WO2012101816A1 - 二次電池、および、電極シートの切断装置 - Google Patents
二次電池、および、電極シートの切断装置 Download PDFInfo
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- WO2012101816A1 WO2012101816A1 PCT/JP2011/051764 JP2011051764W WO2012101816A1 WO 2012101816 A1 WO2012101816 A1 WO 2012101816A1 JP 2011051764 W JP2011051764 W JP 2011051764W WO 2012101816 A1 WO2012101816 A1 WO 2012101816A1
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- insulating layer
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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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
- 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
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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
- H01M4/00—Electrodes
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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
- 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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0483—Processes of manufacture in general by methods including the handling of a melt
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
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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
- H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
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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
- H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
- H01M50/461—Separators, membranes or diaphragms characterised by their combination with electrodes with adhesive layers between electrodes and separators
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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
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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
- 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
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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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/49108—Electric battery cell making
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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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/53—Means to assemble or disassemble
- Y10T29/5313—Means to assemble electrical device
- Y10T29/53135—Storage cell or battery
- Y10T29/53139—Storage cell or battery including deforming means
Definitions
- the present invention relates to a secondary battery and an electrode sheet cutting device.
- second battery means a general electric storage device that can be repeatedly charged, so-called storage batteries such as lithium-ion secondary batteries, nickel-metal hydride batteries, nickel cadmium batteries, and the like. It is a term encompassing power storage elements such as electric double layer capacitors.
- lithium ion secondary battery refers to a secondary battery that uses lithium ions as electrolyte ions and is charged and discharged by the movement of electric charge accompanying the lithium ions between the positive and negative electrodes.
- a battery generally referred to as a “lithium secondary battery” is included in the lithium ion secondary battery in this specification.
- Patent Document 1 discloses a secondary battery including a porous electronic insulating layer bonded to the surface of at least one electrode selected from the group consisting of a positive electrode and a negative electrode.
- the porous electronic insulating layer includes a fine particle filler and a resin binder, and the fine particle filler is a particle including an amorphous particle in which a plurality of primary particles are connected and fixed.
- the fine particle filler includes titanium oxide (titania), aluminum oxide (alumina), zirconium oxide (zirconia), and tungsten oxide.
- Patent Document 2 discloses a non-aqueous electrolyte secondary battery having a porous separator for isolating the positive electrode and the negative electrode on the surface of the positive electrode and / or the negative electrode.
- the separator contains a cross-linked resin, and has sufficient strength and resistance to the non-aqueous electrolyte.
- the crosslinked resin include polyethylene (PE), polypropylene (PP), copolymerized polyolefin, polyolefin derivatives (such as chlorinated polyethylene), styrene-butadiene copolymer, acrylic resin [polyalkyl (metamethyl methacrylate, polymethyl acrylate, etc.
- Patent Document 2 describes that the separator may contain various inorganic fine particles in order to increase its strength.
- the inorganic fine particles are not particularly limited as long as they are electrochemically stable and electrically insulating. However, oxidation of iron oxide, SiO 2 (silica), Al 2 O 3 (alumina), TiO 2 , BaTiO 3, etc.
- Product powder Nitrogen powder such as aluminum nitride and silicon nitride; Covalent crystal powder such as silicon and diamond; Slightly soluble ion crystal powder such as barium sulfate, calcium fluoride and barium fluoride; Montmorillonite; It has been.
- Patent Document 2 discloses that the separator contains fine particles that melt at 80 to 150 ° C., such as polyolefin fine particles, in order to give the battery shutdown characteristics.
- fine-particles microparticles
- copolymer polyolefin examples include ethylene-vinyl monomer copolymer, more specifically, ethylene-vinyl acetate copolymer (EVA), ethylene-acrylic acid copolymer (ethylene-methyl acrylate copolymer, ethylene -Ethyl acrylate copolymer etc.) and the like.
- EVA ethylene-vinyl acetate copolymer
- EVA ethylene-acrylic acid copolymer
- ethylene-methyl acrylate copolymer ethylene-Ethyl acrylate copolymer etc.
- Patent Document 3 an electrode active material is mixed with a binder to prepare a coating solution for forming an electrode. After the coating solution is applied to a current collector, the coating solution is dried, and the current collector is activated. It is disclosed to form a sheet-like electrode in which a substance-containing layer is formed. Further, it is disclosed that the sheet-like electrode is then rolled and cut into a predetermined dimension. In Patent Document 3, it is sufficiently suppressed that cutting waste of the current collector is fused to the side surface of the upper blade when the sheet-like electrode is cut, and that the burr is generated on the cut surface of the current collector. There has been proposed a slitter device that can be suppressed.
- the present inventor considers laminating insulating resin particles such as polyethylene on the active material layer of the positive electrode or the negative electrode as the insulating layer. Then, it is considered that a current collecting foil on which the active material layer and the insulating layer are formed is cut into a predetermined size to obtain an electrode in which the insulating layer is laminated on the active material layer. For example, such an insulating layer is considered to join resin particles together with a binder.
- a mother sheet of a wide current collector is prepared, an active material layer and an insulating layer are formed in this order, and then cut into predetermined dimensions. At this time, if the insulating layer is cut as it is, it is considered that the resin particles can be bonded to each other and partially peeled off.
- the edge of the insulating layer in which the resin particles are laminated is exposed at the edge of the electrode sheet, the insulating layer is easily peeled off from the edge of the insulating layer, and foreign matter is removed in the secondary battery. It can be a factor to be generated.
- a secondary battery according to one embodiment of the present invention is disposed so as to face a positive electrode current collector, a positive electrode active material layer that is held by the positive electrode current collector and includes at least a positive electrode active material, and the positive electrode current collector And a negative electrode active material layer that is held by the negative electrode current collector and contains at least the negative electrode active material.
- the secondary battery further includes a porous insulating layer in which resin particles having insulating properties are laminated so as to cover at least one of the positive electrode active material layer and the negative electrode active material layer. A melted portion in which the resin particles are melted is formed at the edge of the insulating layer.
- the edge of the insulating layer is strong. For this reason, falling off of the resin particles is suppressed, and the insulating layer is hardly peeled off.
- the edge of the insulating layer may have a cut mark.
- the insulating layer may be stacked on the negative electrode active material layer. When the insulating layer covers the positive electrode active material layer, the electrolyte related to the battery reaction may be prevented from being released from the positive electrode active material layer. For this reason, the insulating layer is preferably laminated on the negative electrode active material layer.
- the insulating layer may include an inorganic filler or rubber particles having insulating properties.
- the negative electrode active material layer is wider than the positive electrode active material layer and is disposed to face the positive electrode active material layer, and the negative electrode active material layer is disposed on the side where the insulating layer faces the positive electrode active material layer. It may be laminated on the material layer. In this case, since the negative electrode active material layer is wider than the positive electrode active material layer, even if the edge of the insulating layer stacked on the negative electrode active material layer is melted, the negative electrode active material layer is not in contact with the positive electrode active material layer. Since it can oppose, the function of a positive electrode active material layer is not inhibited.
- the method for manufacturing a secondary battery according to the present invention includes a step of preparing an electrode sheet, a melting step of melting the insulating layer, and a cutting step of cutting the electrode sheet. Specifically, in the step of preparing the electrode sheet, the current collector, the active material layer formed on the surface of the current collector and containing the electrode active material, and the insulating material are covered so as to cover the active material layer. An electrode sheet provided with a porous insulating layer in which resin particles having the same are laminated is prepared. Next, in the melting step, the insulating layer is melted along a predetermined line. In the cutting step, the electrode sheet is cut along the line where the insulating layer is melted in the melting step. According to such a method for manufacturing a secondary battery, before the electrode sheet is cut, the insulating layer is melted at the portion to be cut. For this reason, the insulating layer is hardly peeled off partially in the cutting step.
- the insulating layer may be melted by irradiating the insulating layer with a laser.
- the portion where the insulating layer is melted for example, there are few voids through which the electrolytic solution can pass. For this reason, it is thought that the said part can inhibit the effect
- the width of melting the insulating layer can be more appropriately controlled by irradiating the laser to melt the insulating layer. For this reason, the extent to which the action of the active material layer is inhibited can be reduced.
- the laser is, for example, a CO 2 laser.
- the CO 2 laser has a wavelength (approximately 10.6 ⁇ m) at which a resin (for example, polyethylene) easily absorbs energy. For this reason, the CO 2 laser is suitable for melting the resin particles, and can efficiently melt the resin particles. Further, a cooling step for cooling the electrode sheet may be provided between the melting step and the cutting step. Thereby, the resin melted in the melting step can be solidified more reliably before the cutting step. Thereby, the tact time between the melting step and the cutting step can be shortened.
- a resin for example, polyethylene
- the electrode sheet cutting device is arranged so that the heater arranged to heat the electrode sheet along a predetermined line and the electrode sheet heated by the heater are cut along the line And a cutter.
- the heater arranged to heat the electrode sheet along a predetermined line and the electrode sheet heated by the heater are cut along the line And a cutter.
- the insulating layer is melted. Can be cut.
- the heater may be, for example, a laser device that irradiates the electrode sheet with laser.
- the laser may be, for example, a CO 2 laser.
- the electrode sheet cutting device may include a transport device that transports the electrode sheet along a predetermined transport path. In this case, when the heater and the cutter are fixedly arranged along the conveyance path, it is preferable to provide a position adjustment mechanism that adjusts the position of the electrode sheet with respect to the heater and the cutter.
- the electrode sheet may be a belt-like sheet
- the transport device may be a device that continuously transports the electrode sheet along the transport path.
- the conveying device may include a plurality of guide rolls that convey the electrode sheet while supporting it. And it is good to arrange
- the heater may be displaced in a range of 1 mm or more and 10 mm or less downstream from the site where the electrode sheet is supported by the guide roll.
- a cooling device for cooling the electrode sheet may be provided after being heated by the heater and before being cut by the cutter. Thereby, the tact time can be shortened.
- the cooling device may be a blower that blows air onto the electrode sheet.
- the cooling device may include a metal roll pressed against the electrode sheet and a cooling unit that cools the metal roll.
- FIG. 1 is a diagram illustrating an example of the structure of a lithium ion secondary battery.
- FIG. 2 is a view showing a wound electrode body of a lithium ion secondary battery.
- FIG. 3 is a cross-sectional view showing a III-III cross section in FIG.
- FIG. 4 is a diagram schematically illustrating a state of the lithium ion secondary battery during charging.
- FIG. 5 is a diagram schematically illustrating a state of the lithium ion secondary battery during discharge.
- FIG. 6 is a plan view showing a state where an active material layer and an insulating layer are formed on a current collector in a secondary battery according to an embodiment of the present invention.
- FIG. 1 is a diagram illustrating an example of the structure of a lithium ion secondary battery.
- FIG. 2 is a view showing a wound electrode body of a lithium ion secondary battery.
- FIG. 3 is a cross-sectional view showing a III-III cross section in FIG.
- FIG. 4 is
- FIG. 7 is a cross-sectional view of a negative electrode sheet in a secondary battery according to an embodiment of the present invention.
- FIG. 8 is a plan view showing a melting step and a cutting step in the method for manufacturing a secondary battery according to the embodiment of the present invention.
