JP4301340B2 - Assembled battery - Google Patents

Description

The present invention relates to a battery pack with batteries in which a positive electrode and a negative electrode are laminated alternately.

  In recent years, in order to cope with air pollution and global warming, reduction of the amount of carbon dioxide has been strongly desired. In the automobile industry, there are high expectations for reducing carbon dioxide emissions by introducing electric vehicles (hereinafter also referred to as EVs) and hybrid electric vehicles (hereinafter also referred to as HEVs). Secondary batteries have been actively developed.

  As secondary batteries for motor drive, non-aqueous electrolyte batteries (also called non-aqueous solvent-type secondary batteries), among them lithium-ion secondary batteries having the highest theoretical energy among all batteries, have attracted attention. Currently, development is progressing rapidly.

  Such a lithium ion secondary battery generally includes a positive electrode in which a positive electrode active material or the like is applied to both surfaces of a positive electrode current collector using a binder, and a negative electrode in which a negative electrode active material or the like is applied to both surfaces of the negative electrode current collector using a binder. Have a laminate (power generation element) connected via an electrolyte layer. In addition, electrode terminals (a positive terminal and a negative terminal) are electrically connected to the power generation element for the purpose of extracting electric power to the outside. Furthermore, the power generation element is generally housed in a metal-resin laminate sheet in which a resin sheet is laminated on both sides of a foil made of a lightweight metal such as aluminum so that the electrode terminals are led out to the outside.

  As a current collector of a lithium ion secondary battery, for example, a metal foil such as aluminum is used for the positive electrode current collector, and a metal foil such as copper is generally used for the negative electrode current collector.

  And when manufacturing these positive electrodes and negative electrodes using these foils as a current collector, a slurry in which an electrode active material, a binder or the like was dispersed in a solvent was applied to the surface of the current collector foil and dried. Thereafter, a pressing process is performed using a method such as a roll press. As a result, a flat active material layer having a desired thickness is formed on the surface of the metal foil.

In a lithium ion secondary battery, even when an internal short circuit occurs, the aluminum thin film generates heat due to a short circuit current flowing through the short circuit part and is scattered, thereby recovering insulation of the short circuit part and preventing an increase in battery temperature. There is a prior art as described above (Patent Document 1).
JP 2003-243038 A

However, even if it is a battery currently disclosed by patent document 1, when a short circuit generate | occur | produces between several batteries, when this is electrically connected in series and comprises an assembled battery, the short circuit part of a positive electrode still flow of the short circuit current does not disappear even if the insulation is recovered in the present invention we have found that the temperature of the battery is likely Ru on Noborisu accompanying this has been found in the course of the study.

The present invention has been made in view of the above-described problems, and an object thereof is to provide a battery capable of interrupting the flow of a short-circuit current even when a short circuit occurs between a plurality of batteries. .

In order to solve the above-mentioned problems, the present inventors have intensively studied. As a result, when a conductor having a diameter of 3 mm penetrates at least two batteries from the outside, the first current collector, the conductor, and the second current collector are disposed inside each of the two batteries. The short-circuit portion of the first current collector of the battery is melted by the short-circuit current flowing through the first short-circuit formed from the first current-breaking portion, and the two second current collectors of the two batteries are formed. and as the second conductive fracture portion shorted portions of at least one of the second current collector of said two battery by short-circuit current flowing through the second short circuit formed from said conductor to melt is formed, The inventors have found that the above-mentioned problems can be solved by selecting the thickness and material of the first current collector and the second current collector, and have completed the present invention.

More specifically, the assembled battery of the present invention is formed by electrically connecting a plurality of stacked batteries. The battery includes a power generation element and an exterior material. The power generation element includes a single battery layer including a first electrode, a second electrode, and an electrolyte layer. The first electrode is formed by forming either the positive electrode active material layer or the negative electrode active material layer on the first current collector. The second electrode is formed by forming the other of the positive electrode active material layer and the negative electrode active material layer on the second current collector. The electrolyte layer is located between the first electrode and the second electrode. The assembled battery according to the present invention is configured such that when at least two stacked batteries are electrically connected in series and a conductor having a diameter of 3 mm penetrates the two batteries connected in series from the outside, the two batteries Each of the first current collector of the battery is melted by a short-circuit current flowing through a first short-circuit formed from the first current collector, the conductor, and the second current collector. The first conduction break portion is formed, and the second current collector of the two batteries and the second short circuit current formed from the conductor cause a short-circuit current to flow at least one of the two batteries. 2 The current collector is characterized in that the thickness and material of the first current collector and the second current collector are selected such that the short-circuited portion of the current collector is melted to form the second conduction fracture portion. Have.

According to the present invention, even when a short circuit occurs between a plurality of batteries, the flow of the short circuit current can be interrupted by melting the short circuit part . As a result, the temperature rise of the battery is suppressed et be.

First is a description of preferred embodiments of the battery pack of the present invention is not limited only to the following embodiments. In the description of the drawings, the same elements are denoted by the same reference numerals, and redundant description is omitted. In addition, the dimensional ratios in the drawings are exaggerated for convenience of explanation, and may be different from the actual ratios.

Although the kind of battery which comprises the assembled battery of this invention is not restrict | limited in particular, For example, it is a nonaqueous electrolyte battery. Further, when distinguished by the structure and form of the non-aqueous electrolyte battery, it is not particularly limited, such as a stacked (flat) battery or a wound (cylindrical) battery, and can be applied to any conventionally known structure. .

  Similarly, there is no particular limitation in the case of distinguishing by the form of the electrolyte of the nonaqueous electrolyte battery. For example, the present invention can be applied to any of a liquid electrolyte type battery in which a separator is impregnated with a nonaqueous electrolytic solution, a polymer gel electrolyte type battery also called a polymer battery, and a solid polymer electrolyte (all solid electrolyte) type battery. With respect to the polymer gel electrolyte and the solid polymer electrolyte, these can be used alone, or the polymer gel electrolyte or the solid polymer electrolyte can be used by impregnating the separator.

Moreover, the battery which comprises the assembled battery of this invention may be either a primary battery or a secondary battery. Furthermore, when it sees with the electrode material of a battery, or the metal ion which moves between electrodes, it does not restrict | limit in particular, It can apply to any well-known electrode material. Examples include lithium ion secondary batteries, sodium ion secondary batteries, potassium ion secondary batteries, nickel metal hydride secondary batteries, nickel cadmium secondary batteries, nickel metal hydride batteries, and the like, preferably lithium ion secondary batteries. . This is because in the lithium ion secondary battery, the voltage of the cell (single cell layer) is large, high energy density and high output density can be achieved, and it is excellent as a vehicle driving power source or an auxiliary power source.

Therefore, in the following description, the case where the battery constituting the assembled battery of the present invention is a lithium ion secondary battery will be described as a representative embodiment. However, the technical scope of the present invention is as follows. Is not limited to only.

<First Embodiment>
FIG. 1 shows an overall structure of a stacked non-bipolar lithium ion secondary battery (hereinafter also simply referred to as “lithium ion battery”), which is a typical embodiment of a battery constituting the assembled battery of the present invention. It is the cross-sectional schematic represented typically.

  As shown in FIG. 1, in the lithium ion battery 10 of the present embodiment, a laminate film composed of a polymer and a metal is used for the battery exterior material 22, and the entire peripheral part is bonded by thermal fusion. Thus, the power generation element 17 is housed and sealed. Specific components of the power generation element 17 are as follows.

