CN114094039B - Electrode plate and lithium ion battery comprising same - Google Patents
Electrode plate and lithium ion battery comprising same Download PDFInfo
- Publication number
- CN114094039B CN114094039B CN202111288589.6A CN202111288589A CN114094039B CN 114094039 B CN114094039 B CN 114094039B CN 202111288589 A CN202111288589 A CN 202111288589A CN 114094039 B CN114094039 B CN 114094039B
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- electrolyte
- active material
- electrode sheet
- material layer
- negative electrode
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 60
- 239000003792 electrolyte Substances 0.000 claims abstract description 190
- 238000000576 coating method Methods 0.000 claims abstract description 139
- 239000011248 coating agent Substances 0.000 claims abstract description 138
- 239000011149 active material Substances 0.000 claims abstract description 67
- 239000006258 conductive agent Substances 0.000 claims description 34
- 239000007774 positive electrode material Substances 0.000 claims description 34
- 239000011230 binding agent Substances 0.000 claims description 33
- 239000002033 PVDF binder Substances 0.000 claims description 32
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 32
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 29
- 229910052744 lithium Inorganic materials 0.000 claims description 24
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 23
- 229920000642 polymer Polymers 0.000 claims description 21
- 229920001577 copolymer Polymers 0.000 claims description 17
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims description 17
- 229920002554 vinyl polymer Polymers 0.000 claims description 17
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 15
- 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 claims description 15
- 239000000463 material Substances 0.000 claims description 15
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 15
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 15
- 239000002562 thickening agent Substances 0.000 claims description 15
- 239000007773 negative electrode material Substances 0.000 claims description 13
- 229910003002 lithium salt Inorganic materials 0.000 claims description 12
- 159000000002 lithium salts Chemical class 0.000 claims description 12
- 239000002202 Polyethylene glycol Substances 0.000 claims description 11
- 150000003949 imides Chemical class 0.000 claims description 11
- 229920001223 polyethylene glycol Polymers 0.000 claims description 11
- 229920001940 conductive polymer Polymers 0.000 claims description 10
- 239000004014 plasticizer Substances 0.000 claims description 9
- 125000004386 diacrylate group Chemical group 0.000 claims description 8
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 7
- -1 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 4
- 229920000767 polyaniline Polymers 0.000 claims description 4
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 4
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 3
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 239000008151 electrolyte solution Substances 0.000 claims description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 2
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 claims description 2
- 229920002338 polyhydroxyethylmethacrylate Polymers 0.000 claims description 2
- 229920000128 polypyrrole Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 229920000123 polythiophene Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 239000007784 solid electrolyte Substances 0.000 claims description 2
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 claims description 2
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical group FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 60
- 238000010438 heat treatment Methods 0.000 abstract description 37
- 239000010410 layer Substances 0.000 description 115
- 239000002243 precursor Substances 0.000 description 59
- 239000000243 solution Substances 0.000 description 59
- 239000011267 electrode slurry Substances 0.000 description 56
- 238000002156 mixing Methods 0.000 description 52
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 48
- 238000001035 drying Methods 0.000 description 44
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 35
- 229910052799 carbon Inorganic materials 0.000 description 34
- 239000006255 coating slurry Substances 0.000 description 33
- 239000013543 active substance Substances 0.000 description 31
- 238000002360 preparation method Methods 0.000 description 31
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- 239000006245 Carbon black Super-P Substances 0.000 description 27
- 238000005520 cutting process Methods 0.000 description 27
- 238000009966 trimming Methods 0.000 description 27
- 239000011889 copper foil Substances 0.000 description 26
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 24
- 229910052782 aluminium Inorganic materials 0.000 description 24
- 238000005507 spraying Methods 0.000 description 24
- 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 23
- 238000001723 curing Methods 0.000 description 21
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- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 18
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 17
- 239000003960 organic solvent Substances 0.000 description 17
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 16
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- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 14
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 14
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- 229910002804 graphite Inorganic materials 0.000 description 13
- 238000002791 soaking Methods 0.000 description 13
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- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 10
- 239000010949 copper Substances 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 9
- AUGKLUNRHYPDAM-UHFFFAOYSA-N 3-methylbut-2-enenitrile Chemical compound CC(C)=CC#N AUGKLUNRHYPDAM-UHFFFAOYSA-N 0.000 description 8
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- 239000002994 raw material Substances 0.000 description 6
- 239000011247 coating layer Substances 0.000 description 5
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 5
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- 229910013870 LiPF 6 Inorganic materials 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000013021 overheating Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
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- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000005678 chain carbonates Chemical class 0.000 description 2
- 150000005676 cyclic carbonates Chemical group 0.000 description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000013007 heat curing Methods 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
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- 229910021382 natural graphite Inorganic materials 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
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- 238000007086 side reaction Methods 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- 229910001148 Al-Li alloy Inorganic materials 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
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013188 LiBOB Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 229910020923 Sn-O Inorganic materials 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- QKBJDEGZZJWPJA-UHFFFAOYSA-N ethyl propyl carbonate Chemical compound [CH2]COC(=O)OCCC QKBJDEGZZJWPJA-UHFFFAOYSA-N 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 239000007788 liquid Substances 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
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000005463 sulfonylimide group Chemical group 0.000 description 1
- 238000004804 winding 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
-
- 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
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- 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
- H01M4/134—Electrodes based on metals, Si or alloys
-
- 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
-
- 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
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/572—Means for preventing undesired use or discharge
- H01M50/584—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries
- H01M50/586—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries inside the batteries, e.g. incorrect connections of electrodes
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/572—Means for preventing undesired use or discharge
- H01M50/584—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries
- H01M50/59—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries characterised by the protection means
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Abstract
The invention provides an electrode plate and a lithium ion battery comprising the same. The electrode sheet of the present invention includes: current collector, active material layer, electrolyte and functional coating; wherein the current collector has two opposing surfaces; the active material layer is disposed on at least one surface of the current collector; the electrolyte is arranged inside and/or on the surface of the active material layer; the functional coating is disposed on the active material layer including the electrolyte. According to the invention, by constructing the in-situ cured electrolyte and the functional coating, the needling and heating safety of the battery is improved, the influence of a single functional coating mode on the increase of the internal resistance of the battery is reduced, and the electrical performance of the battery is ensured.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to an electrode plate and a lithium ion battery prepared by the electrode plate.
Background
At present, the development of lithium ion batteries mainly advances to high energy density and ultra-fast charging technologies, such as high nickel ternary materials, silicon-carbon negative electrodes and other materials, so that the intrinsic safety of the batteries is greatly deteriorated, and abuse under various conditions, such as overcharge, overheat, impact and other external uncontrollable factors, frequently occur, so that the improvement of the safety of the batteries is very necessary.
There are many ways to improve the safety of the battery, such as modification of the separator coating, high temperature resistant separator, polymer composite current collector, use of electrolyte flame retardant additives, coating of positive electrode materials, etc. Although these methods have some improvement in safety, there are also many problems such as limited improvement, difficulty in manufacture, high cost, deterioration in battery performance, and the like.
Therefore, more and more new technologies for improving safety are gradually developed, as the prior art discloses coating on the surfaces of the positive electrode and the negative electrode, the coating has high extension and electronic insulation characteristics, and when the battery is punctured by foreign objects, the area of a short circuit area of the positive electrode and the negative electrode can be reduced or even avoided, so that the safety of the battery is improved. However, similar to the pole piece surface coating technology, the electrolyte is still in a liquid system, and under the overheat condition of the battery, the active material is in direct contact with the electrolyte, so that a series of side reactions can occur, and a large amount of heat is emitted to cause the battery to thoroughly generate thermal runaway. Therefore, by adopting a single technical means, the safety problem of the battery under the conditions of needling and overheating is difficult to solve.
Disclosure of Invention
In view of the defects in the prior art, the invention provides the electrode sheet containing the in-situ cured electrolyte and the functional coating and the lithium ion battery containing the electrode sheet, and the needle punching safety of the battery and the safety of the battery under the overheat condition can be improved by constructing the in-situ cured electrolyte and the coating on the electrode sheet.
The present invention provides an electrode sheet comprising: current collector, active material layer, electrolyte and functional coating; wherein,,
the current collector has two opposing surfaces;
the active material layer is disposed on at least one surface of the current collector;
the electrolyte is arranged inside and/or on the surface of the active material layer;
the functional coating is disposed on the active material layer of the electrolyte.
According to an embodiment of the invention, the electrolyte is a solid state electrolyte. Specifically, the solid electrolyte includes a first polymer and an electrolyte solution dispersed therein.
