CN115799507A - Natural graphite negative electrode material with surface connected with binder, and preparation method and application thereof - Google Patents
Natural graphite negative electrode material with surface connected with binder, and preparation method and application thereof Download PDFInfo
- Publication number
- CN115799507A CN115799507A CN202210907908.5A CN202210907908A CN115799507A CN 115799507 A CN115799507 A CN 115799507A CN 202210907908 A CN202210907908 A CN 202210907908A CN 115799507 A CN115799507 A CN 115799507A
- Authority
- CN
- China
- Prior art keywords
- binder
- acrylate
- diisocyanate
- cellulose
- monomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011230 binding agent Substances 0.000 title claims abstract description 136
- 229910021382 natural graphite Inorganic materials 0.000 title claims abstract description 93
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000007773 negative electrode material Substances 0.000 title claims description 61
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000010406 cathode material Substances 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 70
- 239000000178 monomer Substances 0.000 claims description 68
- 229920000058 polyacrylate Polymers 0.000 claims description 49
- 239000000203 mixture Substances 0.000 claims description 35
- 239000003431 cross linking reagent Substances 0.000 claims description 31
- 238000002156 mixing Methods 0.000 claims description 31
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 30
- 229920002678 cellulose Polymers 0.000 claims description 27
- 239000001913 cellulose Substances 0.000 claims description 27
- 229920000642 polymer Polymers 0.000 claims description 27
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 26
- 239000003999 initiator Substances 0.000 claims description 26
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 23
- 239000003054 catalyst Substances 0.000 claims description 23
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 20
- 238000011065 in-situ storage Methods 0.000 claims description 19
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 18
- 239000012948 isocyanate Substances 0.000 claims description 18
- 150000002513 isocyanates Chemical class 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 16
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 16
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 16
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 15
- 239000010405 anode material Substances 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- -1 lithium itaconate monobutyl ester Chemical compound 0.000 claims description 14
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 12
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 12
- 239000011268 mixed slurry Substances 0.000 claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 11
- 229940048053 acrylate Drugs 0.000 claims description 11
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 claims description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 10
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 10
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 10
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 10
- 239000002270 dispersing agent Substances 0.000 claims description 10
- 239000003995 emulsifying agent Substances 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 239000000839 emulsion Substances 0.000 claims description 9
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 8
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 8
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 8
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 8
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 8
- NUMHJBONQMZPBW-UHFFFAOYSA-K bis(2-ethylhexanoyloxy)bismuthanyl 2-ethylhexanoate Chemical compound [Bi+3].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O NUMHJBONQMZPBW-UHFFFAOYSA-K 0.000 claims description 8
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 8
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 8
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 8
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 claims description 7
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 7
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 7
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 7
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 claims description 6
- LSWYGACWGAICNM-UHFFFAOYSA-N 2-(prop-2-enoxymethyl)oxirane Chemical compound C=CCOCC1CO1 LSWYGACWGAICNM-UHFFFAOYSA-N 0.000 claims description 6
- IGDCJKDZZUALAO-UHFFFAOYSA-N 2-prop-2-enoxypropane-1,3-diol Chemical compound OCC(CO)OCC=C IGDCJKDZZUALAO-UHFFFAOYSA-N 0.000 claims description 6
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 6
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 6
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 6
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- 239000002482 conductive additive Substances 0.000 claims description 6
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 6
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 claims description 6
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 claims description 6
- RVCHQYCXJDVJQF-UHFFFAOYSA-N (3,5-diethylphenyl)methanediamine Chemical compound CCC1=CC(CC)=CC(C(N)N)=C1 RVCHQYCXJDVJQF-UHFFFAOYSA-N 0.000 claims description 5
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 claims description 5
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 5
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 claims description 5
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 claims description 4
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 claims description 4
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 claims description 4
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 claims description 4
- MWCADZVQNIHFGT-UHFFFAOYSA-N 1-anilinopropan-2-ol Chemical compound CC(O)CNC1=CC=CC=C1 MWCADZVQNIHFGT-UHFFFAOYSA-N 0.000 claims description 4
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 4
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 claims description 4
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 claims description 4
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims description 4
- GKUYTUPRLYCQOQ-UHFFFAOYSA-N 3-hydroperoxyphenol Chemical compound OOC1=CC=CC(O)=C1 GKUYTUPRLYCQOQ-UHFFFAOYSA-N 0.000 claims description 4
- ZVYGIPWYVVJFRW-UHFFFAOYSA-N 3-methylbutyl prop-2-enoate Chemical compound CC(C)CCOC(=O)C=C ZVYGIPWYVVJFRW-UHFFFAOYSA-N 0.000 claims description 4
- HDMRYQCGZUYLJJ-UHFFFAOYSA-N 4-chloro-2,6-bis(methylsulfanyl)benzene-1,3-diamine Chemical compound CSC1=CC(Cl)=C(N)C(SC)=C1N HDMRYQCGZUYLJJ-UHFFFAOYSA-N 0.000 claims description 4
- NQSLZEHVGKWKAY-UHFFFAOYSA-N 6-methylheptyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C(C)=C NQSLZEHVGKWKAY-UHFFFAOYSA-N 0.000 claims description 4
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 4
- WUKNPIYSKBLCQI-UHFFFAOYSA-N CC(C=C1)=CC=C1C1=CC=C(C)C=C1.N=C=O.N=C=O Chemical compound CC(C=C1)=CC=C1C1=CC=C(C)C=C1.N=C=O.N=C=O WUKNPIYSKBLCQI-UHFFFAOYSA-N 0.000 claims description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000001856 Ethyl cellulose Substances 0.000 claims description 4
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-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
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 claims description 4
- HDONYZHVZVCMLR-UHFFFAOYSA-N N=C=O.N=C=O.CC1CCCCC1 Chemical compound N=C=O.N=C=O.CC1CCCCC1 HDONYZHVZVCMLR-UHFFFAOYSA-N 0.000 claims description 4
- 239000000020 Nitrocellulose Substances 0.000 claims description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 4
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 claims description 4
- MRUXVMBOICABIU-UHFFFAOYSA-N [3,5-bis(methylsulfanyl)phenyl]methanediamine Chemical compound CSC1=CC(SC)=CC(C(N)N)=C1 MRUXVMBOICABIU-UHFFFAOYSA-N 0.000 claims description 4
- JGCWKVKYRNXTMD-UHFFFAOYSA-N bicyclo[2.2.1]heptane;isocyanic acid Chemical compound N=C=O.N=C=O.C1CC2CCC1C2 JGCWKVKYRNXTMD-UHFFFAOYSA-N 0.000 claims description 4
- NSPSPMKCKIPQBH-UHFFFAOYSA-K bismuth;7,7-dimethyloctanoate Chemical compound [Bi+3].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O NSPSPMKCKIPQBH-UHFFFAOYSA-K 0.000 claims description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 4
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 claims description 4
- 229920003064 carboxyethyl cellulose Polymers 0.000 claims description 4
- 229920002301 cellulose acetate Polymers 0.000 claims description 4
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 4
- RXNWFGQCYAZACC-UHFFFAOYSA-L dilithium;2-methylidenebutanedioate Chemical compound [Li+].[Li+].[O-]C(=O)CC(=C)C([O-])=O RXNWFGQCYAZACC-UHFFFAOYSA-L 0.000 claims description 4
- 238000012983 electrochemical energy storage Methods 0.000 claims description 4
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 4
- 229920001249 ethyl cellulose Polymers 0.000 claims description 4
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims description 4
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 claims description 4
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 claims description 4
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- RLQOUIUVEQXDPW-UHFFFAOYSA-M lithium;2-methylprop-2-enoate Chemical compound [Li+].CC(=C)C([O-])=O RLQOUIUVEQXDPW-UHFFFAOYSA-M 0.000 claims description 4
- XSAOIFHNXYIRGG-UHFFFAOYSA-M lithium;prop-2-enoate Chemical compound [Li+].[O-]C(=O)C=C XSAOIFHNXYIRGG-UHFFFAOYSA-M 0.000 claims description 4
- 229920000609 methyl cellulose Polymers 0.000 claims description 4
- 239000001923 methylcellulose Substances 0.000 claims description 4
- 235000010981 methylcellulose Nutrition 0.000 claims description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 4
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 4
- 229920001220 nitrocellulos Polymers 0.000 claims description 4
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 claims description 4
- 239000012934 organic peroxide initiator Substances 0.000 claims description 4
- 150000002902 organometallic compounds Chemical class 0.000 claims description 4
- GYDSPAVLTMAXHT-UHFFFAOYSA-N pentyl 2-methylprop-2-enoate Chemical compound CCCCCOC(=O)C(C)=C GYDSPAVLTMAXHT-UHFFFAOYSA-N 0.000 claims description 4
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 claims description 4
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 4
- 150000002978 peroxides Chemical class 0.000 claims description 4
- 239000012966 redox initiator Substances 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 229940047670 sodium acrylate Drugs 0.000 claims description 4
- 239000004317 sodium nitrate Substances 0.000 claims description 4
- 235000010344 sodium nitrate Nutrition 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 claims description 4
