CN117229732B - Adhesive composition, positive electrode sheet, secondary battery and electric device - Google Patents
Adhesive composition, positive electrode sheet, secondary battery and electric device Download PDFInfo
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- CN117229732B CN117229732B CN202311528200.XA CN202311528200A CN117229732B CN 117229732 B CN117229732 B CN 117229732B CN 202311528200 A CN202311528200 A CN 202311528200A CN 117229732 B CN117229732 B CN 117229732B
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- binder
- formula
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- unit derived
- adhesive
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- 230000001070 adhesive effect Effects 0.000 title claims abstract description 74
- 239000000853 adhesive Substances 0.000 title claims abstract description 72
- 239000000203 mixture Substances 0.000 title claims abstract description 51
- 239000011230 binding agent Substances 0.000 claims abstract description 181
- 239000000178 monomer Substances 0.000 claims abstract description 103
- 239000003292 glue Substances 0.000 claims description 84
- 238000006116 polymerization reaction Methods 0.000 claims description 57
- 238000000034 method Methods 0.000 claims description 51
- 239000011810 insulating material Substances 0.000 claims description 35
- 238000009413 insulation Methods 0.000 claims description 26
- 239000004094 surface-active agent Substances 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 239000002270 dispersing agent Substances 0.000 claims description 25
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000003999 initiator Substances 0.000 claims description 24
- 238000002360 preparation method Methods 0.000 claims description 24
- 239000006185 dispersion Substances 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 18
- 239000003792 electrolyte Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 239000000839 emulsion Substances 0.000 claims description 11
- 229910019142 PO4 Inorganic materials 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- 239000012986 chain transfer agent Substances 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 8
- 239000010452 phosphate Substances 0.000 claims description 8
- 239000012966 redox initiator Substances 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
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- 229910052760 oxygen Inorganic materials 0.000 claims description 6
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- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 6
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- 229920000058 polyacrylate Polymers 0.000 claims description 6
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 150000001408 amides Chemical class 0.000 claims description 5
- 150000003863 ammonium salts Chemical class 0.000 claims description 5
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
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- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 4
- 239000012774 insulation material Substances 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- 229920005614 potassium polyacrylate Polymers 0.000 claims description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
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- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims 3
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- 125000004185 ester group Chemical group 0.000 description 17
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 16
- 239000000463 material Substances 0.000 description 16
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- 238000012360 testing method Methods 0.000 description 12
- 239000002131 composite material Substances 0.000 description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 10
- 239000011888 foil Substances 0.000 description 10
- 125000003161 (C1-C6) alkylene group Chemical group 0.000 description 9
- 230000009286 beneficial effect Effects 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
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- 229910052782 aluminium Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
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- 235000021317 phosphate Nutrition 0.000 description 8
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 239000000654 additive Substances 0.000 description 7
- 239000011889 copper foil Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 6
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 6
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- 230000000052 comparative effect Effects 0.000 description 6
- 239000006258 conductive agent Substances 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
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- 239000007774 positive electrode material Substances 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- 125000002947 alkylene group Chemical group 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 229920001707 polybutylene terephthalate Polymers 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- 238000004321 preservation Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 229920002125 Sokalan® Polymers 0.000 description 4
- 239000002390 adhesive tape Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
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- 238000010438 heat treatment Methods 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
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- 229920000642 polymer Polymers 0.000 description 4
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- 230000035484 reaction time Effects 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 3
- 239000011267 electrode slurry Substances 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 description 3
- 239000002923 metal particle Substances 0.000 description 3
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- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
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- 125000001424 substituent group Chemical group 0.000 description 3
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 3
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- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
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- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229920006172 Tetrafluoroethylene propylene Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical class [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- VIEVWNYBKMKQIH-UHFFFAOYSA-N [Co]=O.[Mn].[Li] Chemical compound [Co]=O.[Mn].[Li] VIEVWNYBKMKQIH-UHFFFAOYSA-N 0.000 description 1
- QTHKJEYUQSLYTH-UHFFFAOYSA-N [Co]=O.[Ni].[Li] Chemical compound [Co]=O.[Ni].[Li] QTHKJEYUQSLYTH-UHFFFAOYSA-N 0.000 description 1
- UMVBXBACMIOFDO-UHFFFAOYSA-N [N].[Si] Chemical class [N].[Si] UMVBXBACMIOFDO-UHFFFAOYSA-N 0.000 description 1
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical class [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- NDPGDHBNXZOBJS-UHFFFAOYSA-N aluminum lithium cobalt(2+) nickel(2+) oxygen(2-) Chemical compound [Li+].[O--].[O--].[O--].[O--].[Al+3].[Co++].[Ni++] NDPGDHBNXZOBJS-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000001246 colloidal dispersion Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000005347 demagnetization Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 1
- QKBJDEGZZJWPJA-UHFFFAOYSA-N ethyl propyl carbonate Chemical compound [CH2]COC(=O)OCCC QKBJDEGZZJWPJA-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- ZYMKZMDQUPCXRP-UHFFFAOYSA-N fluoro prop-2-enoate Chemical compound FOC(=O)C=C ZYMKZMDQUPCXRP-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 1
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002961 polybutylene succinate Polymers 0.000 description 1
- 239000004631 polybutylene succinate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- GEKDEMKPCKTKEC-UHFFFAOYSA-N tetradecane-1-thiol Chemical compound CCCCCCCCCCCCCCS GEKDEMKPCKTKEC-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Abstract
The application provides an adhesive composition, a positive electrode plate, a secondary battery and an electric device. The adhesive composition comprises a first adhesive and a second adhesive, wherein the first adhesive comprises a structural unit derived from a monomer shown in a formula I, a structural unit derived from a monomer shown in a formula II and a structural unit derived from a monomer shown in a formula III; the second binder includes a structural unit derived from a monomer represented by formula IV, a structural unit derived from a monomer represented by formula V, and a structural unit derived from a monomer represented by formula VI. The adhesive combination can realize high-speed coating, has better adhesive force, lower viscosity rebound, lower swelling rate and good abrasion resistance.
Description
Technical Field
The application relates to the technical field of secondary batteries, in particular to an adhesive composition, a preparation method, an insulating glue solution, a positive electrode plate, a secondary battery and an electric device.
Background
In recent years, secondary batteries are widely used in energy storage power supply systems such as hydraulic power, thermal power, wind power and solar power stations, and in various fields such as electric tools, electric bicycles, electric motorcycles, electric automobiles, military equipment, aerospace, and the like. As the demand for secondary batteries is increasing, there is a higher demand for safety performance thereof.
The insulating adhesive film is coated on the edge of the positive electrode plate, so that the safety performance of the secondary battery is improved. The current insulating film coating speed is slow, which results in an increase in the production cost of the secondary battery. Therefore, the existing insulating adhesive film still needs to be improved.
Disclosure of Invention
The present application has been made in view of the above problems, and an object thereof is to provide an adhesive composition, an insulating varnish, and an insulating film. The insulating adhesive film containing the adhesive composition can realize the beneficial effect of high-speed coating.
A first aspect of the present application provides an adhesive composition, characterized in that the adhesive composition comprises a first adhesive and a second adhesive, wherein,
the first binder comprises a structural unit derived from a monomer represented by formula I, a structural unit derived from a monomer represented by formula II, and a structural unit derived from a monomer represented by formula III:
formula I, (-)>Formula II, (-)>The compound of the formula III,
the second binder includes a structural unit derived from a monomer represented by formula IV, a structural unit derived from a monomer represented by formula V, and a structural unit derived from a monomer represented by formula VI:
formula IV>V, & gt>A compound of the formula VI,
wherein R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 、R 11 、R 12 、R 14 、R 15 、R 16 Each independently selected from hydrogen or C1-C6 alkyl; r is R 13 Independently selected from substituted or unsubstituted C1-C20 alkyl, R 17 Independently selected from C1-C6 alkylene ester groups.
The second binder of this application has lower viscosity and quick-drying's characteristic, is favorable to realizing quick coating, and it still has higher adhesion simultaneously for insulating glued membrane is difficult for following the positive pole piece and drops. However, a lower viscosity is disadvantageous in suspending the insulating material, and may result in a decrease in insulating performance of the insulating film. Meanwhile, the cohesion of the second binder is lower, the swelling rate is higher, the abrasion resistance of the insulating adhesive film is possibly reduced, the insulating adhesive film is easy to wear and penetrate, and the safety performance of the secondary battery is further affected. On this basis, the present application incorporates a first binder. The first binder has good wear resistance and high viscosity, but is not easily dried during coating. The insulating glue solution has the advantages that the insulating glue solution is easy to dry and has proper viscosity, and the suspension requirement on insulating materials can be met while the quick coating is realized. Meanwhile, the carboxyl of the first binder and the hydroxyl of the second binder can form intermolecular hydrogen bonds, so that a three-dimensional cross-linked structure is formed, and the abrasion resistance of the insulating adhesive film can be further improved. The binder combination provided by the embodiment of the application can save the preparation and production cost and simultaneously can meet the safety performance of the secondary battery.
In any embodiment, the R 13 Selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, n-dodecyl or n-heptadecyl, said R 17 Selected from-C (O) OCH 2 -、-C(O)O(CH 2 ) 2 -、-C(O)O(CH 2 ) 3 -or-C (O) O (CH) 2 ) 4 -。
The monomer containing ester group has the characteristic of easy drying and is favorable for quick coating. Meanwhile, the acrylate monomer can increase flexibility and enhance adhesion with the substrate.
In any embodiment, the mass ratio of the first binder to the second binder is 1: (2.5-20).
In any embodiment, the mass ratio of the first binder to the second binder is 1: (8-20).
The first binder and the second binder have proper proportions, so that proper proportions of carboxyl, ester and hydroxyl in the binder composition are maintained, and good binding force, swelling rate and abrasion resistance are maintained while the coating speed is considered.
In any embodiment, the viscosity of the first adhesive is 5000cP to 30000cP and the viscosity of the second adhesive is 10cP to 3500cP.
