WO2017051514A1 - Batterie secondaire à électrolyte non aqueux cylindrique - Google Patents
Batterie secondaire à électrolyte non aqueux cylindrique Download PDFInfo
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- WO2017051514A1 WO2017051514A1 PCT/JP2016/004173 JP2016004173W WO2017051514A1 WO 2017051514 A1 WO2017051514 A1 WO 2017051514A1 JP 2016004173 W JP2016004173 W JP 2016004173W WO 2017051514 A1 WO2017051514 A1 WO 2017051514A1
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- secondary battery
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- electrolyte secondary
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- cylindrical
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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
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/443—Particulate material
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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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
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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
- H01M10/058—Construction or manufacture
- H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/491—Porosity
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a cylindrical non-aqueous electrolyte secondary battery, and more particularly to a cylindrical non-aqueous electrolyte secondary battery exhibiting high safety by improving a separator.
- a non-aqueous electrolyte secondary battery having high energy density is used as a power source for mobile devices such as notebook computers and mobile phones.
- non-aqueous electrolyte secondary batteries have become widespread as power sources for electric tools, assist bicycles, and electric vehicles, and a further increase in capacity is required.
- a cylindrical nonaqueous electrolyte secondary battery is often used in a harsh environment as an assembled battery in which a plurality of batteries are connected in series or in parallel. For this reason, the cylindrical nonaqueous electrolyte secondary battery is provided with various means for ensuring safety.
- a cylindrical center pin is inserted into a hollow portion formed in a core portion of a wound electrode body.
- Many center pins are formed by bending a metal plate into a cylindrical shape.
- the center pin so formed has a slit formed on the side surface along the length direction.
- Patent Documents 1 to 3 are cited as prior art documents disclosing a cylindrical non-aqueous electrolyte secondary battery having a center pin.
- a center pin is used to short-circuit the inner periphery of the electrode body when the electrode body is crushed.
- the end portion of the slit of the center pin is deformed outward, and the end portion breaks the inner peripheral portion of the electrode body to promote internal short circuit.
- a short circuit current concentrates on the inner peripheral side of an electrode body, and the temperature rise of the positive electrode active material layer by a short circuit current is suppressed.
- a center pin is used to prevent deformation of the electrode body due to charge / discharge.
- the center pin is not only formed by bending a metal plate into a cylindrical shape, but also in the vicinity of the slit so that the end face of the slit is oriented inside the cylindrical portion of the center pin. Thereby, when the electrode body is crushed, the end surface of the slit of the center pin is deformed toward the inside of the center pin, so that an internal short circuit due to the slit of the center pin is prevented.
- Non-aqueous electrolyte secondary batteries generally use a polyolefin microporous membrane as a separator.
- a separator containing a polyolefin having a low melting point exhibits a shutdown function that suppresses movement of lithium ions between the positive and negative electrodes when the battery temperature rises.
- This shutdown function utilizes the phenomenon that the polyolefin softens with increasing temperature and closes the opening of the separator.
- polyethylene is preferably used as the polyolefin.
- Japanese Patent Laid-Open No. 08-255631 Japanese Patent Laid-Open No. 2003-092148 JP 2003-229177 A JP 2006-032246 A Japanese Patent Laid-Open No. 2007-299612 JP 2010-021033 A JP 2013-105578 A
- Patent Document 1 may not be effective for a high-capacity cylindrical nonaqueous electrolyte secondary battery, and an internal short circuit caused by the center pin when the electrode body is crushed is It is preferably prevented. According to the techniques described in Patent Documents 2 and 3, an internal short circuit caused by the slit of the center pin is suppressed. However, regardless of the presence or absence of slits, when the battery is crushed and the electrode body is crushed, the presence of a center pin applies a large force locally to the electrode plate and separator, so the separator with insufficient mechanical strength breaks. There is a risk.
- the technology for forming a heat-resistant layer on the surface of the base material layer of the separator as in Patent Documents 4 to 7 is effective as a means for preventing an internal short circuit due to shrinkage or melting of the separator.
- this technique is not always effective as a means for ensuring safety when the electrode body is crushed in a crush test or the like.
- the heat-resistant layer is formed on the surface of the base material layer of the separator, it is necessary to reduce the thickness of the base material layer by the thickness of the heat-resistant layer. Therefore, forming a heat-resistant layer on the surface of the separator may lead to a decrease in the mechanical strength of the separator.