- FIG. 9 is a side view showing a configuration example of an electrode sheet cutting device according to an embodiment of the present invention.
- FIG. 10 is a side view showing a configuration example of an electrode sheet cutting device according to another embodiment of the present invention.
- FIG. 11 is a side view showing a configuration example of an electrode sheet cutting device according to another embodiment of the present invention.
- FIG. 12 is a side view showing a configuration example of an electrode sheet cutting device according to another embodiment of the present invention.
- FIG. 13 is a schematic view showing a cross section of an electrode sheet according to an embodiment of the present invention.
- FIG. 14 is a schematic view showing a cross section of an electrode sheet according to an embodiment of the present invention.
- FIG. 15 is a plan view of an electrode sheet according to an embodiment of the present invention.
- FIG. 16 is a cross-sectional view taken along the line AA of FIG.
- FIG. 17 is a plan view of an electrode sheet according to another embodiment of the present invention.
- FIG. 18 is a cross-sectional view showing the AA cross section of FIG.
- FIG. 19 is a diagram showing a mother sheet from which the electrode sheet shown in FIG. 17 is cut out.
- FIG. 20 is a side view showing a configuration example of an electrode sheet cutting device according to an embodiment of the present invention.
- FIG. 20 is a side view showing a configuration example of an electrode sheet cutting device according to an embodiment of the present invention.
- FIG. 21 is a plan view showing a cooling step in a method for manufacturing a secondary battery according to another embodiment of the present invention.
- FIG. 22 is a plan view showing a cooling step in a method for manufacturing a secondary battery according to another embodiment of the present invention.
- FIG. 23 is a diagram showing a vehicle equipped with a lithium ion secondary battery.
- FIG. 1 shows a lithium ion secondary battery 100 as a secondary battery according to an embodiment of the present invention.
- the lithium ion secondary battery 100 includes a wound electrode body 200, a battery case 300, and an electrolytic solution (not shown).
- FIG. 2 is a view showing a wound electrode body 200.
- FIG. 3 shows a III-III cross section in FIG.
- the wound electrode body 200 includes a belt-like positive electrode sheet 220 and a belt-like negative electrode sheet 240 that are stacked and wound.
- the positive electrode sheet 220 includes a positive electrode current collector 221 and a positive electrode active material layer 223.
- a metal foil suitable for the positive electrode can be suitably used.
- a strip-shaped aluminum foil having a predetermined width and a thickness of approximately 10 ⁇ m is used for the positive electrode current collector 221.
- the positive electrode active material layer 223 is held by the positive electrode current collector 221 and contains at least a positive electrode active material.
- the positive electrode active material layer 223 is a layer in which a positive electrode mixture containing a positive electrode active material is applied to the positive electrode current collector 221.
- an uncoated portion 222 is set along an edge portion on one side in the width direction of the positive electrode current collector 221.
- the positive electrode active material layer 223 is formed on both surfaces of the positive electrode current collector 221 except for the uncoated portion 222 set on the positive electrode current collector 221.
- LiNiCoMnO 2 lithium nickel cobalt manganese composite oxide
- LiNiO 2 lithium nickelate
- LiCoO 2 lithium cobaltate
- LiMn 2 O 4 lithium manganate
- LiFePO 4 Lithium transition metal oxides such as lithium iron phosphate
- LiMn 2 O 4 has a spinel structure.
- LiNiO 2 and LiCoO 2 have a layered rock salt structure.
- LiFePO 4 has, for example, an olivine structure.
- LiFePO 4 having an olivine structure includes, for example, nanometer order particles.
- LiFePO 4 having an olivine structure can be further covered with a carbon film.
- the positive electrode active material layer 223 may contain optional components such as a conductive material and a binder (binder) in addition to the positive electrode active material.
- a conductive material include carbon materials such as carbon powder and carbon fiber. One kind selected from such conductive materials may be used alone, or two or more kinds may be used in combination.
- carbon powder various carbon blacks (for example, acetylene black, oil furnace black, graphitized carbon black, carbon black, graphite, ketjen black), graphite powder, and the like can be used.
- a polymer that can be dissolved or dispersed in a solvent to be used can be used.
- cellulosic polymers such as carboxymethylcellulose (CMC) and hydroxypropylmethylcellulose (HPMC) (for example, polyvinyl alcohol (PVA) and polytetrafluoroethylene (PTFE)), tetra Fluorine resins such as fluoroethylene-hexafluoropropylene copolymer (FEP) (for example, vinyl acetate copolymer and styrene butadiene rubber (SBR)), rubbers such as acrylic acid-modified SBR resin (SBR latex); A water-soluble or water-dispersible polymer such as can be preferably used.
- CMC carboxymethylcellulose
- HPMC hydroxypropylmethylcellulose
- PVA polyvinyl alcohol
- PTFE polytetrafluoroethylene
- FEP fluoroethylene-hexafluoropropylene copolymer
- SBR styren
- polymers such as polyvinylidene fluoride (PVDF) and polyvinylidene chloride (PVDC) can be preferably used.
- PVDF polyvinylidene fluoride
- PVDC polyvinylidene chloride
- the polymer material illustrated above may be used for the purpose of exhibiting functions as a thickener and other additives of the composition in addition to the function as a binder.
- the solvent any of an aqueous solvent and a non-aqueous solvent can be used.
- a preferred example of the non-aqueous solvent is N-methyl-2-pyrrolidone (NMP).
- Thickness of positive electrode active material layer 223 is about 27 ⁇ m per side.
- the thickness t1 of the positive electrode active material layer 223 may be measured with reference to the uncoated part 222 of the positive electrode sheet 220, for example.
- the negative electrode sheet 240 includes a negative electrode current collector 241, a negative electrode active material layer 243, and an insulating layer 245.
- a metal foil suitable for the positive electrode can be suitably used.
- a strip-shaped copper foil having a predetermined width and a thickness of approximately 10 ⁇ m is used for the negative electrode current collector 241.
- the negative electrode active material layer 243 is held by the negative electrode current collector 241 and contains at least a negative electrode active material.
- the negative electrode active material layer 243 is a layer in which a negative electrode mixture containing a negative electrode active material is applied to the negative electrode current collector 241.
- an uncoated part 242 is set along the edge.
- the negative electrode active material layer 243 is formed on both surfaces of the negative electrode current collector 241 except for the uncoated portion 242 set on the negative electrode current collector 241.
- ⁇ Negative electrode active material As the negative electrode active material included in the negative electrode active material layer 243, one or more materials conventionally used for lithium ion secondary batteries can be used without any particular limitation.
- a particulate carbon material carbon particles including a graphite structure (layered structure) at least in part. More specifically, so-called graphitic (graphite), non-graphitizable carbon (hard carbon), graphitizable carbon (soft carbon), and a carbon material that combines these can be used.
- graphite particles such as natural graphite can be used.
- an appropriate amount of a thickener is mixed in the negative electrode mixture in order to maintain the dispersion of the negative electrode active material.
- the same thickener, binder and conductive material as those used for the positive electrode mixture can be used.
- Thickness of negative electrode active material layer 243 is about 35 ⁇ m per side.
- the thickness t2 of the negative electrode active material layer 243 may be measured, for example, based on the uncoated portion 242 of the negative electrode sheet 240 after the negative electrode active material layer 243 is formed.
- the insulating layer 245 is a porous layer in which insulating resin particles are laminated so as to cover the negative electrode active material layer.
- the resin particles used for the insulating layer 245 are preferably thermoplastic resin particles.
- polyethylene, polypropylene, a copolymerized polyolefin having a structural unit derived from ethylene of 85 mol% or more, or a polyolefin ball moving body may be used. it can.
- the resin particles may be a mixture of a plurality of different thermoplastic resin particles at an appropriate ratio.
- the resin particle may be added with an appropriate ratio of an insulating material such as an inorganic filler or rubber.
- polyethylene is used for the resin particles.
- the resin particles may be bonded with a binder.
- a binder for example, a binder similar to the binder used for the positive electrode active material layer or the negative electrode active material layer can be used.
- the particle size of the resin particles may be such that an appropriate gap is formed between the particles when the particles are laminated so that a porous layer is formed so that the electrolyte can be sufficiently passed.
- the particle size of the resin particles is, for example, about 1 ⁇ m to 10 ⁇ m. More preferably, it is about 1 ⁇ m to 3 ⁇ m.
- the median diameter (d50) obtained from the particle size distribution measured by the particle size distribution measuring instrument based on the light scattering method is adopted as the particle size.
- the average thickness t3 of the insulating layer 245 is about 25 ⁇ m per side.
- the insulating layer 245 has resin particles laminated as described above. When the temperature inside the battery becomes abnormally high, the resin particles melt at a predetermined temperature, and a film that blocks the flow of the electrolytic solution is formed on the surface of the negative electrode active material layer 243. This can reduce the reaction in the battery (this function is called “shutdown” as appropriate).
- a melted portion 246 is formed at the edge of the insulating layer 245.
- the melting part 246 is a part where the resin particles forming the insulating layer 245 are melted. According to the lithium ion secondary battery 100, since the melted portion 246 in which the resin particles are melted is formed at the edge of the insulating layer 245, the edge of the insulating layer 245 is firmly solidified. 245 is difficult to peel off.
- the width b1 (not including the melted portion 246) of the negative electrode active material layer 243 is slightly wider than the width a1 of the positive electrode active material layer 223.
- the positive electrode sheet 220 and the negative electrode sheet 240 are overlapped with each other as shown in FIG.
- the positive electrode active material layer 223 and the negative electrode active material layer 243 are overlaid.
- the uncoated part 222 of the positive electrode sheet 220 and the uncoated part 242 of the negative electrode sheet 240 are overlapped so as to protrude on opposite sides.
- the width b1 of the negative electrode active material layer 243 is slightly wider than the width a1 of the positive electrode active material layer 223, and the negative electrode active material layer 243 is stacked so as to cover the positive electrode active material layer 223.
- the stacked sheet material (for example, the positive electrode sheet 220) is wound around the winding axis set in the width direction of the sheet material, and the negative electrode active material layer 243 remains the positive electrode active material layer 223 even after winding.
- the state of covering is maintained.
- FIG. 2 shows a state in which the positive electrode sheet 220 and the negative electrode sheet 240 are wound and a part of the wound electrode body 200 deformed into a flat shape is developed.
- the positive electrode active material layer 223 and the negative electrode active material layer 243 are physically separated by an insulating layer 245 covering the negative electrode active material layer 243.
- electrical insulation between the positive electrode active material layer 223 and the negative electrode active material layer 243 is maintained.
- the insulating layer 245 can function as a separator that allows the electrolyte to pass back and forth while physically and electrically separating the positive electrode active material layer 223 and the negative electrode active material layer 243. For this reason, in this embodiment, a separator is not separately disposed between the positive electrode sheet 220 and the negative electrode sheet 240.
- the battery case 300 is a so-called square battery case, and includes a container body 320 and a lid 340.
- the container main body 320 has a bottomed rectangular tube shape and is a flat box-shaped container having one side surface (upper surface) opened.
- the lid 340 is a member that is attached to the opening (opening on the upper surface) of the container body 320 and closes the opening.
