CN116613375A - In-situ cured electrolyte, in-situ solid-state battery containing same and preparation method of in-situ cured electrolyte - Google Patents
In-situ cured electrolyte, in-situ solid-state battery containing same and preparation method of in-situ cured electrolyte Download PDFInfo
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- CN116613375A CN116613375A CN202310617308.XA CN202310617308A CN116613375A CN 116613375 A CN116613375 A CN 116613375A CN 202310617308 A CN202310617308 A CN 202310617308A CN 116613375 A CN116613375 A CN 116613375A
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- Prior art keywords
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- lithium
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- electrolyte
- battery
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- 238000011065 in-situ storage Methods 0.000 title claims abstract description 119
- 239000003792 electrolyte Substances 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 64
- 239000002994 raw material Substances 0.000 claims abstract description 57
- 239000000178 monomer Substances 0.000 claims abstract description 55
- -1 styrene compound Chemical class 0.000 claims abstract description 55
- 239000000654 additive Substances 0.000 claims abstract description 53
- 230000000996 additive effect Effects 0.000 claims abstract description 47
- 239000003999 initiator Substances 0.000 claims abstract description 47
- 239000003960 organic solvent Substances 0.000 claims abstract description 39
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 28
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 28
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 28
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 239000004593 Epoxy Substances 0.000 claims abstract description 5
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 3
- 229940092714 benzenesulfonic acid Drugs 0.000 claims abstract description 3
- 229920000768 polyamine Polymers 0.000 claims abstract description 3
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 3
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 3
- 239000006258 conductive agent Substances 0.000 claims description 41
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 29
- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 claims description 24
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 24
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 21
- 239000002033 PVDF binder Substances 0.000 claims description 17
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 17
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 17
- 229910052744 lithium Inorganic materials 0.000 claims description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 15
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000009461 vacuum packaging Methods 0.000 claims description 13
- 239000007774 positive electrode material Substances 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- 239000007773 negative electrode material Substances 0.000 claims description 10
- 238000004806 packaging method and process Methods 0.000 claims description 9
- 239000011883 electrode binding agent Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 4
- 239000005057 Hexamethylene diisocyanate Substances 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
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 239000004917 carbon fiber Substances 0.000 claims description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 claims description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 4
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 125000004386 diacrylate group Chemical group 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 claims description 2
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 claims description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 2
- LWRXNMLZNDYFAW-UHFFFAOYSA-N 1-octylperoxyoctane Chemical compound CCCCCCCCOOCCCCCCCC LWRXNMLZNDYFAW-UHFFFAOYSA-N 0.000 claims description 2
- PITQFWWNUHMYIC-UHFFFAOYSA-N 1-tert-butyl-4-(4-tert-butylcyclohexyl)peroxycyclohexane Chemical compound C1CC(C(C)(C)C)CCC1OOC1CCC(C(C)(C)C)CC1 PITQFWWNUHMYIC-UHFFFAOYSA-N 0.000 claims description 2
- TVWBTVJBDFTVOW-UHFFFAOYSA-N 2-methyl-1-(2-methylpropylperoxy)propane Chemical compound CC(C)COOCC(C)C TVWBTVJBDFTVOW-UHFFFAOYSA-N 0.000 claims description 2
- NFPBWZOKGZKYRE-UHFFFAOYSA-N 2-propan-2-ylperoxypropane Chemical compound CC(C)OOC(C)C NFPBWZOKGZKYRE-UHFFFAOYSA-N 0.000 claims description 2
- SJHAYVFVKRXMKG-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2-oxide Chemical compound CC1COS(=O)O1 SJHAYVFVKRXMKG-UHFFFAOYSA-N 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- YUEDZVRMWQBEPT-UHFFFAOYSA-N CC1=CC=CC(C(C2=CC=CC=C2)C2=CC=CC=C2)=C1C.N=C=O.N=C=O.N=C=O.N=C=O Chemical compound CC1=CC=CC(C(C2=CC=CC=C2)C2=CC=CC=C2)=C1C.N=C=O.N=C=O.N=C=O.N=C=O YUEDZVRMWQBEPT-UHFFFAOYSA-N 0.000 claims description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 2
- 229910000733 Li alloy Inorganic materials 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- QORUGOXNWQUALA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 Chemical compound N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 QORUGOXNWQUALA-UHFFFAOYSA-N 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 claims description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 2
- 150000007973 cyanuric acids Chemical class 0.000 claims description 2
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 claims description 2
- FYLJKQFMQFOLSZ-UHFFFAOYSA-N cyclohexylperoxycyclohexane Chemical compound C1CCCCC1OOC1CCCCC1 FYLJKQFMQFOLSZ-UHFFFAOYSA-N 0.000 claims description 2
- ZFTFAPZRGNKQPU-UHFFFAOYSA-N dicarbonic acid Chemical compound OC(=O)OC(O)=O ZFTFAPZRGNKQPU-UHFFFAOYSA-N 0.000 claims description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 2
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- 229910021385 hard carbon Inorganic materials 0.000 claims description 2
- 238000003475 lamination Methods 0.000 claims description 2
- 239000001989 lithium alloy Substances 0.000 claims description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 claims description 2
- BDKWOJYFHXPPPT-UHFFFAOYSA-N lithium dioxido(dioxo)manganese nickel(2+) Chemical compound [Mn](=O)(=O)([O-])[O-].[Ni+2].[Li+] BDKWOJYFHXPPPT-UHFFFAOYSA-N 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 2
- 238000003466 welding Methods 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 10
- 150000003384 small molecules Chemical class 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 34
- 239000011230 binding agent Substances 0.000 description 32
- 239000006229 carbon black Substances 0.000 description 28
- 238000005755 formation reaction Methods 0.000 description 22
- 239000002904 solvent Substances 0.000 description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 14
- 239000011149 active material Substances 0.000 description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 14
- 229910052782 aluminium Inorganic materials 0.000 description 14
- 239000011889 copper foil Substances 0.000 description 14
- 239000011888 foil Substances 0.000 description 14
- 239000002391 graphite-based active material Substances 0.000 description 13
- 238000002156 mixing Methods 0.000 description 13
- 239000007788 liquid Substances 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- 239000007784 solid electrolyte Substances 0.000 description 8
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000011244 liquid electrolyte Substances 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 239000007772 electrode material Substances 0.000 description 5
- 239000011267 electrode slurry Substances 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000002161 passivation Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 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 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000977 initiatory effect Effects 0.000 description 4
- 238000009830 intercalation Methods 0.000 description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 2
- ZAYGISOXMIXWHX-UHFFFAOYSA-N 2-methylpropoxycarbonyloxy 2-methylpropyl carbonate Chemical compound CC(C)COC(=O)OOC(=O)OCC(C)C ZAYGISOXMIXWHX-UHFFFAOYSA-N 0.000 description 2
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000000853 adhesive Substances 0.000 description 2
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- 238000005520 cutting process Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 229940018564 m-phenylenediamine Drugs 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000011076 safety test Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- JHRWWRDRBPCWTF-OLQVQODUSA-N captafol Chemical compound C1C=CC[C@H]2C(=O)N(SC(Cl)(Cl)C(Cl)Cl)C(=O)[C@H]21 JHRWWRDRBPCWTF-OLQVQODUSA-N 0.000 description 1
- 239000002388 carbon-based active material Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011066 ex-situ storage Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
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- 239000007924 injection Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical group CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007717 redox polymerization reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Secondary Cells (AREA)
Abstract
The invention provides an in-situ solidified electrolyte, an in-situ solid-state battery containing the same and a preparation method thereof, wherein the preparation raw materials of the in-situ solidified electrolyte comprise a combination of a monomer, an additive, an initiator, an organic solvent and lithium salt; the additive comprises any one or a combination of at least two of aliphatic polyamine, epoxy compound, polyisocyanate, styrene compound or benzenesulfonic acid compound. The selected monomer and additive can be polymerized to form a polymer at normal temperature to form an in-situ cured electrolyte, so that the safety performance of the battery is improved; and the added small molecules can participate in SEI film formation, and after normal temperature formation, due to the existence of polymer components, the formed SEI film is more compact, the internal resistance of the battery is reduced, and the electrical performance is improved.
