JP2015172546A - Electric characteristic measurement device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electric characteristic measurement device capable of improving the working efficiency when the electric characteristic of a solid electrolyte is measured.SOLUTION: An electric characteristic measurement device 1 includes a first electrode 11, a second electrode 12, a cylindrical holder 2, and energizing means 3 for energizing a solid electrolyte 4 in the direction for grasping it between the first electrode 11 and second electrode 12. The holder 2 includes a first end 21 at one end side in the axial direction, and a second end 22 at the other end side in the axial direction. The holder 2 stores the first electrode 11, solid electrolyte 4, and second electrode 12 in a facing manner in this sequence from the first end 21 side. The holder 2 has a slit 24 cut in from the second end 22 side to the first end 21 side.

Description

  The present invention relates to an electrical characteristic measuring apparatus.

  In recent years, the spread of portable terminals such as notebook computers, tablet computers, mobile phones, and smartphones has been remarkable. For such portable terminals, more comfortable portability is required, and downsizing, thinning, weight reduction, high performance, and the like of portable terminals are rapidly progressing. In addition, lithium secondary batteries are frequently used as power sources for portable terminals, and demands for smaller, thinner, lighter, and higher performance are also increasing for batteries as well. .

Since the performance of the lithium secondary battery depends on the performance of the electrolyte held between the electrodes, research and development of higher performance electrolytes continues.
Conventionally, when evaluating the characteristics of an electrolyte, a commercially available battery evaluation cell is used. Many conventional evaluation cells are made to measure the conductivity of a liquid electrolyte. For example, an electrode or other member or an electrolyte containing a metal salt is placed in the cell body, and the exterior of the cell The body is assembled by screwing, tightening and sealing (see, for example, Patent Document 1).

JP 2014-002015 A

Conventional assembly of evaluation cells and measurement of electrical characteristics are performed, for example, in a glove box in a measurement environment in a state where the cell is blocked from outside air. That is, detailed work such as putting electrodes and electrolytes in the cell body and screwing to seal the cell must be performed with the glove attached to the hand. Since it is difficult, there is a problem that work efficiency is low. In the electrolyte research and development stage, it is assumed that many types of samples are measured a plurality of times, so there is a strong demand to improve the efficiency of the measurement work.
In recent years, lithium secondary batteries using a non-aqueous electrolyte as an electrolyte may cause problems such as liquid leakage and short circuit. Therefore, as an alternative electrolyte, for example, a polymer and a metal salt are included, and a solvent is used. Research and development of solid polymer electrolytes that do not contain it are underway. An apparatus for measuring the ionic conductivity of a solid electrolyte is not particularly defined by standards or the like, and a conventional evaluation cell is still used. The creation and measurement of the cell for evaluating the electrical characteristics of the solid electrolyte is also performed inside the glove box in order to prevent the polymer compound from absorbing moisture. Therefore, there is a problem that it takes time to assemble the evaluation cell and the working efficiency is low.

  The objective of this invention is providing the electrical property measuring apparatus which can improve the working efficiency at the time of measuring the electrical property of a solid electrolyte.

  The electrical property measuring apparatus according to an aspect of the present invention includes a first electrode, a second electrode, a first end on one end side in the axial direction, and a second end on the other end side in the axial direction. A cylindrical holder for accommodating the first electrode, the solid electrolyte, and the second electrode facing each other in this order from the first end portion side, and the solid electrolyte between the first electrode and the second electrode Urging means for urging in the direction of being sandwiched by the holder, wherein the holder has a slit cut from the second end side toward the first end side.

  In the electrical characteristic measuring device according to one aspect of the present invention, the biasing means includes an elastic member and a lid, and the elastic member is accommodated on the second end side with respect to the second electrode, The lid member is preferably placed closer to the second end than the elastic member to compress the elastic member.

  In the electrical property measuring apparatus according to one aspect of the present invention, the first electrode has a first contact surface in contact with the solid electrolyte, and the second electrode has a second contact surface in contact with the solid electrolyte. The electrical property measuring apparatus, wherein an area of the second contact surface is smaller than an area of the first contact surface, and an area of the solid electrolyte is larger than an area of the second contact surface.

  In the electrical characteristic measuring device according to one aspect of the present invention, at least one of the first electrode and the second electrode has a knob portion, and the knob portion is inserted from the inside of the holder through the slit. It preferably has a length that protrudes outward.

In the electrical characteristic measuring device according to one aspect of the present invention, the third electrode is accommodated on the first end side with respect to the first electrode and is in contact with the first electrode, and the third electrode is in contact with the first electrode. It is preferable to have a fourth electrode housed on the second end side and in contact with the second electrode.
Furthermore, in the electrical property measuring apparatus according to this aspect, at least one of the third electrode and the fourth electrode has a knob portion, and the knob portion is located outside the holder through the slit. It is preferable to have a length that protrudes toward the center.

