CN113270632A - High-nickel ternary lithium ion battery electrolyte and lithium ion battery containing same - Google Patents
High-nickel ternary lithium ion battery electrolyte and lithium ion battery containing same Download PDFInfo
- Publication number
- CN113270632A CN113270632A CN202110519906.4A CN202110519906A CN113270632A CN 113270632 A CN113270632 A CN 113270632A CN 202110519906 A CN202110519906 A CN 202110519906A CN 113270632 A CN113270632 A CN 113270632A
- Authority
- CN
- China
- Prior art keywords
- ion battery
- lithium ion
- nickel ternary
- battery electrolyte
- electrolyte
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003792 electrolyte Substances 0.000 title claims abstract description 66
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 58
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 35
- 150000001875 compounds Chemical class 0.000 claims abstract description 34
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000654 additive Substances 0.000 claims abstract description 22
- 230000000996 additive effect Effects 0.000 claims abstract description 21
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 11
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 11
- 239000011356 non-aqueous organic solvent Substances 0.000 claims abstract description 5
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 8
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 8
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 8
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 6
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 5
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 claims description 5
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 4
- VMZOBROUFBEGAR-UHFFFAOYSA-N tris(trimethylsilyl) phosphite Chemical compound C[Si](C)(C)OP(O[Si](C)(C)C)O[Si](C)(C)C VMZOBROUFBEGAR-UHFFFAOYSA-N 0.000 claims description 4
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 claims description 3
- KCZQSKKNAGZQSZ-UHFFFAOYSA-N 1,3,5-tris(6-isocyanatohexyl)-1,3,5-triazin-2,4,6-trione Chemical compound O=C=NCCCCCCN1C(=O)N(CCCCCCN=C=O)C(=O)N(CCCCCCN=C=O)C1=O KCZQSKKNAGZQSZ-UHFFFAOYSA-N 0.000 claims description 3
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 3
- 150000003949 imides Chemical class 0.000 claims description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- UVVUGWBBCDFNSD-UHFFFAOYSA-N tetraisocyanatosilane Chemical compound O=C=N[Si](N=C=O)(N=C=O)N=C=O UVVUGWBBCDFNSD-UHFFFAOYSA-N 0.000 claims description 3
- 235000019766 L-Lysine Nutrition 0.000 claims description 2
- 239000004472 Lysine Substances 0.000 claims description 2
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 claims 1
- 230000002829 reductive effect Effects 0.000 abstract description 13
- 239000002904 solvent Substances 0.000 abstract description 12
- 239000011149 active material Substances 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 230000000242 pagocytic effect Effects 0.000 abstract description 3
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 239000002001 electrolyte material Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000012948 isocyanate Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- 238000003860 storage Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 150000002513 isocyanates Chemical class 0.000 description 8
- 238000007599 discharging Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000010405 anode material Substances 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229920006389 polyphenyl polymer Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 229910012258 LiPO Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910001437 manganese ion Inorganic materials 0.000 description 2
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- XGACNCCYEHRDJM-UHFFFAOYSA-N 1,3,5-triisocyanato-2,4,6-trimethylbenzene Chemical compound CC1=C(N=C=O)C(C)=C(N=C=O)C(C)=C1N=C=O XGACNCCYEHRDJM-UHFFFAOYSA-N 0.000 description 1
- PFUKECZPRROVOD-UHFFFAOYSA-N 1,3,5-triisocyanato-2-methylbenzene Chemical compound CC1=C(N=C=O)C=C(N=C=O)C=C1N=C=O PFUKECZPRROVOD-UHFFFAOYSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- YXRKNIZYMIXSAD-UHFFFAOYSA-N 1,6-diisocyanatohexane Chemical compound O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O YXRKNIZYMIXSAD-UHFFFAOYSA-N 0.000 description 1