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to an in-situ solidified electrolyte, an in-situ solid-state battery containing the same and a preparation method of the in-situ solid-state battery.
Background
In recent years, fire and explosion accidents caused by power batteries are frequent, and in order to realize large-scale popularization of electric automobiles, improvement of energy density and safety of lithium ion batteries has become the most important research direction at present.
In the first charge and discharge process of the liquid lithium ion battery, the electrode material reacts with the electrolyte on the solid-liquid phase interface to form a passivation layer covering the surface of the electrode material. The passivation layer is an interface layer, has the characteristic of solid electrolyte, is an electronic insulator but is an excellent conductor of lithium ions, and lithium ions can be freely inserted and extracted through the passivation layer, so that the passivation layer is called a solid electrolyte interface film (solid electrolyte interface), and is called an SEI film for short. The formation of the SEI film has a critical influence on the performance of the electrode material. On one hand, the formation of the SEI film consumes part of lithium ions, so that the irreversible capacity for the first charge and discharge is increased, and the charge and discharge efficiency of the electrode material is reduced; on the other hand, the SEI film has the insolubility of an organic solvent, can exist stably in an organic electrolyte solution, and solvent molecules cannot pass through the passivation film, so that co-intercalation of the solvent molecules can be effectively prevented, and damage to an electrode material caused by co-intercalation of the solvent molecules is avoided. Therefore, there is a need for improving the composition structure and stability of the SEI film, and improving the cycle life, stability, self-discharge property, safety, and the like of the battery. The common film forming additives of Vinylene Carbonate (VC) and fluoroethylene carbonate (FEC) can improve the cycle performance of the battery, and the main principle is that VC can be decomposed on the surface of graphite to generate a polyalkyl lithium carbonate film, so that reduction of solvent and salt anions is inhibited, and an SEI film is formed on the surface of a negative electrode. However, the volume expansion is generated in the lithium intercalation process of the negative electrode, so that the SEI film is damaged, and residual VC and free radicals generated by the decomposition of the VC are subjected to polymerization reaction, so that polymerized VC is generated at the damaged SEI film, and the impedance of the battery is increased.
The in-situ polyelectrolyte is prepared by adding a polymer monomer and an initiator into a liquid electrolyte to form a solid electrolyte precursor, and in-situ initiating the polymerization of monomer molecules by a precursor solution under certain external conditions (such as thermal initiation, ultraviolet initiation, gamma rays and the like) to obtain the polymer electrolyte capable of conducting lithium ions. Because the precursor before solidification has better wettability to the electrode like liquid electrolyte, the gap between the electrolyte and the electrode after polymerization is reduced, and the interface contact can be improved to a certain extent relative to the electrolyte solidified in an ex-situ manner. The precursor is injected into the battery core in the same liquid injection mode of the liquid battery, and a closed system is formed after packaging, so that the thermal initiation is the most suitable polymerization mode. Considering that the material system, the production process and the application technology of the all-solid-state battery are not mature, and are not fully verified, the mass production cannot be realized in a short period of time. In-situ curing technology not only can improve interface contact and promote electrochemical performance of a solid-state battery, but also can be mostly compatible with liquid battery materials, equipment and processes, once the material is mature and mass production is realized, the cost can be basically equal to or even lower than that of the existing liquid battery, industrialization can be realized first, and mass production of the solid-state battery is realized.
CN115911574a relates to an in-situ cured solid-liquid mixed electrolyte and a lithium ion battery, and provides an in-situ cured solid-liquid mixed electrolyte, which comprises polymer monomer, cross-linking agent, thermal initiator and liquid electrolyte, wherein the mass ratio of the polymer monomer to the cross-linking agent to the thermal initiator to the liquid electrolyte is (10-30): 1 (0.05-0.2): 40-120), the polymer monomer comprises polyethylene glycol diacrylate and/or polyethylene glycol monomethyl ether acrylate, the liquid electrolyte comprises organic solvent and lithium salt, the in-situ cured solid-liquid mixed electrolyte has a certain inhibition effect on battery expansion, and can also obviously inhibit battery internal resistance from increasing, and improve normal temperature and high temperature cycle performance and safety performance of the battery, but the curing in the preparation method requires heating, and has larger energy consumption.
CN111786017a relates to a high-cohesiveness solid electrolyte raw material mainly comprising an oligomer containing hydroxyl, a compound containing isocyanate groups and lithium salt, wherein the high-cohesiveness solid electrolyte is prepared by mixing and stirring the oligomer containing hydroxyl groups, the compound containing isocyanate groups and the lithium salt uniformly, adding the mixture into a battery core, and carrying out in-situ polymerization and solidification under heating conditions. The preparation process of the solid-state lithium battery is greatly simplified, interface contact is optimized, dislocation danger is prevented, the safety of the battery is improved, and the prepared battery has poor electrical performance.
CN111490287a relates to a solid electrolyte, which is obtained by in-situ polymerization of a mixed solution comprising lithium salt, an organic solvent, an additive and an initiator, wherein the organic solvent comprises a base solvent and a functional solvent, the functional solvent is a phosphazene solvent, and the additive is a monomer containing unsaturated bonds. A solid-state battery containing the solid-state electrolyte and a method for producing the same, comprising the steps of: 1) Mixing lithium salt, an organic solvent, an additive and an initiator to obtain a mixed solution; 2) Injecting the mixed solution into a battery, heating the mixed solution for 1-5 hours at 60-85 ℃ after the mixed solution is fully soaked, and enabling the mixed solution to undergo in-situ polymerization reaction to form a solid electrolyte; 3) The battery is subjected to formation, degassing and vacuum packaging to complete the preparation of the solid-state battery, and the solid-state electrolyte and the solid-state battery have excellent cycle performance and safety performance, but the preparation method of the solid-state battery needs heating and has high energy consumption.
The electrolyte in the prior art has the problems of poor safety performance, poor electrical performance and heating in the preparation process. Therefore, developing an in-situ cured electrolyte with good safety performance, good electrical performance and low energy consumption in the preparation process so as to meet the application requirements of lithium ion batteries is a problem to be solved in the field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an in-situ solidified electrolyte, an in-situ solid battery containing the same and a preparation method thereof, wherein selected monomers and additives can be polymerized to form a polymer at normal temperature to form the in-situ solidified electrolyte, so that the safety performance of the battery is improved; and the added small molecules can participate in SEI film formation, so that the density and stability of the formed SEI film are improved, the cycle performance and high-temperature storage performance are improved, and the electrical performance of the battery is improved.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a cured in place electrolyte, the preparation raw materials of which comprise a combination of monomers, additives, initiators, organic solvents and lithium salts; the additive comprises any one or a combination of at least two of aliphatic polyamine, epoxy compound, polyisocyanate, styrene compound or benzenesulfonic acid compound.
