CN115044331A - Water dispersible polymer microparticle emulsion binder for lithium ion battery and preparation method thereof - Google Patents
Water dispersible polymer microparticle emulsion binder for lithium ion battery and preparation method thereof Download PDFInfo
- Publication number
- CN115044331A CN115044331A CN202110254669.3A CN202110254669A CN115044331A CN 115044331 A CN115044331 A CN 115044331A CN 202110254669 A CN202110254669 A CN 202110254669A CN 115044331 A CN115044331 A CN 115044331A
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- Prior art keywords
- monomer
- water
- mixture
- core
- monomer mixture
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 178
- 229920000642 polymer Polymers 0.000 title claims abstract description 168
- 239000011859 microparticle Substances 0.000 title claims abstract description 128
- 239000000839 emulsion Substances 0.000 title claims abstract description 126
- 239000011230 binding agent Substances 0.000 title claims abstract description 103
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 35
- 239000000178 monomer Substances 0.000 claims abstract description 185
- 239000000203 mixture Substances 0.000 claims abstract description 106
- 239000006185 dispersion Substances 0.000 claims abstract description 24
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 22
- 150000001993 dienes Chemical class 0.000 claims abstract description 20
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 20
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims abstract description 19
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 12
- 239000002612 dispersion medium Substances 0.000 claims abstract description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 26
- 239000002245 particle Substances 0.000 claims description 22
- 239000003792 electrolyte Substances 0.000 claims description 21
- 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 20
- 239000003995 emulsifying agent Substances 0.000 claims description 20
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 20
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 20
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 16
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 16
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 15
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 14
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 14
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 14
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 14
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 claims description 14
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 14
- 239000003999 initiator Substances 0.000 claims description 14
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- 230000009477 glass transition Effects 0.000 claims description 13
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 12
- 238000007654 immersion Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 125000000524 functional group Chemical group 0.000 claims description 11
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 10
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 10
- 150000008051 alkyl sulfates Chemical class 0.000 claims description 10
- 239000003638 chemical reducing agent Substances 0.000 claims description 10
- 150000002978 peroxides Chemical class 0.000 claims description 10
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 10
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 10
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- CJSBUWDGPXGFGA-UHFFFAOYSA-N 4-methylpenta-1,3-diene Chemical compound CC(C)=CC=C CJSBUWDGPXGFGA-UHFFFAOYSA-N 0.000 claims description 8
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 8
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 8
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 8
- 239000008103 glucose Substances 0.000 claims description 8
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 8
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 8
- 235000010265 sodium sulphite Nutrition 0.000 claims description 8
- PYODKQIVQIVELM-UHFFFAOYSA-M sodium;2,3-bis(2-methylpropyl)naphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S([O-])(=O)=O)=C(CC(C)C)C(CC(C)C)=CC2=C1 PYODKQIVQIVELM-UHFFFAOYSA-M 0.000 claims description 8
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 7
- PNGBYKXZVCIZRN-UHFFFAOYSA-M sodium;hexadecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCCCCCS([O-])(=O)=O PNGBYKXZVCIZRN-UHFFFAOYSA-M 0.000 claims description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 6
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 claims description 6
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 6
- 238000010556 emulsion polymerization method Methods 0.000 claims description 6
- 239000001530 fumaric acid Substances 0.000 claims description 6
- NUMHUJZXKZKUBN-UHFFFAOYSA-N methyl 4-ethenylbenzoate Chemical compound COC(=O)C1=CC=C(C=C)C=C1 NUMHUJZXKZKUBN-UHFFFAOYSA-N 0.000 claims description 6
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 6
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 6
- OCTVDLUSQOJZEK-UHFFFAOYSA-N 4,5-diethylocta-1,3-diene Chemical compound CCCC(CC)C(CC)=CC=C OCTVDLUSQOJZEK-UHFFFAOYSA-N 0.000 claims description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 5
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 5
- ZIWRUEGECALFST-UHFFFAOYSA-M sodium 4-(4-dodecoxysulfonylphenoxy)benzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCOS(=O)(=O)c1ccc(Oc2ccc(cc2)S([O-])(=O)=O)cc1 ZIWRUEGECALFST-UHFFFAOYSA-M 0.000 claims description 5
- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical compound ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-UHFFFAOYSA-N 0.000 claims description 4
- FKKAGFLIPSSCHT-UHFFFAOYSA-N 1-dodecoxydodecane;sulfuric acid Chemical compound OS(O)(=O)=O.CCCCCCCCCCCCOCCCCCCCCCCCC FKKAGFLIPSSCHT-UHFFFAOYSA-N 0.000 claims description 4
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 claims description 4
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 claims description 4
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims description 4
- KXYAVSFOJVUIHT-UHFFFAOYSA-N 2-vinylnaphthalene Chemical compound C1=CC=CC2=CC(C=C)=CC=C21 KXYAVSFOJVUIHT-UHFFFAOYSA-N 0.000 claims description 4
- QTTAWIGVQMSWMV-UHFFFAOYSA-N 3,4-dimethylhexa-1,3-diene Chemical compound CCC(C)=C(C)C=C QTTAWIGVQMSWMV-UHFFFAOYSA-N 0.000 claims description 4
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 4
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 claims description 4
- 239000011258 core-shell material Substances 0.000 claims description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 4
- 239000011976 maleic acid Substances 0.000 claims description 4
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims description 2
- IRQWEODKXLDORP-UHFFFAOYSA-N 4-ethenylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=C)C=C1 IRQWEODKXLDORP-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 2
- 235000001727 glucose Nutrition 0.000 claims description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 2
- XFHJDMUEHUHAJW-UHFFFAOYSA-N n-tert-butylprop-2-enamide Chemical compound CC(C)(C)NC(=O)C=C XFHJDMUEHUHAJW-UHFFFAOYSA-N 0.000 claims description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- WKYAPGVTFGNPSP-UHFFFAOYSA-N benzene;chloroethene Chemical compound ClC=C.C1=CC=CC=C1 WKYAPGVTFGNPSP-UHFFFAOYSA-N 0.000 claims 1
- 239000006258 conductive agent Substances 0.000 abstract description 5
- 239000007772 electrode material Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 102
- 238000006243 chemical reaction Methods 0.000 description 80
- 229910052757 nitrogen Inorganic materials 0.000 description 59
- 238000003756 stirring Methods 0.000 description 44
- 239000008367 deionised water Substances 0.000 description 31
- 229910021641 deionized water Inorganic materials 0.000 description 31
- 238000012360 testing method Methods 0.000 description 21
- 238000001816 cooling Methods 0.000 description 20
- 238000004945 emulsification Methods 0.000 description 20
- 238000010438 heat treatment Methods 0.000 description 20
- 238000010992 reflux Methods 0.000 description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 18
- 239000001301 oxygen Substances 0.000 description 18
- 229910052760 oxygen Inorganic materials 0.000 description 18
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 17
- 238000011156 evaluation Methods 0.000 description 11
- SMVRDGHCVNAOIN-UHFFFAOYSA-L disodium;1-dodecoxydodecane;sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O.CCCCCCCCCCCCOCCCCCCCCCCCC SMVRDGHCVNAOIN-UHFFFAOYSA-L 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 9
- 239000002174 Styrene-butadiene Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 229920003048 styrene butadiene rubber Polymers 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000013543 active substance Substances 0.000 description 4
- OPVLOHUACNWTQT-UHFFFAOYSA-N azane;2-dodecoxyethyl hydrogen sulfate Chemical compound N.CCCCCCCCCCCCOCCOS(O)(=O)=O OPVLOHUACNWTQT-UHFFFAOYSA-N 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- MNNZINNZIQVULG-UHFFFAOYSA-N 2-chloroethylbenzene Chemical compound ClCCC1=CC=CC=C1 MNNZINNZIQVULG-UHFFFAOYSA-N 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 239000007767 bonding agent Substances 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 125000003438 dodecyl 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])C([H])([H])C([H])([H])* 0.000 description 2
- 239000011883 electrode binding agent Substances 0.000 description 2
- BOUCRWJEKAGKKG-UHFFFAOYSA-N n-[3-(diethylaminomethyl)-4-hydroxyphenyl]acetamide Chemical compound CCN(CC)CC1=CC(NC(C)=O)=CC=C1O BOUCRWJEKAGKKG-UHFFFAOYSA-N 0.000 description 2
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 238000005411 Van der Waals force Methods 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
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 229940057950 sodium laureth sulfate Drugs 0.000 description 1
- SXHLENDCVBIJFO-UHFFFAOYSA-M sodium;2-[2-(2-dodecoxyethoxy)ethoxy]ethyl sulfate Chemical compound [Na+].CCCCCCCCCCCCOCCOCCOCCOS([O-])(=O)=O SXHLENDCVBIJFO-UHFFFAOYSA-M 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/003—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
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Abstract
The invention relates to a water dispersible polymer microparticle emulsion binder for lithium ion battery and its preparation method, the binder is water dispersible polymer microparticle emulsion, the dispersion medium is water, the emulsion dispersion is specifically polymer microparticle with core, shell structure, the total weight of monomer containing conjugated diene and aromatic vinyl monomer in the core part accounts for more than 80% (weight) of the total weight of the core part monomer mixture, the total weight of monomer containing acrylate monomer and acrylonitrile and/or methacrylonitrile monomer in the shell part accounts for more than 15% (weight) of the total weight of the shell part monomer mixture. The binder can be used for manufacturing a negative electrode of a lithium ion secondary battery and is used for binding an electrode active material, a conductive agent and a current collector.
