JP6048753B2 - 電池用セパレータ、および、電池用セパレータの製造方法 - Google Patents
電池用セパレータ、および、電池用セパレータの製造方法 Download PDFInfo
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- JP6048753B2 JP6048753B2 JP2013158835A JP2013158835A JP6048753B2 JP 6048753 B2 JP6048753 B2 JP 6048753B2 JP 2013158835 A JP2013158835 A JP 2013158835A JP 2013158835 A JP2013158835 A JP 2013158835A JP 6048753 B2 JP6048753 B2 JP 6048753B2
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- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
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- 238000007754 air knife coating Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- ARCGXLSVLAOJQL-UHFFFAOYSA-N anhydrous trimellitic acid Natural products OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- CJPIDIRJSIUWRJ-UHFFFAOYSA-N benzene-1,2,4-tricarbonyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C(C(Cl)=O)=C1 CJPIDIRJSIUWRJ-UHFFFAOYSA-N 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- JUNWLZAGQLJVLR-UHFFFAOYSA-J calcium diphosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])(=O)OP([O-])([O-])=O JUNWLZAGQLJVLR-UHFFFAOYSA-J 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- GEQHKFFSPGPGLN-UHFFFAOYSA-N cyclohexane-1,3-diamine Chemical compound NC1CCCC(N)C1 GEQHKFFSPGPGLN-UHFFFAOYSA-N 0.000 description 1
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 238000010294 electrolyte impregnation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000007759 kiss coating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 238000007760 metering rod coating Methods 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- NTNWKDHZTDQSST-UHFFFAOYSA-N naphthalene-1,2-diamine Chemical compound C1=CC=CC2=C(N)C(N)=CC=C21 NTNWKDHZTDQSST-UHFFFAOYSA-N 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229940090668 parachlorophenol Drugs 0.000 description 1
- 239000011990 phillips catalyst Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920005678 polyethylene based resin Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 238000007763 reverse roll coating Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- BSWGGJHLVUUXTL-UHFFFAOYSA-N silver zinc Chemical compound [Zn].[Ag] BSWGGJHLVUUXTL-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N tolylenediamine group Chemical group CC1=C(C=C(C=C1)N)N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
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- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
