CN106207184B - A kind of water adhesive for lithium ion battery and its preparation method and application - Google Patents
A kind of water adhesive for lithium ion battery and its preparation method and application Download PDFInfo
- Publication number
- CN106207184B CN106207184B CN201610631551.7A CN201610631551A CN106207184B CN 106207184 B CN106207184 B CN 106207184B CN 201610631551 A CN201610631551 A CN 201610631551A CN 106207184 B CN106207184 B CN 106207184B
- Authority
- CN
- China
- Prior art keywords
- monomer
- preparation
- methyl
- acid
- vinyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000853 adhesive Substances 0.000 title claims abstract description 48
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 147
- -1 acrylic ester Chemical class 0.000 claims abstract description 62
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 48
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 47
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims abstract description 46
- 239000002270 dispersing agent Substances 0.000 claims abstract description 30
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 29
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 28
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 28
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 28
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 26
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 12
- 229920001577 copolymer Polymers 0.000 claims abstract description 12
- 125000005019 carboxyalkenyl group Chemical group 0.000 claims abstract description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 32
- 239000011230 binding agent Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 18
- 239000000839 emulsion Substances 0.000 claims description 16
- 239000003999 initiator Substances 0.000 claims description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- 239000006210 lotion Substances 0.000 claims description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 9
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000006136 alcoholysis reaction Methods 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- VVAAYFMMXYRORI-UHFFFAOYSA-N 4-butoxy-2-methylidene-4-oxobutanoic acid Chemical compound CCCCOC(=O)CC(=C)C(O)=O VVAAYFMMXYRORI-UHFFFAOYSA-N 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 239000002585 base Substances 0.000 claims description 5
- 238000006386 neutralization reaction Methods 0.000 claims description 5
- 150000002978 peroxides Chemical class 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- 238000007127 saponification reaction Methods 0.000 claims description 5
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 4
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 claims description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 238000007334 copolymerization reaction Methods 0.000 claims description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N fumaric acid group Chemical group C(\C=C\C(=O)O)(=O)O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- PVUWSOGHWGLPPX-UHFFFAOYSA-N lithium;2-methylidenebutanedioic acid Chemical compound [Li].OC(=O)CC(=C)C(O)=O PVUWSOGHWGLPPX-UHFFFAOYSA-N 0.000 claims description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 239000012966 redox initiator Substances 0.000 claims description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 125000003368 amide group Chemical group 0.000 claims description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 150000001451 organic peroxides Chemical class 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 claims description 2
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 claims description 2
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 2
- ZVYGIPWYVVJFRW-UHFFFAOYSA-N 3-methylbutyl prop-2-enoate Chemical compound CC(C)CCOC(=O)C=C ZVYGIPWYVVJFRW-UHFFFAOYSA-N 0.000 claims description 2
- NQSLZEHVGKWKAY-UHFFFAOYSA-N 6-methylheptyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C(C)=C NQSLZEHVGKWKAY-UHFFFAOYSA-N 0.000 claims description 2
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 2
- NVKHKMBMLSFNNU-UHFFFAOYSA-N C=CC1=CC=CC=C1.[S] Chemical group C=CC1=CC=CC=C1.[S] NVKHKMBMLSFNNU-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 2
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- NRJLFIBTTMRLAM-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate;sodium Chemical compound [Na].CCOC(=O)C(C)=C NRJLFIBTTMRLAM-UHFFFAOYSA-N 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 2
- RLQOUIUVEQXDPW-UHFFFAOYSA-M lithium;2-methylprop-2-enoate Chemical compound [Li+].CC(=C)C([O-])=O RLQOUIUVEQXDPW-UHFFFAOYSA-M 0.000 claims description 2
- XSAOIFHNXYIRGG-UHFFFAOYSA-M lithium;prop-2-enoate Chemical compound [Li+].[O-]C(=O)C=C XSAOIFHNXYIRGG-UHFFFAOYSA-M 0.000 claims description 2
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 2
- 238000010979 pH adjustment Methods 0.000 claims description 2
- GYDSPAVLTMAXHT-UHFFFAOYSA-N pentyl 2-methylprop-2-enoate Chemical compound CCCCCOC(=O)C(C)=C GYDSPAVLTMAXHT-UHFFFAOYSA-N 0.000 claims description 2
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- 235000010265 sodium sulphite Nutrition 0.000 claims description 2
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 claims description 2
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- 229940068984 polyvinyl alcohol Drugs 0.000 claims 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims 2
- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical compound FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-UHFFFAOYSA-N 0.000 claims 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims 1
- 150000001408 amides Chemical class 0.000 claims 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 claims 1
- 150000004702 methyl esters Chemical class 0.000 claims 1
- 150000004968 peroxymonosulfuric acids Chemical group 0.000 claims 1
- 235000019260 propionic acid Nutrition 0.000 claims 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 claims 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims 1
- 230000007704 transition Effects 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 16
- 239000010703 silicon Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- 238000005259 measurement Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 229940117958 vinyl acetate Drugs 0.000 description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- TVFWYUWNQVRQRG-UHFFFAOYSA-N 2,3,4-tris(2-phenylethenyl)phenol Chemical compound C=1C=CC=CC=1C=CC1=C(C=CC=2C=CC=CC=2)C(O)=CC=C1C=CC1=CC=CC=C1 TVFWYUWNQVRQRG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical group COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical class OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000011883 electrode binding agent Substances 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- YWOITFUKFOYODT-UHFFFAOYSA-N methanol;sodium Chemical compound [Na].OC YWOITFUKFOYODT-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical group CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- 238000000879 optical micrograph Methods 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000011866 silicon-based anode active material Substances 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 239000012453 solvate Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
A kind of water adhesive for lithium ion battery and its preparation method and application.Described adhesive is modified polyvinylalcohol dispersing agent and (methyl) acrylic ester monomer, unsaturated carboxylic acid monomer, vinyl hydrocarbon monomer and optionally other copolymerizable monomer copolymers, comprising in sulfonic group alkenyl monomer, carboxyalkenyl monomer and amido alkenyl monomer any one or at least two combination.When the present invention uses the copolymer containing modified polyvinylalcohol as dispersing agent, can improve polyvinyl alcohol leads Electronic Performance.The water adhesive for lithium ion battery can be used for lithium ion battery.
