WO2010026774A1 - 積層型二次電池 - Google Patents
積層型二次電池 Download PDFInfo
- Publication number
- WO2010026774A1 WO2010026774A1 PCT/JP2009/004412 JP2009004412W WO2010026774A1 WO 2010026774 A1 WO2010026774 A1 WO 2010026774A1 JP 2009004412 W JP2009004412 W JP 2009004412W WO 2010026774 A1 WO2010026774 A1 WO 2010026774A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- separator
- bag
- positive electrode
- negative electrode
- secondary battery
- Prior art date
Links
- 229920003002 synthetic resin Polymers 0.000 claims abstract description 21
- 239000000057 synthetic resin Substances 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims description 16
- 239000000853 adhesive Substances 0.000 claims description 5
- 230000001070 adhesive effect Effects 0.000 claims description 5
- 229920006280 packaging film Polymers 0.000 abstract 1
- 239000012785 packaging film Substances 0.000 abstract 1
- 238000010586 diagram Methods 0.000 description 14
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 13
- 229910001416 lithium ion Inorganic materials 0.000 description 11
- 239000010410 layer Substances 0.000 description 9
- 230000008602 contraction Effects 0.000 description 6
- 238000005304 joining Methods 0.000 description 6
- 239000012790 adhesive layer Substances 0.000 description 5
- 230000004927 fusion Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- -1 polypropylene Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000003522 acrylic cement Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000011255 nonaqueous electrolyte Substances 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
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- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000009783 overcharge test Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/04—Construction or manufacture in general
- H01M10/0436—Small-sized flat cells or batteries for portable equipment
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
- H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
- H01M50/105—Pouches or flexible bags
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/172—Arrangements of electric connectors penetrating the casing
- H01M50/174—Arrangements of electric connectors penetrating the casing adapted for the shape of the cells
- H01M50/178—Arrangements of electric connectors penetrating the casing adapted for the shape of the cells for pouch or flexible bag cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/463—Separators, membranes or diaphragms characterised by their shape
- H01M50/466—U-shaped, bag-shaped or folded
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/543—Terminals
- H01M50/547—Terminals characterised by the disposition of the terminals on the cells
- H01M50/55—Terminals characterised by the disposition of the terminals on the cells on the same side of the cell
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Definitions
- the present invention relates to a laminated secondary battery in which one of a flat positive electrode and a negative electrode is housed in a bag-like separator and a battery element laminated with a counter electrode is sealed with a film-like exterior material.
- Lithium ion batteries with a large charge / discharge capacity are widely used in portable battery-powered devices such as mobile phones.
- secondary batteries having a large charge / discharge capacity and excellent efficiency are required.
- a battery in which a plate-like positive electrode and a plate-like negative electrode are laminated via a separator is used, and the positive electrode is made of lithium on an aluminum foil that acts as a current collector.
- a material obtained by applying transition metal composite oxide particles together with a conductivity imparting material such as carbon black is used.
- a negative electrode is used which is applied to carbon particles such as graphite such as copper foil acting as a current collector together with a conductivity imparting material such as carbon black.
- the plate-like positive electrode and negative electrode are each formed by applying an electrode active material on a strip-shaped aluminum foil or copper foil for a current collector to a predetermined site, and then forming an active material layer to connect a tab for conductive connection
- the parts that are not made are made in one piece.
- a battery element in which a flat positive electrode and a negative electrode are laminated via a separator is sealed with a film-like exterior material.
- a laminated secondary battery sealed with a film-like exterior material is excellent in volumetric energy density and mass energy density, but is not sealed by a rigid exterior container. Since there is a possibility of influence, in a high-capacity stacked secondary battery, measures against overcharging are important.
- a plate-like positive electrode is housed in a bag-like separator and laminated with a negative electrode. Since it is a bag-like separator, a single sheet separator is arranged one by one. It is possible to improve the reliability compared to the case, but when overcharging under severe conditions exceeding the current test standard, the gas pressure generated by the decomposition of the electrolyte or excessive heating of the separator Due to the thermal contraction of the separator, the bag-shaped separator may be deformed and the bonded portion may be broken by thermal fusion or the like, and the positive electrode and the negative electrode may contact each other.