According to an embodiment of the present invention, the first polymer is, for example, at least one of polymethyl methacrylate or a copolymer thereof, polyhydroxyethyl methacrylate or a copolymer thereof, polyethylene glycol diacrylate or a copolymer thereof, polytrimethylolpropane triacrylate or a copolymer thereof, polybutyl acrylate or a copolymer thereof, polyvinyl n-butyl ether or a copolymer thereof, or polyethyl acetate or a copolymer thereof. The copolymer of a certain homopolymer may be a copolymer of a monomer of the homopolymer and at least one monomer of other homopolymers, or a copolymer of a monomer of the homopolymer and another monomer suitable for copolymerization therewith.
According to an embodiment of the present invention, the electrolyte has a content of the electrolyte of 80 to 95wt%.
According to an embodiment of the present invention, the electrolyte may be selected from electrolytes known in the art. Preferably, the electrolyte comprises at least a lithium salt and a solvent. Illustratively, the lithium salt is selected from LiPF 6 、LiBF 4 、LiClO 4 、LiAsF 6 、LiSO 2 CF 3 、LiN(CF 3 SO 2 ) 2 LiBOB, liDFOB or LiN (C) 2 F 5 SO 2 ) 2 At least one of them. Illustratively, the solvent is selected from cyclic carbonates and/or chain carbonates. Illustratively, the cyclic carbonate is selected from at least one of ethylene carbonate, propylene carbonate, or gamma-butyrolactone. Illustratively, the chain carbonate is selected from at least one of dimethyl carbonate, diethyl carbonate, methylethyl carbonate, methylpropyl carbonate, or ethylpropyl carbonate. For example, the electrolyte is lithium hexafluorophosphate (LiPF 6 ) Dissolved in a mixed solvent (for example, a mass ratio of the three is 1:1:1) composed of Ethylene Carbonate (EC), dimethyl carbonate (DEC) and ethylmethyl carbonate (EMC). Specifically, lithium hexafluorophosphate (LiPF 6 ) The content of (C) is 0.1-3mol/L, for example 1mol/L, 2mol/L or 3mol/L.
According to an embodiment of the invention, the electrolyte further comprises a conductive polymer.
According to an embodiment of the present invention, the conductive polymer includes, but is not limited to, at least one of polyarenyl oxadiazole, polythiophene, polypyrrole, polyaniline.
According to an embodiment of the invention, the raw materials forming the electrolyte comprise at least a monomer, an initiator and an electrolyte.
According to an embodiment of the present invention, the electrolyte is obtained by impregnating the raw material into the interior and/or surface of the active material layer by spraying or dipping, and then curing by heating. Preferably, the electrolyte portion forms an electrolyte layer on the surface of the active material layer after heat curing.
According to an embodiment of the invention, the raw material forming the electrolyte further comprises the conductive polymer.
According to an embodiment of the invention, the raw materials forming the electrolyte comprise the following components in mass fraction: 2-10wt% of monomer, 0.2-1% of initiator, 80-95% of electrolyte and 0-10wt% of conductive polymer.
According to an embodiment of the present invention, the electrolyte is obtained by impregnating the raw material into the interior and/or surface of the active material layer by spraying or dipping, and then curing by heating. Preferably, the electrolyte portion forms an electrolyte layer on the surface of the active material layer after heat curing.
According to an embodiment of the present invention, the monomer includes, but is not limited to, at least one of methyl methacrylate, hydroxyethyl methacrylate, polyethylene glycol diacrylate, trimethylolpropane triacrylate, butyl acrylate, vinyl n-butyl ether, and ethyl acetate.
According to an embodiment of the present invention, the initiator includes, but is not limited to, at least one of cumene hydroperoxide, dicumyl peroxide, di-t-butyl peroxide, dibenzoyl peroxide, dodecanoyl peroxide, azobisisobutyronitrile, azobisisoheptonitrile.
According to an embodiment of the invention, the electrolyte and the conductive polymer in the raw materials are as defined above.
According to an embodiment of the invention, the functional coating has a thickness of 0.1 μm to 20 μm.
According to an embodiment of the invention, the functional coating comprises at least a second polymer. Further preferably, the functional coating further comprises a plasticizer.
According to an embodiment of the invention, the functional coating comprises the following components in parts by mass: 30-80 wt% of a second polymer, 0-50wt% of a plasticizer and 0-50wt% of lithium salt.
Preferably, the second polymer includes, but is not limited to, at least one of polyvinylidene fluoride, polyvinyl alcohol, polytetrafluoroethylene, polyvinylidene fluoride-hexafluoropropylene copolymer, polymethyl methacrylate. The second polymer has the main function of swelling electrolyte, ensuring normal conduction of lithium ions, and simultaneously has high breaking elongation after film formation, so that the functional coating wraps the active material coating when a foreign object is penetrated, thereby improving safety.
Preferably, the plasticizer comprises a small molecule material. Further preferably, the small molecule material includes, but is not limited to, at least one of polyvinyl carbonate, ethylene carbonate, succinonitrile, methyl methacrylate, polyethylene glycol methyl ether methacrylate. The plasticizer has the main function of improving the swelling of the polymer in the electrolyte so as to improve the ionic conductivity of the functional coating, and meanwhile, the addition of the plasticizer can reduce the crystallinity of the polymer and improve the breaking elongation of the functional coating.
Preferably, the lithium salt includes, but is not limited to, at least one of lithium bis (trifluoromethylsulfonyl) imide, lithium bis (difluorosulfonyl) imide, lithium bis (oxalato) borate, and lithium difluorooxalato borate. The main function of the lithium salt is to improve the lithium ion conductivity of the functional coating.
According to an embodiment of the present invention, an active material, a binder, and a conductive agent are included in the active material layer. Wherein, the active material, the binder and the conductive agent can be selected from materials known in the technical field, so long as the performance requirements of the active material layer can be met. Illustratively, the binder includes, but is not limited to, at least one of Styrene Butadiene Rubber (SBR), polyvinylidene fluoride (PVDF). Illustratively, the conductive agent includes, but is not limited to, at least one of natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, carbon fiber, and the like. In the present invention, the content of each substance in the active material layer is not particularly limited as long as the performance requirements of the electrode sheet can be satisfied.
Preferably, in the active material layer, the active material layer further includes a thickener including, but not limited to, sodium carboxymethyl cellulose (CMC).
According to an embodiment of the present invention, when the electrode sheet is used for a positive electrode, in the electrode sheet, a current collector is selected from positive electrode current collectors, and the active material layer includes a positive electrode active material.
Preferably, the positive electrode current collector includes, but is not limited to, being composed of an aluminum material, an aluminum/polymer, an aluminum/carbon composite material. Illustratively, the aluminum material, aluminum/polymer, aluminum/carbon composite material may be selected from porous or non-porous aluminum materials, aluminum/polymers, aluminum/carbon composite foils.
Preferably, the positive electrode active material includes a composite oxide containing lithium and at least one element selected from cobalt, manganese and nickel, and preferably, at least one of lithium cobaltate, lithium nickel manganese cobalt ternary material, lithium manganate, lithium nickel manganate, lithium iron phosphate.
According to an embodiment of the present invention, when the electrode sheet is used for a negative electrode, in the electrode sheet, a current collector is selected from negative electrode current collectors, and the active material layer includes a negative electrode active material.
Preferably, the negative electrode current collector includes, but is not limited to, being composed of copper material, copper/polymer, copper/carbon composite. Illustratively, the copper material, copper/polymer, copper/carbon composite may be selected from porous or non-porous copper materials, copper/polymers, or copper/carbon composite foils.
Preferably, the negative electrode active material is selected from natural graphite, artificial graphite, mesophase micro carbon spheres, hard carbon, soft carbon, silicon-carbon composite, li-Sn alloy, li-Sn-O alloy, sn, snO, snO 2 Lithiated TiO of spinel structure 2 -Li 4 Ti 5 O 12 At least one of Li-Al alloy.
The invention also provides a preparation method of the electrode slice, which comprises the following steps:
1) Uniformly mixing an active substance, a conductive agent and a binder to prepare electrode slurry, coating the electrode slurry on at least one surface of a current collector, drying to form an active substance layer, and cold pressing to obtain an electrode sheet of the active substance layer;
2) And (2) dissolving the monomer, the electrolyte and the initiator in a solvent to form an electrolyte precursor solution, and completely soaking the electrode slice obtained in the step (1) in the electrolyte precursor solution in a spraying or dipping mode, and heating to initiate curing to obtain the electrode slice.
According to an embodiment of the present invention, the step 2) specifically includes: and (2) dissolving the monomer, the electrolyte, the conductive polymer and the initiator in a solvent to form an electrolyte precursor solution, and completely soaking the electrode slice obtained in the step (1) in the electrolyte precursor solution in a spraying or dipping mode, and heating to initiate curing to obtain the electrode slice.
According to an embodiment of the present invention, a functional coating layer is further provided on the electrode sheet, specifically including: dissolving a second polymer, a plasticizer and lithium salt in an organic solvent, uniformly mixing to prepare coating slurry, coating the second coating slurry on the surface of the electrode sheet obtained in the step 2), and drying by blowing at 50-100 ℃ to obtain the functional coating.