  In the electrical property measuring apparatus according to one aspect of the present invention, the knob portion is preferably conductive.

According to the electrical characteristic measuring apparatus according to one aspect of the present invention, when the first electrode, the solid electrolyte, and the second electrode are accommodated in the holder or taken out from the holder, the solid electrolyte or the like is gripped through the slit. While being accommodated in the holder, it can be taken out from the holder.
In addition, the solid electrolyte can be easily sandwiched between the first electrode and the second electrode by the biasing means. It is possible to move to measurement work quickly without performing tightening work such as screwing.
As described above, according to the electrical property measuring apparatus according to one aspect of the present invention, measurement preparation, replacement of a measurement object, clean-up after measurement, and the like can be easily performed. It is possible to improve the work efficiency when doing so.

  Moreover, in the electrical characteristic measuring apparatus according to one aspect of the present invention, when the holder is installed with the first end portion side down as long as the biasing means includes the elastic member and the lid member described above, Further, a lid member is placed on the second end side, the elastic member is compressed by the weight of the lid member, and the second electrode is biased toward the first end side of the holder. Therefore, tightening work such as screwing is not necessary, and preparation before measurement can be easily performed. Further, after the measurement, there is no work of loosening the screw, and the lid material is removed, the elastic member is taken out, and the solid electrolyte is taken out. Therefore, the work after the measurement can be easily performed. Therefore, the working efficiency when measuring the electrical characteristics of the solid electrolyte can be further improved.

  Further, in the electrical property measuring apparatus according to one aspect of the present invention, if the relationship that the area of the second contact surface of the second electrode is smaller than the area of the first contact surface of the first electrode, The area facing the electrode of the solid electrolyte (electrode facing area) is determined by the area of the smaller second contact surface. As a result, even when the solid electrolyte is replaced and measured multiple times, the electrode facing area of the solid electrolyte when calculating the ionic conductivity can be fixed and kept constant at the area of the second contact surface each time. Measurement accuracy can be improved. Furthermore, since the area of the second contact surface of the second electrode is smaller, it becomes difficult for air to be caught between the electrode and the solid electrolyte, and the measurement accuracy can be improved. Moreover, since the area of the 2nd contact surface of a 2nd electrode is smaller, when installing a 2nd electrode, a high positional accuracy is not requested | required and workability | operativity in a glove box improves.

  Further, in the electrical characteristic measuring device according to one aspect of the present invention, if at least one of the first electrode and the second electrode has a knob portion having a length protruding from the inside of the holder through the slit to the outside. The electrode and the solid electrolyte can be taken into and out of the holder by holding the knob portion. Therefore, measurement preparation, replacement of a measurement object, clean-up after measurement, and the like can be performed more easily, and the efficiency of measurement work can be further improved.

Further, in the electrical characteristic measuring apparatus according to one aspect of the present invention, if the third electrode and the fourth electrode are provided, the solid electrolyte for measuring the material of the first electrode and the second electrode in contact with the solid electrolyte. The third electrode and the fourth electrode can be appropriately changed according to the characteristics, and can be made of a conductive material different from that of the first electrode and the second electrode. Therefore, the cost increase of the electrical characteristic measuring device can be suppressed. For example, when the first electrode and the second electrode that are in contact with the solid electrolyte are made of an expensive metal, the first electrode and the second electrode are reduced in thickness by reducing the amount of metal used and reducing the cost. Examples of the electrode and the fourth electrode include a mode in which conductivity is ensured as a shape in which the thickness is secured with a relatively inexpensive metal.
Further, in the electrical characteristic measuring apparatus according to one aspect of the present invention, if at least one of the third electrode and the fourth electrode has a knob portion, the efficiency of the measurement work can be further improved as described above. Can do.

  In the electrical characteristic measuring device according to one embodiment of the present invention, if the knob portion is conductive, the knob portion can be used as a lead electrode. Since the conductive knob portion as the lead electrode protrudes from the slit portion to the outside of the holder, for example, the electrical characteristic measuring device and the measuring instrument may be electrically connected via the knob portion. Therefore, the electrical characteristics can be easily measured.

It is a disassembled perspective view of the electrical property measuring device concerning one embodiment of the present invention. It is a longitudinal cross-sectional view of the electrical property measuring apparatus according to the embodiment.

  Hereinafter, the present invention will be described with reference to embodiments. The present invention is not limited to the contents of the embodiment.

