CN114583163A - 一种锂离子电池用分散剂及其制备方法、正极浆料、正极片和锂离子电池 - Google Patents
一种锂离子电池用分散剂及其制备方法、正极浆料、正极片和锂离子电池 Download PDFInfo
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- CN114583163A CN114583163A CN202011361712.8A CN202011361712A CN114583163A CN 114583163 A CN114583163 A CN 114583163A CN 202011361712 A CN202011361712 A CN 202011361712A CN 114583163 A CN114583163 A CN 114583163A
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- Prior art keywords
- dispersant
- positive electrode
- acid
- lithium ion
- ion battery
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- 239000002270 dispersing agent Substances 0.000 title claims abstract description 113
- 239000011267 electrode slurry Substances 0.000 title claims abstract description 30
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 65
- 239000007774 positive electrode material Substances 0.000 claims abstract description 42
- 239000006258 conductive agent Substances 0.000 claims abstract description 17
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000007524 organic acids Chemical class 0.000 claims abstract description 16
- 150000001993 dienes Chemical class 0.000 claims abstract description 14
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 7
- 150000003016 phosphoric acids Chemical class 0.000 claims abstract description 7
- 150000003460 sulfonic acids Chemical class 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 15
- 239000011230 binding agent Substances 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 14
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 8
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 238000005984 hydrogenation reaction Methods 0.000 claims description 6
- -1 methacryloyloxy Chemical group 0.000 claims description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 5
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 claims description 4
- NXBXJOWBDCQIHF-UHFFFAOYSA-N 2-[hydroxy-[2-(2-methylprop-2-enoyloxy)ethoxy]phosphoryl]oxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOP(O)(=O)OCCOC(=O)C(C)=C NXBXJOWBDCQIHF-UHFFFAOYSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 claims description 4