  The power generation element 17 includes a positive electrode in which a positive electrode active material layer 12 is formed on both surfaces of a positive electrode current collector 11, an electrolyte layer 13, and a negative electrode in which a negative electrode active material layer 15 is formed on both surfaces of a negative electrode current collector 14. A plurality of unit cell layers 16 are stacked. At this time, the positive electrode, the electrolyte layer, and the positive electrode active material layer 12 on one side of one positive electrode and the negative electrode active material layer 15 on one side of one negative electrode adjacent to the one positive electrode face each other through the electrolyte layer 13. 13. The negative electrode is laminated in this order. In addition, there is no restriction | limiting in particular in the number of lamination | stacking of the single battery layer 16, For example, Preferably it is 5-40 layers, More preferably, it is 10-30 layers.

  With the above-described configuration, the adjacent positive electrode current collector 11, positive electrode active material layer 12, electrolyte layer 13, negative electrode active material layer 15, and negative electrode current collector 14 constitute one single battery layer 16. Therefore, it can be said that the lithium ion battery 10 of the present embodiment has a configuration in which a plurality of single battery layers 16 are stacked and electrically connected in parallel. Note that the negative electrode active material layer 15 is formed on only one side of the outermost negative electrode current collector 14 a located on both outermost layers of the power generation element 17.

  Further, the positive electrode tab 18 and the negative electrode tab 19 that are electrically connected to the respective electrodes (positive electrode and negative electrode) are connected to the positive electrode current collector 11 and the negative electrode current collector 14 of each electrode through the positive electrode terminal lead 20 and the negative electrode terminal lead 21. Are attached by ultrasonic welding or resistance welding. Thereby, the positive electrode tab 18 and the negative electrode tab 19 have a structure exposed to the exterior of the said battery exterior material 22 from the site | part joined by the heat fusion of the peripheral part of the said laminate film (FIG. 2 also). See

[Current collector]
The current collector is made of a conductive material, and an active material layer is formed on both sides thereof to serve as a battery electrode, and finally forms a battery. In the present embodiment , the current collector can be used in a battery in which the same active material layer having the same polarity (positive electrode / negative electrode) is formed on the surface of each layer. However, in a battery having a power generation element in which a plurality of single battery layers are stacked, the electrode located in the outermost layer does not participate in the battery reaction, and therefore the current collector located in the outermost layer is active only inside the power generation element. It is sufficient that a material layer exists.

  Further, the size of the current collector is determined according to the intended use of the battery. For example, if it is used for a large battery that requires a high energy density, a current collector having a large area is used.

The battery of this embodiment is characterized in that the current collectors (11, 14) are formed with a predetermined thickness. That is, in the battery of this embodiment , the current collectors (11, 14) are relatively thinner than the conventional technique in both the positive electrode and the negative electrode. In particular, in a preferred embodiment, the negative electrode current collector 14 is configured to be extremely thinner than the conventional technique .

  There are no particular restrictions on the materials constituting the positive electrode current collector 11 and the negative electrode current collector 14. For example, a metal or a conductive polymer can be employed. Specifically, metal materials, such as aluminum, nickel, iron, stainless steel, titanium, copper, are mentioned, for example. In addition to these, a clad material of nickel and aluminum, a clad material of copper and aluminum, or a plating material of a combination of these metals can be preferably used. Moreover, the foil by which aluminum is coat | covered on the metal surface may be sufficient. Of these, aluminum and copper are preferable from the viewpoints of electron conductivity and battery operating potential.

In a preferred embodiment, when the melting temperatures (melting points) of the respective metal materials constituting the positive electrode current collector 11 and the negative electrode current collector 14 are different, the melting temperature is lower (referred to as the first current collector). The thickness is made thicker than the other thickness . Yo Ri Preferably, the first current collector and cathode current collector 11, may a second current collector and negative electrode collector 14. That is, the positive electrode current collector 11 may be made of a material having a relatively low melting temperature (for example, aluminum), and the negative electrode current collector 14 may be made of a material having a relatively high melting temperature (for example, copper).

There are no particular restrictions on the specific thicknesses of the positive electrode current collector 11 and the negative electrode current collector 14. The thickness of the positive electrode current collector 11 is preferably 1 to 26 μm, more preferably 1 to 20 μm. The thickness of the negative electrode current collector 14 is preferably 1 to 9 μm. Furthermore, from the viewpoint of sufficiently obtaining the effects of the present embodiment , the thickness when the current collector is made of aluminum is preferably 26 μm or less, more preferably 20 μm or less, and even more preferably 15 μm. Or less, even more preferably 10 μm or less, particularly preferably 6 μm or less, and most preferably 4 μm or less. When the current collector is made of aluminum, the current collector is preferably the positive electrode current collector 11. Further, when the current collector is made of copper, the thickness is preferably 9 μm or less, more preferably 6 μm or less, further preferably 4 μm or less, particularly preferably 3 μm or less, and most preferably 2 μm or less. When the current collector is made of copper, the current collector is preferably the negative electrode current collector 14.

According to one embodiment of the present invention, by setting the thicknesses of the positive electrode current collector 11 and the negative electrode current collector 14 to values within the above-described range, the effects of the present embodiment can be sufficiently obtained. Become. That is, as will be described later with reference to FIG. 4, a short circuit phenomenon peculiar to a case where a conductor penetrates through at least two batteries from the outside is quickly eliminated (before the battery temperature reaches a predetermined value). Is possible. There is no restriction | limiting in particular about the lower limit of the thickness of an electrical power collector. From the viewpoint of improving the productivity by preventing the current collector from being damaged during electrode production, the lower limit when the current collector is made of aluminum is preferably 6 μm or more, and the current collector is made of copper. The lower limit when configured is preferably 4 μm or more. However, the technical scope of the present invention should be determined based on the description of the scope of claims, and is not limited to the specific forms as described above.

[Positive electrode (positive electrode active material layer) and negative electrode (negative electrode active material layer)]
The active material layers 12 and 15 include an active material, and further include other additives as necessary.

The positive electrode active material layer 12 includes a positive electrode active material. As the positive electrode active material, for example, LiMn ₂ O ₄ , LiCoO ₂ , LiNiO ₂ , Li (Ni—Co—Mn) O _2, and lithium-such as those in which a part of these transition metals are substituted with other elements Examples include transition metal composite oxides, lithium-transition metal phosphate compounds, and lithium-transition metal sulfate compounds. In some cases, two or more positive electrode active materials may be used in combination. Preferably, a lithium-transition metal composite oxide is used as the positive electrode active material. Of course, positive electrode active materials other than those described above may be used.

The negative electrode active material layer 15 includes a negative electrode active material. Examples of the negative electrode active material include carbon materials such as graphite, soft carbon, and hard carbon, lithium-transition metal composite oxides (for example, Li ₄ Ti ₅ O ₁₂ ), metal materials, and lithium-metal alloy materials. . In some cases, two or more negative electrode active materials may be used in combination. Preferably, a carbon material or a lithium-transition metal composite oxide is used as the negative electrode active material. Of course, negative electrode active materials other than those described above may be used.

  The average particle diameter of each active material contained in each of the active material layers 12 and 15 is not particularly limited, but is preferably 1 to 20 μm and more preferably 1 to 5 μm from the viewpoint of increasing output. However, it goes without saying that a form outside this range may be adopted. In the present specification, “particle diameter” means the maximum distance L among the distances between any two points on the contour line of the active material particles. As the value of “average particle diameter”, the average particle diameter of particles observed in several to several tens of fields using an observation means such as a scanning electron microscope (SEM) or a transmission electron microscope (TEM). The calculated value shall be adopted.