Description
Technical Field
The invention relates to a water dispersible polymer microparticle emulsion binder for a lithium ion battery and a preparation method thereof.
Background
A lithium ion secondary battery generally consists of a positive electrode, a negative electrode, a separator and an electrolyte. The negative electrode is composed of an active substance, a conductive agent, a binder and a current collector, and the active substance, the conductive agent and the binder are usually mixed into liquid slurry, coated on the current collector, dried and rolled to be manufactured into the negative electrode of the lithium ion battery. The binder, which is one of the internal components of the battery, is capable of connecting the active material and the conductive agent and adhering them to the current collector to form a complete electrode structure. In general, the amount of the binder is only 1.5-5% of the total mass of the electrode, but the binder plays an important role in maintaining the stability of the electrode structure and improving the electrochemistry of the electrode.
The binder for the negative electrode should have the following characteristics: (1) the adhesive can have enough interaction force with the active substance and the current collector to ensure that the active substance is always in a conductive network; (2) by properly swelling the electrolyte, lithium ion conduction inside the electrode can be promoted while the electrode structure is kept stable; (3) the composite material has good mechanical properties; (4) maintaining electrochemical stability over a range of charge/discharge voltages.
Polyvinylidene fluoride (PVDF) is a binder mainly used in the positive and negative electrodes of lithium ion secondary batteries for a long time, has good electrochemical, chemical and thermal stability and higher mechanical strength, meets the basic requirements of serving as an electrode binder and is widely used. However, since PVDF is bonded to an active material only by simple van der waals forces, and has poor adhesion, when it is used as a negative electrode binder, it cannot adapt well to the volume expansion of the active material, and easily causes the negative electrode particles to separate from the conductive network, resulting in excessively rapid degradation of the battery capacity. The sodium carboxymethylcellulose/styrene-butadiene latex (CMC/SBR) mixed bonding system has small elastic modulus, high elongation at break and high bonding strength, and the cycle capacity retention rate of the negative electrode adopting the CMC/SBR composite bonding agent is obviously improved compared with that of the negative electrode adopting the PVDF bonding agent. However, the general SBR binder has poor electrolyte swelling capacity, and the interfacial film resistance and the charge transfer resistance of the electrolyte/electrode are increased, so that the low-temperature performance of the lithium ion battery is poor.
International publication WO2012/128182 reports an SBR composite binder containing dicarboxylic acid, which shows excellent processability and good binding property during electrode preparation, but shows poor low-temperature performance of a lithium ion battery due to poor compatibility with an electrolyte.
CN 101457131B discloses an aqueous binder for an electrode material of an ion battery of a lining and a preparation method thereof, the material is acrylate, a low-polarity polymer is taken as a core, a high-polarity polymer is taken as a shell, and the aqueous binder with a core-shell structure with soft inside and hard outside is formed. The adhesive shows good low-temperature performance of the lithium ion battery, but the adhesive strength is poor.
Disclosure of Invention
Aiming at the problems that the existing PVDF resin binder has low binding power, the polyacrylate binder is easy to expand or slowly dissolve in electrolyte, and the performance is unstable; the polyacrylic acid adhesive is easy to peel off from the electrode plate in the rolling and winding processes, and absorbs water to regain moisture; the CMC/SBR composite binder has poor electrolyte swelling capacity, and the interface film impedance and the charge transfer impedance of the electrolyte/electrode are increased, so that the low-temperature performance of the lithium ion battery is poor. Repeated research proves that the invention provides a water dispersible polymer microparticle emulsion binder for a lithium ion battery and a preparation method thereof, which solve the application problems, and particularly have excellent low-temperature performance.
The adhesive of the invention has excellent adhesive property and good processing property. The ester group with a certain proportion is introduced into the shell part, so that a complete lithium ion transport channel is formed in the electrode, the lithium ion transfer impedance is reduced, the lithium ion conduction rate is improved, the low-temperature performance of the lithium ion battery is improved, and the low-temperature performance is excellent.
The invention relates to a water dispersible polymer microparticle emulsion binder for lithium ion batteries and a preparation method thereof, the binder is water dispersible polymer microparticle emulsion, in particular to polymer microparticles with a core-shell structure, wherein the total amount of a monomer containing conjugated diene and an aromatic vinyl monomer in an inner layer core part accounts for more than 80 percent of the total amount of a monomer mixture of the core part, and the total amount of an acrylate monomer and acrylonitrile and/or methacrylonitrile monomer in an outer layer shell part accounts for more than 15 percent of the total amount of a monomer mixture of the shell part. Drying the water dispersible polymer microparticle emulsion binder to form a film, wherein the film forming condition is 25 deg.C and relative humidity is 75%, and the conductivity of the film is 10 after soaking in 60 deg.C electrolyte for 72 hr -5 s/cm to 10 3 s/cm. The particle size of the water dispersible polymer particles is 120-450nm, the glass transition temperature of the water dispersible polymer is-20-40 ℃, the gel content of the water dispersible polymer is 60-90%, and the pH of the water dispersible polymer particle emulsion binder is 7.5-8.5.
The invention relates to a water dispersible polymer microparticle emulsion binder for a lithium ion battery and a preparation method thereof, wherein the water dispersible polymer microparticle emulsion binder comprises the following components:
a water-dispersed polymer microparticle emulsion binder for lithium ion batteries is characterized in that the binder is a water-dispersed polymer microparticle emulsion, a dispersion medium is water, an emulsion dispersion is polymer microparticles with a core-shell structure, the total weight of a monomer containing conjugated diene and an aromatic vinyl monomer in an inner core part accounts for more than 80 percent of the total weight of a monomer mixture in the core part, and the total weight of an acrylate monomer and acrylonitrile and/or methacrylonitrile monomer in an outer shell part accounts for more than 15 percent of the total weight of a monomer mixture in the shell part.
The water dispersible polymer microparticle emulsion binder for the lithium ion battery is characterized in that the particle size of the water dispersible polymer microparticle is 120-450nm, the glass transition temperature of the water dispersible polymer is-20-40 ℃, and the gel content of the water dispersible polymer is 60-90%.
The water dispersible polymer microparticle emulsion binder for the lithium ion battery is characterized in that a film is formed by drying, wherein the film forming condition is 25 ℃, the relative humidity is 75 percent, and the tensile strength of the film is 1000-5000N/cm 2 The film had a conductivity of 10 after immersion in the electrolyte at 60 ℃ for 72 hours -5 s/cm to 10 3 s/cm。
The preparation method of the water dispersible polymer microparticle emulsion binder for the lithium ion battery is characterized in that a conjugated diene monomer, an aromatic vinyl monomer and an acid functional unsaturated monomer are adopted in a core part, or the conjugated diene monomer, the aromatic vinyl monomer and the acid functional unsaturated monomer and one or more other unsaturated monomers which can be copolymerized with the monomers are adopted; wherein the conjugated diene monomer and the aromatic vinyl monomer together account for 80% or more of the total amount of the core monomer mixture; in the presence of alkyl sulfate emulsifier or/and sulfonate emulsifier aqueous solution and in the presence of water-soluble peroxide initiator or initiator and reducing agent, preparing the core polymer microparticle emulsion by using a discontinuous emulsion polymerization method or/and a stepwise dropwise adding semi-continuous emulsion polymerization method, wherein the polymerization temperature is 30-85 ℃; the shell part adopts conjugated diene monomer, aromatic vinyl monomer, unsaturated monomer containing acid functional group, acrylate monomer and acrylonitrile and/or methacrylonitrile monomer, and the total weight of the monomer containing acrylate monomer and acrylonitrile and/or methacrylonitrile monomer accounts for 15% of the total weight of the monomers of the shell part, under the existence of the core polymer microparticle emulsion, all the monomers are mixed and emulsified by alkyl sulfate emulsifier or/and sulfonate emulsifier, and under the existence of water-soluble peroxide initiator or initiator and reducing agent, the water-dispersible polymer microparticle emulsion binder is prepared by a semi-continuous emulsion polymerization method of batch emulsion polymerization or stepwise dripping, and the polymerization temperature is 35-85 ℃.
