CN111293262A - Composite diaphragm capable of reducing thermal runaway risk of lithium battery, preparation method and lithium battery - Google Patents
Composite diaphragm capable of reducing thermal runaway risk of lithium battery, preparation method and lithium battery Download PDFInfo
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- CN111293262A CN111293262A CN202010191571.3A CN202010191571A CN111293262A CN 111293262 A CN111293262 A CN 111293262A CN 202010191571 A CN202010191571 A CN 202010191571A CN 111293262 A CN111293262 A CN 111293262A
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- Prior art keywords
- lithium battery
- polyethylene
- coating material
- sodium
- ethylene
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 51
- 239000002131 composite material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 109
- 238000000576 coating method Methods 0.000 claims abstract description 75
- 239000011248 coating agent Substances 0.000 claims abstract description 74
- 239000002270 dispersing agent Substances 0.000 claims abstract description 24
- 229920000642 polymer Polymers 0.000 claims abstract description 15
- 239000011230 binding agent Substances 0.000 claims abstract description 14
- 210000002469 basement membrane Anatomy 0.000 claims abstract description 12
- 239000002861 polymer material Substances 0.000 claims abstract description 12
- 238000011049 filling Methods 0.000 claims abstract description 11
- -1 polyethylene Polymers 0.000 claims description 98
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 51
- 239000004743 Polypropylene Substances 0.000 claims description 39
- 229920001155 polypropylene Polymers 0.000 claims description 33
- 239000004698 Polyethylene Substances 0.000 claims description 32
- 239000012528 membrane Substances 0.000 claims description 30
- 210000004379 membrane Anatomy 0.000 claims description 30
- 229920000573 polyethylene Polymers 0.000 claims description 28
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 27
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 27
- 239000002033 PVDF binder Substances 0.000 claims description 26
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 24
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 22
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 22
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 21
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 21
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 20
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 20
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 19
- 239000002202 Polyethylene glycol Substances 0.000 claims description 16
- 229920001223 polyethylene glycol Polymers 0.000 claims description 16
- 239000000919 ceramic Substances 0.000 claims description 15
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 15
- 239000006255 coating slurry Substances 0.000 claims description 14
- 239000004814 polyurethane Substances 0.000 claims description 14
- 239000004816 latex Substances 0.000 claims description 13
- 229920000126 latex Polymers 0.000 claims description 13
- 239000011118 polyvinyl acetate Substances 0.000 claims description 13
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 12
- 239000012752 auxiliary agent Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000004642 Polyimide Substances 0.000 claims description 11
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 11
- 229920001721 polyimide Polymers 0.000 claims description 11
- 229920002635 polyurethane Polymers 0.000 claims description 11
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 11
- 239000004709 Chlorinated polyethylene Substances 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 229920002319 Poly(methyl acrylate) Polymers 0.000 claims description 10
- 229920002367 Polyisobutene Polymers 0.000 claims description 10
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- 230000002378 acidificating effect Effects 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 239000000835 fiber Substances 0.000 claims description 10
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 10
- 229920002401 polyacrylamide Polymers 0.000 claims description 10
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 10
- 229920001610 polycaprolactone Polymers 0.000 claims description 10
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 10
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 10
- 229920002620 polyvinyl fluoride Polymers 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 10
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 10
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 10
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 claims description 10
- 239000004793 Polystyrene Substances 0.000 claims description 9
- 229920001971 elastomer Polymers 0.000 claims description 9
- 239000004417 polycarbonate Substances 0.000 claims description 9
- 239000004800 polyvinyl chloride Substances 0.000 claims description 9
- 239000005033 polyvinylidene chloride Substances 0.000 claims description 9
- 239000004952 Polyamide Substances 0.000 claims description 8
- 229920001328 Polyvinylidene chloride Polymers 0.000 claims description 8
- 239000002174 Styrene-butadiene Substances 0.000 claims description 8
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 8
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 8
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 8
- 229920002492 poly(sulfone) Polymers 0.000 claims description 8
- 229920002647 polyamide Polymers 0.000 claims description 8
- 239000004632 polycaprolactone Substances 0.000 claims description 8
- 229920001451 polypropylene glycol Polymers 0.000 claims description 8
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 8
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 8
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 8
- 239000011115 styrene butadiene Substances 0.000 claims description 8
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 8
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 7
- 239000011256 inorganic filler Substances 0.000 claims description 7
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 7
- 229920000515 polycarbonate Polymers 0.000 claims description 7
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 7
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 6
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 claims description 6
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 6
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000005642 Oleic acid Substances 0.000 claims description 6
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 6
- 229920002223 polystyrene Polymers 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 5
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 5
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 5
- 229920001479 Hydroxyethyl methyl cellulose Polymers 0.000 claims description 5
- 229910010093 LiAlO Inorganic materials 0.000 claims description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 5
- 229920002125 Sokalan® Polymers 0.000 claims description 5
- 239000000853 adhesive Substances 0.000 claims description 5
- 230000001070 adhesive effect Effects 0.000 claims description 5
- 150000003973 alkyl amines Chemical class 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 5
- 150000001408 amides Chemical class 0.000 claims description 5
- 229940077388 benzenesulfonate Drugs 0.000 claims description 5
- VBICKXHEKHSIBG-UHFFFAOYSA-N beta-monoglyceryl stearate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 claims description 5
- 229910001593 boehmite Inorganic materials 0.000 claims description 5