- the present invention provides the performance required as a countermeasure against the current overcharge in a laminated secondary battery in which either a positive electrode or a negative electrode is stored in a bag-shaped separator and a flat positive electrode and a flat negative electrode are laminated.
- An object of the present invention is to provide a laminated secondary battery that does not cause battery runaway even under far exceeding test conditions. Specifically, in the case of a lithium ion battery, 10V- It is an object of the present invention to provide a stacked secondary battery in which runaway does not occur even under the condition of 36V-1C, which is a test condition far exceeding the condition of 1C.
- either the flat positive electrode or the flat negative electrode is accommodated in a bag-shaped separator in which the positive electrode lead terminal or the negative electrode lead terminal is pulled out in the machine direction of the separator.
- a synthetic resin film having an adhesive strength greater than the heat shrinkage stress of the separator and a softening point higher than that of the separator is attached to both surfaces beyond the ridge of the joint.
- a laminated secondary battery in which a laminated body of battery elements laminated with a counter electrode not stored in a bag-shaped separator facing each other is sealed with a film-shaped exterior material.
- a part of the synthetic resin film bonded to both surfaces beyond the ridge of the bonding portion of the bag-shaped separator is the above-described stacked secondary battery in which the positive electrode or the negative electrode inside the bag-shaped separator is present in the portion projected in the stacking direction. is there. Further, in the above-described stacked secondary battery, the outer peripheral portion of the bag-shaped separator and the adjacent two sides excluding the ridge from which the negative electrode lead-out terminal is taken out are aligned and stacked. In the laminated secondary battery, a positive electrode or negative electrode positioning portion to be accommodated is formed inside the bag-shaped separator.
- either the positive electrode or the negative electrode is housed in a bag-shaped separator in which the direction in which the electrode lead-out terminal is taken out coincides with the machine direction of the separator.
- a laminate of a battery element in which a separator containing a positive or negative electrode with a synthetic resin film having a bonding strength greater than the thermal shrinkage stress of the separator past a ridge that coincides with a flat counter electrode is laminated into a film Because it is sealed with an exterior material, it prevents the breakage of the joint of the bag-like separator due to the pressure of gas generated during overcharge due to the application of a voltage exceeding the expectation or the thermal contraction stress of the separator due to heating. Therefore, it is possible to prevent runaway due to contact between the positive electrode and the negative electrode due to breakage of the separator.
- FIG. 1 is a diagram for explaining one embodiment of a laminated secondary battery of the present invention.
- 1A is a perspective view illustrating a stacked secondary battery
- FIG. 1B is a diagram illustrating a cut surface taken along the line AA ′ of FIG. 1A
- FIG. 1C is a diagram of 1C of FIG. 1B. It is a figure which expands and demonstrates a part.
- FIG. 2 is a diagram for explaining the manufacturing process of the multilayer secondary battery of the present invention.
- 2A, 2B, 2C, 2E, and 2F are diagrams illustrating each manufacturing process.
- FIG. 2D is a diagram illustrating a cross section taken along line A-A ′ in FIG. 2B.
- FIG. 3 is a diagram for explaining another embodiment of the multilayer secondary battery of the present invention.
- FIG. 3A is a perspective view illustrating a stacked secondary battery.
- FIG. 3B is a diagram for explaining a cut surface along the line A-A ′ in FIG. 3A.
- FIG. 3C is a figure which expands and demonstrates the part of 1C of FIG. 3B.
- the laminated secondary battery of the present invention is a lithium ion battery
- a laminated lithium ion battery in which a positive electrode is housed in a bag-like separator and a battery element laminated with a negative electrode is sealed with a film-like exterior material. If the battery is charged at a high voltage and high charge rate that far exceed the 10V-1C conditions established as an international safety standard for overcharge, the electrolyte must be The joint of the bag-like separator breaks due to the gas pressure generated by the decomposition of the separator or the thermal contraction stress of the separator, causing a phenomenon such as direct contact between the positive electrode and the negative electrode in the vicinity of the broken portion, and the positive electrode and the negative electrode The focus is on the point of contact.
