CN117727939A - Thick coating slurry for negative electrode, negative electrode and lithium ion battery - Google Patents
Thick coating slurry for negative electrode, negative electrode and lithium ion battery Download PDFInfo
- Publication number
- CN117727939A CN117727939A CN202410178517.3A CN202410178517A CN117727939A CN 117727939 A CN117727939 A CN 117727939A CN 202410178517 A CN202410178517 A CN 202410178517A CN 117727939 A CN117727939 A CN 117727939A
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- Prior art keywords
- negative electrode
- weight percent
- pore
- monomer
- forming agent
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Links
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 10
- 239000006255 coating slurry Substances 0.000 title claims abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 40
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 37
- 239000011230 binding agent Substances 0.000 claims abstract description 35
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000006258 conductive agent Substances 0.000 claims abstract description 13
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000004132 cross linking Methods 0.000 claims abstract description 11
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 10
- 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 abstract description 8
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 8
- 239000011734 sodium Substances 0.000 claims abstract description 8
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 239000011248 coating agent Substances 0.000 claims description 41
- 238000000576 coating method Methods 0.000 claims description 41
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 32
- 239000001099 ammonium carbonate Substances 0.000 claims description 32
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 25
- 239000003792 electrolyte Substances 0.000 claims description 22
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- 239000003999 initiator Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 239000007773 negative electrode material Substances 0.000 claims description 13
- 239000004014 plasticizer Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 9
- 229910002804 graphite Inorganic materials 0.000 claims description 9
- 239000010439 graphite Substances 0.000 claims description 9
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 8
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 8
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 8
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 7
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 239000006245 Carbon black Super-P Substances 0.000 claims description 6
- -1 acrylic ester Chemical class 0.000 claims description 6
- 229960002089 ferrous chloride Drugs 0.000 claims description 6
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 6
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical group COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 4
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 claims description 4
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 4
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 claims description 4
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 claims description 4
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 4
- 239000011790 ferrous sulphate Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 4
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 4
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 4
- 229940001584 sodium metabisulfite Drugs 0.000 claims description 4
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 4
- FYRWKWGEFZTOQI-UHFFFAOYSA-N 3-prop-2-enoxy-2,2-bis(prop-2-enoxymethyl)propan-1-ol Chemical compound C=CCOCC(CO)(COCC=C)COCC=C FYRWKWGEFZTOQI-UHFFFAOYSA-N 0.000 claims description 3
- 239000004641 Diallyl-phthalate Substances 0.000 claims description 3
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical group C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 230000001804 emulsifying effect Effects 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 230000000977 initiatory effect Effects 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-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
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical group CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 2
- 150000002466 imines Chemical class 0.000 claims description 2
- ATEAWHILRRXHPW-UHFFFAOYSA-J iron(2+);phosphonato phosphate Chemical compound [Fe+2].[Fe+2].[O-]P([O-])(=O)OP([O-])([O-])=O ATEAWHILRRXHPW-UHFFFAOYSA-J 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
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 2
- FWFUWXVFYKCSQA-UHFFFAOYSA-M sodium;2-methyl-2-(prop-2-enoylamino)propane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(C)(C)NC(=O)C=C FWFUWXVFYKCSQA-UHFFFAOYSA-M 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 150000003573 thiols Chemical class 0.000 claims description 2
- 239000013543 active substance Substances 0.000 abstract description 2
- 239000006257 cathode slurry Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 21
- 238000012360 testing method Methods 0.000 description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 11
- 239000002245 particle Substances 0.000 description 9
- 239000011148 porous material Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000011267 electrode slurry Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000005096 rolling process Methods 0.000 description 6