- 239000013638 trimer Substances 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- 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 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- 239000006230 acetylene black Substances 0.000 claims description 2
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 claims description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims description 2
- 238000004108 freeze drying Methods 0.000 claims description 2
- 239000000446 fuel Substances 0.000 claims description 2
- 230000009477 glass transition Effects 0.000 claims description 2
- 238000012703 microemulsion polymerization Methods 0.000 claims description 2
- 238000003801 milling Methods 0.000 claims description 2
- 229940038384 octadecane Drugs 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 2
- 229910001415 sodium ion Inorganic materials 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- 235000010265 sodium sulphite Nutrition 0.000 claims description 2
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 2
- 238000001694 spray drying Methods 0.000 claims description 2
- 238000010557 suspension polymerization reaction Methods 0.000 claims description 2
- 239000012970 tertiary amine catalyst Substances 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims 2
- VVAAYFMMXYRORI-UHFFFAOYSA-N 4-butoxy-2-methylidene-4-oxobutanoic acid Chemical compound CCCCOC(=O)CC(=C)C(O)=O VVAAYFMMXYRORI-UHFFFAOYSA-N 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 9
- 230000032683 aging Effects 0.000 abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 28
- 239000002002 slurry Substances 0.000 description 18
- 239000013543 active substance Substances 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- 239000006185 dispersion Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
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- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 7
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- 238000000227 grinding Methods 0.000 description 7
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- 239000004570 mortar (masonry) Substances 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 229920005906 polyester polyol Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 2
- ICLCCFKUSALICQ-UHFFFAOYSA-N 1-isocyanato-4-(4-isocyanato-3-methylphenyl)-2-methylbenzene Chemical compound C1=C(N=C=O)C(C)=CC(C=2C=C(C)C(N=C=O)=CC=2)=C1 ICLCCFKUSALICQ-UHFFFAOYSA-N 0.000 description 2
- MBVGJZDLUQNERS-UHFFFAOYSA-N 2-(trifluoromethyl)-1h-imidazole-4,5-dicarbonitrile Chemical compound FC(F)(F)C1=NC(C#N)=C(C#N)N1 MBVGJZDLUQNERS-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000003376 silicon Chemical class 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- FKOMNQCOHKHUCP-UHFFFAOYSA-N 1-[n-(2-hydroxypropyl)anilino]propan-2-ol Chemical compound CC(O)CN(CC(C)O)C1=CC=CC=C1 FKOMNQCOHKHUCP-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical group 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
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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 provides a natural graphite cathode material with a surface connected with a binder, and a preparation method and application thereof. The natural graphite cathode material can improve the expansion and aging problems in the circulation process, improve the cohesiveness and improve the comprehensive performance of the material, so that the lithium ion battery containing the natural graphite cathode material has high first coulombic efficiency and circulation stability.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, relates to a natural graphite negative electrode material, and a preparation method and application thereof, and particularly relates to a natural graphite negative electrode material with a surface connected with a binder, and a preparation method and application thereof.
Background
Lithium ion batteries have been widely used in the fields of 3C (electronic digital), energy storage, power, and the like, due to their advantages of high energy density, small size, environmental friendliness, and the like. The improvement of the comprehensive performance of the lithium ion battery in the industry, including energy density, cycle life and the like, is of great importance. The existing anode materials which are mature to be applied comprise natural graphite and other anode materials still have some natural problems and defects, such as poor binding force between active substances and a current collector, irreversible expansion of the materials caused by cyclic aging, side reaction with an electrolyte, aging of an SEI film and the like, and the problems of active powder fragmentation and the like are brought along with the problems, so that the capacity and the cyclic stability of the battery are influenced, and the potential safety hazard of the battery is even further caused.
CN113270586A discloses a preparation method and application of an in-situ polymerization coating modified silicon-based negative electrode material, wherein the surface of a silicon-based material is coated with a composite coating layer of an inorganic substance and a polymer, and the silicon-based negative electrode material is subjected to an in-situ polymerization reaction of a monomer of the polymer on the surface of the silicon-based material under the action of a deep eutectic solvent to obtain the composite coating layer in which the inorganic substance is uniformly distributed in the polymer; the inorganic matter is lithium salt, and the thickness of the composite coating layer is 5-15nm. The composite coating layer is formed by in-situ polymerization of inorganic-doped polymer monomers on the surface of the material. The modified silicon-based negative electrode material improves the first coulombic efficiency of the negative electrode material, but the cycling stability of the battery needs to be further improved.
Therefore, in the art, it is desirable to develop a material capable of improving the problem of expansion and aging of the negative electrode material during cycling, and at the same time, improving the adhesion between active materials and between the active materials and the current collector, thereby improving the overall performance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a natural graphite negative electrode material and a preparation method and application thereof, and particularly provides a natural graphite negative electrode material with a surface connected with a binder and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the present invention provides a natural graphite negative electrode material with a surface connected with a binder, where the natural graphite negative electrode material with a surface connected with a binder includes a natural graphite negative electrode material and a binder connected with the surface of the natural graphite negative electrode material, the binder includes a first binder and a second binder, the first binder includes a first polymer, a polymerized monomer of the first polymer includes any one or a combination of at least two of an acrylate monomer, an acrylamide monomer, an acrylonitrile monomer, or a styrene monomer, and the second binder is a bi-component polyacrylate.
In the invention, the first binder is in a particle structure, the second binder is in a non-particle structure, and the first binder and the second binder form a polymer network on the surface of the natural graphite negative electrode material.
According to the invention, the surface of the natural graphite negative electrode material is connected with the first binder and the second binder, the first binder is an acrylate particle structure component, the surface of the active substance is in a dot structure, the second binder is in a non-particle structure, and the first binder and the second binder cooperatively form a polymer coating structure on the surface of the active substance, so that the problem of expansion and aging of the natural graphite negative electrode material in the circulation process can be improved, meanwhile, the cohesiveness among negative electrode active substances and between the negative electrode active substances and a current collector can be improved, and the comprehensive performance of the material is improved.
Preferably, the acrylate monomer is selected from any one of methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, n-pentyl acrylate, isopentyl acrylate, n-hexyl acrylate, isooctyl acrylate, hydroxypropyl acrylate, 2-hydroxyethyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, n-pentyl methacrylate, n-hexyl methacrylate, isooctyl methacrylate, hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate, sodium acrylate, lithium acrylate, acrylic acid, lithium methacrylate, methacrylic acid, lithium itaconate, itaconic acid, lithium itaconate monobutyl ester or a combination of at least two of them.
Preferably, the acrylamide monomer is selected from any one of acrylamide, methacrylamide, N-methylolacrylamide or N, N-dimethylacrylamide or a combination of at least two of the acrylamide, the methacrylamide, the N-methylolacrylamide and the N, N-dimethylacrylamide.
Preferably, the first binder further comprises cellulose, and the cellulose is mixed and intertwined with the first polymer, so that the emulsion dispersion stability in the preparation process of the first polymer can be improved.
Preferably, the cellulose is selected from any one of cellulose acetate, methyl cellulose, ethyl cellulose, hydroxypropyl cellulose (HPC), hydroxyethyl cellulose (HEC), cellulose nitrate, carboxymethyl cellulose (CMC), carboxyethyl cellulose, carboxypropyl cellulose, carboxyisopropyl cellulose, sodium nitrate, or sodium carboxyalkyl cellulose, or a combination of at least two thereof.
Preferably, the raw materials for preparing the two-component polyacrylate comprise isocyanate monomers and hydroxyl-terminated acrylate polymers.
Preferably, the raw material for preparing the bi-component polyacrylate further comprises a cross-linking agent (or chain extender) and/or a catalyst.
Preferably, the isocyanate-based monomer is selected from any one of Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), 1, 5-Naphthalene Diisocyanate (NDI), dimethylbiphenyl diisocyanate (TODI), hexamethylene Diisocyanate (HDI), hexamethylene diisocyanate biuret, hexamethylene diisocyanate trimer, 2, 4-trimethylhexamethylene diisocyanate (TMDI), xylylene Diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), hydrogenated Xylylene Diisocyanate (HXDI), isophorone diisocyanate (IPDI), 4' -dicyclohexylmethane diisocyanate (HMDI), methylcyclohexane diisocyanate (HTDI), 1, 4-cyclohexane diisocyanate, 1, 4-phenylene diisocyanate (PPDI), 1, 3-phenylene diisocyanate or norbornane diisocyanate (NBDI) or a combination of at least two thereof.