- the battery case 300 has a flat rectangular internal space as a space for accommodating the wound electrode body 200.
- the flat internal space of the battery case 300 is slightly wider than the wound electrode body 200.
- the wound electrode body 200 is accommodated in the internal space of the battery case 300.
- the wound electrode body 200 is accommodated in the battery case 300 in a state of being flatly deformed in one direction orthogonal to the winding axis.
- the battery case 300 includes a bottomed rectangular tube-shaped container body 320 and a lid 340 that closes the opening of the container body 320. Electrode terminals 420 and 440 are attached to the lid 340 of the battery case 300. The electrode terminals 420 and 440 pass through the battery case 300 (lid 340) and come out of the battery case 300.
- the lid 340 is provided with a safety valve 360.
- electrode terminals 420 and 440 are attached to the battery case 300 (in this example, the lid 340).
- the wound electrode body 200 is attached to the electrode terminals 420 and 440.
- the wound electrode body 200 is housed in the battery case 300 in a state of being flatly pushed and bent in one direction orthogonal to the winding axis.
- the uncoated part 222 of the positive electrode sheet 220 and the uncoated part 242 of the negative electrode sheet 240 protrude on opposite sides on both sides of the wound electrode body 200 in the winding axis direction.
- one electrode terminal 420 is fixed to the uncoated part 222 of the positive electrode current collector 221
- the other electrode terminal 440 is fixed to the uncoated part 242 of the negative electrode current collector 241 (for example, Welding).
- the wound electrode body 200 is attached to the electrode terminals 420 and 440 fixed to the lid body 340 in a state where the wound electrode body 200 is flatly pushed and bent.
- the wound electrode body 200 is accommodated in the flat internal space of the container body 320.
- the container body 320 is closed by the lid 340 after the wound electrode body 200 is accommodated.
- the joint 322 (see FIG. 1) between the lid 340 and the container main body 320 is welded and sealed, for example, by laser welding.
- the wound electrode body 200 is positioned in the battery case 300 by the electrode terminals 420 and 440 fixed to the lid 340 (battery case 300).
- an electrolytic solution is injected into the battery case 300 from a liquid injection hole provided in the lid 340.
- a so-called non-aqueous electrolytic solution that does not use water as a solvent is used.
- an electrolytic solution in which LiPF 6 is contained at a concentration of about 1 mol / liter in a mixed solvent of ethylene carbonate and diethyl carbonate (for example, a mixed solvent having a volume ratio of about 1: 1) is used. Yes.
- a metal sealing cap is attached to the injection hole (for example, by welding) to seal the battery case 300.
- electrolyte solution it is not limited to this Example, The nonaqueous electrolyte solution conventionally used for a lithium ion secondary battery can be used.
- the positive electrode active material layer 223 has a minute gap that should be referred to as a cavity, for example, between the particles of the positive electrode active material and the conductive material.
- An electrolytic solution (not shown) can penetrate into the minute gaps of the positive electrode active material layer 223.
- the negative electrode active material layer 243 has minute gaps that should also be referred to as cavities, for example, between particles of the negative electrode active material.
- the insulating layer 245 formed so as to cover the negative electrode active material layer 243 is laminated with resin particles, and has a minute gap that should be referred to as a cavity into which the electrolytic solution can permeate.
- a gap (cavity) is appropriately referred to as a “hole”.
- the positive electrode active material layer 223 and the negative electrode active material layer 243 are infiltrated with the electrolytic solution.
- the flat internal space of the battery case 300 is slightly wider than the wound electrode body 200 deformed flat.
- gaps 310 and 312 are provided between the wound electrode body 200 and the battery case 300.
- the gaps 310 and 312 serve as a gas escape path.
- the lithium ion secondary battery 100 having such a configuration has a high temperature when overcharge occurs.
- the electrolyte solution is decomposed to generate gas.
- the generated gas is smoothly discharged to the outside through the gaps 310 and 312 between the wound electrode body 200 and the battery case 300 on both sides of the wound electrode body 200 and the safety valve 360.
- the positive electrode current collector 221 and the negative electrode current collector 241 are electrically connected to an external device through electrode terminals 420 and 440 that penetrate the battery case 300.
- the operation of the lithium ion secondary battery 100 during charging and discharging will be described.
- FIG. 4 schematically shows the state of the lithium ion secondary battery 100 during charging.
- the electrode terminals 420 and 440 (see FIG. 1) of the lithium ion secondary battery 100 are connected to the charger 290. Due to the action of the charger 290, lithium ions (Li) are released from the positive electrode active material in the positive electrode active material layer 223 to the electrolytic solution 280 during charging. In addition, charges are released from the positive electrode active material layer 223. As shown in FIG. 4, the released charge is sent to the positive electrode current collector 221 through a conductive material (not shown), and further sent to the negative electrode 240 through the charger 290. In the negative electrode 240, charges are stored, and lithium ions (Li) in the electrolyte solution 280 are absorbed and stored in the negative electrode active material in the negative electrode active material layer 243.
- FIG. 5 schematically shows the state of the lithium ion secondary battery 100 during discharge.
- electric charge is sent from the negative electrode 240 to the positive electrode 220, and lithium ions (Li ions) stored in the negative electrode active material layer 243 are released into the electrolytic solution 280.
- lithium ions (Li) in the electrolytic solution 280 are taken into the positive electrode active material in the positive electrode active material layer 223.
- lithium ions travel between the positive electrode active material layer 223 and the negative electrode active material layer 243 through the electrolytic solution 280.
- electric charge is sent from the positive electrode active material to the positive electrode current collector 221 through the conductive material.
- the charge is returned from the positive electrode current collector 221 to the positive electrode active material through the conductive material.
- the lithium ion secondary battery 100 includes a positive electrode current collector 221 and a positive electrode that is applied to the positive electrode current collector 221 and includes at least a positive electrode active material, as shown in FIGS. An active material layer 223. Furthermore, the lithium ion secondary battery 100 includes a negative electrode current collector 241 disposed so as to face the positive electrode current collector 221, and a negative electrode active material that is applied to the negative electrode current collector 241 and includes at least a negative electrode active material. A material layer 243. Further, as shown in FIG. 3, the lithium ion secondary battery 100 covers at least one of the positive electrode active material layer 223 and the negative electrode active material layer 243 (in the example shown in FIG.
- a porous insulating layer 245 is formed by laminating resin particles having insulating properties. Further, the lithium ion secondary battery 100 includes a melting portion 246 where resin particles are melted at the edge of the insulating layer 245.
- the positive electrode active material layer 223 and the negative electrode active material layer 243 are physically separated by an insulating layer 245 that covers the negative electrode active material layer 243.
- the insulating layer 245 maintains electrical insulation between the positive electrode active material layer 223 and the negative electrode active material layer 243.
- the insulating layer 245 allows the electrolytic solution 280 to flow between the positive electrode active material layer 223 and the negative electrode active material layer 243.
- the insulating layer 245 forms a film by melting resin particles at a predetermined temperature when the temperature inside the battery becomes abnormally high. Since such a membrane blocks the flow of the electrolyte, the reaction of the battery is suppressed.
- the insulating layer 245 has a so-called shutdown function that suppresses the reaction of the battery when the temperature inside the battery becomes abnormally high.
- no separate separator is disposed between the positive electrode sheet 220 and the negative electrode sheet 240. For this reason, when a part of the insulating layer 245 is peeled off, electrical insulation between the positive electrode active material layer 223 and the negative electrode active material layer 243 may not be maintained, and the lithium ion secondary battery 100 may not function as a battery. There is.
- a melted portion 246 in which resin particles are melted is formed at the edge of the insulating layer 245.
- melting part 246 has strong joining force with the insulating layer 245 except the negative electrode active material layer 243 and the fusion
- the edge of the insulating layer 245 is strong, the insulating layer 245 is hardly peeled off at the edge of the insulating layer 245. Further, since the resin particles are unlikely to fall off from the edge of the insulating layer 245, it is possible to suppress the occurrence of foreign matters in the lithium ion secondary battery 100 due to the resin particles dropping off from the edge of the insulating layer 245.
- the edge of the insulating layer 245 is not melted on the side where the uncoated portion 242 of the negative electrode sheet 240 is provided, but the edge of the insulating layer 245 is melted in other portions.
- the part where the melted portion 246 is formed may be a part where the negative electrode sheet 240 is cut in the process of manufacturing the negative electrode sheet 240 as described later.
- the porous insulating layer 245 is formed by stacking insulating resin particles so as to cover the negative electrode active material layer 243.
- the method for manufacturing a secondary battery includes a step of preparing an electrode sheet, a melting step, and a cutting step.
- Such a method for manufacturing a secondary battery can be applied to, for example, the process of manufacturing the negative electrode sheet 240 in the above-described lithium ion secondary battery 100 (see FIG. 1).
- FIG. 6 is a plan view of the electrode sheet (negative electrode sheet 240) at the stage prepared in the step of preparing the electrode sheet.
- the electrode sheet 10A prepared in the step of preparing the electrode sheet includes a current collector 10 (mother current collector of the negative electrode current collector 241) and an active material layer (negative electrode active material layer 243). And an insulating layer (insulating layer 245).
- the electrode sheet 10A means a mother sheet from which a plurality of negative electrode sheets 240 are cut out.
- the current collector 10 means a current collector from which the negative electrode current collectors 241 of the plurality of negative electrode sheets 240 can be cut out.
- the current collector 10 is a copper foil, and the negative electrode active material layer 243 is formed on the surface of the negative electrode current collector 241.
- the insulating layer 245 covers the negative electrode active material layer 243 (active material layer) and is laminated with resin particles having insulating properties.
- the inventor considers obtaining a plurality of negative electrode sheets 240 from the current collector 10 (mother sheet) as shown in FIG.
- insulating layers 245 (a) to (c) are formed in the active material layers 243 (a) to (c), respectively.
- the insulating layers 245 (a) to (c) cover the active material layers 243 (a) to (c), respectively.
- symbol is attached
- the active material layers 243 (a) to (c) are made of, for example, an electrode mixture obtained by mixing the above-described electrode active materials (positive electrode active material, negative electrode active material), conductive material, binder, thickener, and the like in a solvent.
- the electrode mixture prepared in the composite preparation step is applied to the current collector 10 (application step).
- a conventionally known suitable coating device for example, a slit coater, a die coater, a comma coater, a gravure coater, or the like can be used.
- a long strip-shaped current collector 10 (mother sheet) is used. For this reason, it is good to apply
- the electrode mixture applied to the current collector 10 in the application process is dried (drying process).
- the current collector 10 may be conveyed to a drying furnace set to predetermined drying conditions. At this time, an appropriate drying condition may be set to prevent migration from occurring in the electrode mixture.
- the positive electrode active material layer 223 and the negative electrode active material layer 243 dried in the drying step are pressed in the thickness direction (rolling step). In such a rolling process, a conventionally known roll press method, flat plate press method, or the like can be appropriately employed. In this manner, predetermined active material layers 243 (a) to (c) can be formed on the current collector 10.
- the insulating layers 245 (a) to (c) are formed so as to cover the active material layers 243 (a) to (c).
