CN117487483B - Ionic polymer binder and preparation method and application thereof - Google Patents
Ionic polymer binder and preparation method and application thereof Download PDFInfo
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- CN117487483B CN117487483B CN202311440785.XA CN202311440785A CN117487483B CN 117487483 B CN117487483 B CN 117487483B CN 202311440785 A CN202311440785 A CN 202311440785A CN 117487483 B CN117487483 B CN 117487483B
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- Prior art keywords
- ionic polymer
- polymer binder
- mixing
- solvent
- binder
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- 229920000831 ionic polymer Polymers 0.000 title claims abstract description 92
- 239000002491 polymer binding agent Substances 0.000 title claims abstract description 92
- 238000002360 preparation method Methods 0.000 title claims description 23
- -1 pyridine hexafluorophosphate Chemical compound 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims description 53
- 239000002904 solvent Substances 0.000 claims description 52
- 239000011230 binding agent Substances 0.000 claims description 42
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 32
- 229910001416 lithium ion Inorganic materials 0.000 claims description 32
- 238000006116 polymerization reaction Methods 0.000 claims description 31
- 239000011812 mixed powder Substances 0.000 claims description 30
- 239000011267 electrode slurry Substances 0.000 claims description 26
- 239000000376 reactant Substances 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000011248 coating agent Substances 0.000 claims description 19
- 238000000576 coating method Methods 0.000 claims description 19
- 239000006258 conductive agent Substances 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 238000007069 methylation reaction Methods 0.000 claims description 15
- WJNRCWSLUSRJEM-UHFFFAOYSA-N 2-ethenylpyridine;phosphoric acid Chemical compound OP(O)(O)=O.C=CC1=CC=CC=N1 WJNRCWSLUSRJEM-UHFFFAOYSA-N 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 14
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims description 13
- 239000003112 inhibitor Substances 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 8
- 239000012336 iodinating agent Substances 0.000 claims description 8
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 7
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 7
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 claims description 6
- 150000001450 anions Chemical class 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000007773 negative electrode material Substances 0.000 claims description 6
- 239000006183 anode active material Substances 0.000 claims description 5
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 5
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- VMWGBWNAHAUQIO-UHFFFAOYSA-N 2-ethenyl-6-methylpyridine Chemical compound CC1=CC=CC(C=C)=N1 VMWGBWNAHAUQIO-UHFFFAOYSA-N 0.000 claims description 4
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000004185 ester group Chemical group 0.000 claims description 4
- MKNJJNFVIWDHEM-UHFFFAOYSA-N 1-pyridin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)C1=CC=NC=C1 MKNJJNFVIWDHEM-UHFFFAOYSA-N 0.000 claims description 3
- BRZOWWLQQFFSLC-UHFFFAOYSA-N 3-ethenyl-5-fluoropyridine Chemical compound FC1=CN=CC(C=C)=C1 BRZOWWLQQFFSLC-UHFFFAOYSA-N 0.000 claims description 3
- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 claims description 3
- 239000001230 potassium iodate Substances 0.000 claims description 3
- 235000006666 potassium iodate Nutrition 0.000 claims description 3
- 229940093930 potassium iodate Drugs 0.000 claims description 3
- 235000009518 sodium iodide Nutrition 0.000 claims description 3
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- FGVVTMRZYROCTH-UHFFFAOYSA-N pyridine-2-thiol N-oxide Chemical compound [O-][N+]1=CC=CC=C1S FGVVTMRZYROCTH-UHFFFAOYSA-N 0.000 claims 1
- 229960002026 pyrithione Drugs 0.000 claims 1
- 230000014759 maintenance of location Effects 0.000 abstract description 9
- 239000011149 active material Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 4
- 125000003010 ionic group Chemical group 0.000 abstract description 3
- 229920002717 polyvinylpyridine Polymers 0.000 abstract description 3
- 238000000498 ball milling Methods 0.000 description 34
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 30
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 26
- 229910021383 artificial graphite Inorganic materials 0.000 description 24
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 20
- 238000001035 drying Methods 0.000 description 20
- 229910052744 lithium Inorganic materials 0.000 description 18
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- 238000001291 vacuum drying Methods 0.000 description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 14
- 238000001914 filtration Methods 0.000 description 13
- 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 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 239000002033 PVDF binder Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 229920003048 styrene butadiene rubber Polymers 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 6
- 239000002174 Styrene-butadiene Substances 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000005096 rolling process Methods 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 239000013543 active substance Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000011889 copper foil Substances 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- 239000007774 positive electrode material Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000012982 microporous membrane Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QKHRGPYNTXRMSL-VOTSOKGWSA-N 4-[(e)-2-phenylethenyl]pyridine Chemical compound C=1C=CC=CC=1/C=C/C1=CC=NC=C1 QKHRGPYNTXRMSL-VOTSOKGWSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 238000005349 anion exchange Methods 0.000 description 2
- 239000006256 anode slurry Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000003273 ketjen black Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- YQMUORJJDBQCOV-UHFFFAOYSA-N $l^{1}-phosphanylmethane Chemical compound [P]C YQMUORJJDBQCOV-UHFFFAOYSA-N 0.000 description 1
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 1
- GPKIXZRJUHCCKX-UHFFFAOYSA-N 2-[(5-methyl-2-propan-2-ylphenoxy)methyl]oxirane Chemical compound CC(C)C1=CC=C(C)C=C1OCC1OC1 GPKIXZRJUHCCKX-UHFFFAOYSA-N 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
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- 229910004761 HSV 900 Inorganic materials 0.000 description 1
- 229910004764 HSV900 Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 1
- 241001089723 Metaphycus omega Species 0.000 description 1
- 229910009866 Ti5O12 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 229910007717 ZnSnO Inorganic materials 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
- 230000006978 adaptation Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 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
- 239000000839 emulsion Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000026045 iodination Effects 0.000 description 1
- 238000006192 iodination reaction Methods 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- WKFBZNUBXWCCHG-UHFFFAOYSA-N phosphorus trifluoride Chemical compound FP(F)F WKFBZNUBXWCCHG-UHFFFAOYSA-N 0.000 description 1
- FFUQCRZBKUBHQT-UHFFFAOYSA-N phosphoryl fluoride Chemical compound FP(F)(F)=O FFUQCRZBKUBHQT-UHFFFAOYSA-N 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000007581 slurry coating method Methods 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- BFDWBSRJQZPEEB-UHFFFAOYSA-L sodium fluorophosphate Chemical compound [Na+].[Na+].[O-]P([O-])(F)=O BFDWBSRJQZPEEB-UHFFFAOYSA-L 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- TUTLDIXHQPSHHQ-UHFFFAOYSA-N tin(iv) sulfide Chemical compound [S-2].[S-2].[Sn+4] TUTLDIXHQPSHHQ-UHFFFAOYSA-N 0.000 description 1
- BNEMLSQAJOPTGK-UHFFFAOYSA-N zinc;dioxido(oxo)tin Chemical compound [Zn+2].[O-][Sn]([O-])=O BNEMLSQAJOPTGK-UHFFFAOYSA-N 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
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- 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
- C08F130/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F130/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J143/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Adhesives based on derivatives of such polymers
- C09J143/02—Homopolymers or copolymers of monomers containing phosphorus
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The ionic polymer binder provided by the invention is polyvinyl pyridine hexafluorophosphate containing ionic groups, wherein coulomb force between hexafluorophosphate and active materials can enhance the cohesiveness between materials, so that the electrode structure is more stable; the battery assembled by the ionic polymer binder has the advantages of large specific capacity, good cycle stability and long service life. The results of the examples show that the battery assembled by the ionic polymer binder provided by the invention has 500 cycles of discharge specific capacity of 123.7-128.4 mAh g ‑1 and retention rate of 89.46-90.11% under the condition of cut-off voltage of 2.5-4.2V and multiplying power of 1C.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to an ionic polymer binder, a preparation method and application thereof.