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 claims description 5
- YWDYRRUFQXZJBG-UHFFFAOYSA-N butyl prop-2-enoate;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.CCCCOC(=O)C=C YWDYRRUFQXZJBG-UHFFFAOYSA-N 0.000 claims description 5
- 229910052570 clay Inorganic materials 0.000 claims description 5
- 239000004927 clay Substances 0.000 claims description 5
- 229910052681 coesite Inorganic materials 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 5
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims description 5
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 5
- 239000000806 elastomer Substances 0.000 claims description 5
- VAYDQPPHPFGABZ-UHFFFAOYSA-N ethene prop-2-enoic acid Chemical compound C=C.C=C.OC(=O)C=C.OC(=O)C=C VAYDQPPHPFGABZ-UHFFFAOYSA-N 0.000 claims description 5
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 claims description 5
- 229920006226 ethylene-acrylic acid Polymers 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 5
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 5
- 230000001788 irregular Effects 0.000 claims description 5
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 5
- 229920001684 low density polyethylene Polymers 0.000 claims description 5
- 239000004702 low-density polyethylene Substances 0.000 claims description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 5
- 239000004745 nonwoven fabric Substances 0.000 claims description 5
- 239000011368 organic material Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 5
- 229920002627 poly(phosphazenes) Polymers 0.000 claims description 5
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims description 5
- 239000004584 polyacrylic acid Substances 0.000 claims description 5
- 229920000570 polyether Polymers 0.000 claims description 5
- 229920001195 polyisoprene Polymers 0.000 claims description 5
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 5
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 5
- 229920005614 potassium polyacrylate Polymers 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 229920002545 silicone oil Polymers 0.000 claims description 5
- 239000000661 sodium alginate Substances 0.000 claims description 5
- 235000010413 sodium alginate Nutrition 0.000 claims description 5
- 229940005550 sodium alginate Drugs 0.000 claims description 5
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 5
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 5
- 239000007784 solid electrolyte Substances 0.000 claims description 5
- 229910052682 stishovite Inorganic materials 0.000 claims description 5
- 229920001909 styrene-acrylic polymer Polymers 0.000 claims description 5
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 claims description 5
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 5
- 229910052905 tridymite Inorganic materials 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000005060 rubber Substances 0.000 claims description 4
- 238000003851 corona treatment Methods 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229920001903 high density polyethylene Polymers 0.000 claims 2
- 239000004700 high-density polyethylene Substances 0.000 claims 2
- 239000012994 photoredox catalyst Substances 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002671 adjuvant Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- 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
-
- 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
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
-
- 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
Abstract
The embodiment of the invention relates to a composite diaphragm for reducing the thermal runaway risk of a lithium battery, a preparation method and the lithium battery. The composite separator includes: a base film of 1um to 50um and one or more layers of coating materials of 0.5um to 10um coated on one or both sides of the base film; the coating material is coated on the surface of the basement membrane or coated on the surface of the basement membrane and permeated into the basement membrane; each layer of coating material comprises the following components in percentage by mass: 1-99.98 wt% of polymer heat-sensitive material, 0-80 wt% of inorganic filling material, 0-98.98 wt% of coating material, 0.01-10 wt% of binder, 0-2 wt% of dispersing agent and 0-2 wt% of adjuvant, in which the heat-sensitive polymer material is a polymer material which can be softened at a specific temp. and above, and can make the coating material be softened with it, and the heat-sensitive polymer material can be softened to produce volume expansion greater than or equal to 5%, and its specific temp. is 80 deg.C, and all the components in the coating material can be uniformly distributed, layer-by-layer distributed, gradient distributed or non-uniformly distributed.
Description
Technical Field
The invention relates to the technical field of secondary batteries, in particular to a composite diaphragm for reducing the thermal runaway risk of a lithium battery, a preparation method and the lithium battery.
Background
The safety problem is always the first difficult problem in the research and development of power lithium ion batteries, and the safety problem of the power lithium batteries becomes the focus of attention along with the frequent occurrence of battery fire, explosion accidents and the like.
The thermal stability of the battery material is an important factor of the safety of the power lithium battery, and when the battery is charged, the metallic lithium surface deposition is easy to coalesce into branch-shaped lithium crystal branches, so that the diaphragm is pierced to cause the short circuit of the positive electrode and the negative electrode. And the metallic lithium is very active, can directly react with the electrolyte to release heat, has low melting point, and can be dissolved to cause short circuit only at a slightly high temperature even if the metallic lithium crystal branches on the surface do not pierce the diaphragm. Therefore, the lithium battery separator plays a very important role in preventing thermal runaway.
The lithium battery diaphragm is mainly applied to a traditional liquid lithium ion battery, is an important component of the liquid lithium ion battery, and mainly has the function of isolating positive and negative pole pieces of the lithium ion battery, preventing the positive and negative pole pieces from contacting and short-circuiting and playing a role of lithium ion transmission. The performance of the diaphragm has a decisive influence on the interface structure of the whole battery system and directly influences the capacity, the cycle and the safety performance of the battery, so that the optimization of the diaphragm also plays an important role in improving the comprehensive performance of the battery.
The most widely used composite membrane diaphragm of polypropylene/polyethylene/polypropylene (PP/PE/PP) in the current market still has the safety problems of instability at high temperature, thermal deformation, further thermal runaway and the like; the prior art aims to improve the defects of the prior art and coats a layer of ceramic material on the surface of the separator, but the internal resistance of the battery is inevitably increased and the energy density of the battery is reduced while the thermal stability and the mechanical strength of the separator are improved.
Disclosure of Invention
The invention aims to provide a composite diaphragm for reducing the thermal runaway risk of a lithium battery, a preparation method and the lithium battery.