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 description 1
- OQXNUCOGMMHHNA-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2,2-dioxide Chemical compound CC1COS(=O)(=O)O1 OQXNUCOGMMHHNA-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 229910013075 LiBF Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- NHNSSGSIAOTLKL-UHFFFAOYSA-N N=C=O.S=P(OC1=CC=CC=C1)(OC1=CC=CC=C1)OC1=CC=CC=C1 Chemical compound N=C=O.S=P(OC1=CC=CC=C1)(OC1=CC=CC=C1)OC1=CC=CC=C1 NHNSSGSIAOTLKL-UHFFFAOYSA-N 0.000 description 1
- 206010057249 Phagocytosis Diseases 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XLRGLCLTYMKRRJ-UHFFFAOYSA-N [K].FS(=N)F Chemical compound [K].FS(=N)F XLRGLCLTYMKRRJ-UHFFFAOYSA-N 0.000 description 1
- QABDZOZJWHITAN-UHFFFAOYSA-F [Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[O-]P([O-])(F)=O.[O-]P([O-])(F)=O.[O-]P([O-])(F)=O.[O-]P([O-])(F)=O Chemical compound [Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[O-]P([O-])(F)=O.[O-]P([O-])(F)=O.[O-]P([O-])(F)=O.[O-]P([O-])(F)=O QABDZOZJWHITAN-UHFFFAOYSA-F 0.000 description 1
- ZJPPTKRSFKBZMD-UHFFFAOYSA-N [Li].FS(=N)F Chemical compound [Li].FS(=N)F ZJPPTKRSFKBZMD-UHFFFAOYSA-N 0.000 description 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- PQYORWUWYBPJLQ-UHFFFAOYSA-N buta-1,3-diene;sulfurous acid Chemical compound C=CC=C.OS(O)=O PQYORWUWYBPJLQ-UHFFFAOYSA-N 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000002925 chemical effect Effects 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- KQWGXHWJMSMDJJ-UHFFFAOYSA-N cyclohexyl isocyanate Chemical compound O=C=NC1CCCCC1 KQWGXHWJMSMDJJ-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- XKLXIRVJABJBLQ-UHFFFAOYSA-N lithium;2-(trifluoromethyl)-1h-imidazole-4,5-dicarbonitrile Chemical compound [Li].FC(F)(F)C1=NC(C#N)=C(C#N)N1 XKLXIRVJABJBLQ-UHFFFAOYSA-N 0.000 description 1
- DCWYVUZDHJMHRQ-UHFFFAOYSA-M lithium;ethyl sulfate Chemical compound [Li+].CCOS([O-])(=O)=O DCWYVUZDHJMHRQ-UHFFFAOYSA-M 0.000 description 1
- ALYPSPRNEZQACK-UHFFFAOYSA-M lithium;methyl sulfate Chemical compound [Li+].COS([O-])(=O)=O ALYPSPRNEZQACK-UHFFFAOYSA-M 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000008782 phagocytosis Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000009517 secondary packaging Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- IKXFIBBKEARMLL-UHFFFAOYSA-N triphenoxy(sulfanylidene)-$l^{5}-phosphane Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=S)OC1=CC=CC=C1 IKXFIBBKEARMLL-UHFFFAOYSA-N 0.000 description 1
- YZYKZHPNRDIPFA-UHFFFAOYSA-N tris(trimethylsilyl) borate Chemical compound C[Si](C)(C)OB(O[Si](C)(C)C)O[Si](C)(C)C YZYKZHPNRDIPFA-UHFFFAOYSA-N 0.000 description 1
- QJMMCGKXBZVAEI-UHFFFAOYSA-N tris(trimethylsilyl) phosphate Chemical compound C[Si](C)(C)OP(=O)(O[Si](C)(C)C)O[Si](C)(C)C QJMMCGKXBZVAEI-UHFFFAOYSA-N 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
- 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
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- 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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a high-nickel ternary lithium ion battery electrolyte, which comprises a non-aqueous organic solvent, lithium salt and an additive, wherein the additive comprises a compound with three or more isocyanate groups and a negative electrode film-forming additive. The invention also discloses a lithium ion battery containing the electrolyte. The compound with three or more isocyanate groups can be reduced to form an SEi film before a solvent on a negative electrode interface, can be oxidized to form a CEI film before the solvent on a positive electrode interface, and can be used as a phagocytic agent of water and HF in a battery system, so that damage of acidic substances to electrolyte and active materials is reduced, and various performances of the lithium ion battery are remarkably improved.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a lithium ion battery electrolyte and a lithium ion battery containing the same.
