WO2009142013A1 - 電池 - Google Patents
電池 Download PDFInfo
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- WO2009142013A1 WO2009142013A1 PCT/JP2009/002229 JP2009002229W WO2009142013A1 WO 2009142013 A1 WO2009142013 A1 WO 2009142013A1 JP 2009002229 W JP2009002229 W JP 2009002229W WO 2009142013 A1 WO2009142013 A1 WO 2009142013A1
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- separator
- active material
- physical property
- material layer
- negative electrode
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- 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
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
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- 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
- H01M10/0413—Large-sized flat cells or batteries for motive or stationary systems with plate-like electrodes
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- 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
- H01M10/0431—Cells with wound or folded electrodes
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- 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
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- 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
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- 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
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- 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
- H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
- H01M10/12—Construction or manufacture
- H01M10/125—Cells or batteries with wound or folded electrodes
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/24—Alkaline accumulators
- H01M10/28—Construction or manufacture
- H01M10/286—Cells or batteries with wound or folded electrodes
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/75—Wires, rods or strips
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- 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
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- 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
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
- H01M50/406—Moulding; Embossing; Cutting
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- 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
- H01M50/409—Separators, membranes or diaphragms characterised by the material
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- 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
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/417—Polyolefins
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- 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
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- 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
- H01M50/469—Separators, membranes or diaphragms characterised by their shape tubular or cylindrical
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- 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
- H01M50/528—Fixed electrical connections, i.e. not intended for disconnection
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- 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
- H01M50/531—Electrode connections inside a battery casing
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- 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
- H01M50/572—Means for preventing undesired use or discharge
- H01M50/574—Devices or arrangements for the interruption of current
- H01M50/579—Devices or arrangements for the interruption of current in response to shock
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- H01M2200/00—Safety devices for primary or secondary batteries
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
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- 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
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—Fibrous material
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- 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
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- 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
Definitions
- the present invention relates to a battery in which a separator improved so as to be excellent in safety in batteries typified by a secondary battery and a lithium battery.
- lithium ion secondary batteries which are widely used as power sources for portable electronic devices, use a carbonaceous material capable of occluding and releasing lithium for the negative electrode plate, and a transition metal such as LiCoO 2 and lithium for the positive electrode plate.
- a lithium ion secondary battery having a high potential and a high discharge capacity is realized.
- safety measures should be emphasized. In particular, it is extremely important that the positive electrode plate and the negative electrode plate are not internally short-circuited.
- the start / end portions of the active material layer when the coating material for the active material layer of the positive electrode plate and the negative electrode plate is applied to the current collector, and the positive electrode plate and the negative electrode plate on which the coating film is formed have a desired strip shape. Angular parts such as the cut edge of the coating film, the positive electrode current collector and the negative electrode current collector, the positive electrode lead and the negative electrode lead edge, and the cutting burr that penetrates the separator. There is a risk of short circuit.
- the electrode plate includes an exposed portion from which the current collector 25 is exposed, and an insulating film 23 is attached from the vicinity of the end portion of the active material layer 26 to the exposed portion.
- a method in which the thickness of the end portion of the insulating film 23 is reduced has also been proposed (see, for example, Patent Document 3).
- JP-A-6-103971 Japanese Patent Laid-Open No. 7-320770 JP 2005-235414 A
- the active material layer 26 positioned below the insulating film 23 is bonded to the insulating film 23 by attaching a thick insulating film to the active material layer. Therefore, the expansion and contraction of the electrode plate 28 during winding and charging / discharging is regulated. As a result, at the end of the insulating film 23, a crack occurs between the active material layer 26 fixed to the insulating film 23 and the active material layer 26 not fixed, and lithium deposition on the current collector 25 occurs. Is concerned. In addition, there is a concern that the cross section of the broken active material layer 26 may break through a separator (not shown) during expansion / contraction or winding and cause an internal short circuit.
- the active material layer 26 since a part of the active material layer 26 is strongly fixed by the insulating film 23, the active film having the insulating film 23 fixed on the inner surface of the current collector 25 when the electrode group is wound.
- the material layer 26 cannot be deformed according to the curvature.
- the tensile stress is concentrated on the current collector 25 made of aluminum foil or copper foil, and the current collector 25 is cut.