The preparation method of the water dispersible polymer microparticle emulsion binder for the lithium ion battery is characterized in that the conjugated diene monomer is one or a mixture of more than one of 1, 3-butadiene, isoprene, methylpentadiene, phenylbutadiene, 3, 4-dimethyl-1, 3-hexadiene and 4, 5-diethyl-1, 3-octadiene in any proportion; the aromatic vinyl monomer is styrene, alpha-methyl styrene, 4-tert-butylstyrene, chloroethylbenzene, vinyl toluene, divinylbenzene, p-chloromethylstyrene, methyl 4-vinylbenzoate, 2-vinylnaphthalene, 4-vinylbenzoic acid, methyl 4-vinylbenzoate, 2-vinylpyridine and 4-vinylpyridine; the unsaturated monomer containing acid functional group is one or a mixture of more than one of acrylic acid, methacrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, crotonic acid, fumaric acid, maleic acid, 2-methylmaleic acid and itaconic acid in any proportion; the alkyl sulfate emulsifier is one or a mixture of more than one of sodium dodecyl sulfate, sodium dodecyl ether sulfate and ammonium dodecyl ether sulfate in any proportion; the sulfonate emulsifier is one or a mixture of more than one of sodium dodecyl benzene sulfonate, sodium hexadecylsulfonate, sodium dodecyl diphenyl ether disulfonate and sodium diisobutylnaphthalenesulfonate in any proportion; the water-soluble peroxide initiator is one or a mixture of more than one of potassium persulfate, sodium persulfate, ammonium persulfate, tert-butyl hydroperoxide and hydrogen peroxide in any proportion; the reducing agent is one or a mixture of more than one of glucose, sodium bisulfite and sodium sulfite in any proportion.
The preparation method of the water dispersible polymer microparticle emulsion binder for the lithium ion battery is characterized in that in the process of preparing the core polymer microparticle emulsion, the other unsaturated monomer with copolymerization possibility is one or a mixture of more than one of methyl acrylate, ethyl acrylate, butyl methacrylate, isooctyl acrylate, methyl methacrylate, glycidyl acrylate, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide and N-tert-butyl acrylamide in any proportion.
The preparation method of the water dispersible polymer microparticle emulsion binder for the lithium ion battery is characterized in that in the process of preparing the core polymer microparticle emulsion, the usage amount of the mixture of the conjugated diene monomer and the aromatic vinyl monomer is 99.5-80% (by weight) of the total amount of the core monomer mixture; the acid functional group-containing unsaturated monomer is used in an amount of 0.5 to 9.0% by weight based on the total amount of the core monomer mixture; the other unsaturated monomer having the possibility of copolymerization is used in an amount of 0 to 11.0% by weight based on the total amount of the core monomer mixture; the usage amount of the alkyl sulfate emulsifier or/and the sulfonate emulsifier is 0.05-3.0% (weight) of the total amount of the core monomer mixture; the amount of the water-soluble peroxide initiator is 0.05-3.0 wt% of the total amount of the core monomer mixture; the amount of the reducing agent used is 0 to 0.5% by weight based on the total amount of the core monomer mixture.
The preparation method of the water dispersible polymer microparticle emulsion binder for the lithium ion battery is characterized in that in the process of preparing the shell water dispersible polymer microparticle emulsion binder, the acrylate monomer is one or a mixture of more than one of methyl acrylate, ethyl acrylate, butyl methacrylate, isooctyl acrylate, methyl methacrylate and glycidyl acrylate in any proportion.
The preparation method of the water dispersible polymer microparticle emulsion binder for the lithium ion battery is characterized in that in the process of preparing the shell water dispersible polymer microparticle emulsion binder, the usage amount of the mixture of the conjugated diene monomer and the aromatic vinyl monomer is 84.95-60% (by weight) of the total amount of the shell monomer mixture; the unsaturated monomer containing acid functional group is used in an amount of 0.05 to 10% by weight based on the total amount of the shell-portion monomer mixture; the usage amount of the acrylic monomer and the acrylonitrile and/or methacrylonitrile monomer mixture is 15-30 percent (weight) of the total amount of the shell monomer mixture; the usage amount of the alkyl sulfate emulsifier or/and the sulfonate emulsifier is 0.05 to 3.0 percent (weight) of the total amount of the shell monomer mixture; the amount of the water-soluble peroxide initiator is 0.05-3.0 wt% of the total amount of the shell monomer mixture; the reducing agent is used in an amount of 0 to 0.5% by weight based on the total amount of the shell-portion monomer mixture.
The preparation method of the water dispersible polymer microparticle emulsion binder for the lithium ion battery is characterized in that the weight ratio of the shell monomer mixture to the core monomer mixture is 90:10-20: 80.
The invention also discloses application of the water dispersible polymer microparticle emulsion binder for the lithium ion battery in preparation of a negative electrode of a lithium ion secondary battery, and the binder is used for binding an electrode active material, a conductive agent and a current collector.
Detailed Description
The present invention will be further illustrated by the following specific examples. It should be understood that these examples are only for the purpose of the present invention and are not intended to limit the scope of the present invention. It should be understood that various changes and modifications can be made by those skilled in the art after reading the disclosure of the present invention, and equivalents fall within the scope of the appended claims.
In the following examples, the core monomer mixture comprises a conjugated diene monomer, an aromatic vinyl monomer, an acid functional group-containing unsaturated monomer, and one or more other unsaturated monomers copolymerizable with the above monomers; the shell monomer mixture is a conjugated diene monomer, an aromatic vinyl monomer, an unsaturated monomer containing acid functional groups, an acrylate monomer and an acrylonitrile and/or methacrylonitrile monomer. The low-temperature test evaluation method comprises the following steps: the dispersed polymer microparticle emulsion binder prepared in example was assembled into a 800mAh cylindrical lithium battery, and after standing at 25 ℃ for 24 hours, the battery was charged to 4.3V at 1C, and the charge capacity W at that time was measured 0 After that, the discharge was made to 3.0V at 1C. Then, the resultant was charged to 4.3V at 1C in an atmosphere of-10 ℃ and the charging capacity W at that time was measured 1 . The low-temperature performance is W1/W0 multiplied by 100 percent, the larger the value of the delta W, the better the low-temperature performance。
Example 1
(1) Preparation of core polymer microparticle emulsion:
100g of deionized exchange water, 0.025g of sodium dodecyl sulfate, 40g of styrene, 9g of acrylic acid and 11g of methyl acrylate were added to a pressure-resistant emulsification vessel equipped with a stirring paddle and a nitrogen inlet valve, respectively. After the nitrogen exchange to remove oxygen, 40g of 1, 3-butadiene was taken in, and stirred to obtain a monomer mixture for use.
80g of deionized exchange water and 0.025g of sodium dodecyl sulfate were added to a pressure-resistant reaction vessel equipped with a stirrer, a thermometer, a nitrogen inlet valve and a reflux condenser, and an aqueous potassium persulfate solution (0.04 g of potassium persulfate dissolved in 10g of deionized exchange water) was added to the reaction vessel while stirring and raising the temperature to 30 ℃. And meanwhile, continuously dropwise adding the monomer mixture for 300 minutes, after dropwise adding is completed, adding 0.01g of potassium persulfate and 10g of deionized water, simultaneously heating to 65 ℃, keeping the temperature until the conversion rate is 97%, stopping reaction, and cooling to obtain the core polymer microparticle emulsion for later use.
(2) Preparation of water dispersion type polymer microparticle emulsion binder
1100g of deionized water, 0.45g of sodium lauryl ether sulfate, 364.55g of alpha-methylstyrene, 0.45g of acrylic acid, 35g of methyl acrylate and 100g of acrylonitrile are respectively added into a pressure-resistant emulsification vessel provided with a stirring paddle and a nitrogen inlet valve. After nitrogen exchange to remove oxygen, 400g of 1, 3-butadiene was taken in and stirred to obtain a monomer mixture for use.