Description
Technical field
The invention belongs to field of lithium ion battery, are related to a kind of electrode material of secondary lithium ion battery, and in particular to a kind of
Lithium ion secondary battery aqueous binder and its preparation method and application.
Background technique
Lithium ion battery generallys use graphite carbon material as negative electrode active material at present, and this kind of material is followed in charge and discharge
In ring, volume change is small.But the battery capacity of this kind of carbon material is low, for example, the graphite theoretical capacity of high-crystallinity is 372mAh/
g.And use high discharge capacity such as silicon, tin or silicon stannum alloy as negative electrode active material when, volume change is quite big, and be easy dislike
Change.Such as cubical expansivity is up to 300% when silicon-based active substance embedding lithium, swelling stress causes silica-base material structure to crush, from
And the conductive connection of active material and collector between electrode material is destroyed, so that electrode plates deteriorate.
It the problems such as causing cell deformation, deterioration in order to solve the circulation volume expansion of non-carbonaceous negative electrode active material, needs
It develops high bond strength and is capable of the adhesive of evenly dispersed swelling stress to realize the non-carbonaceous active substance cathode of high capacity
Cyclical stability.
CN 101361212A discloses a kind of degree of polymerization and is greater than the poly (vinyl alcohol) binder that 2500, saponification degree is greater than 90%,
But the present inventor, which studies, to be confirmed, poor to the dispersion performance of slurry when the polyvinyl alcohol that the degree of polymerization is 3000 is as adhesive, especially
Nanoscale conductive black can not be dispersed well, affect the performance of silicon-based anode pole piece performance, while charge and discharge
Pole piece expansion is big after circulation.On the other hand, polyvinyl alcohol electric conductivity is poor, and using as binders for electrodes will increase in electrode
It hinders, a large amount of hydroxyl is contained on polymer chain, can have certain binding force to lithium ion, influence lithium ion electrical conductance.
Many prior arts are modified polyvinyl alcohol progress object phase complex technique to polyvinyl alcohol by taking, and make
For the adhesive of silicon based anode material.
CN 102412401A is compound simultaneously by the polyacrylic acid and polyvinyl alcohol for introducing certain alkali metal hydroxide neutralization
Adhesive of the high-temperature cross-linking as silicon-based anode shows high cohesive force and promotes cycle performance of battery, but such one kind
Adhesive itself is more crisp to be unfavorable for pole piece processing.CN 101507020A prepares polyvinyl alcohol and polyurethanes Semi-IPN
Network adhesive shows preferable cohesive force as silicon-based anode adhesive, the bath resistance having had and improved drawing
Performance is stretched, the capacity or power output performance of battery are promoted.CN 101529625A is by being greater than 3000 and saponification degree for the degree of polymerization
Carried out greater than 80% polyvinyl alcohol and polyvinylpyrrolidone it is compound, as silicon substrate or the adhesive of tin base cathode material, from
And reduce the expansion of pole piece.
CN 104247088A is by vinyl acetate and acrylic acid copolymer and alcoholysis has obtained carboxy-modified polyethylene
Alcohol improves the heat resistance of polyvinyl alcohol, and the adhesive as secondary battery membrane ceramic powders.CN 101260282A
Using polyvinyl alcohol or its acetal derivant as main polymer, takes two or more opposed polarity monomer to be used as and connect
Graft copolymer, prepares highly viscous lotion and the positive electrode binder as battery, solves that positive compacted density is relatively low and pole piece
More crisp problem after drying.
But presently, not occurring one kind yet in the market there is excellent adhesion strength to show excellent dispersion performance again
, excellent high rate performance is shown, the big functional adhesive of the volume expansion especially suitable for silicon-based anode active material.
Summary of the invention
In view of the deficiencies of the prior art, one of the objects of the present invention is to provide a kind of lithium ion battery aqueous binders
Agent.Adhesive of the invention has excellent adhesion strength and dispersion performance and excellent lithium ion electrical conductance and ionic conductivity.
To achieve the goals above, present invention employs following technical solutions:
A kind of water adhesive for lithium ion battery, described adhesive be include modified polyvinylalcohol dispersing agent and (methyl)
Acrylic ester monomer, unsaturated carboxylic acid class monomer, vinyl hydrocarbon monomer and optionally other copolymerisable monomer copolymers；
The polymer molecular chain of the modified polyvinylalcohol dispersing agent include sulfonic group alkenyl monomer, carboxyalkenyl monomer and
In amido alkenyl monomer any one or at least two combination.
The present inventor carrys out Study Polymer Melts molecular chain structure as starting point using water adhesive for lithium ion battery and gathers
Close the relationship between object and the performance of lithium ion battery.The study found that by introducing sulfonic group, carboxyl in polyvinyl alcohol molecule chain
The high rate performance of battery can be promoted with amido, while increasing its cohesive force to active material and collector, and in order to improve
Pole piece prepared by polyvinyl alcohol is easy embrittlement, can be by by modified polyvinylalcohol dispersing agent and (methyl) esters of acrylic acid list
Body, unsaturated carboxylic acid class monomer, vinyl hydrocarbon monomer and other copolymerisable monomer in-situ copolymerizations prepare aqueous binder.