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 5
- 239000003995 emulsifying agent Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000000643 oven drying Methods 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- 102100028667 C-type lectin domain family 4 member A Human genes 0.000 description 3
- 101000766908 Homo sapiens C-type lectin domain family 4 member A Proteins 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 230000008595 infiltration Effects 0.000 description 3
- 238000001764 infiltration Methods 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical group O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000000875 corresponding effect Effects 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- GUYXXEXGKVKXAW-UHFFFAOYSA-N prop-2-enenitrile Chemical compound C=CC#N.C=CC#N GUYXXEXGKVKXAW-UHFFFAOYSA-N 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012966 redox initiator Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- RQMIWLMVTCKXAQ-UHFFFAOYSA-N [AlH3].[C] Chemical compound [AlH3].[C] RQMIWLMVTCKXAQ-UHFFFAOYSA-N 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 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 1
- 238000001035 drying Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Classifications
-
- 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
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the field of new energy sources, and discloses a thick coating slurry for a negative electrode, which comprises a binder, a pore-forming agent, a conductive agent, a negative electrode active substance and a solvent; the binder is polymerized from a composition comprising the following monomers: 30 to 40 weight percent of acrylic monomer, 10 to 20 weight percent of acrylic monomer, 20 to 25 weight percent of acrylamide, 2 to 8 weight percent of 2-acrylamide-2-methylpropanesulfonic acid sodium, 10 to 30 weight percent of acrylonitrile monomer and 0.1 to 0.4 weight percent of crosslinking monomer; the pore-forming agent comprises an ammonium salt pore-forming agent. The cathode slurry can improve the electrochemical performance of the battery after being applied to the battery. Meanwhile, the invention also discloses a negative electrode and a lithium ion battery.
Description
Technical Field
The invention belongs to the field of new energy, and particularly relates to a thick coating paste for a negative electrode, a negative electrode material and a lithium ion battery.
Background
The battery anode-cathode thick coating technology is widely considered to be capable of improving the battery capacity and energy density, but the continuous increase of the coating thickness is not as conceivable as continuous improvement of performance, because ions hardly enter the interior of the coating after the thickness is too thick.
To solve this problem, one technique widely adopted by those skilled in the art is: and heating and pore-forming the thick coating by using a pore-forming agent so as to facilitate the electrolyte to enter the coating.
In the prior art, pore formers are used in a wide variety of ways, most of which are made by adding substances capable of producing gas.
However, pores made of substances capable of generating gas are generally unstable and have poor infiltration effect, so that electrochemical performance is affected. This phenomenon is more pronounced, especially in thick coated cathodes.
Therefore, the technical problem to be solved by the application is as follows: and how to improve the stability of holes in the thick-coated cathode so as to improve the infiltration effect of the electrolyte and the electrochemical performance of the battery.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a thick coating slurry for a negative electrode; the negative electrode slurry is composed of a pore-forming agent and a binder swelled by high electrolyte; the pore forming agent is used for pore forming, and the cathode is fully soaked by the electrolyte after being contacted with the electrolyte, so that micropores can be further enlarged and stabilized, the electrolyte can enter the coating more easily, and the electrochemical performance of the battery is improved.
Meanwhile, the invention also discloses a negative electrode material and a lithium ion battery.
In order to achieve the aim of the invention, the invention adopts the following technical scheme: a thick coating slurry for a negative electrode comprises a binder, a pore-forming agent, a conductive agent, a negative electrode active substance and a solvent; the binder is polymerized from a composition comprising the following monomers: 30 to 40 weight percent of acrylic monomer, 10 to 20 weight percent of acrylic monomer, 20 to 25 weight percent of acrylamide, 2 to 8 weight percent of 2-acrylamide-2-methylpropanesulfonic acid sodium, 10 to 30 weight percent of acrylonitrile monomer and 0.1 to 0.4 weight percent of crosslinking monomer; the pore-forming agent comprises an ammonium salt pore-forming agent.
In practice, the pore-forming agent may also comprise organic volatile components, such as alkanes of low boiling petroleum ethers, such as petroleum ethers having a boiling point between 30-60 ℃; if the pore-forming agent is selected from a mixture of an ammonium salt pore-forming agent and petroleum ether, the petroleum ether should not exceed 20wt% of the total pore-forming agent.