In the present invention, the hydroxyl-terminated acrylate polymer used is a liquid hydroxyl-terminated acrylate polymer, and the hydroxyl-terminated acrylate polymer preferably has a number average molecular weight of 100 to 10000, for example 100, 150, 200, 300, 500, 700, 800, 900, 1000, 2000, 4000, 5000, 7000, 9000, 10000 or the like.
Preferably, the polymerized monomer of the hydroxyl-terminated acrylate polymer includes any one of styrene (St), acrylic Acid (AA), butyl Acrylate (BA), butyl Methacrylate (BMA), hydroxyethyl methacrylate (HEMA), hydroxyethyl acrylate (HEA), hydroxypropyl methacrylate (HPMA), or hydroxypropyl acrylate (HPA), or a combination of at least two thereof.
Preferably, the crosslinking agent is selected from any one of 1, 4-butanediol, ethylene glycol, propylene glycol, diethylene glycol, neopentyl glycol, glycerol, trimethylolpropane, 3-dichloro-4, 4-diaminodiphenylmethane, 3, 5-dimethylthiotoluenediamine, 3, 5-diethyltoluenediamine, 2, 4-diamino-3, 5-dimethylthiochlorobenzene, isophoronediamine, ethanolamine, diethanolamine, triethanolamine, N-bis (2-hydroxypropyl) aniline, 1, 4-cyclohexanediol, hydrogenated bisphenol A, dimethylenephenylenediol, hydroquinone bis-beta-hydroxyethyl ether, resorcinol hydroxyl ether, glycerol allyl ether, glycidyl allyl ether or dicumyl peroxide, or a combination of at least two thereof.
Preferably, the catalyst is selected from any one of a tertiary amine catalyst or an organometallic compound or a combination of at least two thereof.
Preferably, the catalyst is selected from any one of or a combination of at least two of N, N-dimethylcyclohexylamine, dibutyltin dilaurate, bismuth 2-ethylhexanoate, and bismuth neodecanoate.
In the present invention, the glass transition temperature Tg of the polymer of the first binder is in the range of-50 to 200 deg.C, such as-50 deg.C, -20 deg.C, -10 deg.C, 0 deg.C, 5 deg.C, 10 deg.C, 20 deg.C, 50 deg.C, 70 deg.C, 90 deg.C, 100 deg.C, 130 deg.C, 150 deg.C, 180 deg.C or 200 deg.C. The Tg is determined according to differential scanning calorimetry, DSC, testing.
Preferably, the particle size of the first binder is 200nm to 10 μm, such as 200nm, 400nm, 500nm, 800nm, 1 μm, 3 μm, 5 μm, 8 μm or 10 μm.
In the present invention, the first binder may be prepared by emulsion polymerization or microemulsion polymerization or suspension polymerization or microsuspension polymerization.
Preferably, the second binder is obtained by in-situ polymerization on the surface of the natural graphite negative electrode material connected with the first binder.
According to the invention, in-situ polymerization is carried out on the surface of the natural graphite cathode material connected with the first binder, so that an isocyanate monomer and a hydroxyl-terminated acrylate polymer are polymerized to obtain a second binder, the second binder is a polymer with better elasticity, the cohesive elasticity is enhanced, the first binder is an acrylate particle structure component, a dot structure is formed on the surface of an active substance, the second binder is a non-particle structure, and the two components act synergistically to form a polymer coating structure on the surface of the active substance, so that the problem of volume expansion of the natural graphite cathode material in the circulation process can be further alleviated, the cohesive property between the natural graphite cathode material and a current collector is further enhanced, and further the first coulomb efficiency and the circulation stability of the lithium ion battery are improved.
In the invention, the cellulose is added into the first binder, is used as a blending material of the first polymer, and is mixed and wound together with the first polymer, so that the suspension stability of the emulsion and the dispersion stability and the binding force when the emulsion is subsequently mixed with the active substance can be improved.
In another aspect, the present invention provides a method for preparing the natural graphite anode material with the surface connected with the binder, the method comprising the following steps:
(1) Adding the first binder and the natural graphite cathode material into a solvent for wet mixing to obtain mixed slurry, and then removing the solvent in the mixed slurry to obtain a solvent-free mixture;
(2) Mixing isocyanate monomers, hydroxyl-terminated acrylate polymers, optional cross-linking agents and optional catalysts, then mixing the mixture with the solvent-free mixture obtained in the step (1), and carrying out in-situ polymerization reaction to obtain the natural graphite negative electrode material with the surface connected with the binder.
In the invention, a first binder is connected to the surface of a natural graphite negative electrode material in a wet mixing mode, the first binder is an acrylate particle structure component, a dot structure is formed on the surface of an active substance, then an isocyanate monomer and a hydroxyl-terminated acrylate polymer are polymerized in situ to obtain a second binder, the second binder is connected to the surface of the natural graphite negative electrode material, the second binder is a non-particle structure, the second binder component is a polymer with better elasticity, the cohesive elasticity is enhanced, the high molecular component and the natural graphite negative electrode material can be uniformly mixed in the wet mixing process, the mixing uniformity of the high molecular component and the natural graphite negative electrode material can be ensured, the acrylate polymer component subjected to in situ polymerization can be well compatible with the particle polyacrylate component of the first binder, a better polymer network is formed to realize a network coating and connecting structure on the surface of the natural graphite, the problem of more defects on the surface of the natural graphite is solved, the second binder is directly synthesized in situ on the surface of the natural graphite active substance, hydrogen bonds, van der Waals force and the like between the surface functional groups of the active substance increase the bonding effect of the binder and the natural graphite active substance, the natural graphite active substance surface completely coated with the active substance, the two cooperate to form a completely coated polymer structure, and the natural graphite fiber bonding effect is improved, and the graphite fiber bonding state is achieved after the natural graphite fiber is completely coated, and the graphite fiber is better.
Preferably, the preparation method of the first binder in the step (1) comprises the following steps:
adding a first polymerization monomer and an initiator into an aqueous solution containing an emulsifier and/or a dispersant, carrying out a first polymerization reaction to obtain a first binder emulsion, removing solvent water from the obtained binder emulsion to obtain a first binder, wherein the first polymerization monomer comprises any one or a combination of at least two of an acrylate monomer, an acrylamide monomer, an acrylonitrile monomer or a styrene monomer.
Preferably, the total ratio of the dispersing agent to the emulsifying agent is 0.1% to 10.0% (e.g., 0.1%, 0.5%, 1.0%, 3.0%, 5.0%, 8.0%, or 10.0%), the ratio of the first polymerized monomer is 80.0% to 99.8% (e.g., 80.0%, 83.0%, 85.0%, 88.0%, 90.0%, 92.0%, 95.0%, 98.0%, or 99.8%), and the ratio of the initiator is 0.1% to 10.0% (e.g., 0.1%, 0.5%, 1.0%, 3.0%, 5.0%, 8.0%, or 10.0%), based on 100% of the total weight of the emulsifying agent, dispersing agent, first polymerized monomer, and initiator.
Preferably, the total weight percentage of the emulsifier, dispersant, first polymerized monomer, and initiator in the first binder emulsion is 2% to 30%, such as 2%, 5%, 8%, 10%, 13%, 15%, 18%, 20%, 25%, 28%, or 30%.
Preferably, the acrylate monomer is selected from any one of methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, n-pentyl acrylate, isopentyl acrylate, n-hexyl acrylate, isooctyl acrylate, hydroxypropyl acrylate, 2-hydroxyethyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, n-pentyl methacrylate, n-hexyl methacrylate, isooctyl methacrylate, hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate, sodium acrylate, lithium acrylate, acrylic acid, lithium methacrylate, methacrylic acid, lithium itaconate, itaconic acid, lithium itaconate monobutyl ester or a combination of at least two of them.
Preferably, the acrylamide monomer is selected from any one of acrylamide, methacrylamide, N-methylolacrylamide or N, N-dimethylacrylamide or a combination of at least two of the acrylamide, the methacrylamide, the N-methylolacrylamide and the N, N-dimethylacrylamide.
Preferably, cellulose is also added into the system of the first polymerization reaction.
