnesium-air battery 10 can be easily refreshed.
　また、ＤＣ－ＤＣ変換装置３００内に短絡回路３３１を備えるので、ＤＣ－ＤＣ変換装置３００を取り外せば、短絡回路３３１も取り外すことができ、短絡回路３３１の着脱が容易である。従って、短絡回路３３１の交換・点検などのメンテナンス作業も容易に行い易くなる。 Further, since the short circuit 331 is provided in the DC-DC conversion device 300, if the DC-DC conversion device 300 is removed, the short circuit 331 can also be removed, and the short circuit 331 can be easily attached and detached. Therefore, maintenance work such as replacement / inspection of the short circuit 331 can be easily performed.
　以上説明したように、本実施形態の金属空気電池システム１０Ｓは、負極を構成するマグネシウム極１５と正極を構成する空気極１３とを含む閉回路を選択的に形成する回路である開閉式の短絡回路３３１を備えるので、マグネシウム極１５の保護被膜（不動態被膜）の影響などにより電池を休止後に電池反応を再開し難くなる場合でも、電池反応を再開させ易くなる。
　しかも、この短絡回路３３１は、組電池１０Ａのマグネシウム極１５と空気極１３との間に設ければ良く、簡易に設けることができる。従って、部品点数の増大や装置の大型化を抑えることができ、コストアップを抑え易くなる。
　また、この開閉式の短絡回路３３１は、手動式のスイッチで構成されるため、これによっても、簡易に構成でき、且つ、ユーザーが操作し易い。 As described above, the metal air battery system 10S of the present embodiment is a circuit that selectively forms a closed circuit including the magnesium electrode 15 forming the negative electrode and the air electrode 13 forming the positive electrode. Since the circuit 331 is provided, the battery reaction can be easily resumed even when it is difficult to resume the battery reaction after the battery is stopped due to the influence of the protective film (passive film) of the magnesium electrode 15 or the like.
In addition, the short circuit 331 may be provided simply between the magnesium electrode 15 and the air electrode 13 of the battery assembly 10A. Therefore, an increase in the number of parts and an increase in the size of the apparatus can be suppressed, and the cost increase can be easily suppressed.
Further, since the open / close short circuit 331 is formed of a manual switch, it can be simply configured and is easy for the user to operate.
　なお、本実施形態では、短絡回路３３１をＤＣ－ＤＣ変換装置３００の組電池１０Ａ側に設ける場合を説明したが、図４２に示すように、短絡回路３３１をＤＣ－ＤＣ変換装置３００の出力側に設けるようにしても良いし、ＤＣ－ＤＣ変換装置３００外に設けるようにしても良い。つまり、短絡回路３３１の位置は適宜に変更しても良い。 In the present embodiment, the short circuit 331 is provided on the side of the battery pack 10A of the DC-DC converter 300. However, as shown in FIG. 42, the short circuit 331 is connected to the output side of the DC-DC converter 300. , Or may be provided outside the DC-DC conversion device 300. That is, the position of the short circuit 331 may be changed as appropriate.
（金属空気電池システムの第２実施形態）
　図４３（Ａ）は第２実施形態に係る金属空気電池システム１０Ｓの構成を示した図である。なお、以下の説明において、第１実施形態と同様の構成は同一の符号を付して示し、重複する説明は省略する。
　第２実施形態では、組電池１０Ａのマグネシウム極１５と空気極１３の間に、開閉式の抵抗放電回路３３３を設けている。この抵抗放電回路３３３は、抵抗とスイッチとで構成される。この抵抗放電回路３３３によっても、スイッチを開から閉へと一時的に切り替えることによって、組電池１０Ａを含む閉回路を形成することができる。従って、第１実施形態の金属空気電池システム１０Ｓと同様に、簡易な構成で、電池を休止後に一時的に大電流を強制的に流し、電池をリフレッシュさせることができる。これによって、簡易な構成で、電池反応を再開させ易くなる、などの第１実施形態と同様の各種効果を得ることができる。 Second Embodiment of Metal-Air Battery System
FIG. 43 (A) is a view showing the configuration of a metal-air battery system 10S according to the second embodiment. In the following description, the same components as those in the first embodiment are denoted by the same reference numerals, and redundant descriptions will be omitted.
In the second embodiment, a switchable resistance discharge circuit 333 is provided between the magnesium electrode 15 and the air electrode 13 of the battery assembly 10A. The resistive discharge circuit 333 is composed of a resistor and a switch. The resistive discharge circuit 333 can also form a closed circuit including the battery pack 10A by temporarily switching the switch from open to closed. Therefore, similarly to the metal-air battery system 10S of the first embodiment, a large current can be forced to temporarily flow after the battery is paused and the battery can be refreshed with a simple configuration. As a result, various effects similar to those of the first embodiment, such as easy resumption of the battery reaction, can be obtained with a simple configuration.