(Electrical characteristic measuring device)
FIG. 1 is an exploded perspective view of an electrical property measuring apparatus 1 according to an embodiment of the present invention. FIG. 2 shows a longitudinal sectional view of the electrical characteristic measuring apparatus 1.
In the present embodiment, an embodiment in which the ionic conductivity of the solid electrolyte is measured by the electrical property measuring apparatus 1 will be described as an example, but the present invention is not limited to this embodiment.
The electrical characteristic measuring apparatus 1 includes a first electrode 11, a second electrode 12, a third electrode 13, a fourth electrode 14, a holder 2, and an urging means 3. Between the 1st electrode 11 and the 2nd electrode 12, the solid electrolyte 4 which is a measuring object is arrange | positioned.

The holder 2 has a cylindrical main body portion 20 and includes a first end portion 21 on one end side in the axial direction and a second end portion 22 on the other end side in the axial direction. In the present embodiment, the first end 21 side is closed by the bottom 23 and the second end 22 side is open.
The holder 2 has an internal space that can accommodate an electrode and the like inside the main body 20. The holder 2 accommodates the third electrode 13, the first electrode 11, the solid electrolyte 4, the second electrode 12, and the fourth electrode 14 in this order from the first end 21 side. When accommodating these members in the holder 2, the holder 2 may be placed with the bottom 23 facing downward and sequentially inserted from the upper second end 22 side.

  The holder 2 has two slits 24 cut from the second end 22 side toward the first end 21 side on the side surface of the main body 20. The number of slits is not limited to two and may be one or three or more. In the present embodiment, the two slits 24 are formed at positions facing each other. The shape of the slit 24 is not particularly limited. For example, the slit 24 is U-shaped, V-shaped, rectangular, or elliptical when the slit 24 is viewed from the front. Further, the position, shape, width, cut depth, and the like of the two slits 24 may be the same as or different from each other. Note that the electrode and the solid electrolyte 4 may be taken in and out of the holder 2 through the slit 24.

The material of the holder 2 is not particularly limited as long as electrical insulation with an electrode, a solid electrolyte, or the like accommodated therein is ensured. Examples of the material of the holder 2 include synthetic resin, paper material, metal, and wood. Synthetic resins include polyvinyl chloride resin, polyester resin (polyethylene terephthalate, etc.), acrylic resin, polycarbonate resin, polyethylene resin, polypropylene resin, acrylonitrile / butadiene / styrene resin, polyimide resin, polyurethane resin, polystyrene resin, phenol resin, poly Examples thereof include tetrafluoroethylene resin. Examples of the metal include stainless steel, copper, aluminum, and titanium. When the holder is made of metal, a structure in which an insulating treatment is applied to a portion that can come into contact with the accommodated electrode, the solid electrolyte 4 or the like is employed.
In this embodiment, the holder 2 is made of polytetrafluoroethylene resin that is chemically stable and excellent in heat resistance and chemical resistance.

The first electrode 11 and the second electrode 12 are accommodated inside the holder 2 and sandwich the solid electrolyte 4. In the present embodiment, the first electrode 11 and the second electrode 12 are formed in a disk shape.
The first electrode 11 has a first contact surface 11 </ b> A in contact with the solid electrolyte 4, and the second electrode 12 has a second contact surface 12 </ b> A in contact with the solid electrolyte 4. In the present embodiment, the area of the second contact surface 12A is smaller than the area of the first contact surface 11A. The first contact surface 11A and the second contact surface 12A are preferably smooth so that the adhesion to the solid electrolyte 4 is enhanced. The area of the first contact surface 11A is equal to or slightly smaller than the area of a circle on the inner peripheral side when the holder 2 is viewed in the axial direction.

  The material of the first electrode 11 and the second electrode 12 is not particularly limited as long as it has conductivity. For example, examples of the material of the first electrode 11 and the second electrode 12 include stainless steel, gold, platinum, copper, aluminum, nickel, titanium, and other metals, carbon, conductive resin, and the like. The materials of the first electrode 11 and the second electrode 12 that are in contact with the solid electrolyte 4 are preferably selected as appropriate according to the item of electrical characteristics to be measured. For example, when measuring the conductivity of lithium ions, more accurate measurement is possible by selecting an electrode made of a material having a function of blocking ions other than lithium ions. In addition, the electrical property measuring apparatus 1 can measure how much electrons and holes are flowing in the electrolyte. The first electrode 11 and the second electrode 12 do not have to be formed entirely of the same material, and a layer of a desired material is formed on the first contact surface 11A side and the second contact surface 12A side. It may be a configuration. For example, gold (Au) or platinum (Pt) is formed on a stainless steel electrode surface by a sputtering method, and the surface of the gold or platinum coating film is used as the first contact surface 11A and the second contact surface 12A. Good.