Preferably, the cellulose is selected from any one of cellulose acetate, methyl cellulose, ethyl cellulose, hydroxypropyl cellulose (HPC), hydroxyethyl cellulose (HEC), cellulose nitrate, carboxymethyl cellulose (CMC), carboxyethyl cellulose, carboxypropyl cellulose, carboxyisopropyl cellulose, sodium nitrate, or sodium carboxyalkyl cellulose, or a combination of at least two thereof.
Preferably, the cellulose is used in an amount of 0.1% to 5.0%, such as 0.1%, 0.3%, 0.5%, 0.8%, 1.0%, 2.0%, 3.0%, 4.0% or 5.0% by weight of the total weight of the first polymerized monomer.
Preferably, the emulsifier is one or a combination of at least two of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate or sodium dodecyl sulfonate;
preferably, the dispersant is one or a combination of at least two of polyvinyl alcohol, polyvinyl pyrrolidone, tetradecane, hexadecane or octadecane;
preferably, the initiator is independently an organic peroxide initiator, an organic azo initiator, an inorganic peroxide initiator, or a redox initiator.
Preferably, the organic peroxide initiator is benzoyl peroxide or dicumyl peroxide.
Preferably, the organic azo initiator is azobisisobutyronitrile or azobisisoheptonitrile.
Preferably, the inorganic peroxide initiator is ammonium persulfate, sodium persulfate, or potassium persulfate.
Preferably, the redox initiator is ammonium persulfate and sodium sulfite, or ammonium persulfate and sodium bisulfite.
Preferably, the temperature of the first polymerization reaction is 35-98 ℃, such as 35 ℃, 40 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 68 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃ or 98 ℃.
Preferably, the time of the first polymerization reaction is 3 to 15h, such as 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 12h or 15h.
Preferably, the first binder is present in a ratio of 0.5 to 10.0% (e.g., 0.5%, 1.0%, 2.0%, 3.0%, 5.0%, 7.0%, 9.0%, or 10.0%) and the natural graphite negative electrode material is present in a ratio of 90.0 to 99.5% (e.g., 90.0%, 92.0%, 94.0%, 95.0%, 97.0%, 99.0%, or 99.5%) in the mixed slurry of step (1), based on 100% of the total weight of the first binder and the natural graphite negative electrode material.
Preferably, the mixed slurry of step (1) further comprises a conductive additive.
Preferably, the conductive additive comprises one or a combination of at least two of conductive graphite, acetylene black, carbon nanotubes or conductive carbon black.
Preferably, the conductive additive is present in an amount of 0 to 5%, for example, 0.5%, 1.0%, 1.5%, 2.0%, 3.0%, 4.0%, or 5.0%, based on 100% by weight of the first binder and the natural graphite anode material in the mixed slurry of step (1).
Preferably, the wet mixing process of step (1) includes a resonance acoustic mixing process, a high shear process, milling, and the like.
Preferably, the wet mixing operation of step (1) comprises using one or a combination of at least two of a ball mill, an electromagnetic ball mill, a disc mill, a pin mill, a high energy impact mill, a fluid energy impact mill, a counter-jet mill, a fluidized bed jet mill, a hammer mill, or an impact mill.
Preferably, the method for removing the solvent in the mixed slurry in the step (1) is any one of vacuum drying, centrifugation, freeze drying and spray drying or a combination of at least two of the methods.
Preferably, the total weight of the isocyanate-based monomer and the hydroxyl-terminated acrylate polymer of step (2) is 0.1 to 10.0%, such as 0.1%, 0.5%, 1.0%, 2.0%, 3.0%, 4.0%, 5.0%, 6.0%, 7.0%, 8.0%, 9.0% or 10.0% of the weight of the solvent-free mixture.
Preferably, the weight ratio of the isocyanate-based monomer and the hydroxyl-terminated acrylate polymer in step (2) is 1.
Preferably, the amount of the cross-linking agent used in step (2) is 0.1% to 10.0%, for example, 0.1%, 0.5%, 1.0%, 2.0%, 3.0%, 4.0%, 5.0%, 6.0%, 7.0%, 8.0%, 9.0% or 10.0% of the total weight of the isocyanate-based monomer and the hydroxyl-terminated acrylate polymer.
Preferably, the catalyst used in step (2) is 0.1% to 5.0%, such as 0.1%, 0.5%, 1.0%, 2.0%, 3.0%, 4.0% or 5.0% of the total weight of the isocyanate-based monomer and the hydroxyl-terminated acrylate polymer.
Preferably, the isocyanate-based monomer of step (2) is selected from any one of Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), 1, 5-Naphthalene Diisocyanate (NDI), dimethylbiphenyl diisocyanate (TODI), hexamethylene Diisocyanate (HDI), hexamethylene diisocyanate biuret, hexamethylene diisocyanate trimer, 2, 4-trimethylhexamethylene diisocyanate (TMDI), xylylene Diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), hydrogenated Xylylene Diisocyanate (HXDI), isophorone diisocyanate (IPDI), 4' -dicyclohexylmethane diisocyanate (HMDI), methylcyclohexane diisocyanate (HTDI), 1, 4-cyclohexane diisocyanate, 1, 4-phenylene diisocyanate (PPDI), 1, 3-phenylene diisocyanate or norbornane diisocyanate (NBDI), or a combination of at least two thereof.
Preferably, the hydroxyl-terminated acrylate polymer in step (2) is a liquid hydroxyl-terminated acrylate polymer, and the number average molecular weight of the hydroxyl-terminated acrylate polymer is preferably 100-10000.
Preferably, the polymerized monomer of the hydroxyl-terminated acrylate polymer in step (2) includes any one of styrene (St), acrylic Acid (AA), butyl Acrylate (BA), butyl Methacrylate (BMA), hydroxyethyl methacrylate (HEMA), hydroxyethyl acrylate (HEA), hydroxypropyl methacrylate (HPMA), or hydroxypropyl acrylate (HPA), or a combination of at least two thereof.
Preferably, the cross-linking agent in step (2) is selected from any one of or a combination of at least two of a diol cross-linking agent, a triol cross-linking agent, a diamine cross-linking agent, an alcohol amine cross-linking agent, an alicyclic alcohol cross-linking agent, an aromatic alcohol cross-linking agent, glycerol allyl ether, glycidyl allyl ether or dicumyl peroxide.
Preferably, the crosslinking agent in step (2) is selected from any one of 1, 4-butanediol, ethylene glycol, propylene glycol, diethylene glycol, neopentyl glycol, glycerol, trimethylolpropane, 3-dichloro-4, 4-diaminodiphenylmethane, 3, 5-dimethylthiotoluenediamine, 3, 5-diethyltoluenediamine, 2, 4-diamino-3, 5-dimethylthiochlorobenzene, isophoronediamine, ethanolamine, diethanolamine, triethanolamine, N-bis (2-hydroxypropyl) aniline, 1, 4-cyclohexanediol, hydrogenated bisphenol A, dimethylenephenylenediol, hydroquinone bis-beta-hydroxyethyl ether, resorcinol hydroxy ether, glycerol allyl ether, glycidyl allyl ether or dicumyl peroxide, or a combination of at least two thereof.
Preferably, the catalyst of step (2) is selected from any one of tertiary amine catalysts or organometallic compounds or a combination of at least two thereof.
Preferably, the catalyst in the step (2) is selected from any one of N, N-dimethylcyclohexylamine, dibutyltin dilaurate, bismuth 2-ethylhexanoate and bismuth neodecanoate or the combination of at least two of the above.
Preferably, the in situ polymerization reaction of step (2) is carried out at a temperature of 25-100 deg.C, such as 25 deg.C, 30 deg.C, 33 deg.C, 35 deg.C, 40 deg.C, 45 deg.C, 50 deg.C, 55 deg.C, 60 deg.C, 65 deg.C, 70 deg.C, 75 deg.C, 80 deg.C, 85 deg.C, 90 deg.C, 95 deg.C or 100 deg.C.
Preferably, the in situ polymerization reaction of step (2) is carried out for 5 to 50 hours, such as 5 hours, 10 hours, 15 hours, 20 hours, 24 hours, 28 hours, 30 hours, 36 hours, 39 hours, 40 hours, 42 hours, 45 hours, 48 hours or 50 hours.
In another aspect, the present invention provides a negative electrode sheet comprising the natural graphite negative electrode material with a binder attached to the surface thereof as described above.
In another aspect, the present invention provides an electrochemical energy storage device comprising a natural graphite anode material having a binder attached to a surface thereof as described above.