According to an embodiment of the invention, the active material, the conductive agent, the binder, the second polymer, the plasticizer and the lithium salt have the meanings as described above. In the present invention, the active material layer, the functional coating layer, and the electrolyte have the meanings as described above.
According to an embodiment of the present invention, the organic solvent is a solvent commonly used by those skilled in the art, including but not limited to at least one of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone.
The invention also provides application of the electrode plate in an energy storage battery, and the electrode plate is preferably used for a lithium ion battery.
The invention also provides a lithium ion battery, which comprises a positive electrode plate, a negative electrode plate, a diaphragm and electrolyte, wherein the diaphragm is arranged between the positive electrode and the negative electrode, and the positive electrode plate and the negative electrode plate are mutually independent and selected from the electrode plates.
According to an embodiment of the present invention, the functional coating is included in the positive electrode sheet and/or the negative electrode sheet.
According to an exemplary aspect of the present invention, when the positive electrode sheet includes a current collector, an active material layer, and an electrolyte, the negative electrode sheet includes a current collector, an active material layer, an electrolyte, and a functional coating layer.
According to an exemplary aspect of the present invention, when the positive electrode sheet includes a current collector, an active material layer, an electrolyte, and a functional coating layer, the negative electrode sheet includes a current collector, an active material layer, and an electrolyte.
According to an exemplary aspect of the present invention, the positive electrode sheet and the negative electrode sheet each include a current collector, an active material layer, an electrolyte, and a functional coating.
The invention has the beneficial effects that:
the electrode plate of the lithium ion battery prepared by the electrode plate of the invention contains electrolyte and functional coating, and has high extension, electronic insulation property and ion conductivity property, when the battery is punctured by foreign objects, the functional coating plays a role in wrapping active substances in the electrode plate, and the area of a short circuit between an anode and a cathode can be greatly reduced or even avoided, so that the needling safety of the battery is improved. Meanwhile, due to the in-situ solidified electrolyte, lithium ion conduction in the pole piece depends on the electrolyte after solidification, the active substance is not in direct contact with the liquid electrolyte, the occurrence of a series of side reactions of the active substance and the liquid electrolyte is greatly reduced, and under the overheat condition, the solidified electrolyte and the active substance have higher thermal stability, so that the safety of the battery under the overheat condition is improved.
In the electrode slice, the conductive polymer is added in the electrolyte, and the electrolyte is obtained by soaking and in-situ curing in the interior and/or the surface of the active material layer, so that the problem that the functional coating slurry with electronic insulation property is directly coated on the surface of the electrode slice to wrap the active material and increase the electronic resistance in the electrode slice is avoided. Therefore, the invention can reduce the influence of a single-function coating mode on the increase of the internal resistance of the battery and ensure the electrical performance of the battery by constructing the in-situ cured electrolyte.
Drawings
Fig. 1 is a schematic view of an electrode sheet according to a preferred embodiment of the present invention;
fig. 2 is a schematic view of an electrode sheet according to another preferred embodiment of the present invention;
wherein 1 is a current collector, 2 is an active material layer (containing a solidified electrolyte therein), 3 is a solidified electrolyte layer, and 4 is a functional coating.
Detailed Description
The technical scheme of the invention will be further described in detail below with reference to specific embodiments. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
Unless otherwise indicated, the starting materials and reagents used in the following examples were either commercially available or may be prepared by known methods.
The electrolytes used hereinafter all refer to common commercial electrolytes, and specifically include: lithium hexafluorophosphate (LiPF) 6 ) Dissolving in a mixed solvent consisting of Ethylene Carbonate (EC), dimethyl carbonate (DEC) and ethylmethyl carbonate (EMC) (the mass ratio of the three is 1:1:1), and LiPF 6 The concentration was about 1mol/L. The positive electrode active materials used hereinafter are all commercially available NCM high nickel 8-based positive electrodes.
Example 1
1. Preparation of positive plate containing in-situ cured electrolyte and functional coating:
1) Uniformly mixing NCM high nickel 8 series positive electrode (positive electrode active material), conductive agent superconducting carbon (Super-P) and binder polyvinylidene fluoride (PVDF) according to a mass ratio of 97:1.5:1.5 to prepare positive electrode slurry, coating the positive electrode slurry on two surfaces of a current collector aluminum foil, drying at 100 ℃ to form a positive electrode active material layer, and cold pressing to obtain a positive electrode sheet containing the active material layer;
2) Uniformly mixing polyethylene glycol diacrylate, polyaromatic oxadiazole, azodiisobutyronitrile and commercial electrolyte in a mass ratio of 3:1:0.03:95.97 to obtain a uniform precursor solution, then completely soaking the precursor solution in the positive plate containing the active material layer prepared in the step 1) by adopting a spraying mode, heating at 60 ℃ to enable the precursor solution to be cured in situ, and controlling the thickness of a cured electrolyte layer on the surface of the positive plate to be 1 mu m to obtain the positive plate containing the cured electrolyte;
3) Dissolving polyvinylidene fluoride-hexafluoropropylene copolymer, polyvinyl carbonate and lithium bistrifluoromethylsulfonyl imide in an organic solvent N, N-Dimethylacetamide (DMAC) according to the mass ratio of 70:10:20, uniformly mixing to prepare coating slurry, coating the coating slurry on the surface of a positive plate containing a cured electrolyte, and drying by blowing at 80 ℃ to obtain a functional coating with the thickness of 10 mu m, thus obtaining a positive plate containing an in-situ cured electrolyte and the functional coating;
4) And 3) trimming, cutting and slitting the positive plate obtained in the step 3), and taking the positive plate as the positive plate of the lithium ion battery after slitting.
2. Preparation of a negative plate containing in-situ cured electrolyte:
1') preparing negative electrode slurry from negative electrode active substance graphite, conductive agent superconducting carbon (Super-P), thickener sodium carboxymethylcellulose (CMC) and binder styrene-butadiene rubber (SBR) according to the mass ratio of 96.5:1.0:1.0:1.5, coating the negative electrode slurry on a current collector copper foil, drying the current collector copper foil at 90 ℃ to form a negative electrode active substance layer, and then carrying out cold pressing to obtain a negative electrode sheet containing the negative electrode active substance layer;
2 ') uniformly mixing polyethylene glycol diacrylate, polyaromatic oxadiazole, azodiisobutyronitrile and commercial electrolyte in a mass ratio of 3:1:0.03:95.97 to obtain a uniform precursor solution, then adopting a spraying mode to enable the cathode sheet of the step 1 ') to completely infiltrate the precursor solution, and heating and curing at 80 ℃ to obtain a cured electrolyte layer with the thickness of 1 mu m on the surface of the cathode sheet of the step 1 ');
And 3') trimming, cutting and slitting the negative plate obtained in the step 2) to obtain the negative plate of the lithium ion battery.
3. Preparation of electrolyte: the electrolyte is prepared according to the common commercial electrolyte.
4. Preparation of a lithium ion battery: winding the positive plate, the negative plate and the diaphragm into a battery cell, wherein the design capacity of the battery cell is 5Ah, the diaphragm is positioned between the adjacent positive plate and negative plate, the positive plate is led out by aluminum tab spot welding, and the negative plate is led out by nickel tab spot welding; and then placing the battery core in an aluminum-plastic packaging bag, baking, injecting the electrolyte, and finally preparing the lithium ion battery through the procedures of packaging, formation, sorting and the like.
Example 2
1. Preparing a positive plate containing an in-situ cured electrolyte and a functional coating:
1) Uniformly mixing NCM high nickel 8 series positive electrode (positive electrode active material), conductive agent superconducting carbon (Super-P) and binder polyvinylidene fluoride (PVDF) according to a mass ratio of 97:1.5:1.5 to prepare positive electrode slurry, coating the positive electrode slurry on two surfaces of a current collector aluminum foil, drying at 100 ℃ to form a positive electrode active material layer, and cold pressing to obtain a positive electrode sheet containing the active material layer;
2) Uniformly mixing trimethylolpropane triacrylate, polyaromatic oxadiazole, azodiisobutyronitrile and commercial electrolyte in a mass ratio of 3:1:0.03:95.97 to obtain a uniform precursor solution, and then completely soaking the precursor solution in the positive plate containing the active material layer prepared in the step 1) by adopting a spraying mode, heating at 80 ℃ to enable the precursor solution to be cured in situ, and controlling the thickness of a cured electrolyte layer on the surface of a pole piece to be 1 mu m to obtain the positive plate containing the cured electrolyte;
3) Dissolving polyvinylidene fluoride-hexafluoropropylene copolymer, polyvinyl carbonate and lithium bistrifluoromethylsulfonyl imide in an organic solvent DMAC (dimethyl Acrylonitrile) in a mass ratio of 70:10:20, uniformly mixing to prepare coating slurry, coating the coating slurry on the surface of a positive plate containing a precursor solution, and drying by blowing at 80 ℃ to obtain a functional coating with a thickness of 5 mu m, thus obtaining a positive plate containing an in-situ cured electrolyte and the functional coating;
4) And 3) trimming, cutting and slitting the positive plate obtained in the step 3), and taking the positive plate as the positive plate of the lithium ion battery after slitting.