Background
In recent years, lithium ion batteries have the advantages of high energy density, light weight and the like, and are widely applied to the fields of electric automobiles and portable electronic products. The lithium ion battery mainly comprises a positive electrode, a diaphragm and a negative electrode, wherein the bonding strength between a positive electrode material and a negative electrode material and between a conductive agent and a current collector has a non-negligible influence on the cycle stability of the battery. Polyvinylidene fluoride (PVDF) has good chemical resistance and a broad electrochemical window as the most commonly used commercial battery positive electrode binder. However, PVDF can only be combined with an active material by means of van der waals force, and can cause the separation between an electrode and a current collector in a cycle, failing to meet the requirements of a high-performance battery. Coulombic forces between the ionic polymer binder and the active material may enhance the adhesion between the materials. Patent CN111777984a reports that the battery ionic conductivity is improved by sulfonate ion groups, has good binding properties and good conductivity, and improves the cycle capacity of the battery. However, in the cyclic test, the interface contact between the electrodes is poor, so that the internal polarization resistance of the pole piece is increased, the capacity is rapidly attenuated, and the capacity retention rate is low. Therefore, how to improve the adhesive performance of the adhesive and the cycle stability of the battery assembled by using the adhesive are technical problems to be solved in the art.
Disclosure of Invention
The invention aims to provide an ionic polymer binder, and a preparation method and application thereof. The ionic polymer binder provided by the invention has excellent binding performance, and the lithium ion battery assembled by using the binder has the advantages of large specific capacity, good cycle stability and long service life.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides an ionic polymer binder, which has a chemical structure shown in a formula I or a formula II:
In the formula I and the formula II, R 1 is independently hydrogen, alkyl or aralkyl, R 2 is independently alkyl, and R 3 is independently hydrogen, hydroxyl or alkyl;
In the formula I, X is alkoxy, carbonyl or ester group.
Preferably, in the formula I and the formula II, m is independently 20 to 2000.
The invention also provides a preparation method of the ionic polymer binder, which comprises the following steps:
(1) Mixing vinyl pyridine, an iodizing agent, a polymerization inhibitor and a first solvent, and performing methylation reaction to obtain a reactant;
(2) Mixing the reactant obtained in the step (1) with fluorophosphite, and carrying out anion replacement reaction to obtain vinylpyridine phosphate;
(3) And (3) mixing the vinylpyridine phosphate obtained in the step (2), an initiator and a second solvent, and carrying out polymerization reaction to obtain the ionic polymer binder.
Preferably, the vinyl pyridine in the step (1) is at least one of 4-vinyl pyridine, 4-styrene pyridine, 4-vinyl formyl pyridine, ethyl pyridine methacrylate disulfide, 3-fluoro-5-vinyl pyridine and 2-methyl-6-vinyl pyridine.
Preferably, the iodinating agent in the step (1) is at least one of methyl iodide, potassium iodate, sodium iodide and potassium dithioiodide.
Preferably, the polymerization inhibitor in the step (1) is at least one of benzoquinone, tetrachlorobenzoquinone and 1, 4-naphthoquinone.
Preferably, the temperature of the methylation reaction in the step (1) is 10-45 ℃, and the time of the methylation reaction is 1-12 h.
The invention also provides application of the ionic polymer binder in the positive electrode plate and the negative electrode plate of the lithium ion battery or the ionic polymer binder prepared by the preparation method in the technical scheme.
Preferably, the preparation method of the positive plate of the lithium ion battery comprises the following steps:
1) Mixing an ionic polymer binder and a solvent to obtain a binder solution;
2) Mixing an anode active material and a conductive agent to obtain mixed powder;
3) Mixing the binder solution obtained in the step 1), the mixed powder obtained in the step 2) and a solvent to obtain positive electrode slurry;
4) Coating the positive electrode slurry obtained in the step 3) on a current collector to obtain a positive electrode plate of the lithium ion battery;
the step 1) and the step 2) are not in sequence.
Preferably, the preparation method of the lithium ion battery negative electrode plate comprises the following steps:
① Mixing an ionic polymer binder and a solvent to obtain a binder solution;
② Mixing a negative electrode active material and a conductive agent to obtain mixed powder;
③ Mixing the binder solution obtained in the step ①, the mixed powder obtained in the step ② and a solvent to obtain negative electrode slurry;
④ Coating the negative electrode slurry obtained in the step ③ on a current collector to obtain a negative electrode plate of the lithium ion battery;
the steps ① and ② are not sequential.
The invention provides an ionic polymer binder which has a chemical structure shown in a formula I or a formula II. The ionic polymer binder provided by the invention is polyvinyl pyridine hexafluorophosphate containing ionic groups, wherein coulomb force between hexafluorophosphate and active materials can enhance the cohesiveness between materials, so that the electrode structure is more stable; the battery assembled by the ionic polymer binder has the advantages of large specific capacity, good cycle stability and long service life. The results of the examples show that the battery assembled by adopting the ionic polymer binder provided by the invention has 500 cycles of discharge specific capacity of 123.7-128.4 mAh g -1 and retention rate of 89.46-90.11% under the condition of cut-off voltage of 2.5-4.2V and multiplying power of 1C.
Drawings
FIG. 1 is a graph showing the long-cycle charge and discharge performance test of a lithium iron phosphate/lithium metal battery assembled in application example 2 at 25℃and a cut-off voltage of 2.5 to 4.2V and a magnification of 1C;
Fig. 2 is a charge and discharge curve of the lithium iron phosphate/lithium metal battery assembled in application example 2 under the conditions of 25 deg.c, cut-off voltage of 2.5 to 4.2V and multiplying power of 0.5C, 1C, 2C and 3C.
Detailed Description
The invention provides an ionic polymer binder, which has a chemical structure shown in a formula I or a formula II:
In the formula I and the formula II, R 1 is independently hydrogen, alkyl or aralkyl, R 2 is independently alkyl, and R 3 is independently hydrogen, hydroxyl or alkyl;
In the formula I, X is alkoxy, carbonyl or ester group.
In one embodiment of the present invention, the ionic polymer binder has a chemical structure represented by formula I:
In the present invention, in the formula I, R 1 is hydrogen, alkyl or aralkyl, R 2 is alkyl, R 3 is hydrogen, hydroxy or alkyl, and X is alkoxy, carbonyl or ester group, more preferably carbonyl.