The core invention points of the invention are as follows: the acrylic monomer and the acrylamide monomer can form a relatively rich and stable particle internal channel due to the hydrophilicity and the combination of pore-forming agents, and the acrylic monomer and the acrylonitrile monomer can improve the affinity with hydrophobic graphite due to the hydrophobicity, so that the dispersion performance of the graphite is improved; more specifically, when the binder of the present invention is dispersed in water to form a slurry and coated, the hydrophilic monomer absorbs water to swell, and when the binder is heated by roll coating, channels are formed inside binder particles along with evaporation of water and decomposition of pore-forming agent, and electrolyte enters the channels during the process of using the binder in a lithium ion battery to form wetting of the negative electrode plate by the electrolyte, and proper swelling can be formed by combining the hydrophobic monomer.
The 2-acrylamide-2-methylpropanesulfonic acid sodium is taken as a typical reactive emulsifier, which not only plays roles of an emulsifier and a reactive monomer, but also can improve the binding capacity of an ammonium salt pore-forming agent on the surface of the binder particles to form a positive electrode layer and a negative electrode layer; when the ammonium salt is decomposed when being heated, pore-forming gases such as ammonia, carbon dioxide and the like can form fine channels in a micro-crosslinking network formed by the binder.
Most central: the 2-acrylamide-2-methylpropanesulfonic acid sodium can be used as a monomer to participate in polymerization, and can be used as an emulsifier to enrich the surface of particles, so that the pore-forming agent can be fully dispersed in the binder and mixed with the conductive agent, and the pore number of the surface of the binder can be increased after the binder particles are swelled, the channel communicable performance between adjacent binder particles is improved, the efficiency of entering the cathode material by electrolyte and the circulation capacity of the electrolyte among the binder particles are further improved, and the electrochemical performance is improved.
Meanwhile, the binder of the invention uses less crosslinking agent, and the purpose is to construct a certain micro-crosslinking system, so that the collapse difficulty of a pore-forming channel is increased, and the problem of poor swelling performance caused by overlarge crosslinking density is avoided.
The thick coating slurry for the negative electrode further comprises a plasticizer, wherein the weight ratio of the binder to the plasticizer to the pore-forming agent to the conductive agent to the negative electrode active material is 2-3: 0.5 to 1:0.5 to 1:1: 95-100; the solid content of the slurry is 35-45 wt%.
In some preferred embodiments of the invention, the solids content in the slurry is 35wt%, 36wt%, 37wt%, 38wt%, 39wt%, 40wt%, 41wt%, 42wt%, 43wt%, 44wt%, or 45wt%;
in some preferred cases of the present invention, the binder, plasticizer, pore-forming agent, conductive agent, and negative electrode active material are selected from the following materials in parts by weight based on 100 parts by weight: 2. 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9 or 3 parts by weight;
the optional parts by weight of the plasticizer is 0.5, 0.6, 0.7, 0.8, 0.9 or 1.0 parts by weight;
the optional weight part of the pore-forming agent is 0.5, 0.6, 0.7, 0.8, 0.9 or 1.0 weight part;
and the balance of the negative electrode active material.
In the above thick coating paste for a negative electrode, the plasticizer is dioctyl phthalate or diethyl phthalate.
In the thick coating paste of the negative electrode, the conductive agent is Super-P, and the negative electrode active material is graphite; the solvent is water.
In the thick coating slurry for the negative electrode, the ammonium salt pore-forming agent is one or more of ammonium oxalate, ammonium carbonate and ammonium bicarbonate.
In the thick coating paste for the negative electrode, the binder is polymerized by the following monomers:
35 to 40 weight percent of acrylic monomer, 15 to 18 weight percent of acrylic monomer, 20 to 25 weight percent of acrylamide, 4 to 7 weight percent of 2-acrylamido-2-methylpropanesulfonic acid sodium salt, 10 to 25 weight percent of acrylonitrile monomer and 0.1 to 0.2 weight percent of crosslinking monomer.
In the thick coating paste for the negative electrode, the acrylic monomer is acrylic acid or methacrylic acid; the acrylic ester monomer is methyl acrylate or ethyl acrylate; the acrylonitrile monomer is acrylonitrile, alpha-methacrylonitrile or alpha-ethacrylonitrile;
the crosslinking monomer is diallyl phthalate, pentaerythritol triallyl ether or N, N-methylene bisacrylamide.