- AHAREKHAZNPPMI-AATRIKPKSA-N (3e)-hexa-1,3-diene Chemical compound CC\C=C\C=C AHAREKHAZNPPMI-AATRIKPKSA-N 0.000 claims description 3
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 claims description 3
- RZKYDQNMAUSEDZ-UHFFFAOYSA-N prop-2-enylphosphonic acid Chemical compound OP(O)(=O)CC=C RZKYDQNMAUSEDZ-UHFFFAOYSA-N 0.000 claims description 3
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 claims description 3
- YHHHHJCAVQSFMJ-FNORWQNLSA-N (3e)-deca-1,3-diene Chemical compound CCCCCC\C=C\C=C YHHHHJCAVQSFMJ-FNORWQNLSA-N 0.000 claims description 2
- LXKRFDPUBWVICN-SNAWJCMRSA-N (5e)-2-methylhepta-1,5-diene Chemical compound C\C=C\CCC(C)=C LXKRFDPUBWVICN-SNAWJCMRSA-N 0.000 claims description 2
- GSSDUXHQPXODCN-UHFFFAOYSA-N 1-phenylethenylphosphonic acid Chemical compound OP(O)(=O)C(=C)C1=CC=CC=C1 GSSDUXHQPXODCN-UHFFFAOYSA-N 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 claims description 2
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- CFVZILWIXKITDD-UHFFFAOYSA-N 2-acetyloxyprop-2-enoic acid Chemical compound CC(=O)OC(=C)C(O)=O CFVZILWIXKITDD-UHFFFAOYSA-N 0.000 claims description 2
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 claims description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 2
- NKIIKKAXXDXYJS-UHFFFAOYSA-N 1-prop-2-enoyloxypropane-2-sulfonic acid Chemical compound OS(=O)(=O)C(C)COC(=O)C=C NKIIKKAXXDXYJS-UHFFFAOYSA-N 0.000 claims 1
- XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical compound CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 0.000 claims 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 claims 1
- KFNGWPXYNSJXOP-UHFFFAOYSA-N 3-(2-methylprop-2-enoyloxy)propane-1-sulfonic acid Chemical compound CC(=C)C(=O)OCCCS(O)(=O)=O KFNGWPXYNSJXOP-UHFFFAOYSA-N 0.000 claims 1
- 229910019142 PO4 Inorganic materials 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 claims 1
- 239000006185 dispersion Substances 0.000 abstract description 16
- 239000007787 solid Substances 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 12
- 239000002002 slurry Substances 0.000 abstract description 8