In any embodiment, the viscosity of the first adhesive is 10000cP-18000cP and the viscosity of the second adhesive is 1500cP-2800cP.
The first binder and the second binder have suitable viscosities to facilitate the mixing of the two with the suitable viscosities. Suitable viscosity facilitates rapid coating and meets the suspension requirements for the insulating material.
In any embodiment, in the first binder, the molar ratio of the structural unit derived from the monomer of formula I, the structural unit derived from the monomer of formula II, and the structural unit derived from the monomer of formula III is (5-30): (60-80): (5-20); in the second binder, the molar ratio of the structural unit derived from the monomer represented by formula IV, the structural unit derived from the monomer represented by formula V, and the structural unit derived from the monomer represented by formula VI is (5-10): (70-85): (10-20).
In any embodiment, in the first binder, the molar ratio of the structural unit derived from the monomer represented by formula I, the structural unit derived from the monomer represented by formula II, and the structural unit derived from the monomer represented by formula III is (5-15): (65-75): (15-20); in the second binder, the molar ratio of the structural unit derived from the monomer represented by formula IV, the structural unit derived from the monomer represented by formula V, and the structural unit derived from the monomer represented by formula VI is (5-8): (78-82): (13-17).
The monomer shown in the formula I and the monomer shown in the formula VI have proper proportion, and are beneficial to improving the abrasion resistance and the binding force. The monomer shown in the formula II has proper proportion and contributes to improving the abrasion resistance. The monomer of formula III has a suitable duty cycle to help increase the degree of homopolymerization of the first binder. The monomer of formula IV has a suitable ratio to help increase the solubility of the second binder in the solvent while improving its antiwear properties. The monomer shown in the formula V has a proper proportion, and is beneficial to improving flexibility, easy drying capacity and cohesive force. The monomer groups in the first binder and the second binder have a proper ratio, so that the adhesive property can be balanced while the coating speed is improved.
A second aspect of the present application provides a method of preparing the adhesive composition of the first aspect of the present application, the method comprising:
the preparation method of the first binder comprises the following steps:
(1) Adding solvent, units shown in formula I, formula II and formula III into a container, removing oxygen in a reaction system,
(2) Adding a first initiator into the container to perform a first polymerization reaction, adding a second initiator to perform a second polymerization reaction, wherein the first initiator comprises at least one of sodium persulfate, potassium persulfate or ammonium persulfate, and the second initiator is a redox initiator;
Formula I, (-)>Formula II, (-)>The compound of the formula III,
the preparation method of the second binder comprises the following steps:
(1) Adding a first reactive surfactant, units shown in formulas IV, V and VI and a chain transfer agent which are dissolved in a solvent into a container, and removing oxygen in a reaction system to form a pre-emulsion;
(2) Pretreating the second reactive surfactant to obtain a second reactive surfactant solution;
(3) Adding the pre-emulsion and the first initiator into the second reactive surfactant solution to perform a first polymerization reaction to obtain a second binder seed solution;
(4) Adding the first initiator into the second binder seed solution to perform a second polymerization reaction;
formula IV>V, & gt>A compound of the formula VI,
wherein R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 、R 11 、R 12 、R 14 、R 15 、R 16 Each independently selected from hydrogen or C1-C6 alkyl; r is R 13 Independently selected from substituted or unsubstituted C1-C20 alkyl, R 17 Independently selected from C1-C6 alkylene ester groups.
The first binder and the second binder of the present application may be prepared by staged polymerization. In the preparation process of the first binder, the second initiator is introduced and limited to be a redox initiator, so that the reaction rate is improved, and the polymerization reaction is more complete. In the preparation process of the second binder, the reactive surfactant is added and the second reactive surfactant is pretreated, so that the solubility of the monomers shown in the formulas V and VI can be increased, and the yield is improved.
In any embodiment, in the method for preparing the first binder, the temperature of the first polymerization reaction is 40 ℃ to 80 ℃ for 3h to 10h; the temperature of the second polymerization reaction is 70-90 ℃ and the time is 1-3 h.
In any embodiment, in the method for preparing the second binder, the temperature of the first polymerization reaction is 70 ℃ to 95 ℃ for 0.5h to 3h; the temperature of the second polymerization reaction is 70-95 ℃ and the time is 1-5 h.
The proper polymerization temperature and polymerization time are favorable for the polymerization reaction between monomers and improve the polymerization efficiency.
In any embodiment, in the method for preparing the second binder, the pretreatment is performed at a temperature of 70 ℃ to 95 ℃ for a time of 0.5h to 3h.
The proper pretreatment temperature and time are favorable for the second reactive surfactant to form stable micelle in advance and provide reaction sites for the polymerization reaction of the monomers.
A third aspect of the present application provides an insulation cement comprising the binder composition of the first aspect of the present application or the binder composition produced by the production method of the second aspect of the present application.
In any embodiment, the insulating glue further comprises an insulating material.
In any embodiment, the insulating material comprises at least one of alumina, boehmite.
The insulating material is added into the insulating glue solution to be beneficial to improving the insulating property of the insulating glue solution.
In any embodiment, the mass ratio of the binder composition to the insulating material is (5-30): (60-85).
The adhesive combination and the insulating material have proper proportion, so that the insulating performance of the insulating glue solution can be met, and the quick coating performance can be also met.
In any embodiment, the insulation paste further comprises a dispersant.
In any embodiment, the dispersant comprises at least one of a polyacrylate, an amide, an ammonium salt, a polyol, a phosphate salt.
In any embodiment, the dispersant comprises at least one of sodium polyacrylate, potassium polyacrylate, polyacrylamide, ammonium chloride, ethylene glycol, polyoxyethylene ether phosphate.
The dispersing agent is added into the insulating glue solution, so that the dispersing of each component in the insulating glue solution is facilitated, and the uniformity of the insulating glue solution is improved.
In any embodiment, the mass ratio of the dispersant to the insulating material is 0.4: (65-85).
The proper proportion of the dispersing agent and the insulating material is favorable for improving the uniformity of the insulating glue solution.
In any embodiment, the viscosity of the insulating glue is 350cP-1200cP.
In any embodiment, the viscosity of the insulating glue is 400cP-700cP.
The insulating glue solution has proper viscosity, which is helpful for the quick coating of the insulating glue solution, and is helpful for suspending insulating materials and improving the insulating performance of the insulating glue solution.
In any embodiment, the solid content of the insulating glue solution is 20% -40%.
The proper solid content of the insulating glue solution is beneficial to adjusting the viscosity of the insulating glue solution so as to better match the rapid coating process and optimize the coating effect.
A fourth aspect of the present application provides a method for preparing an insulation glue solution according to the third aspect of the present application, where the method includes:
preparing the first binder and the second binder respectively;
adding the dispersing agent into water to obtain a dispersing liquid;
and respectively adding the insulating material, the first binder and the second binder into the dispersion liquid to obtain the insulating glue solution.
The insulating glue solution can be obtained by the preparation method of the insulating glue solution. The insulating material, the first binder and the second binder are dispersed step by step, so that the good dispersion of the components is realized.
A fifth aspect of the present application provides an insulating film comprising the adhesive composition of the first aspect of the present application, or dried from the insulating glue of the third aspect of the present application.
The sixth aspect of the application provides a positive electrode plate, the positive electrode plate comprises a positive electrode current collector and a positive electrode film layer arranged on at least one surface of the positive electrode current collector, and the edge of the positive electrode current collector is covered by the insulating adhesive film in the fifth aspect of the application.
The insulating adhesive film is coated on the edge of the current collector, so that the risk of short circuit of the secondary battery is reduced, and the safety performance of the secondary battery is improved.
In any embodiment, the thickness of the insulating film is 3 μm to 10 μm.
In any embodiment, the thickness of the insulating film is 3 μm to 5 μm.
In the thickness range of this application, the thickness of insulating glued membrane is thinner, helps reserving more spaces for the utmost point ear, is favorable to solving utmost point ear redundancy problem, and then is favorable to reducing the possibility of short circuit, improves the security performance of secondary cell.
A seventh aspect of the present application provides a secondary battery comprising a negative electrode tab, an electrolyte, and a positive electrode tab as described in the sixth aspect of the present application.
An eighth aspect of the present application provides an electric device comprising the secondary battery according to the seventh aspect of the present application.
Drawings
Fig. 1 is a schematic view of a secondary battery according to an embodiment of the present application;
fig. 2 is an exploded view of the secondary battery according to an embodiment of the present application shown in fig. 1;
FIG. 3 is a schematic view of a battery module according to an embodiment of the present application;
FIG. 4 is a schematic view of a battery pack according to an embodiment of the present application;
FIG. 5 is an exploded view of the battery pack of one embodiment of the present application shown in FIG. 4;
fig. 6 is a schematic view of an electric device in which the secondary battery according to an embodiment of the present application is used as a power source.
Reference numerals illustrate:
1, a battery pack; 2, upper box body; 3, lower box body; 4, a battery module; 5 a secondary battery; 51 a housing; 52 electrode assembly; 53 top cap assembly.
Detailed Description
Hereinafter, embodiments of the adhesive composition and the method for producing the same, the insulating glue solution and the method for producing the same, the insulating glue film, the positive electrode sheet, the secondary battery, and the electric device of the present application are specifically disclosed in detail with reference to the accompanying drawings as appropriate. However, unnecessary detailed description may be omitted. For example, detailed descriptions of well-known matters and repeated descriptions of the actual same structure may be omitted. This is to avoid that the following description becomes unnecessarily lengthy, facilitating the understanding of those skilled in the art. Furthermore, the drawings and the following description are provided for a full understanding of the present application by those skilled in the art, and are not intended to limit the subject matter recited in the claims.
The "range" disclosed herein is defined in terms of lower and upper limits, with a given range being defined by the selection of a lower and an upper limit, the selected lower and upper limits defining the boundaries of the particular range. Ranges that are defined in this way can be inclusive or exclusive of the endpoints, and any combination can be made, i.e., any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a particular parameter, it is understood that ranges of 60-110 and 80-120 are also contemplated. Furthermore, if the minimum range values 1 and 2 are listed, and if the maximum range values 3,4 and 5 are listed, the following ranges are all contemplated: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5. In this application, unless otherwise indicated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" have been listed throughout, and "0-5" is simply a shorthand representation of a combination of these values. When a certain parameter is expressed as an integer of 2 or more, it is disclosed that the parameter is, for example, an integer of 2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12 or the like.