2. Preparation of a negative plate containing in-situ cured electrolyte:
1') preparing negative electrode slurry from negative electrode active substance graphite, conductive agent superconducting carbon (Super-P), thickener sodium carboxymethylcellulose (CMC) and binder styrene-butadiene rubber (SBR) according to the mass ratio of 96.5:1.0:1.0:1.5, coating the negative electrode slurry on a current collector copper foil, drying the current collector copper foil at 90 ℃ to form a negative electrode active substance layer, and then carrying out cold pressing to obtain a negative electrode sheet containing the negative electrode active substance layer;
2 ') uniformly mixing trimethylolpropane triacrylate, polyaromatic oxadiazole, azodiisobutyronitrile and commercial electrolyte in a mass ratio of 3:1:0.03:95.97 to obtain a uniform precursor solution, then completely soaking the cathode sheet in the precursor solution by adopting a spraying mode, and heating and curing at 80 ℃ on the surface of the cathode sheet in the step 1') to obtain a cathode sheet with a cured electrolyte layer with a thickness of 1 mu m;
And 3 ') trimming, cutting and slitting the negative plate in the step 2') to obtain the negative plate of the lithium ion battery.
3. Electrolyte and lithium ion battery preparation: the same as in example 1.
Example 3
1. Preparing a positive plate containing an in-situ cured electrolyte and a functional coating:
1) Uniformly mixing NCM8 positive electrode (positive electrode active material), conductive agent superconducting carbon (Super-P) and binder polyvinylidene fluoride (PVDF) according to a mass ratio of 97:1.5:1.5 to prepare positive electrode slurry, coating the positive electrode slurry on two surfaces of a current collector aluminum foil, drying at 100 ℃ to form a positive electrode active material layer, and cold pressing to obtain a positive electrode sheet containing the active material layer;
2) Uniformly mixing trimethylolpropane triacrylate, azodiisobutyronitrile and commercial electrolyte in a mass ratio of 3:0.03:96.97 to obtain a uniform precursor solution, then completely soaking the precursor solution in the positive plate containing the active material layer prepared in the step 1) by adopting a spraying mode, heating at 80 ℃ to in-situ cure the precursor solution, and controlling the thickness of a cured electrolyte layer on the surface of the electrode plate to be 1 mu m to obtain the positive plate containing the cured electrolyte;
3) Dissolving polyvinylidene fluoride-hexafluoropropylene copolymer, polyvinyl carbonate and lithium bistrifluoromethylsulfonyl imide in an organic solvent DMAC (dimethyl Acrylonitrile) in a mass ratio of 70:10:20, uniformly mixing to prepare coating slurry, coating the coating slurry on the surface of a positive plate containing a precursor solution, and drying by blowing at 80 ℃ to obtain a functional coating with a thickness of 5 mu m, thus obtaining a positive plate containing an in-situ cured electrolyte and the functional coating;
4) And 3) trimming, cutting and slitting the positive plate obtained in the step 3), and taking the positive plate as the positive plate of the lithium ion battery after slitting.
2. Preparation of a negative plate containing in-situ cured electrolyte:
1') preparing negative electrode slurry by graphite, conductive agent superconducting carbon (Super-P), thickener sodium carboxymethylcellulose (CMC) and binder styrene-butadiene rubber (SBR) according to the mass ratio of 96.5:1.0:1.0:1.5, coating the negative electrode slurry on a current collector copper foil, drying the current collector copper foil at 90 ℃ to form a negative electrode active material layer, and then carrying out cold pressing to obtain a negative electrode sheet containing the negative electrode active material layer;
2 ') uniformly mixing trimethylolpropane triacrylate, azodiisobutyronitrile and commercial electrolyte in a mass ratio of 3:0.03:96.97 to obtain a uniform precursor solution, and then completely soaking the negative electrode sheet in the step 1') in the precursor solution by adopting a spraying mode, and heating and curing at 80 ℃ to obtain the negative electrode sheet with a cured electrolyte layer with the surface thickness of 1 mu m;
and 3') trimming, cutting and slitting the negative plate obtained in the step 2), and taking the negative plate as the negative plate of the lithium ion battery after slitting.
3. Electrolyte and lithium ion battery preparation: the same as in example 1.
Example 4
1. Preparing a positive plate containing an in-situ cured electrolyte and a functional coating:
1) Uniformly mixing NCM high nickel 8 series positive electrode (positive electrode active material), conductive agent superconducting carbon (Super-P) and binder polyvinylidene fluoride (PVDF) according to a mass ratio of 97:1.5:1.5 to prepare positive electrode slurry, coating the positive electrode slurry on two surfaces of a current collector aluminum foil, drying at 100 ℃ to form a positive electrode active material layer, and cold pressing to obtain a positive electrode sheet containing the active material layer;
2) Uniformly mixing trimethylolpropane triacrylate, polyaniline and azodiisobutyronitrile with commercial electrolyte according to the mass ratio of 7:1:0.07:91.93 to obtain uniform precursor solution, then adopting a spraying mode to completely infiltrate the precursor solution into the positive plate containing the active material layer prepared in the step 1), heating at 80 ℃ to cure the precursor solution, and controlling the thickness of the cured electrolyte layer on the surface of the electrode plate to be 1 mu m to obtain the positive plate containing the cured electrolyte;
3) Dissolving polyvinylidene fluoride-hexafluoropropylene copolymer, methyl methacrylate and lithium bistrifluoromethylsulfonyl imide in an organic solvent N, N-Dimethylformamide (DMF) according to the mass ratio of 70:10:20, uniformly mixing to prepare coating slurry, coating the coating slurry on the surface of a positive plate containing a precursor solution, and drying by blowing at 80 ℃ to obtain a functional coating with the thickness of 5 mu m, thus obtaining a positive plate containing an in-situ cured electrolyte and the functional coating;
4) And 3) trimming, cutting and slitting the positive plate obtained in the step 3), and taking the positive plate as the positive plate of the lithium ion battery after slitting.
2. Preparation of a negative plate containing in-situ cured electrolyte:
1') preparing negative electrode slurry from negative electrode active substance graphite, conductive agent superconducting carbon (Super-P), thickener sodium carboxymethylcellulose (CMC) and binder styrene-butadiene rubber (SBR) according to the mass ratio of 96.5:1.0:1.0:1.5, coating the negative electrode slurry on a current collector copper foil, drying the current collector copper foil at 90 ℃ to form a negative electrode active substance layer, and then carrying out cold pressing to obtain a negative electrode sheet containing the negative electrode active substance layer;
2 ') uniformly mixing trimethylolpropane triacrylate, polyaniline, azodiisobutyronitrile and commercial electrolyte in a mass ratio of 7:1:0.07:91.93 to obtain a uniform precursor solution, and then adopting a spraying mode to completely infiltrate the precursor solution into the anode sheet in the step 1'), and heating and curing at 80 ℃ to obtain the anode sheet with the surface containing the cured electrolyte layer with the thickness of 1 mu m;
and 3') trimming, cutting and slitting the negative plate obtained in the step 2), and taking the negative plate as the negative plate of the lithium ion battery after slitting.
3. Electrolyte and lithium ion battery preparation: the same as in example 1.
Example 5
1. Preparing a positive plate containing an in-situ cured electrolyte and a functional coating:
1) Uniformly mixing NCM8 positive electrode (positive electrode active material), conductive agent superconducting carbon (Super-P) and binder polyvinylidene fluoride (PVDF) according to a mass ratio of 97:1.5:1.5 to prepare positive electrode slurry, coating the positive electrode slurry on two surfaces of a current collector aluminum foil, drying at 100 ℃ to form a positive electrode active material layer, and cold pressing to obtain a positive electrode sheet containing the active material layer;
2) Uniformly mixing polyethylene glycol diacrylate, polyaromatic oxadiazole, azodiisobutyronitrile and commercial electrolyte in a mass ratio of 3:1:0.03:95.97 to obtain a uniform precursor solution, then completely soaking the precursor solution in the positive plate containing the active material layer prepared in the step 1) by adopting a spraying mode, heating at 80 ℃ to cure the precursor solution, and controlling the thickness of a cured electrolyte layer on the surface of the electrode plate to be 5 mu m to obtain the positive plate containing the cured electrolyte;
3) Dissolving polyvinylidene fluoride-hexafluoropropylene copolymer, polyvinyl carbonate and lithium bistrifluoromethylsulfonyl imide in an organic solvent DMAC (dimethyl Acrylonitrile) in a mass ratio of 70:10:20, uniformly mixing to prepare coating slurry, coating the coating slurry on the surface of a positive plate containing a precursor solution, and drying by blowing at 80 ℃ to obtain a functional coating with the thickness of 10 mu m, thus obtaining a positive plate containing an in-situ cured electrolyte and the functional coating;
4) And 3) trimming, cutting and slitting the positive plate obtained in the step 3), and taking the positive plate as the positive plate of the lithium ion battery after slitting.