- the active material layer 26 is cracked by the insulating film 23 attached to the active material layer 26 at the end, and the current collector 25 is cut during winding. It has the problem of being easy.
- Patent Document 3 described above, the incidence rate is reduced by reducing the thickness of the insulating film 23 at the end portion of the insulating film 23 and the end portion of the active material layer 26 in order to suppress breakage of the current collector 25.
- the root of the problem has not been solved, and the current collector 25 is likely to be disconnected.
- an object of the present invention is to provide a battery that can improve the crushing strength of the separator, suppress internal short circuit, and is excellent in safety.
- a battery according to one aspect of the present invention is obtained by winding or laminating a positive electrode plate and a negative electrode plate formed by applying an active material layer on the surface of a strip-shaped current collector through a separator.
- the separator corresponding to the application start / end portion of the active material layer or the end portion of the current collector is strong against crushing. It is characterized by having a certain physical property modifying section.
- Such a configuration can suppress the occurrence of defects that are likely to occur at a specific location such as an internal short circuit.
- the physical property modifying portion of the separator is preferably obtained by subjecting the predetermined portion of the separator to a hot press or a discharge treatment.
- production of a defect can be suppressed with respect to the specific location where an internal short circuit is easy to generate
- the physical property modifying portion of the separator is preferably one obtained by filling, sticking, laminating, or bonding a resin material to the predetermined portion of the separator. Thereby, the crushing strength of the material reforming portion of the separator can be further increased.
- the hole of the surface layer of a separator can be block
- a physical property modifying portion of the separator on the separator surface. This prevents the active material layer from being deformed according to the curvature during winding of the electrode group, relaxes the concentration of tensile stress on the current collector, and suppresses the current collector from being cut. Can do.
- the band-shaped current collector is formed by cutting a sheet-shaped current collector having an active material layer formed on a surface thereof, and a cut end of the active material layer of the separator. It is preferable that a physical property modifying portion of the separator is further provided at a portion corresponding to the portion. Thereby, it can be set as the structure which does not affect the motion of the ion accompanying charging / discharging of a battery in places other than a material modification part.
- a current collecting lead is connected to a portion of the current collector where the active material layer is not formed, and a portion corresponding to the end of the current collecting lead of the separator is connected to the separator. It is preferable that a physical property modifying section is further provided. Thereby, generation
- the portion corresponding to at least the application start / end portion of the active material layer or the end portion of the current collector of the separator is a physical property modifying portion that is strong against crushing. An internal short circuit can be suppressed, thereby providing a battery with excellent safety.
- FIG. 1 is a schematic view showing an electrode group produced by winding a separator for a non-aqueous secondary battery according to an embodiment of the present invention.
- FIG. 2 is a schematic view showing a physical property reforming section of a non-aqueous secondary battery separator according to an embodiment of the present invention.
- 3 (a) and 3 (b) are views of a separator provided with physical property reforming portions on both sides of a separator for a non-aqueous secondary battery according to an embodiment of the present invention.
- FIG. 3 (a) is a cross-sectional view.
- FIG. 3B is a plan view.
- FIG. 1 is a schematic view showing an electrode group produced by winding a separator for a non-aqueous secondary battery according to an embodiment of the present invention.
- FIG. 2 is a schematic view showing a physical property reforming section of a non-aqueous secondary battery separator according to an embodiment of the present invention.
- 3 (a) and 3 (b) are views of
- FIG. 4 is a cross-sectional view of a separator provided with physical property reforming portions on both sides of a separator for a non-aqueous secondary battery according to an embodiment of the present invention.
- FIG. 5 is a cross-sectional view of a separator provided with a physical property modifying portion on one side of a separator for a non-aqueous secondary battery according to an embodiment of the present invention.
- FIG. 6 is a cross-sectional view of a separator provided with a physical property modifying portion on one side of a separator for a non-aqueous secondary battery according to an embodiment of the present invention.
- 7A and 7B are surface SEM photographs of a separator for a non-aqueous secondary battery according to an embodiment of the present invention, and FIG.
- FIG. 7A is an SEM photograph of a surface that has not been subjected to material modification treatment.
- FIG. 7B is a SEM photograph of the surface subjected to the material modification treatment.
- FIG. 8 is a partially cutaway perspective view showing a non-aqueous secondary battery according to an embodiment of the present invention.