  Examples of the additive that can be included in the positive electrode active material layer 12 and the negative electrode active material layer 15 include a binder, a conductive additive, an electrolyte salt (lithium salt), and an ion conductive polymer.

  Examples of the binder include polyvinylidene fluoride (PVdF) and a synthetic rubber binder.

  The conductive auxiliary agent is an additive that is blended to improve the conductivity of the positive electrode active material layer 12 or the negative electrode active material layer 15. Examples of the conductive assistant include carbon materials such as carbon black such as acetylene black, graphite, and vapor grown carbon fiber. When the active material layer (13, 15) contains a conductive additive, an electronic network inside the active material layer is effectively formed, which can contribute to the improvement of the output characteristics of the battery.

Examples of the electrolyte salt (lithium salt) include Li (C ₂ F ₅ SO ₂ ) ₂ N), LiPF ₆ , LiBF ₄ , LiClO ₄ , LiAsF ₆ , LiCF ₃ SO _{3 and the} like.

  Examples of the ion conductive polymer include polyethylene oxide (PEO) -based and polypropylene oxide (PPO) -based polymers.

  The compounding ratio of the components contained in the positive electrode active material layer 12 and the negative electrode active material layer 15 is not particularly limited. The mixing ratio can be adjusted by appropriately referring to known knowledge about the non-aqueous solvent secondary battery.

  The thicknesses of the active material layers 12 and 15 are not particularly limited, and conventionally known knowledge about the battery can be appropriately referred to. As an example, the thickness of each active material layer (12, 15) is about 2 to 100 μm.

[Electrolyte layer]
As the electrolyte constituting the electrolyte layer 13, a liquid electrolyte or a polymer electrolyte can be used.

  The liquid electrolyte has a form in which a lithium salt as a supporting salt is dissolved in an organic solvent as a plasticizer. Examples of the organic solvent that can be used as the plasticizer include carbonates such as ethylene carbonate (EC) and propylene carbonate (PC). Further, as the supporting salt (lithium salt), a compound that can be added to the active material layer of the electrode, such as LiBETI, can be similarly employed.

  On the other hand, the polymer electrolyte is classified into a gel electrolyte containing an electrolytic solution and an intrinsic polymer electrolyte containing no electrolytic solution.

  The gel electrolyte has a configuration in which the above liquid electrolyte is injected into a matrix polymer made of an ion conductive polymer. Examples of the ion conductive polymer used as the matrix polymer include polyethylene oxide (PEO), polypropylene oxide (PPO), and copolymers thereof. In such polyalkylene oxide polymers, electrolyte salts such as lithium salts can be well dissolved.

  In addition, when an electrolyte layer is comprised from a liquid electrolyte or a gel electrolyte, you may use a separator for an electrolyte layer. Specific examples of the separator include a microporous film made of polyolefin such as polyethylene or polypropylene.

  The intrinsic polymer electrolyte has a structure in which a supporting salt (lithium salt) is dissolved in the matrix polymer, and does not include an organic solvent that is a plasticizer. Therefore, when the electrolyte layer is composed of an intrinsic polymer electrolyte, there is no fear of liquid leakage from the battery, and the reliability of the battery can be improved.

  The matrix polymer of the gel electrolyte or the intrinsic polymer electrolyte can exhibit excellent mechanical strength by forming a crosslinked structure. In order to form a crosslinked structure, thermal polymerization, ultraviolet polymerization, radiation polymerization, electron beam polymerization, etc. are performed on a polymerizable polymer (for example, PEO or PPO) for polymer electrolyte formation using an appropriate polymerization initiator. A polymerization treatment may be performed.

[Tab (positive tab and negative tab)]
Tabs (positive electrode tab 18 and negative electrode tab 19) that are electrically connected to each current collector are taken out of the battery exterior material for the purpose of taking out the current outside the battery. Specifically, as shown in FIG. 1, a positive electrode tab 18 electrically connected to each positive electrode current collector 11 and a negative electrode tab 19 electrically connected to each negative electrode current collector 14 are battery exterior materials. 22 is taken out of the laminate sheet.

  The material which comprises a tab (the positive electrode tab 18 and the negative electrode tab 19) is not restrict | limited in particular, The well-known highly electroconductive material conventionally used as a tab for lithium ion batteries can be used. As a constituent material of the tab, for example, metal materials such as aluminum, copper, titanium, nickel, stainless steel (SUS), and alloys thereof are preferable, and aluminum, copper, and the like are more preferable from the viewpoint of light weight, corrosion resistance, and high conductivity. Is preferred. Note that the positive electrode tab 18 and the negative electrode tab 19 may be made of the same material or different materials. Moreover, it is good also as the positive electrode tab 18 and the negative electrode tab 19 by extending each collector 11,14, and the positive electrode tab 18 and the negative electrode tab 19 which were prepared separately may be connected to each collector 11,14. .

[Positive electrode and negative electrode lead]
The positive terminal lead 20 and the negative terminal lead 21 are also used as necessary. For example, when the positive electrode tab 18 and the negative electrode tab 19 that are output electrode terminals are directly taken out from the current collectors 11 and 14, the positive electrode terminal lead 20 and the negative electrode terminal lead 21 may not be used.

  As the material of the positive terminal lead 20 and the negative terminal lead 21, a terminal lead used in a known lithium ion battery can be used. In addition, the part taken out from the battery outer packaging material 22 has a heat insulation property so as not to affect a product (for example, an automobile part, particularly an electronic device, etc.) by contacting with a peripheral device or wiring and leaking electricity. It is preferable to coat with a heat shrinkable tube or the like.

[Battery exterior materials]
As the battery exterior member 22, a known metal can case can be used, and a bag-like case using a laminate film containing aluminum that can cover a power generation element (battery element) can be used. For example, a laminate film having a three-layer structure in which PP, aluminum, and nylon are laminated in this order can be used as the laminate film, but the laminate film is not limited thereto. In the present embodiment , a laminate film that is excellent in high output and cooling performance and can be suitably used for a battery for large-sized equipment for EV and HEV is desirable.

[External structure of lithium-ion battery]
FIG. 2 is a perspective view showing the appearance of a stacked flat (non-bipolar) lithium ion secondary battery which is a typical embodiment of the battery constituting the assembled battery of the present invention.

  As shown in FIG. 2, the laminated flat lithium ion secondary battery 50 has a rectangular flat shape, and a positive electrode tab 58 and a negative electrode tab 59 for taking out electric power from both sides thereof. Has been pulled out. The power generation element (battery element) 57 is encased in the battery exterior material 52 of the lithium ion secondary battery 50. The surroundings are heat-sealed, and the power generation element 57 is sealed with the positive electrode tab 58 and the negative electrode tab 59 pulled out to the outside. Here, the power generation element 57 corresponds to the power generation element 17 of the lithium ion secondary battery 10 shown in FIG. 1 described above. A plurality of single battery layers (single cells) 16 composed of a positive electrode active material layer 12, an electrolyte layer 13, and a negative electrode active material layer 15 are laminated.

The battery constituting the assembled battery of the present invention is not limited to the laminated flat shape as shown in FIGS. 1 and 2, and in the wound type lithium ion battery, the cylindrical shape is used. It may be of a square shape. Such a cylindrical shape may be deformed into a rectangular flat shape. In the case of the cylindrical shape or the rectangular shape, a laminate film may be used as the exterior material, and a conventional cylindrical can (metal can) may be used.