All embodiments and alternative embodiments of the present application may be combined with each other to form new solutions, unless specifically stated otherwise.
All technical features and optional technical features of the present application may be combined with each other to form new technical solutions, unless specified otherwise.
All steps of the present application may be performed sequentially or randomly, preferably sequentially, unless otherwise indicated. For example, the method comprises steps (a) and (b), meaning that the method may comprise steps (a) and (b) performed sequentially, or may comprise steps (b) and (a) performed sequentially. For example, the method may further include step (c), which means that step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c), may include steps (a), (c) and (b), may include steps (c), (a) and (b), and the like.
Reference herein to "comprising" and "including" means open ended, as well as closed ended, unless otherwise noted. For example, the terms "comprising" and "comprises" may mean that other components not listed may be included or included, or that only listed components may be included or included.
The term "or" is inclusive in this application, unless otherwise specified. For example, the phrase "a or B" means "a, B, or both a and B. More specifically, either of the following conditions satisfies the condition "a or B": a is true (or present) and B is false (or absent); a is false (or absent) and B is true (or present); or both A and B are true (or present).
With the wide application of secondary batteries, there is a higher demand for safety performance thereof. Potential safety hazards can be caused by overlarge voltage difference of the battery core, short circuit of the battery and the like. In the battery preparation process, metal particles generated by laser cutting are sputtered at the white-remaining position of the edge of the positive electrode plate, and foreign matters possibly break through a diaphragm corresponding to the white-remaining position, so that the problem of voltage difference or short circuit of a battery core is caused. The insulating adhesive film is coated on the edge of the positive electrode plate, so that the problems can be relieved, and the safety performance of the secondary battery can be improved. Too slow a coating speed of the insulating film causes an increase in production cost. In order to achieve rapid coating of an insulating film, the present application proposes an adhesive composition comprising a first adhesive and a second adhesive. The combination of the first binder and the second binder is favorable for quick coating, and meanwhile, the binder combination provided by the embodiment of the application also has good binding performance, such as good binding force, proper viscosity, certain stability, proper swelling rate and good abrasion resistance.
[ adhesive composition ]
The present application provides an adhesive composition comprising a first adhesive and a second adhesive, wherein,
the first binder comprises structural units derived from a monomer of formula I, structural units derived from a monomer of formula II, and structural units derived from a monomer of formula III:
formula I, (-)>Formula II, (-)>The compound of the formula III,
the second binder comprises structural units derived from a monomer of formula IV, structural units derived from a monomer of formula V, and structural units derived from a monomer of formula VI:
formula IV>V, & gt>A compound of the formula VI,
wherein R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 、R 11 、R 12 、R 14 、R 15 、R 16 Each independently selected from hydrogen or C1-C6 alkyl; r is R 13 Independently selected from substituted or unsubstituted C1-C20 alkyl, R 17 Independently selected from C1-C6 alkylene ester groups.
In this context, the term "binder" refers to a chemical compound, polymer or mixture that forms a colloidal solution or colloidal dispersion in a dispersing medium.
In this context, the term "polymer" includes on the one hand the collection of chemically homogeneous macromolecules prepared by polymerization, but differing in terms of degree of polymerization, molar mass and chain length. The term on the other hand also includes derivatives of such macromolecular assemblies formed by polymerization, i.e. products which can be obtained by reaction, e.g. addition or substitution, of functional groups in the macromolecules described above and which can be chemically homogeneous or chemically inhomogeneous.
In this context, the term "substituted" means that a particular group or moiety carries one or more suitable substituents, wherein the substituents may be attached to the particular group or moiety at one or more positions. For example, an alkyl group substituted with an ester group may indicate that the ester group is attached to one atom of the alkyl group via a bond.
In this context, the term "unsubstituted" means that the specified group carries no substituents.
In this context, the term "C1-C20 alkyl" refers to a straight or branched hydrocarbon chain group consisting of only carbon and hydrogen atoms, which group has no unsaturation, has one to twenty carbon atoms, and is attached to the remainder of the molecule by a single bond, and "C1-C6 alkyl" has a similar definition. Examples of C1-C20 alkyl groups include, but are not limited to: methyl, ethyl, n-propyl, 1-methylethyl (isopropyl), n-butyl, n-pentyl or 1, 1-dimethylethyl (tert-butyl).
As used herein, the term "C1-C6 alkylene" refers to a divalent alkyl group having no unsaturation and from one to six carbon atoms. Can be a C1-C6 alkylene group by extracting a second hydrogen atom from the C1-C6 alkyl group. C1-C6 alkylene includes, but is not limited to, -CH 2 -、-CH(CH 3 )-、-C(CH 3 ) 2 -、-CH 2 CH 2 -、-CH 2 CH(CH 3 )-、-CH 2 C(CH 3 ) 2 -、-CH 2 CH 2 CH 2 -、-CH 2 CH 2 CH 2 CH 2 -、-CH 2 CH 2 CH 2 CH 2 CH 2 -or-CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 -。
As used herein, the term "ester group" refers to-C (O) O-.
As used herein, the term "C1-C6 alkylene ester group" refers to a group in which the ester group is half-bonded to one end of a C1-C6 alkylene group. C1-C6 alkylene ester groups are not limited to-C (O) OCH 2 -、-C(O)OCH(CH 3 )-、-C(O)OC(CH 3 ) 2 -、-C(O)OCH 2 CH 2 -、-C(O)OCH 2 CH(CH 3 )-、-C(O)OCH 2 C(CH 3 ) 2 -、-C(O)OCH 2 CH 2 CH 2 -、-C(O)OCH 2 CH 2 CH 2 CH 2 -、-C(O)OCH 2 CH 2 CH 2 CH 2 CH 2 -or-C (O) OCH 2 CH 2 CH 2 CH 2 CH 2 CH 2 -。
As used herein, "flash coating" or "high-speed coating" refers to a coating speed of 50m/min or more. In some embodiments, rapid coating may refer to a coating speed of 60m/min or greater, 70m/min or greater, 80m/min or greater, 90m/min or 100m/min or greater.
In some embodiments, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 、R 11 、R 12 、R 14 、R 15 、R 16 Each independently selected from hydrogen, methyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, or C6 alkyl.
In some embodiments, R 13 Selected from substituted or unsubstituted methyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl, C8 alkyl, C9 alkyl, C10 alkyl, C11 alkyl, C12 alkyl, C13 alkyl, C14 alkyl, C15 alkyl, C16 alkyl, C17 alkyl, C18 alkyl, C19 alkyl or C20 alkyl.
In some embodiments, R 13 Selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, n-dodecyl or n-heptadecyl.
In some embodiments, R 17 Selected from the group consisting of a methylene ester group, a C2 alkylene ester group, a C3 alkylene ester group, a C4 alkylene ester group, a C5 alkylene ester group, and a C6 alkylene ester group.
In some embodiments, R 17 Is linked to an alkenyl group of a unit of formula VI.
The second binder of this application embodiment has lower viscosity and quick-drying's characteristic, is favorable to realizing insulating glue's quick coating, and it still has higher adhesion simultaneously for insulating glued membrane is difficult for coming off from the positive pole piece. However, a lower viscosity is disadvantageous in suspending the insulating material, and may result in a decrease in insulating performance of the insulating film. Meanwhile, the cohesion of the second binder is lower, the swelling rate is higher, the abrasion resistance of the insulating adhesive film is possibly reduced, the insulating adhesive film is easy to wear and penetrate, and the safety performance of the secondary battery is further affected. On this basis, the present application incorporates a first binder. The first binder has good wear resistance and high viscosity, but is not easily dried during coating. The insulating glue solution and the adhesive can be mixed, so that the insulating glue solution has easy drying performance and proper viscosity, and the suspension requirement on insulating materials can be met while the quick coating is realized. Simultaneously, the carboxyl of the first binder can form a hydrogen bond with the hydroxyl of the second binder, so that a three-dimensional cross-linked structure is formed, and the abrasion resistance and the adhesive force of the insulating adhesive film can be improved. The binder combination of the embodiment of the application saves the preparation cost and meets the safety performance of the secondary battery.
In some embodiments, R 17 Selected from-C (O) OCH 2 -、-C(O)O(CH 2 ) 2 -、-C(O)O(CH 2 ) 3 -or-C (O) O (CH) 2 ) 4 -。
The monomer containing ester group has the characteristic of easy drying and is favorable for quick coating. At the same time, the polyacrylate monomers can enhance adhesion to substrates, especially oily substrates such as aluminum foil, and enhance flexibility.
In some embodiments, the mass ratio of the first binder to the second binder is 1 (2.5-20).
In some embodiments, the mass ratio of the first binder to the second binder is 1 (8-20).
In some embodiments, the mass ratio of the first binder to the second binder may be selected to be 1:2.5, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18, 1:19, 1:20, or a value in the range of any two points set forth above.
The first binder has a low viscosity, is easy to dry, facilitates quick coating, but has poor abrasion resistance and is easy to swell. The second binder has higher viscosity, is not easy to dry, is unfavorable for quick coating, but has better wear resistance and is not easy to swell. The first binder and the second binder have proper proportions, so that each group in the binder combination can be kept at proper proportions, quick coating is facilitated, and the suspension requirement on the insulating material is met. While the coating speed is considered, the coating is also favorable for keeping better binding force, swelling rate and abrasion resistance.
In some embodiments, the viscosity of the first adhesive is 5000cP to 30000cP.
In some embodiments, the viscosity of the first adhesive is 10000cP to 18000cP.