- the present invention has been made in view of the above, and ensures safety during a crushing test of a cylindrical non-aqueous electrolyte secondary battery having a separator having a heat-resistant layer formed on a substrate mainly composed of polyolefin. For the purpose.
- a cylindrical nonaqueous electrolyte secondary battery includes an electrode body in which a positive electrode plate and a negative electrode plate are wound via a separator, a nonaqueous electrolyte, and an electrode body It has a center pin inserted into a hollow portion formed at a position corresponding to the winding shaft portion, and a bottomed cylindrical outer can that accommodates the electrode body and the nonaqueous electrolyte.
- the separator includes a base material layer containing polyolefin as a main component and a heat resistant layer formed on at least one surface of the base material layer and containing a heat-resistant polymer as a main component.
- the maximum height Rz of the surface of the base material layer that is the base of the heat-resistant layer is 0.1 ⁇ m or more and 3 ⁇ m or less.
- the breakage of the separator is suppressed when the cylindrical nonaqueous electrolyte secondary battery is crushed by the crush test or the like. Therefore, according to the present invention, the safety of the cylindrical nonaqueous electrolyte secondary battery can be enhanced.
- FIG. 1 is a cross-sectional perspective view of a cylindrical nonaqueous electrolyte secondary battery according to an embodiment of the present invention.
- FIG. 2 is a cross-sectional view of a main part of a separator according to one embodiment of the present invention.
- a cylindrical nonaqueous electrolyte secondary battery according to an embodiment of the present invention will be described with reference to FIGS.
- this invention is not limited to the following embodiment, In the range which does not change the summary of this invention, it can change suitably and can implement.
- the cylindrical nonaqueous electrolyte secondary battery 10 has an electrode body 14 and a nonaqueous electrolyte housed inside a bottomed cylindrical outer can 20.
- the inside of the cylindrical non-aqueous electrolyte secondary battery 10 is sealed by caulking and fixing the sealing body 21 to the opening of the outer can 20 via the gasket 19.
- the electrode body 14 is produced by winding the positive electrode plate 12 and the negative electrode plate 13 through the separator 11. At this time, the hollow portion 15 is formed at a position corresponding to the winding shaft portion of the electrode body.
- a center pin 16 is inserted into the hollow portion 15. In order to facilitate the insertion of the center pin 16, it is preferable to form the hollow portion 15 so that the cross-sectional shape is a perfect circle.
- a center pin 16 formed by bending a plate-like member into a cylindrical shape is used, and a slit is formed on the side surface along the length direction. Further, the tip of the slit is bent inside the center pin 16. That is, the cross-sectional shape of the center pin 16 is a shape in which the C-shaped tip is bent inward, but is not limited thereto.
- a metal member processed into a pipe shape can be used for the center pin 16, it is preferable from the viewpoint of cost reduction to use the center pin 16 formed of a metal plate in a cylindrical shape as in this embodiment.
- the material of the center pin 16 can be used without limitation as long as it has a strength that can ensure the shape of the hollow portion 15 of the electrode body 14 even when charging and discharging are repeated and corrosion resistance in the nonaqueous electrolyte.
- Examples of preferred materials for the center pin 16 include stainless steel, nickel, titanium, and iron. When iron is used, it is preferable to plate with nickel in order to ensure corrosion resistance in the non-aqueous electrolyte.
- the separator 11 is comprised from the base material layer 11a and the heat-resistant layer 11b formed in the surface, as shown in FIG. It is sufficient that the heat-resistant layer 11b is formed on one surface of the base material layer 11a. In the present embodiment, the heat-resistant layer 11 b is formed only on the side of the separator 11 that faces the positive electrode plate 12. The heat-resistant layer 11b may be formed on the side of the separator 11 facing the negative electrode plate 13, or may be formed on both surfaces of the base material layer 11a.
- the base material layer 11a is made of a microporous film containing polyolefin as a main component, and the polyolefin is preferably polyethylene, polypropylene, or a copolymer of ethylene and propylene.
- polyolefin is preferably polyethylene, polypropylene, or a copolymer of ethylene and propylene.
- the base material layer 11a can contain other polymers together with polyolefin. By appropriately selecting another polymer, shrinkage of the base material layer 11a when the battery temperature rises can be prevented.