To this end, in a first aspect, an embodiment of the present invention provides a composite separator for reducing a risk of thermal runaway of a lithium battery, including: a base film of 1um to 50um and one or more layers of coating materials of 0.5um to 10um coated on one or both sides of the base film; the coating material is coated on the surface of the basement membrane or coated on the surface of the basement membrane and permeated into the basement membrane;
the coating material comprises the following components in percentage by mass: 1-99.98 wt% of polymer heat sensitive material, 0-80 wt% of inorganic filling material, 0-98.98 wt% of coating material, 0.01-10 wt% of binder, 0-2 wt% of dispersing agent and 0-2 wt% of auxiliary agent;
wherein the heat-sensitive polymer material is a polymer material which softens at a specific temperature or above and causes the coating material to soften therewith; softening the heat sensitive polymer material to generate volume expansion of more than or equal to 5 percent; the specific temperature is 80 ℃;
the components in the coating material are uniformly distributed, layered distributed, gradient distributed or non-uniformly distributed.
Preferably, when the coating material is a multi-layer, the softening temperature of the coating material located at the inner layer is higher than the softening temperature of the coating material located at the outer layer.
Preferably, the heat-sensitive material specifically includes: polyethylene oxide PEO, polyacrylonitrile PAN, polyvinylidene fluoride PVDF, polymethyl methacrylate PMMA, polypropylene oxide PPO, polyvinylidene chloride PVDC, polyvinyl chloride PVC, ethylene-vinyl acetate copolymer EVA, high-pressure polyethylene LDPE, high-pressure polyethylene HDPE, polystyrene PS, polyamide PA, polyimide PI, polymethyl acrylate PMA, polyvinyl alcohol PVA, polyvinyl fluoride PVF, polyethylene terephthalate PET, polybutylene terephthalate fiber PBT, polyethylene glycol PEG, ethylene acrylic acid-ethylene acrylic acid copolymer EAA, ethylene-octene copolymer POE, chlorinated polyethylene CPE, thermoplastic polyurethane elastomer rubber TPU, polysulfone PSF, polycarbonate PC, polytetrafluoroethylene PTFE, polycaprolactone PCL, polyurethane PU, polyisoprene PI, polyisobutylene PIB, ethylene-vinyl alcohol copolymer EVAL, polybutadiene-styrene PBS and polyvinyl acetate PVAC materials;
the inorganic filler material comprises Al of inert ceramic oxide class2O3、TiO2、MgO、SiO2AlBr of Lewis acidic inorganic Compounds3、AlCl3BaTiO of ferroelectric ceramic material3ZrO of acidic oxides2Succinonitrile SN, polyphosphazene PZS, zirconyl sulfonate Zr-O-SO4、MgOAl2O4LiAlO of the lithium oxide type2、Li2O, polyvinylidene fluoride PVDF and polymethyl methacrylate PMMA which are organic materials, and one or more of clay, montmorillonite and boehmite;
the adhesive comprises: one or more of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, polytetrafluoroethylene, polymethyl methacrylate, polyacrylonitrile, styrene-butadiene latex, styrene-acrylic latex, polyvinyl alcohol, ethylene-vinyl acetate, sodium alginate, polyacrylamide, polymethyl methacrylate-butyl acrylate, ethylene-vinyl acetate copolymer, polyvinyl acetate, polyurethane, hydroxyethyl cellulose, methyl hydroxyethyl cellulose, sodium carboxymethyl cellulose, polyacrylamide, polyethylene oxide and polytetrafluoroethylene are mixed;
the dispersing agent comprises one or more of stearic acid monoglyceride, tristearin, oleic acid acyl, sodium polyacrylate, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium hexametaphosphate, polyacrylic acid, cetyl trimethyl ammonium bromide, polyethylene glycol, potassium polyacrylate, octyl phenol polyoxyethylene or sulfonate fluorine dispersing agent;
the auxiliary agent comprises one or a combination of more of polydimethylsiloxane, silicone oil, polyethers, sodium polyacrylate, polyvinyl alcohol, alkyl polyoxyethylene ether sodium carboxylate, polyoxyethylene alkylphenol ether, sodium alkyl benzene sulfonate, alkylphenol polyoxyethylene, polyoxyethylene alkylamine and polyoxyethylene amide;
the coating material comprises: nano alumina and nano zirconia;
the base membrane comprises one or more composite membranes of a polypropylene PP membrane, a polyethylene PE membrane, a polypropylene/polyethylene/polypropylene PP/PE/PP composite membrane, a non-woven fabric diaphragm, a fiber diaphragm and a ceramic diaphragm solid electrolyte diaphragm.
Preferably, the shape of the inorganic filling material is spherical, ellipsoidal, rod-shaped, flaky or irregular polygonal particles, and the size of the inorganic filling material is 50nm-5000 nm.
In a second aspect, an embodiment of the present invention provides a preparation method of a composite separator for reducing a risk of thermal runaway of a lithium battery, where the preparation method includes:
adding an inorganic filling material, a dispersing agent, a binder, an auxiliary agent and a solvent into a pre-stirring tank according to a required proportion, and completely dissolving to obtain a first mixture;
gradually adding a polymer heat-sensitive material and a coating material into the first mixture according to a required proportion, and stirring and dispersing at a stirring speed of 10-50rpm and a dispersion speed of 1000-5000rpm to obtain a second mixture;
filtering the second mixture by using a screen to obtain coating slurry;
coating the coating slurry on one side or two sides of a base film at the speed of 1-100 m/min, and drying at the temperature of 40-100 ℃ to obtain the composite diaphragm.