In some embodiments, the viscosity of the first adhesive may be 5000cP, 6000cP, 7000cP, 8000cP, 9000cP, 10000cP, 11000cP, 11500cP, 12000cP, 12500cP, 13000cP, 14000cP, 15000cP, 16000cP, 17000cP, 18000cP, 19000cP, 20000cP, 22000cP, 24000cP, 26000cP, 28000cP, 30000cP, or a value in the range of viscosity compositions of any two of the above first adhesives.
In some embodiments, the viscosity of the second adhesive is 10cP-3500cP.
In some embodiments, the viscosity of the second adhesive is 1500cP-2800cP.
In some embodiments, the viscosity of the second adhesive may be 10cP, 100cP, 200cP, 400cP, 600cP, 800cP, 1000cP, 1200cP, 1400cP, 1600cP, 1800cP, 1900cP, 2000cP, 2100cP, 2200cP, 2300cP, 2400cP, 2500cP, 2600cP, 2700cP, 2800cP, 2900cP, 3000cP, 3300cP, 3500cP, or a value in the range of the viscosity composition of any two of the above second adhesives.
The viscosity may be measured by methods and apparatus known in the art. As an example, a rotational viscometer can be used to test viscosity. In some embodiments, a suitable amount of sample is taken with a beaker, a rotational viscometer rotor is placed into the sample, the rotational speed is set at 12rpm, and the corresponding viscosity is read at 25 ℃ for 6 minutes.
The first binder and the second binder have suitable viscosities to facilitate the mixing of the two with the suitable viscosities. Suitable viscosity facilitates rapid coating and meets the suspension requirements for the insulating material.
In some embodiments, in the first binder, the molar ratio of the structural units derived from the monomer of formula I, the structural units derived from the monomer of formula II, and the structural units derived from the monomer of formula III is (5-30): (60-80): (5-20); in the second binder, the molar ratio of the structural unit derived from the monomer represented by formula IV, the structural unit derived from the monomer represented by formula V, the structural unit derived from the monomer represented by formula VI is (5 to 10): (70-85): (10-20).
In some embodiments, in the first binder, the molar ratio of structural units derived from the monomer of formula I, structural units derived from the monomer of formula II, structural units derived from the monomer of formula III is (5-15): (65-75): (15-20); in the second binder, the molar ratio of the structural unit derived from the monomer represented by formula IV, the structural unit derived from the monomer represented by formula V, the structural unit derived from the monomer represented by formula VI is (5-8): (78-82): (13-17).
In some embodiments, the molar ratio of structural units derived from the monomer of formula I, structural units derived from the monomer of formula II, structural units derived from the monomer of formula III may be 5:80:15, 8:70:22, 10:80:10, 13:77:10, 15:65:20, 20:65:15, 20:60:20, 25:70:5, or 30:62:8.
In some embodiments, in the second binder, the molar ratio of structural units derived from the monomer of formula IV, structural units derived from the monomer of formula V, structural units derived from the monomer of formula VI may be 5:70:20, 5:75:20, 5:80:20, 5:82:20, 8:70:15, 8:75:20, 8:80:20, 8:82:20, 10:80:10, 10:75:20, 10:80:20, 10:82:20.
As used herein, the term "carboxy" refers to-C (O) OH.
As used herein, the term "hydroxy" refers to-OH.
The carboxyl in the monomer shown in the formula I and the hydroxyl in the monomer shown in the formula VI can form intermolecular hydrogen bonds, so that a three-dimensional cross-linked structure is formed, and the abrasion resistance and the binding force are improved. Carboxyl groups can also form intramolecular hydrogen bonds, and excessive intramolecular hydrogen bonds tend to destabilize and raise the viscosity, which is detrimental to rapid coating and maintaining the uniformity of the adhesive. Meanwhile, the carboxyl content is too high, which is unfavorable for the quick drying of the insulating glue solution. The monomer shown in the formula I and the monomer shown in the formula VI have proper proportion, which is beneficial to quick coating, improving the abrasion resistance and the cohesive force and maintaining the stability of the viscosity. The acrylonitrile monomer shown in the formula II is a hard monomer and can provide strength for the adhesive. The monomer shown in the formula II has proper proportion and contributes to improving the abrasion resistance. The monomeric acrylamide of formula III has a suitable duty cycle that helps to increase the degree of homopolymerization of the first binder. The monomer acrylic acid shown in the formula IV has a proper duty ratio, so that the solubility of the second binder in a solvent is improved, and meanwhile, the acrylic acid is a hard monomer, so that the strength of the second binder is improved, and the abrasion resistance of the second binder is improved. The monomer acrylic ester content shown in the formula V is too low, so that the drying of the adhesive composition is not facilitated, the coating speed is not facilitated, the content of carboxyl is reduced due to the too high monomer acrylic ester content shown in the formula V, the abrasion resistance of the insulating adhesive film is reduced, and the acrylic ester has a proper duty ratio, so that the flexibility, quick drying capacity and adhesive force are facilitated to be improved. The monomer groups in the first binder and the second binder have a proper ratio, so that the adhesive property can be balanced while the coating speed is improved.
The present application provides a method of preparing the adhesive composition of the present application, the method comprising:
the preparation method of the first binder comprises the following steps:
(1) Adding solvent, units shown in formula I, formula II and formula III into a container, removing oxygen in a reaction system,
(2) Adding a first initiator into a container to perform a first polymerization reaction, and adding a second initiator to perform a second polymerization reaction, wherein the first initiator comprises at least one of sodium persulfate, potassium persulfate or ammonium persulfate, and the second initiator is a redox initiator;
formula I, (-)>Formula II, (-)>The compound of the formula III,
the preparation method of the second binder comprises the following steps:
(1) Adding a first reactive surfactant, units shown in formulas IV, V and VI and a chain transfer agent which are dissolved in a solvent into a container, and removing oxygen in a reaction system to form a pre-emulsion;
(2) Pretreating the second reactive surfactant to obtain a second reactive surfactant solution;
(3) Adding the pre-emulsion and the first initiator into the second reaction type surfactant solution to perform a first polymerization reaction to obtain a second binder seed solution;
(4) Adding a first initiator into the second binder seed solution to perform a second polymerization reaction;
Formula IV>V, & gt>A compound of the formula VI,
wherein R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 、R 11 、R 12 、R 14 、R 15 、R 16 Each independently selected from hydrogen or C1-C6 alkyl; r is R 13 Independently selected from substituted or unsubstituted C1-C20 alkyl, R 17 Independently selected from C1-C6 alkyl ester groups.
Herein, the term "redox initiator" refers to an initiator that generates radicals by redox reaction for initiating radical polymerization.
As used herein, the term "reactive surfactant" refers to a surfactant with reactive groups that not only has surface activity, but is also capable of chemically reacting with an adsorbed substrate, bonding to the substrate surface as part of the substrate.
As used herein, the term "chain transfer agent" refers to a substance capable of causing chain growth radicals, transmitting radical transfer.
In some embodiments, the redox initiator comprises at least one of ammonium persulfate/sodium sulfite, ammonium persulfate/sodium bisulfite, hydrogen peroxide/ferrous ions.
In some embodiments, in the method of preparing the first binder, the solvent comprises water.
In some embodiments, in the method of preparing the first binder, the method further comprises the steps of vacuumizing, alkali neutralization, filtering and/or demagnetizing after the second polymerization reaction is finished.
In some embodiments, in the method of preparing the second binder, the solvent comprises water.
In some embodiments, the first reactive surfactant and the second reactive surfactant each independently comprise at least one of a double bond containing alcohol ether phosphate, a sodium salt of methacrylamide isopropyl sulfonate, a double bond containing alkyl alcohol ether sulfate, an allyl polyether phosphate, or a double bond containing dialkyl sulfosuccinate salt. In some embodiments, the first and second reactive surfactants are double bond containing bis-alkyl sulfosuccinate salts M-30S.
In some embodiments, the chain transfer agent comprises an aliphatic thiol.
Herein, the term "thiol" refers to a compound having a mercapto group (-SH) by substituting an oxygen atom in a hydroxyl group with a sulfur atom. Mercaptans include aliphatic mercaptans and aromatic mercaptans.
In some embodiments, the chain transfer agent comprises at least one of n-dodecyl mercaptan, n-tetradecyl mercaptan. In some embodiments, the chain transfer agent is n-dodecyl mercaptan.
In some embodiments, in the method of preparing the second binder, the pre-emulsion and the first initiator are added dropwise to the reactive surfactant for 2-4 hours, e.g., may be added dropwise within 2 hours, 2.5 hours, 3 hours, 3.5 hours, or 4 hours.
In some embodiments, in the method of preparing the second binder, the first initiator is added dropwise to the second binder seed solution for 1.5h to 3h, for example, may be added dropwise within 1.5h, 2h, 2.5h, or 3h.
In some embodiments, in the method of preparing the second binder, the second polymerization reaction optionally includes a three-stage reaction, in which the reaction temperature is 70 ℃ to 95 ℃ and the reaction time is 1h to 5h; alternatively, in the second stage reaction, the reaction temperature is 50 ℃ to 70 ℃, the reaction time is 0.5h to 3h, specifically, the reaction temperature may be 50 ℃, 55 ℃, 60 ℃, 65 ℃ or 70 ℃, and the reaction time may be 0.5h, 1h, 1.5h, 2h, 2.5h or 3h; alternatively, in the third stage reaction, the reaction is carried out under reduced pressure and suction at room temperature for 0.5h to 3h, specifically, the reaction time may be 0.5h, 1h, 1.5h, 2h, 2.5h or 3h.
Herein, the term "room temperature" refers to an indoor temperature, for example, 23 ℃ ± 2 ℃, 25 ℃ ± 5 ℃ or 20 ℃ ± 5 ℃.
In some embodiments, in the method of preparing the second binder, a filtration step is further included after the second polymerization reaction is completed.
The first binder and the second binder of the embodiments of the present application may be prepared by staged polymerization. In the preparation process of the first binder, the second initiator is introduced and limited to be a redox initiator, so that the reaction rate is improved, and the polymerization reaction is more complete. In the preparation process of the second binder, the reactive surfactant is added and the second reactive surfactant is pretreated, so that the solubility of the monomers shown in the formulas V and VI can be increased, and the yield is improved.