The third electrode 13 and the fourth electrode 14 are accommodated inside the holder 2 and sandwich the first electrode 11, the solid electrolyte 4 and the second electrode 12.
The third electrode 13 is accommodated closer to the first end portion 21 than the first electrode 11 and is in contact with the first electrode 11. The fourth electrode 14 is accommodated on the second end 22 side of the second electrode 12 and contacts the second electrode 12.
In the present embodiment, the third electrode 13 is formed in a cylindrical shape having a thickness larger than that of the first electrode 11, and the fourth electrode 14 is formed in a cylindrical shape having a thickness larger than that of the second electrode 12. . The third electrode 13 and the fourth electrode 14 are used, for example, to make it easier to attach the lead electrode when the first electrode 11 and the second electrode 12 are thin and the lead electrode is difficult to attach. The area of the circle when the third electrode 13 and the fourth electrode 14 are viewed in the axial direction is not particularly limited as long as the area can be accommodated in the cylindrical holder 2, but the first contact surface 11A of the first electrode 11 and Almost equal.

The third electrode 13 has a knob portion 13A, and the fourth electrode 14 has a knob portion 14A. The knob portion 13A protrudes from the side surface of the columnar third electrode 13, and the knob portion 14A protrudes from the side surface of the columnar fourth electrode 14. The knob portion 13 </ b> A and the knob portion 14 </ b> A have a length that can protrude to the outside of the holder 2 through the slit 24 when the third electrode 13 and the fourth electrode 14 are accommodated in the holder 2, respectively. Further, the knob portion 13A and the knob portion 14A are not particularly limited as long as the knob portion 13A and the knob portion 14A are movable along the slit 24. Examples of the shape of the knob portion 13A and the knob portion 14A include a rod shape and a plate shape. In the present embodiment, the shape is a rod shape. In addition, shapes such as the width and depth of the slit 24 may be set in accordance with the shapes of the knob portion 13A and the knob portion 14A. The knob portion 13A is detachably attached to the third electrode 13, and the knob portion 14A is detachably attached to the fourth electrode 14. For example, the third electrode 13 or the fourth electrode 14 is provided with a screw hole, the knob portion 13A or the knob portion 14A is provided with a screw portion, and the screw hole is provided with the screw. The aspect which screws a part is mentioned. Alternatively, the knob portion 13A or the knob portion 14A may be a screw itself and may be screwed into the screw hole.
The knob portion 13A may be integrally formed with the third electrode 13, or the knob portion 14A may be integrally formed with the fourth electrode 14.

The material of the third electrode 13 and the fourth electrode 14 is not particularly limited as long as it has conductivity. For example, as the material of the third electrode 13 and the fourth electrode 14, the materials exemplified in the description of the first electrode 11 and the second electrode 12 can be cited. The materials of the first electrode 11, the second electrode 12, the third electrode 13, and the fourth electrode 14 may be the same as or different from each other.
The material of the knob portion 13A and the knob portion 14A is not particularly limited, and examples thereof include synthetic resin and metal. The knob portion 13A and the knob portion 14A are preferably made of metal. Further, when the knob portion 13A and the knob portion 14A are made of metal, it is preferable that the third electrode 13 and the knob portion 13A are formed so as to be electrically conductive, and the fourth electrode 14 and the knob portion 14A are formed. It is preferably formed so as to be electrically conductive. In this case, the knob portion 13A and the knob portion 14A can function as lead electrodes.

The solid electrolyte 4 is formed in a film shape having a predetermined thickness. In the present embodiment, the solid electrolyte 4 has a circular shape that can be accommodated in the cylindrical holder 2, and the area of the solid electrolyte 4 is larger than the area of the second contact surface 12 </ b> A of the second electrode 12.
The solid electrolyte 4 is a polymer solid electrolyte containing a polymer compound and a metal salt. The polymer compound contained in the solid electrolyte 4 preferably has a mass average molecular weight of 100,000 or more, more preferably 100,000 or more and 1,000,000 or less.
Specific examples of polymer compounds having a mass average molecular weight of 100,000 or more include ion conductive polymers such as polyethylene oxide, polyethylene carbonate, polyacrylonitrile, polyvinylidene fluoride, polymethyl methacrylate, polyhexafluoropropylene, and polyethylene oxide. Is done.
As said metal salt, a well-known thing can be utilized according to the kind of nonaqueous electrolyte secondary battery and an active material. For example, alkali metal salts such as lithium salts and sodium salts, and alkaline earth metal salts such as magnesium salts and calcium salts can be given. Among these, lithium salt is more preferable because of its high energy density.
In the solid electrolyte, the metal salt can exist as a cation such as an alkali metal and a counter ion of the cation. If the metal salt is a lithium salt, lithium ions are transported through the polymer compound.

Examples of the lithium _{salt, LiClO 4, LiBF 4, LiI} , LiPF 6, LiCF 3 SO 3, LiCF 3 COO, LiNO 3, LiAsF 6, LiSbF 6, LiAlCl 4, LiCl, LiBr, LiB (C 2 H 5) ₄ , LiCH ₃ SO ₃ , LiC ₄ F ₉ SO ₃ , Li (CF ₃ SO ₂ ) ₂ N, Li (C ₂ F ₅ SO ₂ ) N, Li [(CO ₂ ) ₂ ] ₂ B, and the like. it can.