- 230000000052 comparative effect Effects 0.000 description 21
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 17
- 238000001035 drying Methods 0.000 description 16
- 239000006256 anode slurry Substances 0.000 description 15
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 14
- 238000003756 stirring Methods 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 239000003999 initiator Substances 0.000 description 10
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 9
- 239000002033 PVDF binder Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 230000000379 polymerizing effect Effects 0.000 description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 9
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 9
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- 229910021393 carbon nanotube Inorganic materials 0.000 description 8
- 239000002041 carbon nanotube Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 239000010405 anode material Substances 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 5
- 230000001965 increasing effect Effects 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 239000006183 anode active material Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- PRAMZQXXPOLCIY-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethanesulfonic acid Chemical compound CC(=C)C(=O)OCCS(O)(=O)=O PRAMZQXXPOLCIY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910013716 LiNi Inorganic materials 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- PNOXUQIZPBURMT-UHFFFAOYSA-M potassium;3-(2-methylprop-2-enoyloxy)propane-1-sulfonate Chemical compound [K+].CC(=C)C(=O)OCCCS([O-])(=O)=O PNOXUQIZPBURMT-UHFFFAOYSA-M 0.000 description 2
- VSFOXJWBPGONDR-UHFFFAOYSA-M potassium;3-prop-2-enoyloxypropane-1-sulfonate Chemical compound [K+].[O-]S(=O)(=O)CCCOC(=O)C=C VSFOXJWBPGONDR-UHFFFAOYSA-M 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- CJGJYOBXQLCLRG-UHFFFAOYSA-M sodium;2-hydroxy-3-prop-2-enoxypropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)COCC=C CJGJYOBXQLCLRG-UHFFFAOYSA-M 0.000 description 2
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 description 2