- the insulating layers 245 (a) to (c) are porous layers in which resin particles are laminated.
- the method for producing the insulating layers 245 (a) to (c) is, for example, preparing a slurry in which resin particles are dispersed in a solvent and placing the slurry on the active material layers 243 (a) to (c) with a predetermined thickness. It is better to apply it and then dry it.
- the slurry may be applied by a gravure printing technique.
- FIG. 7 shows a cross section of a portion where the active material layers 243 (a) to (c) and the insulating layers 245 (a) to (c) are applied to the electrode sheet 10A.
- active material layers 243 (a) to (c) and insulating layers 245 (a) to (c) are coated on both surfaces of the current collector 10. .
- cutting lines z1 to z5 are provided in the middle in the width direction of the active material layers 243 (a) to (c) and in the middle of the uncoated portion between the active material layers 243 (a) to (c). ing.
- an electrode sheet having an uncoated portion on one side in the width direction here, the negative electrode sheets 240 (a) to (f) )
- Can be cut out in the width direction (six in the example shown in FIG. 6).
- the cutting lines z2 and z4 set in the middle of the uncoated portion between the active material layers 243 (a) to 243 (c) are simply cutters (slitters) because the current collector 10 is exposed. May also be referred to as a).
- the insulating layers 245 (a) to (c) on which the resin particles are laminated cover the active material layers 243 (a) to (c). Is formed. Therefore, when the cutting lines z1, z3, and z5 set in the middle in the width direction of the active material layers 243 (a) to (c) are simply cut with a cutter, the insulating layers 245 (a) to 245 (a) to 245 (a) to (c) are cut. Part of the resin particles forming (c) falls off. In some cases, part of the insulating layers 245 (a) to (c) may be peeled off.
- the melting step is necessary in the step of cutting the intermediate cutting lines z1, z3, z5 in the width direction of the active material layers 243 (a) to (c) on which the insulating layers 245 (a) to (c) are formed. Become.
- FIG. 8 is a plan view showing a step of melting the insulating layer of the electrode sheet and a step of cutting.
- the electrode sheet 10A is cut along cutting lines z2 and z4 set in the middle of the uncoated portion between the active material layers 243 (a) to (c). . Thereafter, as shown in FIG. 8, the cut electrode sheets 10A (a) to (c) are supplied to the melting step (S1) and the cutting step (S2).
- the electrode sheets 10A (a) to (c) are transported along a predetermined transport path by the transport device 40 (see FIG. 9).
- the heater 20 and the cutter 30 are fixedly disposed on the conveyance path.
- the electrode sheets 10A (a) to (c) are belt-like sheets
- the transport device 40 is a device that continuously transports the electrode sheets 10A (a) to (c) along the transport path. It is.
- the transport device 40 includes a plurality of guide rolls 41 and 42 (see FIG. 9) that transport the electrode sheets 10A (a) to (c) while supporting them.
- the insulating layers 245 (a) to (c) of the electrode sheets 10A (a), 10A (b), and 10A (c) prepared in the step of preparing the electrode sheet are converted into predetermined lines z1, This is a step of melting along z3 and z5.
- a width of about 0.1 mm to 5.0 mm for example, about 0.1 mm to 5.0 mm
- the insulating layers 245 (a) to (c) are preferably melted with a width of about 0.5 mm to 1.5 mm. Therefore, in this embodiment, the melting step melts the insulating layers 245 (a) to (c) by irradiating the insulating layers 245 (a) to (c) with the lasers 20A (a) to (c). I am letting.
- the laser has high directivity.
- the width at which the insulating layers 245 (a) to (c) are melted can be adjusted.
- the insulating layer 116 can be melted with a width of about 0.1 mm to 5.0 mm.
- the insulating layers 245 (a) to (c) can be melted without contact with the electrode sheets 10A (a) to (c). Therefore, the active material layers 243 (a) to (c) are hardly affected.
- a CO 2 laser can be preferably used as the laser.
- polyethylene resin particles are used for the insulating layers 245 (a) to 245 (c).
- the wavelength of the CO 2 laser is set to approximately 10.5 so as to be suitable for melting the resin particles.
- the output is 6 ⁇ m and the output is 5 W to 25 W.
- the CO 2 laser has a wavelength of 10.6 ⁇ m, in which a resin (for example, polyethylene) easily absorbs energy.
- the CO 2 laser is suitable for melting the resin particles, and can efficiently melt the resin particles. According to such a CO 2 laser, heat can be efficiently applied to the resin particles constituting the insulating layers 245 (a) to (c).
- the insulating layers 245 (a) to (c) are formed on both surfaces of the electrode sheets 10A (a) to (c). For this reason, as shown in FIG. 9, both surfaces of the electrode sheets 10A (a) to (c) are irradiated with laser, and the insulating layers 245 (a) to (245) on both surfaces of the electrode sheets 10A (a) to (c). c) is melted.
- the insulating layer 245 is porous and has many pores between resin particles. When the insulating layer 245 is melted, it forms a film, and there are almost no voids. For this reason, in the fusion
- the insulating layers 245 (a) to (c) (see FIG. 8) formed on the surfaces irradiated with the lasers 20A (a) to (c) are melted.
- the surface on which the insulating layers 245 (a) to (c) are melted is supported by the back roll.
- reference numerals 20A (a) to (c) and 20B (a) to (c) indicate lasers directly applied to the electrode sheets 10A (a) to (c). Note that a laser device for irradiating the laser is omitted for convenience of illustration.
- the illustrated lasers 20A (a) to (c) and lasers 20B (a) to (c) indirectly indicate the existence of a laser device that irradiates the laser and a device that controls the laser device.
- the insulating layers 245 (a) to (c) are formed on both surfaces of the electrode sheets 10A (a) to (c), the insulating layers 245 (a) to (c) on the both surfaces are formed. It should be melted.
- lasers 20A (a) to (c) and lasers 20B (a) to (c) are sequentially applied to both surfaces of the electrode sheets 10A (a) to (c), so that the insulating layers 245 ( a) to (c) are melted.
- the laser sheets 20A (a) to (c) are irradiated at the portions where the electrode sheets 10A (a) to (c) are supported by the back roll 41 (guide roll).
- Lasers 20A (a) to (c) and lasers 20B (a) to (c) are irradiated to 245 (a) to (c).
- the insulating layers 245 (a) to 245 (a) to (C) can also be melted. If the insulating layers 245 (a) to (c) on the surface supported by the back rolls 41 and 42 are melted, the molten resin adheres to the back rolls 41 and 42, which may cause a problem.
- the lasers 20A (a) to (c) and the lasers 20B (a) to 20C (a) to the portions where the electrode sheets 10A (a) to (c) are supported by the back rolls 41 and 42 are provided.
- irradiating (c) it is necessary to adjust the outputs of the lasers 20B (a) to (c).
- the insulating layers 245 (a) to (c) on the surface directly irradiated with the lasers 20B (a) to (c) are melted, but the laser is not adhered to the back rolls 41 and 42.
- the outputs of 20A (a) to (c) and lasers 20B (a) to (c) may be adjusted.
- the laser 20A (a) is applied to the electrode sheets 10A (a) to (c) at a position shifted from the portion where the electrode sheets 10A (a) to (c) are supported by the back roll 41.
- a laser device (not shown) may be arranged so that (c) to (c) are irradiated.
- the lasers 20B (a) to (c) are applied to the electrode sheets 10A (a) to (c) at positions shifted from the portions where the electrode sheets 10A (a) to (c) are supported by the back roll 42. You may arrange
- the resin in which the insulating layers 245 (a) to (c) are melted on the back rolls 41 and 42 are obtained. Does not adhere.
- the laser irradiation position is too close to the back rolls 41 and 42, there is a high possibility that the molten resin adheres to the back rolls 41 and 42.
- the conveyed electrode sheets 10A (a) to (c) may flutter.
- the electrode sheets 10A (a) to (c) conveyed at the positions where the lasers 20A (a) to (c) and the lasers 20B (a) to (c) are irradiated flutter the electrode sheets 10A (a) to (c)
- the positions where the lasers 20A (a) to (c) and the lasers 20B (a) to (c) are irradiated to c) are not stable. Therefore, the positions at which the lasers 20A (a) to (c) and the lasers 20B (a) to (c) are irradiated to the electrode sheets 10A (a) to (c) are set at the electrode sheets 10A (a) to (c).
- the positions at which the lasers 20A (a) to (c) and the lasers 20B (a) to (c) are irradiated are determined from, for example, the portions where the electrode sheets 10A (a) to (c) are supported by the back rolls 41 and 42. It may be shifted by about 1 mm to 10 mm, more preferably by about 1.5 mm to 8 mm.
- lasers 20A (a) to (c) and lasers 20B (a) to (c) are irradiated on both surfaces of the electrode sheets 10A (a) to (c), respectively.
- a position adjustment mechanism 62 such as an EPC device (edge position control device) or a CPC device (center position control device).
- the position adjusting mechanism 62 supplies the electrode sheet 10A supplied to the position where the laser is irradiated so that the insulating layers 245 (a) to (c) are melted along the lines z1, z3, and z5. The positions in the width direction of (a) to (c) are adjusted.
- the position adjustment mechanism 62 may be disposed in front of the back rolls 41 and 42.
- the insulating layers 245 (a) to (c) on both surfaces of the electrode sheets 10A (a) to (c) are simultaneously melted. May be.
- lasers 20A (a) to (c) are irradiated to one surface of the electrode sheets 10A (a) to (c) at a position deviated from the portion supported by the back roll 41.
- a laser device (not shown) may be disposed.
- the outputs of the lasers 20A (a) to (c) may be adjusted so that the insulating layers 245 (a) to (c) on both surfaces of the electrode sheets 10A (a) to (c) can be melted. Accordingly, the positions where the insulating layers 245 (a) to (c) are melted on both surfaces of the electrode sheets 10A (a) to (c) are difficult to shift.
- lasers 20A (a) to (c) and lasers 20A (a) to (c) are respectively formed on both surfaces of the electrode sheets 10A (a) to (c) at positions shifted from the parts supported by the back roll 41.
- a laser device (not shown) may be arranged so that 20B (a) to (c) are irradiated.
- the lasers 20A (a) to (c) and the lasers 20B (a) to (c) may be adjusted in focus at the same position with respect to the conveyed electrode sheets 10A (a) to (c).
- the positions irradiated with laser on both surfaces of the electrode sheets 10A (a) to (c) are difficult to shift.
- the insulating layers 245 (a) are formed on both surfaces of the electrode sheets 10A (a) to (c) by adjusting the outputs of the lasers 20A (a) to (c) and the lasers 20B (a) to (c). ) To (c) can be melted to the same extent.
- the insulating layers 245 (a) to (c) may be melted along predetermined lines z1, z3, and z5.
- the width for melting the insulating layers 245 (a) to (c) is preferably adjusted according to the width to be cut by the cutters 30 (a) to (c) in the subsequent cutting step (Sc). . That is, when the insulating layers 245 (a) to (c) are melted, the pores of the insulating layers 245 (a) to (c) disappear, so that the electrolyte does not flow through the portions.