  The urging means 3 urges the solid electrolyte 4 in a direction in which the solid electrolyte 4 is sandwiched between the first electrode 11 and the second electrode 12. In the present embodiment, the urging means 3 urges the second electrode 12 accommodated in the holder 2 from the second end 22 side toward the first end 21 side. Since the first end 21 side of the holder 2 is closed by the bottom 23, the solid electrolyte 4 is sandwiched by urging in one direction from the second end 22 side. The biasing means 3 can be biased without tightening by screwing or the like.

The urging unit 3 includes an elastic member 31 and a lid member 32.
The elastic member 31 is accommodated on the second end 22 side with respect to the fourth electrode 14. The elastic member 31 is not particularly limited, and examples thereof include a coil spring, a disc spring, and a leaf spring. Examples of the material include elastic materials such as metal, rubber, and elastomer. It is preferable to have. In the present embodiment, a metal coil spring is used as the elastic member 31.
The lid member 32 is placed closer to the second end portion 22 than the elastic member 31 and compresses the elastic member 31. Specifically, in the present embodiment, the holder 2 is placed with the bottom 23 facing downward, and the third electrode 13, the first electrode 11, the solid electrolyte 4, the second electrode 12, and the fourth from the bottom 23 side. The electrode 14 and the elastic member 31 are accommodated in this order. Then, the elastic member 31 is compressed by the weight of the lid member 32 placed on the second end 22 side and is urged as described above. The material of the lid member 32 is not particularly limited as long as it has a weight that can compress the elastic member 31. The lid member 32 preferably has conductivity. In the present embodiment, the lid member 32 is made of metal and has a weight corresponding to the spring constant of the metal coil spring.

(Electrical characteristics measurement method)
Next, the electrical characteristic measurement method according to this embodiment will be described.
In the present embodiment, the ionic conductivity of the solid electrolyte 4 is measured using the electrical property measuring apparatus 1. Since the measurement and its preparation are carried out in the glove box, the holder 2 and the electrodes are handled by the hand wearing the glove. The inside of the glove box is controlled under predetermined humidity and temperature conditions.
The holder 2 is placed with the bottom 23 facing downward, and the third electrode 13, the first electrode 11, the solid electrolyte 4, the second electrode 12, the fourth electrode 14, and the elastic member 31 are arranged in this order from the bottom 23 side. Accommodate. When the third electrode 13 and the fourth electrode 14 are accommodated, they are accommodated along the slit 24 while gripping the knob portion 13A and the knob portion 14A. Alternatively, the first electrode 11, the solid electrolyte 4, and the second electrode 12 may be stacked in advance on the third electrode 13 and may be accommodated in the holder 2 while gripping the knob portion 13 </ b> A. Alternatively, the first electrode 11, the solid electrolyte 4 and the second electrode 12 may be accommodated while being held with tweezers or the like.
Thereafter, the elastic member 31 is placed on the fourth electrode 14. At this time, a part of the elastic member 31 protrudes from the second end 22 side of the holder 2. By placing the lid member 32 on the second end 22 side, the elastic member 31 is compressed and biased from the second end 22 side toward the first end 21 side.
In the present embodiment, the knob portion 13A and the knob portion 14A are used as lead electrodes, and the electrical characteristic measuring device 1 and an impedance measuring device as a measuring instrument are electrically connected via the lead electrodes. The impedance measuring device measures the impedance of the solid electrolyte 4 and determines the resistance value of the solid electrolyte 4 based on the measurement result. The ion conductivity is calculated based on the obtained resistance value, the thickness of the solid electrolyte 4, and the electrode facing area.
After the measurement is completed, the lid member 32 and the elastic member 31 are removed, and the first electrode 11, the solid electrolyte 4, and the second electrode 12 are placed on the third electrode 13 while holding the knob portion 14 </ b> A of the fourth electrode 14. You may take out, hold | grip the knob part 13A, making it laminate | stack.

(Effect of this embodiment)
According to the electrical property measuring apparatus 1 according to the present embodiment, the holder 2 is held while holding the accommodation (each electrode such as the first electrode 11 or the solid electrolyte 4) accommodated in the holder 2 through the slit 24. Or can be taken out of the holder 2. In addition, the solid electrolyte 4 can be easily sandwiched between the first electrode 11 and the second electrode 12 by using the urging means 3 after the accommodation is accommodated in the holder 2. The solid electrolyte 4 can be held between the electrodes without performing a tightening operation such as screwing, and the measurement operation can be quickly performed. Therefore, according to the electrical property measuring apparatus 1, measurement preparation, replacement of the measurement object, clean-up after the completion of measurement, etc. can be easily performed, so that the work efficiency when measuring the electrical property of the solid electrolyte 4 is improved. Can be made.