In the present invention, in the formula I, m is preferably 20 to 2000.
In another embodiment of the present invention, the ionic polymer binder has a chemical structure represented by formula II:
In the present invention, in the formula II, R 1 is hydrogen, alkyl or aralkyl, preferably phenyl, R 2 is alkyl, preferably methyl, R 3 is hydrogen, hydroxy or alkyl, preferably methyl.
In the present invention, in the formula II, m is preferably 20 to 2000.
The ionic polymer binder provided by the invention is polyvinyl pyridine hexafluorophosphate containing ionic groups, wherein coulomb force between hexafluorophosphate and active materials can enhance the cohesiveness between materials, so that the electrode structure is more stable; the battery assembled by the ionic polymer binder has the advantages of large specific capacity, good cycle stability and long service life, and solves the problems of insufficient cohesiveness and rapid specific capacity decay of the existing binder.
The invention also provides a preparation method of the ionic polymer binder, which comprises the following steps:
(1) Mixing vinyl pyridine, an iodizing agent, a polymerization inhibitor and a first solvent, and performing methylation reaction to obtain a reactant;
(2) Mixing the reactant obtained in the step (1) with fluorophosphite, and carrying out anion replacement reaction to obtain vinylpyridine phosphate;
(3) And (3) mixing the vinylpyridine phosphate obtained in the step (2), an initiator and a second solvent, and carrying out polymerization reaction to obtain the ionic polymer binder.
The sources of the above raw materials are not particularly limited, and commercially available products known to those skilled in the art may be used.
The invention mixes vinyl pyridine, iodizing agent, polymerization inhibitor and first solvent to carry out methylation reaction to obtain reactant.
In the present invention, the vinylpyridine is preferably at least one of 4-vinylpyridine, 4-styrylpyridine, 4-vinylformylpyridine, pyridylmethacrylate disulfide, 3-fluoro-5-vinylpyridine and 2-methyl-6-vinylpyridine. When the vinyl pyridine is two or more of the above, the ratio of the two or more is not particularly limited, and any ratio may be mixed.
In the present invention, the iodinating agent is preferably at least one of methyl iodide, potassium iodate, sodium iodide and potassium dithioiodide. When the iodizing agent is two or more of the above, the present invention is not particularly limited in the ratio between the two or more, and any ratio may be used. In the present invention, the iodinating agent of the above type is selected, whereby the vinyl pyridine can be structurally formed to have an alkyl group by the iodination of the iodinating agent.
In the present invention, the polymerization inhibitor is preferably at least one of benzoquinone, tetrachlorobenzoquinone, and 1, 4-naphthoquinone. When the polymerization inhibitor is two or more of the above, the present invention is not particularly limited in terms of the ratio between the two or more, and any ratio may be used. In the present invention, the polymerization of vinyl pyridine phosphate is prevented by adding the above polymerization inhibitor, and the polymerization monomer is stabilized.
In the present invention, the first solvent is preferably at least one of N-methylpyrrolidone, N-ethylpyrrolidone, N-dimethylformamide, tetrahydrofuran, methylene chloride, toluene, and chloroform. When the first solvent is two or more of the above, the present invention is not particularly limited in terms of the ratio between the two or more, and any ratio may be mixed.
In the present invention, the mass of the polymerization inhibitor is preferably 0.01 to 0.5% by mass of vinylpyridine, more preferably 0.05 to 0.2%. The amount of the solvent is not particularly limited in the present invention, so long as the total mass concentration of the vinylpyridine, the iodinating agent and the fluorophosphite salt is ensured to be within a range of 10% to 35%.
The operation of mixing the vinylpyridine, the iodinating agent, the polymerization inhibitor and the solvent is not particularly limited, and the technical scheme for preparing the mixture is well known to the person skilled in the art.
In the present invention, the temperature of the methylation reaction is preferably 10 to 45 ℃, more preferably 25 to 30 ℃; the time for the methylation reaction is preferably 1 to 12 hours, more preferably 6 to 10 hours. The invention can improve the reaction degree by controlling the temperature and time of methylation reaction.
After the reactant is obtained, the obtained reactant is mixed with fluorophosphite to carry out anion replacement reaction, so that the vinylpyridine phosphate is obtained.
In the present invention, the fluorophosphorus salt is preferably at least one of ammonium hexafluorophosphate, sodium fluorophosphate, phosphorus trifluoride, methylphosphorus and phosphorus oxyfluoride. When the fluorophosphorus salt is two or more of the above, the present invention is not particularly limited in the ratio between the two or more, and any ratio may be used.
In the present invention, the ratio of the amounts of the substances of the vinylpyridine, the iodinating agent and the fluorophosphite salt is preferably (0.1 to 0.3): (0.2-0.4): 1, more preferably (0.23 to 0.25): (0.29 to 0.3): 1.
The operation of mixing the reactant with the fluorophosphoric salt is not particularly limited in the present invention, and the technical scheme for preparing the mixture, which is well known to those skilled in the art, may be adopted.
In the present invention, the temperature of the anion exchange reaction is preferably 10 to 45 ℃, more preferably 25 to 30 ℃; the time for the anion exchange reaction is preferably 1 to 12 hours, more preferably 8 to 10 hours. The invention can improve the reaction degree by controlling the temperature and time of the anion replacement reaction.
After the negative ion replacement reaction is completed, the obtained product is preferably filtered and dried in sequence to obtain the vinylpyridine phosphate.
The filtering operation is not particularly limited in the present invention, and filtering operations well known to those skilled in the art may be employed.
In the present invention, the drying is preferably vacuum drying; the temperature of the vacuum drying is preferably 30-60 ℃, more preferably 50-60 ℃; the time for the vacuum drying is preferably 1 to 24 hours, more preferably 5 to 12 hours.
After the vinylpyridine phosphate is obtained, the vinylpyridine phosphate, an initiator and a second solvent are mixed for polymerization reaction to obtain the ionic polymer binder.
In the present invention, the initiator is preferably at least one of azobisisobutyronitrile, azobicyclohexylcarbonitrile, dimethyl azobisisobutyrate and dibenzoyl peroxide. When the initiator is two or more of the above, the present invention is not particularly limited in the ratio between the two or more, and any ratio may be used.
In the present invention, the second solvent is preferably at least one of water, diethyl ether, acetonitrile, toluene, acetone, N-methylpyrrolidone, N-dimethylformamide, tetrahydrofuran, dichloromethane, and chloroform. When the second solvent is two or more of the above, the present invention is not particularly limited in terms of the ratio between the two or more, and any ratio may be used.
In the present invention, the kind of the initiator is preferably 0.1% to 1% by mass, more preferably 0.3% to 0.5% by mass of the vinylpyridine phosphate. The amount of the solvent used in the present invention is not particularly limited as long as the total mass concentration of the vinylpyridine phosphate is maintained within the range of 10% to 40%.
The operation of mixing the vinylpyridine phosphate, the initiator and the solvent is not particularly limited, and the technical scheme for preparing the mixture, which is well known to the person skilled in the art, can be adopted.