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 description 1
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical compound FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- YWJVFBOUPMWANA-UHFFFAOYSA-H [Li+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Li+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O YWJVFBOUPMWANA-UHFFFAOYSA-H 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 239000011883 electrode binding agent Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- ZJXZSIYSNXKHEA-UHFFFAOYSA-N ethyl dihydrogen phosphate Chemical compound CCOP(O)(O)=O ZJXZSIYSNXKHEA-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- BDKWOJYFHXPPPT-UHFFFAOYSA-N lithium dioxido(dioxo)manganese nickel(2+) Chemical compound [Mn](=O)(=O)([O-])[O-].[Ni+2].[Li+] BDKWOJYFHXPPPT-UHFFFAOYSA-N 0.000 description 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/04—Acids, Metal salts or ammonium salts thereof
- C08F20/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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Abstract
本申请提供了一种锂离子电池用分散剂,该分散剂包括源自N‑乙烯基吡咯烷酮的结构单元A、源自共轭二烯类单体的结构单元B和源自有机酸类单体的结构单元C;其中,所述有机酸类单体包括不饱和磺酸类单体、不饱和磷酸类单体和不饱和羧酸类单体中的一种或多种。较低用量的该分散剂就可使正极活性材料和导电剂等在锂离子电池正极浆料中短时间内达到较好的分散效果,并使正极浆料具有较高的固含量,可提升正极片的制备效率和产品良率、柔韧性等,几乎不影响正极活性材料在正极片中的质量占比。本申请还提供了该分散剂的制备方法、包含其的正极浆料、正极片和锂离子电池。
Description
技术领域
本申请涉及锂离子电池技术领域,具体涉及一种锂离子电池用分散剂及其制备方法、正极浆料、正极片和锂离子电池。
背景技术
随着对电池性能要求的不断提高,对其正极浆料的工艺制程的要求也不断提高。锂离子电池的正极浆料的组分主要包括正极活性材料、导电剂、粘结剂和溶剂,一方面需要提高正极活性材料和导电剂等在其中的分散效果以提高正极片的均匀性,另一方面需要提高正极浆料的固含量以改善正极浆料的涂布性能、提升正极片的良率和产能。其中,通过在正极浆料中添加分散助剂的方法逐渐被电池厂家所采用。向正极浆料中添加分散助剂称为业界提高正极浆料的分散效果及固含量的主流手段。
现有的锂离子电池中可用的分散剂种类较少,主要为聚乙烯吡咯烷酮(PVP)、聚丙烯酰胺(PAM)等。然而,这些分散剂对正极浆料的分散能力有限,其添加量通常较大,但这会相应减少正极活性材料在由正极浆料形成的正极材料层中的质量占比,进而会降低电池的比容量。因此,有必要开发对正极浆料具有优异分散能力的分散剂,以实现通过较少的分散剂用量达到较好的浆料分散效果。
发明内容
鉴于此,本申请实施例提供了一种新型的锂离子电池用分散剂,以在提高正极浆料的分散性和固含量的同时,又可避免因正极活性材料的含量下降带来的电池比容量降低的问题。
具体地,第一方面本申请提供了一种锂离子电池用分散剂,所述分散剂包括源自N-乙烯基吡咯烷酮的结构单元A、源自共轭二烯类单体的结构单元B和源自有机酸类单体的结构单元C;其中,所述有机酸类单体包括不饱和磺酸类单体、不饱和磷酸类单体和不饱和羧酸类单体中的一种或多种。