  According to the electrical characteristic measuring apparatus 1, since the solid electrolyte 4 is sandwiched between the electrodes, the load applied to the solid electrolyte 4 can be reduced, and the destruction of the solid electrolyte 4 can be prevented. Therefore, according to the electrical characteristic measuring apparatus 1, the ionic conductivity of the solid electrolyte 4 can be measured more accurately.

In the electrical property measuring apparatus 1, the urging means 3 is composed of the elastic member 31 and the lid member 32 described above. According to such an urging means 3, the elastic member 31 is compressed by the weight of the lid member 32, and the second electrode 12 is urged toward the first end 21 (bottom 23) side of the holder 2. . Therefore, tightening work such as screwing is unnecessary, and preparation before measurement can be easily performed.
In addition, after the measurement, there is no work of loosening the screw, the cover member 32 is removed, the elastic member 31 is taken out, and the stored material such as the solid electrolyte 4 is taken out in the same manner as described above. It can be carried out. Therefore, the working efficiency when measuring the electrical characteristics of the solid electrolyte 4 can be further improved.

  Further, in the electrical characteristic measuring apparatus 1, the relationship that the area of the second contact surface 12A of the second electrode 12 is smaller than the area of the first contact surface 11A of the first electrode 11 is satisfied. Therefore, the electrode facing area of the solid electrolyte 4 is determined by the area of the second contact surface 12A. Therefore, even when the solid electrolyte 4 is replaced and measured multiple times, the electrode facing area of the solid electrolyte 4 when calculating the ionic conductivity can be fixed and kept constant at the area of the second contact surface 12A each time. Therefore, the measurement accuracy can be improved. Furthermore, since the area of the second contact surface 12A of the second electrode 12 is smaller, air is less likely to be caught between the second electrode 12 and the solid electrolyte 4, and the measurement accuracy can be improved. Further, since the area of the second contact surface 12A of the second electrode 12 is smaller, high positional accuracy is not required when installing the second electrode 12, and workability in the glove box is improved.

  In the electrical characteristic measuring apparatus 1, the knob portion 13 </ b> A of the third electrode 13 and the knob portion 14 </ b> A of the fourth electrode 14 protrude outward from the inside of the holder via the slit 24, and are movable along the slit 24. Has a shape. Therefore, the storage of the solid electrolyte 4 and the like in and out of the holder 2 can be performed by holding the knob portion 13A and the knob portion 14A. Therefore, measurement preparation, replacement of a measurement object, clean-up after measurement, and the like can be performed more easily, and the efficiency of measurement work can be further improved.

  Moreover, in the electrical characteristic measuring apparatus 1, since the knob part 13A and the knob part 14A are conductive, they can be used as lead electrodes. Since the knob portion 13A and the knob portion 14A as lead electrodes protrude from the slit 24 to the outside of the holder 2, for example, the electrical characteristic measuring device 1 and the impedance measuring device are electrically connected via the knob portion. do it. As described above, since the electrical connection between the electrical property measuring apparatus 1 and another apparatus is facilitated, the efficiency of measurement work can be further improved.

  Further, in the electrical property measuring apparatus 1, the elastic member 31 and the lid member 32 are made of metal and have electrical conductivity. Therefore, the fourth electrode 14 and the elastic member 31 are in contact with each other, the elastic member 31 and the lid member 32 are in contact with each other, and the second electrode 12 to the lid member 32 can be electrically connected to the holder 2. It is preferable that In this case, since the lid member 32 can be used as a lead electrode on the second electrode 12 side, electrical connection with the impedance measuring device is facilitated. Therefore, the efficiency of the measurement work can be further improved.

  Moreover, since the electrical property measuring apparatus 1 has a simple configuration, the apparatus cost can be reduced. If a plurality of low-cost electrical characteristic measuring apparatuses 1 are used and measurements are performed in parallel on a plurality of samples, the measurement result can be obtained quickly even when the number of samples is large.

  If the electrical property measuring apparatus 1 is used, the effect of increasing efficiency can be remarkably obtained when the measurement work of the solid electrolyte 4 is performed with the glove attached to the hand inside the glove box.

  It should be noted that the present invention is not limited to the above-described embodiment, and modifications, improvements, etc. within a scope that can achieve the object of the present invention are included in the present invention.

In the said embodiment, although the case where the holder 2 was cylindrical was mentioned as an example and demonstrated, in this invention, the shape of a holder is not limited to a cylindrical shape. For example, the shape when the holder is viewed in the axial direction, such as a square tube, may be a rectangular shape such as a square or a rectangle, or a polygonal shape such as a triangle, a pentagon, or a hexagon. An elliptical shape, an indefinite shape, or the like may be used.
Moreover, in the said embodiment, although the example in which the 1st end part 21 side of the holder 2 was obstruct | occluded by the bottom part 23 was mentioned as an example, this invention is not limited to such an aspect. For example, the first end 21 side may also be open and may be biased by biasing means from both the first end 21 side and the second end 22 side to sandwich the solid electrolyte 4. Alternatively, a holder having an opening on the first end 21 side may be placed on a measurement table, and the measurement table may be the bottom of the holder 2.