In some embodiments, in the method of preparing the first binder, the first polymerization reaction is at a temperature of 40 ℃ to 80 ℃ for a time of 3 hours to 10 hours; the temperature of the second polymerization reaction is 70-90 ℃ and the time is 1-3 h.
In some embodiments, in the method of preparing the first binder, the temperature of the first polymerization reaction is 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, or a value in the range of any two points composition described above.
In some embodiments, in the method of preparing the first binder, the time of the first polymerization reaction is 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, or a value in the range of any two points above.
In some embodiments, in the method of preparing the first binder, the temperature of the second polymerization reaction is 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, or a value in the range of any two points above.
In some embodiments, in the method of preparing the first binder, the time of the first polymerization reaction is 1h, 1.5h, 2h, 2.5h, 3h, or a value in the range of any two points composition described above.
In some embodiments, in the method of preparing the second binder, the first polymerization reaction is at a temperature of 70 ℃ to 95 ℃ for a time of 0.5h to 3h; the temperature of the second polymerization reaction is 70-95 ℃ and the time is 1-5 h.
In some embodiments, in the method of preparing the second binder, the temperature of the first polymerization reaction is 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, or a value in the range of any two points composition described above.
In some embodiments, in the method of preparing the second binder, the time of the first polymerization reaction is 0.5h, 1h, 1.5h, 2h, 2.5h, 3h, or a value in the range of any two points of composition described above.
In some embodiments, in the method of preparing the second binder, the temperature of the second polymerization reaction is 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, or a value in the range of any two points composition described above.
In some embodiments, in the method of preparing the second binder, the second polymerization time is 1h, 2h, 3h, 4h, 5h, or a value in the range of any two points composition described above.
The proper polymerization temperature and polymerization time are favorable for the polymerization reaction between monomers and improve the polymerization efficiency.
In some embodiments, in the method of preparing the second binder, the pretreatment temperature is 70 ℃ to 95 ℃ for 0.5h to 3h.
In some embodiments, in the method of preparing the second binder, the pretreatment temperature is 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, or a value in the range of any two points above.
In some embodiments, in the method of preparing the second binder, the pretreatment time is 0.5h, 1h, 1.5h, 2h, 2.5h, 3h, or a value in the range of any two points above.
The proper pretreatment temperature and time are favorable for the second reactive surfactant to form stable micelle in advance and provide reaction sites for the polymerization reaction of the monomers.
The present application also provides an insulating glue solution comprising the adhesive composition of the present application or the adhesive composition prepared by the preparation method of the present application.
In some embodiments, the insulating paste further comprises an insulating material.
In some embodiments, the insulating material comprises at least one of alumina, boehmite.
The insulating material is added into the insulating glue solution to be beneficial to improving the insulating property of the insulating glue solution.
In some embodiments, the mass ratio of the binder composition to the insulating material is (5-50): (60-85).
In some embodiments, the mass ratio of the binder composition to the insulating material may be 5:85, 10:70, 10:75, 10:80, 15:70, 15:75, 15:80, 20:70, 20:75, 20:80, 25:70, 25:75, 25:80, or 30:60.
The adhesive combination and the insulating material have proper proportion, so that the insulating performance of the insulating glue solution can be met, and the quick coating performance can be also met.
In some embodiments, the insulation paste further comprises a dispersant.
In some embodiments, the dispersant comprises at least one of a polyacrylate, an amide, an ammonium salt, a polyol, a phosphate salt.
As used herein, the term "polyacrylate" refers to a polymer having the formula [ CH ] 2 CH(COOH)]n is a water-soluble high molecular polymer, and the hydrogen atom on the carboxyl in the structural unit can be replaced by metal ions. Polyacrylic acids include, but are not limited to, sodium polyacrylate, potassium polyacrylate.
In this context, the term "amide" refers to a compound in which a hydroxyl group in a carboxylic acid is substituted with an amino group or an amine group. Amides include, but are not limited to, hexenyl distearate, polyacrylamide.
In this context, the term "ammonium salt" refers to a compound consisting of an ammonium ion and an acid ion. Ammonium salts include, but are not limited to, ammonium chloride.
As used herein, the term "polyol" refers to an alcohol containing two or more hydroxyl groups. Polyols include, but are not limited to, ethylene glycol, propylene glycol, butylene glycol.
In some embodiments, the dispersant comprises at least one of sodium polyacrylate, potassium polyacrylate, polyacrylamide, ammonium chloride, ethylene glycol, polyoxyethylene ether phosphate.
The dispersing agent is added into the insulating glue solution, so that the dispersing of each component in the insulating glue solution is facilitated, and the uniformity of the insulating glue solution is improved.
In some embodiments, the mass ratio of dispersant to insulating material is 0.4: (65-85).
In some embodiments, the mass ratio of dispersant to insulating material may be 0.4:65, 0.4:70, 0.4:72, 0.4:74, 0.4:76, 0.4:78, 0.4:80, or 0.4:85.
The proper proportion of the dispersing agent and the insulating material is favorable for improving the uniformity of the insulating glue solution.
In some embodiments, the viscosity of the insulating paste is 350cP to 1200cP.
In some embodiments, the viscosity of the insulating paste is 400cP to 700cP. In some embodiments, the viscosity of the insulating paste may be 350cP, 400cP, 420cP, 450cP, 480cP, 500cP, 520cP, 550cP, 580cP, 600cP, 620cP, 650cP, 680cP, 700cP, 750cP, 800cP, 850cP, 900cP, 950cP, 1000cP, 1100cP, 1200cP, or a value in the range consisting of any two points described above.
The insulating glue solution has proper viscosity, which is helpful for the quick coating of the insulating glue solution, and is helpful for suspending insulating materials and improving the insulating performance of the insulating glue solution.
In some embodiments, the solids content of the insulation paste is 20% -40%.
In some embodiments, the solids content of the insulation paste is 20%, 22%, 25%, 28%, 30%, 32%, 35%, 38%, 40%, or a value in the range of any two points of composition described above.
The proper solid content of the insulating glue solution is beneficial to adjusting the viscosity of the insulating glue solution so as to better match the rapid coating process and optimize the coating effect.
The application provides a preparation method of an insulating glue solution, which comprises the following steps:
preparing a first binder and a second binder respectively;
adding a dispersing agent into water to obtain a dispersing liquid;
and respectively adding the insulating material, the first binder and the second binder into the dispersion liquid to obtain the insulating glue solution.
In some embodiments, the dispersant is added to water and dispersed and stirred to obtain a dispersion. In some embodiments, the stirring time is 5 to 30 minutes and the stirring speed is 100 to 500rpm. In some embodiments, the agitation time is 5min, 10min, 15min, 20min, 25min, 30min, or a value in the range consisting of any two of the above. In some embodiments, the stirring speed is 100rpm, 200rpm, 300rpm, 400rpm, 500rpm, or a value in the range consisting of any two points above.
In some embodiments, the insulating material is added to the dispersion, and the dispersion is stirred to obtain dispersion 1. In some embodiments, the stirring time is 0.5 to 3 hours and the stirring speed is 1000 to 3000rpm. In some embodiments, the stirring time is 0.5h, 1h, 2h, 3h, or a value in the range of any two points above. In some embodiments, the stirring speed is 1000rpm, 1500rpm, 2000rpm, 2500rpm, 3000rpm, or a value in the range of any two points above.
In some embodiments, the first binder is added to dispersion 1 and dispersed and stirred to obtain dispersion 2. In some embodiments, the stirring time is 0.5 to 3 hours and the stirring speed is 1000 to 3000rpm. In some embodiments, the stirring time is 0.5h, 1h, 2h, 3h, or a value in the range of any two points above. In some embodiments, the stirring speed is 1000rpm, 1500rpm, 2000rpm, 2500rpm, 3000rpm, or a value in the range of any two points above.
In some embodiments, a second binder is added to dispersion 2 and dispersed and stirred to obtain an insulating glue. In some embodiments, the stirring time is from 5 to 100 minutes and the stirring speed is from 300 to 1000rpm. In some embodiments, the agitation time is 5min, 10min, 15min, 20min, 30min, 40min, 50min, 60min, 70min, 80min, 90min, 100min, or a value in the range consisting of any two of the foregoing. In some embodiments, the stirring speed is 300rpm, 400rpm, 500rpm, 600rpm, 700rpm, 800rpm, 900rpm, 1000rpm, or a value in the range consisting of any two points above.
The insulating glue solution can be obtained by the preparation method of the insulating glue solution. The insulating material, the first binder and the second binder are dispersed step by step, so that the components can be well dispersed. The proper stirring time and stirring rotation speed are favorable for fully mixing the components in the dispersion liquid and the insulating glue liquid, and the dispersion uniformity is improved.
The application provides an insulating adhesive film, which comprises the adhesive composition or is formed by drying the insulating adhesive solution.
The insulating adhesive film can be coated rapidly, and meanwhile the possibility of short circuit of the secondary battery can be reduced. The polyacrylic acid unit, the polyacrylate unit and the polyacrylonitrile unit in the insulating adhesive film have the performance of high temperature resistance and difficult decomposition, and can effectively resist splashing of metal particles during laser cutting. And the laser cuts on the insulating adhesive film, so that metal bead particles are not easy to generate, and the problem of splashing of the metal particles is further improved. Meanwhile, the insulating adhesive film has good abrasion resistance, can effectively isolate friction between the root part of the electrode lug and the edge of the electrode plate caused by bending of the electrode lug when the battery cell is put into the shell, and is beneficial to solving the problem of short circuit.
[ Positive electrode sheet ]
The application provides a positive pole piece, positive pole piece contain positive pole collector and set up the positive pole rete at least one surface of positive pole collector, and positive pole collector edge is covered by the insulating glued membrane of this application.
In some embodiments, the insulation paste of the examples herein is applied to the edge of the positive current collector using a micro gravure coating technique. The thickness of the obtained insulating adhesive film is controlled by adopting a micro gravure coating technology.
In some embodiments, the thickness of the insulating film is 3 μm to 10 μm.