2. Preparation of a negative plate containing in-situ cured electrolyte:
1') preparing negative electrode slurry from negative electrode active substance graphite, conductive agent superconducting carbon (Super-P), thickener sodium carboxymethylcellulose (CMC) and binder styrene-butadiene rubber (SBR) according to the mass ratio of 96.5:1.0:1.0:1.5, coating the negative electrode slurry on a current collector copper foil, drying the current collector copper foil at 90 ℃ to form a negative electrode active substance layer, and then carrying out cold pressing to obtain a negative electrode sheet containing the negative electrode active substance layer;
2 ') uniformly mixing polyethylene glycol diacrylate, polyaromatic oxadiazole, azodiisobutyronitrile and commercial electrolyte in a mass ratio of 3:1:0.03:95.97 to obtain a uniform precursor solution, and then adopting a spraying mode to enable the cathode sheet in the step 1') to completely infiltrate the precursor solution, and heating and curing at 80 ℃ to obtain the cathode sheet with the surface containing a cured electrolyte layer with the thickness of 5 mu m;
and 3') trimming, cutting and slitting the negative plate obtained in the step 2), and taking the negative plate as the negative plate of the lithium ion battery after slitting.
3. Electrolyte and lithium ion battery preparation: the same as in example 1.
Example 6
1. Preparing a positive plate containing an in-situ cured electrolyte and a functional coating:
1) Uniformly mixing NCM8 positive electrode (positive electrode active material), conductive agent superconducting carbon (Super-P) and binder polyvinylidene fluoride (PVDF) according to a mass ratio of 97:1.5:1.5 to prepare positive electrode slurry, coating the positive electrode slurry on two surfaces of a current collector aluminum foil, drying at 100 ℃ to form a positive electrode active material layer, and cold pressing to obtain a positive electrode sheet containing the active material layer;
2) Uniformly mixing trimethylolpropane triacrylate, polyaromatic oxadiazole, azodiisobutyronitrile and commercial electrolyte in a mass ratio of 3:1:0.03:95.97 to obtain a uniform precursor solution, and then adopting a spraying mode to enable the positive plate containing the active material layer prepared in the step 1) to completely infiltrate the precursor solution, heating and curing at 80 ℃, and controlling the thickness of a cured electrolyte layer on the surface of the electrode plate to be 1 mu m to obtain the positive plate containing the cured electrolyte;
3) Dissolving polyvinylidene fluoride-hexafluoropropylene copolymer, polyvinyl carbonate and lithium bistrifluoromethylsulfonyl imide in an organic solvent DMAC (dimethyl Acrylonitrile) in a mass ratio of 60:10:30, uniformly mixing to prepare coating slurry, coating the coating slurry on the surface of a positive plate containing a precursor solution, and drying by blowing at 80 ℃ to obtain a functional coating with a thickness of 5 mu m, thus obtaining a positive plate containing an in-situ cured electrolyte and the functional coating;
4) And 3) trimming, cutting and slitting the positive plate obtained in the step 3), and taking the positive plate as the positive plate of the lithium ion battery after slitting.
2. Preparation of a negative plate containing in-situ cured electrolyte:
1') preparing negative electrode slurry from negative electrode active substance graphite, conductive agent superconducting carbon (Super-P), thickener sodium carboxymethylcellulose (CMC) and binder styrene-butadiene rubber (SBR) according to the mass ratio of 96.5:1.0:1.0:1.5, coating the negative electrode slurry on a current collector copper foil, drying the current collector copper foil at 90 ℃ to form a negative electrode active substance layer, and then carrying out cold pressing to obtain a negative electrode sheet containing the negative electrode active substance layer;
2 ') uniformly mixing trimethylolpropane triacrylate, polyaromatic oxadiazole, azodiisobutyronitrile and commercial electrolyte in a mass ratio of 3:1:0.03:95.97 to obtain a uniform precursor solution, and then completely soaking the cathode sheet in the step 1') in the precursor solution by adopting a spraying mode, and heating and curing at 80 ℃ to obtain a cured electrolyte layer with the surface thickness of 1 mu m;
and 3') trimming, cutting and slitting the negative plate obtained in the step 2) to obtain the negative plate of the lithium ion battery.
3. Electrolyte and lithium ion battery preparation: the same as in example 1.
Example 7
1. Preparing a positive plate containing an in-situ cured electrolyte and a functional coating:
1) Uniformly mixing NCM8 positive electrode (positive electrode active material), conductive agent superconducting carbon (Super-P) and binder polyvinylidene fluoride (PVDF) according to the mass ratio of 97:1.5:1.5 to prepare positive electrode slurry, coating the positive electrode slurry on two surfaces of a current collector aluminum foil, drying at 100 ℃ to form a positive electrode active material layer, and cold pressing to obtain a positive electrode sheet containing the active material layer;
2) Uniformly mixing trimethylolpropane triacrylate, polyaromatic oxadiazole, azodiisobutyronitrile and commercial electrolyte in a mass ratio of 3:1:0.03:95.97 to obtain a uniform precursor solution, and then adopting a spraying mode to enable the positive plate containing the active material layer prepared in the step 1) to completely infiltrate the precursor solution, heating and curing at 80 ℃, and controlling the thickness of a cured electrolyte layer on the surface of the electrode plate to be 1 mu m to obtain the positive plate containing the cured electrolyte;
3) Dissolving polyvinylidene fluoride-hexafluoropropylene copolymer, polyvinyl carbonate and lithium bistrifluoromethylsulfonyl imide in an organic solvent DMAC (dimethyl Acrylonitrile) in a mass ratio of 70:10:20, uniformly mixing to prepare coating slurry, coating the coating slurry on the surface of a positive plate containing a precursor solution, and drying by blowing at 80 ℃ to obtain a functional coating with a thickness of 5 mu m, thus obtaining a positive plate containing an in-situ cured electrolyte and the functional coating;
4) And 3) trimming, cutting and slitting the positive plate obtained in the step 3), and taking the positive plate as the positive plate of the lithium ion battery after slitting.
2. Preparing a negative plate containing an in-situ cured electrolyte and a functional coating:
1') preparing negative electrode slurry from graphite, conductive agent superconducting carbon (Super-P), thickener sodium carboxymethylcellulose (CMC) and binder styrene-butadiene rubber (SBR) according to the mass ratio of 96.5:1.0:1.0:1.5, coating the negative electrode slurry on a current collector copper foil, drying the current collector copper foil at 90 ℃ to form a negative electrode active material layer, and then carrying out cold pressing to obtain a negative electrode sheet containing the negative electrode active material layer;
2 ') uniformly mixing trimethylolpropane triacrylate, polyaromatic oxadiazole, azodiisobutyronitrile and commercial electrolyte in a mass ratio of 3:1:0.03:95.97 to obtain a uniform precursor solution, then adopting a spraying mode to completely infiltrate the precursor solution into the negative electrode sheet in the step 1'), heating and curing at 80 ℃, and controlling the thickness of a cured electrolyte layer on the surface of the electrode sheet to be 1 mu m to obtain the negative electrode sheet containing the cured electrolyte;
3 ') dissolving polyvinylidene fluoride-hexafluoropropylene copolymer, polyvinyl carbonate and lithium bistrifluoromethylsulfonylimide in an organic solvent DMAC (dimethyl amine) in a mass ratio of 70:10:20, uniformly mixing to prepare coating slurry, coating the coating slurry on the surface of the negative electrode sheet in the step 2'), and drying by blowing at 80 ℃ to obtain a functional coating with a thickness of 5 mu m, thus obtaining the negative electrode sheet containing in-situ cured electrolyte and the functional coating;
And 4 ') trimming, cutting and slitting the negative plate obtained in the step 3') to obtain the negative plate of the lithium ion battery.