- FIG. 9 is a perspective view showing a conventional electrode plate.
- FIG. 10 is a cross-sectional view showing a conventional electrode plate.
- the battery of the present invention includes a positive electrode plate 4 and a negative electrode active material layer in which a positive electrode lead (current collection lead) 7 is connected to a positive electrode current collector 5 in which the positive electrode active material layer 6 is not formed.
- the physical property reforming part 2a in which the negative electrode plate 8 in which the negative electrode lead (collecting lead) 11 is connected to the negative electrode current collector 9 in which the shape 10 is not formed is reduced as shown in FIG.
- a battery is constructed by accommodating an electrode group 13 which is wound and wound through a separator 2 with a fixing tape 12 together with an electrolyte in a battery case 14 as shown in FIG.
- a positive electrode plate 4 using a composite lithium oxide as a positive electrode active material and a negative electrode plate 8 using a material capable of holding lithium as a negative electrode active material are separators.
- the electrode group 13 is configured by being wound in a spiral shape via 2. As shown in FIG. 8, the electrode group 13 is housed in the bottomed cylindrical battery case 14 together with the insulating plate 17, and the negative electrode lead 11 led out from the lower part of the electrode group 13 is connected to the bottom of the battery case 14.
- the positive electrode lead 7 led out from the upper part of the electrode group 13 is connected to the sealing plate 15, and an electrolyte solution (not shown) made of a non-aqueous solvent is injected into the battery case 14.
- a sealing plate 15 having a sealing gasket 16 attached to the periphery is inserted into the opening, and the opening of the battery case 14 is bent inward to be caulked and sealed.
- the separator 2 is not particularly limited as long as it has a composition that can withstand the use range of the nonaqueous electrolyte secondary battery, but it is common to use a microporous film of an olefin-based resin such as polyethylene or polypropylene as a single or a composite. And preferred as an embodiment.
- the thickness of the separator 2 is not particularly limited, but may be 10 to 25 ⁇ m.
- the physical property modification part 2a which gave the physical property modification, reduced the porosity, increased the hardness, and increased the crushing strength is obtained.
- the non-physical property reforming portion other than the physical property reforming portion 2a which is a portion where the positive electrode plate 4 and the negative electrode plate 8 are widely opposed to each other, is subjected to physical property modification such as improvement of crushing strength by reducing porosity. It does not affect the movement of ions accompanying charging / discharging of the battery.
- the method for increasing the crushing strength is, for example, by melting and pressing the resin surface of the separator 2 by hot pressing against the separator 2 as shown in FIG.
- the method for closing the surface layer holes of the porous separator 2 crack expansion can be suppressed from the surface layer holes during the crush test and when a foreign object is stuck, and the crushing strength can be increased.
- FIG. 4 there is no problem even if the physical property reforming treatment is performed over the entire cross section of the separator 2.
- FIGS. 3 (a) and 3 (b) the physical property modifying section 2a as shown in FIGS. 3 (a) and 3 (b) is provided by filling and bonding a resin having a good affinity to the separator 2 instead of melting the separator 2 itself, and the crushing strength is provided. It is also possible to increase this.
- FIG. 3A is a sectional view
- FIG. 3B is a plan view.
- a physical property modifying portion 2 a as shown in FIG. 4 is provided to increase the crushing strength. You can also.
- “sticking” refers to bonding through a binder, and “bonding” refers to mechanical and chemical fusion of materials.
- the crushing strength of a desired surface at a desired location can be increased by creating the physical property modifying portion 2a on only one surface.
- the property modifying portion 2a of the separator 2 may be provided by filling the surface of the separator 2 with an adhesive resin.
- the physical property modifying portion 2a is made a portion having a small gap (or no void), a high voltage resistance, and a strong crushing strength, and by giving the portion stickiness, the end portion of the electrode plate, etc. It is possible to stably dispose the physical property modifying portion 2a at a portion corresponding to the sharp portion. As a result, it is possible to more effectively prevent the internal short circuit from occurring through the separator.
- FIG. 7 (a) shows a surface SEM photograph of the separator in the part not subjected to the physical property modification treatment
- FIG. 7 (b) shows a surface SEM photograph of the separator in the part subjected to the physical property modification treatment. As shown in FIG. 7B, the voids in the material modifying portion 2a are reduced.