- the width at which the insulating layers 245 (a) to (c) are melted depends on the width that the cutters 30 (a) to (c) cut, and the effect of suppressing the falling off of the resin particles is small. It is desirable that the thickness is as thin as possible so that the effects of (a) to (c) are difficult to peel off.
- the laser irradiation method can be adjusted, for example, with a width of about 0.1 mm to 5.0 mm by adjusting the focal length and output of the laser. Thus, the laser irradiation method can easily adjust the position and width at which the insulating layers 245 (a) to (c) are melted.
- a laser device is exemplified as a heater for heating the electrode sheets 10A (a) to (c).
- a heater is not limited to a laser device.
- the heater may be configured by a hot air blower that applies hot air to the electrode sheet, although illustration is omitted.
- a hot air blower that applies hot air to the electrode sheet, although illustration is omitted.
- the temperature of the hot air it is possible to set the temperature of the hot air to about 300 ° C., the wind speed to 30 m / s, and the width to which the hot air is concentrated is about 2 mm.
- the width at which the insulating layers 245 (a) to (c) are melted is likely to vary. For this reason, the melted portions on both surfaces of the electrode sheets 10A (a) to (c) are likely to shift. For this reason, it is necessary to widen the width to be melted.
- the heater may be configured to include a metal roll pressed against the electrode sheet and a heat source for heating the metal roll, although illustration is omitted.
- the width of the metal roll can be set to, for example, about 2 mm, and the surface temperature of the roll can be set to about 300 ° C.
- the melt may adhere to the metal roll and cause a problem.
- the width at which the insulating layers 245 (a) to (c) are melted is likely to vary. For this reason, the melted portions on both surfaces of the electrode sheets 10A (a) to (c) are likely to shift. For this reason, it is necessary to widen the width to be melted.
- the position and width at which the insulating layers 245 (a) to (c) are melted are adjusted by adjusting the focal length of the laser and the output, for example. It can be adjusted more finely. Further, the insulating layers 245 (a) to (c) can be heated without contact with the electrode sheets 10A (a) to (c), and the influence on the active material layers 243 (a) to (c) is small. Therefore, a laser device that irradiates the electrode sheets 10A (a) to (c) with a laser is suitable as the heater for heating the electrode sheets 10A (a) to (c).
- the electrode sheets 10A (a) to (c) obtained by melting the insulating layers 245 (a) to (c) along the preset lines z1, z3, and z5 are supplied to the cutting step.
- the laser irradiation apparatus can be installed in a relatively small space, and the equipment cost can be reduced.
- the laser device detects the position of the electrode sheets 10A (a) to (c), and controls the laser to follow the portion where the insulating layers 245 (a) to (c) are to be melted (not shown). May be added. Accordingly, the laser can appropriately follow the portion where the insulating layers 245 (a) to (c) are to be melted.
- the positions and widths at which the insulating layers 245 (a) to (c) are melted can be adjusted more finely with respect to the fluttering and movement of the electrode sheets 10A (a) to (c).
- FIG. 13 is a schematic diagram illustrating states of the active material layers 243 (a) to (c) and the insulating layers 245 (a) to (c) before being irradiated with the laser.
- FIG. 14 is a schematic diagram showing the states of the active material layers 243 (a) to (c) and the insulating layers 245 (a) to (c) after the laser irradiation.
- the insulating layers 245 (a) to (c) before the laser irradiation are in a state where the resin particles 250 are generally laminated on the active material layers 243 (a) to (c). is there.
- the insulating layers 245 (a) to (c) melt the resin particles 250 at the center of the portion (246) irradiated with the laser, as shown in FIG.
- a part of the molten resin enters the pores of the active material layers 243 (a) to 243 (c) and then solidifies. Therefore, the negative electrode active material layer 243 is firmly bonded. Further, the resin 250 b partially melted around the periphery is bonded to the surrounding resin particles 250.
- the resin particles of the insulating layers 245 (a) to (c) are melted. A part of the molten resin is bonded to the negative electrode active material layer 243 and the surrounding resin particles. For this reason, the fusion
- the edge of the cut insulating layer 245 is strong, the insulating layer 245 is hardly peeled off at the edge of the insulating layer 245.
- the resin particles are unlikely to drop off from the edge of the insulating layer 245, it is possible to suppress the generation of foreign matter in the lithium ion secondary battery 100 due to the resin particles dropping off from the edge of the insulating layer 245.
- the cutting step is a step of cutting the electrode sheet 10A along the lines z1, z3, and z5 in which the insulating layers 245 (a) to (c) are melted by the melting step.
- the electrode sheets 10A (a) to (c) are cut by the cutters 30 (a) to (c).
- the cutters 30 (a) to (c) those capable of appropriately cutting the electrode sheets 10A (a) to (c) from various cutters (also referred to as slitters) may be employed.
- the electrode sheets 10A (a) to (c) are belt-like sheets.
- the transport device 40 continuously transports the electrode sheets 10A (a) to (c) along a predetermined transport path.
- the cutters 30 (a) to (c) are fixedly arranged with respect to the conveyance path of the electrode sheets 10A (a) to (c).
- the fixed cutters 30 (a) to 30 (a) to (c) are cut so that the electrode sheet 10A is cut along the lines z1, z3, and z5 in which the insulating layers 245 (a) to (c) are melted in the melting step.
- the positions of the electrode sheets 10A (a) to (c) may be adjusted with respect to c). Therefore, a position adjusting mechanism 64 such as an EPC device (edge position control device) or a CPC device (center position control device) is arranged in front of the cutters 30 (a) to 30 (c).
- the electrode sheets 10A (a) to (c) cut by the cutters 30 (a) to (c) are melted portions 246 in which resin particles are melted at the edges of the insulating layers 245 (a) to (c), respectively. (A) to (f) are formed. Further, since the edges of the insulating layers 245 (a) to (c) are cut by the cutters 30 (a) to (c), there are cut marks (not shown).
- the electrode sheets 10A (a) to (c) cut by the cutters 30 (a) to (c) are made up of different winding shafts 82 (a) as shown in FIGS. 9 to 12, for example. ) To (c), 84 (a) to (c).
- the insulating layers 245 (a) to (c) are melted at the cut portions. Yes.
- the resin particles are unlikely to fall off from the insulating layers 245 (a) to (c), and the insulating layers 245 (a) to (c) are not easily peeled off.
- the insulating layers 245 (a) to (c) are irradiated with the lasers 20A (a) to (c) as shown in FIG. It is good to melt.
- the position and width at which the insulating layers 245 (a) to (c) are melted can be adjusted more finely. Therefore, the width to be melted can be appropriately narrowed according to the width cut by the cutters 30 (a) to (c).
- the electrode sheet cutting device may include a heater (in the above-described embodiment, a laser device) and cutters 30 (a) to (c).
- the heater may be arranged so as to heat the electrode sheets 10A (a) to (c) along predetermined lines z1, z3, and z5.
- the cutters 30 (a) to (c) can cut the electrode sheets 10A (a) to (c) along the lines z1, z3, and z5 where the insulating layers 245 (a) to (c) are melted.
- the electrode sheet cutting apparatus in the step of cutting the electrode sheets 10A (a) to (c) having the insulating layers 245 (a) to (c) on which the resin particles are laminated, the insulating layer 245 (a) It can be cut after melting (c).
- a transport device 40 for transporting the electrode sheets 10A (a) to (c) along a predetermined transport path may be provided.
- the heater (laser device) and the cutters 30 (a) to (c) may be fixed along the conveyance path.
- position adjusting mechanisms 62 and 64 for adjusting the positions of the electrode sheets 10A (a) to (c) with respect to the heater (laser device) and the cutters 30 (a) to (c) may be provided.
- the electrode sheets 10A (a) to (c) are appropriately conveyed by the position adjusting mechanisms 62 and 64. Therefore, the electrode sheets 10A (a) to (c) can be melted and cut at appropriate positions.
- the transport device 40 uses the electrode sheets 10A (a) to (c) as a transport path. It is good that it is an apparatus which conveys continuously along. Thereby, the electrode sheets 10A (a) to (c) can be continuously melted and cut along the lines z1, z3, and z5. Thereby, an electrode sheet can be obtained efficiently.
- the transport device 40 may include a plurality of guide rolls 41 and 42 that transport the electrode sheets 10A (a) to (c) while supporting them.
- the electrode sheets 10A (a) to (c) are heated by the guide rolls 41 and 42 at positions shifted from the portion where the electrode sheets 10A (a) to (c) are supported to the downstream side in the transport direction.
- a heater laser device that irradiates the lasers 20A (a) to (c)
- the insulating layers 245 (a) to (c) on both surfaces of the electrode sheets 10A (a) to (c) can be melted simultaneously. Therefore, the positions where the insulating layers 245 (a) to (c) are melted on both surfaces of the electrode sheets 10A (a) to (c) are difficult to shift.
- the electrode sheets 10A (a) to (c) are belt-like sheets, and the electrode sheets 10A (a) to (c) are conveyed and cut in the length direction.
- the electrode sheets 10A (a) to (c) are further cut to a predetermined length.
- the resin particles of the insulating layer 245 are preferably melted at the portion to be cut and then cut. Thereby, the resin particles hardly fall off and a part of the insulating layer 245 is hardly peeled off from the edge of the insulating layer 245.
- 16 is a cross-sectional view taken along line AA in FIG.
- the electrode sheet is a belt-like sheet, and the uncoated portion 242 is set along the edge on one side in the width direction.
- the structure of the electrode sheet is a secondary battery. It depends on the structure.
- an electrode sheet 110A shown in FIG. 17 has an uncoated portion 112 formed in the middle portion in the length direction of the strip-shaped current collector 110, and active material layers on both sides thereof. 114 (a) and (b) are formed.
- a tab 120 (a foil serving as an electrical outlet) is attached to an uncoated portion 112 formed in the middle portion of the current collector 110 in the length direction. Also called a center tab.
- FIG. 18 is a cross-sectional view showing an AA cross section in FIG.
- a wide band-shaped current collector 110 (mother current collector) is prepared, and an active material layer 114 is intermittently formed thereon, covering the active material layer 114.
- the insulating layer 116 is formed.
- cutting lines z ⁇ b> 21 and z ⁇ b> 22 are set in the middle between the uncoated portion 112 and the uncoated portion 112.
- cutting lines z ⁇ b> 23 and z ⁇ b> 24 are set along the length direction of the current collector 110 with an interval in the width direction of the current collector 110.
- the electrode sheet 110A is cut along the cutting lines z21 to z24.
- the insulating layer 116 is preferably melted along the cutting lines z21 to z24 before cutting.
- the electrode sheet 110A in which the melted portion 118 is formed at the edges 110a and 110b on both sides in the width direction of the electrode sheet 110A and the edges 110c and 110d on both sides in the length direction is cut out.
- the winding shaft 410 of the winding device 400 for manufacturing the wound electrode body 200 is used. It is preferable that a laser 412 for melting the insulating layer 116 and a cutter 414 for cutting the melted portion are provided in the vicinity of.