The inventors discovered that when modified polyvinylalcohol is as dispersing agent, it can be evenly dispersed to help pulp particle, it plays and mentions
Rise cycle performance of battery.Meanwhile prepared using modified polyvinylalcohol as dispersing agent (methyl) acrylic ester monomer, unsaturation
Carboxylic acid type monomer, vinyl hydrocarbon monomer and other copolymerisable monomer copolymers have high flexibility as adhesive and glue
Power is tied, so that aqueous binder of the invention has excellent adhesive property.
Preferably, the sulfonic group alkenyl monomer is selected from sodium styrene sulfonate, sodium vinyl sulfonate, allyl sulphonic acid
It is sodium, 2- methallylsulfonic acid sodium, ethyl methacrylate sodium sulfonate, any one in 2- acrylamide-2-methyl propane sulfonic
Kind or at least two combination.
Preferably, the carboxyalkenyl monomer is in fumaric acid, (methyl) acrylic acid, itaconic acid, monobutyl itaconate
Any one or at least two combination.
Preferably, the amido alkenyl monomer is selected from (methyl) acrylamide, N hydroxymethyl acrylamide, N, N- dimethyl
In acrylamide any one or at least two combination.
Preferably, the degree of polymerization of the modified polyvinylalcohol dispersing agent be 800-8000, for example, 820,890,950,
1200,1500,1750,1850,1900,2000,2100,2300,2600,3000,3500,4000,4500,5000,5500 etc.,
Preferably 1700~6000, saponification degree 70-99%, for example, 71%, 74%, 78%, 82%, 85%, 88%, 91%,
94%, 98% etc., preferably 80~99%.
Preferably, the modified polyvinylalcohol dispersing agent accounts for 3.0~80wt% of adhesive solids gross mass, for example,
5wt%, 10wt%, 14wt%, 19wt%, 25wt%, 30wt%, 34wt%, 38wt%, 45wt%, 50wt%, 56wt%,
62wt%, 70wt%, 75wt% etc..
Preferably, the sulfonic group alkenyl monomer, carboxyalkenyl monomer and amido alkenyl monomer three's gross mass account for modification
0.01~15wt% of polyvinyl alcohol dispersing agent quality, for example, 0.05wt%, 0.10wt%, 0.4wt%, 0.9wt%,
2.5wt%, 3.0wt%, 5.0wt%, 7.0wt%, 10.0wt%, 12.0wt%, 14.0wt% etc..
Preferably, (methyl) acrylic ester monomer is selected from methyl acrylate, ethyl acrylate, acrylic acid fourth
Ester, isobutyl acrylate, acrylic acid n-pentyl ester, isoamyl acrylate, the just own ester of acrylic acid, Isooctyl acrylate monomer, acrylic acid hydroxyl
Propyl ester, 2-Hydroxy ethyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, methacrylic acid
Butyl ester, Isobutyl methacrylate, n-amylmethacrylate, the just own ester of methacrylic acid, isooctyl methacrylate, methyl
In hydroxypropyl acrylate or methacrylic acid -2- hydroxy methacrylate any one or at least two combination.
Preferably, the unsaturated carboxylic acid class monomer is selected from Lithium acrylate, acrylic acid, lithium methacrylate, metering system
In acid, itaconic acid lithium, itaconic acid, itaconic acid lithium mono-n-butylester or monobutyl itaconate any one or at least two combination.
Preferably, the vinyl hydrocarbon monomer is selected from vinylacetate, styrene, α-methylstyrene, styrene sulphur
In sour sodium or ethylene methacrylic sodium sulfonate any one or at least two combination.
Preferably, other described copolymerisable monomers are selected from acrylamide, N hydroxymethyl acrylamide, N- ethenyl pyrrolidone
In ketone, vinylpyridine, vinyl imidazole, vinyl acetate, vinyl propionate or vinyl butyrate any one or extremely
Few two kinds of mixture.
An object of the present invention, which also resides in, provides the preparation side of water adhesive for lithium ion battery of the present invention
Method, by modified polyvinylalcohol dispersing agent and (methyl) acrylic ester monomer, unsaturated carboxylic acid monomer, vinyl hydrocarbon monomer with
And optionally other copolymerisable monomer in-situ polymerizations obtain above-mentioned aqueous binder.
Preferably, the modified polyvinylalcohol dispersing agent is prepared by method as described below: by vinyl acetate and sulphur
In acidic group alkenyl monomer, carboxyalkenyl monomer and amido alkenyl monomer any one or at least two combination copolymerization so that alcohol
Solution.
Preferably, the described method comprises the following steps:
(a) (methyl) acrylic ester monomer, unsaturated carboxylic acid list are added in modified polyvinylalcohol aqueous dispersant
Body, vinyl hydrocarbon monomer and optionally other copolymerisable monomers and initiator occur polymerization reaction, obtain lotion；
(b) (methyl) acrylic ester monomer, unsaturated carboxylic acid monomer, vinyl are added into lotion obtained by step (a)
Hydrocarbon monomer and optionally other copolymerisable monomers and initiator occur polymerization reaction, obtain copolymer emulsion, i.e. lithium ion
Battery aqueous binder.
Preferably, modified polyvinylalcohol dispersing agent described in step (a) is (methyl) acrylic ester monomer, unsaturated carboxylic
The 3-100wt% of acid monomers, vinyl hydrocarbon monomer and optionally other copolymerisable monomer gross masses, for example, 5wt%,
10wt%, 14wt%, 19wt%, 25wt%, 30wt%, 34wt%, 38wt%, 45wt%, 50wt%, 56wt%, 62wt%,
70wt%, 75wt%, 82wt%, 88wt%, 93wt%, 99wt% etc., preferably 10~80wt%.
Preferably, step (a) or (b) described in initiator be organic peroxide evocating agent, inorganic peroxide cause
In agent or redox initiator any one or at least two combination.
Preferably, the organic peroxide evocating agent is benzoyl peroxide or/and cumyl peroxide.