其中,所述共轭二烯类单体用于为所述分散剂提供其分子骨架作用的结构单元B,并使所述分散剂的分子链具有一定的柔韧性。所述N-乙烯基吡咯烷酮用于为所述分散剂提供能与正极浆料的溶剂(如N-甲基吡咯烷酮(NMP)、N,N-二甲基甲酰胺(DMF)等)有较强亲和力的结构单元A,增加所述分散剂与正极浆料溶剂的相溶性。而所述有机酸类单体用于使所述分散剂具有羧基、磷酸基或磺酸基等极性基团的结构单元C,以便该分散剂可与正极活性材料表面形成氢键、范德华力等。例如,分散剂可与磷酸铁锂、磷酸锰铁锂等正极活性材料表面的磷酸基形成氢键、与三元正极活性材料表面的羟基形成氢键,分散剂还可以与碳纳米管、石墨烯等导电剂表面的羟基、羧基等功能基团形成氢键。
因此,所述分散剂具有双亲性,既亲合溶剂,又亲合被分散颗粒(正极活性材料颗粒、导电剂颗粒等),该分散剂可较容易地吸附在被分散颗粒的表面与溶剂的界面上,可使正极活性材料和导电剂等在锂离子电池正极浆料中达到优异的分散效果,并阻止被分散的颗粒再次团聚,且分散时间短、分散剂用量少;此外,所述分散剂还具有良好柔韧性,更好地发挥其双亲作用,并还可借助其柔韧性来减少各颗粒在正极片中的内应力,从而起到改善正极片柔韧性的作用,便于将正极片组装成电池。
本申请一些实施方式中,所述分散剂包括同时含有上述结构单元A、结构单元B和结构单元C的共聚物。该共聚物可以包含无规、嵌段、交替和接枝共聚结构的任意结构。
可选地,所述分散剂中,所述结构单元A的摩尔占比为30%-90%,所述结构单元B的摩尔占比为5%-50%,所述结构单元C的摩尔占比为1%-30%。这样可以使该分散剂具有一定的亲溶剂性、亲待分散颗粒性及柔韧性,以起到较好的分散效果。
本申请实施方式中,所述共轭二烯类单体的碳原子数在4以上,例如为4-12。作为示例性的共轭二烯类单体可以包括1,3-丁二烯、异戊二烯、2,3-二甲基-1,3-丁二烯、2-氯-1,3-丁二烯、1,3-戊二烯、1,3-己二烯、1,3-癸二烯、2-甲基-1,5-庚二烯等中的一种或多种。
本申请实施方式中,作为示例性的所述不饱和磺酸类单体可以包括乙烯基磺酸及其盐、烯丙基磺酸钠(CAS号:2495-39-8)、甲基烯丙基磺酸钠(1561-92-8)、2-丙烯酰胺-2-甲基丙磺酸、苯乙烯磺酸钠、3-烯丙氧基-2-羟基-1-丙磺酸钠盐(CAS号:52556-42-0)、2-甲基-2-丙烯酸-2-磺乙酯(CAS号:10595-80-9)、甲基丙烯酸3-磺丙酯钾盐(CAS号:31098-21-2)、丙烯酸3-磺丙酯钾盐(CAS号:31098-20-1)等中的一种或多种。
所述不饱和磷酸类单体可以包括乙烯基膦酸(CAS号:1746-03-8)、(1-苯基乙烯基)膦酸(CAS号:3220-5-6)、烯丙基膦酸(CAS号:6833-67-6)、二[2-(甲基丙烯酰基氧基)乙基]磷酸(CAS号:32435-46-4)、2-(甲基丙烯酰氧基)乙基-2-(三甲基氨基)乙基磷酸酯(CAS号:67881-98-5)、2-甲基-2丙烯酸-2-(膦酰基氧基)乙酯(24599-21-1)中的一种或多种,但不限于此。
所述不饱和羧酸类单体可以包括丙烯酸、甲基丙烯酸、2-乙基丙烯酸、α-乙酰氧基丙烯酸、丁烯酸、巴豆酸、马来酸、衣康酸、富马酸等中的一种或多种,但不限于此。
优选地,所述有机酸单体为不饱和磺酸类单体和/或不饱和磷酸类单体。相对于不饱和羧酸类单体,这两种有机酸单体贡献的磷酸基、磺酸基可较易与正极活性材料之间形成氢键、它们与正极活性材料之间的范德华力也更强,进而使所述分散剂对正极活性材料、导电剂等具有更好的分散效果。
本申请一些实施方式中,所述分散剂通过包括N-乙烯基吡咯烷酮、共轭二烯类单体和有机酸类单体的单体原料聚合而成。本申请另一些实施方式中,所述分散剂可以通过所述单体原料依次经聚合、氢化得到。对所述单体原料聚合成的聚合物进行氢化,可以将部分上述结构单元B中的双键还原,增强所述分散剂在高电压下的抗氧化能力。
可选地,所述分散剂的重均分子量为5000-10万。合适的重均分子量的分散剂可以使分散剂具有一定的强度和良好韧性等良好力学性能,便于后续加工利用。可选地,所述分散剂的重均分子量为1万-9万,例如为2万、3万、3.5万、4万、4.5万、5万、5.5万、6万、7万、8万或8.5万。
本申请第一方面提供的所述分散剂,可以以极低的用量就可使正极活性材料和导电剂等在锂离子电池正极浆料中短时间内达到较好的分散效果,并使正极浆料具有较高的固含量,可提升正极片的制备效率和产品良率、柔韧性等,且不会明显降低正极活性材料在正极片中的质量占比。
第二方面,本申请提供了一种锂离子电池用分散剂的制备方法,包括:
将包括N-乙烯基吡咯烷酮、共轭二烯类单体和有机酸类单体的单体原料进行聚合反应。
本申请一些实施方式中,所述制备方法还包括:对所述单体原料经聚合反应形成的聚合物进行氢化反应。换句话说,此时,所述分散剂的制备方法包括:将所述单体原料进行聚合反应得到分散剂前驱体,对所述分散剂前驱体进行氢化反应。通过氢化反应可以将源自共轭二烯类单体的部分或全部结构单元B中的双键还原(优选为全部还原),增强所述分散剂在高电压下的抗氧化能力。
可选地,所述氢化反应可通过Pt作催化剂、氢气作还原剂来进行。