In the thick coating paste for the negative electrode, the binder is prepared by the following method:
uniformly mixing the monomers and water according to the weight ratio of 1:1-2, stirring and emulsifying, heating to an initiation temperature under the protection of inert gas, dripping an initiator for 0.5-1 h, preserving heat for 2-3 h, and adding the initiator to remove unreacted monomers after the reaction is finished.
The initiator may be selected from peroxides such as ammonium persulfate, potassium persulfate, etc., and redox initiators such as benzoyl peroxide/sucrose, t-butyl hydroperoxide/diabolo, t-butyl hydroperoxide/sodium metabisulfite, benzoyl peroxide/N, N-dimethylaniline. Ammonium persulfate/sodium bisulfite, potassium persulfate/sodium bisulfite, hydrogen peroxide/tartaric acid, hydrogen peroxide/sodium metabisulfite, ammonium persulfate/ferrous sulfate, hydrogen peroxide/ferrous sulfate, benzoyl peroxide// N, N-diethylaniline, benzoyl peroxide/ferrous pyrophosphate, potassium persulfate/silver nitrate, persulfate/thiol, cumene hydroperoxide/ferrous chloride, potassium persulfate/ferrous chloride, hydrogen peroxide/ferrous chloride, cumene hydroperoxide/tetraethyl imine, and the like;
the amount of initiator is generally limited to 0.1-2% of the total monomer;
the initiation temperature and the choice of initiator are matched, if a redox initiation system is chosen, the temperature may be suitably lower.
The initiator is used by a conventional method in the field, and the initiator is used in the invention and is not different from the prior art, so that the initiator is not excessively limited;
meanwhile, the invention also discloses a negative electrode, which comprises a current collector and a negative electrode coating prepared from the negative electrode thick coating slurry;
the thickness of the negative electrode coating is 50-400 mu m.
Finally, the invention also discloses a lithium ion battery, which comprises a positive electrode, a negative electrode, electrolyte and a diaphragm, wherein the negative electrode is the negative electrode.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, a pore-forming agent and a binding agent capable of swelling properly in electrolyte are adopted, and 2-acrylamide-2-methylpropanesulfonic acid sodium and the pore-forming agent are matched and pore-formed, wherein the 2-acrylamide-2-methylpropanesulfonic acid sodium part is used as a typical reactive emulsifier which not only plays the role of an emulsifier, but also can improve the binding capacity of the ammonium salt pore-forming agent and the 2-acrylamide-2-methylpropanesulfonic acid sodium on the surface of the binding agent particles to form a positive sub-layer and a negative sub-layer; when the ammonium salt is decomposed, pore-forming gases such as ammonia, carbon dioxide and the like can form fine channels in a micro-crosslinking network formed by the binder; after the negative electrode is contacted with the electrolyte, micropores can be further enlarged and stabilized through infiltration of the electrolyte, so that the electrolyte can enter the coating more easily, and the electrochemical property of the battery is improved.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Preparation of first part adhesive
Examples
The preparation method of the adhesive comprises the following steps:
uniformly mixing the monomers and water according to the weight ratio of 1:1, stirring and emulsifying, heating to 70 ℃ under the protection of inert gas, dropwise adding 90% of initiator for 1h, preserving heat for 3h, and adding the rest 10% of initiator to remove unreacted monomers when the reaction is finished. Spray drying to obtain powder.