In the in-situ curing electrolyte provided by the invention, the curing reaction can be carried out at normal temperature by adding specific types of monomers and additives, so that the safety performance of the battery is improved; meanwhile, the monomer and additive small molecules used in combination with normal temperature formation can also participate in SEI film generation to form a compact, stable and low-impedance SEI film, so that the electrical property of the battery is improved.
Preferably, the additive comprises any one or a combination of at least two of diethylenetriamine, epoxy cyanurates, hexamethylene diisocyanate, dimethyltriphenylmethane tetraisocyanate, triphenylmethane triisocyanate, styrene, a-methylstyrene, p-toluenesulfonic acid or p-toluenesulfonyl chloride.
Preferably, the mass percentage of the additive in the preparation raw material is 1-15%, for example, 1%, 3%, 5%, 8%, 10%, 12%, 15%, and the specific point values among the above point values are limited to the space and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the range.
Preferably, the monomer comprises any one or a combination of at least two of acrylic acid, methacrylic acid, methyl methacrylate, pentaerythritol tetraacrylate, polyethylene glycol diacrylate, pentaerythritol triacrylate, acrylonitrile, ethylene carbonate, ethylene oxide or 1, 3-dioxolane.
Preferably, the mass percentage of the monomer in the preparation raw material is 2-15%, for example, may be 2%, 3%, 5%, 8%, 10%, 12%, 15%, and the specific point values among the above point values are limited in space and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the range.
The initiator may be present in an amount of 0.1 to 1.5% by mass of the monomer, for example, 0.1%, 0.3%, 0.5%, 0.8%, 1%, 1.2%, 1.5%, and specific point values between the above point values, although the specific point values are included in the range for brevity and for brevity, the present invention is not intended to be exhaustive.
Preferably, the initiator comprises any one or a combination of at least two of bis (2, 4-dichlorobenzoyl) peroxide, diacetyl peroxide, dioctyl peroxide, dilauroyl peroxide, dicarbonate, diisopropyl peroxide, diisobutyl peroxide, dicyclohexyl peroxide or bis (p-tert-butylcyclohexyl) peroxide.
Preferably, the organic solvent comprises any one or a combination of at least two of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate, gamma-butyrolactone, methyl formate, dimethoxymethane, acetonitrile, cyclohexylbenzene, propylene sulfite or ethylene sulfate.
Preferably, the mass percentage of the organic solvent in the preparation raw material is 53.5-95.9%, for example, 53.5%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95.9%, and the specific point values between the above point values, which are limited in space and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the range.
Preferably, the lithium salt comprises any one or a combination of at least two of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium bis (difluorosulfonimide), lithium bis (trifluoromethylsulfonimide), lithium bis (oxalato) borate, lithium difluoro (oxalato) borate, or lithium bis (oxalato) borate.
Preferably, the content of lithium salt in the preparation raw material is 1-15% by mass, for example, may be 1%, 3%, 5%, 8%, 10%, 12%, 15%, and specific point values among the above point values, which are limited in space and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the range.
Preferably, the concentration of the lithium salt in the preparation raw material is 0.2 to 3mol/L, for example, may be 0.2mol/L, 0.5mol/L, 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L, 3mol/L, and specific point values among the above point values are limited in terms of space and for the sake of brevity, and the present invention is not exhaustive to list the specific point values included in the range.
Preferably, the preparation of the in situ cured electrolyte is performed in a glove box.
Preferably, the glove box has an oxygen content of < 0.1ppm and a moisture content of < 0.1ppm.
In a second aspect, the present invention provides an in-situ solid state battery comprising the in-situ solid state electrolyte of the first aspect.
In a third aspect, the present invention provides a method for preparing an in-situ solid-state battery according to the second aspect, the method comprising the steps of:
(1) Assembling the positive electrode plate, the negative electrode plate and the diaphragm to obtain an electric core;
(2) Injecting the preparation raw material of the in-situ solidified electrolyte in the first aspect into the battery core obtained in the step (1), standing and packaging, and solidifying and forming at normal temperature to obtain the in-situ solid-state battery.
The term "normal temperature" in normal temperature curing and normal temperature formation in the invention means that the temperature is 22-28 ℃.
The invention has simple and effective process, can use the existing equipment for manufacturing and detecting the battery core, has industrial amplifying prospect, does not need high temperature for curing and formation, reduces energy consumption, can be used for different in-situ curing precursors and different battery systems, and has wide applicability.
The monomer, additive and initiator undergo free radical polymerization and redox polymerization if the additive is a tertiary amine, forming an in situ cured electrolyte. The monomer and additive have double bond and unsaturated bond in small molecule, and can be used for pre-generating SEI film to form ROCOOLi as SEI film main component, such as (CH) 2 OCOOLi) 2 、LiCH 2 CH 2 OCO 2 Li、CH 3 OCO 2 Li and the like, and the SEI film formed after formation is more uniform and compact.
Preferably, the positive electrode sheet in the step (1) includes a positive electrode current collector and a positive electrode material layer disposed on a surface of the positive electrode current collector, and the positive electrode material layer includes a combination of a positive electrode active material, a positive electrode conductive agent, and a positive electrode binder.
Preferably, the positive electrode active material includes any one or a combination of at least two of lithium iron phosphate, lithium cobalt oxide, lithium manganate, lithium nickel manganate, ternary nickel cobalt manganese, or ternary nickel cobalt aluminum.
Preferably, the positive electrode conductive agent includes any one or a combination of at least two of conductive carbon black, conductive graphite, carbon fiber or carbon nanotube.
Preferably, the positive electrode binder comprises polyvinylidene fluoride.
Preferably, the positive electrode material layer further includes a solvent.
Preferably, the solvent comprises N-methylpyrrolidone.
Preferably, the positive electrode material layer includes 90-98 parts of positive electrode active material, 2-4 parts of conductive agent, and 1-5 parts of binder.
Preferably, the preparation of the positive electrode sheet in the step (1) includes: and mixing 90-98 parts of positive electrode active material, 2-4 parts of conductive agent, 1-5 parts of binder and solvent uniformly, and obtaining the positive electrode slurry with 70% of solid content. And then uniformly coating the slurry on the two sides of the positive electrode current collector, and drying, rolling, cutting and the like to obtain the required positive electrode plate.
Preferably, the negative electrode tab in step (1) includes a negative electrode current collector and a negative electrode material layer disposed on a surface of the negative electrode current collector, and the negative electrode material layer includes a combination of a negative electrode active material, a negative electrode conductive agent, and a negative electrode binder.
Preferably, the negative active material includes any one or a combination of at least two of metallic lithium, metallic lithium alloy, graphite, hard carbon, silicon carbon, tin-based, or silicon oxygen materials.
Preferably, the negative electrode conductive agent includes any one or a combination of at least two of conductive carbon black, conductive graphite, carbon fiber or carbon nanotube.
Preferably, the negative electrode binder includes any one or a combination of at least two of polyvinyl alcohol, polyacrylic acid, styrene-butadiene rubber, or sodium carboxymethyl cellulose.
Preferably, the anode material layer further includes a solvent.
Preferably, the solvent comprises deionized water.