In some embodiments, the thickness of the insulating film is 3 μm to 5 μm. In some embodiments, the thickness of the insulating film is 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, or a value in the range of any two points composition described above.
In the thickness range of this application embodiment, the thickness of insulating glued membrane is thinner, helps reserving more spaces for the utmost point ear, is favorable to solving utmost point ear redundancy problem, and then is favorable to reducing the possibility of short circuit, improves the security performance of secondary cell.
In some embodiments, as an example, the positive electrode current collector has two surfaces opposite in the thickness direction thereof, and the positive electrode film layer is provided on either or both of the two surfaces opposite to the positive electrode current collector.
In some embodiments, the positive current collector may employ a metal foil or a composite current collector. For example, as the metal foil, aluminum foil may be used. The composite current collector may include a polymeric material base layer and a metal layer formed on at least one surface of the polymeric material base layer. The composite current collector may be formed by forming a metal material (aluminum, aluminum alloy, nickel alloy, titanium alloy, silver alloy, etc.) on a polymer material substrate (such as a substrate of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
In some embodiments, the positive electrode active material may employ a positive electrode active material for a battery, which is well known in the art. As an example, the positive electrode active material may include the following materialsAt least one of the following materials: olivine structured lithium-containing phosphates, lithium transition metal oxides and their respective modified compounds. However, the present application is not limited to these materials, and other conventional materials that can be used as a battery positive electrode active material may be used. These positive electrode active materials may be used alone or in combination of two or more. Examples of lithium transition metal oxides may include, but are not limited to, lithium cobalt oxide (e.g., liCoO) 2 ) Lithium nickel oxide (e.g. LiNiO) 2 ) Lithium manganese oxide (e.g. LiMnO 2 、LiMn 2 O 4 ) Lithium nickel cobalt oxide, lithium manganese cobalt oxide, lithium nickel manganese oxide, lithium nickel cobalt manganese oxide (e.g., liNi) 1/3 Co 1/3 Mn 1/3 O 2 (also referred to as NCM) 333 ）、LiNi 0.5 Co 0.2 Mn 0.3 O 2 (also referred to as NCM) 523 ）、LiNi 0.5 Co 0.25 Mn 0.25 O 2 (also referred to as NCM) 211 ）、LiNi 0.6 Co 0.2 Mn 0.2 O 2 (also referred to as NCM) 622 ）、LiNi 0.8 Co 0.1 Mn 0.1 O 2 (also referred to as NCM) 811 ) Lithium nickel cobalt aluminum oxide (e.g. LiNi 0.85 Co 0.15 Al 0.05 O 2 ) And at least one of its modified compounds and the like. Examples of olivine structured lithium-containing phosphates may include, but are not limited to, lithium iron phosphate (e.g., liFePO 4 (also abbreviated as LFP)), composite material of lithium iron phosphate and carbon, and manganese lithium phosphate (such as LiMnPO) 4 ) At least one of a composite material of lithium manganese phosphate and carbon, and a composite material of lithium manganese phosphate and carbon.
In some embodiments, the positive electrode film layer further optionally includes a binder. As an example, the binder may include at least one of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), a vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, a vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, a tetrafluoroethylene-hexafluoropropylene copolymer, and a fluoroacrylate resin.
In some embodiments, the positive electrode film layer further optionally includes a conductive agent. As an example, the conductive agent may include at least one of superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
In some embodiments, the positive electrode sheet may be prepared by: dispersing the above components for preparing the positive electrode sheet, such as the positive electrode active material, the conductive agent, the binder and any other components, in a solvent (such as N-methylpyrrolidone) to form a positive electrode slurry; the positive electrode slurry is coated on a positive electrode current collector, and meanwhile, the insulating adhesive film is coated on the edge of the positive electrode current collector, and the positive electrode plate can be obtained after the procedures of drying, cold pressing and the like.
[ negative electrode sheet ]
The negative electrode plate comprises a negative electrode current collector and a negative electrode film layer arranged on at least one surface of the negative electrode current collector. The negative electrode film layer includes a negative electrode active material.
As an example, the anode current collector has two surfaces opposing in its own thickness direction, and the anode film layer is provided on either one or both of the two surfaces opposing the anode current collector.
In some embodiments, the negative electrode current collector may employ a metal foil or a composite current collector. For example, as the metal foil, copper foil may be used. The composite current collector may include a polymeric material base layer and a metal layer formed on at least one surface of the polymeric material base material. The composite current collector may be formed by forming a metal material (copper, copper alloy, nickel alloy, titanium alloy, silver alloy, etc.) on a polymer material substrate (such as a substrate of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
In some embodiments, the anode active material may employ an anode material for a battery, which is well known in the art. As an example, the anode active material may include at least one of the following materials: artificial graphite, natural graphite, soft carbon, hard carbon, silicon-based materials, tin-based materials, lithium titanate, and the like. The silicon-based material may be at least one selected from elemental silicon, silicon oxygen compounds, silicon carbon composites, silicon nitrogen composites, and silicon alloys. The tin-based material may be at least one selected from elemental tin, tin oxide, and tin alloys. However, the present application is not limited to these materials, and other conventional materials that can be used as a battery anode material may be used. These negative electrode materials may be used alone or in combination of two or more.
In some embodiments, the negative electrode film layer further optionally includes a binder. The binder may be at least one selected from Styrene Butadiene Rubber (SBR), polyacrylic acid (PAA), sodium Polyacrylate (PAAs), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium Alginate (SA), polymethacrylic acid (PMAA), and carboxymethyl chitosan (CMCS).
In some embodiments, the negative electrode film layer further optionally includes a conductive agent. The conductive agent is at least one selected from superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene and carbon nanofibers.
In some embodiments, the negative electrode film layer may optionally further include other adjuvants, such as thickening agents (e.g., sodium carboxymethyl cellulose (CMC-Na)), and the like.
In some embodiments, the negative electrode sheet may be prepared by: dispersing the above components for preparing the anode film layer, such as anode material, conductive agent, binder and any other components, in a solvent (such as deionized water) to form anode slurry; and coating the negative electrode slurry on a negative electrode current collector, and obtaining a negative electrode plate after the procedures of drying, cold pressing and the like.
[ electrolyte ]
The electrolyte plays a role in ion conduction between the positive electrode plate and the negative electrode plate. The type of electrolyte is not particularly limited in this application, and may be selected according to the need. For example, the electrolyte may be liquid, gel, or all solid.
In some embodiments, the electrolyte is an electrolyte. The electrolyte includes an electrolyte salt and a solvent.
In some embodiments, the electrolyte salt may be selected from at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium bis-fluorosulfonyl imide, lithium bis-trifluoromethanesulfonyl imide, lithium trifluoromethanesulfonate, lithium difluorophosphate, lithium difluorooxalato borate, lithium difluorodioxaato phosphate, and lithium tetrafluorooxalato phosphate.
In some embodiments, the solvent may be selected from at least one of ethylene carbonate, propylene carbonate, methylethyl carbonate, diethyl carbonate, dimethyl carbonate, dipropyl carbonate, methylpropyl carbonate, ethylpropyl carbonate, butylene carbonate, fluoroethylene carbonate, methyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate, 1, 4-butyrolactone, sulfolane, dimethyl sulfone, methyl sulfone, and diethyl sulfone.
In some embodiments, the electrolyte further optionally includes an additive. For example, the additives may include negative electrode film-forming additives, positive electrode film-forming additives, and may also include additives capable of improving certain properties of the battery, such as additives that improve the overcharge performance of the battery, additives that improve the high or low temperature performance of the battery, and the like.
[ isolation Membrane ]
In some embodiments, a separator is further included in the secondary battery. The type of the separator is not particularly limited, and any known porous separator having good chemical stability and mechanical stability may be used.
In some embodiments, the material of the isolation film may be at least one selected from polyethylene, polypropylene, polyvinylidene fluoride, aramid, polyethylene terephthalate, polytetrafluoroethylene, polyacrylonitrile, polyimide, polyamide, polyester, and natural fiber. The separator may be a single-layer film or a multilayer composite film, and is not particularly limited. When the separator is a multilayer composite film, the materials of the respective layers may be the same or different, and are not particularly limited.
In some embodiments, the positive electrode tab, the negative electrode tab, and the separator may be manufactured into an electrode assembly through a winding process or a lamination process.
Secondary battery
The application provides a secondary battery, which comprises a negative electrode plate, electrolyte and a positive electrode plate.
In some embodiments, the secondary battery may include an outer package. The outer package may be used to encapsulate the electrode assembly and electrolyte described above.
In some embodiments, the outer package of the secondary battery may be a hard case, such as a hard plastic case, an aluminum case, a steel case, or the like. The exterior package of the secondary battery may also be a pouch type pouch, for example. The material of the flexible bag may be plastic, and examples of the plastic include polypropylene, polybutylene terephthalate, and polybutylene succinate.
The shape of the secondary battery is not particularly limited in the present application, and may be cylindrical, square, or any other shape. For example, fig. 1 is a secondary battery 5 of a square structure as an example, and fig. 2 is an exploded view of the secondary battery 5.
In some embodiments, referring to fig. 2, the outer package may include a housing 51 and a cover 53. The housing 51 may include a bottom plate and a side plate connected to the bottom plate, where the bottom plate and the side plate enclose a receiving chamber. The housing 51 has an opening communicating with the accommodation chamber, and the cover plate 53 can be provided to cover the opening to close the accommodation chamber. The positive electrode tab, the negative electrode tab, and the separator may be formed into the electrode assembly 52 through a winding process or a lamination process. The electrode assembly 52 is packaged in the receiving chamber. A non-newtonian fluid electrolyte composition wets in electrode assembly 52. The number of electrode assemblies 52 included in the secondary battery 5 may be one or more, and those skilled in the art may select according to specific practical requirements.
[ electric device ]
Provided is an electric device including a secondary battery of the present application.
In some embodiments, the powered device comprises at least one of any of the secondary batteries of any of the embodiments, the battery modules of any of the embodiments, or the battery packs of any of the embodiments.