Preferably, the electrochemical energy storage device is selected from one of a lithium ion battery, a sodium ion battery, a supercapacitor, a fuel cell or a solar cell.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the first binder and the second binder are connected on the surface of the natural graphite negative electrode material, so that the problem of expansion and aging of the natural graphite negative electrode material in the circulation process can be solved, meanwhile, the cohesiveness among the natural graphite negative electrode materials and between the natural graphite negative electrode material and the current collector can be improved, the comprehensive performance of the material is improved, and the lithium ion battery containing the material has high first coulombic efficiency and high circulation stability.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
In this embodiment, a natural graphite anode material with a surface connected with a binder is provided, and a preparation method thereof includes the following steps:
(1) Placing 800.0g of aqueous solution dispersed with 5.0g of polyvinyl alcohol PVA in a 2000L reaction kettle, introducing nitrogen with the purity of more than or equal to 99.9% under the stirring state of the rotation speed of 250rpm, adding a first polymerization reaction monomer comprising 90.0g of methyl acrylate, 20.0g of acrylamide monomer and 10.0g of acrylonitrile, adding 0.5g of azodiisobutyronitrile AIBN serving as an initiator, continuously stirring, continuously introducing nitrogen, heating the solution to 75 ℃, carrying out a first polymerization reaction for 10 hours to obtain a polymerization product, reducing the pressure of the polymerization product by using a vacuum pump until the vacuum degree is lower than 0.1MPa, and removing residual unreacted monomer components to obtain the first binder.
(2) 97 parts by weight of a natural graphite negative electrode material (CONE-P, carbon one in Zhejiang) and 3 parts by weight of a first binder are added with metered deionized water to prepare dispersed slurry with the solid content of 40%, and the slurry is uniformly dispersed by adopting a dispersion machine with 800 revolutions of 30S and 2000 revolutions of 10min. And (4) drying the dispersed slurry at room temperature in vacuum to remove the moisture of the solvent, thereby obtaining a solvent-free mixture.
(3) 5.00g of dehydrated hexamethylene diisocyanate and 4.00g of a hydroxyl terminated acrylate polymer (UT-1001, soken Seikagaku Co., ltd.) were put together in a mixing pot, 0.30g of 1, 4-butanediol as a crosslinking agent and 0.01g of dibutyltin dilaurate as a catalyst were added, and the mixture was mixed in a defoaming machine at 2000rpm for 10 minutes to obtain a mixture. 1 part by weight of this mixture and 99 parts by weight of the solvent-free mixture obtained in step (2) were taken and mixed in a defoaming machine at 2000rpm for 10min. And then standing at normal temperature for 12h for in-situ polymerization reaction until the binder is solidified, and then grinding the obtained product into fine powder through a mortar to obtain the natural graphite cathode material with the surface connected with the binder.
Example 2
In this embodiment, a natural graphite anode material with a surface connected with a binder is provided, and a preparation method thereof includes the following steps:
(1) Placing 800.0g of aqueous solution dispersed with 5.0g of polyvinyl alcohol PVA in a 2000L reaction kettle, introducing nitrogen with the purity of more than or equal to 99.9% under the stirring state of the rotation speed of 250rpm, adding a first polymerization reaction monomer comprising 50.0g of methyl acrylate, 10.0g of acrylamide monomer, 20.0g of acrylonitrile and 10.0g of styrene, adding 0.5g of azodiisobutyronitrile AIBN serving as an initiator, continuously stirring, continuously introducing nitrogen, heating the solution to 90 ℃, carrying out a first polymerization reaction for 8 hours to obtain a polymerization product, reducing the vacuum degree of the polymerization product to be lower than 0.1MPa by using a vacuum pump, and removing residual unreacted monomer components to obtain the first binder.
(2) Taking 92 parts by weight of a natural graphite negative electrode material (CONE-P, zhejiang carbon I) and 8 parts by weight of a first binder, adding metered deionized water to prepare dispersed slurry with the solid content of 40%, mixing, and uniformly dispersing the slurry by adopting a dispersion machine for 30s by 800 revolutions and 10min by 2000 revolutions. And (4) drying the dispersed slurry at room temperature in vacuum to remove the water in the solvent, thereby obtaining a solvent-free mixture.
(3) 5.00g of the toluene diisocyanate after water removal and 4.00g of a hydroxyl-terminated acrylate polymer (Soken chemical Co., ltd., UT-1001) were charged together into a mixing pot, and 0.30g of propylene glycol as a crosslinking agent and 0.02g of dibutyltin dilaurate as a catalyst were added thereto, and mixed in a defoaming machine at 2000rpm for 10 minutes to obtain a mixture. 1 part by weight of this mixture and 99 parts by weight of the solvent-free mixture obtained in step (2) were taken and mixed in a defoaming machine at 2000rpm for 10min. And then standing at normal temperature for 15h to react until the binder is solidified, and grinding the obtained product into fine powder through a mortar to obtain the natural graphite negative electrode material with the surface connected with the binder.
Example 3
In this embodiment, a natural graphite anode material with a surface connected with a binder is provided, and a preparation method thereof includes the following steps:
(1) Placing 800.0g of aqueous solution dispersed with 8.0g of polyvinyl alcohol PVA in a 2000L reaction kettle, introducing nitrogen with the purity of more than or equal to 99.9% under the stirring state of the rotation speed of 250rpm, adding a first polymerization reaction monomer comprising 50.0g of methyl acrylate, 15.0g of acrylamide monomer, 15.0g of acrylonitrile and 5.0g of styrene, adding 0.5g of azodiisobutyronitrile AIBN serving as an initiator, continuously stirring, continuously introducing nitrogen, heating the solution to 80 ℃, carrying out a first polymerization reaction for 10 hours to obtain a polymerization product, reducing the vacuum degree of the polymerization product to be lower than 0.1MPa by using a vacuum pump, and removing residual unreacted monomer components to obtain the first binder.
(2) Taking 99 parts by weight of natural graphite negative electrode material (CONE-P, carbon one in Zhejiang), 0.5 part by weight of first binder and 0.5 part by weight of conductive carbon black, adding metered deionized water to prepare dispersed slurry with the solid content of 40%, mixing, and mixing for 10min by adopting a dispersion machine with 800 revolutions for 30s and 2000 revolutions for uniform dispersion of the slurry. And (4) drying the dispersed slurry at room temperature in vacuum to remove the water in the solvent, thereby obtaining a solvent-free mixture.
(3) 5.00g of tetramethylxylylene diisocyanate after water removal and 4.50g of a hydroxyl-terminated acrylate polymer (Soken Kabushiki Kaisha, UT-1001) were charged together into a mixing pot, and 0.60g of 3, 5-diethyltoluenediamine as a crosslinking agent and 0.02g of bismuth 2-ethylhexanoate as a catalyst were added and mixed in a defoaming machine at 2000rpm for 10 minutes to obtain a mixture. 5 parts by weight of this mixture and 95 parts by weight of the solvent-free mixture obtained in step (2) were mixed in a defoaming machine at 2000rpm for 10 minutes. And then standing at normal temperature for 24h to react until the binder is solidified, and then grinding the obtained product into fine powder by a mortar to obtain the natural graphite cathode material with the surface connected with the binder.
Example 4
In this embodiment, a natural graphite anode material with a surface connected with a binder is provided, and a preparation method thereof includes the following steps:
(1) Placing 800.0g of aqueous solution dispersed with 2.0g of polyvinyl alcohol PVA and 3.0g of sodium dodecyl benzene sulfonate into a 2000L reaction kettle, introducing nitrogen with the purity of more than or equal to 99.9% under the stirring state of the rotation speed of 250rpm, adding a first polymerization reaction monomer comprising 100.0g of methyl acrylate, 10.0g of acrylamide monomer, 10.0g of acrylonitrile and 10.0g of styrene, adding 0.5g of azodiisobutyronitrile AIBN serving as an initiator, continuously stirring, continuously introducing nitrogen, heating the solution to 95 ℃, carrying out a first polymerization reaction for 3 hours to obtain a polymerization product, reducing the vacuum degree of the polymerization product to be lower than 0.1MPa by using a vacuum pump, and removing residual unreacted monomer components to obtain the first binder.
(2) Taking 92 parts by weight of a natural graphite negative electrode material (CONE-P, carbon I in Zhejiang), 6 parts by weight of a first binder and 2 parts by weight of conductive carbon black, adding metered deionized water to prepare dispersed slurry with the solid content of 40%, mixing, and mixing for 10min by adopting a dispersion machine with 800 revolutions for 30s and a dispersion machine with 2000 revolutions for uniformly dispersing the slurry. And (4) drying the dispersed slurry at room temperature in vacuum to remove the water in the solvent, thereby obtaining a solvent-free mixture.