The core polymer microparticle emulsion prepared above was charged into a pressure-resistant reaction vessel equipped with a stirring paddle, a thermometer, a nitrogen inlet valve and a reflux condenser, the temperature was raised to 35 ℃ and an aqueous potassium persulfate solution (0.40 g of potassium persulfate dissolved in 150g of deionized exchange water) was charged into the reaction vessel. Simultaneously, continuously dripping the monomer mixture at 300 minutes, after finishing dripping, adding 0.05g of potassium persulfate and 50g of deionized water, simultaneously heating to 75 ℃, keeping the temperature until the conversion rate is 97%, stopping the reaction, cooling, finally removing residual monomers, and adjusting the pH value to 7.5 to obtain the water dispersible polymer microparticle emulsion binder, wherein the particle size of the water dispersible polymer microparticles is 450nm, the glass transition temperature of the water dispersible polymer is 9 ℃, and the gel content of the water dispersible polymer is 60%.
(3) Aqueous dispersion type polymer microparticle emulsion binder performance
The prepared water dispersible polymer microparticle emulsion binder is dried to form a film, wherein the film forming condition is 25 ℃, the relative humidity is 75%, and the tensile strength of the film is 1650N/cm 2 The film had a conductivity of 2X 10 after immersion in an electrolyte at 60 ℃ for 72 hours -2 s/cm。
The prepared water dispersible polymer microparticle emulsion binder was used for battery test, and evaluation of Δ W was 77% in a low temperature test at-10 ℃.
Example 2
(1) Preparation of core polymer microparticle emulsion:
100g of deionized exchange water, 1.5g of sodium lauryl ether sulfate, 48g of alpha-methylstyrene, 0.5g of methacrylic acid and 0.5g of ethyl acrylate were placed in a pressure-resistant emulsification vessel equipped with a stirring paddle and a nitrogen inlet valve, respectively. After oxygen was removed by nitrogen exchange, 41g of isoprene was taken in, and the monomer mixture was obtained by stirring.
80g of deionized exchange water and 1.5g of sodium lauryl ether sulfate were added to a pressure-resistant reaction vessel equipped with a stirrer, a thermometer, a nitrogen inlet valve and a reflux condenser, and heated to 50 ℃ with stirring, and an aqueous solution of sodium persulfate (2.5 g of sodium persulfate dissolved in 10g of deionized exchange water) was added to the reaction vessel. And meanwhile, continuously dropwise adding the monomer mixture for 300 minutes, after dropwise adding is completed, adding 0.5g of sodium persulfate and 10g of deionized water, simultaneously heating to 75 ℃, keeping the temperature until the conversion rate is 97%, stopping reaction, and cooling to obtain the core polymer microparticle emulsion for later use.
(2) Preparation of water dispersion type polymer microparticle emulsion binder
0.05g of deionized water, 0.75g of sodium lauryl ether sulfate, 7.5g of alpha-methyl styrene, 2.5g of methacrylic acid, 2.5g of ethyl acrylate and 5g of methacrylonitrile are respectively added into a pressure-resistant emulsification vessel provided with a stirring paddle and a nitrogen inlet valve. After the nitrogen exchange to remove oxygen, 7.5g of isoprene was taken in, and stirred to obtain a monomer mixture for use.
The core polymer microparticle emulsion prepared above was added to a pressure-resistant reaction vessel equipped with a stirring paddle, a thermometer, a nitrogen inlet valve and a reflux condenser, the temperature was raised to 55 ℃, and an aqueous solution of sodium persulfate (0.6 g of sodium persulfate dissolved in 3g of deionized exchange water) was added to the reaction vessel. Meanwhile, continuously dripping the monomer mixture at the dripping temperature of 300 minutes, after the dripping is finished, adding 0.15g of sodium persulfate and 1g of deionized water, simultaneously heating to 85 ℃, keeping the temperature until the conversion rate is 97%, stopping the reaction, cooling, finally removing residual monomers, and adjusting the pH value to 8.0 to obtain the water dispersible polymer microparticle emulsion binder, wherein the particle size of the water dispersible polymer microparticles is 120nm, the glass transition temperature of the water dispersible polymer is 13 ℃, and the gel content of the water dispersible polymer is 90%.
(3) Aqueous dispersion type polymer microparticle emulsion binder performance
Drying the prepared water dispersible polymer microparticle emulsion binder to form a film, wherein the film forming condition is 25 ℃, the relative humidity is 75%, and the tensile strength of the film is 1020N/cm 2 The film had a conductivity of 1.2X 10 after immersion in an electrolyte at 60 ℃ for 72 hours -1 s/cm。
The prepared water dispersible polymer microparticle emulsion binder was used for battery test, and evaluation of Δ W was 79% in a low temperature test at-10 ℃.
Example 3
(1) Preparation of core polymer microparticle emulsion:
100g of deionized exchange water, 0.5g of ammonium lauryl ether sulfate, 0.5g of sodium dodecylbenzenesulfonate, 30g of 4-tert-butylstyrene, 3g of 2-acrylamido-2-methylpropanesulfonic acid, and 2g of butyl acrylate were added to a pressure-resistant emulsification vessel equipped with a stirring paddle and a nitrogen inlet valve, respectively. After the nitrogen exchange to remove oxygen, 65g of methylpentadiene was sucked in and stirred to obtain a monomer mixture for further use.
80g of deionized exchange water, 0.5g of ammonium laureth sulfate and 0.5g of sodium dodecylbenzenesulfonate were charged into a pressure-resistant reaction vessel equipped with a stirring paddle, a thermometer, a nitrogen inlet valve and a reflux condenser, and while stirring, a temperature was raised to 55 ℃ to add an aqueous solution of tert-butyl hydroperoxide (1.0 g of tert-butyl hydroperoxide dissolved in 10g of deionized exchange water) to the reaction vessel. And meanwhile, continuously dropwise adding the monomer mixture for 300 minutes, after dropwise adding is completed, adding 0.3g of tert-butyl hydroperoxide and 10g of deionized water, simultaneously heating to 85 ℃, keeping the temperature until the conversion rate is 97%, stopping reaction, and cooling to obtain the core polymer microparticle emulsion for later use.
(2) Preparation of water dispersion type polymer microparticle emulsion binder
400g of deionized water, 2.0g of ammonium lauryl ether sulfate, 2.0g of sodium dodecylbenzene sulfonate, 180g of 4-tert-butylstyrene, 8g of 2-acrylamido-2-methylpropanesulfonic acid, 47g of butyl methacrylate, 10g of acrylonitrile and 15g of methacrylonitrile are respectively added into a pressure-resistant emulsification vessel provided with a stirring paddle and a nitrogen inlet valve. After nitrogen exchange to remove oxygen, 140g of methylpentadiene was sucked in and stirred to obtain a monomer mixture for further use.
The prepared core polymer microparticle emulsion was added to a pressure-resistant reaction vessel equipped with a stirring paddle, a thermometer, a nitrogen inlet valve, and a reflux condenser tube, and the temperature was raised to 65 ℃ to add aqueous tert-butyl hydroperoxide (3 g of tert-butyl hydroperoxide dissolved in 100g of deionized exchange water) to the reaction vessel. Meanwhile, continuously dripping the monomer mixture at the dripping temperature of 300 minutes, after the dripping is finished, adding 1g of tert-butyl hydroperoxide and 50g of deionized water, simultaneously heating to 80 ℃, keeping the temperature until the conversion rate is 97%, stopping the reaction, cooling, finally removing residual monomers, and adjusting the pH value to 8.5 to obtain the water dispersible polymer microparticle emulsion binder, wherein the particle size of the water dispersible polymer microparticles is 150nm, the glass transition temperature of the water dispersible polymer is 20 ℃, and the gel content of the water dispersible polymer is 75%.
(3) Aqueous dispersion type polymer microparticle emulsion binder performance
Drying the prepared water dispersible polymer microparticle emulsion binder to form a film, wherein the film forming condition is 25 ℃, the relative humidity is 75%, and the tensile strength of the film is 1730N/cm 2 The film had a conductivity of 2.3X 10 after immersion in the electrolyte at 60 ℃ for 72 hours 0 s/cm。
The prepared water dispersible polymer microparticle emulsion binder was used for battery test, and evaluation of Δ W was 80% in a-10 ℃ low temperature test.