Preferably, before the coating slurry is applied to one side or both sides of the base film at a speed of 1m/min to 100m/min, the method further comprises: and carrying out corona treatment on the base film.
Preferably, the heat-sensitive material specifically includes: polyethylene oxide PEO, polyacrylonitrile PAN, polyvinylidene fluoride PVDF, polymethyl methacrylate PMMA, polypropylene oxide PPO, polyvinylidene chloride PVDC, polyvinyl chloride PVC, ethylene-vinyl acetate copolymer EVA, high-pressure polyethylene LDPE, high-pressure polyethylene HDPE, polystyrene PS, polyamide PA, polyimide PI, polymethyl acrylate PMA, polyvinyl alcohol PVA, polyvinyl fluoride PVF, polyethylene terephthalate PET, polybutylene terephthalate fiber PBT, polyethylene glycol PEG, ethylene acrylic acid-ethylene acrylic acid copolymer EAA, ethylene-octene copolymer POE, chlorinated polyethylene CPE, thermoplastic polyurethane elastomer rubber TPU, polysulfone PSF, polycarbonate PC, polytetrafluoroethylene PTFE, polycaprolactone PCL, polyurethane PU, polyisoprene PI, polyisobutylene PIB, ethylene-vinyl alcohol copolymer EVAL, polybutadiene-styrene PBS and polyvinyl acetate PVAC materials;
the inorganic filler material comprises Al of inert ceramic oxide class2O3、TiO2、MgO、SiO2AlBr of Lewis acidic inorganic Compounds3、AlCl3BaTiO of ferroelectric ceramic material3ZrO of acidic oxides2Succinonitrile SN, polyphosphazene PZS, zirconyl sulfonate Zr-O-SO4、MgOAl2O4LiAlO of the lithium oxide type2、Li2O, polyvinylidene fluoride PVDF and polymethyl methacrylate PMMA which are organic materials, and one or more of clay, montmorillonite and boehmite;
the adhesive comprises: one or more of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, polytetrafluoroethylene, polymethyl methacrylate, polyacrylonitrile, styrene-butadiene latex, styrene-acrylic latex, polyvinyl alcohol, ethylene-vinyl acetate, sodium alginate, polyacrylamide, polymethyl methacrylate-butyl acrylate, ethylene-vinyl acetate copolymer, polyvinyl acetate, polyurethane, hydroxyethyl cellulose, methyl hydroxyethyl cellulose, sodium carboxymethyl cellulose, polyacrylamide, polyethylene oxide and polytetrafluoroethylene are mixed;
the dispersing agent comprises one or more of stearic acid monoglyceride, tristearin, oleic acid acyl, sodium polyacrylate, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium hexametaphosphate, polyacrylic acid, cetyl trimethyl ammonium bromide, polyethylene glycol, potassium polyacrylate, octyl phenol polyoxyethylene or sulfonate fluorine dispersing agent;
the auxiliary agent comprises one or a combination of more of polydimethylsiloxane, silicone oil, polyethers, sodium polyacrylate, polyvinyl alcohol, alkyl polyoxyethylene ether sodium carboxylate, polyoxyethylene alkylphenol ether, sodium alkyl benzene sulfonate, alkylphenol polyoxyethylene, polyoxyethylene alkylamine and polyoxyethylene amide;
the coating material comprises: nano alumina and nano zirconia;
the base membrane comprises one or more composite membranes of a polypropylene PP membrane, a polyethylene PE membrane, a polypropylene/polyethylene/polypropylene PP/PE/PP composite membrane, a non-woven fabric diaphragm, a fiber diaphragm and a ceramic diaphragm solid electrolyte diaphragm.
Further preferably, the shape of the inorganic filling material is spherical, ellipsoidal, rod-like, sheet-like or irregular polygonal particles, and the size is 50nm-5000 nm.
In a third aspect, an embodiment of the present invention provides a lithium battery with a composite diaphragm for reducing a risk of thermal runaway of the lithium battery in the first aspect, where the lithium battery includes any one of a liquid lithium battery, a semi-solid lithium battery, a quasi-solid lithium battery, an all-solid lithium battery, and a metal lithium battery.
The composite diaphragm provided by the embodiment of the invention comprises the thermal sensitive polymer coating material coated on one side or two sides of the base film, and when the battery is at a certain higher temperature, the coating material coated on the surface of the diaphragm is softened, internal pores are closed, and lithium ion transmission is blocked, so that thermal runaway can be effectively prevented, and the safety performance of the lithium battery is greatly improved.
Drawings
FIG. 1 is a scanning electron microscope image of the composite diaphragm prepared in example 1 and used for reducing the thermal runaway risk of the lithium battery;
FIG. 2 is a flow chart of a method for preparing a composite separator for reducing the risk of thermal runaway of a lithium battery according to the present invention;
fig. 3 is a graph showing the change of the resistance of the separators according to examples 1 and 2 of the present invention and comparative example 1 with temperature.
Detailed Description
The technical solution of the present invention is further described in detail by the accompanying drawings and embodiments.
The embodiment of the invention provides a composite diaphragm for reducing the thermal runaway risk of a lithium battery, and fig. 1 is a scanning electron microscope image of the composite diaphragm prepared in the following embodiment 1.