- the fuse function of the separator is activated to prevent breakage of the joint of the bag-shaped separator before the separator is blocked from permeating ions, so that a higher voltage and a higher rate of overcharge than expected can be achieved. It has been found that it is possible to provide a stacked secondary battery that does not affect the surroundings even if it is performed.
- FIG. 1 is a diagram for explaining one embodiment of a laminated secondary battery of the present invention.
- FIG. 1A is a perspective view illustrating a stacked secondary battery.
- 1B is a diagram for explaining a cut surface along the line AA ′ in FIG. 1A
- FIG. 1C is a diagram for explaining an enlarged portion of 1C in FIG. 1B.
- the laminated secondary battery 1 of the present invention has been described by taking a lithium ion battery as an example, and is composed of a rectangular plate-like positive electrode and a rectangular plate-like negative electrode.
- the battery element 3 is sealed with a film-like packaging material 5, and the battery element 3 includes a bag-like separator 30 that houses a rectangular plate-like positive electrode 10 and a rectangular plate-like body.
- a negative electrode 20 is laminated via a bag-like separator 30.
- a positive electrode active material layer 14 is formed on a positive electrode current collector 12, and a plurality of positive electrode lead terminals 16 bonded to the positive electrode are bonded to each other and then bonded to the positive electrode terminal 18 to seal the sealing portion 7. It is taken out through.
- the negative electrode 20 has a negative electrode active material layer 24 formed on a negative electrode current collector 22, and a plurality of negative electrode lead terminals 26 bonded to the negative electrode are joined to each other and are externally connected from a negative electrode terminal (not shown). Has been taken out.
- the bag-like separator 30 is formed with a joining portion 32 by heat fusion or the like except for a ridge portion where the positive electrode lead terminal 16 is located.
- the synthetic resin film 40 crosses the ridge 36 of the bag-like separator at the joint portion 32 in the width direction positioned perpendicular to the direction in which the positive electrode lead terminal is taken out.
- the adhesive layer 42 is bonded to the outer surface of the bonding portion 32.
- the synthetic resin film 40 is stuck with an adhesive strength greater than the thermal shrinkage stress of the separator.
- the synthetic resin film 40 may have a high heat resistance that does not soften below the softening temperature of the separator.
- a separator raw is manufactured through a step of forming an opening having a predetermined porosity at the same time as stretching the separator material or in a step different from stretching. Therefore, the fibers are oriented in the machine direction at the time of manufacture, that is, MD, and are generally wound in the machine direction. Therefore, when a bag-shaped separator is manufactured from the separator raw, it is wound in the machine direction, and when manufacturing a bag-shaped separator, the length direction of a rectangular electrode is generally matched with the machine direction. Is used.
- the MD end joint portion 32 ⁇ / b> M located at the end portion in the MD direction among the joint portions of the bag-like separator does not have to attach a synthetic resin film. There is virtually no effect on the properties.
- FIG. 2 is a diagram for explaining the manufacturing process of the multilayer secondary battery of the present invention.
- the bag-like separator 30 is manufactured by cutting the separator raw material into a predetermined size and forming the joint portion 32 by heat fusion or the like on the three sides excluding the portion that accommodates the positive electrode. . It has a machine direction that is the fiber direction of the separator, that is, MD and a direction TD perpendicular to the machine direction, and is drawn from the roll-shaped raw fabric in the machine direction and cut into a predetermined size, and then the long side of the rectangular positive electrode After being arranged so that the machine direction is positioned along the side of the shape, it is joined at the joint portion 32 to form a bag.
- the bag-shaped separator when a bag-shaped separator is manufactured by bonding the separator, the bag-shaped separator is arranged so that the positive electrode is located at a predetermined distance from the outer periphery of the separator when the positive electrode is stored in the bag-shaped separator.