- polystyrene examples include polystyrene, rubber-containing polystyrene, and styrene polymers such as acrylonitrile-styrene copolymers; polyesters such as polyethylene terephthalate; polyamides such as polyamide 6 and polyamide 12; acrylic polymers such as polymethyl methacrylate; cellulose derivatives; Examples are thermoplastic polymers such as thermoplastic elastomers.
- the content of polyolefin in the base material layer 11a is preferably 40 to 100% by mass, more preferably 50 to 100% by mass.
- the thickness of the base material layer 11a is preferably 3 to 220 ⁇ m.
- the average pore diameter of the base material layer 11a is preferably 0.05 to 2 ⁇ m.
- the porosity of the base material layer 11a is preferably 25 to 80% by volume, more preferably 25 to 75% by volume.
- the puncture strength of the base material layer 11a is preferably 300 gf or more, more preferably 400 gf or more.
- the heat-resistant layer 11b is mainly composed of a polymer having heat resistance. It is a necessary condition for the heat resistance that the melting point and heat shrinkage starting temperature of the polymer are higher than the melting point and heat shrinkage starting temperature of the base material layer 11a, respectively.
- a polymer having a melting point higher than 150 ° C. and lower than or equal to 350 ° C., more preferably higher than or equal to 170 ° C. and lower than or equal to 300 ° C. can be used.
- amide bond-containing polymers amide bond-containing polymers, fluorine-containing polymers, and imide bond-containing polymers are preferable.
- aramid polyvinylidene fluoride (PVDF), vinylidene fluoride-hexafluoropropylene (VDF-HFP) copolymer, polyimide ( PI) and polyamideimide (PAI) are more preferable.
- the above polymers can be used alone or in combination of two or more.
- the heat-resistant layer 11b can contain another polymer other than the heat-resistant polymer as the main component as long as the heat resistance is not impaired. It is preferable that content of the said other polymer is 10 mass% or less with respect to the mass of the heat-resistant layer 11b.
- the heat-resistant layer 11b can contain an inorganic filler made of insulating inorganic particles in addition to the heat-resistant polymer as the main component.
- an inorganic filler inorganic oxides such as silicon oxide (SiO 2 ), aluminum oxide (Al 2 O 3 ), titanium oxide (TiO 2 ), magnesium oxide (MgO), and zirconium oxide (ZrO 2 ) are preferable.
- the thickness of the heat-resistant layer 11b can be selected from the range of 0.01 to 50 ⁇ m, preferably 0.1 to 20 ⁇ m, more preferably 0.5 to 10 ⁇ m.
- the average pore diameter of the heat-resistant layer 11b is preferably 0.05 to 2 ⁇ m.
- the porosity of the heat-resistant layer 11b is preferably 25 to 80% by volume, more preferably 25 to 75% by volume.
- the heat-resistant layer 11b can be formed by applying a coating liquid containing a main component polymer on the base material layer 11a by a known coating method and drying it.
- a coating liquid containing a main component polymer on the base material layer 11a by a known coating method and drying it.
- the coating liquid a solution in which the main component polymer is dissolved in a solvent, or a dispersion liquid in which the main component polymer is dispersed in a dispersion medium can be used.
- solvent or dispersion medium for the coating solution examples include alcohols such as methanol, ethanol, and ethylene glycol (such as C2-4 alkanol or C2-4 alkanediol); ketones such as acetone; ethers such as diethyl ether and tetrahydrofuran; dimethylformamide, and the like Nitriles such as acetonitrile; sulfoxides such as dimethyl sulfoxide; N-methyl-2-pyrrolidone (NMP) and the like.
- alcohols such as methanol, ethanol, and ethylene glycol (such as C2-4 alkanol or C2-4 alkanediol)
- ketones such as acetone
- ethers such as diethyl ether and tetrahydrofuran
- dimethylformamide and the like
- Nitriles such as acetonitrile
- sulfoxides such as dimethyl sulfoxide
- NMP N-methyl-2-pyrrolidone
- the positive electrode plate 12 is composed of a positive electrode current collector and a positive electrode active material layer formed on the surface thereof.
- a positive electrode current collector for example, aluminum, an aluminum alloy, stainless steel, titanium, or a metal foil formed of a titanium alloy can be used.