  In the said embodiment, although the aspect using the 3rd electrode 13 and the 4th electrode 14 was mentioned as an example and demonstrated, this invention is not limited to such an aspect. For example, the solid electrolyte 4 may be sandwiched between the first electrode 11 and the second electrode 12 without using the third electrode 13 and the fourth electrode 14. In this case, it is preferable that the first electrode 11 and the second electrode 12 each have a knob part as described above, and the knob part is conductive, and the first electrode 11 and the second electrode 12 More preferably, it is formed to be electrically conductive.

The first electrode 11 has a first knob portion, the second electrode 12 has a second knob portion, the third electrode 13 has a third knob portion, and the fourth electrode 14 has a fourth knob portion. It is good also as an aspect which has. These first to fourth knobs can also have the same configuration as described in the above embodiment.
Further, the number of knobs provided on each electrode is not limited to one, and two or more knobs may be provided on one electrode. For example, if one electrode has two knob portions corresponding to the positions of the two slits 24, the electrode can be accommodated in the holder 2 while being held in the holder 2, or taken out from the holder 2. Work efficiency is improved.

  In the said embodiment, although the aspect which an electrode has a knob part was mentioned as an example, this invention is not limited to such an aspect. For example, each electrode may not have a knob portion. In this case, since the slit is formed in the holder, each electrode and the solid electrolyte can be accommodated in the holder while being gripped by gripping means such as tweezers. Even after the measurement is completed, the electrode or the like inside the holder can be gripped through the slit and removed from the holder. In a cylindrical holder that does not have a slit, it is difficult to house the electrode or the like while holding the electrode or the like, and to take out the holder from the holder. For example, the solid electrolyte may be damaged during the housing operation.

  The electrical property measuring device may further include temperature control means such as a heater or a cooling device. By this temperature control means, it becomes possible to control the temperature of the solid electrolyte contained in the holder of the electrical property measuring apparatus, and the temperature dependence of the electrical property can be measured.

  Moreover, the electrical property measuring method is not limited to the method described in the above embodiment. A step of accommodating the first electrode, the solid electrolyte, and the second electrode in this order in a cylindrical holder having a slit cut from the second end side toward the first end side, and the solid electrolyte What is necessary is just to have the process of energizing in the direction clamped between a 1st electrode and said 2nd electrode, and the process of measuring the electrical property of a solid electrolyte.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

(Example of production of solid electrolyte)
Polyethylene oxide having a mass average molecular weight of 600,000 purchased from Sigma Aldrich Co., Ltd. and lithium bistrifluoromethanesulfonylimide (Li (CF ₃ SO ₂ ) ₂ N) are mixed in acetonitrile so that the mass ratio is 10: 5. Dissolved. This solution was cast on a petri dish made of polytetrafluoroethylene resin. After film formation, the film was allowed to stand for 24 hours in an argon atmosphere in which the dew point was controlled to −60 ° C. or lower. Thereafter, the solvent was removed by allowing to stand at 80 ° C. under reduced pressure for 24 hours to obtain a polymer solid electrolyte membrane.

Example 1
Using the electrical property measuring apparatus 1 described in the above embodiment, the ionic conductivity of the polymer solid electrolyte membrane obtained in the above-described production example was measured. The measurement and preparation of ionic conductivity were performed in a glove box controlled to a dew point of −60 ° C. or lower.
The polymer solid electrolyte membrane was used after being cut out into a circular shape having a diameter of 16 mm. The first electrode and the second electrode were platinum disk electrodes. The diameter of the first electrode was 20 mm, and the diameter of the second electrode was 10 mm. From the bottom side of a cylindrical holder made of polytetrafluoroethylene resin, a stainless steel third electrode, a first electrode, a polymer solid electrolyte membrane, a second electrode, a stainless steel fourth electrode, and a metal coil spring Were housed in this order. A stainless steel lid was placed on the opening side of the holder to compress the coil spring, and urged in a direction to sandwich the polymer solid electrolyte membrane between the first electrode and the second electrode. In this way, the polymer solid electrolyte membrane and the electrode were brought into close contact.
For the impedance measurement, an AC impedance method was used in which an alternating current (applied voltage is 50 mV) was applied between the electrodes and the resistance component was measured. The ion conductivity was calculated based on the value of the real impedance intercept of the obtained Cole-Cole plot. The measurement environment was 25 ° C. and 60 ° C.
The resistance value was measured with an As-510-ECA apparatus (manufactured by NF Circuit Design Block Co., Ltd.).