  Further, the tabs 58 and 59 shown in FIG. 2 are not particularly limited, and the positive electrode tab 58 and the negative electrode tab 59 may be pulled out from the same side. The positive electrode tab 58 and the negative electrode tab 59 may be divided into a plurality of parts and taken out from each side, and the present invention is not limited to the one shown in FIG. Further, in a wound type lithium ion battery, instead of a tab, for example, a terminal may be formed using a cylindrical can (metal can).

[Battery]
Battery of this embodiment, Ru is a plurality electrically connected to and assembled battery.

  FIG. 3 is an external view of a typical embodiment of an assembled battery including the battery of the present embodiment, FIG. 3A is a plan view of the assembled battery, FIG. 3B is a front view of the assembled battery, FIG. 3C is a side view of the assembled battery.

  As shown in FIG. 3, the assembled battery 300 includes a plurality of lithium ion batteries of the first embodiment connected in series and in parallel to form an assembled battery 250 that can be attached and detached. A plurality of the assembled batteries 250 are connected in series and in parallel. As a result, it is possible to form the assembled battery 300 suitable for a vehicle driving power source and an auxiliary power source that require high volume energy density and high volume output density.

  The prepared assembled / removable assembled batteries 250 are connected to each other using an electrical connecting means such as a bus bar, and the assembled batteries 250 are stacked in a plurality of stages using a connecting jig 310. How many batteries are connected to create the assembled battery 250 and how many stages of the assembled battery 250 are stacked to produce the assembled battery 300 depend on the battery capacity of the vehicle (electric vehicle or the like) to be mounted. It may be determined according to the output.

  The present inventors have intensively studied to solve the above-described problems in the prior art and to develop a technique that can be applied to batteries for large equipment such as EV and HEV. In the process, it was found that when a short circuit occurs across a plurality of batteries, a short circuit current may continue to flow. This will be described in detail below.

  FIG. 4 shows an example in which when two batteries are connected in series, a conductor passes through the two batteries from the outside, and a short circuit is formed between the two batteries via the conductor. It is the cross-sectional schematic which shows typically the condition at the time of testing by making these two batteries connect and generating a short circuit.

  When FIG. 4 is referred, the electroconductive member 30 has penetrated the assembled battery 40 by which two lithium ion batteries (10a, 10b) are electrically connected in series.

  Here, considering the occurrence of short circuits in individual batteries unrelated to other batteries, conventionally, if at least one of the positive electrode current collector or the negative electrode current collector burns out due to heat generation and is scattered, the short circuit phenomenon is eliminated. It was thought to be. However, as shown in FIG. 4, even if one of the current collectors 11 or 14 is burned out by melting (FIG. 4 shows the case where the positive electrode current collector foil 11 is burned out), the two current collectors 11 or 14 connected in series In the battery 40, there is a possibility that a short circuit occurs between the batteries (10a, 10b) and the current flow cannot be interrupted. The present inventors have found the above findings for the first time, and have been able to provide means capable of interrupting the flow of current when a short circuit occurs between a plurality of batteries connected in series.

  For example, when the case where the conductive member 30 penetrates so as to communicate two batteries (10a, 10b) is considered, the positive electrode current collector 11 in contact with the conductive member 30 is melted even in the prior art, and current is supplied to the short-circuit portion. It is possible to form the conductive breaking portion 27 that does not flow. Thereby, the short circuit (current flow) generated inside each battery (10a, 10b) can be interrupted (the cross in FIG. 4 indicates the conduction breakage portion = the current flow interrupt location). .

On the other hand, in the state where the two batteries are electrically connected in series (the state of 40 shown in FIG. 4), it has not been conceivable in the past, but through the connection terminal 25 between the batteries (10a, 10b), A new short circuit is formed between the unmelted negative electrode current collectors 14 of the plurality of batteries (10a, 10b). As a result, the short-circuit current I continues to flow through the connection terminals 25 between the batteries and the conductive member 30 (see the arrows indicating the short-circuit current i and the ion flow shown in FIG. 4). As a result, the battery performance may be impaired due to the continuation of the short circuit. On the other hand, according to the present embodiment , as described above, by setting the thickness of the current collector to be relatively thin, the portions of both the positive electrode current collector 11 and the negative electrode current collector 14 that are in contact with the conductive member 30 The (short-circuited part) is melted by the heat generated due to the short-circuit current and eventually burned out. As a result, the flow of the short-circuit current through the conductive member 30 can be interrupted. Here, it is presumed that the short-circuit between the batteries, which has not been conventionally known, can be blocked by reducing the thickness of the current collector due to the following mechanism. In other words, the current collector's heat capacity decreases as the current collector's thickness is reduced, and the current collector's temperature rises when the amount of heat from the short-circuit current is constant, resulting in melting of the current collector. It is thought that it became easy. However, it is not limited to such a mechanism.

  A general battery is designed with a certain capacity margin with respect to the standard capacity. Therefore, even if the periphery of the short-circuited part burns out due to melting, the area that does not contribute to the reaction due to melting of the short-circuited part and its surroundings, which occupies the reaction area of the entire battery, is relatively small and should be compensated within the margin. Can do. As a result, after that, it can be used without any problem for charging and discharging.

As mentioned above, although the specific embodiment for obtaining the operation and effect of the present embodiment has been illustrated, the present invention is not limited to such a form, and various modifications are possible. When trying to deform, for example, the thickness of the current collector from which the effects of the present embodiment can be obtained may vary, but as described above for aluminum and copper, the thickness of the current collector is reduced to some extent. As a result, it is possible to obtain the same effect. In the case where the current collector is configured using other materials, the following guidelines may be referred to in order to obtain the upper limit value of the current collector thickness in which the effects of the present embodiment can be obtained.

  That is, whether or not the current collector is burned out by melting due to a short circuit and contributes to the interruption of the short circuit depends on the amount of heat (heat generation amount Q) generated in the short circuit site by the current flowing through the short circuit site due to the short circuit and the current collection. It is determined by the magnitude relationship with the amount of heat required to melt the electric body (the amount of heat of fusion C). In other words, when Q exceeds C (Q> C), the short-circuit portion of the current collector is melted and burned out.

  Here, the calorific value Q [J] is proportional to the electrical resistance value (Rn [Ω]) of the short-circuited part and proportional to the square of the short-circuit current value (I [A]). Rn is proportional to the specific resistivity (λ [Ω · cm]) of the constituent material of the current collector and inversely proportional to the volume of the current collector.

On the other hand, the heat of fusion C [J] of the current collector is the density of the current collector (ρ [g / cm ³ ]), the specific heat of the current collector (Cp [J / g · ° C.]), the melting of the current collector. The temperature (Tm [° C.]) is proportional to the volume of the current collector.

  From the above, when the current collector material is fixed, if the current collector thickness is reduced, the current collector volume decreases, resulting in an increase in Q and a decrease in C. Finally, it is possible to satisfy Q> C.

Moreover, the specific numerical range of the thickness of the current collector described above is a preferable range corresponding to the case where the battery has a form described in Examples described later. When the specific configuration of the battery (the thickness of the electrode active material layer and the number of single battery layers) is changed, the upper limit value of the thickness at which the effect of the present embodiment is obtained also changes accordingly. For example, as the thickness of the electrode active material layer and the number of stacked layers increase, the battery capacity increases and the electrode resistance (Rb [Ω]) also increases. Then, since the short-circuit current value (I) that flows when a short-circuit occurs is a value obtained by dividing the battery voltage (E [V]) by Rb, I decreases relatively as Rb increases. Since Q also decreases as I decreases, it is necessary to further reduce C in order to satisfy Q> C in such a case. For example, it is possible to finally satisfy Q> C by further reducing the thickness of the current collector.