The secondary battery, the battery module, or the battery pack may be used as a power source of the electric device, and may also be used as an energy storage unit of the electric device. The power utilization device may include, but is not limited to, mobile devices (e.g., cell phones, notebook computers, etc.), electric vehicles (e.g., electric only vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf carts, electric trucks, etc.), electric trains, ships and satellites, energy storage systems, and the like.
As the electricity consumption device, a secondary battery, a battery module, or a battery pack may be selected according to the use requirements thereof.
Fig. 6 is an electrical device as an example. The electric device is a pure electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle or the like. In order to meet the high power and high energy density requirements of the secondary battery by the power consumption device, a battery pack or a battery module may be employed.
As another example, the device may be a cell phone, tablet computer, notebook computer, or the like. The device is generally required to be light and thin, and a secondary battery can be used as a power source.
Examples
Hereinafter, embodiments of the present application are described. The embodiments described below are exemplary only for the purpose of illustrating the present application and are not to be construed as limiting the present application. The examples are not to be construed as limiting the specific techniques or conditions described in the literature in this field or as per the specifications of the product. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
1. Preparation method
Example 1
(1) Preparation of the first adhesive
300g of deionized water was added to the reaction vessel at room temperature, followed by sequentially adding 24.57g of acrylic acid, 63.32g of acrylonitrile and 12.11g of acrylamide, stirring and dispersing at a stirring speed of 200rpm, and introducing nitrogen (flow rate of 2L/h) for 1h.
First polymerization: heating to 50 ℃, adding 0.001mol of initiator potassium persulfate after the temperature is stable, and reacting for 7 hours;
second polymerization: the temperature is regulated to 80 ℃, and 0.001mol of redox initiator ammonium persulfate and 0.001mol of sodium bisulphite are added for 2 hours;
Post-treatment: after the second polymerization reaction was completed, vacuum was applied for 1 hour to an absolute vacuum of 10Kpa. Lithium hydroxide monohydrate was added for base neutralization to a pH of 7.5. Adding deionized water for dilution to obtain yellowish glue solution, sieving the glue solution with a 150-mesh sieve, and performing demagnetization by using a super-strong magnetic rod demagnetizer to obtain a first adhesive with a solid content of 6%.
(2) Preparation of the second Binder
Preparation of the pre-emulsion: at 20 ℃, 4.2g of double bond-containing dialkyl sulfosuccinate M-30S (solid content 50 wt%) is dissolved in 58g of deionized water, then 2.84g of acrylic acid, 39.47g of n-butyl acrylate and 7.70g of hydroxypropyl acrylate are sequentially added, 0.048g of n-dodecyl mercaptan serving as a chain transfer agent is added, the rotating speed is 300rpm, the mixture is mixed for 30min, and nitrogen is introduced during the period for deoxidization protection, wherein the flow rate of the introduced nitrogen is 100ml/min, so that the pre-emulsion is formed. The pre-emulsion is heated to 85 ℃ at a heating rate of 2 ℃/min and is kept for 30min.
Preparation of a reactive surfactant solution: 2.8g of double bond-containing bis-alkyl sulfosuccinate salt M-30S were dissolved in 51.3g of deionized water. The mixed solution was added to a reaction vessel, and nitrogen was introduced into the reaction vessel at a flow rate of 100 ml/min. Setting the rotating speed of the reaction kettle to 300rpm, heating the reaction temperature to 86 ℃ at a heating speed of 2 ℃/min, and preserving the temperature for 30min to obtain the reactive surfactant solution.
First polymerization: 3g of ammonium persulfate was added to deionized water to prepare a 2.5Wt% ammonium persulfate solution. And simultaneously and continuously dripping the pre-emulsion and the ammonium persulfate solution which are subjected to heat preservation into the reaction kettle, wherein the dripping is completed for 150min, and the heat preservation is performed for 0.5h after the dripping is completed, so as to obtain a second binder seed solution.
Second polymerization: 1.0g of ammonium persulfate was added to deionized water to prepare a 5Wt% ammonium persulfate solution. And (3) dropwise adding the ammonium persulfate solution into the second binder seed solution, wherein the dropwise adding is completed for 120min, and the temperature is kept for 2h after the dropwise adding is completed. After the heat preservation is finished, the temperature is reduced to 65 ℃ at the speed of 2 ℃/min, and the heat preservation is carried out for 30min at the temperature. After the heat preservation is finished, naturally cooling to room temperature, decompressing and pumping to enable the vacuum degree in the reaction kettle to be lower than 0.09mpa, keeping for 30min under the condition, and then deflating to atmospheric pressure.
Post-treatment: and (3) passing the obtained glue solution through 300-mesh filter cloth to obtain the glue solution with the solid content of 50%. And regulating the pH value of the glue solution to 7-8 to obtain the second binder, wherein the solid content of the second binder is 50%.
(3) Insulating glue solution
Adding 0.8g of dispersant sodium polyacrylate into deionized water, and dispersing and stirring for 15min at a rotating speed of 300rpm to obtain a first dispersion liquid;
Adding 150g of insulating material boehmite into the first dispersion liquid, and dispersing and stirring for 75min at a rotating speed of 1500rpm to obtain a second dispersion liquid;
60.33g of a first binder (solid content: 6%) was added to the second dispersion, and the mixture was stirred at 1500rpm for 60 minutes to obtain a third dispersion;
72.4g of a second binder (solid content: 50%) was added to the third dispersion, and the dispersion was stirred at a rotation speed of 500rpm for 60 minutes to obtain the insulating glue solution, the solid content of the glue solution being 30%.
(4) Insulating adhesive film
And (3) placing the insulating glue solution in a glue tank of micro gravure coating equipment, carrying out experiments (the speed ratio is 0.8) at a coating speed of 80m/min, coating the insulating glue solution on the edge of the aluminum foil, and conveying the aluminum foil to an oven at 120 ℃ to obtain the insulating glue film.
Examples 2-5 differ from example 1 in the molar ratio of the monomers used to prepare the first binder, as shown in Table 1.
Examples 6-9 differ from example 1 in the molar ratio of the monomers used to prepare the second binder, as shown in Table 1.
Examples 10 to 13 are different from example 1 in that the mass ratio of the first binder to the second binder is different from example 1, and the total amount of both is the same as example 1, and specific parameters are shown in table 1.
Examples 14 to 15 differ from example 1 in the type of monomer used to prepare the second binder, as shown in Table 1.
Examples 16 to 19 are different from example 1 in the amount of the insulating material added when the insulating paste was prepared, and the specific parameters are shown in Table 1.
Example 20 differs from example 1 in the kind of insulating material, as shown in table 1.
Examples 21 to 24 differ from example 1 in the amount of dispersant used, as shown in Table 1.
Example 25 differs from example 1 in the type of dispersant, as shown in Table 1.
Comparative example 1 differs from example 1 in that the second binder is not contained, and the mass of the first binder is the same as the total amount of the first binder and the second binder in example 1.
Comparative example 2 differs from example 1 in that the first binder is not contained and the mass of the second binder is the same as the total amount of the first binder and the second binder in example 1.
The parameters related to examples 1-25 and comparative examples 1-2 are shown in Table 1.
2. Performance testing
(1) Viscosity of first binder, second binder and insulating glue
The viscosity (25 ℃, rotation speed 12rpm, for 6 min) of the sample was measured with a rotary viscometer (a digital ram display rotor brookfield viscometer TH-NDJ 5S), and the results are recorded in table 2.
(2) Viscosity rebound of insulation glue
The viscosity V at the completion of the preparation of the insulating glue was measured by a rotary viscometer (25 ℃ C., rotation speed: 12rpm, duration: 6 min) 1 Then placing the insulating glue solution into a stirring tank, stirring at 100rpm, testing viscosity V after 72 hr 2 Viscosity rebound (%) = (V 2 -V 1 ）/V 1 *100% the viscosity rebound results are recorded in Table 2.
(3) Cohesive force
The 180 ° peel strength of the insulating film on the aluminum foil was tested with a universal material tester (INSTRON 5969), test conditions: the stretching rate was 50mm/min, the pre-stretching length was 5mm, and the results are recorded in Table 2.
(4) Highest coating speed
And (3) placing the insulating glue solution in a glue tank of micro gravure coating equipment, coating the insulating glue solution on an aluminum foil at a certain speed (for example, 50 m/min), and passing a conveyor belt through a baking oven at 120 ℃ to observe the drying condition of the insulating glue solution. If the drying is good, the coating speed is increased and the cycle is repeated until the highest coating speed is obtained by the test, and the results are shown in Table 2. When the drying condition is poor, the problem that the coating equipment is stopped due to the sticking roll of the insulating glue solution can occur.
(5) Swelling ratio
Pouring the insulating glue solution into a surface dish, placing in an oven at 80 ℃ for 3 days, taking out a dried insulating glue solution sheet (thickness 1-2 cm) after complete drying, and weighing the insulating glue solution sheet with weight of X 1 . Soaking the insulating glue solution sheet in 500ml electrolyte for 7 days, taking out the insulating glue solution sheet, sucking the residual electrolyte on the surface by using dust-free paper, and weighing the insulating glue solution sheet again to obtain a weight X 2 Swelling ratio (%) = (X) was calculated 2 -X 1 ）/X 1 *100%, the results are recorded in table 2.
(6) Cohesive force
And (3) coating the insulating glue solution on the carbon coating layer of the carbon-coated copper foil, and drying to obtain a sample piece, wherein one surface of the sample piece is a copper foil surface, and the other surface of the sample piece is a glue layer formed by the insulating glue solution. The sample piece was cut into a specimen strip having a size of 2cm wide and 6cm long. The copper foil face of the bar was adhered to the surface of a hard substrate (steel plate) with a 3M-55230H double sided tape (note no bubbles during adhesion). Bonding the adhesive layer surface of the fixed spline with 3M-55230H double faced adhesive tape, and covering copper foil with the same size as the double faced adhesive tape on the surface of the double faced adhesive tape (note that no bubbles exist in the bonding process), wherein the double faced adhesive tape has the same size for two times, so as to obtain a test sample;
the copper foil at the first end of the test specimen was manually peeled off from the double-sided tape integrally in the 180 deg. direction for a distance such that it was 1cm back beyond the opposite (i.e., second) end of the entire test specimen. And one end of the tensile testing machine is fixed at a first end (a hard substrate, a carbon-coated copper foil and a glue layer) by a clamp, the other end of the tensile testing machine is fixed at a second end by a clamp, the tensile speed of the tensile testing machine is set to be 50mm/min, and the test tensile length is set to be 100mm for testing. The peel force data obtained in the test is the cohesion of the coating material and the results are recorded in table 2.