- the positioning part 34 for positioning the positive electrode may be formed at the same time.
- a portion 32A located on the inner surface of the bag-like separator 30 of the joint portion 32 may be used as the positioning portion.
- FIG. 2B shows an enlarged view of the portion cut along the line AA ′ in FIG. 2B.
- a synthetic resin film 40 is pasted on both surfaces of the outer surface of the joint portion 32 beyond the ridge 36 of the joint portion 32 of the bag-shaped separator 30.
- a film having a softening point higher than that of a separator such as a polypropylene film and that is not deformed by the heat shrinkage stress of the separator can be used.
- films such as polystyrene and polyimide can be used.
- the adhesive layer 42 formed on the synthetic resin film 40 a material having good chemical resistance such as an acrylic adhesive can be used.
- the positive electrode 10 is accommodated in the bag-shaped separator 30.
- the positive electrode 10 is positioned by the positioning portion 34 provided inside the bag-shaped separator or the joining portion inner surface 32A of the bag-shaped separator 30 acting in place of the positioning portion.
- the width of the outer shape projected on a plane parallel to the positive electrode stacking surface of the bag-shaped separator containing the positive electrode was X
- the height was Y
- the positive electrode was disposed at a position separated from the outer shape by a predetermined distance.
- a bag-like separator is obtained.
- FIG. 2F a predetermined number of the negative electrode having the width X and the height Y shown in FIG. 2E and the bag-shaped separator containing the positive electrode shown in FIG.
- the positive electrode lead terminals 16 of the positive electrodes and the negative electrode lead terminals 26 of the negative electrodes are joined. Furthermore, after a positive electrode terminal is joined to the positive electrode lead terminal and a negative electrode terminal is joined to the negative electrode lead terminal to produce a battery element, it is sealed with a film-like exterior material to produce a laminated secondary battery. .
- the stacked secondary battery is a lithium ion battery has been described.
- a battery in which the area of the negative electrode is made larger than that of the opposing positive electrode is described as an example.
- it can produce similarly by accommodating a negative electrode in a bag-shaped separator.
- FIG. 3 is a diagram for explaining another embodiment of the present invention.
- FIG. 3A is a perspective view illustrating a stacked secondary battery.
- FIG. 3B is a diagram illustrating a cut surface taken along the line AA ′ of FIG. 3A.
- FIG. 3C is a figure which expands and demonstrates the part of 1C of FIG. 3B.
- the stacked secondary battery shown in FIGS. 3A, 3B, and 3C has the same configuration as the stacked secondary battery described in FIG. 1, and is positioned in a direction perpendicular to the direction in which the positive electrode extraction terminal is taken out.
- the joining position of the synthetic resin film 40 joined to the joining portion 32 in the width direction is different from that of the multilayer secondary battery shown in FIG.
- the battery element 3 is sealed with the film-shaped outer packaging material 5, and the battery element 3 includes a bag-like separator 30 containing a rectangular plate-like positive electrode 10 and a rectangular plate.
- a body-shaped negative electrode 20 is laminated via a bag-shaped separator 30.
- a positive electrode active material layer 14 is formed on a positive electrode current collector 12, and a plurality of positive electrode lead terminals 16 bonded to the positive electrode are bonded to each other and then bonded to the positive electrode terminal 18 to seal the sealing portion 7. It is taken out through.
- the negative electrode 20 has a negative electrode active material layer 24 formed on a negative electrode current collector 22, and a plurality of negative electrode lead terminals 26 bonded to the negative electrode are joined to each other and are externally connected from a negative electrode terminal (not shown). Has been taken out.
- the bag-like separator 30 is formed with a joining portion 32 by heat fusion or the like except for a ridge portion where the positive electrode lead terminal 16 is located. As illustrated in FIG. 3C, the joint portion is enlarged, and the synthetic resin film 40 is attached to the bag-like separator by the adhesive layer 42 in the joint portion 32 in the width direction, which is located in a direction perpendicular to the direction in which the positive electrode lead terminal is taken out. It is joined to the outer surface of the joint portion 32 beyond the ridge 36 with an adhesive strength greater than the thermal contraction stress of the separator.