As described above, the specific values of Q and C vary depending on various conditions such as the material constituting the current collector. However, according to the above guidelines, the current collector's effect is obtained so that the effects of the present embodiment can be obtained. It is possible to adjust the thickness as appropriate. If specific values of Q and C can be calculated theoretically, Q / C> 1.2 is preferable, and Q / C> 1.5 is more preferable.

In particular, in the present embodiment , both the positive electrode and the negative electrode current collector 1 satisfy the relational expression of Q> C described above. It can cope with a unique phenomenon in which a short-circuit current continues to flow.

According to the battery of the present embodiment , even when the short circuit is formed by an external factor as shown in FIG. 4, the temperature of the battery reaches a predetermined value due to the heat generated by the current flowing through the short circuit. In addition, the short circuit portion of the positive electrode current collector 11 and the negative electrode current collector 14 is melted to interrupt the short circuit. Here, the predetermined value of the battery temperature is a temperature at which the function of the battery may be stopped. This predetermined value can vary depending on the specific specifications of the battery (materials such as electrode active material, electrolyte, separator, etc.), so it is difficult to unambiguously define it, and it is set appropriately according to the specific specifications. Is possible. As an example, the predetermined value may be set to about 60 to 70 ° C. (see Examples). For example, if the battery is made of a material having a relatively high heat resistance, the predetermined value is increased. Conversely, if the battery is made of a material having a relatively low heat resistance, the predetermined value will be low.

[vehicle]
The battery of this embodiment can be mounted on a vehicle, for example, in the form of the assembled battery described above. A battery mounted on a vehicle can be used as a power source for driving a motor of the vehicle, for example.

  FIG. 5 is a conceptual diagram of a vehicle equipped with the assembled battery shown in FIG.

  As shown in FIG. 5, in order to mount the assembled battery 300 on a vehicle such as the electric vehicle 400, the battery pack 300 is mounted under the seat at the center of the vehicle body of the electric vehicle 400. This is because if it is installed under the seat, the interior space and the trunk room can be widened. The place where the assembled battery 300 is mounted is not limited to the position under the seat, but may be a lower part of the rear trunk room or an engine room in front of the vehicle. The electric vehicle 400 using the assembled battery 300 as described above has high durability and can provide sufficient output even when used for a long period of time. Furthermore, it is possible to provide electric vehicles and hybrid vehicles that are excellent in fuel efficiency and running performance.

[Battery manufacturing method]
The battery manufacturing method of the present embodiment is not particularly limited, and can be manufactured by applying a conventionally known method.

When the electrolyte is a liquid electrolyte, the battery is made from a positive electrode and a negative electrode, which are prepared by applying (coating) an electrode slurry containing an electrode material such as an active material or a conductive aid to both surfaces of the current collector foil. Increase to cut out. Each of them is used after being dried for one day in a 90 ° C. vacuum dryer. Between the positive electrode and the negative electrode, the positive electrode and the negative electrode are alternately laminated so that the outermost side becomes a negative electrode through a porous film such as polypropylene having an appropriate thickness (for example, about 25 μm). Then, each positive electrode and negative electrode are bundled and leads are welded, and this laminate is placed in an aluminum laminate film bag with a structure in which the positive and negative electrode leads are taken out, and an electrolytic solution is injected with a liquid injector. The end is sealed under reduced pressure to obtain a battery.

  In addition to batteries with electrolyte as electrolyte, batteries with gels as electrolytes and batteries with all solid polymers can be manufactured with reference to our well-known technology, so the description is omitted here.

Second Embodiment
The second embodiment is the same as the first embodiment except that the negative electrode current collector has a multilayer structure. Specifically, the negative electrode current collector has a structure in which a conductive layer and a reinforcing layer are stacked. The “reinforcing layer” is a layer for reinforcing the rigidity of the current collector.

  FIG. 6 is a cross-sectional view taken along a direction perpendicular to the surface direction of the negative electrode current collector in the lithium ion battery of this embodiment. As shown in FIG. 6, the negative electrode current collector 14 of the present embodiment has a structure including a reinforcing layer 14c and a metal layer 14b formed on both surfaces of the reinforcing layer 14c.

In the present embodiment, the negative electrode current collector 14 is formed with an active material layer on one surface or both surfaces thereof as an electrode (negative electrode), similarly to a general battery current collector, and finally constitutes a battery. To do. Although FIG. 6 illustrates a configuration in which the metal layer 14b is formed on both surfaces of the reinforcing layer 14c, in the present embodiment , the negative electrode current collector 14 in which the metal layer is formed only on one surface of the reinforcing layer is also illustrated. In some cases, it can be used. The metal layer may be a conductive layer made of a conductive material other than metal (for example, a conductive polymer).

  By adopting the configuration of this embodiment, in addition to the effects of the first embodiment, when the metal layer is thinned, the metal is produced during battery production (particularly during electrode application to the current collector). Layer breakage is unlikely to occur, and there is an advantage that the yield of battery manufacturing is improved. Further, when the battery vibrates (when mounted in a vehicle), the reinforcing layer absorbs the vibration in the battery, so that there is an advantage that vibration resistance is improved. In addition, in this embodiment, it cannot be overemphasized that "the short circuit part of the negative electrode collector 14" means the short circuit part in the metal layer 14b of the negative electrode collector 14. FIG.

  In the present embodiment, the specific types of the metal constituting the metal layer 14b of the negative electrode current collector 14 having a multilayer structure and the material constituting the reinforcing layer 14c are not particularly limited, and conventionally used as a current collector material for a battery. A used metal or a known insulator can be appropriately employed.

  As an example, as the metal constituting the metal layer 14b, the material exemplified as the constituent material of the current collector in the above-described column of the first embodiment may be similarly used.

  In addition, examples of the material constituting the reinforcing layer 14c include insulating materials such as resin, ceramic, and a composite of ceramic and resin. Among these, from the viewpoint of reducing the weight of the reinforcing layer, the constituent material of the reinforcing layer is A resin is preferred. Although there is no restriction | limiting in particular as resin, For example, a polyimide (PI), a polyethylene terephthalate (PET), a polyacrylonitrile (PAN), a polypropylene (PP), polyethylene (PE) etc. can be used. Among these, from the viewpoint of heat resistance, polyimide or polyethylene terephthalate is preferable, and polyimide is particularly preferable. A specific name for polyimide is Kapton (registered trademark).

In the present embodiment, the thickness of the metal layer 14b and the reinforcing layer 14c of the negative electrode current collector 14 is not particularly limited. However, in order to obtain the operation effect of the present embodiment , that is, in order to interrupt the short circuit when a short circuit is formed by passing through a conductor from the outside to at least two batteries, The thickness of the reinforcing layer 14c may be controlled. Here, in order to interrupt the short circuit, the metal layer 14b of the negative electrode current collector 14 needs to be melted together with the positive electrode current collector 11 by the heat generated by the current flowing through the short circuit (short circuit current). is there. If the reinforcing layer 14c is thicker than necessary at this time, the heat generated by the short-circuit current is taken away with an increase in the heat capacity of the reinforcing layer 14c, and the heat necessary for melting the metal layer 14b cannot be secured sufficiently. I guess that. Therefore, in a preferable form of the present embodiment, the thickness of the reinforcing layer 14c is set so as not to deprive the heat quantity necessary for melting the short-circuit portion (the metal layer 14b) of the negative electrode current collector 14 at the time of short circuit. It is presumed that the operational effects of the present embodiment can be obtained by controlling the distance.