The composite diaphragm provided by the embodiment of the invention comprises: a base film of 1um to 50um and one or more layers of coating materials of 0.5um to 10um coated on one or both sides of the base film; wherein, the coating material is coated on the surface of the basement membrane or coated on the surface of the basement membrane and permeated into the basement membrane;
the coating material comprises the following components in percentage by mass: 1-99.98 wt% of polymer heat sensitive material, 0-80 wt% of inorganic filling material, 0-98.98 wt% of coating material, 0.01-10 wt% of binder, 0-2 wt% of dispersant and 0-2 wt% of assistant;
wherein the heat-sensitive polymer material is a polymer material which softens at a specific temperature of 80 ℃ or above and causes the coating material to soften therewith; softening the heat sensitive polymer material to generate volume expansion of more than or equal to 5 percent; when the coating material is multi-layered, the softening temperature of the coating material located at the inner layer is higher than the softening temperature of the coating material of the outer layer.
The components in the coating material are respectively distributed uniformly, in layers, in gradients or non-uniformly.
The base film may include: polypropylene (PP) membrane, Polyethylene (PE) membrane, polypropylene/polyethylene/polypropylene (PP/PE/PP) composite membrane, non-woven fabric diaphragm, fiber diaphragm, ceramic diaphragm, solid electrolyte diaphragm, or a combination thereof.
Among the components of the above coating material:
the heat-sensitive material specifically includes: polyethylene oxide (PEO), Polyacrylonitrile (PAN), polyvinylidene fluoride (PVDF), polymethyl methacrylate (PMMA), polypropylene oxide (PPO), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), ethylene-vinyl acetate copolymer (EVA), high-pressure polyethylene (LDPE), high-pressure polyethylene (HDPE), Polystyrene (PS), Polyamide (PA), Polyimide (PI), polymethyl acrylate (PMA), polyvinyl alcohol (PVA), polyvinyl fluoride (PVF), polyethylene terephthalate (PET), polybutylene terephthalate fiber (PBT), polyethylene glycol (PEG), ethylene acrylic acid-ethylene acrylic acid copolymer (EAA), ethylene-octene copolymer (POE), Chlorinated Polyethylene (CPE), thermoplastic polyurethane elastomer (TPU), Polysulfone (PSF), Polycarbonate (PC), Polytetrafluoroethylene (PTFE), One or more of Polycaprolactone (PCL), Polyurethane (PU), Polyisoprene (PI), Polyisobutylene (PIB), ethylene-vinyl alcohol copolymer (EVA L), polybutadiene-styrene (PBS) and polyvinyl acetate (PVAC) materials;
the inorganic filler material comprises Al of the class of inert ceramic oxides2O3、TiO2、MgO、SiO2AlBr of Lewis acidic inorganic Compounds3、AlCl3BaTiO of ferroelectric ceramic material3ZrO of acidic oxides2Succinonitrile (SN), Polyphosphazene (PZS), zirconyl sulfonate Zr-O-SO4、MgOAl2O4LiAlO of the lithium oxide type2、Li2O, polyvinylidene fluoride (PVDF) of organic materials, polymethyl methacrylate (PMMA), and one or more combinations of clay, montmorillonite, boehmite; the shape of the organic filling material is spherical, ellipsoidal, rod-shaped, flaky or irregular polygonal particles, and the size is 50nm-5000 nm.
The adhesive comprises: one or more of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, polytetrafluoroethylene, polymethyl methacrylate, polyacrylonitrile, styrene-butadiene latex, styrene-acrylic latex, polyvinyl alcohol, ethylene-vinyl acetate, sodium alginate, polyacrylamide, polymethyl methacrylate-butyl acrylate, ethylene-vinyl acetate copolymer, polyvinyl acetate, polyurethane, hydroxyethyl cellulose, methyl hydroxyethyl cellulose, sodium carboxymethyl cellulose, polyacrylamide, polyethylene oxide and polytetrafluoroethylene are mixed;
the dispersant comprises one or more of stearic acid monoglyceride, tristearin, oleic acid acyl, sodium polyacrylate, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium hexametaphosphate, polyacrylic acid, cetyl trimethyl ammonium bromide, polyethylene glycol, potassium polyacrylate, octyl phenol polyoxyethylene or sulfonate fluorine dispersant;
the auxiliary agent comprises one or more of polydimethylsiloxane, silicone oil, polyethers, sodium polyacrylate, polyvinyl alcohol, alkyl polyoxyethylene ether sodium carboxylate, polyoxyethylene alkylphenol ether, sodium alkyl benzene sulfonate, alkylphenol polyoxyethylene, polyoxyethylene alkylamine or polyoxyethylene amide;
the coating material comprises: nano alumina and nano zirconia;
when the temperature of the battery is higher than the softening temperature, the coating material coated on the surface of the diaphragm is softened, the internal pores are closed, and the lithium ion transmission is blocked, so that the occurrence of thermal runaway can be effectively prevented, and the safety performance of the lithium battery is greatly improved.
The material of the invention is prepared by the method flow shown in figure 2. According to FIG. 2, the preparation method comprises the following steps:
and step 140, coating the coating slurry on one side or two sides of the base film at the speed of 1-100 m/min, and drying at the temperature of 40-100 ℃ to obtain the composite diaphragm.
Wherein, before the coating slurry is coated on one side or two sides of the base film at the speed of 1-100 m/min, the base film can be subjected to corona treatment.
In the case of a composite separator prepared with multiple layers of coating materials, the above steps 120 and 130 may prepare a second mixture having different softening temperatures multiple times. Then, in step 140, a plurality of separate coatings are applied.
During the drying process of step 140, a portion of the components of the material will preferentially deposit, and thus the components will be uniformly distributed, layered, graded, or non-uniformly distributed in the coating material, respectively.
It is further noted that in some implementations, the addition of the polymeric heat sensitive material may also be performed at step 110.