本申请一些实施方式中,所述单体原料包括如下质量分数的各组分:30%-90%的N-乙烯基吡咯烷酮,5%-40%的共轭二烯单体,以及1%-40%的有机酸类单体。采用这样配比的单体原料可以使制得的分散剂具有较好的分散能力。优选地,所述单体原料包括如下质量分数的各组分:45%-80%的N-乙烯基吡咯烷酮,10%-30%的共轭二烯单体,以及10%-30%的有机酸类单体。
上述聚合反应的方法没有特殊限定,例如可采用溶液聚合法、乳液聚合法、悬浮聚合法或本体聚合法等,优选采用溶液聚合法。其中,所述溶液聚合法包括:将上述单体原料与引发剂溶于溶剂中,在一定的温度下进行聚合,将得到的反应液经固液分离、干燥得到。
其中,所述引发剂可以为热引发剂和/或光引发剂;优选为热引发剂。对于热引发剂可以列举过硫酸钾、过硫酸钠、过硫酸铵等水性引发剂中的一种或多种,或者偶氮二异丁腈、偶氮二异庚腈、过氧化苯甲酰等油性引发剂中的一种或多种。此时,聚合反应的温度可以是40-80℃,聚合反应的时间可以是2-24h。水性引发剂或油性引发剂可根据单体原料及所用溶剂进行选择。
可选地,在溶液聚合工艺中,还可以向溶剂中加入链转移剂,以控制所得聚合物的分子链长度。示例性的链转移剂可以列举乙酸乙酯、乙酸丁酯、丙酮、碳酸二乙酯、甲基叔丁基醚、异丙醇、乙醇、甲醇、十二硫醇等。
本申请第二方面提供的分散剂的制备方法,简便易操作,能耗低,反应程度可控,可工业化生产。
本申请第三方面还提供了一种正极浆料,所述正极浆料包括正极活性材料、导电剂、粘结剂、分散剂和溶剂,所述分散剂如本申请第一方面所述,或者通过本申请第二方面所述的制备方法制备得到。
可用于正极浆料的现有分散剂(如PVP)为达到良好分散效果的用量通常在正极活性材料质量的0.5%以上,且通常为0.8%-2%,但这会大大降低正极活性材料在正极浆料中的质量占比。而本申请中所述分散剂的质量不超过所述正极活性材料质量的0.4%。例如,分散剂的质量可以是正极活性材料质量的0.1%-0.3%。
上述正极活性材料、粘结剂和导电剂为电池领域的常规选择。其中,粘结剂可以选自聚偏氟乙烯(PVDF)、聚四氟乙烯(PTFE)、聚乙烯醇(PVA)、丁苯橡胶(SBR)、聚丙烯腈(PAN)、聚酰亚胺(PI)、聚丙烯酸(PAA)、聚丙烯酸酯、聚烯烃、羧甲基纤维素钠(CMC)和海藻酸钠中的一种或多种。其中,所述正极活性材料可以为磷酸铁锂、磷酸锰锂、磷酸锰铁锂、磷酸钒锂、磷酸钴锂、钴酸锂(LiCoO2)、锰酸锂、镍酸锂、镍钴酸锂、镍锰酸锂,以及镍钴锰(NCM)三元材料、镍钴铝(NCA)三元材料中的至少一种。导电剂可以包括碳纳米管、炭黑以及石墨烯中的至少一种,但不限于此。其中,导电剂的表面可以具有功能化基团,如羧基、羟基等,以便在正极浆料中分散。上述分散剂对正极活性材料颗粒和粘结剂颗粒均具有良好的亲和力。
本申请第三方面提供的正极浆料的固含量高,特别是正极活性材料的含量较高,且该正极浆料的分散性好,不易沉降,可放置较长时间。
本申请第四方面还提供了一种正极片,所述正极片包括集流体和设置在所述集流体上的正极材料层,所述正极材料层包括正极活性材料、导电剂、粘结剂和分散剂,其中,所述分散剂如本申请第一方面所述,或者通过本申请第二方面所述的制备方法制备得到。
其中,所述正极材料层可以通过本申请第三方面所述的正极浆料经涂覆、干燥而成。该正极浆料中的固含量高、溶剂量少,可在较短时间内干燥得到正极片,提高正极片的制备效率;由于干燥处理的时间短,正极片不易开裂、良品率高。此外,该正极片还具有良好的柔韧性,便于组装成电池。
本申请第五方面还提供了一种锂离子电池,该锂离子电池包括本申请第四方面所述的正极片。其中,所述锂离子电池还包括负极片,以及位于正极片、负极片之间的隔膜和电解液。这些为电池的常规结构,不再赘述。
由于正极片中的正极活性材料的含量高,该电池可具有较高的比容量。
具体实施方式
以下所述是本申请的示例性实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本申请原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也视为本申请的保护范围。
下面通过具体的实施例对本申请进行进一步的说明。
实施例1
一种锂离子电池用分散剂的制备方法,包括:
将N-乙烯基吡咯烷酮、1,3-丁二烯、乙烯基膦酸按质量比70:20:10溶于N,N-二甲基甲酰胺(DMF)中,加入引发剂-偶氮二异丁腈,链转移剂-十二硫醇,在一定压力下,于60℃聚合4h,冷却以终止反应,将所得反应物经洗涤、干燥后,得到分散剂1’,对其进行氢化处理,得到分散剂1。测得分散剂1的重均分子量约为5万。
一种正极片的制备方法,包括:将2g的粘结剂PVDF溶于40g的NMP(N-甲基吡咯烷酮)中,充分溶解后加入0.3g的上述分散剂1,搅拌20min;再加入20g的碳纳米管分散液(溶剂为NMP,固含量为5%),搅拌20min;最后加入97g的磷酸铁锂正极活性材料,继续搅拌1.5h,得到正极浆料;将该正极浆料涂布于铝箔上,在130℃下烘干30min,形成正极材料层,完成磷酸铁锂正极片的制作。