  The specific values of the thickness of the metal layer 14b and the reinforcing layer 14c of the negative electrode current collector 14 in the present embodiment are not particularly limited as long as the above-described effects can be obtained, and can be adjusted as appropriate. is there. However, as an example, the thickness of the metal layer 14b (the total thickness when formed on both surfaces of the reinforcing layer 14c) is within the range described in the column of the current collector of the first embodiment described above. A thickness is preferred. Further, the thickness of the reinforcing layer 14c may be about 4 to 20 μm. In the present embodiment, the total thickness of the negative electrode current collector 14 is preferably 6 to 12 μm, and more preferably 8 to 10 μm. As a particularly preferred embodiment, when the metal layer 14b is made of copper, the thickness of the metal layer 14b is preferably 0.1 to 6 μm, more preferably 0.1 to 2 μm.

The case where the negative electrode current collector 14 has a multilayer structure has been described above as an example, but in the present embodiment , the positive electrode current collector 11 may have a similar multilayer structure. In such a form, the thickness of the metal layer and the reinforcing layer of the positive electrode current collector 11 is not particularly limited. However, in order to obtain the effect of the present embodiment in which the short circuit is interrupted when a short circuit is formed by the conductor penetrating from the outside into at least two batteries, as described above, the metal The thickness of the layer and the reinforcing layer may be controlled.

  The specific values of the thickness of the metal layer and the reinforcing layer of the positive electrode current collector 11 having a multilayer structure are not particularly limited as long as the above-described effects can be obtained, and can be appropriately adjusted. However, as an example, the thickness of the metal layer (the total thickness when formed on both sides of the reinforcing layer) is a thickness within the range described in the column of the current collector of the first embodiment described above. It is preferable that Further, the thickness of the reinforcing layer may be about 8 to 19 μm. In such a form, the total thickness of the positive electrode current collector 11 is preferably 5 to 20 μm, more preferably 5 to 10 μm. As a particularly preferred embodiment, when the metal layer is made of aluminum, the thickness of the metal layer is preferably 1.4 to 12 μm, more preferably 1.4 to 8 μm.

  The various thickness values described above can be measured by a conventionally known technique (for example, SEM observation of a cross section).

As described above, in the second embodiment relating to the form in which the current collector includes the reinforcing layer, when determining the thickness of the current collector (the metal layer thereof) according to the guidelines described in the column of the first embodiment, It is also necessary to consider the thickness of the reinforcing layer. That is, in order to interrupt the short circuit, the metal layer 14b needs to melt. At this time, if the reinforcing layer 14c is thicker than necessary, it is estimated that the metal layer 14b does not melt. This is presumed to be because heat generated by the short-circuit current is taken away with an increase in the heat capacity of the reinforcing layer 14c, and heat necessary for melting the metal layer 14b is not sufficiently secured. Therefore, in the design of the current collector of the second embodiment, the thickness of the reinforcing layer 14c is excessively deprived of the amount of heat necessary for the short-circuit portion (the metal layer 14b) of the negative electrode current collector 14 to melt at the time of a short circuit. It is presumed that the effect of this embodiment can be obtained by controlling the thickness so as not to exist.

  In the following examples and comparative examples, assembled batteries were formed using non-aqueous electrolyte batteries produced by changing the thickness of the current collector, and temperature rise during short-circuit discharge was confirmed.

  Specifically, the assembled batteries of Comparative Example 1 and Examples 1 to 5 were produced as follows.

(Preparation of negative electrode)
Copper foils having thicknesses shown in Table 1 were prepared as negative electrode current collectors.

  Hard carbon (90 parts by mass), which is a negative electrode active material, and PVdF (10 parts by mass), which is a binder, are dispersed in appropriate amounts of N-methyl-2-pyrrolidone (NMP), which is a slurry viscosity adjusting solvent. A material slurry was prepared.

  The prepared negative electrode active material slurry is applied to both surfaces of the negative electrode current collector prepared above using a coating apparatus, dried, and subjected to a press treatment using a roll press, and the negative electrode active material layer (single-side thickness) 75 μm) was formed. Then, it was cut into a size of 10 cm × 5 cm, and a negative electrode lead made of Ni was welded to the negative electrode current collector to produce a negative electrode.

(Preparation of positive electrode)
Aluminum foils having thicknesses shown in Table 1 were prepared as positive electrode current collectors.

LiMn ₂ O ₄ (85 parts by mass) as a positive electrode active material, acetylene black (5 parts by mass) as a conductive additive, and PVdF (10 parts by mass) as a binder are dispersed in an appropriate amount of NMP as a slurry viscosity adjusting solvent. A positive electrode active material slurry was prepared.

  The prepared positive electrode active material slurry is applied to both surfaces of the positive electrode current collector prepared above using a coating apparatus, dried, and subjected to press treatment using a roll press machine, and the positive electrode active material layer (single-side thickness) 110 μm). And it cut into the size of 9.5 cm x 4.5 cm, and welded the positive electrode lead made from Al to the positive electrode electrical power collector, and produced the positive electrode.

(Production of batteries and assembled batteries)
A polyethylene microporous film (thickness: 30 μm, size: 10.5 cm × 5.5 cm) was prepared as a separator. Further, as the electrolyte, LiPF ₆ is a lithium salt in an equal volume mixture of ethylene carbonate (EC) di methyl carbonate (DMC) was prepared a solution of a concentration of 1M.

  The 11 positive electrodes, 10 negative electrodes, and 11 separators prepared above were sequentially laminated so that the positive electrode active material layer and the negative electrode active material layer of the adjacent positive electrode and negative electrodes face each other with the separator interposed therebetween. Element) (see FIG. 1).

  Next, each positive electrode lead and negative electrode lead are welded to the positive electrode and negative electrode tab, and the obtained laminate (power generation element) is placed in an exterior body made of an aluminum laminate sheet so that the positive electrode tab and the negative electrode tab are led out to the outside. It was. Thereafter, the electrolytic solution prepared above was injected and sealed to complete a stacked lithium ion battery (see FIG. 2).

  Then, the laminated lithium ion battery obtained above was connected in series using a cell connection bus bar as shown in FIG. 3 to produce an assembled battery, which was used in a short circuit test described later.

<Temperature rise confirmation test during discharge by short circuit test>
The assembled batteries of Examples 1 to 5 and Comparative Example 1 were initially charged to 0.5 C after assembly to a fully charged state (4.2 V: battery terminal voltage), aged for 1 week in a fully charged state, and 2 at 1 C. The capacity was measured by first discharging to 0.0 V (battery terminal voltage). Thereafter, each assembled battery or battery was charged to a fully charged state at 0.5 C, and then a conductive member having a diameter of 3 mm was passed through the entire assembled battery as a short circuit test as shown in FIG. Subsequently, 100C discharge was performed to 2.0V (battery terminal voltage), and the battery surface temperature at the time of discharge was measured. The battery surface temperature was measured by measuring the maximum temperature rise of the battery by attaching a thermocouple to the central portion (location indicated by symbol G in FIG. 2) of the laminate outer packaging material. In the assembled battery, thermocouples were attached to all three batteries, and the average value of the maximum rising temperatures of each battery was defined as the battery surface temperature. The experimental results are shown in Table 1.

  As shown in Table 1, in the assembled batteries of Examples 1 to 5, the temperature rise remained at 75 ° C. or lower. From this, it is expected that the short-circuit current was interrupted within 500 msec from the occurrence. It was also possible to use the battery again. On the other hand, in the assembled battery of Comparative Example 1, the short-circuit current was not interrupted and a temperature increase was observed up to 120 ° C., and the battery could not be used again.