Preferably, the inorganic peroxide initiator is any in ammonium persulfate, sodium peroxydisulfate or potassium peroxydisulfate
It is a kind of or at least two combination.
Preferably, the redox initiator is selected from the combination of ammonium persulfate/sodium sulfite or ammonium persulfate/Asia
The combination of sodium bisulfate.
Preferably, the quality of the initiator is (methyl) acrylic ester monomer, unsaturated carboxylic acid monomer, vinyl hydrocarbon
0.1~2wt% of class monomer and optionally other copolymerisable monomer gross masses, for example, 0.3wt%, 0.6wt%,
1.0wt%, 1.4wt%, 1.8wt% etc..
Preferably, in step (b) (methyl) acrylic ester monomer, unsaturated carboxylic acid monomer, vinyl hydrocarbon monomer with
And the gross mass of optionally other copolymerisable monomers account for (methyl) acrylic ester monomer being added in step (a) and step (b),
0~85wt% of unsaturated carboxylic acid monomer, vinyl hydrocarbon monomer and optionally other copolymerisable monomer gross masses, for example,
19wt%, 25wt%, 30wt%, 34wt%, 38wt%, 45wt%, 50wt%, 56wt%, 62wt%, 70wt%, 75wt%,
82wt% etc..
Preferably, the modified polyvinylalcohol dispersing agent and (methyl) acrylic ester monomer, unsaturated carboxylic acid monomer, second
The glass transition temperature of alkenyl hydrocarbon monomer and other copolymerisable monomer copolymers is -25~30 DEG C.
Preferably, the temperature of polymerization reaction is 30~90 DEG C in step (a) and step (b), preferably 60~90 DEG C, step
(a) and in step (b) temperature of polymerization reaction may be the same or different.
Preferably, the time of polymerization reaction described in step (a) and step (b) is 3~6h, for example, 3.2h, 3.8h,
4.5h, 5.0h, 5.2h, 5.7h etc..The time of polymerization reaction may be the same or different in step (a) and step (b).
Preferably, step (b) is repeated 0~3 time.
Preferably, polymerization reaction occurs under agitation.
Preferably, the method also includes (c): after polymerization reaction, adjusting the process of multiple emulsion pH.
Preferably, multiple emulsion pH to 6~10 is adjusted.
Preferably, pH adjustment process can be realized by alkali neutralization.
Preferably, the described method comprises the following steps:
(a ') passes through any in vinyl acetate and sulfonic group alkenyl monomer, carboxyalkenyl monomer and amido alkenyl monomer
A kind of or at least two combination copolymerization and then alcoholysis prepare modified polyvinylalcohol dispersing agent；
(a) in modified poly ethylene alcohol solution plus, be added (methyl) acrylic ester monomer, unsaturated carboxylic acid monomer,
Vinyl hydrocarbon monomer and optionally other copolymerisable monomers and initiator, at 60~90 DEG C, stirring polymerization reaction 3~
6h prepares lotion；
(b) at 60~90 DEG C, in the lotion that obtains to step (2), (methyl) acrylic ester monomer, unsaturation is added
Carboxylic acid monomer, vinyl hydrocarbon monomer and optionally other copolymerisable monomers and initiator stir polymerization reaction；
(c) alkali neutralization obtains the copolymer emulsion that pH is 6-10, i.e. water adhesive for lithium ion battery.
An object of the present invention, which also resides in, provides a kind of purposes of water adhesive for lithium ion battery as described above,
It is used for lithium ion battery.
Compared with the prior art, the invention has the following beneficial effects:
The present invention, which introduces sulfonic group, carboxyl and amido using polyvinyl alcohol molecule chain, can promote the excellent bonding of adhesive
Intensity, dispersion performance and excellent lithium ion electrical conductance and ionic conductivity；(the first prepared using modified polyvinylalcohol as dispersing agent
Base) acrylic ester monomer, unsaturated carboxylic acid monomer, vinyl hydrocarbon monomer and other copolymerisable monomer copolymers are as viscous
Mixture has high flexibility and cohesive force, so that aqueous binder of the invention has excellent adhesive property, it is particularly suitable
In silicon-based anode adhesive.
Detailed description of the invention
Fig. 1 is that the SEM of 1 pole piece of embodiment schemes；
Fig. 2 is that the SEM of 1 pole piece of comparative example schemes.
Specific embodiment
To further illustrate the technical scheme of the present invention below with reference to the accompanying drawings and specific embodiments.
Embodiment 1
The preparation of dispersing agent:
350 mass parts Methanols, 1000 mass parts vinylacetates, 2- acrylamide-are added in the dry four-hole bottle of 2000mL
75 mass parts of 2- methyl propane sulfonic acid methanol solution (40w%) are warming up to 45 DEG C, under nitrogen protection, and 0.4 mass parts azo two is added
Isobutyronitrile causes polymerization, and stirring polymerization 2 hours obtains sulfonic acid modified polyvinyl acetate copolymer.Hydroxide is added under room temperature
Sodium methanol solution is stirred to react 1 hour, removes methanol solvate, is washed and dry, is obtained tristyrylphenol ethoxylate of sulfonic acid modified polyvinyl alcohol copolymer,
The degree of polymerization 2500, alcoholysis degree 99%.
Adhesive agent emulsion preparation:
In the deionized water of 550 mass parts, 50 mass parts sulfonic acid modified polyethylene and ethylene copolymers are added, is warming up to 70 DEG C and stirs
It mixes down, styrene 40wt%, the butyl acrylate 58wt% and acrylic acid 2wt% mix monomer for containing 50 mass parts is added, and add
Enter the ammonium persulfate of 0.25 mass parts, react 6 hours, reaction terminates to adjust pH=7.0 with 10% lithium hydroxide solution, obtains
Adhesive agent emulsion.