实施例2
一种锂离子电池用分散剂的制备方法,包括:
将N-乙烯基吡咯烷酮、1,3-戊二烯、二[2-(甲基丙烯酰基氧基)乙基]磷酸按质量比50:20:30溶于二氧六环中,加入引发剂-偶氮二异丁腈,链转移剂-十二硫醇,在一定压力下,于60℃聚合4h,冷却以终止反应,将所得反应物经洗涤、干燥后,得到分散剂3。测得分散剂3的重均分子量为1万。
根据实施例1制备正极片的方式,将0.3g的分散剂2制备成磷酸铁锂正极片。
实施例3
一种锂离子电池用分散剂的制备方法,包括:
将N-乙烯基吡咯烷酮、1,3-己二烯、2-乙基丙烯酸按质量比90:5:5溶于二氧六环中,加入引发剂-偶氮二异丁腈,链转移剂-乙酸乙酯,在一定压力下,于60℃聚合4h,冷却以终止反应,将所得反应物经洗涤、干燥后,得到分散剂3。测得分散剂4的重均分子量约为8.6万。
根据实施例1制备正极片的方式,将0.3g的分散剂3制备成磷酸铁锂正极片。
实施例4
一种锂离子电池用分散剂的制备方法,包括:
将N-乙烯基吡咯烷酮、异戊二烯、乙烯基磺酸按质量比65:30:5溶于DMF中,加入引发剂-偶氮二异丁腈,链转移剂-十二硫醇,在一定压力下,于60℃聚合4h,冷却以终止反应,将所得反应物经洗涤、干燥后,得到分散剂4’,对其进行氢化处理,得到分散剂4。测得分散剂4的重均分子量约为2.2万。
一种正极片的制备方法,包括:将1g的粘结剂PVDF溶于30g的NMP中,充分溶解后加入0.3g的分散剂4,搅拌20min;再加入10g的碳纳米管的NMP分散液(固含量5%)和1.5g的炭黑作导电剂,搅拌20min;最后加入97g的正极活性材料NCM622(LiNi0.6Co0.2Mn0.2O2),继续搅拌1.5h,得到正极浆料;将该正极浆料涂布于铝箔上,在130℃下烘干30min,形成正极材料层,完成NCM三元正极片的制作。
实施例5
一种锂离子电池用分散剂的制备方法,包括:
将N-乙烯基吡咯烷酮、1,3-丁二烯、2-丙烯酰胺-2-甲基丙磺酸按质量比60:30:10溶于DMF中,加入引发剂-偶氮二异丁腈,链转移剂-乙酸乙酯,在一定压力下,于60℃聚合4h,冷却终止反应,洗涤、干燥得到分散剂4。冷却以终止反应,将所得反应物经洗涤、干燥后,得到分散剂5’,对其进行氢化处理,得到分散剂5。测得分散剂5的重均分子量约为4万。
根据实施例4制备正极片的方式,将0.3g的分散剂5制备成NCM三元正极片。
实施例6
一种锂离子电池用分散剂的制备方法,包括:
将N-乙烯基吡咯烷酮、异戊二烯、马来酸按质量比50:35:15溶于二氧六环中,加入引发剂-偶氮二异丁腈,链转移剂-十二硫醇,在一定压力下,于60℃聚合4h,冷却以终止反应,将所得反应物经洗涤、干燥后,得到分散剂6’,对其进行氢化处理,得到分散剂6。测得分散剂6的重均分子量为5.5万。
根据实施例4制备正极片的方式,将0.3g的分散剂6制备成NCM三元正极片。
为突出本申请的有益效果,设置以下对比例1-2。
对比例1
对比例1与实施例1中磷酸铁锂正极片的主要区别在于:在制备磷酸铁锂正极片时,未加入分散剂,但溶剂用量增多。
具体地,对比例1中磷酸铁锂正极片的制备方法包括:将2g的粘结剂PVDF溶于50g的NMP中,充分溶解;再加入20g的碳纳米管的NMP分散液(固含量5%),搅拌20min;最后加入97g的磷酸铁锂正极活性材料,继续搅拌3h,得到正极浆料;将该正极浆料涂布于铝箔上,在130℃下烘干30min,形成正极材料层,完成磷酸铁锂正极片的制作。
对比例2
对比例2与实施例1中磷酸铁锂正极片主要区别在于:在制备磷酸铁锂正极片时,加入1.0g的现有分散剂PVP。
具体地,对比例2中磷酸铁锂正极片制备方法包括:将2g的粘结剂PVDF溶于40g的NMP中,充分溶解后加入1.0g的分散剂PVP,搅拌20min;再加入20g的碳纳米管的NMP分散液(固含量5%),搅拌20min;最后加入97g的磷酸铁锂正极活性材料,继续搅拌1.5h,得到正极浆料;将该正极浆料涂布于铝箔上,在130℃下烘干30min,形成正极材料层,完成磷酸铁锂正极片的制作。
对比例3
对比例2与实施例4中三元正极片的主要区别在于:在制备NCM三元正极片时,未加入分散剂,但溶剂用量增多。
具体地,对比例2中三元正极片的制备方法包括:将1g的粘结剂PVDF溶于40g的NMP中,充分溶解;再加入10g的碳纳米管分散液(5%)和1.5g的炭黑作导电剂,搅拌20min;最后加入97g的正极活性材料NCM622(LiNi0.6Co0.2Mn0.2O2),继续搅拌3h,得到正极浆料;将该正极浆料涂布于铝箔上,在130℃下烘干30min,形成正极材料层,完成NCM三元正极片的制作。
对比例4
对比例4与实施例4中三元正极片主要区别在于:在制备NCM三元正极片时,加入1.0g的分散剂PVP。