- the positive electrode plate 4 is not particularly limited, a metal foil made of aluminum, aluminum alloy, nickel, or nickel alloy having a thickness of 5 ⁇ m to 30 ⁇ m can be used as the positive electrode current collector 5.
- a positive electrode active material, a conductive material, and a binder are mixed and dispersed in a dispersion medium by a dispersing machine such as a planetary mixer. Is made.
- the positive electrode active material, conductive material, and binder are placed in an appropriate dispersion medium, mixed and dispersed by a disperser such as a planetary mixer, and adjusted to an optimum viscosity for application to the current collector. By doing so, a positive electrode mixture paint is produced.
- a disperser such as a planetary mixer
- Examples of the positive electrode active material include lithium cobaltate and modified products thereof (such as lithium cobaltate in which aluminum or magnesium is dissolved), lithium nickelate and modified products thereof (such as nickel partially substituted with cobalt). And composite oxides such as lithium manganate and modified products thereof.
- carbon black such as acetylene black, ketjen black, channel black, furnace black, lamp black, thermal black, and various graphites may be used alone or in combination.
- binder for the positive electrode for example, polyvinylidene fluoride (PVdF), a modified polyvinylidene fluoride, polytetrafluoroethylene (PTFE), a rubber particle binder having an acrylate unit, and the like can be used.
- PVdF polyvinylidene fluoride
- PTFE polytetrafluoroethylene
- a rubber particle binder having an acrylate unit for example, polyvinylidene fluoride (PVdF), a modified polyvinylidene fluoride, polytetrafluoroethylene (PTFE), a rubber particle binder having an acrylate unit, and the like can be used.
- PVdF polyvinylidene fluoride
- PTFE polytetrafluoroethylene
- the positive electrode mixture paint prepared as described above using a die coater is applied onto the positive electrode current collector 5 made of aluminum foil, then dried, and then compressed to a predetermined thickness with a press, thereby positive electrode active material layer 6 A positive electrode plate 4 is obtained.
- the negative electrode plate 8 is not particularly limited, but a copper or copper alloy metal foil having a thickness of 5 ⁇ m to 25 ⁇ m can be used as the negative electrode current collector 9.
- a negative electrode mixture paint applied on the negative electrode current collector 9 a negative electrode active material, a binder, and if necessary, a conductive material and a thickener are mixed in a dispersion medium by a disperser such as a planetary mixer. Disperse to prepare a negative electrode mixture paint.
- the negative electrode active material and the binder are placed in an appropriate dispersion medium, mixed and dispersed by a dispersing machine such as a planetary mixer, and adjusted to the optimum viscosity for application to the current collector and then kneaded.
- a dispersing machine such as a planetary mixer
- the negative electrode active material various natural graphites and artificial graphites, silicon-based composite materials such as silicide, and various alloy composition materials can be used.
- binders such as PVdF and modified products thereof can be used as the binder for the negative electrode at this time.
- SBR styrene-butadiene copolymer rubber particles
- CMC carboxymethylcellulose
- the negative electrode mixture paint prepared as described above using a die coater is applied onto the negative electrode current collector 9 made of copper foil, dried, and then compressed to a predetermined thickness with a press, thereby negative electrode active material layer 10 Thus, a negative electrode plate 8 is obtained.
- ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), and methyl ethyl carbonate (MEC) can be used alone or in combination as a solvent. It is also preferable to use vinylene carbonate (VC), cyclohexylbenzene (CHB), and modified products thereof in order to form a good film on the positive and negative electrode plates and to ensure stability during overcharge.
- VC vinylene carbonate
- CHB cyclohexylbenzene
- the electrode group 13 formed by winding the positive electrode plate 4 and the negative electrode plate 8 through the separator 2 as shown in FIG. 1 is insulated inside the bottomed cylindrical battery case 14 as shown in FIG.
- the negative electrode lead 11 housed together with the plate 17 and led out from the lower part of the electrode group 13 is connected to the bottom of the battery case 14, and then the positive electrode lead 7 led out from the upper part of the electrode group 13 is connected to the sealing plate 15.
- a sealing plate 15 having a sealing gasket 16 attached to the periphery is inserted into the opening of the battery case 14 to insert the opening of the battery case 14 into the opening.
- a non-aqueous secondary battery is manufactured by bending in a direction and sealing.