  In addition, the reference example was implemented in order to show that the short circuit can be interrupted when the battery used in Comparative Example 1 is short-circuited alone. Specifically, the battery used in Comparative Example 1 was used as a reference example without being used as an assembled battery. Reference Example 2 was carried out by the same method as Reference Example 1 except that the thickness of the aluminum foil as the positive electrode current collector was 20 μm. As shown in Table 1, in Reference Examples 1 and 2, the temperature rise of the battery remained at 60 to 65 ° C., and the battery could be used again.

<Confirmation of current collector burnout (breakage)>
For each of the assembled batteries of Examples 1 to 5 and Comparative Example 1 and the batteries of Reference Examples 1 and 2, after confirming whether charging / discharging was possible after discharging at 100 C, these assembled batteries and batteries were disassembled to collect current. The presence or absence of burnout (breakage) of the foil was confirmed.

  In the assembled battery of Examples 1-5, it has confirmed that the periphery of the short circuit site | part of all the collectors burned out and the conduction fracture | rupture part was formed. On the other hand, in the assembled battery of Comparative Example 1 and the batteries of Reference Examples 1 and 2, the periphery of the short-circuited portion of the aluminum foil was burned out and the current flow to the short-circuited portion of the aluminum foil was interrupted. The area around the short circuit area was not burned out.

  From the above, it is considered that the rise in battery temperature was different between Reference Example 1 and Comparative Example 1 in which the battery configurations were exactly the same, for the following reason. That is, when an assembled battery is used as in Comparative Example 1, a new conduction path is formed between the copper foil, the short-circuit member, and the inter-battery terminal of each battery as shown in FIG. It is considered that the temperature of the battery rose to 120 ° C. because the short circuit current continued to flow. On the other hand, in the batteries of Reference Examples 1 and 2 in which the burnout (breakage) of the aluminum foil as in Comparative Example 1 was confirmed, a new conduction path in the assembled battery as shown in FIG. 4 was not formed. Therefore, it is considered that only the aluminum foil is burned out, whereby the current flow to the short-circuited portion of the current collector foil can be cut off, and the temperature rise of the battery can be suppressed to 60 to 65 ° C.

From the above, not be solved by a conventional battery can block the short circuit alone problem blocking a short circuit between the battery when the assembled battery, is resolved according to the assembled battery of this embodiment It can be shown.

<Example 6>
(Preparation of negative electrode)
A negative electrode current collector was prepared by laminating Cu (film thickness 3 μm) / PI (film thickness 4 μm) / Cu (film thickness 3 μm) in this order.

  Disperse hard carbon (90 parts by mass) as a negative electrode active material and polyvinylidene fluoride (PVdF) (10 parts by mass) as a binder in appropriate amounts of N-methyl-2-pyrrolidone (NMP) as a slurry viscosity adjusting solvent. Thus, a negative electrode active material slurry was prepared.

  The prepared negative electrode active material slurry was applied to both surfaces of the negative electrode current collector prepared above using a coating apparatus and dried. Next, using a roll press machine, the obtained laminated electrode was pressed to form a negative electrode active material layer (thickness: 75 μm). Then, it was cut into a size of 10 cm × 5 cm, and a negative electrode lead made of Ni was welded to the negative electrode current collector to produce a negative electrode plate.

(Preparation of positive electrode)
An Al foil (film thickness 20 μm) was prepared as a positive electrode current collector.

LiMn ₂ O ₄ (85 parts by mass) as a positive electrode active material, acetylene black (5 parts by mass) as a conductive auxiliary agent, and polyvinylidene fluoride (PVdF) (10 parts by mass) as a binder are slurry viscosity adjusting solvents. A positive electrode active material slurry was prepared by dispersing an appropriate amount of N-methyl-2-pyrrolidone (NMP).

  The prepared positive electrode active material slurry was applied to both surfaces of the positive electrode current collector prepared above using a coating apparatus and dried. Next, using a roll press machine, the obtained multilayer electrode was pressed to form a positive electrode active material layer (thickness: 110 μm). And it cut into the size of 9.5 cm x 4.5 cm, the positive electrode lead made from Al was welded to the edge part of a positive electrode electrical power collector, and the positive electrode was produced.

(Production of assembled battery)
A polyethylene microporous membrane (PE separator) (thickness: 30 μm, size: 10.5 cm × 5.5 cm) was prepared as a separator. Further, as an electrolytic solution, a solution in which LiPF _{6 as a} lithium salt was dissolved at a concentration of 1M in an equal volume mixed solution of ethylene carbonate (EC) and dimethyl carbonate (DMC) was prepared.

  Ten stacked electrodes (11 positive electrodes, 10 negative electrodes) and 11 separators prepared above were sequentially stacked so that the positive electrode active material layer and the negative electrode active material layer of adjacent stacked electrodes face each other.

  In addition, the formation of the active material layer of the multilayer electrode located in the outermost layer is omitted, and an Al positive electrode lead is welded to the current collector (Al surface) of the multilayer electrode located in the outermost layer on the positive electrode side. A negative electrode lead made of Ni was welded to the current collector (Cu surface) of the laminated electrode located in the outermost layer on the negative electrode side.

  Next, the obtained laminate (power generation element) is placed in an exterior made of an aluminum laminate sheet so that the positive electrode lead and the negative electrode lead are led out to the outside, and the electrolytic solution prepared above is injected and sealed. As a result, a laminated battery was completed.

  Thereafter, the two stacked batteries obtained above were connected in series using a cell connection bus bar as shown in FIG. 3 to produce an assembled battery.

<Example 7>
A battery and an assembled battery having the same electrode composition and number of layers as those of Example 1 were prepared except that Cu / PI / Cu foil (film thickness 2.5 μm / 5 μm / 2.5 μm) was used for the negative electrode current collector.

<Example 8>
A battery and an assembled battery having the same electrode composition and number of layers as those of Example 1 were prepared except that Cu / PI / Cu foil (film thickness: 1 μm / 8 μm / 1 μm) was used for the negative electrode current collector.

<Example 9>
A battery and an assembled battery having the same electrode composition and the same number of layers as those of Example 1 were prepared except that Cu / PI / Cu foil (film thickness 0.5 μm / 9 μm / 0.5 μm) was used for the negative electrode current collector.

<Example 10>
A battery and an assembled battery having the same electrode composition and the same number of layers as those of Example 1 were prepared except that Cu / PI / Cu foil (film thickness: 0.3 μm / 9.4 μm / 0.3 μm) was used for the negative electrode current collector. did.

<Example 11>
A battery and an assembled battery having the same electrode composition and the same number of layers as those of Example 1 were prepared except that Cu / PI / Cu foil (film thickness: 0.1 μm / 9.8 μm / 0.1 μm) was used for the negative electrode current collector. did.

<Example 12>
A battery and an assembled battery having the same electrode composition and the same number of layers as those of Example 1 were prepared except that Cu / PI / Cu foil (film thickness 0.05 μm / 9.9 μm / 0.05 μm) was used for the negative electrode current collector. did.

<Example 13>
A battery and an assembled battery having the same electrode composition and number of layers as those of Example 1 were prepared except that Cu / PET / Cu foil (film thickness: 1 μm / 8 μm / 1 μm) was used for the negative electrode current collector.

<Comparative example 2>
A battery and an assembled battery having the same electrode composition and the same number of layers as those of Example 6 were prepared except that a Cu foil (film thickness: 10 μm) was used for the negative electrode current collector.