　図４３（Ｂ）は抵抗放電回路３３３にサーキットプロテクタスイッチ３３３Ｓを適用した具体例を示している。サーキットプロテクタスイッチ３３３Ｓは、スイッチ３３３Ｓを開から閉と切り替えた場合にできる閉回路を流れる電流値が予め定めた閾値を超えると、スイッチ開となるスイッチであり、サーキットプロテクタとも称する。
　サーキットプロテクタスイッチ３３３Ｓを使用することにより、電流値が許容電流以下に設定された所定値を超える前に自動的にスイッチ開にすることができ、回路の保護などを図り易くなる。また、スイッチ開にする操作を不要にすることができるとともに、無断に放電しなくて良いので、放電電力のロスも低減することもできる。また、サーキットプロテクタスイッチ３３３Ｓは広く流通する部品であるため、コストアップ低減にも有利である。 FIG. 43B shows a specific example in which the circuit protector switch 333 S is applied to the resistive discharge circuit 333. The circuit protector switch 333S is a switch that opens when the current value flowing through the closed circuit, which can be switched from opening to closing the switch 333S, exceeds a predetermined threshold, and is also referred to as a circuit protector.
By using the circuit protector switch 333S, the switch can be automatically opened before the current value exceeds a predetermined value set to the allowable current or less, which facilitates protection of the circuit. Further, the switch opening operation can be made unnecessary, and since it is not necessary to discharge without permission, the loss of discharge power can also be reduced. In addition, since the circuit protector switch 333S is a widely distributed part, it is also advantageous for cost increase reduction.
　なお、図４３（Ａ）および図４３（Ｂ）では、抵抗放電回路３３３（サーキットプロテクタスイッチ３３３Ｓを含む）を、ＤＣ－ＤＣ変換装置３００の組電池１０Ａ側に設ける場合を説明したが、図４４に示すように、抵抗放電回路３３３をＤＣ－ＤＣ変換装置３００の出力側に設けるようにしても良いし、ＤＣ－ＤＣ変換装置３００外に設けるようにしても良い。つまり、抵抗放電回路３３３の位置は適宜に変更しても良い。 Although FIGS. 43A and 43B illustrate the case where the resistive discharge circuit 333 (including the circuit protector switch 333S) is provided on the battery pack 10A side of the DC-DC conversion device 300, FIG. As shown in FIG. 5, the resistive discharge circuit 333 may be provided on the output side of the DC-DC converter 300 or may be provided outside the DC-DC converter 300. That is, the position of the resistive discharge circuit 333 may be changed as appropriate.
（金属空気電池システムの第３実施形態）
　図４５（Ａ）は第３実施形態に係る金属空気電池システム１０Ｓの構成を示した図である。第３実施形態は、ＤＣ－ＤＣ変換装置３００を備えていない金属空気電池システム１０Ｓを示している。この金属空気電池システム１０Ｓにおいても、組電池１０Ａのマグネシウム極１５と空気極１３の間に、開閉式の短絡回路３３１を設けることにより、電池反応を再開させ易くなる、などの第１実施形態と同様の各種効果を得ることができる。 (Third Embodiment of Metal-Air Battery System)
FIG. 45 (A) is a view showing the configuration of a metal-air battery system 10S according to the third embodiment. The third embodiment shows a metal air battery system 10S not provided with the DC-DC converter 300. Also in the metal-air battery system 10S, the battery reaction can be easily resumed by providing the open / close short circuit 331 between the magnesium electrode 15 and the air electrode 13 of the battery pack 10A. Similar various effects can be obtained.
（金属空気電池システムの第４実施形態）
　図４５（Ｂ）は第４実施形態に係る金属空気電池システム１０Ｓの構成を示した図である。第４実施形態は、図４５（Ａ）の短絡回路３３１に代えて、抵抗放電回路３３３を設けた構成である。この構成により、第２実施形態の金属空気電池システム１０Ｓと同様の各種効果を得ることができる。また、抵抗放電回路３３３にサーキットプロテクタスイッチ３３３Ｓを適用しても良い。 (Fourth Embodiment of Metal-Air Battery System)
FIG. 45 (B) is a view showing the configuration of a metal-air battery system 10S according to the fourth embodiment. The fourth embodiment has a configuration in which a resistive discharge circuit 333 is provided instead of the short circuit circuit 331 of FIG. 45 (A). With this configuration, various effects similar to those of the metal-air battery system 10S of the second embodiment can be obtained. Alternatively, the circuit protector switch 333 S may be applied to the resistive discharge circuit 333.
（金属空気電池システムの第５実施形態）
　図４６は第５実施形態に係る金属空気電池システム１０Ｓの構成を示した図である。
　第５実施形態は、積算電流検出部３３５を設けている。この積算電流検出部３３５は、マグネシウム空気電池１０を含む閉回路を流れる電流値を積算して積算電流値を検出する機能と、積算電流値に応じて短絡回路３３１をスイッチ開に切り替える自動スイッチ機能とを備えている。 Fifth Embodiment of Metal-Air Battery System
FIG. 46 is a view showing the configuration of a metal-air battery system 10S according to the fifth embodiment.
In the fifth embodiment, an integrated current detection unit 335 is provided. The integrated current detection unit 335 integrates the current flowing through the closed circuit including the magnesium air battery 10 to detect the integrated current value, and the automatic switch function to switch the short circuit 331 to the open state according to the integrated current value. And have.