Preferably, the negative electrode material layer includes 90-98 parts of a negative electrode active material, 2-4 parts of a conductive agent, and 1-5 parts of a binder.
Preferably, the preparation of the negative electrode piece in the step (1) includes: and mixing 90-98 parts of anode active material, 2-4 parts of conductive agent, 1-5 parts of binder and solvent uniformly, and obtaining the anode slurry with the solid content of 50%. And then uniformly coating the slurry on the two sides of the positive current collector, and drying, rolling, cutting and the like to obtain the required negative electrode plate.
Preferably, the method of assembling in step (1) specifically comprises: and (3) the positive pole piece, the negative pole piece and the diaphragm are subjected to lamination, lug welding, top sealing and side sealing to obtain the battery cell.
Preferably, the standing in the step (2) is vacuum standing.
Preferably, the packaging in step (2) is vacuum packaging.
Preferably, the pressure of the room temperature curing in the step (2) is 0.1-0.5MPa/pcs, for example, 0.1MPa/pcs, 0.2MPa/pcs, 0.3MPa/pcs, 0.4MPa/pcs, 0.5MPa/pcs, and specific point values between the above point values, which are limited in space and for brevity, the present invention is not exhaustive.
Preferably, the curing time at room temperature in step (2) is 1-7 days, for example, 1 day, 2 days, 3 days, 4 days, 5 days, 6 days, 7 days, and the specific point values between the above point values, which are limited in space and for the sake of brevity, the present invention is not intended to exhaustively list the specific point values included in the range.
Preferably, the pressure of the room temperature forming in the step (2) is 0.1-0.5MPa/pcs, for example, 0.1MPa/pcs, 0.2MPa/pcs, 0.3MPa/pcs, 0.4MPa/pcs, 0.5MPa/pcs, and specific point values among the above point values, which are limited in space and for brevity, the present invention is not exhaustive.
Preferably, the normal temperature formation in the step (2) comprises a small current formation.
Preferably, the current of the normal temperature formation is 0.01-0.2C, for example, 0.01C, 0.05C, 0.1C, 0.15C, 0.2C, and specific point values among the above point values, which are limited in space and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the range.
Preferably, the separator of step (2) comprises any one or a combination of at least two of a polyolefin separator, a ceramic composite separator, a cellulose nonwoven membrane or glass fibers.
By forming an in-situ cured electrolyte and assembling an in-situ solid state battery, the safety performance and the electrical performance are improved compared with those of a liquid state battery by curing and forming at normal temperature.
The invention forms in-situ solidified electrolyte at normal temperature, and the network structure of the polymer can restrict the liquid electrolyte, thereby improving the thermal stability of the electrolyte and the safety performance of the battery.
Compared with the prior art, the invention has the following beneficial effects:
in the in-situ cured electrolyte provided by the invention, the selected monomers and additives can be polymerized at normal temperature to form a polymer, so that the in-situ cured electrolyte is formed, and the safety performance of the battery is improved; and the added small molecules can participate in SEI film formation, and after normal temperature formation, due to the existence of polymer components, the formed SEI film is more compact, the internal resistance of the battery is reduced, the irreversible capacity is reduced, the first circle coulomb efficiency of the battery is improved, the cycle performance is improved, the preparation method of the in-situ solid-state battery can be used for different in-situ curing precursors and different battery systems, the method has wide applicability, the process is simple and effective, the existing equipment can be used for manufacturing and detecting the battery core, the industrial amplification prospect is realized, the high temperature is not needed for curing and formation, and the energy consumption is reduced.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The experimental materials used in the examples and comparative examples of the present invention are as follows:
(1) Diaphragm, brand SC16-S4, manufacturer Jin Li;
(2) The adhesive is polyvinylidene fluoride with the trade mark 5130 and is manufactured by Suwei;
(3) Styrene-butadiene rubber as adhesive, BM-430B, manufacturer's Rui Wen;
(4) The mark of the conductive agent is 250G, and the manufacturer is high in specific rice;
example 1
The embodiment provides an in-situ cured electrolyte, which is prepared from the following raw materials in parts by weight: 10 parts of monomer pentaerythritol triacrylate, 7 parts of additive diethylenetriamine, 1 part of initiator di (2, 4-dichlorobenzoyl) peroxide and 72 parts of organic solvent ethylene carbonate; the preparation raw material further comprises 10 parts of lithium hexafluorophosphate which is a lithium salt, and the concentration of the lithium hexafluorophosphate in the preparation raw material is 1mol/L.
The embodiment also provides an in-situ cured battery containing the in-situ cured electrolyte and a preparation method thereof, and the in-situ cured battery specifically comprises the following steps:
(1) 97 parts of positive ternary nickel-cobalt-manganese active material, 2 parts of conductive agent carbon black, 1 part of binder polyvinylidene fluoride, a positive pole piece made of positive current collector aluminum foil, 96 parts of negative graphite active material, 2 parts of conductive agent carbon black, 2 parts of binder styrene-butadiene rubber, a negative pole piece made of negative current collector copper foil and SC16-S4 are assembled to obtain the battery cell.
(2) According to the formula amount, monomer pentaerythritol triacrylate, additive diethylenetriamine, initiator bis (2, 4-dichlorobenzoyl) peroxide, organic solvent ethylene carbonate and lithium hexafluorophosphate are uniformly mixed, injected into the battery core obtained in the step (1), and after vacuum standing and vacuum packaging, the battery core is cured at normal temperature (the pressure is 0.2MPa/pcs for 3 days) and converted at normal temperature (the pressure is 0.2MPa/pcs and the current is 0.1C), so that the in-situ cured battery is obtained.
Example 2
The embodiment provides an in-situ cured electrolyte, which is prepared from the following raw materials in parts by weight: 10 parts of monomer pentaerythritol triacrylate, 7 parts of additive diethylenetriamine, 1 part of initiator di (2, 4-dichlorobenzoyl) peroxide and 72 parts of organic solvent ethylene carbonate; the preparation raw material further comprises 10 parts of lithium hexafluorophosphate which is a lithium salt, and the concentration of the lithium hexafluorophosphate in the preparation raw material is 1mol/L.
The embodiment also provides an in-situ cured battery containing the in-situ cured electrolyte and a preparation method thereof, and the in-situ cured battery specifically comprises the following steps:
(1) 97 parts of positive electrode lithium iron phosphate active material, 2 parts of conductive agent carbon black, 1 part of binder polyvinylidene fluoride, a positive electrode plate made of positive electrode current collector aluminum foil, 96 parts of negative electrode silicon carbon active material, 2 parts of conductive agent carbon black, 2 parts of binder styrene-butadiene rubber, a negative electrode plate made of negative electrode current collector copper foil and SC16-S4 are assembled to obtain the battery cell.
(2) According to the formula amount, monomer pentaerythritol triacrylate, additive diethylenetriamine, initiator bis (2, 4-dichlorobenzoyl) peroxide, organic solvent ethylene carbonate and lithium hexafluorophosphate are uniformly mixed, injected into the battery core obtained in the step (1), and after vacuum standing and vacuum packaging, the battery core is cured at normal temperature (the pressure is 0.2MPa/pcs for 3 days) and converted at normal temperature (the pressure is 0.2MPa/pcs and the current is 0.1C), so that the in-situ cured battery is obtained.