In the present invention, the temperature of the polymerization reaction is preferably 45 to 80 ℃, more preferably 50 to 70 ℃; the polymerization time is preferably 6 to 24 hours, more preferably 7 to 12 hours. The invention can further improve the reaction degree by controlling the technological parameters of the polymerization reaction.
In the present invention, the polymerization reaction is preferably carried out under an inert atmosphere; the gas of the inert atmosphere is preferably nitrogen or argon. In the present invention, the inert atmosphere can avoid the interference of air with the polymerization reaction.
After the polymerization reaction is completed, the product obtained by the polymerization reaction is preferably mixed with a precipitant, and then filtered and dried in sequence to obtain the ionic polymer binder.
In the present invention, the precipitant is preferably at least one of diethyl ether, petroleum ether, n-hexane and methanol. When the precipitating agent is two or more of the above, the invention is not particularly limited in the ratio between the two or more, and any ratio may be used. The invention adopts a precipitant for separating the ionic polymer binder from the reaction liquid.
The amount of the precipitant is not particularly limited, and the precipitant can be adjusted according to conventional operation to sufficiently precipitate the product obtained by the polymerization reaction.
The operation of the filtration is not particularly limited in the present invention, and may be an operation well known to those skilled in the art.
In the present invention, drying is preferably vacuum drying; the temperature of the vacuum drying is preferably 30-60 ℃; the time of the vacuum drying is preferably 1 to 24 hours.
On one hand, the ionic polymer binder synthesized by the invention has stronger coulomb force between hexafluorophosphate radical and active material, thus having excellent cohesiveness; on the other hand, the ionic polymer binder can be used for the positive electrode and the negative electrode of a lithium ion battery; in addition, the battery assembled by the ionic polymer binder has the advantages of large specific capacity, good cycle stability and long service life.
The invention also provides the application of the ionic polymer binder in the technical scheme or the ionic polymer binder prepared by the preparation method in the technical scheme in the positive electrode plate of the lithium ion battery and the negative electrode plate of the lithium ion battery.
In the invention, the preparation method of the positive plate of the lithium ion battery preferably comprises the following steps:
1) Mixing an ionic polymer binder and a solvent to obtain a binder solution;
2) Mixing an anode active material and a conductive agent to obtain mixed powder;
3) Mixing the binder solution obtained in the step 1), the mixed powder obtained in the step 2) and a solvent to obtain positive electrode slurry;
4) Coating the positive electrode slurry obtained in the step 3) on a current collector to obtain a positive electrode plate of the lithium ion battery;
the step 1) and the step 2) are not in sequence.
The present invention preferably mixes the ionic polymer binder with a solvent to obtain a binder solution.
In the present invention, the solvent is preferably at least one of N-methylpyrrolidone, tetrahydrofuran and acetonitrile. When the solvent is two or more of the above, the present invention is not particularly limited in terms of the ratio between the two or more, and any ratio may be mixed.
The amount of the solvent used in the present invention is not particularly limited as long as the viscosity of the binder solution is ensured to be in the range of 0.2 to 20pa·s.
In the present invention, the temperature at which the ionic polymer binder and the solvent are mixed is preferably room temperature; the time for mixing the ionic polymer binder and the solvent is preferably 1 to 12 hours.
In the present invention, the viscosity of the binder solution is preferably 0.2 to 20pa·s.
In the present invention, the positive electrode active material and the conductive agent are preferably mixed to obtain a mixed powder.
In the present invention, the positive electrode active material is preferably one of lithium iron phosphate (LiFePO 4), lithium cobalt oxide (LiCoO 2), lithium manganate (LiMn 2O4), nickel cobalt manganese (LiNi 0.8Co0.1Mn0.1O2), and lithium titanate (Li 4Ti5O12); the conductive agent is preferably at least one of superconducting carbon, carbon nanotubes, acetylene black and ketjen black. When the conductive agent is two or more of the above, the invention is not particularly limited in the ratio between the two or more, and any ratio may be mixed.
In the present invention, the mass ratio of the positive electrode active material, the conductive agent and the ionic polymer binder is preferably (60 to 98%): (1-20%): (1-20%), more preferably (70-90%): (5-15%): (5-15%).
In the present invention, the mixing of the positive electrode active material and the conductive agent is preferably ball-milling mixing; the ball-milling mixing is preferably carried out in a ball mill; the rotation speed of the ball milling and mixing is preferably 600-1200 rpm; the time of the ball-milling mixing is preferably 1 to 4 hours, more preferably 2 to 3 hours. The type of the ball mill is not particularly limited, and the ball mill can be manufactured by instruments and equipment well known to those skilled in the art. The ball milling mixing is adopted in the invention, so that the raw materials can be mixed more uniformly.
After the binder solution and the mixed powder are obtained, the binder solution, the mixed powder and the solvent are preferably mixed to obtain the positive electrode slurry.
In the present invention, the solvent is preferably at least one of N-methylpyrrolidone, tetrahydrofuran and acetonitrile. When the solvent is two or more of the above, the present invention is not particularly limited in terms of the ratio between the two or more, and any ratio may be mixed.
The amount of the solvent used in the present invention is not particularly limited as long as the viscosity of the positive electrode slurry is ensured to be 0.2 to 30pa·s.
In the present invention, the binder solution, the mixed powder and the solvent are preferably mixed by first ball-milling the binder solution and the mixed powder, and then adding the solvent for secondary ball-milling.
In the invention, the rotating speed of the primary ball milling and mixing is preferably 600-1200 rpm; the time of the primary ball milling is preferably 1 to 10 hours, more preferably 5 to 8 hours.
In the invention, the rotation speed of the secondary ball milling mixing is preferably 600-1200 rpm; the time of the secondary ball milling mixing is preferably 1 to 4 hours, more preferably 2 to 3 hours.
After the positive electrode slurry is obtained, the positive electrode slurry is coated on a current collector to obtain the positive electrode plate of the lithium ion battery.
In the present invention, the current collector is preferably aluminum foil. The size of the aluminum foil is not particularly limited, and the aluminum foil can be adjusted according to actual needs.
In the present invention, the coating is preferably performed using a blade coater. The type of the blade coater is not particularly limited, and the blade coater may be any type of blade coater known to those skilled in the art.
In the present invention, the thickness of the coating is preferably 60 to 500 μm.
After the coating is finished, the product obtained by the coating is dried, rolled and cut into pieces in sequence to obtain the positive plate of the lithium ion battery.
In the present invention, the drying preferably includes normal pressure drying and vacuum drying which are sequentially performed; the temperature of the normal pressure drying is preferably 40-60 ℃; the time of normal pressure drying is preferably 6-24 hours; the temperature of the vacuum drying is preferably 80 ℃; the time of the vacuum drying is preferably 6 to 24 hours.
The operation of the rolling and cutting is not particularly limited in the present invention, and may be an operation well known to those skilled in the art.