- both ends 44 and 46 of the joined synthetic resin film 40 are joined to the lamination direction of the positive electrode end part.
- the separator is reinforced by the synthetic resin film.
- Example 1 A slurry comprising 63 parts by mass of a lithium manganese composite oxide, 4.2 parts by mass of acetylene black having a number average particle size of 7 ⁇ m, 2.8 parts by mass of polyvinylidene fluoride, and 50 parts by mass of N-methyl-2-pyrrolidone was prepared.
- a positive electrode having a thickness of 20 ⁇ m and an aluminum foil having a width of 150 mm, a non-coated length of 20 mm, an intermittent coating with a coating length of 130 mm, drying and pressing, and a thickness of 180 ⁇ m
- An active material layer was formed.
- a positive electrode having a coating width of 65 mm and a coating length of 125 mm was prepared so that the electrode lead-out terminal was formed with a width of 13 mm and a length of 17 mm in the uncoated portion.
- the positive electrode was covered with a polypropylene separator having a thickness of 25 ⁇ m, and 1.5 mm at the end of the positive electrode was joined by thermal fusion.
- a 30 ⁇ m-thick polypropylene tape having an acrylic adhesive layer it is pasted from the end of the separator in the machine direction to a length of 1 mm from the end of the projection portion in the stacking direction on the positive electrode separator. did.
- a laminated secondary battery in which either a flat plate-like positive electrode or a negative electrode is housed in a bag-like separator in which the direction of taking out the positive electrode lead-out terminal coincides with the machine direction of the separator, the joints on both sides outside the bag-like separator
- the separator containing a positive electrode on which a synthetic resin film having a higher adhesive strength than the thermal contraction stress of the separator and having a higher softening point than the separator is past the ridge extending in the machine direction of the separator; Since the battery element stack with a flat plate negative electrode is sealed with a film-like exterior material, the bag-shaped separator can prevent the battery from running away even when charged at a high charge rate with a higher voltage than expected. It is possible to provide a stacked secondary battery excellent in safety performance to prevent.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Cell Separators (AREA)