Example 3
The embodiment provides an in-situ cured electrolyte, which is prepared from the following raw materials in parts by weight: 15 parts of monomer methyl methacrylate, 8 parts of additive diethylenetriamine, 1 part of initiator bis (2, 4-dichlorobenzoyl) peroxide and 66 parts of organic solvent ethylene carbonate; the preparation raw material further comprises 10 parts of lithium hexafluorophosphate which is a lithium salt, and the concentration of the lithium hexafluorophosphate in the preparation raw material is 1mol/L.
The embodiment also provides an in-situ cured battery containing the in-situ cured electrolyte and a preparation method thereof, and the in-situ cured battery specifically comprises the following steps:
(1) 97 parts of positive ternary nickel-cobalt-manganese active material, 2 parts of conductive agent carbon black, 1 part of binder polyvinylidene fluoride, a positive pole piece made of positive current collector aluminum foil, 96 parts of negative graphite active material, 2 parts of conductive agent carbon black, 2 parts of binder styrene-butadiene rubber, a negative pole piece made of negative current collector copper foil and SC16-S4 are assembled to obtain the battery cell.
(2) According to the formula amount, uniformly mixing monomer methyl methacrylate, additive diethylenetriamine, initiator bis (2, 4-dichlorobenzoyl) peroxide, organic solvent ethylene carbonate and lithium hexafluorophosphate, injecting into the battery core obtained in the step (1), standing in vacuum, vacuum packaging, curing at normal temperature (pressure 0.2MPa/pcs for 4 days), and performing normal temperature formation (pressure 0.2MPa/pcs and current 0.1C) to obtain the in-situ cured battery.
Example 4
The embodiment provides an in-situ cured electrolyte, which is prepared from the following raw materials in parts by weight: 10 parts of monomer pentaerythritol triacrylate, 4 parts of additive hexamethylene diisocyanate, 1 part of initiator bis (2, 4-dichlorobenzoyl) peroxide and 75 parts of organic solvent ethylene carbonate; the preparation raw material further comprises 10 parts of lithium hexafluorophosphate which is a lithium salt, and the concentration of the lithium hexafluorophosphate in the preparation raw material is 1mol/L.
The embodiment also provides an in-situ cured battery containing the in-situ cured electrolyte and a preparation method thereof, and the in-situ cured battery specifically comprises the following steps:
(1) 97 parts of positive ternary nickel-cobalt-manganese active material, 2 parts of conductive agent carbon black, 1 part of binder polyvinylidene fluoride, a positive pole piece made of positive current collector aluminum foil, 96 parts of negative graphite active material, 2 parts of conductive agent carbon black, 2 parts of binder styrene-butadiene rubber, a negative pole piece made of negative current collector copper foil and SC16-S4 are assembled to obtain the battery cell.
(2) According to the formula amount, monomer pentaerythritol triacrylate, additive hexamethylene diisocyanate, initiator bis (2, 4-dichlorobenzoyl) peroxide, organic solvent ethylene carbonate and lithium hexafluorophosphate are uniformly mixed, injected into the battery core obtained in the step (1), and after vacuum standing and vacuum packaging, the battery core is cured at normal temperature (the pressure is 0.2MPa/pcs for 2 days), and is formed at normal temperature (the pressure is 0.2MPa/pcs and the current is 0.1C), so that the in-situ cured battery is obtained.
Example 5
The embodiment provides an in-situ cured electrolyte, which is prepared from the following raw materials in parts by weight: 10 parts of monomer pentaerythritol triacrylate, 7 parts of additive diethylenetriamine, 1 part of initiator diisobutyl peroxydicarbonate and 72 parts of organic solvent ethylene carbonate; the preparation raw material further comprises 10 parts of lithium hexafluorophosphate which is a lithium salt, and the concentration of the lithium hexafluorophosphate in the preparation raw material is 1mol/L.
The embodiment also provides an in-situ cured battery containing the in-situ cured electrolyte and a preparation method thereof, and the in-situ cured battery specifically comprises the following steps:
(1) 97 parts of positive ternary nickel-cobalt-manganese active material, 2 parts of conductive agent carbon black, 1 part of binder polyvinylidene fluoride, a positive pole piece made of positive current collector aluminum foil, 96 parts of negative graphite active material, 2 parts of conductive agent carbon black, 2 parts of binder styrene-butadiene rubber, a negative pole piece made of negative current collector copper foil and SC16-S4 are assembled to obtain the battery cell.
(2) And (3) according to the formula amount, uniformly mixing monomer pentaerythritol triacrylate, additive diethylenetriamine, initiator diisobutyl peroxydicarbonate, organic solvent ethylene carbonate and lithium salt lithium hexafluorophosphate, injecting into the battery core obtained in the step (1), and carrying out vacuum standing and vacuum packaging, normal-temperature curing (the pressure is 0.2MPa/pcs for 1 day), and normal-temperature formation (the pressure is 0.2MPa/pcs and the current is 0.1C) to obtain the in-situ cured battery.
Example 6
The embodiment provides an in-situ cured electrolyte, which is prepared from the following raw materials in parts by weight: 10 parts of monomer pentaerythritol triacrylate, 7 parts of additive diethylenetriamine, 1 part of initiator di (2, 4-dichlorobenzoyl) peroxide and 72 parts of organic solvent diethyl carbonate; the preparation raw material further comprises 10 parts of lithium hexafluorophosphate which is a lithium salt, and the concentration of the lithium hexafluorophosphate in the preparation raw material is 1mol/L.
The embodiment also provides an in-situ cured battery containing the in-situ cured electrolyte and a preparation method thereof, and the in-situ cured battery specifically comprises the following steps:
(1) 97 parts of positive ternary nickel-cobalt-manganese active material, 2 parts of conductive agent carbon black, 1 part of binder polyvinylidene fluoride, a positive pole piece made of positive current collector aluminum foil, 96 parts of negative graphite active material, 2 parts of conductive agent carbon black, 2 parts of binder styrene-butadiene rubber, a negative pole piece made of negative current collector copper foil and SC16-S4 are assembled to obtain the battery cell.
(2) And (3) according to the formula amount, uniformly mixing monomer pentaerythritol triacrylate, additive diethylenetriamine, initiator di (2, 4-dichlorobenzoyl) peroxide, organic solvent diethyl carbonate and lithium salt bis (trifluoromethyl) sulfonimide lithium, injecting into the battery core obtained in the step (1), standing in vacuum, vacuum packaging, curing at normal temperature (the pressure is 0.2MPa/pcs for 3 days), and forming at normal temperature (the pressure is 0.2MPa/pcs and the current is 0.1C), thereby obtaining the in-situ cured battery.
Example 7
The embodiment provides an in-situ cured electrolyte, which is prepared from the following raw materials in parts by weight: 10 parts of monomer pentaerythritol triacrylate, 7 parts of additive diethylenetriamine, 1 part of initiator di (2, 4-dichlorobenzoyl) peroxide and 72 parts of organic solvent ethylene carbonate; the preparation raw material further comprises 10 parts of lithium hexafluorophosphate which is a lithium salt, and the concentration of the lithium hexafluorophosphate in the preparation raw material is 1mol/L.
The embodiment also provides an in-situ cured battery containing the in-situ cured electrolyte and a preparation method thereof, and the in-situ cured battery specifically comprises the following steps:
(1) 97 parts of positive ternary nickel-cobalt-manganese active material, 2 parts of conductive agent carbon black, 1 part of binder polyvinylidene fluoride, a positive pole piece made of positive current collector aluminum foil, 96 parts of negative graphite active material, 2 parts of conductive agent carbon black, 2 parts of binder styrene-butadiene rubber, a negative pole piece made of negative current collector copper foil and SC16-S4 are assembled to obtain the battery cell.