The production of battery pole piece
Adhesive described in above-described embodiment is used for the production of silicon substrate/composite cathode material of silicon/carbon/graphite pole piece.
As silicon substrate/composite cathode material of silicon/carbon/graphite, preferably SiOx/ C or Si-C composite material and natural stone containing Si and C
Ink or artificial graphite carry out compound preparation.
The present invention, it is preferred to use gram volume is silicon substrate/composite cathode material of silicon/carbon/graphite of 500mAh/g.
Silicon substrate composite negative pole material mass fraction is 92.0wt%, conductive black 4.0wt%, the mass fraction in terms of solid content
Aqueous binder described in embodiment for 4w% (is denoted as m-PVA), is added according to the ratio that total solid composition is 45% appropriate
Battery pole piece slurry is made in deionized water.After finely dispersed slurry is sieved with 100 mesh sieve net, it is coated on 10 μ as collector
On m thickness copper foil, 120 DEG C of dryings after five minutes, at room temperature with 10 × 104The linear load of N/m rolls and obtains electrode pole
Piece.
Embodiment 2
In addition to 2- acrylamide-2-methyl propane sulfonic is substituted for monobutyl itaconate, with side same as Example 1
Formula prepares adhesive.
Embodiment 3
In addition to 2- acrylamide-2-methyl propane sulfonic is substituted for acrylamide, make in the same manner as example 1
Standby adhesive.
Embodiment 4
Adhesive agent emulsion preparation: tristyrylphenol ethoxylate of sulfonic acid modified polyvinyl alcohol dispersing agent usage amount is down to 10 mass parts by 50 mass parts, mixes
It closes monomer to increase to other than 90 mass parts, prepares adhesive in the same manner as in example 1.
Embodiment 5
Embodiment 1 obtains adhesive agent emulsion and is followed by warming up to again under 70 DEG C of stirrings, and the styrene for containing 50 mass parts is added
45wt%, butyl acrylate 53wt% and acrylic acid 2wt% mix monomer, and the ammonium persulfate of 0.25 mass parts is added, reaction 6
Hour, reaction terminates to adjust pH=7.0 with 10% lithium hydroxide solution, obtains adhesive agent emulsion.
Embodiment 6
The step of in 5 gained lotion of embodiment according to embodiment 5, carries out 2 polymerizations again, obtains adhesive agent emulsion.
Comparative example 1
Adhesive agent emulsion preparation: except the degree of polymerization 2500 is used, the unmodified polyethylene alcohol of alcoholysis degree 99% is as dispersing agent
In addition, adhesive is prepared in the same manner as example 1.
Comparative example 2
Adhesive of the sulfonic group modified polyvinyl alcohol of the preparation of embodiment 1 as lithium ion battery is used alone.
The lithium ion secondary battery aqueous binder of the method for the invention preparation has carried out the measurement of following performance and has commented
Valence, associated pole piece production formula and test evaluation the results are shown in Table 1:
The measurement of average grain diameter
Use the average grain diameter and its particle diameter distribution of laser particle analyzer measurement composition polymer.
The measurement of glass transition temperature
Heat analysis is carried out to multiple emulsion using DSC thermal analyzer.
The measurement of peel strength
The electrode plates of embodiment and comparative example are cut into the strip of 20cm × 2.5cm, in afflux side double-sided adhesive
It is bonded the steel plate of thickness 1mm, in coating layer side stickup adhesive tape, with cupping machine with the speed of 100mm/min towards 180 ° of sides
To removing, and measure peel stress.
The evaluation of pole piece flexibility
Diameter of phi=3mm plug is placed into the collector side of pole piece after the roll-in of embodiment and comparative example, and is carried out curved
It reckons the actual amount after a discount and tests, by the state of optical microphotograph sem observation pole piece at this time, pole piece is intact to be denoted as zero, falls off or cracks and is denoted as
×。
Cell Performance Evaluation
Above-mentioned pole piece is made into simulated battery and the initial coulomb efficiency of its charge and discharge cycles is tested using constant flow method and is followed
Coulombic efficiency and capacity retention ratio after ring 50 times, after charge and discharge cycles 50 weeks, the embedding lithium state inferior pole piece thickness value added of pole piece
Pole piece expansion rate (%) is denoted as with the ratio of pole piece thickness before charge and discharge.
Table 1
Such as find out from table 1 above, compared with using the electrode of the adhesive of comparative example 1,2, use is real according to the present invention
The electrode for applying the adhesive of a 1-6 shows quite high cohesive force, and after 50 weeks charge and discharge cycles, capacity retention ratio is high, pole piece
Expansion rate is below comparative example 1 and 2.
Fig. 1 is pole piece SEM figure prepared by embodiment 1, and display conductive black is evenly dispersed in pole piece；Fig. 2 is comparative example 1
The pole piece SEM of preparation schemes, and shows that apparent agglomeration occurs in pole piece for conductive black.
The Applicant declares that the present invention is explained by the above embodiments method detailed of the invention, but the present invention not office
Be limited to above-mentioned method detailed, that is, do not mean that the invention must rely on the above detailed methods to implement.Technical field
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., all of which fall within the scope of protection and disclosure of the present invention.
Claims (32)
1. a kind of water adhesive for lithium ion battery, which is characterized in that described adhesive be include modified polyvinylalcohol dispersion
Agent and (methyl) acrylic ester monomer, unsaturated carboxylic acid class monomer, vinyl hydrocarbon monomer and optionally other are copolymerizable
Monomer copolymer；
The polymer molecular chain of the modified polyvinylalcohol dispersing agent includes sulfonic group alkenyl monomer, carboxyalkenyl monomer and amido
In alkenyl monomer any one or at least two combination；
The degree of polymerization of the modified polyvinylalcohol dispersing agent is 800-8000, saponification degree 70-99%；
The unsaturated carboxylic acid class monomer be selected from Lithium acrylate, acrylic acid, lithium methacrylate, methacrylic acid, itaconic acid lithium,
In itaconic acid, itaconic acid lithium mono-n-butylester or monobutyl itaconate any one or at least two combination.