- Example 1 The application start / end portion 6a of the positive electrode active material layer 6 and the application start / end portion 10a of the negative electrode active material layer 10, the cut end portion 10b of the positive electrode active material layer 6, and the cut end of the negative electrode active material layer 10 have a thickness of 20 ⁇ m.
- the plasma irradiation apparatus is applied from a distance of 10 mm to a region having a width of about 5 mm at the corresponding portions of the end portions of the portion 10b, the positive electrode lead 7 and the negative electrode lead 11, and the end portions of the positive electrode current collector 5 and the negative electrode current collector 9.
- the separator 2 in which the physical property reforming part 2a was formed by performing plasma irradiation for 0.5 seconds at a voltage LOW setting was used as the separator 2 of Example 1.
- an electrode group 13 constituted by winding the positive electrode plate 4 and the negative electrode plate 8 through the separator 2 of Example 1 as shown in FIG. 1 is formed in the inside of the bottomed cylindrical battery case 14 as shown in FIG.
- the negative electrode lead 11 led out from the lower part of the electrode group 13 is connected to the bottom part of the battery case 14, and then the positive lead 7 led out from the upper part of the electrode group 13 is connected to the sealing plate 15,
- a sealing plate 15 having a sealing gasket 16 attached to the periphery is inserted into the opening of the battery case 14, and the opening of the battery case 14 is inserted.
- the non-aqueous secondary battery produced by folding the cable inward and crimping and sealing was used as the non-aqueous secondary battery of Example 1.
- Example 2 The application start / end portion 6a of the positive electrode active material layer 6 and the application start / end portion 10a of the negative electrode active material layer 10, the cut end portion 6b of the positive electrode active material layer 6, and the cut end of the negative electrode active material layer 10 having a thickness of 20 ⁇ m.
- the metal heater and the metal plate are used for the region having a width of about 5 mm in the corresponding portions of the end portions of the portion 10b, the positive electrode lead 7 and the negative electrode lead 11, and the end portions of the positive electrode current collector 5 and the negative electrode current collector 9.
- the separator 2 of Example 2 was formed by sandwiching it with a load of 1 N, setting the heater at 150 ° C., and performing physical pressing for 10 minutes to form the property modifying portion 2a.
- an electrode group 13 formed by winding the positive electrode plate 4 and the negative electrode plate 8 through the separator 2 of Example 2 as shown in FIG. 1 is formed in the inside of the bottomed cylindrical battery case 14 as shown in FIG.
- the negative electrode lead 11 led out from the lower part of the electrode group 13 is connected to the bottom part of the battery case 14, and then the positive electrode lead 7 led out from the upper part of the electrode group 13 is connected to the sealing plate 15.
- a sealing plate 15 having a sealing gasket 16 attached to the periphery is inserted into the opening of the battery case 14, and the opening of the battery case 14 is inserted.
- the non-aqueous secondary battery produced by bending the cable inward and crimping and sealing was used as the non-aqueous secondary battery of Example 2.
- Example 3 The application start / end portion 6a of the positive electrode active material layer 6 and the application start / end portion 10a of the negative electrode active material layer 10, the cut end portion 6b of the positive electrode active material layer 6, and the cut end of the negative electrode active material layer 10 having a thickness of 20 ⁇ m.
- the plasma discharge processing apparatus from a distance of 10 mm to the region having a width of about 5 mm in the corresponding portions of the end portions of the portion 10b, the positive electrode lead 7 and the negative electrode lead 11, and the end portions of the positive electrode current collector 5 and the negative electrode current collector 9 Then, after radiating plasma discharge for 0.5 seconds with the voltage LOW setting, the metal heater and the metal plate are sandwiched with a load of 1N, the heater setting is set to 150 ° C., and hot pressing is performed for 10 minutes.
- the separator 2 formed with the physical property reforming portion 2a was used as the separator 2 of Example 3.
- an electrode group 13 constituted by winding the positive electrode plate 4 and the negative electrode plate 8 through the separator 2 of Example 3 as shown in FIG. 1 is formed in the inside of the bottomed cylindrical battery case 14 as shown in FIG.
- the negative electrode lead 11 led out from the lower part of the electrode group 13 is connected to the bottom part of the battery case 14, and then the positive electrode lead 7 led out from the upper part of the electrode group 13 is connected to the sealing plate 15.