(2) According to the formula amount, monomer pentaerythritol triacrylate, additive diethylenetriamine, initiator bis (2, 4-dichlorobenzoyl) peroxide, organic solvent ethylene carbonate and lithium hexafluorophosphate are uniformly mixed, injected into the battery core obtained in the step (1), and after vacuum standing and vacuum packaging, the battery core is cured at normal temperature (the pressure is 0.2MPa/pcs for 3 days), and is formed at normal temperature (the pressure is 0.3MPa/pcs and the current is 0.05C), so that the in-situ cured battery is obtained.
Comparative example 1
The comparative example provides an in-situ cured electrolyte, which is prepared from the following raw materials in parts by weight: 10 parts of monomer trimethylolpropane triacrylate, 7 parts of additive diethylenetriamine, 1 part of initiator bis (2, 4-dichlorobenzoyl) peroxide and 72 parts of organic solvent ethylene carbonate; the preparation raw material further comprises 10 parts of lithium hexafluorophosphate which is a lithium salt, and the concentration of the lithium hexafluorophosphate in the preparation raw material is 1mol/L.
The comparative example also provides an in-situ cured battery comprising the aforementioned in-situ cured electrolyte and a method for preparing the same, specifically comprising:
(1) 97 parts of positive ternary nickel-cobalt-manganese active material, 2 parts of conductive agent carbon black, 1 part of binder polyvinylidene fluoride, a positive pole piece made of positive current collector aluminum foil, 96 parts of negative graphite active material, 2 parts of conductive agent carbon black, 2 parts of binder styrene-butadiene rubber, a negative pole piece made of negative current collector copper foil and SC16-S4 are assembled to obtain the battery cell.
(2) Uniformly mixing monomer trimethylolpropane triacrylate, additive diethylenetriamine, initiator di (2, 4-dichlorobenzoyl) peroxide, organic solvent ethylene carbonate and lithium hexafluorophosphate, injecting into the battery core obtained in the step (1), and curing at normal temperature (pressure 0.2MPa/pcs for 3 days) and at normal temperature (pressure 0.2MPa/pcs and current 0.1C) after vacuum standing and vacuum packaging to obtain the in-situ cured battery.
Comparative example 2
The comparative example provides an in-situ cured electrolyte, which is prepared from the following raw materials in parts by weight: 10 parts of monomer pentaerythritol triacrylate, 7 parts of additive m-phenylenediamine, 1 part of initiator di (2, 4-dichlorobenzoyl) peroxide and 72 parts of organic solvent ethylene carbonate; the preparation raw material further comprises 10 parts of lithium hexafluorophosphate which is a lithium salt, and the concentration of the lithium hexafluorophosphate in the preparation raw material is 1mol/L.
The comparative example also provides an in-situ cured battery comprising the aforementioned in-situ cured electrolyte and a method for preparing the same, specifically comprising:
(1) 97 parts of positive ternary nickel-cobalt-manganese active material, 2 parts of conductive agent carbon black, 1 part of binder polyvinylidene fluoride, a positive pole piece made of positive current collector aluminum foil, 96 parts of negative graphite active material, 2 parts of conductive agent carbon black, 2 parts of binder styrene-butadiene rubber, a negative pole piece made of negative current collector copper foil and SC16-S4 are assembled to obtain the battery cell.
(2) Uniformly mixing monomer pentaerythritol triacrylate, additive m-phenylenediamine, initiator di (2, 4-dichlorobenzoyl) peroxide, organic solvent ethylene carbonate and lithium hexafluorophosphate, injecting into the battery core obtained in the step (1), standing in vacuum, packaging in vacuum, curing at normal temperature (pressure 0.2MPa/pcs for 3 days), and performing normal temperature formation (pressure 0.2MPa/pcs and current 0.1C) to obtain the in-situ cured battery.
Comparative example 3
The comparative example provides an in-situ cured electrolyte, which is prepared from the following raw materials in parts by weight: 10 parts of monomer pentaerythritol triacrylate, 7 parts of additive diethylenetriamine, 1 part of initiator azobisisobutyronitrile and 72 parts of organic solvent ethylene carbonate; the preparation raw material further comprises 10 parts of lithium hexafluorophosphate which is a lithium salt, and the concentration of the lithium hexafluorophosphate in the preparation raw material is 1mol/L.
The comparative example also provides an in-situ cured battery comprising the aforementioned in-situ cured electrolyte and a method for preparing the same, specifically comprising:
(1) 97 parts of positive ternary nickel-cobalt-manganese active material, 2 parts of conductive agent carbon black, 1 part of binder polyvinylidene fluoride, a positive pole piece made of positive current collector aluminum foil, 96 parts of negative graphite active material, 2 parts of conductive agent carbon black, 2 parts of binder styrene-butadiene rubber, a negative pole piece made of negative current collector copper foil and SC16-S4 are assembled to obtain the battery cell.
(2) And (3) uniformly mixing monomer pentaerythritol triacrylate, additive diethylenetriamine, initiator azodiisobutyronitrile, organic solvent ethylene carbonate and lithium salt lithium hexafluorophosphate, injecting into the battery core obtained in the step (1), and carrying out vacuum standing and vacuum packaging, and then curing at normal temperature (the pressure is 0.2MPa/pcs for 3 days) and forming at normal temperature (the pressure is 0.2MPa/pcs and the current is 0.1C) to obtain the in-situ cured battery.
Comparative example 4
The comparative example provides an in-situ cured electrolyte, which is prepared from the following raw materials in parts by weight: 20 parts of monomer pentaerythritol triacrylate, 7 parts of additive diethylenetriamine, 3 parts of initiator di (2, 4-dichlorobenzoyl) peroxide and 60 parts of organic solvent ethylene carbonate; the preparation raw material further comprises 10 parts of lithium hexafluorophosphate which is a lithium salt, and the concentration of the lithium hexafluorophosphate in the preparation raw material is 1mol/L.
The comparative example also provides an in-situ cured battery comprising the aforementioned in-situ cured electrolyte and a method for preparing the same, specifically comprising:
(1) 97 parts of positive ternary nickel-cobalt-manganese active material, 2 parts of conductive agent carbon black, 1 part of binder polyvinylidene fluoride, a positive pole piece made of positive current collector aluminum foil, 96 parts of negative graphite active material, 2 parts of conductive agent carbon black, 2 parts of binder styrene-butadiene rubber, a negative pole piece made of negative current collector copper foil and SC16-S4 are assembled to obtain the battery cell.
(2) Uniformly mixing monomer pentaerythritol triacrylate, additive diethylenetriamine, initiator di (2, 4-dichlorobenzoyl) peroxide, organic solvent ethylene carbonate and lithium hexafluorophosphate, injecting into the battery core obtained in the step (1), standing in vacuum, packaging in vacuum, curing at normal temperature (pressure 0.2MPa/pcs for 3 days), and performing normal temperature formation (pressure 0.2MPa/pcs and current 0.1C) to obtain the in-situ cured battery.