Background
The high energy density ternary lithium ion battery is the main development and application direction for developing power batteries and energy storage products at present. At present, the improvement of the energy density is mainly to improve the proportion of nickel in the anode material or the working upper limit voltage of the anode material. The increase of the nickel content or the increase of the working voltage can cause the increase of the thermal instability and the surface activity of the anode material, and the surface of the anode material exposed in the electrolyte can continuously react with organic components in the electrolyte, thereby causing the impedance of the anode of the battery to be increased, and causing the problem of cycle decay. The side reaction of the cathode interface can be accelerated by the structural change and the enhanced surface activity of the cathode material. It is therefore desirable to create a stable anode/electrolyte interface. The main problems existing at present for the high-nickel and medium-nickel high-voltage ternary system are as follows:
(1) the high oxidation state metal oxide has stronger oxidability, so that after the transition metal nickel and manganese ions in the anode material are dissolved out, on one hand, the effect of catalytically decomposing the electrolyte is achieved, the consumption of the electrolyte is accelerated, and on the other hand, the transition metal nickel and manganese ions enter the cathode along with the migration of charges to damage an SEI film to cause the failure of the cathode; the thickening and the impedance increase of the CEI film of the anode and the failure of the cathode material are caused; (2) the positive electrode material is easy to generate cracks in the charging and discharging processes, and high-activity-state oxygen is formed along with the release of lattice oxygen, so that gas is generated in the use or storage process of the battery easily, the service life of the battery is shortened, and the safety problem of the battery is caused; (3) HF and POF are easily generated by decomposition of lithium hexafluorophosphate in a battery system and unstable components in an electrolyte under a high-temperature environment3And PF5The damage to the electrolyte and interfacial film is accelerated to cause the failure of the battery. (4) The ternary anode material is extremely harsh to the production process of the battery, has high sensitivity to moisture, can convert the moisture into HF in an electrolyte system, accelerates the decomposition of the electrolyte, greatly loses the activity of the active material of the battery, and develops the water-removing and acid-inhibiting additive with the phagocytosis function, which is also the important direction of the high specific energy density at present.
The isocyanate compound has multifunctional property, can have better effect of participating in passive film formation on the interfaces of a negative electrode and a positive electrode, has removal effect on moisture and acidity in electrolyte, and has potential application in a high-nickel and high-pressure system.
For example, CN104752763A discloses a novel lithium ion electrolyte additive, which contains Propylene Carbonate (PC) and isocyanate-based organic compound, wherein the number of isocyanate groups contained in the isocyanate-based compound is at least 2, and preferably: 1, 5-diisocyanate-2-methylpentane, 1-diisocyanate-4- [ (4-isocyanatocyclohexane) methyl ] cyclohexane, 3 ' -dimethoxy-4, 4 ' -biphenyl diisocyanate, isophorone diisocyanate, 4-chloro-6-methyl m-phenyl diisocyanate, 4 ' -sulfonyl dibenzoic acid diisocyanate, 1,3, 5-triisocyanato-2, 4, 6-trimethylbenzene, 1,3, 5-triisocyanato-2-methylbenzene and 3- (3-isocyanato) -5-methyl-1, 2, 4-oxadiazole oxide. The electrolyte formed by the electrolyte and the solvent can be suitable for the lithium ion battery with the charging potential not lower than 4.2V (relative Li/Li +), and the cycle performance of the lithium ion battery is effectively improved. The disadvantage is that the electrolyte interface impedance is increased more, which has obvious negative effect on the low-temperature performance.
Also for example CN112713306A discloses an air or moisture curable electrolyte comprising an air or moisture curable multi-functional component, a solvent, an electrolyte and at least one functional additive, and a method of preparation and use. The moisture-curable component is an isocyanate, preferably at least one of Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), Hexamethylene Diisocyanate (HDI), Lysine Diisocyanate (LDI), triphenylmethane triisocyanate, trimer of hexamethylene diisocyanate (HDI trimer), and polyphenyl polymethylene polyisocyanate (PAPI); polyphenyl polymethylene polyisocyanates (PAPIs) are preferred. The electrolyte can simultaneously realize high ionic conductivity and high safety of the battery. The disadvantages are that polyphenyl compounds are easy to continuously oxidize, the cathode interfacial film is gradually thickened in the long-term high-temperature storage process, so that the possibility of failure exists, and particularly, the negative effects are obvious in a high-nickel or high-voltage system due to the high addition amount of the polyphenyl compounds. In the embodiment of the invention, the addition amount of isocyanate is higher, and researches show that when the addition amount of isocyanate in the secondary lithium ion battery is too high, the viscosity of the electrolyte is obviously increased, the interface impedance of the anode and the cathode of the battery is rapidly increased, the dynamic performance of the battery is obviously influenced, meanwhile, isocyanate components which are not fully reacted at the early stage can remain in the battery system, and the long-term storage performance is deteriorated due to the instability of the isocyanate components.