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- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/32—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed at least two layers being foamed and next to each other
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/14—Polyamide-imides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
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- H01M50/411—Organic 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
- 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
- H01M50/446—Composite material consisting of a mixture of organic and inorganic 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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
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- 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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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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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
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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
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- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Cell Separators (AREA)
Description
(1)ポリエチレン系樹脂を含む多孔質膜Aに耐熱性樹脂および無機粒子または架橋高分子粒子を含む多孔質膜Bが積層された電池用セパレータにおいて、多孔質膜Bに含まれる無機粒子または架橋高分子粒子の含有量が80重量%以上98重量%以下であり、
多孔質膜Aが下記式(a)〜(c)を満足し、電池用セパレータ全体が(d)〜(f)を満足する電池用セパレータ。
t(A)は多孔質膜Aの厚さ
0.01μm≦R(A)≦1.0μm ・・・・・式(b)
R(A)は多孔質膜Aの平均孔径
30%≦V(A)≦70% ・・・・・式(c)
V(A)は多孔質膜Aの空孔率
t(T)≦13μm ・・・・・式(d)
t(T)は電池用セパレータの厚さ
F(A/B)≧1.0N/25mm ・・・・・式(e)
F(A/B)は多孔質膜Aと多孔質膜Bの界面での剥離強度
20≦Y−X≦100 ・・・・・式(f)
Xは多孔質膜Aの透気抵抗度(sec/100ccAir)
Yは電池用セパレータ全体の透気抵抗度(sec/100ccAir)
(2)電池用セパレータの透気抵抗度Yが50〜600sec/100ccAirである前記(1)に記載の電池用セパレータ。
(3)耐熱性樹脂がポリアミドイミド樹脂、ポリイミド樹脂又はポリアミド樹脂を含むことを特徴とする前記(1)又は(2)に記載の電池用セパレータ。
(4)以下の工程(i)及び(ii)を含む前記(1)〜(3)のいずれかに記載の電池用セパレータの製造方法。
工程(ii):工程(i)で得られた耐熱性樹脂膜が積層された複合膜を、凝固浴に浸漬させて耐熱性樹脂膜を多孔質膜Bに変換させ、洗浄、乾燥し、電池用セパレータを得る工程
これら粒子の平均粒径はポリエチレン系多孔質膜Aの平均細孔径の1.5倍以上、50倍以下であることが好ましい。さらに好ましくは2.0倍以上、20倍以下である。
ポリエチレン系樹脂からなる多孔質膜A上に耐熱樹脂と無機粒子または架橋高分子粒子を含むワニスを塗布した後、
絶対湿度0.5g/m3以上、絶対湿度6g/m3未満の低湿度ゾーンと
絶対湿度7.0g/m3以上、絶対湿度25.0g/m3未満の高湿度ゾーンを通過させて多孔質膜A上に耐熱性樹脂膜を形成する工程
工程(ii):工程(i)で得られた耐熱性樹脂膜が積層された複合膜を、凝固浴に浸漬させて耐熱性樹脂膜を多孔質膜Bに変換させ、洗浄、乾燥し、電池用セパレータを得る工程
さらに詳細に説明する。
1.膜厚
接触式膜厚計(ソニーマニュファクチュアリングシステムズ(株)製 デジタルマイクロメーター M−30)を使用して測定した。
2.多孔質膜Bの密着性
実施例及び比較例で得られたセパレータの多孔質膜B面に粘着テープ(ニチバン(株)製、405番;24mm幅)を貼り、幅24mm、長さ150mmに裁断し、試験用サンプルを作製した。
3.平均孔径
多孔質膜Aの平均孔径は以下の方法で行った。
4.透気抵抗度
テスター産業(株)製のガーレー式デンソメーターB型を使用して、電池用セラレーターをクランピングプレートとアダプタープレートの間にシワが入らないように固定し、JIS P 8117に従って測定した。試料は10cm角とし、測定点は試料の中央部と4隅の計5点として、その平均値を透気抵抗度[sec/100ccAir]として用いた。