- the electrode sheet 110A is not limited to the above-described embodiment, and can take various forms. Regardless of the form of the electrode sheet 110A, for example, as shown in FIG. 18, when the insulating layer 116 in which the resin particles are laminated so as to cover the active material layer 114 is formed, the insulating layer 116 is formed. When cutting the formed portion, the insulating layer 116 may be melted before cutting. Accordingly, the resin particles are unlikely to drop off from the insulating layer 116, and a part of the insulating layer 116 is difficult to peel off from the edge of the insulating layer 116. Note that as described above, as a means for melting the insulating layer 116, the insulating layer 116 may be irradiated with a laser. At this time, a CO 2 laser is preferably used.
- the portions (insulating layers 245 (a) to (c) are melted by the heater (laser device that irradiates the lasers 20A (a) to (c) and the lasers 20B (a) to (c)).
- the heater laser device that irradiates the lasers 20A (a) to (c)
- the lasers 20B a) to (c)
- the method for manufacturing a secondary battery includes a cooling step (Sr) for cooling the electrode sheet between the melting step (Sm) and the cutting step (Sc). May be.
- a cooling step (Sr) for cooling the electrode sheet between the melting step (Sm) and the cutting step (Sc) the resin melted in the melting step is solidified more reliably before the cutting step. be able to. Thereby, the tact time between the melting step and the cutting step can be shortened.
- the cutters 30 (a) to (c) ) Is provided with a cooling device 36 for cooling the electrode sheets 10A (a) to (c).
- the electrode sheets 10A (a) to (c) are belt-like sheets
- the transport device 40 is a device that continuously transports the electrode sheets 10A (a) to (c) along the transport path. is there.
- the cooling device 36 includes a heater (laser device that irradiates lasers 20A (a) to (c) and lasers 20B (a) to (c)), and cutters 30 (a) to (c) along the conveyance path. It is provided between.
- the cooling device 36 can be constituted by, for example, a blower that blows air onto the electrode sheets 10A (a) to (c). In this case, the electrode sheets 10A (a) to (c) are cooled in a non-contact manner.
- the cooling device 36 may include a metal roll 37 pressed against the electrode sheets 10A (a) to (c) and a cooling unit 38 for cooling the metal roll 37.
- the cooling unit 38 may cool the metal roll 37 in a portion that is not pressed against the electrode sheets 10A (a) to (c).
- the structure of the cooling unit 38 may be any structure that absorbs heat from the metal roll 37.
- the cooling unit 38 may have a structure in which cold air is applied to the metal roll 37 in a portion that is not pressed against the electrode sheets 10A (a) to (c).
- the cooling unit 38 may have a structure in which the metal roll 37 has a hollow structure and the coolant is circulated in the metal roll 37. In this case, the electrode sheets 10A (a) to (c) can be quickly cooled. This shortens the tact time.
- the width of the negative electrode active material layer 243 is wider than that of the positive electrode active material layer 223. Further, the negative electrode active material layer 243 is disposed to face the positive electrode active material layer 223.
- the insulating layer 245 covers the negative electrode active material layer 243 of the negative electrode sheet 240. Accordingly, lithium ions (Li) released from the positive electrode active material layer 223 are easily absorbed by the negative electrode active material layer 243, and more lithium ions (Li) are generated between the positive electrode active material layer 223 and the negative electrode active material layer 243. Go back and forth stably.
- the insulating layer 245 may be formed so as to cover the positive electrode active material layer 223, or may be formed on both the positive electrode active material layer 223 and the negative electrode active material layer 243. As described above, the insulating layer 245 may be formed on any of the positive electrode active material layer 223 and the negative electrode active material layer 243.
- the structure of the secondary battery is not limited to the structure shown in FIGS.
- the insulating layer 245 functions as a separator, and no separator is provided separately.
- the structure of the secondary battery is not limited to such a form.
- the structure of the positive electrode sheet 220 and the negative electrode sheet 240 is provided.
- a separator may be provided between them.
- the melted portion 246 in which the resin particles are melted is formed at the edge of the insulating layer 245.
- the secondary battery has the melted portion 246 in which the resin particles are melted at the edge of the insulating layer 245. Therefore, the insulating layer 245 is difficult to peel off from the edge of the insulating layer 245, and is highly safe. In addition to this, safety can be further improved by providing a separate separator between the positive electrode sheet 220 and the negative electrode sheet 240.
- the insulating layer 245 includes resin particles laminated, for example, when the temperature inside the battery becomes abnormally high, the resin particles melt at a predetermined temperature, and the negative electrode active material layer 243 A film that blocks the flow of the electrolytic solution is formed on the surface of the substrate. Thereby, reaction can be stopped within a battery.
- the insulating layer 245 is preferably formed on each side of the negative electrode sheet 240 with a predetermined thickness (for example, a thickness of about 20 ⁇ m to 40 ⁇ m).
- the insulating layer 245 is a porous layer in which resin particles having insulating properties are laminated.
- the insulating layer 245 has an appropriate amount (for example, 50 wt% or less, more preferably 40 wt% or less) such that the insulating particles do not interfere with the shutdown function of the insulating layer 245. It may be mixed. Examples of the particles mixed in the insulating layer 245 include insulating inorganic fillers and rubber particles.
- the inorganic filler has heat resistance against abnormal heat generation of the lithium ion secondary battery and is electrochemically stable within the use range of the battery.
- Such inorganic fillers include metal oxide particles and other metal compound particles.
- the inorganic filler include alumina (Al 2 O 3 ), alumina hydrate (for example, boehmite (Al 2 O 3 .H 2 O)), zirconia (ZrO 2 ), magnesia (MgO), aluminum hydroxide (Al ( Examples thereof include metal compounds such as OH) 3 ), magnesium hydroxide (Mg (OH) 2 ), and magnesium carbonate (MgCO 3 ).
- One or more of such inorganic fillers may be added to the inorganic filler contained in the insulating layer 245.
- rubber particles are added to the insulating layer 245, one kind or two or more kinds of rubber particles may be added.
- the heat resistance of the insulating layer 245 is improved.
- the particle size of the inorganic filler may be, for example, about 0.1 ⁇ m to 6 ⁇ m, more preferably about 0.5 ⁇ m to 4 ⁇ m.
- the insulating inorganic filler may be contained in the insulating layer 245, for example, 5 wt% or more, preferably 10 wt% or more, more preferably 15 wt% or more. Only an inorganic filler may be added to the insulating layer 245, or only rubber particles may be added. In addition, both the inorganic filler and rubber particles may be added to the insulating layer 245.
- the active material layers 243 (a) to (c) are arranged in three rows, and six negative electrode sheets 240 can be cut out in the width direction, but the example shown in FIG. 6 is an example. There is no limitation to this. More simply, as shown in FIG. 8, an active material layer 243 is formed at the center in the width direction of the current collector 10 having a width corresponding to two electrode sheets, and the active material layer 243 is covered. Alternatively, the insulating layer 245 may be formed. As a simple form, for example, an active material layer 243 is formed in the center portion in the width direction of the current collector 10 having a width of two electrode sheets (negative electrode sheet 240) to be obtained, and the active material layer 243 is formed. The insulating layer 245 may be formed so as to cover the surface.
- the above shows an example of a lithium ion secondary battery.
- the lithium ion secondary battery is not limited to the above form.
- an electrode sheet in which an electrode mixture is applied to a metal foil is used in various other battery forms.
- cylindrical batteries and laminated batteries are known as other battery types.
- a cylindrical battery is a battery in which a wound electrode body is accommodated in a cylindrical battery case.
- a laminate type battery is a battery in which a positive electrode sheet and a negative electrode sheet are stacked with a separator interposed therebetween.
- the method for manufacturing a secondary battery and the electrode sheet cutting device described above are used when an insulating layer in which resin particles are laminated is formed so as to cover the active material layer of the electrode sheet. It can be widely applied to the process of cutting.
- the electrode sheets 10A (a) to (c) are band-shaped sheets, but the electrode sheets may not be band-shaped sheets.
- a laminate type secondary battery a plurality of electrode sheets having a predetermined shape are prepared. In this case, the mother sheet of the electrode sheet does not necessarily have a belt shape.
- the secondary battery, the method for manufacturing the secondary battery, and the electrode sheet cutting device according to the embodiment of the present invention have been described. Note that the present invention is not limited to any of the above-described embodiments unless otherwise specified.
- the method for manufacturing a secondary battery and the electrode sheet cutting apparatus cut the electrode sheet when an insulating layer in which resin particles are laminated is formed so as to cover the active material layer.
- the process Widely applicable to the process.
- stacked the resin particle is formed so that an active material layer may be covered, it contributes to the reliability improvement of a secondary battery.
- it can be particularly suitably applied to secondary batteries for vehicles such as hybrid vehicles and electric vehicles that require high output and stable performance.
- the secondary battery according to the embodiment of the present invention is suitably used as a battery 1000 (vehicle driving battery) for driving a motor (electric motor) of a vehicle 1 such as an automobile as shown in FIG. obtain.
- the vehicle driving battery 1000 may be an assembled battery in which a plurality of secondary batteries are combined.