The raw materials are shown in the following table 1:
table 1 recipe table units: parts by weight of
| Acrylic acid | Acrylic acid methyl ester | Acrylic acid ethyl ester | Acrylamide | Acrylamide-2-methylpropanesulfonic acid sodium salt | Acrylonitrile (Acrylonitrile) | N, N-methylenebisacrylamide | Ammonium persulfate | |
| Example 1 | 38 | 10 | 6 | 25 | 5 | 16 | 0.1 | 0.3 |
| Example 2 | 35 | 8 | 10 | 20 | 7 | 20 | 0.1 | 0.2 |
| Example 3 | 40 | 8 | 8 | 22 | 4 | 18 | 0.1 | 0.4 |
| Example 4 | 40 | 18 | 0 | 25 | 7 | 10 | 0.1 | 0.3 |
| Example 5 | 35 | 0 | 15 | 20 | 5 | 25 | 0.1 | 0.3 |
| Example 6 | 38 | 10 | 6 | 25 | 5 | 16 | 0.2 | 0.3 |
| Example 7 | 38 | 10 | 6 | 25 | 5 | 16 | 0.3 | 0.3 |
| Example 8 | 38 | 10 | 6 | 25 | 5 | 16 | 0.4 | 0.3 |
| Example 9 | 38 | 10 | 6 | 25 | 5 | 16 | Pentaerythritol triallyl ether/0.1 | 0.3 |
| Example 10 | 38 | 10 | 6 | 25 | 5 | 16 | Diallyl phthalate/0.1 | 0.3 |
Comparative example
Reference to the preparation of the examples, the formulation is given in table 2:
table 2 recipe table units: parts by weight of
| Acrylic acid | Acrylic acid methyl ester | Acrylic acid ethyl ester | Acrylamide | Acrylamide-2-methylpropanesulfonic acid sodium salt | Acrylonitrile (Acrylonitrile) | N, N-methylenebisacrylamide | Ammonium persulfate | |
| Comparative example 1 | 20 | 19 | 15 | 25 | 5 | 16 | 0.1 | 0.3 |
| Comparative example 2 | 45 | 0 | 6 | 25 | 5 | 19 | 0.1 | 0.3 |
| Comparative example 3 | 45 | 0 | 0 | 30 | 5 | 20 | 0.1 | 0.3 |
| Comparative example 4 | 40 | 10 | 10 | 15 | 5 | 20 | 0.1 | 0.3 |
| Comparative example 5 | 33 | 10 | 6 | 30 | 5 | 16 | 0.1 | 0.3 |
| Comparative example 6 | 38 | 10 | 6 | 25 | Sodium dodecyl allyl sulfosuccinate/5 | 16 | 0.1 | 0.3 |
| Comparative example 7 | 43 | 10 | 6 | 30 | 5 | 6 | 0.1 | 0.3 |
| Comparative example 8 | 24 | 5 | 6 | 20 | 5 | 40 | 0.1 | 0.3 |
| Comparative example 9 | 38 | 10 | 6 | 25 | 5 | 16 | 0.5 | 0.3 |
| Comparative example 10 | 38 | 10 | 6 | 25 | 5 | 16 | 0.6 | 0.3 |
Preparation of the second partial negative electrode
Binder, plasticizer, pore-forming agent, conductive agent Super-P and negative electrode active material graphite according to the mass ratio of 2.5:0.7:0.8:1:95, adding into deionized water according to the solid content of 40wt%, stirring thoroughly to obtain uniform negative electrode slurry, sieving with 100 mesh sieve, coating on negative electrode current collector Cu foil, oven drying at 110deg.C, and using roller to obtain a slurry with 10×10 4 And rolling the load of N/m in unit length to obtain the negative electrode plate.
The coating amount on the negative electrode plate is 23g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The coating thickness was 226 μm.