5.対数粘度
耐熱性樹脂0.5gを100mlのNMPに溶解した溶液を25℃でウベローデ粘度管を用いて測定した。
6.融点
エスアイアイ・ナノテクノロジー(株)製の示差走査熱量計(DSC)DSC6220を用い、窒素ガス雰囲気下で樹脂試料5mgを昇温速度20℃/分で昇温したとき観察される融解ピークの頂点温度を融点とした。
7.ガラス転移温度
樹脂溶液、または電池用セパレータを良溶媒に漬けて耐熱性樹脂層のみを溶解させた樹脂溶液を、アプリケーターによってPETフィルム(東洋紡(株)製E5001)あるいはポリプロピレンフィルム(東洋紡(株)製パイレン−OT)に適当なギャップで塗布し、120℃10分間予備乾燥した後に剥離して、適当な大きさの金枠に耐熱粘着テープで固定した状態で、さらに真空下で200℃12時間乾燥し、乾式フィルムを得た。得られた乾式フィルムから幅4mm×長さ21mmの試験片を切り取り、測定長15mmで動的粘弾性測定装置(アイティー計測制御(株)製DVA―220)を用いて、110Hz、昇温速度4℃/分の条件下で室温から450℃までの範囲で測定した時の貯蔵弾性率(E’)の屈折点において、ガラス転移温度以下のベースラインの延長線と、屈折点以上における最大傾斜を示す接線との交点の温度をガラス転移温度とした。
8.空孔率
10cm角の試料を用意し、その試料体積(cm3)と質量(g)を測定し得られた結果から次式を用いて空孔率(%)を計算した。
9.カール性(ソリ)の評価
実施例および比較例で得られた電池用セパレータを幅方向100mm×長手方向300mmの大きさに切り取り、徐電ブラシで十分徐電した後、多孔質膜Bを上にして水平に置かれたガラス板上に置いた。次いで、幅方向の両端10mmを固定し、長手方向端部の浮き上がり高さを両端部についてそれぞれ測定し、平均値を求めた。
実施例A-1
(耐熱性樹脂の合成)
温度計、冷却管、窒素ガス導入管のついた4ツ口フラスコにトリメリット酸無水物(TMA)1モル、o−トリジンジイソシアネート(TODI)0.8モル、2,4−トリレンジイソシアネート(TDI)0.2モル、フッ化カリウム0.01モルを固形分濃度が20%となるようにN−メチル−2−ピロリドンと共に仕込み、100℃で5時間攪拌した後、固形分濃度が14%となるようにN−メチル−2−ピロリドンで希釈してポリアミドイミド樹脂溶液(PI-a)を合成した。得られたポリアミドイミド樹脂の対数粘度は1.35dl/g、ガラス転移温度は320℃であった。
実施例A-2
低湿度ゾーンの絶対湿度を4.0g/m3とした以外は実施例A-1と同様にして電池用セパレータを得た。
実施例A-3
低湿度ゾーンの絶対湿度を5.5g/m3とした以外は実施例A-1と同様にして電池用セパレータを得た。
実施例A-4
高湿度ゾーンの絶対湿度を7.0g/m3とした以外は実施例A-3と同様にして電池用セパレータを得た。
実施例A-5
高湿度ゾーンの絶対湿度を16.0g/m3とした以外は実施例A-3と同様にして電池用セパレータを得た。
実施例A-6
ポリアミドイミド樹脂溶液(PI-a)及び平均粒径0.50μmのアルミナ粒子、N−メチル−2−ピロリドンの配合比率をそれぞれ26:15:59の重量比率とした以外は実施例A-3と同様にして電池用セパレータを得た。
実施例A-7
ポリアミドイミド樹脂溶液(PI-a)及び平均粒径0.50μmのアルミナ粒子、N−メチル−2−ピロリドンの配合比率をそれぞれ15:41:44の重量比率とした以外は実施例A-3と同様にして電池用セパレータを得た。
実施例A-8
多孔質フィルムAとして厚み9.5μm、空孔率40%、平均孔径0.15μm、透気抵抗度300sec/100ccAirのポリエチレン製多孔質フィルムを用いた以外は実施例A-3と同様にして電池用セパレータを得た。
実施例A-9
多孔質フィルムAとして厚み7.0μm、空孔率40%、平均孔径0.15μm、透気抵抗度220sec/100ccAirのポリエチレン製多孔質フィルムを用いた以外は実施例A-3と同様にして電池用セパレータを得た。
実施例A-10
多孔質フィルムAとして厚み5.0μm 空孔率40%、平均孔径0.15μm、透気抵抗度200sec/100ccAirのポリエチレン製多孔質フィルムを用いた以外は実施例A-3と同様にして電池用セパレータを得た。
実施例A-11
ワニスの塗布量を調整し最終厚み10.5μmとした以外は実施例A-3と同様にして電池用セパレータを得た。
実施例A-12
温度計、冷却管、窒素ガス導入管のついた4ツ口フラスコにトリメリット酸無水物(TMA)1モル、o−トリジンジイソシアネート(TODI)0.80モル、ジフェニルメタン−4,4’−ジイソシアネート(MDI)0.20モル、フッ化カリウム0.01モルを固形分濃度が20%となるようにN−メチル−2−ピロリドンと共に仕込み、100℃で5時間攪拌した後、固形分濃度が14%となるようにN−メチル−2−ピロリドンで希釈してポリアミドイミド樹脂溶液(PI-b)を合成した。得られたポリアミドイミド樹脂の対数粘度は1.05dl/g、ガラス転移温度は313℃であった。
実施例A-13
温度計、冷却管、窒素ガス導入管のついた4ツ口フラスコにトリメリット酸無水物(TMA)1モル、o−トリジンジイソシアネート(TODI)0.60モル、ジフェニルメタン−4,4’−ジイソシアネート(MDI)0.40モル、フッ化カリウム0.01モルを固形分濃度が20%となるようにN−メチル−2−ピロリドンと共に仕込み、100℃で5時間攪拌した後、固形分濃度が14%となるようにN−メチル−2−ピロリドンで希釈してポリアミドイミド樹脂溶液(PI-c)を合成した。得られたポリアミドイミド樹脂の対数粘度は0.85dl/g、ガラス転移温度は308℃であった。
実施例A-14