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Abstract
Description
図1は、本発明の一実施形態に係る二次電池としてのリチウムイオン二次電池100を示している。リチウムイオン二次電池100は、図1に示すように、捲回電極体200と電池ケース300と電解液(図示省略)とを備えている。また、図2は、捲回電極体200を示す図である。図3は、図2中のIII-III断面を示している。この実施形態では、捲回電極体200は、図2に示すように、帯状の正極シート220と帯状の負極シート240とが重ねられ、かつ、捲回されている。
正極シート220は、正極集電体221と、正極活物質層223とを備えている。正極集電体221には、正極に適する金属箔が好適に使用され得る。この実施形態では、正極集電体221には、所定の幅を有し、厚さが凡そ10μmの帯状のアルミニウム箔が用いられている。正極活物質層223は、正極集電体221に保持され、少なくとも正極活物質が含まれている。この実施形態では、正極活物質層223は、正極活物質を含む正極合剤が正極集電体221に塗工された層である。この実施形態では、正極集電体221の幅方向片側の縁部に沿って未塗工部222が設定されている。正極活物質層223は、正極集電体221に設定された未塗工部222を除いて、正極集電体221の両面に形成されている。
正極活物質層223に含まれる正極活物質には、リチウムイオン二次電池の正極活物質として用いられる物質を使用することができる。正極活物質の例を挙げると、LiNiCoMnO2(リチウムニッケルコバルトマンガン複合酸化物)、LiNiO2(ニッケル酸リチウム)、LiCoO2(コバルト酸リチウム)、LiMn2O4(マンガン酸リチウム)、LiFePO4(リン酸鉄リチウム)などのリチウム遷移金属酸化物が挙げられる。ここで、LiMn2O4は、例えば、スピネル構造を有している。また、LiNiO2やLiCoO2は層状の岩塩構造を有している。また、LiFePO4は、例えば、オリビン構造を有している。オリビン構造のLiFePO4には、例えば、ナノメートルオーダーの粒子がある。また、オリビン構造のLiFePO4は、さらにカーボン膜で被覆することができる。
正極活物質層223には、正極活物質の他に、導電材、バインダ(結着剤)などの任意成分を必要に応じて含有し得る。導電材としては、例えば、カーボン粉末やカーボンファイバーなどのカーボン材料が例示される。このような導電材から選択される一種を単独で用いてもよく二種以上を併用してもよい。カーボン粉末としては、種々のカーボンブラック(例えば、アセチレンブラック、オイルファーネスブラック、黒鉛化カーボンブラック、カーボンブラック、黒鉛、ケッチェンブラック)、グラファイト粉末などのカーボン粉末を用いることができる。
また、バインダとしては、使用する溶媒に溶解または分散可能なポリマーを用いることができる。例えば、水性溶媒を用いた正極合剤においては、カルボキシメチルセルロース(CMC)、ヒドロキシプロピルメチルセルロース(HPMC)などのセルロース系ポリマー(例えば、ポリビニルアルコール(PVA)やポリテトラフルオロエチレン(PTFE)など)、テトラフルオロエチレン-ヘキサフルオロプロピレン共重合体(FEP)などのフッ素系樹脂(例えば、酢酸ビニル共重合体やスチレンブタジエンゴム(SBR)など)、アクリル酸変性SBR樹脂(SBR系ラテックス)などのゴム類;などの水溶性または水分散性ポリマーを好ましく採用することができる。また、非水溶媒を用いた正極合剤においては、ポリフッ化ビニリデン(PVDF)、ポリ塩化ビニリデン(PVDC)などのポリマーを好ましく採用することができる。なお、上記で例示したポリマー材料は、バインダとしての機能の他に、上記組成物の増粘剤その他の添加剤としての機能を発揮する目的で使用されることもあり得る。溶媒としては、水性溶媒および非水溶媒の何れも使用可能である。非水溶媒の好適例として、N-メチル-2-ピロリドン(NMP)が挙げられる。
この実施形態では、正極活物質層223の平均の厚さt1は、片面当り27μm程度である。かかる正極活物質層223の厚さt1は、例えば、正極シート220の未塗工部222を基準にして測定するとよい。
負極シート240は、負極集電体241と、負極活物質層243と、絶縁層245とを備えている。負極集電体241には、正極に適する金属箔が好適に使用され得る。この実施形態では、この負極集電体241には、所定の幅を有し、厚さが凡そ10μmの帯状の銅箔が用いられている。負極活物質層243は、負極集電体241に保持され、少なくとも負極活物質が含まれている。この実施形態では、負極活物質層243は、負極活物質を含む負極合剤が負極集電体241に塗工された層である。負極集電体241の幅方向片側には、縁部に沿って未塗工部242が設定されている。負極活物質層243は、負極集電体241に設定された未塗工部242を除いて、負極集電体241の両面に形成されている。
負極活物質層243に含まれる負極活物質には、従来からリチウムイオン二次電池に用いられる材料の一種または二種以上を特に限定なく使用することができる。例えば、少なくとも一部にグラファイト構造(層状構造)を含む粒子状の炭素材料(カーボン粒子)が挙げられる。より具体的には、いわゆる黒鉛質(グラファイト)、難黒鉛化炭素質(ハードカーボン)、易黒鉛化炭素質(ソフトカーボン)、これらを組み合わせた炭素材料を用いることができる。例えば、天然黒鉛のような黒鉛粒子を使用することができる。また、負極合剤には、負極活物質の分散を維持するべく、負極合剤には適量の増粘剤が混ぜられている。負極合剤には、正極合剤に使われるのと同様の増粘剤やバインダや導電材を使用することができる。
この実施形態では、負極活物質層243の平均の厚さt2は、片面当り35μm程度である。かかる負極活物質層243の厚さt2は、例えば、負極活物質層243が形成された後において、負極シート240の未塗工部242を基準にして測定するとよい。
絶縁層245は、この実施形態では、負極活物質層を覆うように、絶縁性を有する樹脂粒子を積層した多孔質の層である。絶縁層245に用いられる樹脂粒子は、好適には、熱可塑性樹脂の粒子であり、例えば、ポリエチレン、ポリプロピレン、エチレン由来の構造単位が85mol%以上の共重合ポリオレフィンまたはポリオレフィン球動体などを用いることができる。また、樹脂粒子は、複数の異なる熱可塑性樹脂の粒子を適当な割合で混合してもよい。また、樹脂粒子は、無機フィラーやゴムなどで絶縁性を有する材料が適当な割合で添加されていてもよい。この実施形態では、樹脂粒子には、ポリエチレンが用いられている。樹脂粒子は、例えば、バインダで接着するとよい。かかるバインダには、例えば、正極活物質層または負極活物質層に用いられるバインダと同様のバインダを用いることができる。
この実施形態では、絶縁層245の平均の厚さt3は、片面当り25μm程度である。かかる絶縁層245の厚さt3は、例えば、絶縁層245が形成された後において、負極シート240の未塗工部242を基準に、負極活物質層243と絶縁層245と合わせた厚さt4を測定し、上述した負極活物質層243の厚さt2との差分(t3=t4-t2)により算出するとよい。
また、この実施形態では、絶縁層245の縁には溶融部246が形成されている。溶融部246は、絶縁層245を形成する樹脂粒子が溶融した部分である。かかるリチウムイオン二次電池100によれば、絶縁層245の縁に、樹脂粒子が溶融した溶融部246が形成されているので、絶縁層245の縁が強固に固まっており、当該縁から絶縁層245が剥がれ難い。図2および図3に示す例では、負極活物質層243の幅b1(溶融部246を含まず)は、正極活物質層223の幅a1よりも少し広い。
この例では、正極シート220と負極シート240は、図2に示すように、長さ方向を揃えて重ねられている。この際、正極活物質層223と負極活物質層243が重ねられる。また、正極シート220と負極シート240の幅方向において、正極シート220の未塗工部222と負極シート240の未塗工部242とが互いに反対側にはみ出るように重ねられている。また、負極活物質層243の幅b1は正極活物質層223の幅a1よりも少し広く、負極活物質層243は正極活物質層223を覆うように重ねられている。重ねられたシート材(例えば、正極シート220)は、当該シート材の幅方向に設定された捲回軸周りに捲回されており、捲回後も負極活物質層243が正極活物質層223を覆う状態が維持されている。なお、図2は、正極シート220と負極シート240を捲回し、扁平に変形した捲回電極体200の一部展開した状態を示している。
また、この例では、電池ケース300は、図1に示すように、いわゆる角型の電池ケースであり、容器本体320と、蓋体340とを備えている。容器本体320は、有底四角筒状を有しており、一側面(上面)が開口した扁平な箱型の容器である。蓋体340は、当該容器本体320の開口(上面の開口)に取り付けられて当該開口を塞ぐ部材である。
その後、蓋体340に設けられた注液孔から電池ケース300内に電解液が注入される。電解液は、水を溶媒としていない、いわゆる非水電解液が用いられている。この例では、電解液は、エチレンカーボネートとジエチルカーボネートとの混合溶媒(例えば、体積比1:1程度の混合溶媒)にLiPF6を約1mol/リットルの濃度で含有させた電解液が用いられている。その後、注液孔に金属製の封止キャップを取り付けて(例えば溶接して)電池ケース300を封止する。なお、電解液としては、かかる実施例に限定されず、従来からリチウムイオン二次電池に用いられる非水電解液を使用することができる。
ここで、正極活物質層223は、例えば、正極活物質と導電材の粒子間などに、空洞とも称すべき微小な隙間を有している。かかる正極活物質層223の微小な隙間には電解液(図示省略)が浸み込み得る。また、負極活物質層243は、例えば、負極活物質の粒子間などに、空洞とも称すべき微小な隙間を有している。また、負極活物質層243を覆うように形成された絶縁層245は、樹脂粒子が積層されており、電解液がしみこみうる空洞とも称すべき微小な隙間を有している。ここでは、かかる隙間(空洞)を適宜に「空孔」と称する。このように、リチウムイオン二次電池100の内部では正極活物質層223と負極活物質層243には、電解液が染み渡っている。
また、この例では、当該電池ケース300の扁平な内部空間は、扁平に変形した捲回電極体200よりも少し広い。捲回電極体200の両側には、捲回電極体200と電池ケース300との間に隙間310、312が設けられている。当該隙間310、312は、ガス抜け経路になる。
図4は、かかるリチウムイオン二次電池100の充電時の状態を模式的に示している。充電時においては、図4に示すように、リチウムイオン二次電池100の電極端子420、440(図1参照)は、充電器290に接続される。充電器290の作用によって、充電時には、正極活物質層223中の正極活物質からリチウムイオン(Li)が電解液280に放出される。また、正極活物質層223からは電荷が放出される。放出された電荷は、図4に示すように、導電材(図示省略)を通じて正極集電体221に送られ、さらに、充電器290を通じて負極240へ送られる。また、負極240では電荷が蓄えられるとともに、電解液280中のリチウムイオン(Li)が、負極活物質層243中の負極活物質に吸収され、かつ、貯蔵される。
図5は、かかるリチウムイオン二次電池100の放電時の状態を模式的に示している。放電時には、図5に示すように、負極240から正極220に電荷が送られるとともに、負極活物質層243に貯蔵されたリチウムイオン(Liイオン)が、電解液280に放出される。また、正極では、正極活物質層223中の正極活物質に電解液280中のリチウムイオン(Li)が取り込まれる。
上述したように、このリチウムイオン二次電池100は、図1および図2に示すように、正極集電体221と、正極集電体221に塗工され、少なくとも正極活物質が含まれた正極活物質層223とを備えている。さらに、リチウムイオン二次電池100は、正極集電体221に対向するように配置された負極集電体241と、負極集電体241に塗工され、少なくとも負極活物質が含まれた負極活物質層243とを備えている。また、リチウムイオン二次電池100は、図3に示すように、正極活物質層223または負極活物質層243の少なくとも一方(図3に示す例では、負極活物質層243)を覆うように、絶縁性を有する樹脂粒子を積層した多孔質の絶縁層245が形成されている。さらに、このリチウムイオン二次電池100は、かかる絶縁層245の縁に、樹脂粒子が溶融した溶融部246を備えている。