In order to better explain the technical scheme of the invention, some specific examples are described below.
Example 1
The embodiment provides a composite diaphragm for reducing the thermal runaway risk of a lithium battery, which comprises a base film and a coating material coated on the base film and permeated into the base film. Wherein the base film is polypropylene porous membrane, and thickness is 10um, and the single face coating mode is adopted in the coating, and coating thickness includes according to the mass ratio at 4um, coating slurry: 20% of the composition and 80% of deionized water; wherein the composition is prepared according to the mass ratio: 90% of polymer heat sensitive material, 6% of coating material, 1.5% of binder, 1.5% of dispersant and 1% of auxiliary agent.
In the example, the polymer heat-sensitive material is polyethylene oxide (PEO), the coating material is nano alumina, and the binder is prepared by mixing the following components in a mass ratio of 1: 2, sodium carboxymethylcellulose and styrene-butadiene latex, wherein the dispersing agent is prepared from the following components in a mass ratio of 2: 1, sodium dodecyl benzene sulfonate and octyl phenol polyoxyethylene, and polyvinyl alcohol as an auxiliary agent.
The composite diaphragm in the embodiment is prepared by the following method, and the method comprises the following specific steps:
(1) adding sodium carboxymethyl cellulose as a binder, styrene-butadiene latex, sodium dodecyl benzene sulfonate as a dispersant, octylphenol polyoxyethylene as an auxiliary agent, polyvinyl alcohol and deionized water into a pre-stirring tank according to the proportion, and completely dissolving to obtain a mixture I;
(2) gradually adding a polymer heat-sensitive material polyethylene oxide (PEO) and a coating material nano-alumina into the mixture I, stirring and dispersing for 4 hours at a stirring rotating speed of 50rpm and for 4 hours at a dispersing rotating speed of 3000rpm to obtain a mixture II;
(3) filtering the mixture II by using a 400-mesh screen to obtain coating slurry;
(4) and coating the coating slurry on one surface of a base film at a coating speed of 5m/min, drying at 50 ℃, and drying to obtain the composite diaphragm for reducing the thermal runaway risk of the lithium battery.
Example 2
The embodiment provides a composite diaphragm for reducing the thermal runaway risk of a lithium battery, which comprises a base film and a coating material coated on the base film and permeated into the base film. Wherein the base film is polypropylene porous membrane, and thickness is 10um, and the single face coating mode is adopted in the coating, and coating thickness is at 4um, and coating slurry mass ratio is: 30% of the composition and 70% of deionized water; wherein the composition is prepared according to the mass ratio: 10% of polymer heat sensitive material, 86% of coating material, 2% of binder and 2% of dispersing agent.
In the example, the polymer heat sensitive material is Polyacrylonitrile (PAN), the coating material is nano alumina, and the binder is a mixture of 1: 1, sodium carboxymethylcellulose and styrene-butadiene latex, wherein the dispersing agent is prepared from the following components in a mass ratio of 1: 1 sodium polyacrylate and polyethylene glycol.
The method of preparing the composite separator was the same as in example 1.
Example 3
The embodiment provides a composite diaphragm for reducing the thermal runaway risk of a lithium battery, which comprises a base film and a coating material coated on the base film and permeated into the base film. Wherein the base film is polypropylene porous membrane, and thickness is 10um, and the single face coating mode is adopted in the coating, and coating thickness is at 4um, and coating slurry mass ratio is: 30% of the composition and 70% of N-methylpyrrolidone; wherein the composition is prepared according to the mass ratio: 90% of polymer heat sensitive material, 6% of coating material, 2% of binder and 2% of dispersing agent.
In this example, the polymeric heat sensitive material is 1: 1 Polyacrylonitrile (PAN) and polymethyl methacrylate (PMMA), the coating material is nano zirconia, the binder is polyvinylidene fluoride, and the dispersant is oleic acid acyl.
The method of preparing the composite separator was the same as in example 1.
Comparative example 1
This comparative example provides a polypropylene porous membrane coated with alumina on one side, the thickness of the base membrane being 10um, and the alumina coating being 4 um.
Comparative example 2
The separator of this comparative example was a polypropylene porous film.
The separators provided in the above examples and comparative examples were tested for stability at different high temperatures according to the same assembly conditions.
Table 1 shows the results of the air permeability test at different temperatures for the inventive example and the comparative example.
Table 2 shows the comparison of the properties of example 1 and example 2 according to the invention with comparative example 1.
| Closed cell temperature | Closed pore resistance | Temperature of film rupture | Resistance value of rupture of membrane | |
| Example 1 | 143.4 | 1019.06 | 154.6 | 1001.88 |
| Example 2 | 141.3 | 1002.89 | 168.6 | 13477 |
| Comparative example 1 | 161.5 | 1068.1 | 169.3 | 1003.59 |
From table 1 and table 2, it can be seen that the composite diaphragm provided by the embodiment of the present invention has good high temperature stability, and can avoid thermal runaway.
Fig. 3 is a graph showing the change of the resistance of the separator according to the present invention with temperature in examples 1 and 2 and comparative example 1, and it can be seen that the temperature of the different examples and comparative examples has an influence on the electrochemical performance. Both example 1 and example 2 had lower closed cell temperatures than comparative example 1. Having a lower closed cell temperature indicates that the separator will close the cells earlier during the temperature rise of the cell, rapidly increasing the internal resistance of the cell and cutting off the transport of lithium ions. The battery is prevented from further thermal runaway, so that the battery has better safety performance and can effectively prevent the thermal runaway.