Disclosure of Invention
The invention aims to provide a high-nickel ternary lithium ion battery electrolyte and a lithium ion battery containing the electrolyte, aiming at the defects of the prior art. According to the invention, various performances of the lithium ion battery are better improved by optimizing the electrolyte formula.
In order to achieve the purpose, the invention adopts the technical scheme that: the high-nickel ternary lithium ion battery electrolyte comprises a non-aqueous organic solvent, lithium salt and an additive, wherein the additive comprises a compound with three or more isocyanate groups and a negative electrode film-forming additive.
The compound with three or more isocyanate groups can be reduced to form an SEi film before a solvent on a negative electrode interface, and oxidized to form a CEI film before the solvent on a positive electrode interface, and can be used as a phagocytic agent of water and HF in a battery system, so that the damage of acidic substances to electrolyte and active materials is reduced, and the performances of the battery are improved. Preferably, the compound having three or more isocyanate groups is at least one selected from the group consisting of L-lysine triisocyanate, 1,3, 6-hexane triisocyanate, triisocyanatoethylsilane, triphenyl phosphorothioate, (2,4, 6-trioxotriazine-1, 3,5(2H,4H,6H) -triyl) tris (hexamethylene) isocyanate, and tetraisocyanatosilane.
Preferably, the mass percentage of the compound with three or more isocyanate groups in the high-nickel ternary lithium ion battery electrolyte is 0.1-1.5%, and more preferably 0.2-1%.
The negative film forming additive can be at least one selected from fluoroethylene carbonate, vinylene carbonate, ethylene sulfate, propylene sulfate, 4-methyl ethylene sulfate, vinyl ethylene carbonate, 4-ethyl ethylene sulfate, 1, 3-propane sultone, vinyl ethylene sulfite, tri (trimethylsilyl) borate, triallyl isocyanurate, tri (trimethylsilyl) phosphate and tri (trimethylsilyl) phosphite. Preferably a mixture of at least two of fluoroethylene carbonate (FEC), ethylene sulfate (DTD), Vinylene Carbonate (VC), tris (trimethylsilyl) phosphite (TMSP), 1, 3-Propane Sultone (PS).
Preferably, the mass percentage of the negative electrode film-forming additive in the high-nickel ternary lithium ion battery electrolyte is 0.5-15%.
In the present invention, the lithium salt may be at least one selected from the group consisting of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bisoxalato borate, lithium difluorobisoxalato phosphate, lithium difluorosulfimide, lithium bistrifluoromethanesulfonylimide, lithium difluorophosphate, lithium tetrafluorophosphate, potassium difluorosulfimide, lithium 4, 5-dicyano-2-trifluoromethyl-imidazole, lithium methylsulfate, lithium ethylsulfate and lithium bis (nonafluorobutylsulfonyl) imide. Preferably, the lithium salt is selected from lithium hexafluorophosphate (LiPF)6) Lithium tetrafluoroborate (LiBF)4) Lithium difluorobis (oxalato) phosphate (LiDFOP), lithium bis (fluorosulfonylimide) (LiFSI), lithium difluorophosphate (LiDFP/LiPO)2F2) And lithium bis (nonafluorobutylsulfonyl) imide.
Preferably, the mass percentage of the lithium salt in the electrolyte of the high-nickel ternary lithium ion battery is 10-20%.
Preferably, the non-aqueous organic solvent is a mixture of Ethylene Carbonate (EC), diethyl carbonate (DEC) and Ethyl Methyl Carbonate (EMC), and the mass ratio of Ethylene Carbonate (EC), diethyl carbonate (DEC) and Ethyl Methyl Carbonate (EMC) in the mixture is 3:1: 6.
The invention also provides a lithium ion battery, and the lithium ion battery contains the high-nickel ternary lithium ion battery electrolyte.
According to the invention, the anchoring effect on metal ions is adjusted by changing the unsaturation degree of the isocyanate compound, the electrostatic acting force between the compound and an active interface is enhanced, and the effect of improving the protection of the positive electrode is achieved by increasing the number of isocyanate groups of the isocyanate compound.