<Comparative Example 3>
A battery and an assembled battery having the same electrode composition and number of layers as those of Example 1 were prepared except that Cu / PET / Cu foil (film thickness: 2 μm / 6 μm / 2 μm) was used for the negative electrode current collector.

<(Capacitance measurement) Short-circuit test>
For each of the assembled batteries of Examples 6 to 13 and Comparative Examples 2 and 3, the battery was first charged and discharged at 0.5 C after battery assembly, and then aged in a fully charged state (4.2 V) for 1 week, and the capacity was measured at a 1 C rate. I did it. Thereafter, each assembled battery was discharged at 100 C, and the battery surface temperature at the time of discharge (a thermocouple was installed at the center of the laminate exterior part; installed at a position indicated by symbol G in FIG. 2) was measured. The results are shown in Table 2 below. A graph showing the relative energy density based on the comparative example 2 is shown in FIG. 7, and a graph showing the relative temperature rise based on the comparative example 2 is shown in FIG.

<Confirmation of metal layer burnout (breakage)>
For each of the assembled batteries of Examples 6 to 13 and Comparative Examples 2 and 3, after confirming whether charging / discharging was possible after the discharge of 100 C described above, these assembled batteries and batteries were disassembled, and the current collector foil was baked. The presence or absence of cutting (breaking) was confirmed.

  As a result, in all of the examples, it was confirmed that the periphery of the short-circuited portion of all the current collectors was burnt out and a conductive fracture portion was formed. On the other hand, in the assembled batteries of Comparative Examples 2 and 3, the periphery of the short-circuited portion of the aluminum foil was burned out, and the current flow to the short-circuited portion of the aluminum foil was interrupted. It was not burned out.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic cross-sectional view schematically showing an overall structure of a lithium ion battery which is a typical embodiment of a battery constituting an assembled battery of the present invention. It is the perspective view showing the external appearance of the lithium ion battery which is typical embodiment of the battery which comprises the assembled battery of this invention. It is the external view which represented typically embodiment of the assembled battery comprised from the battery of 1st Embodiment typically. 3A is a plan view of the assembled battery, FIG. 3B is a front view of the assembled battery, and FIG. 3C is a side view of the assembled battery. It is a figure showing the mechanism at the time of the short circuit generation | occurrence | production between the some batteries which comprise an assembled battery. Specifically, when two batteries are connected in series, an example in which a conductor is passed through the two batteries from the outside, and a short circuit is formed between the two batteries via the conductor, It is the cross-sectional schematic which shows typically the condition at the time of testing by making a short circuit by connecting two batteries. It is a conceptual diagram of the vehicle carrying the assembled battery shown in FIG. It is sectional drawing cut | disconnected in the direction perpendicular | vertical to the surface direction of the negative electrode collector in the lithium ion battery of 2nd Embodiment. It is a graph showing the relative energy density on the basis of the assembled battery of the comparative example 2 about each assembled battery of Examples 6-13 and Comparative Examples 2 and 3. FIG. It is a graph showing the relative temperature rise on the basis of the assembled battery of the comparative example 2 about each assembled battery of Examples 6-13 and Comparative Examples 2 and 3. FIG.

Explanation of symbols

1 current collector (current collector foil),
10, 10a, 10b lithium ion battery,
11 positive electrode current collector,
12 positive electrode active material layer,
13 electrolyte layer,
14 negative electrode current collector,
14a outermost layer negative electrode current collector,
14b metal layer,
14c reinforcing layer,
15 negative electrode active material layer,
16 cell layer,
17, 57 Power generation element,
18, 58 positive electrode tab,
19, 59 negative electrode tab,
20 positive terminal lead,
21 negative terminal lead,
22, 52 Battery exterior material (laminate film),
25 Connection terminal between batteries,
27 conduction breaking part (space part),
30 conductive member,
40 battery packs,
50 lithium ion battery,
250 small battery pack,
300 battery packs,
310 connection jig,
400 electric car,
D thickness of current collector,
E battery voltage,
I short circuit current,
Rb electrode resistance,
Rn Resistance of the short circuit part.

Claims (16)

A first electrode in which one of a positive electrode active material layer or a negative electrode active material layer is formed on a first current collector;
A second electrode in which the other of the positive electrode active material layer and the negative electrode active material layer is formed on the second current collector;
An electrolyte layer positioned between the first electrode and the second electrode;
A power generation element comprising a cell layer having
An exterior material enclosing the power generation element;
Is a battery pack in which a plurality of stacked batteries are electrically connected,
At least two batteries are electrically connected in series;
When a conductor with a diameter of 3 mm penetrates two batteries connected in series from the outside,
In each of the two batteries, a short-circuit current flowing in a first short circuit formed from the first current collector, the conductor, and the second current collector causes the first current collector of the battery to The short-circuited portion is melted to form the first conduction break portion,
Melts the two two shorted portions of the second current collector and at least one of the second current collector of said two battery by short-circuit current flowing through the second short circuit formed from the conductor of the battery An assembled battery in which thicknesses and materials of the first current collector and the second current collector are selected so that a second conduction break portion is formed.   The assembled battery according to claim 1, wherein the second conductive break portion is formed after the first conductive break portion is formed. The assembled battery according to claim 1 or 2 , wherein the first current collector and the second current collector are formed with such a thickness that the conductive breakage portion is formed. The assembled battery according to any one of claims 1 to 3 , wherein the first current collector and the second current collector are formed of a material capable of forming the conduction break portion. The melting temperature of the conductive material constituting the first current collector is lower than the melting temperature of the conductive material constituting the second current collector, and the first current collector is lower than the second current collector. thick, the battery pack according to any one of claims 1-4. The assembled battery according to any one of claims 1 to 5, wherein a constituent material of the first current collector is different from a constituent material of the second current collector. The first current collector is made of aluminum, the second consists of current collector is copper, the battery pack according to any one of claims 1-6. A battery is a lithium ion secondary battery configuring the assembled battery, the assembled battery according to any one of claims 1-7. The assembled battery according to any one of claims 1 to 8 , wherein the thickness of the first current collector is 1 to 26 µm, and the thickness of the second current collector is 1 to 9 µm. The said 2nd electrical power collector consists of a reinforcement layer for reinforcing the rigidity of an electrical power collector, and the electroconductive layer formed in both surfaces of the said reinforcement layer, The any one of Claims 1-8. The assembled battery described in 1. The assembled battery according to claim 10, wherein the total thickness of the conductive layer is 0.1 to 6 μm, and the total thickness of the second current collector is 6 to 12 μm.   The stacked battery is a lithium ion secondary battery,
  The first current collector is made of aluminum, and the thickness of the first current collector is 1 to 26 μm;
  The second current collector comprises a reinforcing layer for reinforcing the rigidity of the current collector, and a conductive layer made of copper formed on both surfaces of the reinforcing layer. The assembled battery according to claim 1, wherein the total thickness is 0.1 to 6 μm. The assembled battery according to claim 10 or 11 , wherein the reinforcing layer is made of a resin. Wherein the resin is a polyimide or polyethylene terephthalate, assembled battery according to claim 13. The stacked battery is a lithium ion secondary battery,
The first current collector is composed of aluminum, the second current collector is composed of copper,
The assembled battery according to claim 1 , wherein the thickness of the first current collector is 1 to 26 µm, and the thickness of the second current collector is 1 to 9 µm. A vehicle comprising the assembled battery according to any one of claims 1 to 15 as a motor driving power source.

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