The ionic conductivity σ was determined by the following equation (1).
σ = L / (R × A) (1)
In the above formula (1), σ is ionic conductivity (unit is S / cm), R is resistance (unit is Ω), and A is an electrode facing area (unit is measured) of the polymer solid electrolyte membrane. cm ² ), and L is the distance between electrodes (unit: cm). In addition, the electrode facing area A of the polymer solid electrolyte membrane was calculated as the area of the second contact surface of the second electrode.

(Comparative Example 1)
Using a simple evaluation cell (manufactured by Toyo System Co., Ltd.), the ionic conductivity of the polymer solid electrolyte membrane obtained in the above-described production example was measured. The measurement and preparation of ionic conductivity were performed in a glove box controlled to a dew point of −60 ° C. or lower.
A polymer solid electrolyte membrane cut into a circular shape having a diameter of 16 mm was sandwiched between disc-shaped platinum electrodes having a diameter of 15 mm and set in a simple evaluation cell, and the outer body of the cell was screwed and tightened. For other points, impedance measurement was performed in the same manner as in Example 1.

The measurement result of the ionic conductivity of Example 1 was 3.36 × 10 ⁻⁶ [S / cm] at 25 ° C. and 6.62 × 10 ⁻⁴ [S / cm] at 60 ° C. .
The measurement result of the ionic conductivity of Comparative Example 1 was 3.24 × 10 ⁻⁶ [S / cm] at 25 ° C. and 6.55 × 10 ⁻⁴ [S / cm] at 60 ° C. .
Thus, it was found that the ionic conductivity of Example 1 measured using the electrical property measuring apparatus according to one aspect of the present invention has the same measurement accuracy as that of a conventional evaluation cell.
Furthermore, the working efficiency of the measurement and preparation of the ionic conductivity performed in the glove box was significantly better in Example 1 than in Comparative Example 1. In Comparative Example 1, since fine work such as screw tightening was necessary with the glove attached to the hand, it took time and labor for measurement and preparation, and the work efficiency was low.

  The present invention can be used as an apparatus for measuring electrical characteristics of a solid electrolyte.

  DESCRIPTION OF SYMBOLS 1 ... Electrical property measuring apparatus, 11 ... 1st electrode, 1A ... 1st contact surface, 12 ... 2nd electrode, 12A ... 2nd contact surface, 13 ... 3rd electrode, 13A ... Knob part, 14 ... 4th electrode, DESCRIPTION OF SYMBOLS 14A ... Knob part, 2 ... Holder, 21 ... 1st end part, 22 ... 2nd end part, 24 ... Slit, 3 ... Biasing means, 31 ... Elastic member, 32 ... Cover material, 4 ... Solid electrolyte.

Claims (7)

A first electrode;
A second electrode;
A first end is provided on one end side in the axial direction, a second end is provided on the other end side in the axial direction, and the first electrode, the solid electrolyte, and the second electrode are arranged in this order from the first end side. A cylindrical holder for receiving and facing
Biasing means for biasing the solid electrolyte in a direction to sandwich the solid electrolyte between the first electrode and the second electrode;
The electrical property measuring apparatus, wherein the holder has a slit cut from the second end side toward the first end side. In the electrical property measuring device according to claim 1,
The biasing means includes an elastic member and a lid member,
The elastic member is accommodated on the second end side than the second electrode,
The electrical characteristic measuring device, wherein the lid member is placed closer to the second end than the elastic member and compresses the elastic member. In the electrical property measuring device according to claim 1 or 2,
The first electrode has a first contact surface in contact with the solid electrolyte,
The second electrode has a second contact surface in contact with the solid electrolyte,
The area of the second contact surface is smaller than the area of the first contact surface,
The area of the said solid electrolyte is larger than the area of said 2nd contact surface, The electrical property measuring apparatus characterized by the above-mentioned. In the electrical property measuring device according to any one of claims 1 to 3,
At least one of the first electrode and the second electrode has a knob portion,
The electrical property measuring apparatus according to claim 1, wherein the knob portion has a length protruding outward from the inside of the holder through the slit. In the electrical property measuring device according to any one of claims 1 to 3,
A third electrode accommodated on the first end side of the first electrode and in contact with the first electrode;
An electrical property measuring apparatus comprising: a fourth electrode that is accommodated on the second end side with respect to the second electrode and contacts the second electrode. In the electrical property measuring device according to claim 5,
At least one of the third electrode and the fourth electrode has a knob portion,
The electrical property measuring apparatus according to claim 1, wherein the knob portion has a length protruding outward from the inside of the holder through the slit. In the electrical property measuring device according to claim 4 or 6,
The knob part is an electrical property measuring device characterized by being conductive.

Images