(3) 5.50g of 4,4' -dicyclohexylmethane diisocyanate after water removal was added to a compounding pot together with 4.50g of a hydroxyl-terminated acrylate polymer (Tiantai chemical, TT 310), and 0.20g of a crosslinking agent 1, 4-cyclohexanediol and 0.01g of a catalyst bismuth 2-ethylhexanoate were added and mixed in a defoaming machine at 2000rpm for 10 minutes to obtain a mixture. 0.5 part by weight of this mixture and 99.5 parts by weight of the solvent-free mixture obtained in step (2) were taken and mixed in a defoaming machine at 2000rpm for 10min. And then standing at normal temperature for 5h to react until the binder is solidified, and then grinding the obtained product into fine powder through a mortar to obtain the natural graphite cathode material with the surface connected with the binder.
Example 5
In this embodiment, a natural graphite anode material with a surface connected with a binder is provided, and a preparation method thereof includes the following steps:
(1) Placing 800.0g of aqueous solution dispersed with 2.0g of polyvinyl alcohol PVA in a 2000L reaction kettle, introducing nitrogen with the purity of more than or equal to 99.9% under the stirring state of the rotation speed of 250rpm, adding a first polymerization reaction monomer comprising 100.0g of methyl acrylate, 10.0g of acrylamide monomer, 10.0g of acrylonitrile and 10.0g of styrene, adding 0.5g of azodiisobutyronitrile AIBN serving as an initiator, continuously stirring, continuously introducing nitrogen, heating the solution to 50 ℃, carrying out a first polymerization reaction for 15h to obtain a polymerization product, reducing the vacuum degree of the polymerization product to be lower than 0.1MPa by using a vacuum pump, and removing residual unreacted monomer components to obtain the first binder.
(2) Taking 98 parts by weight of a natural graphite negative electrode material (CONE-P, zhejiang carbon I), 1.5 parts by weight of a first binder and 0.5 part by weight of conductive carbon black, adding metered deionized water to prepare a dispersion slurry with the solid content of 45%, mixing, and mixing for 10min by adopting a dispersion machine with 800 revolutions for 30s and 2000 revolutions for uniform dispersion of the slurry. And (4) drying the dispersed slurry at room temperature in vacuum to remove the water in the solvent, thereby obtaining a solvent-free mixture.
(3) 4.50g of isophorone diisocyanate after water removal was added to a mixing pot together with 5.00g of a hydroxyl-terminated acrylate polymer (Soken Seiko chemical Co., ltd., UT-1001), and 0.80g of N, N-bis (2-hydroxypropyl) aniline as a crosslinking agent and 0.02g of bismuth 2-ethylhexanoate as a catalyst were added and mixed in a defoaming machine at 2000rpm for 10 minutes to obtain a mixture. 10 parts by weight of this mixture and 90 parts by weight of the solvent-free mixture obtained in step (2) were mixed in a defoamer at 2000rpm for 10min. And then standing at 40 ℃ for 30h to react until the binder is solidified, and then grinding the obtained product into fine powder through a mortar to obtain the natural graphite negative electrode material with the surface connected with the binder.
Example 6
In this embodiment, a natural graphite anode material with a surface connected with a binder is provided, and a preparation method thereof includes the following steps:
(1) Placing 800.0g of aqueous solution dispersed with 5.0g of polyvinyl alcohol PVA in a 2000L reaction kettle, introducing nitrogen with the purity of more than or equal to 99.9% under the stirring state of the rotation speed of 250rpm, adding a first polymerization reaction monomer comprising 80.0g of methyl acrylate, 10.0g of acrylamide monomer, 5.0g of acrylonitrile and 10.0g of styrene, adding 0.5g of azodiisobutyronitrile AIBN serving as an initiator, continuously stirring, continuously introducing nitrogen, heating the solution to 75 ℃, carrying out a first polymerization reaction for 8 hours to obtain a polymerization product, reducing the vacuum degree of the polymerization product to be lower than 0.1MPa by using a vacuum pump, removing residual unreacted monomer components, and obtaining the first binder.
(2) Taking 93 parts by weight of natural graphite negative electrode material (CONE-P, carbon I in Zhejiang), 3 parts by weight of first binder and 4 parts by weight of conductive carbon black, adding metered deionized water to prepare dispersed slurry with the solid content of 40%, mixing, and mixing for 10min by adopting a dispersion machine with 800 revolutions for 30s and 2000 revolutions for uniformly dispersing the slurry. And (4) drying the dispersed slurry at room temperature in vacuum to remove the water in the solvent, thereby obtaining a solvent-free mixture.
(3) 5.50g of 1, 5-naphthalene diisocyanate after water removal and 3.50g of a hydroxyl-terminated acrylate polymer (Soken Seiko chemical Co., ltd., UT-1001) were put together in a compounding pot, and 0.40g of triethanolamine as a crosslinking agent and 0.01g of bismuth 2-ethylhexanoate as a catalyst were added and mixed in a defoaming machine at 2000rpm for 10 minutes to obtain a mixture. Mixing 8 parts by weight of the mixture and 92 parts by weight of the solvent-free mixture obtained in step (2) in a defoaming machine at 2000rpm for 10min. And then standing at 100 ℃ for 5h to react until the binder is solidified, and then grinding the obtained product into fine powder by a mortar to obtain the natural graphite cathode material with the surface connected with the binder.
Example 7
The only difference from example 1 is that step (1) is as follows:
(1) Placing 800.0g of aqueous solution dispersed with 5.0g of polyvinyl alcohol PVA in a 2000L reaction kettle, introducing nitrogen with the purity of more than or equal to 99.9% under the stirring state of the rotation speed of 250rpm, adding a first polymerization reaction monomer comprising 90.0g of methyl acrylate, 20.0g of acrylamide monomer and 10.0g of acrylonitrile, adding 0.5g of hydroxypropyl cellulose, adding 0.5g of azodiisobutyronitrile AIBN serving as an initiator, continuously stirring, continuously introducing nitrogen, heating the solution to 75 ℃, carrying out a first polymerization reaction for 10 hours to obtain a polymerization product, reducing the pressure of the polymerization product by using a vacuum pump until the vacuum degree is lower than 0.1MPa, and removing residual unreacted monomer components to obtain the first binder. The other steps were the same as in example 1.
Example 8
The only difference from example 7 is that the amount of hydroxypropylcellulose used therein was 6g.
Example 9
The difference from example 1 is only that the first polymerization monomer in step (1) includes only 99g of methyl acrylate and 21g of acrylamide monomer.
Example 10
The only difference from example 1 is that the first polymerization monomer in step (1) contained 108g of methyl acrylate and 12g of acrylonitrile.
Example 11
The difference from example 2 is only that the first polymerization monomer in step (1) includes only 75g of methyl acrylate and 15g of styrene.
Example 12
The only difference from example 1 is that the first polymerization monomer in step (1) included only 120g of methyl acrylate.
Example 13
The only difference from example 1 is that the first polymerization monomer in step (1) includes only 120g of acrylamide monomer.
Example 14
The difference from example 2 is only that the first polymerization monomer in step (1) includes only 90g of styrene.
Example 15
The only difference from example 1 is that the first polymerization monomer in step (1) includes only 120g of acrylonitrile.
Comparative example 1
The only difference from example 1 is that the hydroxyl terminated acrylate polymer was replaced with a polyester polyol (polyester polyol) in step (3).
Comparative example 2
The only difference from example 1 is that the hydroxyl-terminated acrylate polymer in step (3) is replaced with a hydroxyl-terminated ethylene oxide polymer (Tiantai chemical, TT 310).
Comparative example 3
The difference from example 1 is that the in-situ polymerization of step (3) is not performed, and the solvent-free mixture obtained in step (2) is directly used as a natural graphite anode material with a surface-attached binder.
Comparative example 4
The comparative example provides a modified natural graphite negative electrode material, and the preparation method comprises the following steps:
5.00g of dehydrated hexamethylene diisocyanate and 4.00g of a hydroxyl-terminated acrylate polymer (Soken chemical Co., ltd., UT-1001) were charged together into a mixing pot, and 0.30g of 1, 4-butanediol as a crosslinking agent and 0.01g of dibutyltin dilaurate as a catalyst were added thereto, and the materials were mixed in a defoaming machine at 2000rpm for 10 minutes to obtain a mixture. 1 part by weight of the mixture and 99 parts by weight of natural graphite cathode material are mixed for 10min at 2000rpm in a defoaming machine. And then standing at normal temperature for 12h for in-situ polymerization reaction until the binder is solidified, and then grinding the obtained product into fine powder through a mortar to obtain the natural graphite cathode material with the surface connected with the binder.