- the thickness of the positive electrode current collector is, for example, 1 to 100 ⁇ m, preferably 5 to 70 ⁇ m, more preferably 10 to 50 ⁇ m.
- the positive electrode active material layer can contain a binder and a conductive agent in addition to the positive electrode active material.
- the positive electrode active material any material that can electrochemically occlude and release lithium ions can be used without limitation.
- the positive electrode active material LiCoO 2 , LiNiO 2 , LiCo x Ni 1-x O 2 (0 ⁇ x ⁇ 1), LiMn 2 O 4 , LiNi 0.4 Mn 1.6 O 4 , LiCoPO 4 , LiFePO 4 , LiCoPO 4 4-y F y (0 ⁇ y ⁇ 1), LiFePO 4-z F z (0 ⁇ z ⁇ 1), Li 4 Ti 5 O 12, Li 4 Fe 0.5 Ti 4.5 O 12, and Li 4 Examples include lithium transition metal composite oxides such as Zn 0.5 Ti 4.5 O 12 ; metal oxides such as V 2 O 5 and MnO 2 ; sulfides such as TiS 2 and LiFeS 2 . These can be used alone or in combination of two or more. These may be used by adding
- the conductive agent examples include carbon black such as acetylene black, ketjen black, channel black, furnace black, lamp black, and thermal black; graphite such as natural graphite and artificial graphite; and conductive fiber such as carbon fiber and metal fiber. Is done.
- the binder polyvinylidene fluoride (PVDF), a modified product of polyvinylidene fluoride (PVDF), and a fluororesin such as polytetrafluoroethylene (PTFE); styrene-butadiene rubber (SBR), styrene-butadiene rubber (SBR) )
- rubber particle binders such as polymers having acrylate units; and cellulose derivatives such as carboxymethylcellulose (CMC).
- the thickness of the positive electrode active material layer is not particularly limited, but is, for example, 0.1 to 150 ⁇ m, preferably 1 to 100 ⁇ m, more preferably 10 to 90 ⁇ m.
- the negative electrode plate 13 is composed of a negative electrode current collector and a negative electrode active material layer formed on the surface thereof.
- a negative electrode current collector for example, a metal foil formed of copper, a copper alloy, nickel, a nickel alloy, or stainless steel can be used.
- the thickness of the negative electrode current collector is, for example, 1 to 100 ⁇ m, preferably 2 to 50 ⁇ m, more preferably 3 to 30 ⁇ m.
- the negative electrode active material layer can contain a binder and a conductive agent in addition to the negative electrode active material.
- any material capable of electrochemically occluding and releasing lithium ions can be used without limitation.
- Carbon materials such as graphite and carbon nanotubes as the negative electrode active material; metal materials containing at least one selected from the group consisting of Li, Al, Zn, Sn, In, Si, Ta, and Nb or oxides thereof; Li 4 Lithium titanium oxide having a spinel structure such as Ti 5 O 12 , Li 4 Fe 0.5 Ti 4.5 O 12 , and Li 4 Zn 0.5 Ti 4.5 O 4 ; Sulfide such as TiS 4 ; LiCo Examples include nitrides such as 2.6 O 0.4 N and Ta 3 N 5 .
- a small amount of dissimilar metal may be added to the metal material, oxide, sulfide, and nitride.
- the conductive agent and binder used for the negative electrode plate 13 those exemplified as the conductive agent and binder used for the positive electrode plate 12 can be used.
- the thickness of the negative electrode active material layer is not particularly limited, but is, for example, 0.1 to 150 ⁇ m, preferably 1 to 120 ⁇ m, more preferably 10 to 100 ⁇ m.
- Known methods can be used for forming the positive electrode active material layer and the negative electrode active material layer. For example, wet coating methods such as a die coating method and a gravure coating method, a sputtering method, a physical vapor deposition method, a chemical vapor deposition method, and a screen. The printing method is mentioned.
- wet coating methods such as a die coating method and a gravure coating method, a sputtering method, a physical vapor deposition method, a chemical vapor deposition method, and a screen.
- the printing method is mentioned.
- Each of the positive electrode active material layer and the negative electrode active material layer may be formed only on one side of the current collector, or may be formed on both sides.
- non-aqueous electrolyte a solution obtained by dissolving a lithium salt as an electrolyte salt in a non-aqueous solvent can be used.