Example 4
(1) Preparation of core polymer microparticle emulsion:
100g of deionized exchange water, 0.6g of sodium lauryl sulfate, 0.5g of sodium hexadecylsulfonate salt, 41g of chloroethylbenzene and 5g of crotonic acid were fed into a pressure-resistant emulsification vessel equipped with a stirring paddle and a nitrogen inlet valve, respectively. After the nitrogen exchange to remove oxygen, 54g of phenylbutadiene was taken in, and the mixture was stirred to obtain a monomer mixture.
80g of deionized exchange water and 0.6g of sodium dodecyl sulfate were added to a pressure-resistant reaction vessel equipped with a stirring paddle, a thermometer, a nitrogen inlet valve and a reflux condenser tube, and an aqueous ammonium persulfate solution (1.2 g of ammonium persulfate dissolved in 10g of deionized exchange water) was added to the reaction vessel while stirring and raising the temperature to 43 ℃. And meanwhile, continuously dropwise adding the monomer mixture for 300 minutes, after dropwise adding is completed, adding 0.7g of ammonium persulfate and 10g of deionized water, simultaneously heating to 77 ℃, keeping the temperature until the conversion rate is 97%, stopping reaction, and cooling to obtain the nuclear polymer microparticle emulsion for later use.
(2) Preparation of water dispersion type polymer microparticle emulsion binder
150g of deionized water, 1.2g of sodium dodecyl sulfate, 0.5g of sodium hexadecylsulfonate, 42g of chloroethylbenzene, 8g of crotonic acid, 20g of butyl acrylate, 12g of acrylonitrile and 18g of methacrylonitrile are respectively added into a pressure-resistant emulsification vessel provided with a stirring paddle and a nitrogen inlet valve. After the oxygen was removed by nitrogen exchange, 100g of phenylbutadiene was taken in, and the mixture was stirred to obtain a monomer mixture.
The prepared nuclear polymer microparticle emulsion was added to a pressure-resistant reaction vessel equipped with a stirring paddle, a thermometer, a nitrogen inlet valve, and a reflux condenser tube, the temperature was raised to 58 ℃, and an aqueous ammonium persulfate solution (1.3 g of ammonium persulfate dissolved in 80g of deionized exchange water) was added to the reaction vessel. Meanwhile, continuously dripping the monomer mixture at the dripping temperature of 300 minutes, after the dripping is finished, adding 0.6g of ammonium persulfate and 20g of deionized water, simultaneously heating to 83 ℃, keeping the temperature until the conversion rate is 97%, stopping the reaction, cooling, finally removing residual monomers, and adjusting the pH value to 8.4 to obtain the water dispersible polymer microparticle emulsion binder, wherein the particle size of the water dispersible polymer microparticles is 180nm, the glass transition temperature of the water dispersible polymer is-20 ℃, and the gel content of the water dispersible polymer is 65%.
(3) Aqueous dispersion type polymer microparticle emulsion binder performance
Drying the prepared water dispersible polymer microparticle emulsion binder to form a film, wherein the film forming condition is 25 ℃, the relative humidity is 75%, and the tensile strength of the film is 3300N/cm 2 The film had a conductivity of 3.3X 10 after immersion in an electrolyte at 60 ℃ for 72 hours 2 s/cm。
The prepared water dispersible polymer microparticle emulsion binder was used for battery test, and evaluation of Δ W was 84% in a low temperature test at-10 ℃.
Example 5
(1) Preparation of core polymer microparticle emulsion:
100g of deionized exchange water, 1.2g of sodium dodecyl diphenyl oxide disulfonate, 30g of vinyl toluene, 7g of fumaric acid, and 1g of isooctyl acrylate were placed in a pressure-resistant emulsification vessel equipped with a stirring paddle and a nitrogen inlet valve, respectively. After oxygen gas was removed by nitrogen exchange, 62g of 3, 4-dimethyl-1, 3-hexadiene was aspirated, and the mixture was stirred to obtain a monomer mixture for use.
80g of deionized exchange water and 0.2g of sodium dodecyldiphenylether disulfonate were fed into a pressure-resistant reaction vessel equipped with a stirrer, a thermometer, a nitrogen inlet valve and a reflux condenser, and an aqueous solution of potassium persulfate and sodium persulfate (0.3 g of potassium persulfate and 0.1g of sodium persulfate dissolved in 10g of deionized exchange water) was fed into the reaction vessel while raising the temperature to 39 ℃ under stirring. And simultaneously, continuously dropwise adding the monomer mixture for 300 minutes, after dropwise adding is completed, adding 0.1g of potassium persulfate, 0.1g of sodium persulfate and 10g of deionized water, simultaneously heating to 70 ℃, keeping the temperature until the conversion rate is 97%, stopping reaction, and cooling to obtain the core polymer microparticle emulsion for later use.
(2) Preparation of water dispersion type polymer microparticle emulsion binder
10g of deionized water, 0.8g of sodium dodecyl diphenyl oxide disulfonate, 12g of vinyl toluene, 7g of fumaric acid, 8g of isooctyl acrylate, 5g of acrylonitrile and 18g of methacrylonitrile are respectively added into a pressure-resistant emulsification vessel provided with a stirring paddle and a nitrogen inlet valve. After the oxygen gas was removed by nitrogen exchange, 50g of 3, 4-dimethyl-1, 3-hexadiene was aspirated, and the mixture was stirred to obtain a monomer mixture.
The core polymer fine particle emulsion prepared above was charged into a pressure-resistant reaction vessel equipped with a stirrer, a thermometer, a nitrogen inlet valve and a reflux condenser, the temperature was raised to 54 ℃, and an aqueous solution of potassium persulfate and sodium persulfate (0.5 g of potassium persulfate and 0.8g of sodium persulfate dissolved in 60g of deionized exchange water) was charged into the reaction vessel. Meanwhile, continuously dripping the monomer mixture at 300 minutes, after finishing dripping, adding 0.2g of potassium persulfate, 0.3g of sodium persulfate and 30g of deionized water, simultaneously heating to 82 ℃, keeping the temperature until the conversion rate is 97%, stopping reaction, cooling, finally removing residual monomers, and adjusting the pH value to 7.6 to obtain the water dispersible polymer microparticle emulsion binder, wherein the particle size of the water dispersible polymer microparticle is 235nm, the glass transition temperature of the water dispersible polymer is-18 ℃, and the gel content of the water dispersible polymer is 66%.
(3) Aqueous dispersion type polymer microparticle emulsion binder performance
Drying the prepared water dispersible polymer microparticle emulsion binder to form a film, wherein the film forming condition is 25 ℃, the relative humidity is 75%, and the tensile strength of the film is 1450N/cm 2 The film has a conductivity of 72 hours after immersion in an electrolyte at 60 DEG C6.8×10 1 s/cm。
The obtained water dispersible polymer microparticle emulsion binder was used for battery test, and evaluation of Δ W was 83% in a-10 ℃ low temperature test.
Example 6
(1) Preparation of core polymer microparticle emulsion:
100g of deionized exchange water, 0.9g of sodium diisobutylnaphthalenesulfonate, 41g of divinylbenzene, 4g of maleic acid and 10g of methyl methacrylate were charged into a pressure-resistant emulsification vessel equipped with a stirring paddle and a nitrogen inlet valve, respectively. After exchanging with nitrogen to remove oxygen, 45g of 4, 5-diethyl-1, 3-octadiene was taken in, and stirred to obtain a monomer mixture for later use.
80g of deionized exchange water and 0.5g of sodium diisobutylnaphthalenesulfonate were added to a pressure-resistant reaction vessel equipped with a stirring paddle, a thermometer, a nitrogen inlet valve and a reflux condenser, and the temperature was raised to 57 ℃ while stirring, and an aqueous hydrogen peroxide solution (0.8 g of hydrogen peroxide dissolved in 10g of deionized exchange water) was added to the reaction vessel. And meanwhile, continuously dropwise adding the monomer mixture for 300 minutes, after dropwise adding is completed, adding 0.4g of hydrogen peroxide and 10g of deionized water, simultaneously heating to 77 ℃, keeping the temperature until the conversion rate is 97%, stopping reaction, and cooling to obtain the nuclear polymer microparticle emulsion for later use.
(2) Preparation of aqueous dispersion type polymer microparticle emulsion binder
1g of deionized water, 0.75g of sodium diisobutylnaphthalenesulfonate, 20g of divinylbenzene, 4g of maleic acid, 1g of methyl methacrylate and 13g of methacrylonitrile were respectively added to a pressure-resistant emulsification vessel equipped with a stirring paddle and a nitrogen inlet valve. After exchange with nitrogen to remove oxygen, 21g of 4, 5-diethyl-1, 3-octadiene was taken in, and the mixture was stirred to obtain a monomer mixture.