- Sealing Battery Cases Or Jackets (AREA)
- Connection Of Batteries Or Terminals (AREA)
Abstract
Description
板状の正極、負極は、それぞれ集電体用の帯状のアルミニウム箔あるいは銅箔上に電極活物質を所定の部位に塗布した後、導電接続用のタブを接続するために活物質層を形成していない部分を一体に作製している。
フィルム状外装材によって封口した積層型二次電池は、容積エネルギー密度、質量エネルギー密度に優れているものの剛体の外装容器によって封口されていないので、過充電時に電池要素に膨張等が起こると周囲に影響を及ぼす可能性があるので、高容量の積層型二次電池においては、過充電時の対策が重要となっている。
袋状セパレータの接合部の稜を越えた両面に接合された合成樹脂フィルムの一部は、袋状セパレータ内部の正極又は負極を積層方向に投影した部分に存在する前記の積層型二次電池である。
また、袋状セパレータの外周部と負極の電極引出端子を取り出した稜を除く隣接する2辺によって位置合わせして積層したものである前記の積層型二次電池である。
袋状セパレータの内部には収納する正極又は負極の位置決め部を形成した前記の積層型二次電池である。
そこで、セパレータのヒューズ機能が作動して、セパレータのイオンの透過が遮断される前に袋状セパレータの接合部が破断することを防止することによって、想定を超える高電圧と高率の過充電が行われても周囲に影響を及ぼすことがない積層型二次電池を提供することが可能であることを見出したものである。
図1は、本発明の積層型二次電池の一実施例を説明する図である。図1Aは、積層型二次電池を説明する斜視図である。また、図1Bは、図1AのA-A’線における切断面を説明する図であり、図1Cは、図1Bの1Cの部分を拡大して説明する図である。
本発明の積層型二次電池1は、リチウムイオン電池を例に挙げて説明しており、矩形状である板状の正極と、矩形状である板状の負極から構成されている。
積層型二次電池1は、電池要素3がフィルム状外装材5によって封口されており、電池要素3は、矩形の板状体状の正極10を収納した袋状セパレータ30と矩形の板状体状の負極20が袋状セパレータ30を介して積層されている。
正極10は正極集電体12上に正極活物質層14が形成されており、正極に結合した正極引出端子16の複数個が相互に接合された後に正極端子18に結合して封口部7を介して外部へ取り出されている。同様に、負極20は負極集電体22上に負極活物質層24が形成されており、負極に結合した負極引出端子26の複数個が相互に接合されて負極端子(図示せず)から外部へ取り出されている。
前記合成樹脂製フィルム40は、セパレータの熱収縮応力よりも大きな接着強度で貼着されている。また、前記合成樹脂フィルム40はセパレータの軟化温度以下では軟化することがない耐熱性が大きなものを用いることができる。
したがって、セパレータ原反から袋状セパレータを製造する際には、機械方向に巻き取られており、袋状セパレータを製造する際には、一般に矩形状の電極の長さ方向を機械方向に一致させたものが用いられている。
したがって、図1で示す積層型二次電池にあっては、袋状セパレータの接合部のうちMD方向の端部に位置するMD端部接合部32Mは、合成樹脂フィルムを貼着しなくても実質的に特性には影響を及ぼすことがない。
図2Aに示すように、袋状セパレータ30は、セパレータ原反を所定の大きさに裁断して、正極を収納する部分を除く三方を熱融着等によって接合部32を形成することによって製造する。
セパレータの繊維方向である機械方向すなわちMDと機械方向に直角方向TDを有しており、ロール状の原反から機械方向に引出して所定の大きさに裁断した後に、長方形状の正極の長辺状の辺に沿って機械方向が位置するように配置した後に接合部32において接合されて袋状とされる。
また、位置決め部34の形成に代えて、接合部32の袋状セパレータ30の内面に位置する部分32Aを位置決め部としても良い。
図2Bにおいて、A-A’線で切断した部分を拡大した図を図2Dに示す。
袋状セパレータの30の接合部32の稜36を越えて接合部32の外面の両面には、合成樹脂製フィルム40が貼着されている。
合成樹脂製フィルム40としては、ポリプロピレンフィルム等のセパレータに比べて軟化点が高く、またセパレータの熱収縮応力によっては変形することがないものを用いることができる。具体的には、ポリスチレン、ポリイミド等のフィルムを挙げることができる。また、合成樹脂製フィルム40に形成する粘着層42には、アクリル系粘着剤等の耐薬品性が良好なものを用いることができる。
更に、正極引出端子には正極端子を接合し、負極引出端子には負極端子を接合して電池要素を作製した後に、フィルム状外装材によって封口して積層型二次電池を作製することができる。
以上の説明では、積層型二次電池がリチウムイオン電池である場合について説明を行った。すなわち、負極の面積を対向する正極よりも大きくする電池を例に挙げて述べたものである。これに対して、正極を負極の面積よりも大きくする場合には、袋状セパレータに負極を収納することによって同様に作製することができる。