2. aqueous binder according to claim 1, which is characterized in that the sulfonic group alkenyl monomer is selected from styrene sulphur
Sour sodium, sodium vinyl sulfonate, Sodium Allyl Sulfonate, 2- methallylsulfonic acid sodium, ethyl methacrylate sodium sulfonate, 2- propylene
In amide -2- methyl propane sulfonic acid any one or at least two combination.
3. aqueous binder according to claim 1, which is characterized in that the carboxyalkenyl monomer is selected from fumaric acid, (first
Base) acrylic acid, itaconic acid, in monobutyl itaconate any one or at least two combination.
4. aqueous binder according to claim 1, which is characterized in that the amido alkenyl monomer is selected from (methyl) propylene
Amide, N hydroxymethyl acrylamide, N, in N- dimethylacrylamide any one or at least two combination.
5. aqueous binder according to claim 1, which is characterized in that the degree of polymerization of the modified polyvinylalcohol dispersing agent
It is 1700~6000, saponification degree is 80~99%.
6. aqueous binder according to claim 1, which is characterized in that the modified polyvinylalcohol dispersing agent accounts for adhesive
3.0~80wt% of solid gross mass.
7. aqueous binder according to claim 1, which is characterized in that the sulfonic group alkenyl monomer, carboxyalkenyl list
Body and amido alkenyl monomer three's gross mass account for 0.01~15wt% of modified polyvinylalcohol dispersing agent quality.
8. aqueous binder according to claim 1, which is characterized in that (methyl) acrylic ester monomer is selected from third
E pioic acid methyl ester, ethyl acrylate, butyl acrylate, isobutyl acrylate, acrylic acid n-pentyl ester, isoamyl acrylate, acrylic acid
Just own ester, Isooctyl acrylate monomer, hydroxypropyl acrylate, 2-Hydroxy ethyl acrylate, lauryl acrylate, methyl methacrylate
Ester, ethyl methacrylate, butyl methacrylate, Isobutyl methacrylate, n-amylmethacrylate, methacrylic acid
In just own ester, isooctyl methacrylate, hydroxy propyl methacrylate or methacrylic acid -2- hydroxy methacrylate any one or
At least two combination.
9. aqueous binder according to claim 1, which is characterized in that the vinyl hydrocarbon monomer is selected from vinyl acetate
In ester, styrene, α-methylstyrene, sodium styrene sulfonate or ethylene methacrylic sodium sulfonate any one or at least two group
It closes.
10. aqueous binder according to claim 1, which is characterized in that other described copolymerisable monomers are selected from acryloyl
Amine, N hydroxymethyl acrylamide, n-vinyl pyrrolidone, vinylpyridine, vinyl imidazole, vinyl acetate, propionic acid second
In enester or vinyl butyrate any one or at least two mixture.
11. a kind of preparation method of the described in any item water adhesive for lithium ion battery of claim 1-10, will be modified poly-
Vinyl alcohol dispersing agent and (methyl) acrylic ester monomer, unsaturated carboxylic acid monomer, vinyl hydrocarbon monomer and optionally its
He obtains above-mentioned aqueous binder by copolymerisable monomer in-situ polymerization.
12. preparation method according to claim 11, which is characterized in that the modified polyvinylalcohol dispersing agent is by following institute
State method preparation: by any in vinyl acetate and sulfonic group alkenyl monomer, carboxyalkenyl monomer and amido alkenyl monomer
A kind of or at least two combinations are copolymerized and then alcoholysis.
13. preparation method according to claim 12, which comprises the following steps:
(a) (methyl) acrylic ester monomer, unsaturated carboxylic acid monomer, second are added in modified polyvinylalcohol aqueous dispersant
Alkenyl hydrocarbon monomer and optionally other copolymerisable monomers and initiator occur polymerization reaction, obtain lotion；
(b) (methyl) acrylic ester monomer, unsaturated carboxylic acid monomer, vinyl hydro carbons are added into lotion obtained by step (a)
Monomer and optionally other copolymerisable monomers and initiator occur polymerization reaction, obtain copolymer emulsion, i.e. lithium ion battery
Use aqueous binder.
14. preparation method according to claim 13, which is characterized in that the dispersion of modified polyvinylalcohol described in step (a)
Agent is (methyl) acrylic ester monomer, unsaturated carboxylic acid monomer, vinyl hydrocarbon monomer and optionally other copolymerizable lists
The 3-100wt% of body gross mass.
15. preparation method according to claim 14, which is characterized in that the dispersion of modified polyvinylalcohol described in step (a)
Agent is (methyl) acrylic ester monomer, unsaturated carboxylic acid monomer, vinyl hydrocarbon monomer and optionally other copolymerizable lists
10~80wt% of body gross mass.
16. preparation method according to claim 13, which is characterized in that step (a) or (b) described in initiator be it is organic
In peroxide initiator, inorganic peroxide initiator or redox initiator any one or at least two group
It closes.
17. preparation method according to claim 16, which is characterized in that the organic peroxide evocating agent is peroxidating
Benzoyl or/and cumyl peroxide.
18. preparation method according to claim 16, which is characterized in that the inorganic peroxide initiator is selected from over cure
In sour ammonium, sodium peroxydisulfate or potassium peroxydisulfate any one or at least two combination.
19. preparation method according to claim 16, which is characterized in that the redox initiator is selected from persulfuric acid
The combination of ammonium/sodium sulfite or the combination of ammonium persulfate/sodium hydrogensulfite.