3. Electrolyte and lithium ion battery preparation: the same as in example 1.
Example 8
1. Preparation of positive plate containing in-situ cured electrolyte:
1) Uniformly mixing NCM8 positive electrode (positive electrode active material), conductive agent superconducting carbon (Super-P) and binder polyvinylidene fluoride (PVDF) according to a mass ratio of 97:1.5:1.5 to prepare positive electrode slurry, coating the positive electrode slurry on two surfaces of a current collector aluminum foil, drying at 100 ℃ to form a positive electrode active material layer, and cold pressing to obtain a positive electrode sheet containing the active material layer;
2) Uniformly mixing trimethylolpropane triacrylate, polyaromatic oxadiazole, azodiisobutyronitrile and commercial electrolyte in a mass ratio of 3:1:0.03:95.97 to obtain a uniform precursor solution, and then completely soaking the positive plate containing the active material layer prepared in the step 1) in the precursor solution by adopting a spraying mode, and heating and curing at 80 ℃ to obtain a cured electrolyte layer with the surface thickness of 1 mu m;
3) And (3) trimming, cutting and slitting the positive plate obtained in the step (2), and taking the positive plate as the positive plate of the lithium ion battery after slitting.
2. Preparation of a negative plate containing in-situ cured electrolyte and a functional coating:
1') preparing negative electrode slurry from negative electrode active substance graphite, conductive agent superconducting carbon (Super-P), thickener sodium carboxymethylcellulose (CMC) and binder styrene-butadiene rubber (SBR) according to the mass ratio of 96.5:1.0:1.0:1.5, coating the negative electrode slurry on a current collector copper foil, drying the current collector copper foil at 90 ℃ to form a negative electrode active substance layer, and then carrying out cold pressing to obtain a negative electrode sheet containing the negative electrode active substance layer;
2 ') uniformly mixing trimethylolpropane triacrylate, polyaromatic oxadiazole, azodiisobutyronitrile and commercial electrolyte in a mass ratio of 3:1:0.03:95.97 to obtain a uniform precursor solution, then adopting a spraying mode to completely infiltrate the precursor solution into the negative electrode sheet in the step 1'), heating and curing at 80 ℃, and controlling the thickness of a cured electrolyte layer on the surface of the electrode sheet to be 1 mu m to obtain the negative electrode sheet containing the cured electrolyte;
3 ') dissolving polyvinylidene fluoride-hexafluoropropylene copolymer, polyvinyl carbonate and lithium bistrifluoromethylsulfonylimide in an organic solvent DMAC (dimethyl amine) in a mass ratio of 70:10:20, uniformly mixing to prepare coating slurry, coating the coating slurry on the surface of the negative electrode sheet in the step 2'), and drying by blowing at 80 ℃ to obtain a functional coating with a thickness of 5 mu m, thus obtaining the negative electrode sheet containing in-situ cured electrolyte and the functional coating;
And 4 ') trimming, cutting and slitting the negative plate obtained in the step 3') to obtain the negative plate of the lithium ion battery.
3. Electrolyte and lithium ion battery preparation: the same as in example 1.
Comparative example 1
1. Preparing a positive plate:
1) Uniformly mixing NCM8 positive electrode (positive electrode active material), conductive agent superconducting carbon (Super-P) and binder polyvinylidene fluoride (PVDF) according to a mass ratio of 97:1.5:1.5 to prepare positive electrode slurry, coating the positive electrode slurry on two surfaces of a current collector aluminum foil, drying at 100 ℃ to form a positive electrode active material layer, and cold pressing to obtain a positive electrode sheet containing the active material layer;
2) And (3) trimming, cutting and slitting the positive plate obtained in the step (1), and taking the positive plate as the positive plate of the lithium ion battery after slitting.
2. Preparing a negative plate:
1') preparing negative electrode slurry from graphite, conductive agent superconducting carbon (Super-P), thickener sodium carboxymethylcellulose (CMC) and binder styrene-butadiene rubber (SBR) according to the mass ratio of 96.5:1.0:1.0:1.5, coating the negative electrode slurry on a current collector copper foil, drying the current collector copper foil at 90 ℃ to form a negative electrode active material layer, and then carrying out cold pressing to obtain a negative electrode sheet containing the negative electrode active material layer;
and 2') trimming, cutting and slitting the negative plate obtained in the step 1) to obtain the negative plate of the lithium ion battery.
3. Electrolyte and lithium ion battery preparation: the same as in example 1.
Comparative example 2
1. Preparing a positive plate containing a functional coating:
1) Uniformly mixing NCM8 positive electrode (positive electrode active material), conductive agent superconducting carbon (Super-P) and binder polyvinylidene fluoride (PVDF) according to a mass ratio of 97:1.5:1.5 to prepare positive electrode slurry, coating the positive electrode slurry on two surfaces of a current collector aluminum foil, drying at 100 ℃ to form a positive electrode active material layer, and cold pressing to obtain a positive electrode sheet containing the active material layer;
2) Dissolving polyvinylidene fluoride-hexafluoropropylene copolymer, polyethylene glycol methyl ether methacrylate and lithium bistrifluoromethyl sulfonyl imide in an organic solvent DMAC (dimethyl Acrylonitrile) in a mass ratio of 70:10:20, uniformly mixing to prepare coating slurry, coating the coating slurry on the surface of an anode active material layer, and drying by blowing at 80 ℃ to obtain a functional coating with a thickness of 6 mu m;
3) And (3) trimming, cutting and slitting the positive plate obtained in the step (2), and taking the positive plate as the positive plate of the lithium ion battery after slitting.
2. Preparing a negative plate: the same as in example 1.
3. Electrolyte and lithium ion battery preparation: the same as in comparative example 1.
Comparative example 3
1. Preparation of positive plate containing in-situ cured electrolyte:
1) Uniformly mixing NCM8 positive electrode (positive electrode active material), conductive agent superconducting carbon (Super-P) and binder polyvinylidene fluoride (PVDF) according to a mass ratio of 97:1.5:1.5 to prepare positive electrode slurry, coating the positive electrode slurry on two surfaces of a current collector aluminum foil, drying at 100 ℃ to form a positive electrode active material layer, and cold pressing to obtain a positive electrode sheet containing the active material layer;
2) Uniformly mixing trimethylolpropane triacrylate, polyaromatic oxadiazole, azodiisobutyronitrile and commercial electrolyte in a mass ratio of 3:1:0.03:95.97 to obtain a uniform precursor solution, and then completely infiltrating the precursor solution into the positive plate containing the active material layer prepared in the step 1) by adopting a spraying mode, and heating at 80 ℃ to perform in-situ curing to obtain the positive plate containing the cured electrolyte layer with the thickness of 6 mu m on the surface;
3) And (3) trimming, cutting and slitting the positive plate containing the solidified electrolyte in the step (2), and taking the positive plate as the positive plate of the lithium ion battery after slitting.
2. Preparation of a negative plate containing in-situ cured electrolyte:
1') preparing negative electrode slurry from negative electrode active substance graphite, conductive agent superconducting carbon (Super-P), thickener sodium carboxymethylcellulose (CMC) and binder styrene-butadiene rubber (SBR) according to the mass ratio of 96.5:1.0:1.0:1.5, coating the negative electrode slurry on a current collector copper foil, drying the current collector copper foil at 90 ℃ to form a negative electrode active substance layer, and then carrying out cold pressing to obtain a negative electrode sheet containing the negative electrode active substance layer;
2 ') uniformly mixing trimethylolpropane triacrylate, polyaromatic oxadiazole, azodiisobutyronitrile and commercial electrolyte in a mass ratio of 3:1:0.03:95.97 to obtain a uniform precursor solution, then completely infiltrating the precursor solution into the negative electrode sheet in the step 1'), and heating at 80 ℃ for in-situ curing to obtain the negative electrode sheet with the surface containing a cured electrolyte layer with the thickness of 6 mu m;
and 3 ') trimming, cutting and slitting the negative plate containing the solidified electrolyte in the step 2') to obtain the negative plate of the lithium ion battery.
3. Electrolyte and lithium ion battery preparation: the same as in example 1.
Comparative example 4
1. Preparation of positive plate containing in-situ cured electrolyte:
1) Uniformly mixing NCM8 positive electrode (positive electrode active material), conductive agent superconducting carbon (Super-P) and binder polyvinylidene fluoride (PVDF) according to a mass ratio of 97:1.5:1.5 to prepare positive electrode slurry, coating the positive electrode slurry on two surfaces of a current collector aluminum foil, drying at 100 ℃ to form a positive electrode active material layer, and cold pressing to obtain a positive electrode sheet containing the active material layer;
2) Uniformly mixing trimethylolpropane triacrylate, polyaromatic oxadiazole, azodiisobutyronitrile and commercial electrolyte in a mass ratio of 3:1:0.03:95.97 to obtain a uniform precursor solution, and then completely infiltrating the precursor solution into the positive plate containing the active material layer prepared in the step 1) by adopting a spraying mode, and heating at 80 ℃ to perform in-situ curing to obtain the positive plate containing the cured electrolyte layer with the thickness of 6 mu m on the surface;
3) And (3) trimming, cutting and slitting the positive plate containing the solidified electrolyte in the step (2), and taking the positive plate as the positive plate of the lithium ion battery after slitting.