The nuclear polymer microparticle emulsion prepared above was added to a pressure-resistant reaction vessel equipped with a stirring paddle, a thermometer, a nitrogen inlet valve and a reflux condenser, the temperature was raised to 53 ℃, and an aqueous hydrogen peroxide solution (0.8 g of hydrogen peroxide dissolved in 40g of deionized exchange water) was added to the reaction vessel. Meanwhile, continuously dripping the monomer mixture at the dripping temperature of 300 minutes, after the dripping is finished, adding 0.7g of hydrogen peroxide and 14g of deionized water, simultaneously heating to 80 ℃, keeping the temperature until the conversion rate is 97%, stopping the reaction, cooling, finally removing residual monomers, and adjusting the pH value to 7.7 to obtain the water dispersible polymer microparticle emulsion binder, wherein the particle size of the water dispersible polymer microparticles is 350nm, the glass transition temperature of the water dispersible polymer is-15 ℃, and the gel content of the water dispersible polymer is 72%.
(3) Aqueous dispersion type polymer microparticle emulsion binder performance
Drying the prepared water dispersible polymer microparticle emulsion binder to form a film, wherein the film forming condition is 25 ℃, the relative humidity is 75 percent, and the tensile strength of the film is 1010N/cm 2 The film had a conductivity of 3.8X 10 after immersion in an electrolyte at 60 ℃ for 72 hours -3 s/cm。
The prepared water dispersible polymer microparticle emulsion binder was used for battery test, and evaluation of Δ W was 76% in a-10 ℃ low temperature test.
Example 7
(1) Preparation of core polymer microparticle emulsion:
100g of deionized exchange water, 0.2g of sodium dodecyl sulfate, 0.3g of sodium diisobutylnaphthalenesulfonate, 30g of p-chloromethyl styrene, 8g of 2-methyl maleic acid and 4g of glycidyl acrylate are respectively added into a pressure-resistant emulsification vessel provided with a stirring paddle and a nitrogen inlet valve. After the nitrogen exchange to remove oxygen, 58g of 1, 3-butadiene was taken in, and stirred to obtain a monomer mixture for use.
80g of deionized exchange water, 0.2g of sodium dodecyl sulfate and 0.3g of sodium diisobutylnaphthalenesulfonate were added to a pressure-resistant reaction vessel equipped with a stirrer, a thermometer, a nitrogen inlet valve and a reflux condenser, and heated to 60 ℃ with stirring, and an aqueous solution of potassium persulfate and glucose (2.0 g of potassium persulfate and 0.1g of glucose dissolved in 10g of deionized exchange water) was added to the reaction vessel. And meanwhile, continuously dropwise adding the monomer mixture for 300 minutes, after dropwise adding is completed, adding 0.1g of potassium persulfate, 0.05g of glucose and 10g of deionized water, simultaneously heating to 82 ℃, keeping the temperature until the conversion rate is 97%, stopping reaction, and cooling to obtain the core polymer microparticle emulsion for later use.
(2) Preparation of water dispersion type polymer microparticle emulsion binder
1g of deionized water, 0.5g of sodium dodecyl sulfate, 0.8g of sodium diisobutylnaphthalenesulfonate, 27g of p-chloromethyl styrene, 3g of 2-methyl maleic acid, 5g of glycidyl acrylate and 5g of acrylonitrile are respectively added into a pressure-resistant emulsification vessel provided with a stirring paddle and a nitrogen inlet valve. After exchanging with nitrogen gas to remove oxygen, 10g of 4, 5-diethyl-1, 3-octadiene was taken in, and stirred to obtain a monomer mixture for further use.
The core polymer fine particle emulsion prepared above was charged into a pressure-resistant reaction vessel equipped with a stirrer, a thermometer, a nitrogen inlet valve, and a reflux condenser, and the temperature was raised to 53 ℃ to charge the reaction vessel with an aqueous solution of potassium persulfate and glucose (1.0 g of potassium persulfate and 0.05g of glucose dissolved in 15g of deionized exchange water). Simultaneously, continuously dripping the monomer mixture at the dripping temperature of 300 minutes, after finishing dripping, adding 0.1g of potassium persulfate, 0.05g of glucose and 9g of deionized water, simultaneously heating to 80 ℃, keeping the temperature until the conversion rate is 97%, stopping reaction, cooling, finally removing residual monomers, and adjusting the pH value to be 7.9 to obtain the water dispersible polymer microparticle emulsion binder, wherein the particle size of the water dispersible polymer microparticle is 400nm, the glass transition temperature of the water dispersible polymer is 15 ℃, and the gel content of the water dispersible polymer is 74%.
(3) Aqueous dispersion type polymer microparticle emulsion binder performance
Drying the prepared water dispersible polymer microparticle emulsion binder to form a film, wherein the film forming condition is 25 ℃, the relative humidity is 75%, and the tensile strength of the film is 2400N/cm 2 The film had a conductivity of 1.3X 10 after immersion in an electrolyte at 60 ℃ for 72 hours 1 s/cm。
The prepared water dispersible polymer microparticle emulsion binder was used for battery test, and evaluation of Δ W was 82% in a-10 ℃ low temperature test.
Example 8
(1) Preparation of core polymer microparticle emulsion:
100g of deionized exchange water, 0.1g of sodium lauryl ether sulfate, 1.2g of sodium hexadecylsulfonate salt, 40g of methyl 4-vinylbenzoate, 2.5g of itaconic acid and 1g of acrylonitrile were placed in a pressure-resistant emulsification vessel equipped with a stirring paddle and a nitrogen inlet valve, respectively. After oxygen was removed by nitrogen exchange, 55g of 1, 3-butadiene and 1.5g of isoprene were sucked in and stirred to obtain a monomer mixture for further use.
80g of deionized exchange water, 0.1g of sodium lauryl ether sulfate and 1.2g of sodium hexadecylsulfonate were charged into a pressure-resistant reaction vessel equipped with a stirring paddle, a thermometer, a nitrogen inlet valve and a reflux condenser, and heated to 56 ℃ with stirring, and an aqueous solution of ammonium persulfate and sodium bisulfite (0.8 g of ammonium persulfate and 0.09g of sodium bisulfite dissolved in 10g of deionized exchange water) was charged into the reaction vessel. And meanwhile, continuously dropwise adding the monomer mixture for 300 minutes, after dropwise adding is completed, adding 0.5g of ammonium persulfate, 0.01g of sodium bisulfite and 10g of deionized water, simultaneously heating to 84 ℃, keeping the temperature until the conversion rate is 97%, stopping reaction, and cooling to obtain the core polymer microparticle emulsion for later use.
(2) Preparation of water dispersion type polymer microparticle emulsion binder
100g of deionized water, 0.8g of sodium lauryl ether sulfate, 2.2g of sodium hexadecylsulfonate, 59g of methyl 4-vinylbenzoate, 6g of itaconic acid, 5g of methyl acrylate, 10g of glycidyl acrylate and 20g of acrylonitrile are respectively added into a pressure-resistant emulsification vessel provided with a stirring paddle and a nitrogen inlet valve. After removing oxygen by nitrogen exchange, 80g of 1, 3-butadiene and 20g of isoprene were sucked in and stirred to obtain a monomer mixture for later use.
The core polymer fine particle emulsion prepared above was charged into a pressure-resistant reaction vessel equipped with a stirring paddle, a thermometer, a nitrogen inlet valve and a reflux condenser, and the temperature was raised to 61 ℃ to charge an aqueous solution of ammonium persulfate and sodium bisulfite (1.5 g of ammonium persulfate and 0.03g of sodium bisulfite dissolved in 100g of deionized exchange water) into the reaction vessel. Meanwhile, continuously dripping the monomer mixture at the dripping temperature of 300 minutes, after the dripping is finished, adding 0.4g of ammonium persulfate, 0.01g of sodium bisulfite and 50g of deionized water, simultaneously heating to 84 ℃, keeping the temperature until the conversion rate is 97%, stopping the reaction, cooling, finally removing residual monomers, and adjusting the pH value to 8.1 to obtain the water dispersible polymer microparticle emulsion binder, wherein the particle size of the water dispersible polymer microparticles is 220nm, the glass transition temperature of the water dispersible polymer is-5 ℃, and the gel content of the water dispersible polymer is 81%. (3) Aqueous dispersion type polymer microparticle emulsion binder performance
The prepared water dispersible polymer microparticle emulsion binder is dried to form a film, wherein the film forming condition is 25 ℃, the relative humidity is 75%, and the tensile strength of the film is 2800N/cm 2 The film had a conductivity of 1.6X 10 after immersion in the electrolyte at 60 ℃ for 72 hours 1 s/cm。
The prepared water dispersible polymer microparticle emulsion binder was used for battery test, and evaluation of Δ W was 83% in a low temperature test at-10 ℃.