20. preparation method according to claim 16, which is characterized in that the quality of the initiator is (methyl) acrylic acid
Esters monomer, unsaturated carboxylic acid monomer, vinyl hydrocarbon monomer and optionally other copolymerisable monomer gross masses 0.1~
2wt%.
21. preparation method according to claim 13, which is characterized in that (methyl) acrylic ester monomer in step (b),
The gross mass of unsaturated carboxylic acid monomer, vinyl hydrocarbon monomer and optionally other copolymerisable monomers accounts for step (a) and step
(b) (methyl) acrylic ester monomer, unsaturated carboxylic acid monomer, the vinyl hydrocarbon monomer and optionally other being added in
0~85wt% of comonomer gross mass.
22. preparation method according to claim 13, which is characterized in that the modified polyvinylalcohol dispersing agent and (methyl)
The vitrifying of acrylic ester monomer, unsaturated carboxylic acid monomer, vinyl hydrocarbon monomer and other copolymerisable monomer copolymers
Transition temperature is -25~30 DEG C.
23. preparation method according to claim 13, which is characterized in that the temperature of polymerization reaction in step (a) and step (b)
Degree is 30~90 DEG C.
24. preparation method according to claim 23, which is characterized in that the temperature of polymerization reaction in step (a) and step (b)
Degree is 60~90 DEG C.
25. preparation method according to claim 13, which is characterized in that polymerization reaction described in step (a) and step (b)
Time be 0.5~6h.
26. preparation method according to claim 13, which is characterized in that repeat step (b) 0~3 time.
27. preparation method according to claim 13, which is characterized in that polymerization reaction occurs under agitation.
28. preparation method according to claim 13, which is characterized in that further include (c): after polymerization reaction, adjusting
The process of multiple emulsion pH.
29. preparation method according to claim 28, which is characterized in that adjust multiple emulsion pH to 6~10.
30. preparation method according to claim 28, which is characterized in that pH adjustment process is realized by alkali neutralization.
31. the described in any item preparation methods of 1-30 according to claim 1, which is characterized in that the described method comprises the following steps:
(a ') passes through any one in vinyl acetate and sulfonic group alkenyl monomer, carboxyalkenyl monomer and amido alkenyl monomer
Or at least two combination copolymerization and then alcoholysis prepare modified polyvinylalcohol dispersing agent；
(a) add in modified poly ethylene alcohol solution, (methyl) acrylic ester monomer, unsaturated carboxylic acid monomer, ethylene is added
Base hydrocarbon monomer and optionally other copolymerisable monomers and initiator stir 0.5~6h of polymerization reaction at 60~90 DEG C,
Prepare lotion；
(b) at 60~90 DEG C, in the lotion that obtains to step (2), (methyl) acrylic ester monomer, unsaturated carboxylic acid is added
Monomer, vinyl hydrocarbon monomer and optionally other copolymerisable monomers and initiator stir polymerization reaction；
(c) alkali neutralization obtains the copolymer emulsion that pH is 6-10, i.e. water adhesive for lithium ion battery.
32. the purposes of the described in any item water adhesive for lithium ion battery of claim 1-10, which is characterized in that it is used for
Lithium ion battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610631551.7A CN106207184B (en) | 2016-08-03 | 2016-08-03 | A kind of water adhesive for lithium ion battery and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610631551.7A CN106207184B (en) | 2016-08-03 | 2016-08-03 | A kind of water adhesive for lithium ion battery and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106207184A CN106207184A (en) | 2016-12-07 |
| CN106207184B true CN106207184B (en) | 2019-03-01 |
Family
ID=57498519
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610631551.7A Active CN106207184B (en) | 2016-08-03 | 2016-08-03 | A kind of water adhesive for lithium ion battery and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106207184B (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107641170B (en) * | 2017-09-27 | 2020-09-11 | 贵州理工学院 | Polymer emulsion, preparation method, prepared water-based adhesive, method and application |
| CN109957360B (en) * | 2017-12-22 | 2020-09-15 | 宁德时代新能源科技股份有限公司 | Water-based binder and secondary battery |
| CN108832125B (en) * | 2018-05-28 | 2022-04-12 | 九江华先新材料有限公司 | Lithium battery negative electrode aqueous binder, preparation method thereof and electrode plate preparation method |
| CN110616055B (en) * | 2018-06-20 | 2022-08-05 | 贝特瑞新材料集团股份有限公司 | Water-based binder and preparation method and application thereof |
| KR20210019442A (en) * | 2018-06-20 | 2021-02-22 | 니폰 제온 가부시키가이샤 | Method for producing slurry for secondary battery functional layer |
| CN111384397B (en) * | 2018-12-27 | 2022-03-25 | 中创新航科技股份有限公司 | Composite binder for silicon-based lithium ion battery cathode, preparation method of composite binder and silicon-based lithium ion battery |
| CN110854368B (en) * | 2019-11-21 | 2021-09-28 | 陕西煤业化工技术研究院有限责任公司 | High-capacity silicon-carbon negative electrode precursor material and preparation method thereof |
| CN111354948B (en) * | 2020-03-27 | 2021-04-27 | 成都翊昂科技有限公司 | Ternary high-nickel positive electrode adhesive for lithium ion battery and preparation method thereof |
| TWI752700B (en) * | 2020-10-30 | 2022-01-11 | 長興材料工業股份有限公司 | Graft copolymer and use thereof |
| CN112795247B (en) * | 2021-01-08 | 2022-05-03 | 厦门大学 | High-viscosity PVDF (polyvinylidene fluoride) coated diaphragm and preparation method thereof |
| CN113991118B (en) * | 2021-10-29 | 2023-07-04 | 西安交通大学 | Silicon-carbon negative electrode material adhesive and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001123138A (en) * | 1999-10-26 | 2001-05-08 | Konishi Co Ltd | Synthetic resin emulsion adhesive |