- a sealing plate 15 having a sealing gasket 16 attached to the periphery is inserted into the opening of the battery case 14, and the opening of the battery case 14 is inserted.
- the non-aqueous secondary battery produced by bending the cable inward and crimping and sealing was used as the non-aqueous secondary battery of Example 3.
- Example 4 The application start / end portion 6a of the positive electrode active material layer 6 and the application start / end portion 10a of the negative electrode active material layer 10, the cut end portion 6b of the positive electrode active material layer 6, and the cut end of the negative electrode active material layer 10 having a thickness of 20 ⁇ m.
- the resin of the same type as the melted separator is applied to the region having a width of about 5 mm at the corresponding portions of the end portions of the portion 10b, the positive electrode lead 7 and the negative electrode lead 11, and the end portions of the positive electrode current collector 5 and the negative electrode current collector 9.
- the separator 2 applied in Example 4 and cooled in a state in which the thickness was regulated to form the property modifying portion 2a was designated as the separator 2 of Example 4.
- an electrode group 13 constituted by winding the positive electrode plate 4 and the negative electrode plate 8 through the separator 2 of Example 3 as shown in FIG. 1 is formed in the inside of the bottomed cylindrical battery case 14 as shown in FIG.
- the negative electrode lead 11 led out from the lower part of the electrode group 13 is connected to the bottom part of the battery case 14, and then the positive lead 7 led out from the upper part of the electrode group 13 is connected to the sealing plate 15,
- a sealing plate 15 having a sealing gasket 16 attached to the periphery is inserted into the opening of the battery case 14, and the opening of the battery case 14 is inserted.
- the non-aqueous secondary battery produced by bending the cable inward and crimping and sealing was used as the non-aqueous secondary battery of Example 4.
- Comparative Example 1 The separator 2 having a thickness of 20 ⁇ m and not forming the physical property modification portion was used as the separator 2 of Comparative Example 1. Further, an electrode group 13 formed by winding the positive electrode plate 4 and the negative electrode plate 8 through the separator 2 of Comparative Example 1 as shown in FIG. 1 is formed in the bottomed cylindrical battery case 14 as shown in FIG.
- the negative electrode lead 11 led out from the lower part of the electrode group 13 is connected to the bottom part of the battery case 14, and then the positive lead 7 led out from the upper part of the electrode group 13 is connected to the sealing plate 15, After injecting a predetermined amount of an electrolyte solution (not shown) made of a non-aqueous solvent into the case 14, a sealing plate 15 having a sealing gasket 16 attached to the periphery is inserted into the opening of the battery case 14, and the opening of the battery case 14 is inserted.
- the non-aqueous secondary battery produced by bending the cable inward and crimping and sealing was used as the non-aqueous secondary battery of Comparative Example 1.
- Table 1 shows the result of comparison of the physical property reforming part 2a manufactured under the above conditions by the crushing strength test.
- the separator 2 was fixed with a washer having a diameter of 12 mm, and a pin was pierced into the fixed separator 2 at a speed of 100 mm / min, and the maximum load (N) at that time was determined as the crushing strength.
- the pin shape was such that the pin diameter was 1 mm and the tip was 0.5R.
- the evaluation of the leak occurrence rate was performed by using 100 positive electrode leads 7 and 11 negative electrode leads 11 each of which was manufactured by winding the positive electrode plate 4 and the negative electrode plate 8 through the separators 2 of the examples and comparative examples.
- a voltage of 800V was applied to the electrode group 13, and the electrode group 13 in which the current flowed 0.1 mA or more was counted as a leaked product, and a value obtained by dividing by the parameter 100 was defined as a leak rate (%).
- the battery capacity was evaluated by comparing Examples 1 to 3 with the discharge capacity of the nonaqueous secondary battery manufactured using the separator 2 of Examples 1 to 3 and the comparative example as the comparative example 100. did.
- the separator 2 of Example 2 the voids in the separator 2 are crushed by the hot press treatment as shown in FIG. In particular, it is difficult to tear, and the effect of suppressing internal short circuit can be expected.
- the separator 2 of Example 3 which performed the heat press process with the plasma discharge process
- the effect of the hot press performed in the separator 2 of Example 2 has a large influence on the physical property value, and the influence of the plasma discharge process is the crushing strength.