Compared with the prior art, the invention has the advantages that:
1. in the lithium ion battery electrolyte, compounds with a specific structural formula and three or more isocyanate groups can form an SEI film on a negative electrode interface before the reduction of a solvent to inhibit the continuous contact of the solvent and the positive electrode interface, so that the stability of the negative electrode interface is improved, other negative electrode film-forming additives are introduced into an electrolyte system at the same time, the content of the compounds with three or more isocyanate groups is controlled to be 0.1-1.5%, excessive participation in negative electrode reaction is reduced, and the formation of a negative electrode interface film is regulated or modified, so that the influence of the compounds on the normal-temperature circulation and low-temperature discharge performance of a battery is reduced; meanwhile, the compound with three or more isocyanate groups can be partially oxidized and decomposed in the cathode side before the solvent to form a CEI interface film, so that the possibility of contact between the electrolyte and the active point of the cathode is reduced, the compound can fully react in the battery manufacturing stage by controlling the addition amount of the compound, the residue after formation and capacity grading is reduced, the problem that the internal resistance is increased due to continuous reaction with the cathode in the later use process of the battery or the chemical effects such as polymerization reaction and the like due to thermodynamic instability is avoided, and the problems of impedance increase and the like due to excessive introduction are avoided; in addition, the isocyanate structure in the compound with three or more isocyanate groups can be used as a phagocytic agent of HF and water in a battery system, so that the decomposition of the active material and electrolyte is reduced.
2. According to the invention, through optimizing the formula of the lithium ion battery electrolyte, the compound containing three or more isocyanate groups is introduced, so that the high-temperature storage performance and the high-temperature cycle performance of the high-nickel battery are obviously improved, and especially under the synergistic action of the uniquely combined mixed lithium salt, the negative film-forming additive and the compound containing three or more isocyanate groups, the advantages of the compound and the negative film-forming additive are respectively exerted, so that the normal-temperature cycle performance of the high-nickel battery is ensured, the gas production of the battery in a high-temperature environment is reduced, the internal resistance of the battery is delayed to increase, and the electrochemical performance of the lithium ion battery is improved.
3. In the lithium ion battery electrolyte, the compound with a specific structural formula and three or more isocyanate groups is less in dosage, raw materials are easy to obtain, and the cost is effectively reduced while the electrochemical performance of the lithium ion battery is improved.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention. It is to be understood that the following description is only illustrative of the present invention and is not to be construed as limiting the present invention.
The isocyanate group-containing compounds in the examples and comparative examples are illustrated below:
A1：l-lysine triisocyanateThe structural formula is as follows:
a2: 1,3, 6-hexane triisocyanate of the formula:
a3: triisocyanatoethylene silane of the formula:
a4: triphenyl thiophosphate isocyanate of the formula:
a5: (2,4, 6-trioxotriazine-1, 3,5(2H,4H,6H) -triyl) tris (hexamethylene) isocyanate of the formula:
a6: a tetraisocyanatosilane of the formula:
example 1
Preparing an electrolyte: ethylene Carbonate (EC), diethyl carbonate (DEC) and Ethyl Methyl Carbonate (EMC) were mixed uniformly in a mass ratio of 30:10:60 in an argon-filled glove box (moisture < 10ppm, oxygen < 1ppm) to obtain a mixed solution, and lithium hexafluorophosphate (LiPF) was added to the mixed solution in an amount of 14% based on the total mass of the electrolyte6) Stirring until it is completely dissolved, and then adding 0.5% of isocyanate group-containing compound A1, 1% of vinyl sulfate (DTD), 0.5% of Vinylene Carbonate (VC), 1% of lithium difluorophosphate (LiDFP/LiPO) based on the total mass of the electrolyte2F2) And 2% of lithium bis (fluorosulfonyl) imide (LiFSI), and stirring uniformly to obtain the lithium ion battery electrolyte of example 1.
Examples 2 to 21
Examples 2 to 21 are also specific examples of the preparation of the electrolyte, and the parameters and preparation method are the same as those of example 1 except that the composition ratios of the components of the electrolyte are added as shown in Table 1. The electrolyte formulation is shown in table 1.