　積算電流値を検出することにより、マグネシウム空気電池１０をリフレッシュできたか否かを判断可能な情報を得ることができる。自動スイッチ機能においては、例えば、マグネシウム空気電池１０をリフレッシュさせるのに十分な積算電流値に至ると、短絡回路３３１をスイッチ開に切り替えるように予め閾値が設定される。これによって、積算電流値が閾値に至ると自動的に開回路に切り替わり、リフレッシュ動作を終了させることができる。従って、開回路に切り替えるためのユーザー操作を不要にすることができ、且つ、放電電力のロスを低減することができる。 By detecting the integrated current value, it is possible to obtain information capable of determining whether or not the magnesium-air battery 10 can be refreshed. In the automatic switch function, for example, a threshold value is set in advance so that the short circuit 331 is switched to open when the integrated current value sufficient to refresh the magnesium-air battery 10 is reached. As a result, when the integrated current value reaches the threshold value, the circuit is automatically switched to the open circuit, and the refresh operation can be ended. Therefore, the user operation for switching to the open circuit can be made unnecessary, and the loss of discharge power can be reduced.
　積算電流検出部３３５については公知の構成を広く適用可能である。
　また、変形例として、自動スイッチ機能を省略しても良い。この場合、積算電流検出部３３５は、検出した積算電流値が所定値に至ると、その旨をユーザーに報知することが好ましい。これにより、ユーザーに対し、スイッチ操作のタイミングを知らせることができる。従って、ユーザーは適切なタイミングでスイッチ操作することができる。なお、ユーザーに報知する装置としては、点灯や表示により情報を伝える表示装置、音により情報を伝える音声出力装置などの公知の報知装置を広く適用可能である。また、短絡回路３３１に代えて、抵抗放電回路３３３を設けるようにしても良い。
　なお、本実施形態では積算電流値を検出し、その値に応じて短絡回路３３１のスイッチの切替動作を行ったが、積算電流値に代えて電流値を検出し、その値に応じて短絡回路３３１のスイッチの切替動作を行っても良い。 A wide range of known configurations can be applied to the integration current detection unit 335.
Also, as a modification, the automatic switch function may be omitted. In this case, preferably, when the detected integrated current value reaches a predetermined value, the integrated current detection unit 335 notifies the user to that effect. This allows the user to be notified of the switch operation timing. Therefore, the user can operate the switch at an appropriate timing. In addition, as a device for notifying the user, a known notification device such as a display device for transmitting information by lighting or display, an audio output device for transmitting information by sound, or the like can be widely applied. Also, instead of the short circuit 331, a resistive discharge circuit 333 may be provided.
In this embodiment, the integrated current value is detected, and the switching operation of the switch of the short circuit 331 is performed according to the value. However, instead of the integrated current value, the current value is detected, and the short circuit is detected according to the value. The switching operation of the switch 331 may be performed.
（金属空気電池システムの第６実施形態）
　図４７は第６実施形態に係る金属空気電池システム１０Ｓの構成を示した図である。
　第６実施形態は、時間検出部３３７を設けている。この時間検出部３３７は、閉回路にしてからの経過時間を検出（測定）する機能と、検出した経過時間に応じて短絡回路３３１をスイッチ開に切り替える自動スイッチ機能とを備えている。 Sixth Embodiment of Metal-Air Battery System
FIG. 47 is a view showing the configuration of a metal-air battery system 10S according to the sixth embodiment.
In the sixth embodiment, a time detection unit 337 is provided. The time detection unit 337 has a function of detecting (measuring) an elapsed time after the circuit is closed and an automatic switch function of switching the short circuit 331 to the open state in accordance with the detected elapsed time.
　経過時間を検出することにより、マグネシウム空気電池１０をリフレッシュできたか否かを判断可能な情報を得ることができる。自動スイッチ機能においては、例えば、マグネシウム空気電池１０をリフレッシュさせるのに十分な経過時間に至ると、短絡回路３３１をスイッチ開に切り替えるように予め閾値が設定される。これによって、経過時間が閾値に至ると自動的に開回路に切り替わり、適切なタイミングでリフレッシュ動作を終了させることができる。従って、開回路に切り替えるためのユーザー操作を不要にすることができ、且つ、放電電力のロスを低減することができる。 By detecting the elapsed time, it is possible to obtain information that can determine whether or not the magnesium-air battery 10 can be refreshed. In the automatic switch function, for example, a threshold value is set in advance so that the short circuit 331 is switched to open when an elapsed time sufficient to refresh the magnesium-air battery 10 is reached. As a result, when the elapsed time reaches the threshold value, the circuit is automatically switched to the open circuit, and the refresh operation can be ended at an appropriate timing. Therefore, the user operation for switching to the open circuit can be made unnecessary, and the loss of discharge power can be reduced.
　時間検出部３３７については公知の構成を広く適用可能である。
　また、変形例として、自動スイッチ機能を省略しても良い。この場合、時間検出部３３７は、検出した経過時間が所定値に至ると、その旨をユーザーに報知することが好ましい。これにより、ユーザーに対し、スイッチ操作のタイミングを知らせることができ、ユーザーは適切なタイミングでスイッチ操作することができる。なお、短絡回路３３１に代えて、抵抗放電回路３３３を設けるようにしても良い。 A well-known configuration can be widely applied to the time detection unit 337.
Also, as a modification, the automatic switch function may be omitted. In this case, it is preferable that the time detection unit 337 notify the user of that when the detected elapsed time reaches a predetermined value. Thus, the user can be notified of the switch operation timing, and the user can perform switch operation at an appropriate timing. Note that instead of the short circuit 331, a resistive discharge circuit 333 may be provided.