- the porosity is the same value as in Example 2.
- Example 4 the separator 2 subjected to the filling treatment of Example 4 is filled with the resin in the gaps compared to Examples 1 to 3, so that the volume of the separator 2 itself is increased, the hardness is increased, and the crushing strength is increased. Has led to an increase. Further, the leak occurrence rate of the electrode group 13 using the separator 2 of each example was improved in the example 1 as compared with the comparative example having a low crushing strength, and no leak occurred in the examples 2 and 3. . Moreover, in the capacity
- the lithium ion secondary battery has been described, but the same effect can be obtained in other batteries in which ions are exchanged between the positive electrode plate 4 and the negative electrode plate 8 via the separator 2 such as an alkaline storage battery and a lithium battery. It goes without saying that it is obtained.
- the nonaqueous secondary battery according to the present invention is useful as a power source for portable electronic devices such as lithium ion secondary batteries, alkaline storage batteries, and lithium batteries.
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Abstract
Description
厚みが20μmでセパレータ2の正極活物質層6の塗布始終端部6aおよび負極活物質層10の塗布始終端部10a、正極活物質層6の切断端部10bおよび負極活物質層10の切断端部10b、正極リード7および負極リード11の端部、正極集電体5および負極集電体9の端部の対応する部位のおよそ5mmの幅の領域に対し、10mmの距離からプラズマ照射装置を用いて、電圧LOW設定にて0.5秒間のプラズマ照射を実施し、物性改質部2aを成形されたセパレータ2を実施例1のセパレータ2とした。
厚みが20μmでセパレータ2の正極活物質層6の塗布始終端部6aおよび負極活物質層10の塗布始終端部10a、正極活物質層6の切断端部6bおよび負極活物質層10の切断端部10b、正極リード7および負極リード11の端部、正極集電体5および負極集電体9の端部の対応する部位のおよそ5mmの幅の領域に対し、金属製のヒータと金属板で1Nの荷重で挟み、ヒータの設定を150℃とし、10分間、熱プレスを行って物性改質部2aを成形したセパレータ2を実施例2のセパレータ2とした。
厚みが20μmでセパレータ2の正極活物質層6の塗布始終端部6aおよび負極活物質層10の塗布始終端部10a、正極活物質層6の切断端部6bおよび負極活物質層10の切断端部10b、正極リード7および負極リード11の端部、正極集電体5および負極集電体9の端部の対応する部位のおよそ5mmの幅の領域に対し、10mmの距離からプラズマ放電処理装置において、電圧LOW設定にて0.5秒間のプラズマ放電を照射した後、金属製のヒータと金属板で1Nの荷重で挟み、ヒータの設定を150℃とし、10分間、熱プレス処理を行って物性改質部2aを成形したセパレータ2を実施例3のセパレータ2とした。
厚みが20μmでセパレータ2の正極活物質層6の塗布始終端部6aおよび負極活物質層10の塗布始終端部10a、正極活物質層6の切断端部6bおよび負極活物質層10の切断端部10b、正極リード7および負極リード11の端部、正極集電体5および負極集電体9の端部の対応する部位のおよそ5mmの幅の領域に対し、溶融したセパレータと同種の樹脂を塗布し、金属板に挟み厚みを規正した状態で冷却して物性改質部2aを成形したセパレータ2を実施例4のセパレータ2とした。
厚みが20μmで物性改質部を形成しないセパレータ2を比較例1のセパレータ2とした。