The composite diaphragm provided by the embodiment of the invention comprises the thermal sensitive polymer coating material coated on one side or two sides of the base film, and when the battery is at a certain higher temperature, the coating material coated on the surface of the diaphragm is softened, internal pores are closed, and lithium ion transmission is blocked, so that thermal runaway can be effectively prevented, and the safety performance of the lithium battery is greatly improved.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (9)
1. A composite separator for reducing the risk of thermal runaway in a lithium battery, the composite separator comprising: a base film of 1um to 50um and one or more layers of coating materials of 0.5um to 10um coated on one or both sides of the base film; the coating material is coated on the surface of the basement membrane or coated on the surface of the basement membrane and permeated into the basement membrane;
the coating material comprises the following components in percentage by mass: 1-99.98 wt% of polymer heat sensitive material, 0-80 wt% of inorganic filling material, 0-98.98 wt% of coating material, 0.01-10 wt% of binder, 0-2 wt% of dispersant and 0-2 wt% of assistant;
wherein the heat-sensitive polymer material is a polymer material which softens at a specific temperature or above and causes the coating material to soften therewith; softening the heat sensitive polymer material to generate volume expansion of more than or equal to 5 percent; the specific temperature is 80 ℃;
the components in the coating material are uniformly distributed, layered distributed, gradient distributed or non-uniformly distributed.
2. The composite separator for reducing the risk of thermal runaway of a lithium battery as claimed in claim 1, wherein when the coating material is multi-layered, the softening temperature of the coating material located at the inner layer is higher than the softening temperature of the coating material located at the outer layer.
3. The composite separator for reducing the risk of thermal runaway in a lithium battery as claimed in claim 1,
the heat-sensitive material specifically includes: polyethylene oxide PEO, polyacrylonitrile PAN, polyvinylidene fluoride PVDF, polymethyl methacrylate PMMA, polypropylene oxide PPO, polyvinylidene chloride PVDC, polyvinyl chloride PVC, ethylene-vinyl acetate copolymer EVA, high-pressure polyethylene LDPE, high-pressure polyethylene HDPE, polystyrene PS, polyamide PA, polyimide PI, polymethyl acrylate PMA, polyvinyl alcohol PVA, polyvinyl fluoride PVF, polyethylene terephthalate PET, polybutylene terephthalate fiber PBT, polyethylene glycol PEG, ethylene acrylic acid-ethylene acrylic acid copolymer EAA, ethylene-octene copolymer POE, chlorinated polyethylene CPE, thermoplastic polyurethane elastomer rubber TPU, polysulfone PSF, polycarbonate PC, polytetrafluoroethylene PTFE, polycaprolactone PCL, polyurethane PU, polyisoprene PI, polyisobutylene PIB, ethylene-vinyl alcohol copolymer EVAL, polybutadiene-styrene PBS and polyvinyl acetate PVAC materials;
the inorganic filler material comprises Al of inert ceramic oxide class2O3、TiO2、MgO、SiO2AlBr of Lewis acidic inorganic Compounds3、AlCl3BaTiO of ferroelectric ceramic material3ZrO of acidic oxides2Succinonitrile SN, polyphosphazene PZS, zirconyl sulfonate Zr-O-SO4、MgOAl2O4LiAlO of the lithium oxide type2、Li2O, polyvinylidene fluoride PVDF and polymethyl methacrylate PMMA which are organic materials, and one or more of clay, montmorillonite and boehmite;
the adhesive comprises: one or more of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, polytetrafluoroethylene, polymethyl methacrylate, polyacrylonitrile, styrene-butadiene latex, styrene-acrylic latex, polyvinyl alcohol, ethylene-vinyl acetate, sodium alginate, polyacrylamide, polymethyl methacrylate-butyl acrylate, ethylene-vinyl acetate copolymer, polyvinyl acetate, polyurethane, hydroxyethyl cellulose, methyl hydroxyethyl cellulose, sodium carboxymethyl cellulose, polyacrylamide, polyethylene oxide and polytetrafluoroethylene are mixed;
the dispersing agent comprises one or more of stearic acid monoglyceride, tristearin, oleic acid acyl, sodium polyacrylate, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium hexametaphosphate, polyacrylic acid, cetyl trimethyl ammonium bromide, polyethylene glycol, potassium polyacrylate, octyl phenol polyoxyethylene or sulfonate fluorine dispersing agent;
the auxiliary agent comprises one or a combination of more of polydimethylsiloxane, silicone oil, polyethers, sodium polyacrylate, polyvinyl alcohol, alkyl polyoxyethylene ether sodium carboxylate, polyoxyethylene alkylphenol ether, sodium alkyl benzene sulfonate, alkylphenol polyoxyethylene, polyoxyethylene alkylamine and polyoxyethylene amide;
the coating material comprises: nano alumina and nano zirconia;
the base membrane comprises one or more composite membranes of a polypropylene PP membrane, a polyethylene PE membrane, a polypropylene/polyethylene/polypropylene PP/PE/PP composite membrane, a non-woven fabric diaphragm, a fiber diaphragm and a ceramic diaphragm solid electrolyte diaphragm.
4. The composite separator for reducing the risk of thermal runaway of a lithium battery as claimed in claim 3, wherein the morphology of the inorganic filler material is spherical, ellipsoidal, rod-like, flake-like, or irregular polygonal particles with a size of 50nm to 5000 nm.