In this section, referring to table 3, three pore formers were selected for the experiment, ammonium oxalate, ammonium carbonate, isopropanol, respectively:
table 3 formulation table of application example
| Adhesive agent | Pore-forming agent | |
| Application example 1 | Example 1 | Ammonium oxalate |
| Application example 2 | Example 1 | Ammonium carbonate |
| Application example 3 | Example 1 | Isopropyl alcohol |
| Application example 4 | Example 4 | Ammonium carbonate |
| Application example 5 | Example 5 | Ammonium bicarbonate |
| Application example 6 | Example 6 | Ammonium oxalate |
| Application example 7 | Example 6 | Ammonium carbonate |
| Application example 8 | Example 6 | Isopropyl alcohol |
| Application example 9 | Example 9 | Ammonium carbonate |
| Application example 10 | Example 10 | Ammonium carbonate |
| Application example 11 | Comparative example 1 | Ammonium carbonate |
| Application example 12 | Comparative example 2 | Ammonium carbonate |
| Application example 13 | Comparative example 3 | Ammonium carbonate |
| Application example 14 | Comparative example 4 | Ammonium carbonate |
| Application example 15 | Comparative example 5 | Ammonium carbonate |
| Application example 16 | Comparative example 6 | Ammonium carbonate |
| Application example 17 | Comparative example 7 | Ammonium carbonate |
| Application example 18 | Comparative example 8 | Ammonium carbonate |
| Application example 19 | Comparative example 9 | Ammonium carbonate |
| Application example 20 | Comparative example 10 | Ammonium carbonate |
Application example 21
Binder (example 2), plasticizer, pore-forming agent (ammonium carbonate), conductive agent Super-P and negative electrode active material graphite according to the mass ratio of 2:0.5:0.5:1:96, adding deionized water at a ratio of 40wt% to obtain uniform negative electrode slurry, sieving with 100 mesh sieve, coating on negative electrode current collector Cu foil, oven drying at 110deg.C, and rolling at 10×10 4 And rolling the load of N/m in unit length to obtain the negative electrode plate.
The coating amount on the negative electrode plate is 35g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The coating thickness was 345 μm.
Application example 22
Binder (example 3), plasticizer, pore-forming agent (ammonium carbonate), conductive agent Super-P and negative electrode active material graphite are mixed according to the mass ratio of 3:0.5:0.5:1:97, adding into deionized water according to the solid content of 40wt%, stirring thoroughly to obtain uniform negative electrode slurry, sieving with 100 mesh sieve, coating on negative electrode current collector Cu foil, oven drying at 110deg.C, and using roller to obtain a slurry with 10×10 4 And rolling the load of N/m in unit length to obtain the negative electrode plate.
The coating amount on the negative electrode plate is 40g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The coating thickness was 396 μm.
Application example 23
Binder (example 7), plasticizer, pore-forming agent (ammonium carbonate), conductive agent Super-P and negative electrode active material graphite according to the mass ratio of 2.5:1:1:1:100, adding into deionized water according to the solid content of 40wt%, stirring thoroughly to obtain uniform negative electrode slurry, sieving with 100 mesh sieve, coating on negative electrode current collector Cu foil, oven drying at 110deg.C, and using roller to obtain a slurry with 10×10 4 And rolling the load of N/m in unit length to obtain the negative electrode plate.
The coating amount on the negative electrode plate is 5g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The coating thickness was 50 μm.
Performance test 1
Performance testing is carried out on the anode material, and the test items are as follows:
test item 1: porosity of the porous material;
the true density of the negative graphite is 2.2g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The compacted density of the pole piece is Y; porosity= (1-Y/2.2) 100%.
Test item 2: peel force test
The surface to be tested is fixed on a rigid bracket by double faced adhesive tape, the other surface is stuck on a stainless steel plate, then the stainless steel plate and the current collector are fixed on two clamps of the equipment, the equipment starts to test, the equipment operates at a certain speed and load, and the force when the current collector is completely peeled off is the peeling force.
Preparation of the third cell
The negative electrode sheet of the application example of the second part is adopted as a negative electrode;
the positive electrode is: adding a certain amount of adhesive polyvinylidene fluoride powder into N-methyl pyrrolidone solvent, stirring and mixing uniformly to prepare the glue solution with the solid content of 8%. Adding conductive carbon black and polyvinylidene fluoride into a stirrer according to the mass ratio of 97.5:0.4:0.5:1.6, fully and uniformly stirring to obtain positive electrode slurry, coating the prepared slurry on a current collector, coating the current collector with carbon aluminum foil with the thickness of 16 mu m, and drying in an oven, rolling and cutting to form a positive electrode plate for preparing a battery;
the electrolyte is as follows: the electrolyte comprises lithium salt, organic solvent and additive, wherein LiPF 6 The concentration of the lithium salt is 1mol/L, and the organic solvent is EC (ethylene carbonate), DMC (dimethyl carbonate) and EMC (methyl ethyl carbonate), and the volume ratio is 1:1:1.