- a cyclic carbonate, a chain carbonate, a cyclic carboxylic acid ester and a chain carboxylic acid ester can be used, and these are preferably used in a mixture of two or more.
- the cyclic carbonate include ethylene carbonate (EC), propylene carbonate (PC), and butylene carbonate (BC).
- a cyclic carbonate in which part of hydrogen is substituted with fluorine, such as fluoroethylene carbonate (FEC) can also be used.
- the chain carbonate include dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), and methyl propyl carbonate (MPC).
- Examples of cyclic carboxylic acid esters include ⁇ -butyrolactone ( ⁇ -BL) and ⁇ -valerolactone ( ⁇ -VL).
- Examples of chain carboxylic acid esters include methyl pivalate, ethyl pivalate, methyl isobutyrate and methyl Pionate is exemplified.
- LiPF 6 , LiBF 4 , LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 2 ) 2 , LiN (CF 3 SO 2 ) (C 4 F 9 SO 2 ) , LiC (CF 3 SO 2 ) 3 , LiC (C 2 F 5 SO 2 ) 3 , LiAsF 6 , LiClO 4 , Li 2 B 10 Cl 10 and Li 2 B 12 Cl 12 are exemplified.
- LiPF 6 is particularly preferable, and the concentration of the lithium salt in the nonaqueous electrolyte is preferably 0.5 to 2.0 mol / L.
- Other lithium salts such as LiBF 4 may be mixed with LiPF 6 .
- Example 1 (Preparation of separator) As the base material layer 11a, a polyethylene microporous film having a thickness of 20 ⁇ m was used. This microporous membrane was produced by extruding molten polyethylene and forming it into a sheet shape, and stretching the obtained molded product in a biaxial direction. The base material layer 11a having a maximum surface height Rz of 0.1 ⁇ m was prepared by adjusting the conditions for stretching the melted polyethylene.
- a polyamide as a heat-resistant polymer is dissolved in N-methyl-2-pyrrolidone (NMP) as a solvent, and 2 parts by mass of aluminum oxide (Al 2 O 3 , average particle diameter is 1 part by mass of polyamide) 0.013 ⁇ m) was added to the solvent to prepare a coating solution.
- the coating liquid was applied to one side of the base material layer 11a and dried to form a heat-resistant layer 11b having a thickness of 3.5 ⁇ m. In this way, the separator 11 according to Example 1 was produced.
- the piercing strength of the base material layer 11a was 420 gf.
- the puncture strength was determined by applying a needle-like terminal with a tip of ⁇ 1 mm to the base material layer 11a applied with tension from both ends at 200 mm / min. And measured at a constant speed.
- the maximum load when the base material layer 11a broke was defined as the piercing strength.
- Preparation of positive electrode plate 100 parts by mass of lithium nickel cobalt aluminum oxide represented by LiNi 0.82 Co 0.15 Al 0.03 O 2 as a positive electrode active material, 1 part by mass of acetylene black as a conductive agent, and as a binder It mixed so that polyvinylidene fluoride (PVDF) might be 0.9 mass part.
- the mixture was put into N-methyl-2-pyrrolidone (NMP) as a dispersion medium and kneaded to prepare a positive electrode mixture slurry.
- NMP N-methyl-2-pyrrolidone
- the positive electrode mixture slurry was intermittently applied to both surfaces of a strip-shaped aluminum foil having a thickness of 15 ⁇ m as a positive electrode current collector, and dried to form a positive electrode active material layer.
- the positive electrode active material layer was compressed to a predetermined thickness with a roll.
- the positive electrode lead 12a made of aluminum was ultrasonically welded to the exposed portion of the positive electrode current collector where the positive electrode active material layer was not formed.
- a positive electrode plate 12 was produced by applying a polyimide insulating tape so as to cover the positive electrode lead 12a.
- the scale-like graphite as the negative electrode active material is 100 parts by mass
- the styrene-butadiene rubber (SBR) as the binder is 1 part by mass
- the sodium salt of carboxymethyl cellulose (CMC) as the thickener is 1 part by mass.
- the mixture was put into water as a dispersion medium and kneaded to prepare a negative electrode mixture slurry.
- the negative electrode mixture slurry was intermittently applied to both surfaces of a strip-shaped copper foil having a thickness of 10 ⁇ m as a negative electrode current collector, and dried at 110 ° C. for 30 minutes to form a negative electrode active material layer.