具体地,对比例4中NCM正极片制备方法包括:将1g的粘结剂PVDF溶于30g的NMP中,充分溶解后加入1.0g的分散剂PVP,搅拌20min;再加入10g的碳纳米管分散液(5%)和1.5g的炭黑作导电剂,搅拌20min;最后加入97g的正极活性材料NCM622,继续搅拌1.5h,得到正极浆料;将该正极浆料涂布于铝箔上,在130℃下烘干30min,形成正极材料层,完成NCM三元正极片的制作。
为对本申请的有益效果进行有利支持,现将各实施例及对比例中正极浆料的粘度及固含量的结果、正极材料层中正极活性材料含量、正极片柔韧性的观察结果汇总在下表1中。
表1各实施例及对比例的结果汇总
其中,上表1中正极浆料的粘度是通过流变仪,参考型号为Anton Paar公司MCR302。其中,正极片的柔韧性是通过将正极片在相同条件下进行对折后,肉眼观察得到。
由表1可以获知,由实施例1-3与对比例1的对比,以及由实施例4-6与对比例2的对比可以获知,各正极浆料的粘度接近,在正极材料层中正极活性材料的含量几乎不变(或变动极小)的情况下,含少量的本申请实施例提供的分散剂的正极浆料的固含量较高,制得分散效果好的正极浆料的时间也较短。另外,由实施例1-3与对比例2的对比,以及实施例4-6与对比例4的对比可以获知,在正极浆料具有相同的固含量时,PVP的添加量远大于本申请实施例提供的分散剂,这使得对比例的正极材料层中的活性物质占比变少,后续会降低电池的比容量。这些结果表明,本申请提供的分散剂对正极浆料具有较高的分散能力。此外,含有本申请实施例的分散剂的正极片的柔韧性也大于对应的对比例的正极片,经对折后不易断裂、透光,表明本申请实施例的正极片可具有较好的加工性能。
以上所述实施例仅表达了本申请的几种实施方式,其描述较为具体和详细,但并不能因此而理解为对本申请专利范围的限制。应当指出的是,对于本领域的普通技术人员来说,在不脱离本申请构思的前提下,还可以做出若干变形和改进,这些都属于本申请的保护范围。因此,本申请专利的保护范围应以所附权利要求为准。
Claims (12)
1.一种锂离子电池用分散剂,其特征在于,所述分散剂包括源自N-乙烯基吡咯烷酮的结构单元A、源自共轭二烯类单体的结构单元B和源自有机酸类单体的结构单元C;其中,所述有机酸类单体包括不饱和磺酸类单体、不饱和磷酸类单体和不饱和羧酸类单体中的一种或多种。
2.如权利要求1所述的分散剂,其特征在于,所述分散剂中,所述结构单元A的摩尔占比为30%-90%,所述结构单元B的摩尔占比为5%-50%,所述结构单元C的摩尔占比为1%-30%。
3.如权利要求1所述的分散剂,其特征在于,所述不饱和磺酸类单体包括乙烯基磺酸、烯丙基磺酸、甲基烯丙基磺酸、2-丙烯酰胺-2-甲基丙磺酸、苯乙烯磺酸、3-烯丙氧基-2-羟基丙磺酸、2-甲基-2-丙烯酸-2-磺乙酯、丙烯酸3-磺丙酯、甲基丙烯酸3-磺丙酯以及它们的盐中的一种或多种;
所述不饱和磷酸类单体包括乙烯基膦酸、(1-苯基乙烯基)膦酸、烯丙基膦酸、二[2-(甲基丙烯酰基氧基)乙基]磷酸、2-(甲基丙烯酰氧基)乙基-2-(三甲基氨基)乙基磷酸酯、2-甲基-2丙烯酸-2-(膦酰基氧基)乙酯中的一种或多种;
所述不饱和羧酸类单体包括丙烯酸、甲基丙烯酸、2-乙基丙烯酸、α-乙酰氧基丙烯酸、丁烯酸、巴豆酸、马来酸、衣康酸、富马酸中的一种或多种。
4.如权利要求1所述的分散剂,其特征在于,所述共轭二烯类单体包括1,3-丁二烯、异戊二烯、2,3-二甲基-1,3-丁二烯、2-氯-1,3-丁二烯、1,3-戊二烯、1,3-己二烯、1,3-癸二烯、2-甲基-1,5-庚二烯中的一种或多种。
5.如权利要求1-4任一项所述的分散剂,其特征在于,所述分散剂的重均分子量为5000-10万。
6.一种锂离子电池用分散剂的制备方法,其特征在于,包括以下步骤:
将包括N-乙烯基吡咯烷酮、共轭二烯类单体和有机酸类单体的单体原料进行聚合反应;其中,所述有机酸类单体包括不饱和磺酸类单体、不饱和磷酸类单体和不饱和羧酸类单体中的一种或多种。
7.如权利要求6所述的制备方法,其特征在于,所述制备方法还包括:对所述单体原料经聚合反应形成的聚合物进行氢化反应。
8.如权利要求6或7所述的制备方法,其特征在于,所述单体原料包括如下质量分数的各组分:30%-90%的N-乙烯基吡咯烷酮,5%-40%的共轭二烯单体,以及1%-40%的有机酸类单体。
9.一种正极浆料,其特征在于,包括正极活性材料、导电剂、粘结剂、分散剂和溶剂,所述分散剂如权利要求1-5任一项所述,或者通过权利要求6-8任一项所述的制备方法制备得到。
10.如权利要求9所述的正极浆料,其特征在于,所述分散剂的质量不超过所述正极活性材料质量的0.4%。
11.一种正极片,其特征在于,所述正极片包括集流体和设置在所述集流体上的正极材料层,其中,所述正极材料层包括正极活性材料、导电剂、粘结剂和分散剂,所述分散剂如权利要求1-5任一项所述,或者通过权利要求6-8任一项所述的制备方法制备得到。
12.一种锂离子电池,其特征在于,所述锂离子电池包括如权利要求11所述的正极片。
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