　なお、金属空気電池システム１０Ｓは上述の実施形態に限定されるものではなく、本発明の技術思想に基づいて各種の変形および変更が可能である。例えば、上述の実施形態では、アルミニウムと亜鉛を添加したマグネシウム極１５を備えるマグネシウム空気電池１０に本発明を適用する場合を説明したが、これに限らず、少なくとも亜鉛を添加したＭｇ－Ｚｎ系合金の金属空気電池に本発明を適用しても良い。
　さらに、亜鉛を含まないマグネシウム極を備える金属空気電池や、マグネシウム以外の金属極を備える金属空気電池であっても、本発明を適用しても良い。要は、金属極の素材などにより休止後に電池反応の再開が困難になるおそれのある金属空気電池に、本発明を広く適用可能である。 In addition, the metal air battery system 10S is not limited to the above-mentioned embodiment, Based on the technical thought of this invention, various deformation | transformation and change are possible. For example, although the above-mentioned embodiment explained the case where the present invention was applied to magnesium air battery 10 provided with magnesium electrode 15 which added aluminum and zinc, it is not restricted to this, but Mg-Zn system alloy which added zinc at least The present invention may be applied to a metal-air battery.
Furthermore, the present invention may be applied to a metal-air battery provided with a magnesium electrode not containing zinc, or a metal-air battery provided with a metal electrode other than magnesium. The point is that the present invention can be widely applied to a metal-air battery in which reactivation of the battery reaction may become difficult after a pause due to the material of the metal electrode or the like.
　以上、本発明を実施するための形態について述べたが、本発明は既述の実施形態に限定されるものではなく、本発明の技術思想に基づいて各種の変形、および変更が可能である。 As mentioned above, although the form for implementing this invention was described, this invention is not limited to embodiment as stated above, A various deformation | transformation and change are possible based on the technical thought of this invention.
　１　金属空気電池ユニット
　１０　マグネシウム空気電池（金属空気電池）
　１０Ａ　組電池
　１０Ｓ　金属空気電池システム
　１１　外装体
　１３　空気極
　１３Ｔ　空気極のタブ部
　１５　マグネシウム極（金属極）
　１５Ｔ　金属極のタブ部
　２１　底板部
　２２　前壁部
　２２Ｋ　開口部
　２３　後壁部
　２４Ｆ、２４Ｒ　側壁部構成片（側壁部）
　２５Ｆ、２５Ｒ　上板部構成片（支持用折り曲げ部、蓋部）
　２５Ｆ１、２５Ｒ１　第１折り曲げ部
　２５Ｆ２、２５Ｒ２　第２折り曲げ部（折り返し部）
　２５Ｆ３、２５Ｒ３　第３折り曲げ部（折り返し部）
　２５Ｘ　タブ部側の分割部
　２５Ｙ　非タブ部側の分割部
　２６Ｆ、２６Ｒ　シート片
　３５　底板シート部
　４１　電解質収容体
　４２　極板装着シート
　４２Ｂ　嵌合部（規制部）
　４２Ｃ　上側嵌合部（規制部）
　４３　袋体
　８１（８１Ａ、８１Ｂ）　突片
　１００　打ち抜きシート
　１０１　シート材
　１２１、１２２、１２５、１３１　フィルム（非透液性材料）
　２１０　外箱
　２２０、２７０　ダンボール紙
　２３０　スペーサ
　２３２Ｋ　空気極開口部
　２４４　枠部材
　２５０　ポケット（電池収容部）
　２５１　フローティング支持部
　２６０　滞留部（空気が滞留する間隙）
　３００　ＤＣ－ＤＣ変換装置（電力変換装置）
　３３１　短絡回路
　３３３　抵抗放電回路
　３３３Ｓ　サーキットプロテクタスイッチ
　３３５　積算電流検出部
　３３７　時間検出部
　ＳＦ、ＳＲ　隙間
　ＭＸ　疎水性の薬剤
　ＨＸ　ホットメルト
　ＵＬ　電解液の液面 1 Metal air battery unit 10 Magnesium air battery (metal air battery)
DESCRIPTION OF SYMBOLS 10A assembled battery 10S metal air battery system 11 exterior body 13 air pole 13T tab of the air pole 15 magnesium electrode (metal pole)
15T metal pole tab 21 bottom plate 22 front wall 22K opening 23 back wall 24F, 24R side wall constituting piece (side wall)
25F, 25R Upper plate part configuration piece (Bending part for support, lid part)
25F1, 25R1 first bent portion 25F2, 25R2 second bent portion (folded portion)
25F3, 25R3 third bend (folded back)
25X Tab side split portion 25Y Non-tab side split portion 26F, 26R Sheet piece 35 Bottom plate sheet portion 41 Electrolyte container 42 Electrode plate mounting sheet 42B Fitting portion (Regulation portion)
42C upper fitting part (regulation part)
43 bag body 81 (81A, 81B) projecting piece 100 punching sheet 101 sheet material 121, 122, 125, 131 film (impermeable material)
210 Outer box 220, 270 corrugated paper 230 spacer 232 K air pole opening 244 frame member 250 pocket (battery housing)
251 Floating support part 260 Retaining part (gap where air stays)
300 DC-DC Converter (Power Converter)
331 Short circuit circuit 333 Resistive discharge circuit 333 S Circuit protector switch 335 Integrated current detector 337 Time detector SF, SR Gap MX Hydrophobic agent HX Hot melt UL Electrolyte liquid level

Claims (46)

  1. 　空気極を有するとともに前記空気極と対向する金属極を収容する外装体を備える金属空気電池において、
    　前記外装体は、紙を含有するシート材で形成されることを特徴とする金属空気電池。     A metal-air battery comprising an outer case having an air electrode and containing a metal electrode facing the air electrode,
    The said exterior body is formed with the sheet material containing paper, The metal air battery characterized by the above-mentioned.