Example 9
(1) Preparation of core polymer microparticle emulsion:
100g of deionized exchange water, 1.3g of ammonium lauryl ether sulfate, 0.1g of sodium dodecyl diphenyl ether disulfonate, 53g of 2-vinylnaphthalene, 5g of acrylic acid, 1g of itaconic acid and 2g of methacrylonitrile are respectively added into a pressure-resistant emulsification vessel provided with a stirring paddle and a nitrogen inlet valve. After removing oxygen by nitrogen exchange, 20g of isoprene and 20g of methylpentadiene were sucked in and stirred to obtain a monomer mixture for further use.
80g of deionized exchange water, 1.3g of ammonium laureth sulfate and 0.1g of sodium laureth sulfate were fed into a pressure-resistant reaction vessel equipped with a stirrer, a thermometer, a nitrogen inlet valve and a reflux condenser, and heated to 63 ℃ with stirring, and an aqueous solution of sodium persulfate and sodium sulfite (1.5 g of sodium persulfate and 0.08g of sodium sulfite dissolved in 10g of deionized exchange water) was fed into the reaction vessel. And simultaneously, continuously dropwise adding the monomer mixture for 300 minutes, after dropwise adding is completed, adding 0.1g of sodium persulfate, 0.05g of sodium sulfite and 10g of deionized water, simultaneously heating to 75 ℃, keeping the temperature until the conversion rate is 97%, stopping reaction, and cooling to obtain the core polymer microparticle emulsion for later use.
(2) Preparation of water dispersion type polymer microparticle emulsion binder
150g of deionized water, 3.0g of ammonium lauryl ether sulfate, 2.0g of sodium dodecyl diphenyl ether disulfonate, 87g of 2-vinyl naphthalene, 15g of acrylic acid, 3g of itaconic acid, 10g of ethyl acrylate, 5g of butyl acrylate and 50g of acrylonitrile are respectively added into a pressure-resistant emulsification container provided with a stirring paddle and a nitrogen inlet valve. After nitrogen exchange was performed to remove oxygen, 30g of isoprene and 50g of methylpentadiene were sucked in, and stirred to obtain a monomer mixture for further use.
The core polymer fine particle emulsion obtained above was charged into a pressure-resistant reaction vessel equipped with a stirring paddle, a thermometer, a nitrogen inlet valve and a reflux condenser, and the temperature was raised to 68 ℃ to charge the reaction vessel with an aqueous solution of sodium persulfate and sodium sulfite (2.0 g of sodium persulfate and 0.2g of sodium sulfite dissolved in 150g of deionized exchange water). Meanwhile, continuously dripping the monomer mixture at the dripping temperature of 300 minutes, after the dripping is finished, adding 0.2g of sodium persulfate, 0.1g of sodium sulfite and 25g of deionized water, simultaneously heating to 79 ℃, keeping the temperature until the conversion rate is 97%, stopping the reaction, cooling, finally removing residual monomers, and adjusting the pH value to 8.3 to obtain the water dispersible polymer microparticle emulsion binder, wherein the particle size of the water dispersible polymer microparticles is 380nm, the glass transition temperature of the water dispersible polymer is 2 ℃, and the gel content of the water dispersible polymer is 83%.
(3) Aqueous dispersion type polymer microparticle emulsion binder performance
Drying the prepared water dispersible polymer microparticle emulsion binder to form a film, wherein the film forming condition is 25 ℃, the relative humidity is 75%, and the tensile strength of the film is 3300N/cm 2 The film had a conductivity of 1.3X 10 after immersion in an electrolyte at 60 ℃ for 72 hours -1 s/cm。
The prepared water dispersible polymer microparticle emulsion binder was used for battery test, and evaluation of Δ W was 80% in a low temperature test at-10 ℃.
Example 10
(1) Preparation of core polymer microparticle emulsion:
100g of deionized exchange water, 0.5g of sodium lauryl ether sulfate, 0.4g of sodium dodecylbenzenesulfonate, 75g of 4-vinylpyridine, 2g of crotonic acid, 3g of fumaric acid and 5g of acrylamide were placed in a pressure-resistant emulsification vessel equipped with a stirring paddle and a nitrogen inlet valve, respectively. After removing oxygen by nitrogen exchange, 10g of methylpentadiene and 5g of phenylbutadiene were sucked in and stirred to obtain a monomer mixture for further use.
80g of deionized exchange water, 0.5g of sodium lauryl ether sulfate and 0.4g of sodium dodecylbenzenesulfonate were charged into a pressure-resistant reaction vessel equipped with a stirring paddle, a thermometer, a nitrogen inlet valve and a reflux condenser, and heated to 51 ℃ with stirring, and an aqueous solution of hydrogen peroxide and sodium bisulfite (1.6 g of hydrogen peroxide and 0.01g of sodium bisulfite dissolved in 10g of deionized exchange water) was charged into the reaction vessel. And meanwhile, continuously dropwise adding the monomer mixture for 300 minutes, after dropwise adding is completed, adding 0.5g of hydrogen peroxide, 0.05g of sodium bisulfite and 10g of deionized water, simultaneously heating to 80 ℃, keeping the temperature until the conversion rate is 97%, stopping reaction, and cooling to obtain the core polymer microparticle emulsion for later use.
(2) Preparation of water dispersion type polymer microparticle emulsion binder
200g of deionized water, 3.5g of sodium lauryl ether sulfate, 2.4g of sodium dodecylbenzenesulfonate, 229g of 4-vinylpyridine, 10g of crotonic acid, 13g of fumaric acid, 10g of ethyl acrylate, 8g of butyl acrylate and 50g of acrylonitrile were placed in a pressure-resistant emulsification vessel equipped with a stirring paddle and a nitrogen inlet valve, respectively. After removing oxygen by nitrogen exchange, 20g of methylpentadiene and 10g of phenylbutadiene were aspirated and stirred to obtain a monomer mixture for further use.
The core polymer microparticle emulsion prepared above was charged into a pressure-resistant reaction vessel equipped with a stirring paddle, a thermometer, a nitrogen inlet valve and a reflux condenser, and the temperature was raised to 52 ℃ to charge an aqueous solution of hydrogen peroxide and sodium hydrogen sulfite (4.0 g of hydrogen peroxide and 0.1g of sodium hydrogen sulfite dissolved in 200g of deionized water) into the reaction vessel. Meanwhile, continuously dripping the monomer mixture at the dripping temperature of 300 minutes, after the dripping is finished, adding 1.5g of hydrogen peroxide, 0.05g of sodium bisulfite and 75g of deionized water, simultaneously heating to 81 ℃, keeping the temperature until the conversion rate is 97%, stopping the reaction, cooling, finally removing residual monomers, and adjusting the pH value to 8.2 to obtain the water dispersible polymer microparticle emulsion binder, wherein the particle size of the water dispersible polymer microparticles is 270nm, the glass transition temperature of the water dispersible polymer is 40 ℃, and the gel content of the water dispersible polymer is 88%. (3) Aqueous dispersion type polymer microparticle emulsion binder performance
Drying the prepared water dispersible polymer microparticle emulsion binder to form a film, wherein the film forming condition is 25 ℃, the relative humidity is 75%, and the tensile strength of the film is 3800N/cm 2 The film had a conductivity of 2.0X 10 after immersion in an electrolyte at 60 ℃ for 72 hours -1 s/cm。
The prepared water dispersible polymer microparticle emulsion binder was used for battery test, and evaluation of Δ W was 80% in a-10 ℃ low temperature test.
Claims (10)
1. A water-dispersed polymer microparticle emulsion binder for lithium ion batteries is characterized in that the binder is a water-dispersed polymer microparticle emulsion, a dispersion medium is water, an emulsion dispersion is polymer microparticles with a core-shell structure, the total weight of a monomer containing conjugated diene and an aromatic vinyl monomer in an inner core part accounts for more than 80 percent of the total weight of a monomer mixture in the core part, and the total weight of an acrylate monomer and acrylonitrile and/or methacrylonitrile monomer in an outer shell part accounts for more than 15 percent of the total weight of a monomer mixture in the shell part.