In the invention, the preparation method of the lithium ion battery negative electrode plate preferably comprises the following steps:
① Mixing an ionic polymer binder and a solvent to obtain a binder solution;
② Mixing a negative electrode active material and a conductive agent to obtain mixed powder;
③ Mixing the binder solution obtained in the step ①, the mixed powder obtained in the step ② and a solvent to obtain negative electrode slurry;
④ Coating the negative electrode slurry obtained in the step ③ on a current collector to obtain a negative electrode plate of the lithium ion battery;
the steps ① and ② are not sequential.
The present invention preferably mixes the ionic polymer binder with a solvent to obtain a binder solution.
In the present invention, the solvent is preferably at least one of N-methylpyrrolidone, tetrahydrofuran and acetonitrile. When the solvent is two or more of the above, the present invention is not particularly limited in terms of the ratio between the two or more, and any ratio may be mixed.
The amount of the solvent used in the present invention is not particularly limited as long as the viscosity of the binder solution is ensured to be in the range of 0.2 to 20pa·s.
In the present invention, the temperature at which the ionic polymer binder and the solvent are mixed is preferably room temperature; the time for mixing the ionic polymer binder and the solvent is preferably 1 to 12 hours.
In the present invention, the viscosity of the binder solution is preferably 0.2 to 20pa·s.
In the present invention, the negative electrode active material and the conductive agent are preferably mixed to obtain a mixed powder.
In the present invention, the negative electrode active material is preferably one of artificial graphite, silicon carbide (SiC), zinc stannate (ZnSnO 3), tricobalt tetraoxide (Co 3O4), and tin disulfide (SnS 2); the conductive agent is preferably at least one of superconducting carbon, carbon nanotubes, acetylene black and ketjen black. When the conductive agent is two or more of the above, the invention is not particularly limited in the ratio between the two or more, and any ratio may be mixed.
In the present invention, the mass ratio of the anode active material, the conductive agent and the ionic polymer binder is preferably (60 to 98%): (1-20%): (1-20%), more preferably (70-90%): (5-15%): (5-15%).
In the present invention, the mixing of the anode active material and the conductive agent is preferably ball-milling mixing; the ball-milling mixing is preferably carried out in a ball mill; the rotation speed of the ball milling and mixing is preferably 600-1200 rpm; the time of the ball-milling mixing is preferably 1 to 4 hours, more preferably 2 to 3 hours. The type of the ball mill is not particularly limited, and the ball mill can be manufactured by instruments and equipment well known to those skilled in the art. The ball milling mixing is adopted in the invention, so that the raw materials can be mixed more uniformly.
After the binder solution and the mixed powder are obtained, the binder solution, the mixed powder and the solvent are preferably mixed to obtain the negative electrode slurry.
In the present invention, the solvent is preferably at least one of N-methylpyrrolidone, tetrahydrofuran and acetonitrile. When the solvent is two or more of the above, the present invention is not particularly limited in terms of the ratio between the two or more, and any ratio may be mixed.
The amount of the solvent used in the present invention is not particularly limited as long as the viscosity of the negative electrode slurry is ensured to be 0.2 to 30pa·s.
In the present invention, the binder solution, the mixed powder and the solvent are preferably mixed by first ball-milling the binder solution and the mixed powder, and then adding the solvent for secondary ball-milling.
In the invention, the rotating speed of the primary ball milling and mixing is preferably 600-1200 rpm; the time of the primary ball milling is preferably 1 to 10 hours, more preferably 5 to 8 hours.
In the invention, the rotation speed of the secondary ball milling mixing is preferably 600-1200 rpm; the time of the secondary ball milling mixing is preferably 1 to 4 hours, more preferably 2 to 3 hours.
After the negative electrode slurry is obtained, the negative electrode slurry is coated on a current collector to obtain the negative electrode plate of the lithium ion battery.
In the present invention, the current collector is preferably copper foil. The invention has no special limitation on the size of the copper foil, and the copper foil can be adjusted according to actual needs.
In the present invention, the coating is preferably performed using a blade coater. The type of the blade coater is not particularly limited, and the blade coater may be any type of blade coater known to those skilled in the art.
In the present invention, the thickness of the coating is preferably 60 to 500 μm.
After the coating is finished, the product obtained by the coating is dried, rolled and cut into pieces in sequence to obtain the positive plate of the lithium ion battery.
In the present invention, the drying preferably includes normal pressure drying and vacuum drying which are sequentially performed; the temperature of the normal pressure drying is preferably 40-60 ℃; the time of normal pressure drying is preferably 6-24 hours; the temperature of the vacuum drying is preferably 80 ℃; the time of the vacuum drying is preferably 6 to 24 hours.
The operation of the rolling and cutting is not particularly limited in the present invention, and may be an operation well known to those skilled in the art.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The ionic polymer binder has the following chemical structure:
the preparation method of the ionic polymer binder comprises the following steps:
(1) 200g of 4-vinylpyridine, 332g of methyl iodide and 0.30g of benzoquinone are dissolved in 4000g of methylene dichloride, and the mixture is stirred for 6 hours at 25 ℃ to carry out methylation reaction to obtain a reactant;
(2) 1297g of ammonium hexafluorophosphate is added into the reactant obtained in the step (1), the mixture is stirred for 8 hours at 25 ℃ for negative ion replacement reaction, white solid is obtained after filtration, and then the white solid is dried for 12 hours at 60 ℃ in vacuum to obtain 498g of 4-vinyl-N-picoline quaternary ammonium hexafluorophosphate;
(3) 200g of 4-vinyl-N-methylpyridine quaternary ammonium hexafluorophosphate obtained in the step (2), 1.0g of azobisisobutyronitrile and 1800g N-methylpyrrolidone are mixed in a reaction kettle, the temperature is raised to 70 ℃ for polymerization reaction for 7 hours, then the reactants are precipitated into 4000g of diethyl ether, the filtration is carried out, and the precipitate is dried in vacuum at 40 ℃ for 12 hours to obtain 163g of ionic polymer binder which is marked as A1.
Example 2
The ionic polymer binder has the following chemical structure:
the preparation method of the ionic polymer binder comprises the following steps:
(1) And (2) the same as in example 1;
(3) Mixing 317g of 4-vinyl-N-methylpyridine quaternary ammonium hexafluorophosphate obtained in the step (2), 1.0g of azodiisobutyronitrile and 1800g N-methylpyrrolidone in a reaction kettle, heating to 70 ℃ for polymerization reaction for 7h, precipitating the reactants into 4000g of diethyl ether, filtering, and vacuum-drying the precipitate at 40 ℃ for 12h to obtain 268g of ionic polymer binder which is marked as A2.
Example 3
The ionic polymer binder has the following chemical structure:
the preparation method of the ionic polymer binder comprises the following steps:
(1) And (2) the same as in example 1;
(3) 450g of 4-vinyl-N-methylpyridine quaternary ammonium hexafluorophosphate obtained in the step (2), 1.0g of azodiisobutyronitrile and 1800g N-methylpyrrolidone are mixed in a reaction kettle, the temperature is raised to 70 ℃ for polymerization reaction for 7 hours, then the reactants are precipitated into 4000g of diethyl ether, filtration is carried out, and the precipitate is dried in vacuum at 40 ℃ for 12 hours to obtain 368g of ionic polymer binder which is marked as A3.