2. Preparation of a negative plate containing a functional coating:
1') preparing negative electrode slurry from negative electrode active substance graphite, conductive agent superconducting carbon (Super-P), thickener sodium carboxymethylcellulose (CMC) and binder styrene-butadiene rubber (SBR) according to the mass ratio of 96.5:1.0:1.0:1.5, coating the negative electrode slurry on a current collector copper foil, drying the current collector copper foil at 90 ℃ to form a negative electrode active substance layer, and then carrying out cold pressing to obtain a negative electrode sheet containing the negative electrode active substance layer;
2 ') dissolving polyvinylidene fluoride-hexafluoropropylene copolymer, polyvinyl carbonate and lithium bistrifluoromethylsulfonylimide in an organic solvent DMAC (dimethyl amine) in a mass ratio of 70:10:20, uniformly mixing to prepare coating slurry, coating the coating slurry on the surface of the negative electrode sheet in the step 1'), and drying by blowing at 80 ℃ to obtain a functional coating with a thickness of 5 mu m, thus obtaining the negative electrode sheet containing the functional coating;
and 3') trimming, cutting and slitting the negative plate obtained in the step 2) to obtain the negative plate of the lithium ion battery.
3. Electrolyte and lithium ion battery preparation: the same as in example 1.
Comparative example 5
1. Preparing a positive plate containing a functional coating:
1) Uniformly mixing NCM8 positive electrode (positive electrode active material), conductive agent superconducting carbon (Super-P) and binder polyvinylidene fluoride (PVDF) according to a mass ratio of 97:1.5:1.5 to prepare positive electrode slurry, coating the positive electrode slurry on two surfaces of a current collector aluminum foil, drying at 100 ℃ to form a positive electrode active material layer, and cold pressing to obtain a positive electrode sheet containing the active material layer;
2) Dissolving polyvinylidene fluoride-hexafluoropropylene copolymer, polyvinyl carbonate and lithium bistrifluoromethylsulfonyl imide in an organic solvent DMAC (dimethyl Acrylonitrile) in a mass ratio of 70:10:20, uniformly mixing to prepare coating slurry, coating the coating slurry on the surface of a positive plate, and drying by blowing at 80 ℃ to obtain a functional coating with a thickness of 10 mu m, thus obtaining the positive plate only comprising the functional coating;
3) And (3) trimming, cutting and slitting the positive plate obtained in the step (2), and taking the positive plate as the positive plate of the lithium ion battery after slitting.
2. Preparation of a negative plate containing in-situ cured electrolyte and a functional coating:
1') preparing negative electrode slurry from graphite, conductive agent superconducting carbon (Super-P), thickener sodium carboxymethylcellulose (CMC) and binder styrene-butadiene rubber (SBR) according to the mass ratio of 96.5:1.0:1.0:1.5, coating the negative electrode slurry on a current collector copper foil, drying the current collector copper foil at 90 ℃ to form a negative electrode active material layer, and then carrying out cold pressing to obtain a negative electrode sheet containing the negative electrode active material layer;
2 ') uniformly mixing polyethylene glycol diacrylate, polyaromatic oxadiazole, azodiisobutyronitrile and commercial electrolyte in a mass ratio of 3:1:0.03:95.97 to obtain a uniform precursor solution, then completely soaking the cathode sheet in the step 1') in the precursor solution by adopting a spraying mode, heating at 80 ℃ to cure the precursor solution, and controlling the thickness of a cured electrolyte layer on the surface of the electrode sheet to be 5 mu m to obtain the cathode sheet containing the cured electrolyte;
3 ') dissolving polyvinylidene fluoride-hexafluoropropylene copolymer, polyvinyl carbonate and lithium bistrifluoromethylsulfonylimide in an organic solvent DMAC (dimethyl amine) in a mass ratio of 70:10:20, uniformly mixing to prepare coating slurry, coating the coating slurry on the surface of the negative electrode sheet in the step 2'), and drying by blowing at 80 ℃ to obtain a functional coating with the thickness of 10 mu m, thus obtaining the negative electrode sheet containing in-situ cured electrolyte and the functional coating;
and 4 ') trimming, cutting and slitting the negative plate obtained in the step 3') to obtain the negative plate of the lithium ion battery.
3. Electrolyte and lithium ion battery preparation: the same as in example 1.
Comparative example 6
1. Preparing a positive plate containing a functional coating:
1) Uniformly mixing NCM8 positive electrode (positive electrode active material), conductive agent superconducting carbon (Super-P) and binder polyvinylidene fluoride (PVDF) according to a mass ratio of 97:1.5:1.5 to prepare positive electrode slurry, coating the positive electrode slurry on two surfaces of a current collector aluminum foil, drying at 100 ℃ to form a positive electrode active material layer, and cold pressing to obtain a positive electrode sheet containing the active material layer;
2) Dissolving polyvinylidene fluoride-hexafluoropropylene copolymer, polyvinyl carbonate and lithium bistrifluoromethylsulfonyl imide in an organic solvent DMAC (dimethyl Acrylonitrile) in a mass ratio of 60:10:30, uniformly mixing to prepare coating slurry, coating the coating slurry on the surface of a positive plate, and drying by blowing at 80 ℃ to obtain a functional coating with a thickness of 5 mu m, thus obtaining the positive plate containing the functional coating;
3) And (3) trimming, cutting and slitting the positive plate obtained in the step (2), and taking the positive plate as the positive plate of the lithium ion battery after slitting.
2. Preparing a negative plate containing in-situ cured electrolyte and a functional coating:
1') preparing negative electrode slurry from graphite, conductive agent superconducting carbon (Super-P), thickener sodium carboxymethylcellulose (CMC) and binder styrene-butadiene rubber (SBR) according to the mass ratio of 96.5:1.0:1.0:1.5, coating the negative electrode slurry on a current collector copper foil, drying the current collector copper foil at 90 ℃ to form a negative electrode active material layer, and then carrying out cold pressing to obtain a negative electrode sheet containing the negative electrode active material layer;
2 ') uniformly mixing trimethylolpropane triacrylate, polyaromatic oxadiazole, azodiisobutyronitrile and commercial electrolyte in a mass ratio of 3:1:0.03:95.97 to obtain a uniform precursor solution, and then completely soaking the cathode sheet in the step 1') in the precursor solution by adopting a spraying mode, heating at 80 ℃ to cure the precursor solution, and controlling the thickness of a cured electrolyte layer on the surface of the electrode sheet to be 1 mu m to obtain the cathode sheet containing the cured electrolyte;
3 ') dissolving polyvinylidene fluoride-hexafluoropropylene copolymer, polyvinyl carbonate and lithium bistrifluoromethylsulfonylimide in an organic solvent DMAC (dimethyl amine) according to the mass ratio of 60:10:30, uniformly mixing to prepare coating slurry, coating the coating slurry on the surface of the negative electrode sheet in the step 2'), and drying by blowing at 80 ℃ to obtain a functional coating with the thickness of 5 mu m, thus obtaining the negative electrode sheet containing in-situ cured electrolyte and the functional coating;
4') trimming, cutting and slitting the negative plate obtained in the step 3) to obtain the negative plate of the lithium ion battery
3. Electrolyte and lithium ion battery preparation: the same as in example 1.
Test case
Performance test:
the lithium ion batteries prepared in the above examples and comparative examples were subjected to a needling test, a heating test, and an internal resistance and capacity test. (since NCM8 was used as the positive electrode active material in each of examples and comparative examples, the 100% SOC cutoff voltage was set to 4.2V, and when other materials such as lithium cobaltate and lithium manganate were used as the positive electrode, the cutoff voltage was adjusted to the corresponding cutoff voltage.)
1. Needling test conditions: in the testing environment of (25+/-5) DEG C, the battery is fully charged to 4.2V, a high temperature resistant steel needle with the diameter phi of 5mm (the conical angle of the needle point is 45-60 DEG, the surface of the needle is smooth and clean, no rust, no oxide layer and no greasy dirt) penetrates from the direction vertical to the large surface of the battery at the speed of (25+/-5) mm/s, the penetrating position is preferably close to the geometric center of the penetrated surface, and the steel needle stays in the battery core. The battery was observed for ignition, explosion, and the temperature rise and pressure drop of the battery were recorded.
2. Heating test conditions: charging 0.5C to upper limit voltage at 25+ -5deg.C, stopping 0.05C, standing for 10min, placing in a thermal shock test box, heating to 150deg.C at 5+ -2deg.C/min, maintaining for 60min, and monitoring whether fire is in failure. And if the battery does not fire, the heating test is qualified.
3. Internal resistance test: obtained by electrochemical impedance spectroscopy analysis.
4. Capacity test: in a test environment of (25+/-5) DEG C, charging to 4.2V (100% SOC) at a constant current of 0.33C, standing for 10min, discharging to 2.8V at a constant current of 0.33C, and recording the discharge capacity as C 0 Standing for 10min, charging to 4.2V (100% SOC) at constant current of 0.33C, standing for 10min, discharging to 2.8V at constant current of 1C, and recording the discharge capacity as C 1 。
The results of the above tests are shown in Table 1.