  2. 　前記シート材は、熱融着性樹脂でラミネート加工された紙であることを特徴とする請求項１に記載の金属空気電池。 The metal-air battery according to claim 1, wherein the sheet material is a paper laminated with a heat-fusible resin.
  3. 　前記シート材は、隙間を空けて前記金属極を覆うとともに、前記シート材の一部を折り曲げて前記隙間を横断し、前記金属極を支える支持用折り曲げ部を一体に備えることを特徴とする請求項１又は２に記載の金属空気電池。 The sheet material covers the metal electrode while leaving a gap, bends a part of the sheet material, traverses the gap, and integrally includes a support bending portion for supporting the metal electrode. The metal air battery as described in claim 1 or 2.
  4. 　前記支持用折り曲げ部は、前記金属極を前記空気極から離間させた位置に保持することを特徴とする請求項３に記載の金属空気電池。 The metal air battery according to claim 3, wherein the supporting bent portion holds the metal electrode at a position separated from the air electrode.
  5. 　前記支持用折り曲げ部は、前記シート材における前記金属極に対して前記空気極側の壁部、および、前記空気極と反対側の壁部の少なくとも一方から前記金属極に向けて折り曲げられた第１折り曲げ部と、前記第１折り曲げ部の先端から折り曲げられて前記金属極に当接する第２折り曲げ部とを有することを特徴とする請求項４に記載の金属空気電池。 The support bending portion is bent toward at least one of a wall portion on the air electrode side with respect to the metal electrode in the sheet material and a wall portion on the opposite side of the air electrode toward the metal electrode. 5. The metal-air battery according to claim 4, further comprising: a bent portion; and a second bent portion bent from a tip end of the first bent portion and in contact with the metal electrode.
  6. 　前記第１折り曲げ部は、前記外装体内の電解液の液面よりも上方に設けられるとともに、前記金属極に向かって斜め下方に傾斜することを特徴とする請求項５に記載の金属空気電池。 The metal air battery according to claim 5, wherein the first bent portion is provided above the liquid surface of the electrolytic solution in the outer package, and is inclined obliquely downward toward the metal electrode.
  7. 　前記金属極が上方に突出するタブ部を有するとともに、前記支持用折り曲げ部が前記金属極の幅に渡って延在し、
    　前記支持用折り曲げ部は、前記金属極の幅方向で、前記タブ部と、前記タブ部のない非タブ部との境を基準にして分割され、前記タブ部側の分割部と前記非タブ部側の分割部のいずれか一方が、前記金属極の空気極側への移動を規制し、他方が前記金属極の空気極の反対側への移動を規制することを特徴とする請求項３乃至６のいずれかに記載の金属空気電池。     The metal pole has a tab portion projecting upward, and the supporting bent portion extends across the width of the metal pole,
    The support bending portion is divided on the basis of the boundary between the tab portion and the non-tab portion without the tab portion in the width direction of the metal pole, and the tab portion-side divided portion and the non-tab portion 4. The apparatus according to claim 3, wherein one of the divided portions on the side regulates movement of the metal electrode to the air electrode side, and the other regulates movement of the metal electrode to the opposite side of the air electrode. The metal air battery in any one of 6.
  8. 　前記支持用折り曲げ部は、前記空気極側の壁部、および、前記空気極の反対側の壁部から前記金属極に沿って外装体内側に折り曲げられるとともに、その反対側に折り返されて前記金属極よりも外装体外側に張り出す折り返し部を有し、
    　各折り返し部の一部で前記金属極を挟持するとともに、残りの外装体外側に突出した部分を互いに接合して折り返し部間を封止していることを特徴とする請求項４又は５に記載の金属空気電池。     The support bending portion is bent from the wall portion on the air electrode side and the wall portion on the opposite side of the air electrode along the metal electrode to the inside of the outer package, and is folded back to the opposite side. Has a folded back portion that overhangs the exterior of the body than the pole,
    The metal pole is held by a part of each of the folded back portions, and the remaining portions protruding to the outside of the outer package are joined to each other to seal between the folded back portions. Metal air battery.
  9. 　前記外装体は、前記金属極の下端が嵌る下方凸形状に折り曲げられた底板部を有することを特徴とする請求項１乃至８のいずれかに記載の金属空気電池。 The metal air battery according to any one of claims 1 to 8, wherein the exterior body has a bottom plate portion bent in a downward convex shape in which the lower end of the metal electrode is fitted.