以下、本発明の一実施形態に係る二次電池の製造方法および電極シートの切断装置を説明する。この実施形態では、二次電池の製造方法は、電極シートを用意する工程と、溶融工程と、切断工程とを含んでいる。かかる二次電池の製造方法は、例えば、上述したリチウムイオン二次電池100(図1参照)のうち負極シート240を製造する工程に適用することができる。以下、上述したリチウムイオン二次電池100の負極シート240を例に挙げて、本発明の一実施形態に係る二次電池の製造方法および電極シートの切断装置を説明する。図6は、電極シートを用意する工程で用意される段階での電極シート(負極シート240)の平面図である。
電極シートを用意する工程で用意される電極シート10Aは、図6に示すように、集電体10(負極集電体241のマザー集電体)と、活物質層(負極活物質層243)と、絶縁層(絶縁層245)とを備えている。ここでは、電極シート10Aは、複数の負極シート240が切り出されるマザーシートを意味している。また、集電体10は、複数の負極シート240の負極集電体241が切り出され得る集電体を意味している。
溶融工程は、電極シートを用意する工程で用意された電極シート10A(a)、10A(b)、10A(c)の絶縁層245(a)~(c)を、予め定められたラインz1、z3、z5に沿って溶融させる工程である。
図9に示す例では、電極シート10A(a)~(c)をバックロール41(ガイドロール)に支持させた状態で、バックロール41とは反対側の面に形成された絶縁層245(a)~(c)にレーザ20A(a)~(c)を照射している。そして、当該レーザ20A(a)~(c)が照射された面に形成された絶縁層245(a)~(c)(図8参照)を溶融させる。次に、当該絶縁層245(a)~(c)を溶融させた面をバックロール42に支持させる。そして、当該バックロール42に支持させた状態で、バックロール42とは反対側の面に形成された絶縁層245(a)~(c)にレーザ20B(a)~(c)を照射している。ここでは、符号20A(a)~(c)および20B(a)~(c)は、直接的には電極シート10A(a)~(c)に照射されるレーザを示している。なお、当該レーザを照射するレーザ装置は、図示の便宜上、省略されている。図示されるレーザ20A(a)~(c)およびレーザ20B(a)~(c)は、当該レーザを照射するレーザ装置およびレーザ装置を制御する装置の存在を間接的に示している。
図13は、レーザが照射される前の活物質層243(a)~(c)と絶縁層245(a)~(c)の状態を示す模式図である。また、図14は、レーザが照射された後の活物質層243(a)~(c)と絶縁層245(a)~(c)の状態を示す模式図である。
次に切断工程を説明する。
上述した実施形態では、ヒーター(レーザ20A(a)~(c)やレーザ20B(a)~(c)を照射するレーザ装置)によって、絶縁層245(a)~(c)を溶融させる部位と、電極シート10A(a)~(c)を切断する部位との間は少し距離がある。このため、電極シート10A(a)~(c)が当該距離を進む間に温度が下がり、電極シート10A(a)~(c)が切断される前に溶融工程で溶融した樹脂が十分に固化し得る。この場合、絶縁層245(a)~(c)を溶融させる部位と、電極シート10A(a)~(c)を切断する部位との間は、常温(約25度)において、少なくとも0.5秒以上、より好ましくは、0.8秒以上掛けて搬送するとよい。
溶融工程で溶融した樹脂が十分に固化する前に、切断工程に供給されると、カッター30(a)~(c)に樹脂が付着するなど不具合を生じさせうる。また、溶融工程と切断工程との間で十分な間隔をあけるには、タクトタイムが長くなる。このため、二次電池の製造方法は、例えば、図21に示すように、溶融工程(Sm)と、切断工程(Sc)との間に、電極シートを冷却する冷却工程(Sr)を備えていてもよい。溶融工程(Sm)と、切断工程(Sc)との間に、電極シートを冷却する冷却工程(Sr)を設けることによって、溶融工程で溶融した樹脂を切断工程の前に、より確実に固化させることができる。これにより、溶融工程と切断工程との間のタクトタイムを短くできる。
例えば、図21に示す形態では、ヒーター(レーザ20A(a)~(c)やレーザ20B(a)~(c)を照射するレーザ装置)によって加熱された後、カッター30(a)~(c)によって切断される前に、電極シート10A(a)~(c)を冷却する冷却装置36を備えている。この実施形態では、電極シート10A(a)~(c)は帯状のシートであり、搬送装置40は、電極シート10A(a)~(c)を搬送経路に沿って連続的に搬送する装置である。冷却装置36は、搬送経路に沿って、ヒーター(レーザ20A(a)~(c)やレーザ20B(a)~(c)を照射するレーザ装置)と、カッター30(a)~(c)との間に設けられている。冷却装置36は、例えば、電極シート10A(a)~(c)に空気を吹き付ける送風機で構成することができる。この場合、電極シート10A(a)~(c)は非接触で冷却される。
また、冷却装置36は、図22に示すように、電極シート10A(a)~(c)に押し当てられる金属ロール37と、金属ロール37を冷やす冷却部38とを備えているとよい。当該冷却部38は、電極シート10A(a)~(c)に押し付けられていない部分において、金属ロール37を冷却するとよい。冷却部38の構成としては、金属ロール37から吸熱する構造であれば良い。冷却部38は、例えば、電極シート10A(a)~(c)に押し付けられていない部分において、金属ロール37に冷気を当てる構造でもよい。また、冷却部38は、金属ロール37を中空構造とし、金属ロール37内に冷媒を循環させる構造でもよい。この場合、電極シート10A(a)~(c)を早急に冷却することができる。これにより、タクトタイムが短くなる。
また、絶縁層245は、例えば、上述したように、樹脂粒子が積層されており、電池内部の温度が異常に高くなった際に、所定の温度で樹脂粒子が溶融し、負極活物質層243の表面に、電解液の流通を遮断する膜を形成する。これにより、電池内で反応を停止させることができる。絶縁層245は、負極シート240の両面にそれぞれ所定の厚さ(例えば、20μm~40μm程度の厚さ)で形成するとよい。
なお、上記はリチウムイオン二次電池の一例を示すものである。リチウムイオン二次電池は上記形態に限定されない。また、同様に金属箔に電極合剤が塗工された電極シートは、他にも種々の電池形態に用いられる。例えば、他の電池形態として、円筒型電池やラミネート型電池などが知られている。円筒型電池は、円筒型の電池ケースに捲回電極体を収容した電池である。また、ラミネート型電池は、正極シートと負極シートとをセパレータを介在させて積層した電池である。
10A 電極シート
20 ヒーター
20A レーザ
20B レーザ
30 カッター
36 冷却装置
37 金属ロール
38 冷却部
40 搬送装置
41、42 ガイドロール(バックロール)
62、64 位置調整機構
82、84 巻取り軸
100 リチウムイオン二次電池(二次電池)
110 集電体
110A 電極シート
110a、110b、110c、110d 電極シートの縁
112 未塗工部
114 活物質層
116 絶縁層
118 溶融部
120 タブ
200 捲回電極体
220 正極シート
221 正極集電体
222 未塗工部
223 正極活物質層
240 負極シート
241 負極集電体
242 未塗工部
243 活物質層
243 負極活物質層
245 絶縁層
246 溶融部
250 樹脂粒子
250a 樹脂粒子250が溶融した部分
250b 一部が溶融した樹脂
280 電解液
290 充電器
300 電池ケース
310 隙間
320 容器本体
322 蓋体340と容器本体320の合わせ目
340 蓋体
360 安全弁
400 捲回装置
410 巻取軸
412 レーザ
414 カッター
420 電極端子
440 電極端子
1000 車両駆動用電池(二次電池)
z1-z5 ライン(切断ライン)
z21-z24 ライン(切断ライン)
Sm 溶融工程
Sc 切断工程
Sf 冷却工程
Claims (22)
- 正極集電体と、
前記正極集電体に保持され、少なくとも正極活物質が含まれた正極活物質層と、
前記正極集電体に対向するように配置された負極集電体と、
前記負極集電体に保持され、少なくとも負極活物質が含まれた負極活物質層と、
前記正極活物質層または前記負極活物質層の少なくとも一方を覆うように、絶縁性を有する樹脂粒子を積層した多孔質の絶縁層と、
前記絶縁層の縁に形成され、前記樹脂粒子が溶融した溶融部と
を備えた、二次電池。 - 前記絶縁層は、絶縁性を有する無機フィラーが含まれている、請求項1に記載された二次電池。
- 前記絶縁層は、絶縁性を有するゴムの粒子が含まれている、請求項1又は2に記載された二次電池。
- 前記絶縁層の縁は切断痕を有する、請求項1から3までの何れか一項に記載された二次電池。
- 前記絶縁層は、前記負極活物質層に積層された、請求項1から4までの何れか一項に記載された二次電池。
- 前記負極活物質層は、前記正極活物質層よりも幅が広く、かつ、前記正極活物質層に対向させて配置されており、前記絶縁層が前記正極活物質層に対向する側において、前記負極活物質層に積層された、請求項1から5までの何れか一項に記載された二次電池。
- 集電体、前記集電体の表面に形成され、電極活物質が含まれた活物質層、および、前記活物質層を覆うように、絶縁性を有する樹脂粒子を積層した多孔質の絶縁層を備えた電極シートを用意する工程;
前記電極シートを用意する工程で用意された前記電極シートの絶縁層を、予め定められたラインに沿って溶融させる溶融工程;および、
前記溶融工程によって前記絶縁層を溶融させた前記ラインに沿って、前記電極シートを切断する切断工程;を含む二次電池の製造方法。 - 前記溶融工程では、前記絶縁層にレーザを照射することによって、前記絶縁層を溶融させる、請求項7に記載された二次電池の製造方法。
- 前記レーザは、CO2レーザである、請求項8に記載された二次電池の製造方法。
- 前記溶融工程と、前記切断工程との間に、前記電極シートを冷却する冷却工程を備えた、請求項7から9までの何れか一項に記載された二次電池の製造方法。
- 前記電極シートを用意する工程において用意される電極シートは、前記絶縁層に絶縁性を有する無機フィラーが含まれている、請求項7から10までの何れか一項に記載された二次電池の製造方法。
- 前記電極シートを用意する工程において用意される電極シートは、前記絶縁層に絶縁性を有するゴムの粒子が含まれている、請求項7から11までの何れか一項に記載された二次電池の製造方法。
- 予め定められたラインに沿って電極シートを加熱するように配置された前記ヒーターと、
前記ヒーターによって加熱された電極シートが前記ラインに沿って切断されるように配置されたカッターと、
を備えた、電極シートの切断装置。 - 前記ヒーターが、前記電極シートに対してレーザを照射するレーザ装置である、請求項13に記載された電極シートの切断装置。
- 前記レーザ装置がCO2レーザを照射する装置である、請求項14に記載された電極シートの切断装置。
- 前記電極シートを予め定められた搬送経路に沿って搬送する搬送装置を備えており、
前記ヒーターとカッターとが前記搬送経路に沿って固定的に配置されており、前記ヒーターとカッターに対して、電極シートの位置を調整する位置調整機構を備えた、請求項13から15までの何れか一項に記載された電極シートの切断装置。 - 前記電極シートは帯状のシートであり、前記搬送装置は、当該電極シートを搬送経路に沿って連続的に搬送する装置である、請求項16に記載された電極シートの切断装置。
- 前記搬送装置は、前記電極シートを支持しつつ搬送するガイドロールを複数備えており、
前記ガイドロールによって前記電極シートが支持された部位から搬送方向下流側にずれた位置において、前記電極シートが加熱されるように前記ヒーターが配置されている、請求項17に記載された電極シートの切断装置。 - 前記ヒーターは、前記ガイドロールによって前記電極シートが支持された部位から搬送方向下流側に1mm以上10mm以下の範囲でずれている、請求項18に記載された電極シートの切断装置。
- 前記ヒーターによって加熱された後、前記カッターによって切断される前に、前記電極シートを冷却する冷却装置を備えた、請求項13から19までの何れか一項に記載された電極シートの切断装置。
- 前記冷却装置は、電極シートに空気を吹き付ける送風機である、請求項20に記載された電極シートの切断装置。
- 前記冷却装置は、前記電極シートに押し当てられる金属ロールと、当該金属ロールを冷やす冷却部とを備えた、請求項21に記載された電極シートの切断装置。
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