5. A method for preparing a composite separator for reducing the risk of thermal runaway of a lithium battery as defined in claim 1, the method comprising:
adding an inorganic filling material, a dispersing agent, a binder, an auxiliary agent and a solvent into a pre-stirring tank according to a required proportion, and completely dissolving to obtain a first mixture;
gradually adding a polymer heat-sensitive material and a coating material into the first mixture according to a required proportion, and stirring and dispersing at a stirring speed of 10-50rpm and a dispersion speed of 1000-5000rpm to obtain a second mixture;
filtering the second mixture by using a screen to obtain coating slurry;
coating the coating slurry on one side or two sides of a base film at the speed of 1-100 m/min, and drying at the temperature of 40-100 ℃ to obtain the composite diaphragm.
6. The method of claim 5, wherein before the step of applying the coating slurry to one or both sides of the base film at a speed of 1m/min to 100m/min, the method further comprises: and carrying out corona treatment on the base film.
7. The production method according to claim 5,
the heat-sensitive material specifically includes: polyethylene oxide PEO, polyacrylonitrile PAN, polyvinylidene fluoride PVDF, polymethyl methacrylate PMMA, polypropylene oxide PPO, polyvinylidene chloride PVDC, polyvinyl chloride PVC, ethylene-vinyl acetate copolymer EVA, high-pressure polyethylene LDPE, high-pressure polyethylene HDPE, polystyrene PS, polyamide PA, polyimide PI, polymethyl acrylate PMA, polyvinyl alcohol PVA, polyvinyl fluoride PVF, polyethylene terephthalate PET, polybutylene terephthalate fiber PBT, polyethylene glycol PEG, ethylene acrylic acid-ethylene acrylic acid copolymer EAA, ethylene-octene copolymer POE, chlorinated polyethylene CPE, thermoplastic polyurethane elastomer rubber TPU, polysulfone PSF, polycarbonate PC, polytetrafluoroethylene PTFE, polycaprolactone PCL, polyurethane PU, polyisoprene PI, polyisobutylene PIB, ethylene-vinyl alcohol copolymer EVAL, polybutadiene-styrene PBS and polyvinyl acetate PVAC materials;
the inorganic filler material comprises Al of inert ceramic oxide class2O3、TiO2、MgO、SiO2AlBr of Lewis acidic inorganic Compounds3、AlCl3BaTiO of ferroelectric ceramic material3ZrO of acidic oxides2Succinonitrile SN, polyphosphazene PZS, zirconyl sulfonate Zr-O-SO4、MgOAl2O4LiAlO of the lithium oxide type2、Li2O, polyvinylidene fluoride PVDF and polymethyl methacrylate PMMA which are organic materials, and one or more of clay, montmorillonite and boehmite;
the adhesive comprises: one or more of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, polytetrafluoroethylene, polymethyl methacrylate, polyacrylonitrile, styrene-butadiene latex, styrene-acrylic latex, polyvinyl alcohol, ethylene-vinyl acetate, sodium alginate, polyacrylamide, polymethyl methacrylate-butyl acrylate, ethylene-vinyl acetate copolymer, polyvinyl acetate, polyurethane, hydroxyethyl cellulose, methyl hydroxyethyl cellulose, sodium carboxymethyl cellulose, polyacrylamide, polyethylene oxide and polytetrafluoroethylene are mixed;
the dispersing agent comprises one or more of stearic acid monoglyceride, tristearin, oleic acid acyl, sodium polyacrylate, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium hexametaphosphate, polyacrylic acid, cetyl trimethyl ammonium bromide, polyethylene glycol, potassium polyacrylate, octyl phenol polyoxyethylene or sulfonate fluorine dispersing agent;
the auxiliary agent comprises one or a combination of more of polydimethylsiloxane, silicone oil, polyethers, sodium polyacrylate, polyvinyl alcohol, alkyl polyoxyethylene ether sodium carboxylate, polyoxyethylene alkylphenol ether, sodium alkyl benzene sulfonate, alkylphenol polyoxyethylene, polyoxyethylene alkylamine and polyoxyethylene amide;
the coating material comprises: nano alumina and nano zirconia;
the base membrane comprises one or more composite membranes of a polypropylene PP membrane, a polyethylene PE membrane, a polypropylene/polyethylene/polypropylene PP/PE/PP composite membrane, a non-woven fabric diaphragm, a fiber diaphragm and a ceramic diaphragm solid electrolyte diaphragm.
8. The method according to claim 7, wherein the inorganic filler has a shape of spherical, ellipsoidal, rod-like, plate-like or irregular polygonal particles with a size of 50nm to 5000 nm.
9. A lithium battery comprising the composite separator for reducing the risk of thermal runaway in a lithium battery as claimed in any one of claims 1 to 5, wherein the lithium battery comprises any one of a liquid lithium battery, a semi-solid lithium battery, a quasi-solid lithium battery, an all-solid lithium battery and a metal lithium battery.
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| CN112701420A (en) * | 2021-01-23 | 2021-04-23 | 山东天瀚新能源科技有限公司 | Multifunctional diaphragm for lithium battery, preparation method and application |
| CN112778459A (en) * | 2021-01-11 | 2021-05-11 | 江苏宇博塑业有限公司 | Polymer EVA roll core technology |
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| CN114156595A (en) * | 2021-12-02 | 2022-03-08 | 新乡市中科科技有限公司 | Composite diaphragm for semi-solid lithium battery and preparation method thereof |
| WO2022120654A1 (en) * | 2020-12-09 | 2022-06-16 | 宁德新能源科技有限公司 | Polymer binder, laminated porous membrane, battery, and electronic apparatus |
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| CN114156595B (en) * | 2021-12-02 | 2024-04-02 | 新乡市中科科技有限公司 | Composite diaphragm for semisolid lithium battery and preparation method thereof |
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