Example 4
The ionic polymer binder has the following chemical structure:
the preparation method of the ionic polymer binder comprises the following steps:
(1) 230g of 4-styrylpyridine, 221g of methyl iodide and 0.30g of benzoquinone are dissolved in 4000g of methylene dichloride, and the mixture is stirred for 6 hours at 25 ℃ to carry out methylation reaction to obtain a reactant;
(2) Adding 863g of ammonium hexafluorophosphate into the reactant obtained in the step (1), stirring at 25 ℃ for 8 hours to carry out negative ion replacement reaction, filtering to obtain a white solid, and then drying the white solid at 60 ℃ in vacuum for 12 hours to obtain 425g of 4-styryl-N-methylpyridine quaternary ammonium hexafluorophosphate;
(3) Mixing 317g of 4-styryl-N-methylpyridine quaternary ammonium hexafluorophosphate obtained in the step (2), 1.0g of azobisisobutyronitrile and 1800g of N-methylpyrrolidone in a reaction kettle, heating to 70 ℃ for polymerization reaction for 7h, precipitating the reactants into 4000g of diethyl ether, filtering, and vacuum-drying the precipitate at 40 ℃ for 12h to obtain 261g of ionic polymer binder which is marked as A4.
Example 5
The ionic polymer binder has the following chemical structure:
the preparation method of the ionic polymer binder comprises the following steps:
(1) 152g of 2-methyl-6-vinylpyridine, 221g of methyl iodide and 0.30g of benzoquinone are dissolved in 4000g of methylene dichloride, and the mixture is stirred for 6 hours at 25 ℃ to carry out methylation reaction to obtain a reactant;
(2) Adding 863g of ammonium hexafluorophosphate into the reactant obtained in the step (1), stirring at 25 ℃ for 8 hours to carry out anion replacement reaction, filtering to obtain a white solid, and then drying the white solid at 60 ℃ in vacuum for 12 hours to obtain 347g of 2-methyl-6-vinyl-N-methylpyridine quaternary ammonium hexafluorophosphate;
(3) Mixing 317g of 2-methyl-6-vinyl-N-methylpyridine quaternary ammonium hexafluorophosphate obtained in the step (2), 1.0g of azobisisobutyronitrile and 1800g of N-methylpyrrolidone in a reaction kettle, heating to 70 ℃ for polymerization reaction for 7h, precipitating the reactants into 4000g of diethyl ether, filtering, and vacuum-drying the precipitate at 40 ℃ for 12h to obtain 277g of ionic polymer binder which is marked as A5.
Example 6
The ionic polymer binder has the following chemical structure:
the preparation method of the ionic polymer binder comprises the following steps:
(1) 254g of 4-vinylformylpyridine, 332g of methyl iodide and 0.30g of benzoquinone are dissolved in 4000g of methylene dichloride, and the mixture is stirred for 6 hours at 25 ℃ to carry out methylation reaction to obtain a reactant;
(2) 1297g of ammonium hexafluorophosphate is added into the reactant obtained in the step (1), the mixture is stirred for 8 hours at 25 ℃ for negative ion replacement reaction, white solid is obtained after filtration, and then the white solid is dried for 12 hours at 60 ℃ in vacuum to obtain 498g of 4-vinylformyl-N-picoline quaternary ammonium hexafluorophosphate;
(3) 317g of 4-vinylformyl-N-methylpyridine quaternary ammonium hexafluorophosphate obtained in the step (2), 1.0g of azobisisobutyronitrile and 1800g of N-methylpyrrolidone are mixed in a reaction kettle, the temperature is raised to 70 ℃ for polymerization reaction for 7h, then the reactants are precipitated into 4000g of diethyl ether, filtration is carried out, and the precipitate is dried in vacuum at 40 ℃ for 12h to obtain 263g of ionic polymer binder which is marked as A6.
Comparative example 1
400G of PVDF (HSV 900) and 3600g of N-methylpyrrolidone are mixed in a reaction vessel and stirred for 12h at 25℃to give a binder solution, designated B1.
Comparative example 2
100G of sodium carboxymethylcellulose powder (Shenzhengke crystal, MAC500 LC), 428g of styrene-butadiene rubber emulsion (Shenzhengke crystal, S2919, mass fraction of polymer is 35%) and 197g of purified water (resistivity greater than 0.1 M.OMEGA.cm) were mixed in a reaction kettle, and stirred at 25℃for 12 hours to obtain a binder solution, denoted as B2.
Application examples 1 to 6
The preparation method of the lithium ion battery positive electrode plate by using the ionic polymer binder prepared in the examples 1-6 comprises the following specific steps:
1) Adding 10g of an ionic polymer binder and 90g of N-methylpyrrolidone into a container, and standing at room temperature for 3 hours until the ionic polymer binder and the 90g of N-methylpyrrolidone are dissolved to obtain a binder solution;
2) Ball milling 80g of lithium iron phosphate and 10g of superconducting carbon black for 2 hours at 1008rpm to obtain mixed powder;
3) Adding 100g of the binder solution obtained in the step 1) into the mixed powder obtained in the step 2), ball-milling for 4 hours at 1008rpm, adding 100g of N-methylpyrrolidone, and ball-milling for 4 hours to obtain anode slurry;
4) Coating the positive electrode slurry obtained in the step 3) on aluminum foil by a knife coater, drying at 60 ℃ and normal pressure for 12 hours, then drying at 80 ℃ and vacuum for 12 hours, and then sequentially rolling and cutting to obtain lithium iron phosphate positive electrode plates C1-C6 (the positive electrode plate prepared by using the ionic polymer binder of the embodiment 1 is C1, and the following steps are repeated).
Application examples 7 to 12
The preparation method of the lithium ion battery negative electrode plate by using the ionic polymer binder prepared in the examples 1-6 comprises the following specific steps:
1) Adding 10g of an ionic polymer binder and 90g of N-methylpyrrolidone into a container, and standing at room temperature for 3 hours until the ionic polymer binder and the 90g of N-methylpyrrolidone are dissolved to obtain a binder solution;
2) Ball milling 80g of artificial graphite and 10g of superconducting carbon black for 2 hours at 1008rpm to obtain mixed powder;
3) Adding 100g of the binder solution obtained in the step 1) into the mixed powder obtained in the step 2), ball-milling for 4 hours at 1008rpm, adding 100g of N-methylpyrrolidone, and ball-milling for 4 hours to obtain negative electrode slurry;
4) Coating the negative electrode slurry obtained in the step 3) on a copper foil by a knife coater, drying at 60 ℃ and normal pressure for 12 hours, then drying at 80 ℃ and vacuum for 12 hours, and sequentially rolling and cutting to obtain lithium iron phosphate negative electrode plates C7-C12 (the negative electrode plate prepared by using the ionic polymer binder of the embodiment 1 is C7, and the following steps are analogized).