  10. 　前記外装体は、前記金属極の上方を覆う蓋部に連なって前記金属極の側方を覆う側壁部に接合されるシート片を備えることを特徴とする請求項１乃至９のいずれかに記載の金属空気電池。 The said exterior body is connected with the cover part which covers the upper direction of the said metal pole, and is provided with the sheet piece joined to the side wall part which covers the side of the said metal pole, It is characterized by the above-mentioned. Metal air battery.
  11. 　紙を含有するシート材であって、前記金属極の下端が嵌る下方凸形状に折り曲げられた底板シート部を備え、
    　前記底板シート部は、前記外装体を形成するシート材に前後一対の端部の少なくとも一方が接合されることを特徴とする請求項１乃至１０のいずれかに記載の金属空気電池。     A sheet material containing paper, comprising a bottom plate sheet portion bent in a downward convex shape into which the lower end of the metal electrode fits,
    The metal air battery according to any one of claims 1 to 10, wherein in the bottom plate sheet portion, at least one of a pair of front and rear end portions is joined to a sheet material forming the exterior body.
  12. 　前記外装体を形成するシート材を上方に開口する凹状に折り曲げて前記外装体の底板部を形成し、
    　前記底板シート部は、前記外装体を形成するシート材を平面状に展開した状態で、前記底板部を跨ぐように該シート材に前後一対の端部の少なくとも一方が接合され、該シート材を上方に開口する前記凹状に折り曲げた際に、前記底板部から離間するように外装体内側に起立する一対の起立部を有し、前記一対の起立部間に前記金属極の下端が嵌まることを特徴とする請求項１１に記載の金属空気電池。     Forming a bottom plate portion of the exterior body by bending a sheet material forming the exterior body into a concave shape opening upward;
    In the bottom plate sheet portion, in a state in which the sheet material forming the exterior body is spread in a planar shape, at least one of a pair of front and rear end portions is joined to the sheet material so as to straddle the bottom plate portion. It has a pair of standing parts which stand up inside the exterior body so that it may estrange from the bottom plate part when it bends in the concave which opens upwards, and a lower end of the metal pole fits between a pair of standing parts. The metal air battery according to claim 11, characterized in that
  13. 　前記金属極における前記空気極と反対側の面に、前記外装体内に水を注ぎ入れることによって電池として作動させるための電解質を収容する電解質収容体を設けていることを特徴とする請求項１乃至１２のいずれかに記載の金属空気電池。 An electrolyte container for containing an electrolyte for operating as a battery by pouring water into the outer package is provided on the surface of the metal electrode opposite to the air electrode. The metal air battery in any one of 12.
  14. 　前記電解質収容体は、紙を含有するシート材であって前記金属極における前記空気極と反対側の面に装着される極板装着シートと、前記極板装着シートに接合されて前記電解質を収容する袋体とを備えることを特徴とする請求項１３に記載の金属空気電池。 The electrolyte container is a sheet material containing paper, and is attached to an electrode plate attachment sheet attached to the surface of the metal electrode opposite to the air electrode, and is joined to the electrode plate attachment sheet to accommodate the electrolyte. The metal air battery according to claim 13, comprising: a bag body.
  15. 　前記極板装着シートは前記金属極に圧着固定され、前記袋体は前記極板装着シートに融着されることを特徴とする請求項１４に記載の金属空気電池。 The metal air battery according to claim 14, wherein the electrode plate mounting sheet is crimped to the metal electrode, and the bag body is fused to the electrode plate mounting sheet.
  16. 　前記極板装着シートは、当該シートの一部を折り曲げて当該シートに対する前記金属極の移動を規制する規制部を有し、
    　前記極板装着シートを前記外装体に保持させることによって前記金属極を前記外装体に保持していることを特徴とする請求項１４又は１５に記載の金属空気電池。     The electrode plate mounting sheet has a restricting portion that bends a part of the sheet to restrict movement of the metal electrode with respect to the sheet.
    The metal air battery according to claim 14 or 15, wherein the metal electrode is held on the case by holding the electrode plate mounting sheet on the case.
  17. 　前記シート材は、隙間を空けて前記金属極を覆うとともに、少なくとも内面側が非透液性に形成され、
    　前記外装体には、前記空気極が外面側から装着される開口部が設けられ、前記開口部の端面には、内部に注液した電解液の浸透を防止する端面処理が施されていることを特徴とする請求項１に記載の金属空気電池。     The sheet material covers the metal electrode with a gap, and at least the inner surface side is formed to be liquid impermeable.
    The exterior body is provided with an opening where the air electrode is mounted from the outer surface side, and an end surface of the opening is subjected to end surface treatment for preventing permeation of the electrolytic solution injected into the inside. The metal air battery according to claim 1, characterized in that
  18. 　前記開口部の端面は、前記端面処理として、前記シート材の縁部が外方に向かって折り返されることを特徴とする請求項１７に記載の金属空気電池。 The metal air battery according to claim 17, wherein an edge of the sheet material is folded outward as the end surface treatment of the end face of the opening.
  19. 　前記開口部の端面は、前記端面処理として、シート状の非透液性材料により被覆されることを特徴とする請求項１７又は１８に記載の金属空気電池。 The metal air battery according to claim 17 or 18, wherein the end face of the opening is covered with a sheet-like liquid impermeable material as the end face treatment.