3. Analysis of test results for examples and comparative examples
Each of the examples and comparative examples was prepared according to the above-described method, and each of the performance parameters was measured, and the results are shown in Table 2.
TABLE 1
TABLE 2
According to the results of the table, as can be seen from the comparison of examples 1-25 and comparative examples 1-2, the combination of the first binder and the second binder can effectively improve the coating speed, and simultaneously has better binding force, so that the situation that the insulating adhesive film falls off from the edge of the current collector is reduced; the adhesive film has better cohesion, so that the insulating adhesive film has better abrasion resistance and the safety of the secondary battery is improved; has proper swelling rate and lower viscosity rebound property.
As is clear from examples 1 to 5, in the first binder, the molar ratio of the monomer represented by the formula I, the monomer represented by the formula II and the monomer represented by the formula III was controlled to be (5 to 30): (60-80): (5-20), which is helpful to further improve the coating speed and the binding force and control the viscosity of the insulating glue solution within a proper range.
From examples 1,6 to 9, in the second adhesive, the molar ratio of the monomer represented by formula IV, the monomer represented by formula V, and the monomer represented by formula VI was controlled to be (5 to 10): (70-85): (10-20), which contributes to further improvement of coating speed and adhesion while having an appropriate swelling ratio.
As is clear from examples 1 and 10 to 13, when the mass ratio of the first binder to the second binder is 1 (2.5 to 20), it is advantageous to further increase the coating speed of the insulating glue solution, and at the same time, to increase the adhesion and cohesion thereof, maintaining a suitable swelling ratio and a lower viscosity rebound property.
As is evident from examples 1, 14 to 15, R of the unit of formula V of the second adhesive 13 R of the radical and of the unit of the formula VI 15 There are various types of groups.
As can be seen from examples 1, 20 and 25, the insulation paste of the present application is adaptable to different types of dispersants and insulation materials.
The present application is not limited to the above embodiment. The above embodiments are merely examples, and embodiments having substantially the same configuration and the same effects as those of the technical idea within the scope of the present application are included in the technical scope of the present application. Further, various modifications that can be made to the embodiments and other modes of combining some of the constituent elements in the embodiments, which are conceivable to those skilled in the art, are also included in the scope of the present application within the scope not departing from the gist of the present application.
Claims (27)
1. An adhesive composition, characterized in that the adhesive composition comprises a first adhesive and a second adhesive, wherein,
The first binder comprises a structural unit derived from a monomer represented by formula I, a structural unit derived from a monomer represented by formula II, and a structural unit derived from a monomer represented by formula III:
formula I, (-)>Formula II, (-)>The compound of the formula III,
the second binder includes a structural unit derived from a monomer represented by formula IV, a structural unit derived from a monomer represented by formula V, and a structural unit derived from a monomer represented by formula VI:
formula IV>V, & gt>A compound of the formula VI,
wherein R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 、R 11 、R 12 、R 14 Each independently selected from the group consisting of hydrogen,
R 15 、R 16 each independently selected from hydrogen, or R 15 Selected from methyl and R 16 Selected from ethyl;
R 13 selected from ethyl, n-butyl;
R 17 selected from-C (O) O (CH) 2 ) 3 -；
In the first binder, the molar ratio of the structural unit derived from the monomer represented by formula I, the structural unit derived from the monomer represented by formula II, and the structural unit derived from the monomer represented by formula III is (5-30): (60-80): (5-20);
in the second binder, the molar ratio of the structural unit derived from the monomer represented by formula IV, the structural unit derived from the monomer represented by formula V, and the structural unit derived from the monomer represented by formula VI is (5-10): (70-85): (10-20);
the mass ratio of the first binder to the second binder is 1: (2.5-20).
2. The adhesive composition of claim 1, wherein the mass ratio of the first adhesive to the second adhesive is 1: (8-20).
3. The adhesive composition according to claim 1 or 2, wherein the viscosity of the first adhesive is 5000cP-30000cP and the viscosity of the second adhesive is 10cP-3500cP.
4. The adhesive composition of claim 1 or 2, wherein the first adhesive has a viscosity of 10000cP-18000cP and the second adhesive has a viscosity of 1500cP-2800cP.
5. The adhesive composition according to claim 1 or 2, wherein in the first adhesive, the molar ratio of the structural unit derived from the monomer of formula I, the structural unit derived from the monomer of formula II, the structural unit derived from the monomer of formula III is (5-15): (65-75): (15-20);
in the second binder, the molar ratio of the structural unit derived from the monomer represented by formula IV, the structural unit derived from the monomer represented by formula V, and the structural unit derived from the monomer represented by formula VI is (5-8): (78-82): (13-17).
6. A method of preparing the adhesive composition according to any one of claims 1 to 5, comprising:
the preparation method of the first binder comprises the following steps:
(1) Adding solvent, units shown in formula I, formula II and formula III into a container, removing oxygen in a reaction system,
(2) Adding a first initiator into the container to perform a first polymerization reaction, adding a second initiator to perform a second polymerization reaction, wherein the first initiator comprises at least one of sodium persulfate, potassium persulfate or ammonium persulfate, and the second initiator is a redox initiator;
formula I, (-)>Formula II, (-)>The compound of the formula III,
the preparation method of the second binder comprises the following steps:
(1) Adding a first reactive surfactant, units shown in formulas IV, V and VI and a chain transfer agent which are dissolved in a solvent into a container, and removing oxygen in a reaction system to form a pre-emulsion;
(2) Pretreating the second reactive surfactant to obtain a second reactive surfactant solution;
(3) Adding the pre-emulsion and the first initiator into the second reactive surfactant solution, and performing a first polymerization reaction of a second binder to obtain a second binder seed solution;
(4) Adding the first initiator into the second binder seed solution to perform a second polymerization reaction of a second binder;
formula IV>V, & gt>A compound of the formula VI,
wherein R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 、R 11 、R 12 、R 14 Each independently selected from hydrogen;
R 15 、R 16 each independently selected from hydrogen, or R 15 Selected from methyl and R 16 Selected from ethyl;
R 13 selected from ethyl, n-butyl;
R 17 selected from-C (O) O (CH) 2 ) 3 -。
7. The method according to claim 6, wherein in the method for producing the first binder, the temperature of the first polymerization reaction is 40 ℃ to 80 ℃ for 3 hours to 10 hours; the temperature of the second polymerization reaction is 70-90 ℃ and the time is 1-3 h.
8. The method according to claim 6 or 7, wherein in the method for producing the second binder, the temperature of the first polymerization reaction of the second binder is 70 ℃ to 95 ℃ for 0.5h to 3h; the second polymerization reaction of the second binder is carried out at a temperature of 70-95 ℃ for 1-5 h.
9. The method according to claim 6 or 7, wherein in the method for producing the second binder, the pretreatment is carried out at a temperature of 70 ℃ to 95 ℃ for a time of 0.5h to 3h.
10. An insulation cement, characterized in that the insulation cement comprises the binder composition according to any one of claims 1 to 5 or the binder composition produced by the production method according to any one of claims 6 to 9.
11. The insulation paste of claim 10, wherein the insulation paste further comprises an insulation material.
12. The insulating cement according to claim 11, wherein the insulating material comprises at least one of alumina and boehmite.
13. The insulation paste according to claim 11, wherein a mass ratio of the binder composition to the insulation material is (5-30): (60-85).
14. The insulation paste of claim 11, wherein the insulation paste further comprises a dispersant.
15. The insulation paste of claim 14, wherein the dispersant comprises at least one of a polyacrylate, an amide, an ammonium salt, a polyol, and a phosphate.
16. The insulation paste of claim 14, wherein the dispersant comprises at least one of sodium polyacrylate, potassium polyacrylate, polyacrylamide, ammonium chloride, ethylene glycol, polyoxyethylene ether phosphate.
17. The insulation paste according to claim 14, wherein a mass ratio of the dispersant to the insulation material is 0.4: (65-85).
18. The insulation paste according to any one of claims 10 to 17, wherein the viscosity of the insulation paste is 350cP-1200cP.
19. The insulation paste according to any one of claims 10 to 17, wherein the viscosity of the insulation paste is 400cP-700cP.
20. An insulation paste according to any one of claims 10 to 17, wherein the solid content of the insulation paste is 20% -40%.
21. A method of preparing an insulation paste according to any one of claims 10 to 20, comprising:
preparing the first binder and the second binder respectively;
adding a dispersing agent into water to obtain a dispersing liquid;
and respectively adding an insulating material, the first binder and the second binder into the dispersion liquid to obtain the insulating glue solution.
22. An insulating film, characterized in that it comprises the adhesive composition according to any one of claims 1 to 5, or is dried from the insulating glue solution according to any one of claims 10 to 20.
23. A positive electrode sheet comprising a positive electrode current collector and a positive electrode film layer provided on at least one surface of the positive electrode current collector, the positive electrode current collector edge being covered with the insulating film according to claim 22.
24. The positive electrode sheet according to claim 23, wherein the thickness of the insulating film is 3 μm to 10 μm.
25. The positive electrode sheet according to claim 23 or 24, wherein the thickness of the insulating film is 3 μm to 5 μm.
26. A secondary battery characterized in that the secondary battery comprises a negative electrode tab, an electrolyte, and a positive electrode tab according to any one of claims 23 to 25.
27. An electric device, characterized in that the electric device comprises the secondary battery according to claim 26.
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