TABLE 1
From the test results of example 1, it can be seen that the lithium ion battery prepared from the electrode sheet comprising the in-situ cured electrolyte and the functional coating did not fire during needling and exhibited lower temperature rise and pressure drop. While the positive and negative electrode sheets of comparative example 1 were not modified at all, the battery prepared therefrom was ignited by needling, and the temperature rise reached 563 c, the voltage was reduced to almost zero, and the ignition occurred under overheat conditions. Therefore, the lithium ion battery prepared by the pole piece containing the in-situ cured electrolyte and the functional coating has higher safety under the needling and overheating conditions, and the in-situ cured electrolyte and the functional coating have obvious improvement on the safety under the needling and overheating conditions.
In comparative example 2, the positive electrode sheet contained only the functional coating layer, without any other modification. As can be seen from table 1, the battery of comparative example 2 did not fire under the needling condition and had a low temperature rise, but did fire under the overheating condition; it can thus be seen that the in situ curing electrolyte plays a decisive role in the safety of heating.
The positive and negative electrode sheets of comparative example 3 both contained an in-situ cured electrolyte, but neither had a functional coating. As can be seen from table 1, the battery of comparative example 3 did not fire under the overheat condition of the battery, but the battery did fire under the needling condition. It can thus be seen that the functional coating plays a decisive role for the needle punching safety.
Comparative example 4 positive electrode sheet contained in-situ cured electrolyte and negative electrode sheet contained functional coating, as seen from table 1, the battery was on fire under overheat conditions, but no fire by needling and only low temperature rise and pressure drop. Therefore, the positive electrode and the negative electrode are required to contain solidified electrolyte so as to ensure that no fire occurs under the heating condition.
Compared with example 1, the positive electrode sheet in example 2 has reduced thickness of the functional coating, the functional coating has a thickness of 5 μm, and it can be seen that under the heating and needling test, the battery of example 2 still does not generate fire, and the internal resistance is reduced, so that the electrical performance is better. Therefore, the thickness of the functional coating is properly reduced, and the electrical performance can be improved under the condition of ensuring safety.
Example 3 is an in-situ cured electrolyte without the addition of conductive polymer, and it can be seen that no ignition still occurs under heating and needling, but the internal resistance increases and the electrical properties slightly decrease compared to the battery of example 2. Therefore, the in-situ solidified electrolyte is free of conductive agent, the electronic conduction in the pole piece is slightly reduced, and the electric performance is affected to a certain extent.
In example 4, the monomer content of the in-situ curable electrolyte was increased as compared with example 2, and it can be seen that although the battery did not fire during the heating and needling test, the internal resistance was slightly increased and the electrical properties were affected. Therefore, when the monomer is excessively added, the ion conductivity of the in-situ curing electrolyte is reduced, the internal resistance is increased, and the electric performance is influenced to a certain extent.
As can be seen from the results of table 1, the battery of example 5 still did not fire but had an increased internal resistance and slightly decreased electrical properties under heating and needling, as compared to example 2, in which the thickness of the in-situ cured electrolyte coating of the positive and negative electrode sheets was increased to 5 μm. Therefore, the thickness of the in-situ cured electrolyte on the electrode plate is reduced as much as possible on the premise of ensuring the safety.
As can be seen from table 1, the battery internal resistance of example 6 is smaller, which means that increasing lithium salt can increase ion conductance, facilitating lithium ion transport, but it is also recognized that increasing lithium salt can result in increased cost and more severe environmental requirements in the preparation process, as compared with example 2.
Compared with example 2, the positive and negative electrode sheets of example 7 both contain in-situ cured electrolyte and functional coating, and as can be seen from table 1, no ignition still occurs under heating and needling, the temperature rise and pressure drop are lower, but the internal resistance is significantly increased, and the electrical performance is reduced. While example 7 is comparable to example 1 in internal resistance, but has slightly reduced electrical properties. Therefore, when the positive electrode plate and the negative electrode plate both contain functional coatings, the function of the overall insulation characteristic of the battery is increased, and the electrical performance of the battery is influenced to a certain extent.
The positive electrode sheet of example 8 had only the in-situ cured electrolyte, while the negative electrode contained the in-situ cured electrolyte and the functional coating, compared to example 2, it was found that the needling safety of the battery could be ensured regardless of whether the functional coating was on the positive electrode or the negative electrode.
Compared to example 8, the positive electrode sheet of comparative example 5 replaced the in-situ cured electrolyte with a functional coating; the thickness of the functional coating of comparative example 6 was reduced as compared to comparative example 5. It can be seen that the increase or decrease of the overall functional coating thickness of the battery is a major cause of the increase or decrease of the internal resistance of the battery, and thus it is required to reduce the overall functional coating thickness in the battery while ensuring the safety of the battery.
The above description has been given of exemplary embodiments of the present invention. However, the present invention is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, or the like, which are within the spirit and principles of the present invention, should be made by those skilled in the art, and are intended to be included within the scope of the present invention.
Claims (10)
1. An electrode sheet, characterized in that the electrode sheet comprises: current collector, active material layer, electrolyte and functional coating; wherein,,
the current collector has two opposing surfaces;
the active material layer is disposed on at least one surface of the current collector;
the electrolyte is arranged inside and/or on the surface of the active material layer; the electrolyte is a solid electrolyte; the electrolyte includes a first polymer and an electrolyte solution dispersed therein; the first polymer is at least one selected from polymethyl methacrylate or a copolymer thereof, polyhydroxyethyl methacrylate or a copolymer thereof, polyethylene glycol diacrylate or a copolymer thereof, polytrimethylolpropane triacrylate or a copolymer thereof, polybutyl acrylate or a copolymer thereof, polyvinyl n-butyl ether or a copolymer thereof, or polyethyl acetate or a copolymer thereof;
The functional coating is disposed on the active material layer including the electrolyte; the functional coating consists of the following components in percentage by mass: 30-80 wt% of a second polymer, 0-50wt% of a plasticizer and 0-50wt% of lithium salt.
2. The electrode sheet of claim 1, wherein the electrolyte further comprises a conductive polymer.
3. The electrode sheet of claim 1, wherein the electrolyte comprises at least a lithium salt and a solvent.
4. The electrode sheet according to claim 2, wherein the conductive polymer is at least one selected from the group consisting of polyarenoxadiazole, polythiophene, polypyrrole, polyaniline.
5. The electrode sheet according to claim 1, wherein the functional coating has a thickness of 0.1 μm to 20 μm.
6. The electrode sheet of claim 1, wherein the second polymer comprises at least one of polyvinylidene fluoride, polyvinyl alcohol, polytetrafluoroethylene, polyvinylidene fluoride-hexafluoropropylene copolymer, polymethyl methacrylate;
and/or the plasticizer comprises a small molecular material, wherein the small molecular material comprises at least one of polyvinyl carbonate, ethylene carbonate, succinonitrile, methyl methacrylate and polyethylene glycol methyl ether methacrylate;
And/or the lithium salt comprises at least one of lithium bis (trifluoromethylsulfonyl) imide, lithium bis (difluorosulfonyl) imide, lithium bis (oxalato) borate and lithium difluoro (oxalato) borate.
7. The electrode sheet according to any one of claims 1 to 6, wherein the active material layer includes an active material, a binder, and a conductive agent.
8. The electrode sheet of claim 7, wherein in the active material layer, the active material layer further comprises a thickener comprising sodium carboxymethyl cellulose.
9. The electrode sheet according to any one of claims 1 to 6, wherein, when the electrode sheet is used for a positive electrode, a current collector is selected from positive electrode current collectors in the electrode sheet, and the active material layer includes a positive electrode active material;
and/or, when the electrode sheet is used for a negative electrode, in the electrode sheet, a current collector is selected from negative electrode current collectors, and the active material layer includes a negative electrode active material.
10. A lithium ion battery comprising a positive electrode sheet, a negative electrode sheet, and a separator and an electrolyte, the separator being disposed between the positive electrode and the negative electrode, wherein the positive electrode sheet and the negative electrode sheet are selected from the electrode sheets of any one of claims 1-9 independently of each other.
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| CN115411228A (en) * | 2022-11-01 | 2022-11-29 | 江苏贝特瑞纳米科技有限公司 | Lithium iron manganese phosphate positive plate and preparation method thereof |
| CN116111038A (en) * | 2023-04-12 | 2023-05-12 | 四川新能源汽车创新中心有限公司 | Electrode plate, preparation method thereof and lithium battery |
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| CN113488609A (en) * | 2021-06-07 | 2021-10-08 | 东莞塔菲尔新能源科技有限公司 | Safety coating, electrode plate, preparation method of electrode plate and lithium ion battery |
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