Comparative example 5
The comparative example provides an in-situ cured electrolyte, which is prepared from the following raw materials in parts by weight: 10 parts of monomer pentaerythritol triacrylate, 7 parts of additive diethylenetriamine, 1 part of initiator di (2, 4-dichlorobenzoyl) peroxide and 72 parts of organic solvent ethylene carbonate; the preparation raw material further comprises 10 parts of lithium hexafluorophosphate which is a lithium salt, and the concentration of the lithium hexafluorophosphate in the preparation raw material is 1mol/L.
The comparative example also provides an in-situ cured battery comprising the aforementioned in-situ cured electrolyte and a method for preparing the same, specifically comprising:
(1) 97 parts of positive ternary nickel-cobalt-manganese active material, 2 parts of conductive agent carbon black, 1 part of binder polyvinylidene fluoride, a positive pole piece made of positive current collector aluminum foil, 96 parts of negative graphite active material, 2 parts of conductive agent carbon black, 2 parts of binder styrene-butadiene rubber, a negative pole piece made of negative current collector copper foil and SC16-S4 are assembled to obtain the battery cell.
(2) Uniformly mixing monomer pentaerythritol triacrylate, additive diethylenetriamine, initiator di (2, 4-dichlorobenzoyl) peroxide, organic solvent ethylene carbonate and lithium hexafluorophosphate, injecting into the battery core obtained in the step (1), standing in vacuum, packaging in vacuum, solidifying (temperature 45 ℃, pressure 0.05MPa/pcs for 8 hours), and carrying out normal temperature formation (pressure 0.2MPa/pcs and current 0.1C) to obtain the in-situ solidified battery.
Comparative example 6
The comparative example provides an in-situ cured electrolyte, which is prepared from the following raw materials in parts by weight: 10 parts of monomer pentaerythritol triacrylate, 7 parts of additive diethylenetriamine, 1 part of initiator di (2, 4-dichlorobenzoyl) peroxide and 72 parts of organic solvent ethylene carbonate; the preparation raw material further comprises 10 parts of lithium hexafluorophosphate which is a lithium salt, and the concentration of the lithium hexafluorophosphate in the preparation raw material is 1mol/L.
The comparative example also provides an in-situ cured battery comprising the aforementioned in-situ cured electrolyte and a method for preparing the same, specifically comprising:
(1) 97 parts of positive ternary nickel-cobalt-manganese active material, 2 parts of conductive agent carbon black, 1 part of binder polyvinylidene fluoride, a positive pole piece made of positive current collector aluminum foil, 96 parts of negative graphite active material, 2 parts of conductive agent carbon black, 2 parts of binder styrene-butadiene rubber, a negative pole piece made of negative current collector copper foil and SC16-S4 are assembled to obtain the battery cell.
(2) Uniformly mixing monomer pentaerythritol triacrylate, additive diethylenetriamine, initiator di (2, 4-dichlorobenzoyl) peroxide, organic solvent ethylene carbonate and lithium hexafluorophosphate, injecting into the battery core obtained in the step (1), standing in vacuum, packaging in vacuum, curing at normal temperature (the pressure is 0.1MPa/pcs for 3 days), and forming (the temperature is 45 ℃, the pressure is 0.2MPa/pcs, and the current is 0.5C), thus obtaining the in-situ cured battery.
Comparative example 7
The comparative example provides an in-situ solid-state battery, the in-situ cured battery and the preparation method thereof, which specifically comprises: (1) 92 parts of positive ternary nickel-cobalt-manganese active material, 5 parts of conductive agent carbon black and 3 parts of binder polyvinylidene fluoride are dissolved in N-methyl pyrrolidone and uniformly mixed to prepare positive electrode slurry, then the positive electrode slurry is uniformly coated on a positive electrode plate prepared by aluminum foil of a current collector, 95.5 parts of negative electrode graphite active material, 1.5 parts of conductive agent carbon black, 1 part of thickener sodium carboxymethyl cellulose and 2 parts of binder styrene-butadiene rubber are dissolved in deionized water and uniformly mixed to prepare negative electrode slurry, and then the negative electrode slurry is uniformly coated on a negative electrode plate prepared by front and back surfaces of the copper foil of the current collector and a polypropylene diaphragm to assemble to obtain the battery core.
(2) And (3) injecting 20 parts of monomer acrylic acid, 5 parts of additive vinylene carbonate, 0.4 part of initiator azodiisobutyronitrile and 74.6 parts of organic solvent, wherein the mass ratio of ethylene carbonate to methyl ethyl carbonate to diethyl carbonate is 3:5:2, and lithium hexafluorophosphate and 1.5mol/L of lithium bisoxalato borate into the battery core obtained in the step (1), and curing at 70 ℃ after vacuum standing and vacuum packaging (pressure 0MPa/pcs for 4 hours), and forming (temperature 45 ℃, pressure 0.2MPa/pcs and current 0.2C) to obtain the in-situ cured battery.
The in-situ solid-state batteries obtained in examples 1 to 7 and comparative examples 1 to 7 were subjected to performance test by the following methods:
(1) Electrical properties-rate discharge properties: after the battery is charged to 100% SOC, discharging to cut-off voltage by constant current of 0.2C/0.5C/1C/2C/3C respectively;
(2) Electrical properties-normal temperature cycle properties: after the battery 1C is charged to 100% SOC, the constant current of the battery 1C is discharged to 0% SOC, and the charge-discharge cycle is repeated until the capacity retention rate is reduced to 80%;
(3) Electrical properties-60 ℃ storage: after capacity calibration, the battery was charged to 100% SOC at 60 DEG C
After 28 days of storage in the oven, testing the capacity retention rate and the recovery rate;
(4) Safety performance-150 ℃ hot box: the 100% SOC battery was placed in a high and low temperature wet heat test chamber.
The temperature of the test box is raised at the temperature rise rate of 5 ℃ per minute, and when the temperature in the test box reaches 150℃ (+)
Keeping the temperature at 2 ℃ and lasting for 30min; and then returned to room temperature, the battery surface temperature was recorded,
it is observed whether the battery will explode on fire.
The in-situ solid-state batteries obtained in examples 1 to 7 and comparative examples 1 to 7 were tested for each performance according to the above-described performance test method, and the test results are shown in table 1.
TABLE 1
From the data in Table 1, it is understood that in comparative examples 1 to 7, the battery is better in rate discharge performance, normal temperature cycle performance and 60 ℃ storage performance by selecting the appropriate content of monomer, additive, initiator, solvent, curing condition and formation condition, and in example 2, the positive electrode is lithium iron phosphate, so that the normal temperature cycle performance is superior to other examples. Comparative example 1 and comparative example 1 can conclude that, using monomers outside the scope of the present application, the electrolyte cannot be cured under the environmental conditions specified in the present application, resulting in a decrease in the electrical properties and safety properties of the battery; as is clear from comparative examples 1 and 2, if the additive is a compound other than the present application, the curing reaction speed is too slow, the strength of the cured electrolyte is small, the electrical properties are poor, and the normal temperature cycle performance, the rate capability and the high temperature storage life of the prepared in-situ cured battery are poor and cannot pass through a 150 ℃ hot box; as is clear from comparative example 3, after the initiator is changed to the medium temperature initiator, the initiator cannot be decomposed at normal temperature, the curing reaction cannot occur, and thus an in-situ cured electrolyte cannot be formed, and the battery performance is lowered; in comparative example 4, although the types of monomers and initiators in the range of the present application were used, the contents of the monomers and the initiators exceeded the prescribed range, and after the addition of an excessive amount of monomers and initiators, the battery still passed the safety test, but the electrical properties were significantly reduced compared with examples 1 to 7 and comparative examples 1 to 3, indicating that the raw material contents for preparing the in-situ cured electrolyte had to be within the prescribed range of the present application to give the battery better performance; in comparative example 5, the curing temperature is increased, the curing pressure is reduced, and the curing time is reduced, so that the curing reaction speed is too high, the gas generated in the reaction process cannot be discharged in time, the formed curing layer is uneven, the uniformity and the compactness of the SEI film are affected, and the battery performance is reduced; in comparative example 6, the formation temperature and the current level were increased, and although the SEI film growth speed became fast, uniformity and density were lowered, and thermal stability was poor, resulting in lower battery performance than in example 1; comparing the battery performance data of comparative example 7 with examples 1-7, comparative examples 1-6, it can be concluded that the electrical performance was worst and failed the safety test when the curing temperature was raised to 70 c, the curing time was shortened to 4h, the curing was pressureless, and the formation temperature was raised to 45 c using additives other than those of the present application. Under the reaction condition, the monomer and the additive participate in SEI film generation, so that the formed SEI film is unstable, and is easy to crack in long-time circulation and high-temperature storage, so that serious side reaction continuously occurs at the interface between the electrode and the electrolyte, the electrolyte is consumed, and side reaction products are generated.