Comparative examples 1 to 5
Comparative examples 1 to 5 the parameters and preparation method were the same as in example 1 except that the composition ratios of the respective components of the electrolyte were changed as shown in Table 1. The electrolyte formulation is shown in table 1.
TABLE 1 electrolyte compositions of comparative examples and examples
Note: the concentration of the lithium salt is the mass percentage content in the electrolyte;
the content of the compound containing isocyanate groups is the mass percentage content in the electrolyte;
the content of each component in the negative electrode film forming additive is the mass percentage content in the electrolyte;
the proportion of each component in the solvent is mass ratio.
Lithium ion battery performance testing
Preparing an NCM811/SiOx-4.2V battery: LiNi as positive electrode active material0.8Co0.1Mn0.1O2(811) The positive electrode plate is obtained by coating the mixture on an Al foil, drying, cold pressing and vermicelli after fully stirring and uniformly mixing acetylene black serving as a conductive agent, a carbon nano tube and polyvinylidene fluoride (PVDF) serving as a binder in a N-methylpyrrolidone solvent system in a dry environment filled with nitrogen according to the mass ratio of 95: 2.8: 0.2: 2, and obtaining the positive electrode plate with the compaction density of 3.45g/cm 3.
And (2) fully stirring and uniformly mixing the negative active material graphite, the conductive agent acetylene black, the carbon nano tube, the binder Styrene Butadiene Rubber (SBR) and the thickening agent sodium carboxymethyl cellulose (CMC) in a deionized water solvent system according to the mass ratio of 96: 1.8: 0.2: 1, coating the mixture on a Cu foil, drying and cold pressing to obtain the negative pole piece.
Polyethylene (PE) is used as a base film (14 μm) and a nano alumina coating (2 μm) is coated on the base film to be used as a diaphragm.
And stacking the positive pole piece, the diaphragm and the negative pole piece in sequence to enable the diaphragm to be positioned between the positive pole piece and the negative pole piece to play an isolating role, and winding to obtain the bare cell. Placing a bare cell in an outer package, injecting the electrolyte prepared in comparative examples 1-5 and examples 1-21, and carrying out procedures of packaging, laying aside, formation, aging, secondary packaging, capacity grading and the like to obtain a high-nickel NCM811/AG-4.25V ternary cathode material soft package lithium ion battery, and carrying out performance test according to the following method, wherein the test results are shown in Table 2:
1. normal temperature cycle performance
Charging the NCM811/AG-4.25V lithium ion battery to 4.25V at a constant current and a constant voltage of 1C and a cut-off current of 0.05C at normal temperature (25 +/-2 ℃); standing for 5min, then discharging at constant current to 2.75V, standing for 5min, performing charge and discharge in such a circulating manner, and recording the cycle life of the battery when the charge and discharge cycle capacity reaches 80% of the initial capacity.
2. High temperature cycle performance
Under the condition of high temperature (45 +/-2 ℃), charging the NCM811/AG-4.25V lithium ion battery to 4.25V at a constant current and a constant voltage of 1C, wherein the cut-off current is 0.05C; standing for 5min, then discharging at constant current to 2.75V, standing for 5min, performing charge and discharge in such a circulating manner, and recording the cycle life of the battery when the charge and discharge cycle capacity reaches 80% of the initial capacity.
3. High temperature storage Properties
Under the condition of normal temperature (25 +/-2 ℃), the lithium ion battery is subjected to primary 1C/1C charging and discharging (the discharge capacity is recorded as DC)0) Recording the initial thickness as D1 and the initial internal resistance R1, and then charging the NCM811/AG-4.25V battery to 4.25V under the condition of 1C constant current and constant voltage; storing the fully charged lithium ion battery in a 60 ℃ high-temperature box for 7 days, immediately measuring the thickness D2 after taking out, and performing 1C discharge (the discharge capacity is recorded as DC) at normal temperature1) (ii) a Measuring internal resistance R2 with an AC internal resistance meter, and performing 1C/1C charging and discharging (discharge capacity is recorded as DC)2) And calculating the thickness change rate, the internal resistance change rate, the DCR change rate, the capacity retention rate and the capacity recovery rate of the lithium ion battery by using the following formulas:
4. low temperature-20 deg.C discharge performance
Under the condition of normal temperature (25 ℃), respectively charging a 4.25V NCM811/AG-4.25V battery to 4.25V full charge under the condition of 1C constant current and constant voltage; then discharging the fully charged lithium ion battery to 2.5V at a constant current of 1C, and recording the normal-temperature discharge capacity of A1; and then fully charging the battery again according to the same manner, placing the battery in an environment at the temperature of minus 20 ℃ for standing for 4 hours, discharging the battery to 2.5V at a constant current of 1C, recording the discharge capacity A2 at the temperature of minus 20 ℃, and calculating the 1C discharge efficiency of the lithium ion battery at the temperature of minus 20 ℃ by using the following formula:
table 2 performance data for comparative and example cells
As can be seen from comparative examples 1-2, the high nickel ternary battery system has the problem of easy gas generation, and the high temperature storage performance and the high temperature cycle performance are poor under the condition of no high temperature type additive, and particularly the high temperature storage problem is more prominent in the system containing fluoroethylene carbonate or lithium oxalate.