Comparative application example 1
The positive electrode plate of the lithium ion battery is prepared by using the adhesive prepared in the comparative example 1, and the specific steps are as follows:
1) Ball milling 80g of lithium iron phosphate and 10g of superconducting carbon black for 2 hours at 1008rpm to obtain mixed powder;
2) Adding 100g of the binder prepared in the comparative example 1 into the mixed powder obtained in the step 1), ball-milling for 4 hours at 1008rpm, adding 100g of N-methylpyrrolidone, and ball-milling for 4 hours to obtain anode slurry;
3) Coating the positive electrode slurry obtained in the step 2) on aluminum foil by using a knife coater, firstly drying at 60 ℃ and normal pressure for 12 hours, then drying at 80 ℃ and vacuum for 12 hours, and then sequentially rolling and cutting to obtain the lithium iron phosphate positive electrode plate which is marked as C13.
Comparative application example 2
The preparation method of the negative electrode plate of the lithium ion battery by using the SBR/CMC binder prepared in comparative example 2 comprises the following specific steps:
1) Ball milling 80g of artificial graphite and 10g of superconducting carbon black for 2 hours at 1008rpm to obtain mixed powder;
2) Adding 200g of SBR/CMC binder into the mixed powder obtained in the step 1), ball-milling for 4 hours at 1008rpm, adding 150g of water, and ball-milling for 4 hours to obtain negative electrode slurry;
3) Coating the negative electrode slurry obtained in the step 2) on a copper foil by using a knife coater, firstly drying at 60 ℃ and normal pressure for 12 hours, then drying at 80 ℃ and vacuum for 12 hours, and then sequentially rolling and cutting to obtain the artificial graphite negative electrode plate which is marked as C14.
Characterization of ionic Polymer Binders
The viscosity average molecular weight M η of the ionic polymer binder is measured according to GB/T10247-2008 test method; the thermal decomposition temperature of the ionic polymer binder was determined by thermogravimetric analysis (German relaxation resistance, TG 209) and was increased from 25℃to 600℃under a nitrogen atmosphere at a rate of 10℃min -1. The specific results are shown in Table 1.
TABLE 1 Performance index of ionic Polymer binders
As can be seen from table 1, the molecular weight of the ionic polymer binder is in the range of 3 x 10 4～8×104 Da, which is far lower than that of commercial PVDF, such as PVDF HSV900 (molecular weight 6.0 x 10 5 Da), so that slurries prepared with the ionic polymer binder of the invention can be expected to have lower viscosity and be easier to coat under the same conditions; the thermal decomposition of the ionic polymer binder is higher than that of PVDF (316 ℃), so that the ionic polymer binder has good heat resistance and can meet the requirement of the battery for running at high temperature.
Characterization of battery pole piece and cycle performance
The method for assembling the battery by adopting the C1-C6 and C13 lithium iron phosphate pole pieces comprises the following steps:
Lithium hexafluorophosphate is dissolved in a solution formed by ethylene carbonate, dimethyl carbonate and diethyl carbonate to be used as an electrolyte, a polypropylene microporous membrane (Celgard 2325) is used as a diaphragm, and lithium metal is used as a counter electrode to assemble a lithium ion battery; wherein, the lithium iron phosphate pole piece is the battery anode, and lithium metal is the battery cathode.
Fig. 1 is a long-cycle charge and discharge performance test curve of a lithium iron phosphate/lithium metal battery assembled in application example 2 under the conditions of 25 ℃ and cut-off voltages of 2.5 to 4.2V and 1C.
The specific capacity of the battery refers to the initial discharge specific capacity and 500-cycle discharge specific capacity of the assembled lithium iron phosphate/metal lithium battery under the current density of 1C, the battery cycle tester (Wuhan blue electricity, CT 3002A) of the tester is 2.5-4.2V in terms of voltage, the testing temperature is 25 ℃, the multiplying power is 1C, and the standard specific capacity of an active substance is 170mAh/g. The results of testing the surface density, peel strength, initial specific discharge capacity of the battery, specific discharge capacity at 500 th turn and retention (ratio of specific discharge capacity to initial specific discharge capacity) of the obtained lithium iron phosphate sheet are shown in table 2; the peel strength between the current collector and the surface dry coating of the current collector in the pole piece is measured according to the GB/T2791-1995 test method, and the surface density of the pole piece active substance is calculated as the mass of lithium iron phosphate in unit area.
TABLE 2 Performance index of lithium iron phosphate/lithium Metal batteries
As can be seen from fig. 1 and table 2, under the condition of similar surface density of lithium iron phosphate, the lithium iron phosphate pole pieces C1 to C6 prepared by adopting the ionic polymer binder of the present invention have higher peel strength; compared with the lithium iron phosphate/metal lithium battery assembled by the pole piece C13 adopting the PVDF binder, the lithium iron phosphate/metal lithium battery assembled by the lithium iron phosphate pole pieces C1-C6 prepared by using the ionic polymer binder has higher initial discharge specific capacity and higher discharge specific capacity and capacity retention rate after 500 cycles of circulation under the current density of 1C.
Fig. 2 is a charge and discharge curve of the lithium iron phosphate/lithium metal battery assembled in application example 2 under the conditions of 25 deg.c, cut-off voltage of 2.5 to 4.2V and multiplying power of 0.5C, 1C, 2C and 3C.
As can be seen from fig. 2, the lithium iron phosphate/lithium metal battery can exhibit a higher specific discharge capacity at each current density. Even at high current densities of 3C, the desired specific capacity is still exhibited. When the current density returns again to 0.5C, the specific capacity also smoothly returns to the value just started.
The method for assembling the battery by adopting the C7-C12 and C14 artificial graphite pole pieces comprises the following steps:
Lithium hexafluorophosphate is dissolved in a solution formed by ethylene carbonate, dimethyl carbonate and diethyl carbonate to be used as an electrolyte, a polypropylene microporous membrane (Celgard 2325) is used as a diaphragm, and lithium metal is used as a counter electrode to assemble a lithium ion battery; wherein the artificial graphite pole piece is a battery anode, and the lithium metal is a battery cathode.
The specific capacity of the battery refers to the initial discharge specific capacity and 500-cycle discharge specific capacity of the assembled artificial graphite/metal lithium battery under the current density of 1C, the battery cycle tester (Wuhan blue electricity, CT 3002A) of the testing instrument is 0.005-1.5V in voltage, the testing temperature is 25 ℃, the multiplying power is 1C, and the standard specific capacity of the active substance is 374mAh/g. The results of testing the surface density, peel strength, initial specific discharge capacity of the battery, specific discharge capacity at 500 th turn and retention (ratio of specific discharge capacity to specific initial discharge capacity) of the obtained artificial graphite electrode sheet are shown in table 3; wherein the surface density of the pole piece active substance is the mass of the artificial graphite on the unit area, which is obtained by calculation; the peel strength between the dried slurry coating on the current collector surface in the pole piece and the current collector was determined according to the GB/T2791-1995 test method.