- the negative electrode active material layer was compressed to a predetermined thickness with a roll.
- the negative electrode lead 13b made of nickel was resistance-welded to the exposed portion of the negative electrode current collector on which the negative electrode active material layer was not formed, and the negative electrode plate 13 was produced.
- An electrode body 14 was produced as follows using a core composed of two core rods having a semicircular cross-sectional shape. First, a separator was sandwiched between winding core rods, and only the separator 11 was wound. Next, the positive electrode plate 12 and the negative electrode plate 13 were each inserted between the separators 11 at a predetermined timing, and the positive electrode plate 12 and the negative electrode plate 13 were wound with the separator 11 interposed therebetween. Finally, the end of the outermost winding end was fixed with an insulating tape, and the winding core was pulled out to produce an electrode body 14 having a hollow portion 15 formed at a position corresponding to the winding shaft portion.
- the center pin 16 was produced by forming a stainless steel plate having a thickness of 0.25 mm into a cylindrical shape.
- the cross-sectional shape orthogonal to the length direction of the center pin 16 was a shape in which the C-shaped tip was bent inward.
- a non-aqueous electrolyte is injected into the outer can 20 and the sealing body 21 is caulked and fixed to the grooved portion of the outer can 20 via the gasket 19, whereby a cylinder having a diameter of 18 mm and a height of 65 mm shown in FIG.
- a nonaqueous electrolyte secondary battery 10 was produced.
- the volume energy density of the cylindrical nonaqueous electrolyte secondary battery 10 was 680 Wh / L.
- Example 2 to 7 As shown in Table 1, the maximum height Rz of the surface of the base material layer 11a was changed to any value in the range of 0.5 to 3.0 ⁇ m. Cylindrical nonaqueous electrolyte secondary batteries 10 according to Examples 2 to 7 were produced. The piercing strengths of the base material layers 11a of Examples 2 to 7 were 410 gf, 415 gf, 410 gf, 407 gf, 410 gf, and 400 gf, respectively.
- a cylindrical non-aqueous electrolyte secondary battery having a volume energy density of 680 Wh / L was used.
- the present invention provides a cylindrical non-aqueous electrolyte secondary battery having a volume energy density of 650 Wh / L or more. It is effective.
- a cylindrical nonaqueous electrolyte secondary battery excellent in safety can be provided.
- the present invention is effective for a high-capacity cylindrical nonaqueous electrolyte secondary battery having a volume energy density of 650 Wh / L or more. Therefore, the industrial applicability of the present invention is great.
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Abstract
Cette batterie secondaire à électrolyte non aqueux cylindrique comprend : un corps d'électrode qui est obtenu par enroulement d'une électrode plane positive et d'une électrode plane négative, un séparateur étant intercalé entre celles-ci ; une solution électrolytique ; une broche centrale qui est insérée dans une partie creuse qui est formée dans une position correspondant à l'axe d'enroulement du corps d'électrode ; et un récipient de boîtier externe cylindrique à fond qui contient le corps d'électrode et la solution électrolytique. Le séparateur comprend une couche de base et une couche résistant à la chaleur qui est formée sur au moins une surface de la couche de base. La couche de base contient une polyoléfine en tant que composant principal ; et la couche résistant à la chaleur contient un polymère résistant à la chaleur en tant que composant principal. La hauteur maximale Rz de la surface de la couche de base, ladite surface servant de base pour la couche résistant à la chaleur, est de 0,1 μm à 3 μm (inclus).
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2019065787A1 (fr) * | 2017-09-29 | 2019-04-04 | 東レ株式会社 | Film poreux, séparateur pour batteries secondaires et batterie secondaire |
WO2019181286A1 (fr) * | 2018-03-20 | 2019-09-26 | 三洋電機株式会社 | Batterie secondaire à électrolyte non aqueux et procédé de fabrication de batterie secondaire à électrolyte non aqueux |
WO2020059874A1 (fr) * | 2018-09-20 | 2020-03-26 | 株式会社村田製作所 | Batterie secondaire |
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WO2019065787A1 (fr) * | 2017-09-29 | 2019-04-04 | 東レ株式会社 | Film poreux, séparateur pour batteries secondaires et batterie secondaire |
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WO2020059874A1 (fr) * | 2018-09-20 | 2020-03-26 | 株式会社村田製作所 | Batterie secondaire |
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