The diaphragm is: polyethylene porous polymeric film.
Assembling the materials into a lithium ion battery;
the negative electrode sheets used in the batteries 1 to 23 correspond to application examples 1 to 23, respectively.
Performance test 2
The following performance tests were performed for lithium ion batteries:
test item 3: testing the first effect of the battery;
test item 4: DCIR, test method refers to "Nickel cobalt lithium manganate electrochemical Performance test-Direct Current Internal Resistance (DCIR) test method".
Test results of the anode material and test results of the battery refer to table 4:
table 4 test results
Analysis of results:
1. as can be seen from application examples 1 to 3 and application examples 6 to 8, the results of the porosity of the cases using ammonium oxalate and ammonium carbonate are significantly better than those of the cases using isopropyl alcohol, and there is no significant difference between the cases using ammonium oxalate and ammonium carbonate in terms of adhesion (peel force test); this indicates that the type of pore-forming agent is selected with no significant effect on adhesion.
2. As can be seen from comparison of application examples 1, 4, 5, 6, 9 and 10, no matter whether ammonium oxalate, ammonium carbonate or ammonium bicarbonate is used, the effect of the porosity of ammonium bicarbonate is slightly poor, which may be caused by that the decomposition temperature of ammonium oxalate is about 100 ℃, the decomposition temperature of ammonium carbonate is about 58 ℃, the thermal decomposition temperature of ammonium bicarbonate is about 30 ℃, the decomposition speed of ammonium bicarbonate is too fast, resulting in that a large amount of gas instantaneously causes excessive air pressure in the binder, the gas is concentrated in a few channels, the number of channels is small, the channel diameter is too large, and the corresponding effect is deteriorated.
3. As can be seen from application examples 11 to 20, the relative performance is weaker than that of application example 1, but in the root, the application example 11 uses less acrylic acid, resulting in poor hydrophilicity of the binder, poor dispersibility in pulping, and failure to maintain a proper wetting rate in the electrolyte, resulting in a corresponding decrease in porosity and adhesion; the application examples 12 and 13, which have a relatively large amount of acrylic acid and a relatively small amount of acrylic acid ester, have a relatively good dispersibility in the pulping process, but have a too low wettability in the electrolyte, which makes it difficult to sufficiently establish channels, and thus causes a decrease in porosity; the acrylamide content of application example 14 was smaller, the results were similar to those of application example 11, and the decrease in acrylamide also resulted in a decrease in porosity; however, the adhesion was better than in application example 11, indicating that acrylamide has significantly less effect on adhesion than acrylic acid; the acrylamide content of application example 15 was higher, and the porosity and other parameters were better than those of application example 11, but the related properties were still weaker than those of application example 1. Application example 16 has a porosity superior to application example 11 but weaker than application example 1, indicating that the properties of other polymerizable surfactants without amide groups may be slightly inferior in the dispersion of the pore former, in the aggregation capacity on the particle surface;
application example 17-application example 18 the acrylonitrile was tested too much and too little, respectively, and the acrylonitrile was too little and too much, and the porosity was not as good as that of application example 1; too much crosslinking agent resulted in significantly deteriorated electrolyte wettability, reduced porosity and increased adhesion in application examples 19 and 20, wherein the adhesion was maximized when the crosslinking agent was used at 0.5%.
4. As can be seen from the battery performance test, application examples 1 to 10 are significantly better than application examples 11 to 20, demonstrating that the porosity is closely related to the first-effect, DCIR, i.e. the establishment of electrolyte channels is closely related to the electrochemical performance.
5. It can be seen from application examples 21, 22 and 23 that the different coating thicknesses of the present invention can have better electrochemical performance effects.
The applicant states that the process of the invention is illustrated by the above examples, but the invention is not limited to the above process steps, which do not mean that the invention must be carried out in dependence on the above process steps. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of selected raw materials, addition of auxiliary components, selection of specific modes, etc. fall within the scope of the present invention and the scope of disclosure.