TABLE 3 Performance index of artificial graphite/metallic lithium batteries
As can be seen from table 3, under similar areal density conditions, the peel strength of the artificial graphite pole pieces C7 to C12 prepared with the ionic polymer binder of the present invention was higher than that of the artificial graphite pole piece C14 prepared with the CMC/SBR binder; compared with the artificial graphite/metal lithium battery assembled by the pole piece C14 using the CMC/SBR binder, the artificial graphite/metal lithium battery assembled by the artificial graphite pole pieces C7-C12 prepared by using the ionic polymer binder has similar initial discharge specific capacity, and after 500 circles of circulation under the current density of 1C, the artificial graphite pole piece prepared by using the ionic polymer binder has higher or similar discharge specific capacity and capacity retention rate, so that the long-cycle performance is better.
Full cell parameters
The method for assembling the lithium iron phosphate/artificial graphite battery by taking the prepared C2 or C13 as a lithium iron phosphate positive electrode plate and taking the prepared C9 or C14 as an artificial graphite negative electrode plate comprises the following steps:
lithium hexafluorophosphate is dissolved in a solution formed by ethylene carbonate, dimethyl carbonate and diethyl carbonate to be used as an electrolyte, and a polypropylene microporous membrane (Celgard 2325) is used as a diaphragm to obtain the lithium iron phosphate/artificial graphite battery.
And (3) carrying out battery cycle test on the assembled lithium iron phosphate/artificial graphite battery No. 1-4 in a battery cycle tester (Wuhan blue electricity, CT 3002A), wherein the cut-off voltage is 2.5-4.2V, the test temperature is 25 ℃, the multiplying power is 1C, and the standard specific capacity of an active substance is 170mAh/g. The results of the test to obtain the initial specific capacity of the battery cycle, the specific capacity of the 1000 th turn discharge and the capacity retention (the ratio of the specific capacity of discharge to the specific capacity of initial discharge) are shown in table 4.
TABLE 4 Performance index of lithium iron phosphate/artificial graphite batteries
As can be seen from table 4, the full battery assembled by the lithium iron phosphate positive electrode sheet C2 and the artificial graphite negative electrode sheet C9 prepared by the ionic polymer binder of the present invention, and the full battery assembled by the lithium iron phosphate positive electrode sheet C13 prepared by the artificial graphite negative electrode sheet C14 and the PVDF binder prepared by the SBR/CMC binder, respectively, has a higher or similar specific discharge capacity and a long cycle capacity retention rate of the battery after 1000 cycles at a current density of 1C, and in particular, the D1 full battery performance is optimal, compared with the full battery assembled by the lithium iron phosphate positive electrode sheet C13 prepared by the PVDF binder and the artificial graphite negative electrode sheet C14 prepared by the SBR/CMC binder.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. An ionic polymeric binder having a chemical structure of formula I or formula II:
In the formula I and the formula II, R 1 is independently hydrogen, alkyl or aralkyl, R 2 is independently alkyl, and R 3 is independently hydrogen, hydroxyl or alkyl;
In the formula I, X is alkoxy, carbonyl or ester group.
2. The ionic polymer binder of claim 1, wherein m is independently 20 to 2000 in formula i and formula II.
3. A method of preparing the ionic polymer binder of claim 1 or 2, comprising the steps of:
(1) Mixing vinyl pyridine, an iodizing agent, a polymerization inhibitor and a first solvent, and performing methylation reaction to obtain a reactant;
(2) Mixing the reactant obtained in the step (1) with fluorophosphite, and carrying out anion replacement reaction to obtain vinylpyridine phosphate;
(3) And (3) mixing the vinylpyridine phosphate obtained in the step (2), an initiator and a second solvent, and carrying out polymerization reaction to obtain the ionic polymer binder.
4. The method according to claim 3, wherein the vinyl pyridine in the step (1) is at least one of 4-vinyl pyridine, 4-styrene pyridine, 4-vinylformyl pyridine, ethyl pyrithione methacrylate, 3-fluoro-5-vinyl pyridine and 2-methyl-6-vinyl pyridine.
5. The method according to claim 3, wherein the iodinating agent in the step (1) is at least one of methyl iodide, potassium iodate, sodium iodide and potassium dithioiodide.
6. The method according to claim 3, wherein the polymerization inhibitor in the step (1) is at least one of benzoquinone, tetrachlorobenzoquinone and 1, 4-naphthoquinone.
7. The process according to claim 3, wherein the temperature of the methylation reaction in the step (1) is 10 to 45℃and the time of the methylation reaction is 1 to 12 hours.
8. Use of the ionic polymer binder according to any one of claims 1-2 or the ionic polymer binder prepared by the preparation method according to any one of claims 3-7 in positive electrode plates of lithium ion batteries and negative electrode plates of lithium ion batteries.
9. The use according to claim 8, wherein the method for preparing the positive electrode sheet of the lithium ion battery comprises the following steps:
1) Mixing an ionic polymer binder and a solvent to obtain a binder solution;
2) Mixing an anode active material and a conductive agent to obtain mixed powder;
3) Mixing the binder solution obtained in the step 1), the mixed powder obtained in the step 2) and a solvent to obtain positive electrode slurry;
4) Coating the positive electrode slurry obtained in the step 3) on a current collector to obtain a positive electrode plate of the lithium ion battery;
the step 1) and the step 2) are not in sequence.
10. The use according to claim 8, wherein the preparation method of the lithium ion battery negative electrode sheet comprises the following steps:
① Mixing an ionic polymer binder and a solvent to obtain a binder solution;
② Mixing a negative electrode active material and a conductive agent to obtain mixed powder;
③ Mixing the binder solution obtained in the step ①, the mixed powder obtained in the step ② and a solvent to obtain negative electrode slurry;
④ Coating the negative electrode slurry obtained in the step ③ on a current collector to obtain a negative electrode plate of the lithium ion battery;
the steps ① and ② are not sequential.
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| CN110504452A (en) * | 2019-09-04 | 2019-11-26 | 中国科学院青岛生物能源与过程研究所 | A kind of polymeric binder of high-peeling strength and its application in serondary lithium battery |
| CN111635478A (en) * | 2020-06-10 | 2020-09-08 | 珠海冠宇电池股份有限公司 | Low-impedance binder and preparation method and application thereof |
| CN113024748A (en) * | 2021-03-04 | 2021-06-25 | 浙江大学衢州研究院 | Preparation method of fluorine-containing water-based electrode binder |
| KR20210083061A (en) * | 2019-12-26 | 2021-07-06 | 인천대학교 산학협력단 | Binder for lithium secondary battery, and electrode and lithium secondary battery comprising the same |
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| CN110504452A (en) * | 2019-09-04 | 2019-11-26 | 中国科学院青岛生物能源与过程研究所 | A kind of polymeric binder of high-peeling strength and its application in serondary lithium battery |
| KR20210083061A (en) * | 2019-12-26 | 2021-07-06 | 인천대학교 산학협력단 | Binder for lithium secondary battery, and electrode and lithium secondary battery comprising the same |
| CN111635478A (en) * | 2020-06-10 | 2020-09-08 | 珠海冠宇电池股份有限公司 | Low-impedance binder and preparation method and application thereof |
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