2. The binder as claimed in claim 1, wherein the particle size of the water dispersible polymer particles is 120-450nm, the glass transition temperature of the water dispersible polymer is-20-40 ℃, the gel content of the water dispersible polymer is 60-90%, and the pH of the water dispersible polymer particle emulsion binder is 7.5-8.5.
3. The aqueous dispersion type polymer particle emulsion binder for lithium ion battery as claimed in claim 1, wherein the binder is dried to form a film, wherein the film forming conditions are 25 ℃ and 75% relative humidity, and the tensile strength of the film is 1000- 2 The film had a conductivity of 10 after immersion in the electrolyte at 60 ℃ for 72 hours -5 s/cm to 10 3 s/cm。
4. The method for preparing a fine emulsion binder of water dispersible polymer particles for lithium ion battery as claimed in claim 1, 2 or 3, wherein the core portion comprises a conjugated diene monomer, an aromatic vinyl monomer, an acid functional group-containing unsaturated monomer, or a conjugated diene monomer, an aromatic vinyl monomer, an acid functional group-containing unsaturated monomer, and one or more other unsaturated monomers copolymerizable with the above monomers; wherein the conjugated diene monomer and the aromatic vinyl monomer together account for 80% or more of the total amount of the core monomer mixture; under the existence of alkyl sulfate emulsifier or/and sulfonate emulsifier aqueous solution and the existence of water-soluble peroxide initiator or initiator and reducing agent, preparing the core polymer microparticle emulsion by using a batch emulsion polymerization method or/and a step-by-step dropwise semi-continuous emulsion polymerization method, wherein the polymerization temperature is 30-85 ℃; the shell part adopts conjugated diene monomer, aromatic vinyl monomer, unsaturated monomer containing acid functional group, acrylate monomer and acrylonitrile and/or methacrylonitrile monomer, and the total weight of the monomer containing acrylate monomer and acrylonitrile and/or methacrylonitrile monomer accounts for 15% of the total weight of the monomers of the shell part, under the existence of the core polymer microparticle emulsion, all the monomers are mixed and emulsified by alkyl sulfate emulsifier or/and sulfonate emulsifier, and under the existence of water-soluble peroxide initiator or initiator and reducing agent, the water-dispersible polymer microparticle emulsion binder is prepared by a semi-continuous emulsion polymerization method of batch emulsion polymerization or stepwise dripping, and the polymerization temperature is 35-85 ℃.
5. The method of claim 4, wherein the conjugated diene monomer is one or a mixture of 1, 3-butadiene, isoprene, methylpentadiene, phenylbutadiene, 3, 4-dimethyl-1, 3-hexadiene and 4, 5-diethyl-1, 3-octadiene in any proportion; the aromatic vinyl monomer is styrene, alpha-methyl styrene, 4-tert-butyl styrene, chloroethylene benzene, vinyl toluene, divinyl benzene, p-chloromethyl styrene, methyl 4-vinylbenzoate, 2-vinyl naphthalene, 4-vinyl benzoic acid, methyl 4-vinyl benzoate, 2-vinyl pyridine and 4-vinyl pyridine; the unsaturated monomer containing acid functional group is one or a mixture of more than one of acrylic acid, methacrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, crotonic acid, fumaric acid, maleic acid, 2-methylmaleic acid and itaconic acid in any proportion; the alkyl sulfate emulsifier is one or a mixture of more than one of sodium dodecyl sulfate, sodium dodecyl ether sulfate and ammonium dodecyl ether sulfate in any proportion; the sulfonate emulsifier is one or a mixture of more than one of sodium dodecyl benzene sulfonate, sodium hexadecylsulfonate, sodium dodecyl diphenyl ether disulfonate and sodium diisobutylnaphthalenesulfonate in any proportion; the water-soluble peroxide initiator is one or a mixture of more than one of potassium persulfate, sodium persulfate, ammonium persulfate, tert-butyl hydroperoxide and hydrogen peroxide in any proportion; the reducing agent is one or a mixture of more than one of glucose, sodium bisulfite and sodium sulfite in any proportion.
6. The method of claim 4, wherein the other unsaturated monomer that may be copolymerized in the preparation of the core polymer particle emulsion is one or a mixture of more than one of methyl acrylate, ethyl acrylate, butyl methacrylate, isooctyl acrylate, methyl methacrylate, glycidyl acrylate, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, and N-t-butylacrylamide.
7. The method of claim 4, wherein the conjugated diene monomer and the aromatic vinyl monomer are used in an amount of 99.5 to 80 wt% based on the total amount of the core monomer mixture in the preparation of the core polymer particle emulsion; the acid functional group-containing unsaturated monomer is used in an amount of 0.5 to 9.0% by weight based on the total amount of the core monomer mixture; the amount of said other unsaturated monomer having the possibility of copolymerization used is 0 to 11.0% by weight based on the total amount of the core monomer mixture; the usage amount of the alkyl sulfate emulsifier or/and the sulfonate emulsifier is 0.05-3.0% (weight) of the total amount of the core monomer mixture; the amount of the water-soluble peroxide initiator is 0.05-3.0 wt% of the total amount of the core monomer mixture; the amount of the reducing agent used is 0 to 0.5% by weight based on the total amount of the core monomer mixture.
8. The method of claim 4, wherein the acrylate monomer is one or a mixture of at least one of methyl acrylate, ethyl acrylate, butyl methacrylate, isooctyl acrylate, methyl methacrylate, and glycidyl acrylate.
9. The method of claim 4, wherein the amount of the conjugated diene monomer and the aromatic vinyl monomer mixture used in the preparation of the shell-portion water-dispersible polymer microparticle emulsion binder is 84.95-60 wt% of the total amount of the shell-portion monomer mixture; the acid-functional unsaturated monomer is used in an amount of 0.05 to 10% by weight based on the total amount of the shell-monomer mixture; the usage amount of the acrylic monomer and the acrylonitrile and/or methacrylonitrile monomer mixture is 15-30 percent (weight) of the total amount of the shell monomer mixture; the usage amount of the alkyl sulfate emulsifier or/and the sulfonate emulsifier is 0.05 to 3.0 percent (weight) of the total amount of the shell monomer mixture; the usage amount of the water-soluble peroxide initiator is 0.05 to 3.0 percent (weight) of the total amount of the shell monomer mixture; the reducing agent is used in an amount of 0 to 0.5% by weight based on the total amount of the shell-portion monomer mixture.
10. The method of claim 4, wherein the weight ratio of the shell portion monomer mixture to the core portion monomer mixture is 90:10 to 20: 80.
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| JPH07157736A (en) * | 1993-12-03 | 1995-06-20 | Mitsui Toatsu Chem Inc | Pressure-sensitive adhesive for information-carrying sheet |
| KR100512366B1 (en) * | 2003-06-27 | 2005-09-02 | 주식회사 엘지화학 | Method for Preparing Styrene-Butadienes Latex |
| CN107338011B (en) * | 2016-08-16 | 2019-06-07 | 南京工业大学 | A kind of water-dispersed polymer particulate emulsion binder and preparation method thereof |
| CN108929401A (en) * | 2018-06-25 | 2018-12-04 | 重庆云天化瀚恩新材料开发有限公司 | A kind of lithium battery silicium cathode adhesive and preparation method thereof |
| CN112437996B (en) * | 2018-08-29 | 2023-07-25 | 日本瑞翁株式会社 | Composition for adhesive layer, battery member, laminate, and method for manufacturing battery |
| CN110183584B (en) * | 2019-05-05 | 2023-05-05 | 欣旺达惠州动力新能源有限公司 | Acrylonitrile polymer emulsion binder and preparation method thereof |
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2021
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115332540A (en) * | 2022-10-18 | 2022-11-11 | 江苏道赢科技有限公司 | Negative electrode binder for secondary battery and preparation method thereof |
| CN115332540B (en) * | 2022-10-18 | 2023-01-31 | 江苏道赢科技有限公司 | Negative electrode binder for secondary battery and preparation method thereof |
| CN115842132A (en) * | 2022-12-29 | 2023-03-24 | 江苏道赢科技有限公司 | Lithium battery composite binder and preparation method thereof |
| CN115842132B (en) * | 2022-12-29 | 2023-09-22 | 江苏道赢科技有限公司 | Lithium battery composite binder and preparation method thereof |
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| CN115044331B (en) | 2023-05-09 |
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