さらに、正極板4と負極板8とを比較例1のセパレータ2を介し図1のように巻回して構成した電極群13を図8に示したように有底円筒形の電池ケース14の内部に絶縁板17と共に収容し、電極群13の下部より導出した負極リード11を電池ケース14の底部に接続し、次いで電極群13の上部より導出した正極リード7を封口板15に接続し、電池ケース14に所定量の非水溶媒からなる電解液(図示せず)を注液した後に電池ケース14の開口部に封口ガスケット16を周縁に取り付けた封口板15を挿入し電池ケース14の開口部を内方向に折り曲げてかしめ封口することにより作製した非水系二次電池を比較例1の非水系二次電池とした。
圧壊強度試験は、セパレータ2を直径が12mmのワッシャで固定し、固定されたセパレータ2に、ピンを100mm/分の速度で突刺し、その際の最大荷重(N)を圧壊強度として求めた。ピンの形状は、ピンの直径が1mm、先端が0.5Rとした。
また、プラズマ放電処理と共に熱プレス処理を施した実施例3のセパレータ2においては実施例2のセパレータ2で行った熱プレスの効果が物性値に与える影響が大きく、プラズマ放電処理の影響は圧壊強度を微増させる程度にとどまり、空隙率は実施例2の場合と同等な値となる。
また、各実施例のセパレータ2を用いた電極群13のリーク発生率は、圧壊強度の低い比較例に対して、実施例1では改善し、実施例2,3においてはリーク発生が起こらなかった。
また、各実施例のセパレータ2を用いた非水系二次電池の容量確認においては比較例に対し、実施例1から実施例4において電池容量の低下は見られなかった。
2a 物性改質部
4 正極板
5 正極集電体
6 正極活物質層
6a 塗布始終端部
6b 切断端部
7 正極リード
8 負極板
9 負極集電体
10 負極活物質層
10a 塗布始終端部
10b 切断端部
11 負極リード
12 巻き止めテープ
13 電極群
14 電池ケース
15 封口板
16 封口ガスケット
17 絶縁板
Claims (7)
- 帯状の集電体の表面に活物質層を塗布して形成した正極板と負極板とをセパレータを介して巻回または積層して構成した電極群と電解液とを電池ケースに封入してなる電池において、
前記セパレータの少なくとも前記活物質層の塗布始終端部または前記集電体の端部に対応する部位を、圧壊に対して強度のある物性改質部としたことを特徴とする電池。 - 前記セパレータの物性改質部は、前記セパレータの前記所定の部位に、熱プレスまたは放電処理を施したものであることを特徴とする請求項1に記載の電池。
- 前記セパレータの物性改質部は、前記セパレータの前記所定の部位に、樹脂材を充填、貼付または結合したものであることを特徴とする請求項1に記載の電池。
- 前記セパレータの物性改質部をセパレータの内部に設けたことを特徴とする請求項1に記載の電池。
- 前記セパレータの物性改質部をセパレータ表面に設けたことを特徴とする請求項1に記載の電池。
- 前記帯状の集電体は、表面に前記活物質層が形成されたシート状の集電体を切断して形成されたものであり、
前記セパレータの前記活物質層の切断端部に対応する部位に、前記セパレータの物性改質部がさらに設けられていることを特徴とする請求項1に記載の電池。 - 前記集電体の前記活物質層が形成されていない部位に、集電用リードが接続されており、
前記セパレータの前記集電用リードの端部に対応する部位に、前記セパレータの物性改質部がさらに設けられていることを特徴とする請求項1に記載の電池。
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JP5687443B2 (ja) * | 2010-06-24 | 2015-03-18 | トヨタ自動車株式会社 | 電池 |
JP5559287B2 (ja) | 2012-11-07 | 2014-07-23 | ファナック株式会社 | 高温エリアにおいてワークをハンドリングするロボットハンド |
JP2014232703A (ja) * | 2013-05-30 | 2014-12-11 | 株式会社Gsユアサ | 蓄電素子及び蓄電素子の製造方法 |
KR101841307B1 (ko) * | 2013-12-18 | 2018-03-22 | 주식회사 엘지화학 | 안전성 향상을 위한 코팅층이 형성된 이종 분리막을 포함하는 전극조립체 및 이를 포함하는 리튬 이차전지 |
JP6578818B2 (ja) * | 2014-09-04 | 2019-09-25 | トヨタ自動車株式会社 | 二次電池の製造方法 |
WO2018030810A1 (ko) * | 2016-08-12 | 2018-02-15 | 주식회사 엘지화학 | 전극과 분리막이 부분 결착된 전극조립체 |
KR102171213B1 (ko) * | 2016-09-16 | 2020-10-28 | 가부시키가이샤 무라타 세이사쿠쇼 | 리튬 이온 이차 전지용 부극, 리튬 이온 이차 전지, 전지 팩, 전동 차량, 전력 저장 시스템, 전동 공구 및 전자 기기 |
CN113557620A (zh) * | 2019-03-13 | 2021-10-26 | 松下知识产权经营株式会社 | 非水电解质二次电池及非水电解质二次电池的制造方法 |
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CN101911339A (zh) | 2010-12-08 |
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