| CN101260282A (en) * | 2008-03-18 | 2008-09-10 | 成都中科来方能源科技有限公司 | Water adhesive for lithium ion battery, preparation method thereof and lithium ion battery positive plate |
| CN101319021A (en) * | 2007-06-04 | 2008-12-10 | 昭和高分子株式会社 | Aqueous latex |
| CN102746462A (en) * | 2012-07-19 | 2012-10-24 | 安徽皖维高新材料股份有限公司 | Method for preparing water-soluble polyvinyl acetate (PVA) resin through vinyl acetate-acrylic acid copolymerization |
| CN104497192A (en) * | 2014-12-12 | 2015-04-08 | 安徽皖维高新材料股份有限公司 | Preparation method capable of rapidly dissolving PVA resin |
| CN105261759A (en) * | 2015-09-22 | 2016-01-20 | 深圳市贝特瑞新能源材料股份有限公司 | Aqueous adhesive for lithium battery and preparation method of aqueous adhesive, and lithium battery plate |
-
2016
- 2016-08-03 CN CN201610631551.7A patent/CN106207184B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001123138A (en) * | 1999-10-26 | 2001-05-08 | Konishi Co Ltd | Synthetic resin emulsion adhesive |
| CN101319021A (en) * | 2007-06-04 | 2008-12-10 | 昭和高分子株式会社 | Aqueous latex |
| CN101260282A (en) * | 2008-03-18 | 2008-09-10 | 成都中科来方能源科技有限公司 | Water adhesive for lithium ion battery, preparation method thereof and lithium ion battery positive plate |
| CN102746462A (en) * | 2012-07-19 | 2012-10-24 | 安徽皖维高新材料股份有限公司 | Method for preparing water-soluble polyvinyl acetate (PVA) resin through vinyl acetate-acrylic acid copolymerization |
| CN104497192A (en) * | 2014-12-12 | 2015-04-08 | 安徽皖维高新材料股份有限公司 | Preparation method capable of rapidly dissolving PVA resin |
| CN105261759A (en) * | 2015-09-22 | 2016-01-20 | 深圳市贝特瑞新能源材料股份有限公司 | Aqueous adhesive for lithium battery and preparation method of aqueous adhesive, and lithium battery plate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106207184A (en) | 2016-12-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106207184B (en) | A kind of water adhesive for lithium ion battery and its preparation method and application | |
| CN105131875B (en) | A kind of water adhesive for lithium ion battery, preparation method and its usage | |
| CN111139002B (en) | Water-soluble adhesive for lithium ion battery, preparation method of water-soluble adhesive, electrode plate and battery | |
| CN111825804B (en) | Copolymer latex for lithium ion secondary battery cathode, preparation method and application | |
| KR100644063B1 (en) | Composite binder for an electrode with dispersants chemically bound | |
| CN110616055B (en) | Water-based binder and preparation method and application thereof | |
| CN115050922B (en) | Water-based adhesive and preparation method and application thereof | |
| CN106866846A (en) | A kind of lithium ion battery aqueous binders and preparation method thereof and electrodes of lithium-ion batteries | |
| CN107868160B (en) | Composition of binder for lithium ion secondary battery cathode and preparation method thereof | |
| WO2001029917A1 (en) | Binder composition for electrodes of lithium ion secondary batteries and use thereof | |
| JPH11149929A (en) | Battery binder composition, battery electrode slurry, lithium secondary battery electrode, and lithium secondary battery | |
| CN114243011B (en) | Piezoelectric material for battery cathode and preparation method thereof | |
| JP2013004229A (en) | Binder for lithium secondary battery electrode, method for producing binder for lithium secondary battery electrode, lithium secondary battery electrode, and lithium secondary battery | |
| CN111234105A (en) | Vinylene carbonate modified binder and lithium ion battery containing same | |
| CN114573751A (en) | Dispersing agent for lithium ion battery, preparation method of dispersing agent, positive electrode slurry, positive plate and lithium ion battery | |
| CN113480695A (en) | Core-shell binder material and preparation method thereof | |
| CN112259913A (en) | Diaphragm slurry and preparation method and application thereof | |
| CN113563531B (en) | Graft copolymer aqueous binder, preparation method and application thereof in silicon carbon negative electrode | |
| JP2000100436A (en) | Polymer particle, polymer dispersing composition, slurry for battery electrode, electrode and battery | |
| CN116462792A (en) | Lithium battery carbon-coated foil conductive slurry, modified acrylic composite resin emulsion and preparation method thereof | |
| CN112375179B (en) | Bimolecular-weight-distribution binder for negative electrode and preparation method and application thereof | |
| JP4240604B2 (en) | Binder composition, slurry for battery electrode, electrode and battery | |
| CN114335895A (en) | Functional layer material for coating lithium ion battery diaphragm | |
| CN117678043A (en) | Binder composition for negative electrode | |
| JP2011100665A (en) | Binder resin composition for electrode |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20180912 Address after: 242099 Anhui Xuancheng economic and Technological Development Zone, Qingyi Jiangxi Road, Xuancheng science and Technology Park, C4, C7 Applicant after: Xuancheng research and development Amperex Technology Limited Address before: 518106 Guangdong Shenzhen Guangming New District Gongming office, saitan community high tech Industrial Park eighth Applicant before: Shenzhen BTR New Energy Material Co., Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20200319 Address after: B901, building 1, Yinxing Zhijie phase II, No. 1301-76, Xinlan community sightseeing Road, Guanlan street, Longhua District, Shenzhen City, Guangdong Province Patentee after: Shenzhen Yanyi New Material Co., Ltd Address before: 242099 Anhui Xuancheng economic and Technological Development Zone, Qingyi Jiangxi Road, Xuancheng science and Technology Park, C4, C7 Patentee before: Xuancheng research and development Amperex Technology Ltd. |