図3A,図3Bおよび図3Cに示した積層型二次電池は図1で説明した積層型二次電池と同様の構成を有しており、正極引出端子を取り出した方向と直角方向に位置する幅方向の接合部32に接合した合成樹脂製フィルム40の接合位置が図1に示した積層型二次電池とは異なっている。
すなわち、積層型二次電池1は、電池要素3がフィルム状外装材5によって封口されており、電池要素3は、矩形の板状体状の正極10を収納した袋状セパレータ30と矩形の板状体状の負極20が袋状セパレータ30を介して積層されている。
正極10は正極集電体12上に正極活物質層14が形成されており、正極に結合した正極引出端子16の複数個が相互に接合された後に正極端子18に結合して封口部7を介して外部へ取り出されている。同様に、負極20は負極集電体22上に負極活物質層24が形成されており、負極に結合した負極引出端子26の複数個が相互に接合されて負極端子(図示せず)から外部へ取り出されている。
また、接合された合成樹脂製フィルム40の両端部44,46は、正極を積層方向に投影した投影部は袋状セパレータと接合されているので、正極の端部の積層方向への投影部のセパレータは、合成樹脂フィルムによって補強されることとなる。
その結果、セパレータが熱収縮によって正極面と平行方向に引っ張られた際にも、セパレータが正極の角部との接触によって裂けたり穴が生じることを防止することができるので、合成樹脂製フィルムの接合による効果をより大きくすることができる。
リチウムマンガン複合酸化物63質量部、個数平均粒径7μmのアセチレンブラック4.2質量部、ポリフッ化ビニリデン2.8質量部、N-メチル-2-ピロリドン50質量部からなるスラリーを調製した。
集電体用の厚さ20μm、幅150mmのアルミニウム箔の全幅に、塗布していない長さを20mmとして、塗布長さ130mmで間欠的に塗布し、乾燥して押圧して厚さ180μmの正極活物質層を形成した。
塗布していない部分に電極引出端子が幅13mm、長さ17mmで形成されるようにして塗布幅65mm、塗布長さ125mmの正極を作製した。
次いで正極を厚さ25μmのポリプロピレン製セパレータで覆い、正極の端部の1.5mmを熱融着によって接合した。
次いで、アクリル系粘着層を有する厚さ30μmのポリプロピレン製テープを用いてセパレータの機械方向の端部を越えて、正極のセパレータへの積層方向の投影部の端部から1mmまでの長さに接着した。
得られた10個のリチウムイオン電池を1Cの電流で36Vに達するまで過充電状態に通電したが発煙は生じたリチウムイオン電池はなかった。
セパレータの接合部を越えて粘着層を有する合成樹脂製テープを接合しない点を除き実施例1と同様に10個のリチウムイオン電池を作製して同様に過充電試験を行ったところ、1Cの電流で25Vに達すると4のリチウムイオン電池に発煙を生じた。
3 電池要素
5 フィルム状外装材
7 封口部
10 正極
12 正極集電体
14 正極活物質層
16 正極引出端子
18 正極端子
20 負極
22 負極集電体
24 負極活物質層
26 負極引出端子
30 袋状セパレータ
32 接合部
32A 接合部内面、
32M MD端部接合部
34 位置決め部
36 袋状セパレータの稜
40 合成樹脂製フィルム
42 粘着層
44,46 両端部
50 位置決め治具
Claims (4)
- 平板状の正極又は平板状の負極のいずれか一方は、正極引出端子又は負極引出端子の取り出し方向をセパレータの機械方向に一致させた袋状セパレータに収納されており、袋状セパレータの接合部の稜を越えた両面にはセパレータの熱収縮応力よりも接着強度が大きく、軟化点がセパレータよりも高い合成樹脂フィルムが貼着されており、袋状セパレータに収納した正極又は負極を、袋状セパレータに収納していない対極とを対向させて積層した電池要素の積層体をフィルム状外装材によって封口したことを特徴とする積層型二次電池。
- 袋状セパレータの接合部の稜を越えた両面に接合された合成樹脂フィルムはの一部は、袋状セパレータ内部の正極又は負極を積層方向に投影した部分に存在することを特徴とする請求項1記載の積層型二次電池。
- 袋状セパレータの外周部と負極の電極引出端子を取り出した稜を除く隣接する2辺によって位置合わせして積層したものであることを特徴とする請求項1又は2記載の積層型二次電池。
- 袋状セパレータの内部には収納する正極又は負極の位置決め部を形成したことを特徴とする請求項1~3のいずれか1項記載の積層型二次電池。
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JP2014238958A (ja) * | 2013-06-07 | 2014-12-18 | オートモーティブエナジーサプライ株式会社 | 非水系電池 |
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TWI459613B (zh) | 2014-11-01 |
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CN102210053B (zh) | 2014-04-23 |
JP2010062109A (ja) | 2010-03-18 |
CN102210053A (zh) | 2011-10-05 |
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