Application examples 1 to 15 and comparative application examples 1 to 4
The prepared natural graphite negative electrode material is prepared into a negative electrode sheet, and specifically comprises the following steps: the natural graphite negative electrode materials obtained in examples 1 to 15 and comparative examples 1 to 4 were mixed with a conductive agent carbon black (Surper P) PAA binder at a mass ratio of 96.5.
Assembling the prepared negative pole piece and a lithium metal pole piece into a lithium ion button cell, and preparing LiPF 6 Dissolving in an electrolyte of ethylene carbonate/diethyl carbonate/ethyl methyl carbonate =2 at a concentration of 1 mol/l, and after the assembly of the charging, performing tests such as capacity first coulombic efficiency and cycle according to the following steps: standing for 2h; constant temperatureCurrent discharge: 0.10C to 0.005V;0.08C to 0.001V;0.05C to 0.001V;0.02C to 0.001V; standing for 10min; constant current charging: 0.10C to 1.500V.
The capacity first coulombic efficiency and cycling test results are shown in table 1.
TABLE 1
The results in table 1 show that the natural graphite negative electrode material with the surface connecting adhesive of the invention can enable the first coulombic efficiency of a battery using the natural graphite negative electrode material to reach more than 94%, the capacity retention rate of 1000 cycles of the battery to reach more than 86%, and the natural graphite negative electrode material has good battery efficiency and cycle stability.
In comparative example 1, the hydroxyl-terminated acrylate polymer in the second binder is replaced by polyester polyol, and the polyester polyol has weaker surface acting force than that of natural graphite, so that the first coulombic efficiency of the battery is reduced, and the cycle stability is reduced.
In comparative example 2, since the hydroxyl-terminated acrylate polymer in the second binder is replaced with the hydroxyl-terminated ethylene oxide polymer, the hydroxyl-terminated ethylene oxide polymer has a weaker surface acting force than that of natural graphite, which results in a decrease in the first coulombic efficiency of the battery and a decrease in the cycle stability.
In comparative example 3, the in-situ polymerization of step (3) is not performed, so that the binder in the obtained natural graphite negative electrode material with the surface connected with the binder only comprises the first binder, and the binder in the natural graphite negative electrode material with the surface connected with the binder only comprises the second binder, which cannot form a good polymer coating network structure, so that the first coulombic efficiency of the batteries of comparative examples 3 and 4 is reduced, and the cycle stability is reduced.
The applicant states that the present invention is illustrated by the above examples of the natural graphite negative electrode material with the surface bonding binder of the present invention, and the preparation method and application thereof, but the present invention is not limited to the above examples, i.e. it does not mean that the present invention must be implemented by the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The natural graphite negative electrode material with the surface connected with the binder is characterized in that the natural graphite negative electrode material with the surface connected with the binder comprises a natural graphite negative electrode material and the binder connected with the surface of the natural graphite negative electrode material, the binder comprises a first binder and a second binder, the first binder comprises a first polymer, a polymerization monomer of the first polymer comprises any one or a combination of at least two of an acrylate monomer, an acrylamide monomer, an acrylonitrile monomer or a styrene monomer, and the second binder is a bi-component polyacrylate.
2. The natural graphite anode material with the surface connected with the binder as claimed in claim 1, wherein the first binder is in a particle structure, the second binder is in a non-particle structure, and the first binder and the second binder form a polymer network on the surface of the natural graphite anode material;
preferably, the acrylate monomer is selected from any one of methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, n-pentyl acrylate, isopentyl acrylate, n-hexyl acrylate, isooctyl acrylate, hydroxypropyl acrylate, 2-hydroxyethyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, n-pentyl methacrylate, n-hexyl methacrylate, isooctyl methacrylate, hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate, sodium acrylate, lithium acrylate, acrylic acid, lithium methacrylate, methacrylic acid, lithium itaconate, itaconic acid, lithium itaconate monobutyl ester or a combination of at least two of them;
preferably, the acrylamide monomer is selected from any one or a combination of at least two of acrylamide, methacrylamide, N-methylolacrylamide or N, N-dimethylacrylamide;
preferably, the first binder further comprises cellulose, the cellulose being mixed with a first polymer;
preferably, the cellulose is selected from any one of cellulose acetate, methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, cellulose nitrate, carboxymethyl cellulose, carboxyethyl cellulose, carboxypropyl cellulose, carboxyisopropyl cellulose, sodium nitrate cellulose or sodium carboxyalkyl cellulose, or a combination of at least two thereof;
preferably, the raw materials for preparing the bi-component polyacrylate comprise isocyanate monomers and hydroxyl-terminated acrylate polymers;
preferably, the raw materials for preparing the bi-component polyacrylate also comprise a cross-linking agent and/or a catalyst;
preferably, the isocyanate-based monomer is selected from any one of toluene diisocyanate, diphenylmethane diisocyanate, 1, 5-naphthalene diisocyanate, dimethylbiphenyl diisocyanate, hexamethylene diisocyanate biuret, hexamethylene diisocyanate trimer, 2, 4-trimethylhexamethylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, 4' -dicyclohexylmethane diisocyanate, methylcyclohexane diisocyanate, 1, 4-cyclohexane diisocyanate, 1, 4-phenylene diisocyanate, 1, 3-phenylene diisocyanate or norbornane diisocyanate, or a combination of at least two thereof.
3. The natural graphite negative electrode material with the surface connected with the binder as claimed in claim 1 or 2, wherein the hydroxyl-terminated acrylate polymer is a liquid hydroxyl-terminated acrylate polymer, and the number average molecular weight of the hydroxyl-terminated acrylate polymer is preferably 100-10000;
preferably, the polymerized monomer of the hydroxyl-terminated acrylate polymer comprises any one or a combination of at least two of styrene, acrylic acid, butyl acrylate, butyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate or hydroxypropyl acrylate;
preferably, the crosslinking agent is selected from any one or a combination of at least two of 1, 4-butanediol, ethylene glycol, propylene glycol, diethylene glycol, neopentyl glycol, glycerol, trimethylolpropane, 3-dichloro-4, 4-diaminodiphenylmethane, 3, 5-dimethylthiotoluenediamine, 3, 5-diethyltoluenediamine, 2, 4-diamino-3, 5-dimethylthiochlorobenzene, isophoronediamine, ethanolamine, diethanolamine, triethanolamine, N-bis (2-hydroxypropyl) aniline, 1, 4-cyclohexanediol, hydrogenated bisphenol a, dimethylenephenylenediol, hydroquinone bis- β -hydroxyethyl ether, resorcinol hydroxyl ether, glycerol allyl ether, glycidyl allyl ether or dicumyl peroxide;
preferably, the catalyst is selected from any one of a tertiary amine catalyst or an organometallic compound or a combination of at least two thereof;
preferably, the catalyst is selected from any one of or a combination of at least two of N, N-dimethylcyclohexylamine, dibutyltin dilaurate, bismuth 2-ethylhexanoate, and bismuth neodecanoate.
4. The natural graphite negative electrode material with the surface connected with the binder as claimed in any one of claims 1 to 3, wherein the glass transition temperature Tg of the first polymer is in the range of-50 to 200 ℃;
preferably, the particle size of the first binder is 200nm to 10 μm;
preferably, the first binder is polymerized by emulsion polymerization, microemulsion polymerization, suspension polymerization or microsuspension polymerization;
preferably, the second binder is obtained by in-situ polymerization on the surface of the natural graphite negative electrode material connected with the first binder.
5. The method for preparing the natural graphite anode material with the surface connected with the binder, according to any one of claims 1 to 4, wherein the method comprises the following steps:
(1) Adding the first binder and the natural graphite cathode material into a solvent for wet mixing to obtain mixed slurry, and then removing the solvent in the mixed slurry to obtain a solvent-free mixture;
(2) And (2) mixing an isocyanate monomer, a hydroxyl-terminated acrylate polymer, a cross-linking agent and a catalyst, then mixing with the solvent-free mixture obtained in the step (1), and carrying out in-situ polymerization reaction to obtain the natural graphite negative electrode material with the surface connected with the binder.