アルミナ粒子を酸化チタン粒子(チタン工業(株)製、商品名:KR−380、平均粒子径0.38μm)に替えたワニスを用いた以外は実施例A-3と同様にして電池用セパレータを得た。
実施例A-15
多孔質フィルムAとして厚み9.0μm、空孔率38%、平均孔径0.15μm、透気抵抗度130sec/100ccAirのポリエチレン製多孔質フィルムを用いた以外は実施例A-3と同様にして電池用セパレータを得た。
実施例A-16
アルミナ粒子を架橋高分子粒子(ポリメタクリル酸メチル系架橋物粒子(製品名“エポスター”(登録商標)MA、タイプ1002、(株)日本触媒製、平均粒子径2.5μm))に替えたワニスを用いた以外は実施例A-3と同様にして電池用セパレータを得た。
実施例A-17
厚み50μmのポリエチレンテレフタレート樹脂フィルム(東洋紡(株)製E5101)のコロナ処理面に実施例1と同様のワニスをブレードコート法にて塗布し、温度25℃、絶対湿度1.8g/m3の低湿度ゾーンを8秒間、引き続き温度25℃、絶対湿度12.0g/m3の高湿度ゾーンを5秒間で通過させ、1.7秒後に多孔質フィルムA(ポリエチレン製、厚み9.0μm、空孔率45%、平均孔径0.15μm、透気抵抗度240sec/100ccAir)を、上記のゲル状耐熱性樹脂面に重ね、N−メチル−2−ピロリドンを5重量%含有する水溶液中に進入させ、その後、純水で洗浄した後、70℃の熱風乾燥炉を通過させることで乾燥し、最終厚み11.5μmの電池用セパレータを得た。
比較例A-1
低湿度ゾーンを絶対湿度7.0g/m3とした以外は実施例A-3と同様にして電池用セパレータを得た。
比較例A-2
高湿度ゾーンの絶対湿度5.0g/m3とした以外は実施例A-3と同様にして電池用セパレータを得た。
比較例A-3
温度計、冷却管、窒素ガス導入管のついた4ツ口フラスコにトリメリット酸無水物(TMA)1モル、o−トリジンジイソシアネート(TODI)0.76モル、2,4−トリレンジイソシアネート(TDI)0.19モル、フッ化カリウム0.01モルを固形分濃度が20%となるようにN−メチル−2−ピロリドンと共に仕込み、100℃で5時間攪拌した後、固形分濃度が14%となるようにN−メチル−2−ピロリドンで希釈してポリアミドイミド樹脂溶液(PI-d)を合成した。得られたポリアミドイミド樹脂の対数粘度は0.45dl/g、ガラス転移温度は315℃であった。
比較例A-4
多孔質膜Aとして厚み10μm、空孔率45%、平均孔径0.15μm、透気抵抗度240sec/100ccAirのポリエチレン製多孔質膜を用い、低加湿ゾーン、高加湿ゾーン共に絶対湿度18.4g/m3とした以外は実施例A-3と同様にして電池用セパレータを得た。
比較例A-5
ワニスの塗布量を調整し、最終厚み14.0μmとした以外は実施例A-3と同様にして電池用セパレータを得た。
Claims (4)
- ポリエチレン系樹脂を含む多孔質膜Aに耐熱性樹脂および無機粒子または架橋高分子粒子を含む多孔質膜Bが積層された電池用セパレータにおいて、多孔質膜Bに含まれる無機粒子または架橋高分子粒子の含有量が80重量%以上98重量%以下であり、
多孔質膜Aが下記式(a)〜(c)を満足し、電池用セパレータ全体が(d)〜(f)を満足する電池用セパレータ。
t(A)<10μm ・・・・・式(a)
t(A)は多孔質膜Aの厚さ
0.01μm≦R(A)≦1.0μm ・・・・・式(b)
R(A)は多孔質膜Aの平均孔径
30%≦V(A)≦70% ・・・・・式(c)
V(A)は多孔質膜Aの空孔率
t(T)≦13μm ・・・・・式(d)
t(T)は電池用セパレータの厚さ
F(A/B)≧1.0N/25mm ・・・・・式(e)
F(A/B)は多孔質膜Aと多孔質膜Bの界面での剥離強度
20≦Y−X≦100 ・・・・・式(f)
Xは多孔質膜Aの透気抵抗度(sec/100ccAir)
Yは電池用セパレータ全体の透気抵抗度(sec/100ccAir) - 電池用セパレータの透気抵抗度Yが50〜600sec/100ccAirである請求項1に記載の電池用セパレータ。
- 耐熱性樹脂がポリアミドイミド樹脂、ポリイミド樹脂又はポリアミド樹脂を含むことを特徴とする請求項1又は2に記載の電池用セパレータ。
- 以下の工程(i)及び(ii)を含む請求項1〜3のいずれかに記載の電池用セパレータの製造方法。
工程(i):ポリエチレン系樹脂からなる多孔質膜A上に耐熱樹脂と無機粒子を含むワニスを塗布した後、絶対湿度0.5g/m3以上、絶対湿度6g/m3未満の低湿度ゾーンと絶対湿度7.0g/m3以上、絶対湿度25.0g/m3未満の高湿度ゾーンを通過させて多孔質膜A上に耐熱性樹脂膜を形成する工程
工程(ii):工程(i)で得られた耐熱性樹脂膜が積層された複合膜を、凝固浴に浸漬させて耐熱性樹脂膜を多孔質膜Bに変換させ、洗浄、乾燥し、電池用セパレータを得る工程
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JP5387871B1 (ja) | 2014-01-15 |
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US20150228949A1 (en) | 2015-08-13 |
WO2013121971A1 (ja) | 2013-08-22 |
JP2013239458A (ja) | 2013-11-28 |
MY167416A (en) | 2018-08-27 |
KR20140046077A (ko) | 2014-04-17 |
CN103797614A (zh) | 2014-05-14 |
JPWO2013121971A1 (ja) | 2015-05-11 |
CN103797614B (zh) | 2015-05-13 |
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