  20. 　前記シート材の両面に前記非透液性材料を貼り付け、前記非透液性材料同士を接合して前記端面を被覆したことを特徴とする請求項１９に記載の金属空気電池。 20. The metal-air battery according to claim 19, wherein the liquid impermeable material is attached to both sides of the sheet material, and the liquid impermeable materials are joined to cover the end face.
  21. 　前記非透液性材料により前記端面を包み込んで前記端面を被覆したことを特徴とする請求項１９に記載の金属空気電池。 20. The metal-air battery according to claim 19, wherein the end face is covered by covering the end face with the liquid impermeable material.
  22. 　前記開口部の端面は、前記端面処理として、疎水性の薬剤が含浸されることを特徴とする請求項１７乃至１９のいずれかに記載の金属空気電池。 The metal air battery according to any one of claims 17 to 19, wherein the end face of the opening is impregnated with a hydrophobic agent as the end face treatment.
  23. 　前記端面処理として、前記シート材から前記空気極に渡ってホットメルトを塗布し、前記ホットメルトにより前記開口部の端面を覆ったことを特徴とする請求項１７に記載の金属空気電池。 The metal air battery according to claim 17, wherein a hot melt is applied from the sheet material over the air electrode as the end surface treatment, and the end surface of the opening is covered with the hot melt.
  24. 　前記端面処理として、前記シート材から前記空気極に渡ってシート状の非透液性材料を貼り付け、前記非透液性材料により前記開口部の端面を覆ったことを特徴とする請求項１７に記載の金属空気電池。 A sheet-like impermeable material is pasted from the sheet material to the air electrode as the end surface treatment, and the end surface of the opening is covered with the impermeable material. Metal-air battery as described in.
  25. 　前記非透液性材料は、前記開口部の縁部に渡って延出する一体型の枠状であることを特徴とする請求項２４に記載の金属空気電池。 25. A metal-air battery according to claim 24, wherein the liquid impermeable material is an integral frame extending across the edge of the opening.
  26. 　前記非透液性材料は、前記開口部の縁部に渡って延出する枠状となるように複数の短冊状の非透液材料を接続したことを特徴とする請求項２４に記載の金属空気電池。 The metal according to claim 24, wherein the non-liquid-permeable material is formed by connecting a plurality of strip-like non-liquid-permeable materials in a frame shape extending over the edge of the opening. Air battery.
  27. 　前記金属極は、
    　電解液の注入前には、表面に不動態被膜が形成されておらず、
    　電解液の注入後に電池反応で発生する酸化物により、表面に不動態被膜が形成される金属極であり、
    　前記金属極と前記空気極とを有する前記金属空気電池は、前記不動態被膜を除去するため負荷を接続しない状態で前記金属極と前記空気極とを含む閉回路を選択的に形成する回路を備えることを特徴とする請求項１に記載の金属空気電池。     The metal electrode is
    Before injection of the electrolyte, no passivation film is formed on the surface,
    It is a metal electrode on which a passivation film is formed on the surface by the oxide generated in the battery reaction after injection of the electrolyte solution,
    The metal-air battery having the metal electrode and the air electrode selectively forms a closed circuit including the metal electrode and the air electrode in a state in which no load is connected to remove the passive film. A metal-air battery according to claim 1, comprising.
  28. 　前記回路は、前記金属極と前記空気極の間に設けられる開閉式の短絡回路であることを特徴とする請求項２７に記載の金属空気電池。 The metal air battery according to claim 27, wherein the circuit is a switchable short circuit provided between the metal electrode and the air electrode.
  29. 　前記回路は、前記金属極と前記空気極との間に設けられる開閉式の抵抗放電回路であることを特徴とする請求項２８に記載の金属空気電池。 The metal air battery according to claim 28, wherein the circuit is a switchable resistance discharge circuit provided between the metal electrode and the air electrode.
  30. 　前記抵抗放電回路は、当該回路を流れる電流値が所定値を超えるとスイッチ開となるサーキットプロテクタスイッチであることを特徴とする請求項２９に記載の金属空気電池。 The metal air battery according to claim 29, wherein the resistive discharge circuit is a circuit protector switch which opens when the current value flowing through the circuit exceeds a predetermined value.
  31. 　前記金属極と前記空気極とを備える複数の単位電池が直列接続され、
    　前記複数の単位電池からなる組電池の両端の前記金属極と前記空気極との間に、前記回路を設けたことを特徴とする請求項２７乃至３０のいずれかに記載の金属空気電池。     A plurality of unit cells comprising the metal electrode and the air electrode are connected in series;
    31. The metal air battery according to any one of claims 27 to 30, wherein the circuit is provided between the metal electrode and the air electrode at both ends of a battery pack including the plurality of unit batteries.
  32. 　前記閉回路を流れる電流値を検出する電流検出部を設けたことを特徴とする請求項２７乃至３１のいずれかに記載の金属空気電池。 The metal air battery according to any one of claims 27 to 31, further comprising a current detection unit that detects a current value flowing through the closed circuit.
  33. 　前記電流検出部は、検出した電流値に応じて回路を開回路にすることを特徴とする請求項３２に記載の金属空気電池。 The metal air battery according to claim 32, wherein the current detection unit opens the circuit in accordance with the detected current value.