6. The method according to claim 5, wherein the method of preparing the first binder of step (1) comprises the steps of:
adding a first polymerization monomer and an initiator into an aqueous solution containing an emulsifier and/or a dispersant, carrying out a first polymerization reaction to obtain a first binder emulsion, removing solvent water from the obtained binder emulsion to obtain a first binder, wherein the first polymerization monomer comprises any one or a combination of at least two of an acrylate monomer, an acrylamide monomer, an acrylonitrile monomer or a styrene monomer;
preferably, the total proportion of the emulsifier to the dispersant is 0.1% -10.0%, the proportion of the first polymerization monomer to the initiator is 80.0% -99.8%, and the proportion of the first polymerization monomer to the initiator is 0.1% -10.0% based on 100% of the total weight of the emulsifier, the dispersant, the first polymerization monomer and the initiator;
preferably, the total weight percentage of the emulsifier, the dispersant, the first polymerized monomer and the initiator in the first binder emulsion is 2% -30%;
preferably, the acrylate monomer is selected from any one or a combination of at least two of methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, n-pentyl acrylate, isopentyl acrylate, n-hexyl acrylate, isooctyl acrylate, hydroxypropyl acrylate, 2-hydroxyethyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, n-pentyl methacrylate, n-hexyl methacrylate, isooctyl methacrylate, hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate, sodium acrylate, lithium acrylate, acrylic acid, lithium methacrylate, methacrylic acid, lithium itaconate, itaconic acid, lithium itaconate monobutyl ester or monobutyl itaconate;
preferably, the acrylamide monomer is selected from any one or a combination of at least two of acrylamide, methacrylamide, N-methylolacrylamide or N, N-dimethylacrylamide;
preferably, cellulose is also added into the system of the first polymerization reaction;
preferably, the cellulose is selected from any one of cellulose acetate, methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, cellulose nitrate, carboxymethyl cellulose, carboxyethyl cellulose, carboxypropyl cellulose, carboxyisopropyl cellulose, sodium nitrate cellulose or sodium carboxyalkyl cellulose, or a combination of at least two thereof;
preferably, the cellulose is used in an amount of 0.1 to 5.0% by weight based on the total weight of the first polymerized monomer.
Preferably, the emulsifier is one or a combination of at least two of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate or sodium dodecyl sulfonate;
preferably, the dispersant is one or a combination of at least two of polyvinyl alcohol, polyvinyl pyrrolidone, tetradecane, hexadecane or octadecane;
preferably, the initiator is independently an organic peroxide initiator, an organic azo-type initiator, an inorganic peroxide initiator or a redox initiator;
preferably, the organic peroxide initiator is benzoyl peroxide or dicumyl peroxide;
preferably, the organic azo initiator is azobisisobutyronitrile or azobisisoheptonitrile;
preferably, the inorganic peroxide initiator is ammonium persulfate, sodium persulfate or potassium persulfate;
preferably, the redox initiator is ammonium persulfate and sodium sulfite, or ammonium persulfate and sodium bisulfite;
preferably, the temperature of the first polymerization reaction is 35 to 98 ℃;
preferably, the time of the first polymerization reaction is 3 to 15 hours.
7. The preparation method according to claim 5 or 6, wherein the first binder accounts for 0.5-10.0% and the natural graphite negative electrode material accounts for 90.0-99.5% of the mixed slurry in step (1) based on 100% of the total weight of the first binder and the natural graphite negative electrode material;
preferably, the mixed slurry in the step (1) further comprises a conductive additive;
preferably, the conductive additive comprises one or a combination of at least two of conductive graphite, acetylene black, carbon nanotubes or conductive carbon black;
preferably, the conductive additive accounts for 0-5% of the mixed slurry in the step (1) by taking the total weight of the first binder and the natural graphite negative electrode material as 100%;
preferably, the wet mixing process of step (1) comprises a resonance acoustic mixing process, a high shear process and a milling process;
preferably, the wet mixing operation of step (1) comprises using one or a combination of at least two of a ball mill, an electromagnetic ball mill, a disc mill, a pin mill, a high energy impact mill, a fluid energy impact mill, a counter-jet mill, a fluidized bed jet mill, a hammer mill, or an impact mill;
preferably, the method for removing the solvent in the mixed slurry in the step (1) is any one of vacuum drying, centrifugation, freeze drying and spray drying or a combination of at least two of the above.
8. The method according to any one of claims 5 to 7, wherein the total weight of the isocyanate monomer and the hydroxyl-terminated acrylate polymer in step (2) is 0.1 to 10.0% of the weight of the solvent-free mixture;
preferably, the weight ratio of the isocyanate monomer and the hydroxyl-terminated acrylate polymer in the step (2) is 1;
preferably, the amount of the cross-linking agent in the step (2) is 0.1-10.0% of the total weight of the isocyanate monomer and the hydroxyl-terminated acrylate polymer;
preferably, the amount of the catalyst used in the step (2) is 0.1-5.0% of the total weight of the isocyanate monomer and the hydroxyl-terminated acrylate polymer;
preferably, the isocyanate-based monomer in step (2) is selected from any one of toluene diisocyanate, diphenylmethane diisocyanate, 1, 5-naphthalene diisocyanate, dimethylbiphenyl diisocyanate, hexamethylene diisocyanate biuret, hexamethylene diisocyanate trimer, 2, 4-trimethylhexamethylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, 4' -dicyclohexylmethane diisocyanate, methylcyclohexane diisocyanate, 1, 4-cyclohexane diisocyanate, 1, 4-phenylene diisocyanate, 1, 3-phenylene diisocyanate or norbornane diisocyanate, or a combination of at least two thereof. (ii) a
Preferably, the hydroxyl-terminated acrylate polymer in step (2) is a liquid hydroxyl-terminated acrylate polymer, and the number average molecular weight of the hydroxyl-terminated acrylate polymer is preferably 100-10000;
preferably, the polymerized monomer of the hydroxyl-terminated acrylate polymer in step (2) comprises any one or a combination of at least two of styrene, acrylic acid, butyl acrylate, butyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate and hydroxypropyl acrylate;
preferably, the crosslinking agent in step (2) is selected from any one or a combination of at least two of a dihydric alcohol crosslinking agent, a trihydric alcohol crosslinking agent, a diamine crosslinking agent, an alcohol amine crosslinking agent, an alicyclic alcohol crosslinking agent, an aromatic alcohol crosslinking agent, glycerol allyl ether, glycidyl allyl ether or dicumyl peroxide;
preferably, the crosslinking agent in step (2) is selected from any one of 1, 4-butanediol, ethylene glycol, propylene glycol, diethylene glycol, neopentyl glycol, glycerol, trimethylolpropane, 3-dichloro-4, 4-diaminodiphenylmethane, 3, 5-dimethylthiotoluenediamine, 3, 5-diethyltoluenediamine, 2, 4-diamino-3, 5-dimethylthiochlorobenzene, isophoronediamine, ethanolamine, diethanolamine, triethanolamine, N-bis (2-hydroxypropyl) aniline, 1, 4-cyclohexanediol, hydrogenated bisphenol A, dimethylenephenylenediol, hydroquinone bis-beta-hydroxyethyl ether, resorcinol hydroxy ether, glycerol allyl ether, glycidyl allyl ether or dicumyl peroxide, or a combination of at least two thereof;
preferably, the catalyst of step (2) is selected from any one of tertiary amine catalysts or organometallic compounds or a combination of at least two thereof;
preferably, the catalyst in the step (2) is selected from any one or a combination of at least two of N, N-dimethylcyclohexylamine, dibutyltin dilaurate, bismuth 2-ethylhexanoate and bismuth neodecanoate;
preferably, the temperature of the in-situ polymerization reaction in the step (2) is 25-100 ℃;
preferably, the in-situ polymerization reaction time of the step (2) is 5-50h.
9. A negative electrode sheet comprising the natural graphite negative electrode material with the surface-attached binder according to any one of claims 1 to 4.
10. An electrochemical energy storage device comprising the binder surface-attached natural graphite negative electrode material of any one of claims 1-4;
preferably, the electrochemical energy storage device is selected from one of a lithium ion battery, a sodium ion battery, a supercapacitor, a fuel cell or a solar cell.
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| CN202210907908.5A CN115799507B (en) | 2022-07-29 | 2022-07-29 | Natural graphite negative electrode material with surface connected with binder, and preparation method and application thereof |
| PCT/CN2023/108044 WO2024022181A1 (en) | 2022-07-29 | 2023-07-19 | Negative electrode material with surface connected with binder, and preparation method therefor and use thereof |
| KR1020237037402A KR20240017341A (en) | 2022-07-29 | 2023-07-19 | Anode material with adhesive attached to the surface, manufacturing method and application thereof |
| EP23789480.3A EP4343892A1 (en) | 2022-07-29 | 2023-07-19 | Negative electrode material with surface connected with binder, and preparation method therefor and use thereof |
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| CN117229732A (en) * | 2023-11-16 | 2023-12-15 | 宁德时代新能源科技股份有限公司 | Adhesive composition, positive electrode sheet, secondary battery and electric device |
| WO2024022181A1 (en) * | 2022-07-29 | 2024-02-01 | 碳一新能源集团有限责任公司 | Negative electrode material with surface connected with binder, and preparation method therefor and use thereof |
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