Claims (10)
1. The thick coating slurry for the negative electrode is characterized by comprising a binder, a pore-forming agent, a conductive agent, a negative electrode active material and a solvent; the binder is polymerized from a composition comprising the following monomers: 30 to 40 weight percent of acrylic monomer, 10 to 20 weight percent of acrylic monomer, 20 to 25 weight percent of acrylamide, 2 to 8 weight percent of 2-acrylamide-2-methylpropanesulfonic acid sodium, 10 to 30 weight percent of acrylonitrile monomer and 0.1 to 0.4 weight percent of crosslinking monomer; the pore-forming agent comprises an ammonium salt pore-forming agent.
2. The thick coating paste for negative electrode according to claim 1, further comprising a plasticizer, wherein the weight ratio of the binder, the plasticizer, the pore-forming agent, the conductive agent, and the negative electrode active material is 2 to 3:0.5 to 1:0.5 to 1:1: 95-100; the solid content of the slurry is 35-45 wt%.
3. The negative electrode thick coating paste according to claim 2, wherein the plasticizer is dioctyl phthalate or diethyl phthalate; the conductive agent is Super-P, and the negative electrode active material is graphite; the solvent is water.
4. The thick coating paste for the negative electrode according to claim 1, wherein the ammonium salt pore-forming agent is one or more of ammonium oxalate, ammonium carbonate and ammonium bicarbonate;
and/or the number of the groups of groups,
the pore-forming agent also comprises petroleum ether with the boiling point between 30 and 60 ℃; the petroleum ether is not more than 20wt% of the total amount of the pore-forming agent.
5. The negative electrode thick coating paste of claim 1, wherein the binder is polymerized from the following monomers:
35 to 40 weight percent of acrylic monomer, 15 to 18 weight percent of acrylic monomer, 20 to 25 weight percent of acrylamide, 4 to 7 weight percent of 2-acrylamido-2-methylpropanesulfonic acid sodium salt, 10 to 25 weight percent of acrylonitrile monomer and 0.1 to 0.2 weight percent of crosslinking monomer.
6. The negative electrode thick coating paste according to claim 1 or 5, wherein the acrylic monomer is acrylic acid or methacrylic acid; the acrylic ester monomer is methyl acrylate or ethyl acrylate; the acrylonitrile monomer is acrylonitrile, alpha-methacrylonitrile or alpha-ethacrylonitrile;
the crosslinking monomer is diallyl phthalate, pentaerythritol triallyl ether or N, N-methylene bisacrylamide.
7. The negative electrode thick coating paste of claim 6, wherein the binder is prepared by the following method:
uniformly mixing the monomers and water according to the weight ratio of 1:1-2, stirring and emulsifying, heating to an initiation temperature under the protection of inert gas, dripping an initiator for 0.5-1 h, preserving heat for 2-3 h, and adding the initiator to remove unreacted monomers after the reaction is finished.
8. The thick coating paste for negative electrode according to claim 7, wherein the initiator is ammonium persulfate, potassium persulfate benzoyl peroxide/sucrose, t-butyl hydroperoxide/diabolo, t-butyl hydroperoxide/sodium metabisulfite, benzoyl peroxide/N, N-dimethylaniline; ammonium persulfate/sodium bisulfite, potassium persulfate/sodium bisulfite, hydrogen peroxide/tartaric acid, hydrogen peroxide/sodium metabisulfite, ammonium persulfate/ferrous sulfate, hydrogen peroxide/ferrous sulfate, benzoyl peroxide// N, N-diethylaniline, benzoyl peroxide/ferrous pyrophosphate, potassium persulfate/silver nitrate, persulfate/thiol, cumene hydroperoxide/ferrous chloride, potassium persulfate/ferrous chloride, hydrogen peroxide/ferrous chloride, cumene hydroperoxide/tetraethyl imine;
the initiator is used in an amount of 0.1 to 2% by weight based on the total weight of the monomers.
9. A negative electrode comprising a current collector and a negative electrode coating prepared from the negative electrode thick coating paste according to any one of claims 1 to 8;
the thickness of the negative electrode coating is 50-400 mu m.
10. A lithium ion battery comprising a positive electrode, an electrolyte, a separator, and the negative electrode of claim 9.
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