  34. 　前記閉回路を流れる積算電流値を検出する積算電流検出部を設けたことを特徴とする請求項２７乃至３１のいずれかに記載の金属空気電池。 The metal air battery according to any one of claims 27 to 31, further comprising an integrated current detection unit for detecting an integrated current value flowing through the closed circuit.
  35. 　前記積算電流検出部は、検出した積算電流値に応じて回路を開回路にすることを特徴とする請求項３４に記載の金属空気電池。 The metal air battery according to claim 34, wherein the integrated current detection unit opens the circuit in accordance with the detected integrated current value.
  36. 　前記閉回路にしてからの経過時間を検出する時間検出部を設けたことを特徴とする請求項２７乃至３１のいずれかに記載の金属空気電池。 The metal air battery according to any one of claims 27 to 31, further comprising a time detection unit that detects an elapsed time after the closed circuit.
  37. 　前記時間検出部は、検出した経過時間に応じて回路を開回路にすることを特徴とする請求項３６に記載の金属空気電池。 The metal-air battery according to claim 36, wherein the time detection unit opens the circuit according to the detected elapsed time.
  38. 　前記金属極は、少なくとも亜鉛を含むマグネシウム合金で形成されることを特徴とする請求項１乃至３７のいずれか一項に記載の金属空気電池。 The metal-air battery according to any one of claims 1 to 37, wherein the metal electrode is formed of a magnesium alloy containing at least zinc.
  39. 　請求項１乃至３８のいずれかに記載の複数の前記金属空気電池が、空気が滞留する間隙をあけて外箱内に収納され、前記外箱の側面部に、前記間隙内に突出して前記外装体を支える突片を備えたことを特徴とする金属空気電池ユニット。 The plurality of metal air batteries according to any one of claims 1 to 38 are housed in an outer case with a gap for air to be accumulated therein, and are projected into the gap on the side portion of the outer case and the outer case The metal air battery unit characterized by having the protrusion which supports a body.
  40. 　前記突片が前記外箱の側面部に上下方向に間隔をあけて複数設けられていることを特徴とする請求項３９に記載の金属空気電池ユニット。 40. The metal-air battery unit according to claim 39, wherein a plurality of the projecting pieces are provided at intervals in the vertical direction on the side surface portion of the outer case.
  41. 　前記金属空気電池間にスペーサが配置され、前記スペーサに前記突片が係止されることを特徴とする請求項３９又は４０に記載の金属空気電池ユニット。 The metal-air battery unit according to claim 39 or 40, wherein a spacer is disposed between the metal-air batteries, and the projecting piece is engaged with the spacer.
  42. 　前記スペーサは立体的なスペーサであって、中央部に空気が滞留する滞留部を備え、この滞留部の両側部に、空気極を対向させて金属空気電池が配置されるポケットを備えたことを特徴とする請求項４１に記載の金属空気電池ユニット。 The spacer is a three-dimensional spacer, and has a retention portion in the central portion where air is retained, and provided on both sides of this retention portion a pocket in which an air electrode is opposed and a metal-air battery is disposed. 42. A metal-air battery unit according to claim 41, characterized in that.
  43. 　前記スペーサは一枚のシート状のダンボールを折り曲げて立体的に形成されていることを特徴とする請求項４２に記載の金属空気電池ユニット。 The metal-air battery unit according to claim 42, wherein the spacer is three-dimensionally formed by bending a sheet of sheet cardboard.
  44. 　前記外装体の側面に枠部材が配置され、この枠部材の開口部に前記空気極が配置され、前記突片が前記枠部材を支えることを特徴とする請求項３９乃至４３のいずれかに記載の金属空気電池ユニット。 The frame member is disposed on the side surface of the exterior body, the air electrode is disposed in the opening of the frame member, and the projection piece supports the frame member. Metal air battery unit.
  45. 　前記外箱が紙製であることを特徴とする請求項３９乃至４４のいずれかに記載の金属空気電池ユニット。 The metal-air battery unit according to any one of claims 39 to 44, wherein the outer box is made of paper.
  46. 　前記突片が前記外箱の側面部に一部の切り離し予定部を介して連結され、前記切り離し予定部が切り離されて前記間隙内に突出し前記空気極を支えることを特徴とする請求項４５に記載の金属空気電池ユニット。 46. The apparatus according to claim 45, wherein the projecting piece is connected to the side surface of the outer case through a part to be separated, the part to be separated is separated, protrudes into the gap, and supports the air electrode. Metal-air battery unit as described.
PCT/JP2014/080033 2013-11-19 2014-11-13 Metal-air battery and metal-air battery unit WO2015076172A1 (en)

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JP2013-238628 2013-11-19
JP2013238628 2013-11-19
JP2014-009265 2014-01-22
JP2014009265A JP5687782B1 (en) 2014-01-22 2014-01-22 Metal air battery
JP2014-017606 2014-01-31
JP2014017606 2014-01-31
JP2014-017122 2014-01-31
JP2014017122A JP5684929B1 (en) 2014-01-31 2014-01-31 Metal air battery
JP2014-185154 2014-09-11
JP2014185154A JP5687795B1 (en) 2013-11-19 2014-09-11 Metal air battery
JP2014-229002 2014-11-11
JP2014229002A JP5690443B1 (en) 2014-01-31 2014-11-11 Metal-air battery unit

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