The applicant states that the present invention is illustrated by the above examples as an in-situ solidified electrolyte, an in-situ solid state battery comprising the same and a method of preparing the same, but the present invention is not limited to the above examples, i.e., it does not mean that the present invention must be practiced depending on the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (10)
1. The in-situ curing electrolyte is characterized in that the preparation raw materials of the in-situ curing electrolyte comprise a combination of a monomer, an additive, an initiator, an organic solvent and a lithium salt; the additive comprises any one or a combination of at least two of aliphatic polyamine, epoxy compound, polyisocyanate, styrene compound or benzenesulfonic acid compound.
2. The cured in place electrolyte of claim 1 wherein the additive comprises any one or a combination of at least two of diethylenetriamine, epoxy cyanurates, hexamethylene diisocyanate, dimethyltriphenylmethane tetraisocyanate, triphenylmethane triisocyanate, styrene, a-methylstyrene, p-toluene sulfonic acid or p-toluene sulfonyl chloride;
Preferably, the mass percentage of the additive in the preparation raw materials is 1-15%.
3. The cured in place electrolyte of claim 1 or 2, wherein the monomer comprises any one or a combination of at least two of acrylic acid, methacrylic acid, methyl methacrylate, polyethylene glycol diacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, acrylonitrile, ethylene carbonate, ethylene oxide, or 1, 3-dioxolane;
preferably, the mass percentage of the monomer in the preparation raw material is 2-15%.
4. A cured in place electrolyte according to any one of claims 1 to 3, wherein the mass of the initiator is 0.1 to 1.5% of the mass of the monomer;
preferably, the initiator comprises any one or a combination of at least two of bis (2, 4-dichlorobenzoyl) peroxide, diacetyl peroxide, dioctyl peroxide, dilauroyl peroxide, dicarbonate, diisopropyl peroxide, diisobutyl peroxide, dicyclohexyl peroxide or bis (p-tert-butylcyclohexyl) peroxide.
5. The cured in place electrolyte of any one of claims 1-4, wherein the organic solvent comprises any one or a combination of at least two of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methylethyl carbonate, gamma-butyrolactone, methyl formate, dimethoxymethane, acetonitrile, cyclohexylbenzene, propylene sulfite, or ethylene sulfate;
Preferably, the mass percentage of the organic solvent in the preparation raw materials is 53.5-95.9%.
6. The cured in place electrolyte of any one of claims 1-5, wherein the lithium salt comprises any one or a combination of at least two of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium bis-difluorosulfonimide, lithium bis-trifluoromethylsulfonimide, lithium bis-oxalato borate, lithium difluoro-oxalato borate, or lithium bis-oxalato borate;
preferably, the mass percentage of lithium salt in the preparation raw material is 1-15%;
preferably, the concentration of lithium salt in the preparation raw material is 0.2-3mol/L.
7. An in-situ solid state battery, characterized in that the in-situ solid state battery comprises an in-situ solid state electrolyte as claimed in any one of claims 1-6.
8. A method of preparing an in-situ solid state battery as claimed in claim 7, comprising the steps of:
(1) Assembling the positive electrode plate, the negative electrode plate and the diaphragm to obtain an electric core;
(2) Injecting the preparation raw material of the in-situ solidified electrolyte according to any one of claims 1 to 6 into the cell obtained in the step (1), standing and packaging, solidifying at normal temperature, and forming at normal temperature to obtain the in-situ solid-state battery.
9. The method of manufacturing according to claim 8, wherein the positive electrode sheet of step (1) includes a positive electrode current collector and a positive electrode material layer disposed on a surface of the positive electrode current collector, the positive electrode material layer including a combination of a positive electrode active material, a positive electrode conductive agent, and a positive electrode binder;
preferably, the positive electrode active material includes any one or a combination of at least two of lithium iron phosphate, lithium cobalt oxide, lithium manganate, lithium nickel manganate, ternary nickel cobalt manganese, or ternary nickel cobalt aluminum;
preferably, the positive electrode conductive agent comprises any one or a combination of at least two of conductive carbon black, conductive graphite, carbon fiber or carbon nanotube;
preferably, the positive electrode binder comprises polyvinylidene fluoride;
preferably, the negative electrode sheet in the step (1) comprises a negative electrode current collector and a negative electrode material layer arranged on the surface of the negative electrode current collector, wherein the negative electrode material layer comprises a combination of a negative electrode active material, a negative electrode conductive agent and a negative electrode binder;
preferably, the negative electrode active material includes any one or a combination of at least two of metallic lithium, metallic lithium alloy, graphite, hard carbon, silicon carbon, tin-based, or silicon oxygen materials;
preferably, the negative electrode conductive agent comprises any one or a combination of at least two of conductive carbon black, conductive graphite, carbon fiber or carbon nanotube;
Preferably, the negative electrode binder comprises any one or a combination of at least two of polyvinyl alcohol, polyacrylic acid, styrene-butadiene rubber or sodium carboxymethyl cellulose;
preferably, the method of assembling in step (1) specifically comprises: and (3) the positive pole piece, the negative pole piece and the diaphragm are subjected to lamination, lug welding, top sealing and side sealing to obtain the battery cell.
10. The method of claim 8 or 9, wherein the standing in step (2) is vacuum standing;
preferably, the packaging of step (2) is a vacuum packaging;
preferably, the pressure of the normal temperature curing in the step (2) is 0.1-0.5MPa/pcs;
preferably, the normal temperature curing time in the step (2) is 1-7 days;
preferably, the pressure of the normal temperature formation in the step (2) is 0.1-0.5MPa/pcs;
preferably, the normal temperature formation in the step (2) comprises a small current formation;
preferably, the current of the normal temperature formation is 0.01-0.2C.
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| CN117673461A (en) * | 2023-12-01 | 2024-03-08 | 东莞市创明电池技术有限公司 | Solid polymer electrolyte, preparation method thereof, and application in secondary batteries |
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| CN117673461A (en) * | 2023-12-01 | 2024-03-08 | 东莞市创明电池技术有限公司 | Solid polymer electrolyte, preparation method thereof, and application in secondary batteries |
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