As can be seen from examples 11 to 14 and comparative example 3, the performance of the compound containing three or more isocyanate groups provided by the present invention is better than that of the HDI additive containing two isocyanate groups in comparative example 3 in terms of the same content of isocyanate compound.
As can be seen from examples 1 to 21 and comparative examples 4 to 5, the cycle performance and high and low temperature performance of the battery are closely related to the addition amount of the compound containing three or more isocyanate groups, and when the addition amount of the compound containing three or more isocyanate groups is increased from 0.2% to 1%, the high temperature performance tends to be gradually enhanced, the rate of change in thickness after storage at 60 ℃ for 14 days tends to be gradually reduced, the residual capacity and recovery capacity tend to be increased, and further increased to 2%, the expansion of the thickness does not change significantly, but the rate of retention and recovery of the high temperature storage capacity is rather decreased, which may not completely react with the positive and negative electrode interfaces at the early stage of the reaction when the addition amount of the isocyanate compound is too large, on the one hand, the impedance continues to increase due to the action of the active potential of the positive electrode interface in the high SOC state during the later stage of storage, and on the other hand, the isocyanate additive which does not sufficiently react exists in the electrolyte in a free state, the battery has thermodynamic instability under the catalysis of acidity and heat, and also increases the internal resistance of the battery, so that the capacity is reduced quickly; however, as shown in comparative example 4, when the amount of addition is too low, a film cannot be formed on the positive and negative electrode interfaces, and the improvement of battery performance is limited. Therefore, the compound containing three or more isocyanate groups is preferably added in an amount of 0.2 to 1%.
It can be seen from examples 1-21 that the invention, by optimizing the formulation of the lithium ion battery electrolyte and introducing the compound containing three or more isocyanate groups, significantly improves the high temperature storage performance and high temperature cycle performance of the high nickel battery, and especially under the synergistic effect of the uniquely combined mixed lithium salt, the negative film-forming additive and the compound containing three or more isocyanate groups, exerts advantages of each of them, not only ensures the normal temperature cycle performance of the high nickel battery, but also reduces the gas generation of the battery in a high temperature environment, and delays the increase of the internal resistance of the battery, thereby improving the electrochemical performance of the lithium ion battery.
Claims (10)
1. The high-nickel ternary lithium ion battery electrolyte comprises a non-aqueous organic solvent, lithium salt and an additive, and is characterized in that the additive comprises a compound with three or more isocyanate groups and a negative electrode film-forming additive.
2. The high-nickel ternary lithium ion battery electrolyte according to claim 1, wherein the compound having three or more isocyanate groups is at least one selected from the group consisting of L-lysine triisocyanate, 1,3, 6-hexane triisocyanate, triisocyanatoethylsilane, triphenylisocyanate thiophosphate, (2,4, 6-trioxotriazine-1, 3,5(2H,4H,6H) -triyl) tris (hexamethylene) isocyanate, and tetraisocyanatosilane.
3. The high-nickel ternary lithium ion battery electrolyte according to claim 1, wherein the compound having three or more isocyanate groups is contained in the high-nickel ternary lithium ion battery electrolyte in an amount of 0.1 to 1.5% by mass.
4. The high-nickel ternary lithium ion battery electrolyte according to claim 3, wherein the compound having three or more isocyanate groups is contained in the high-nickel ternary lithium ion battery electrolyte in an amount of 0.2 to 1% by mass.
5. The high-nickel ternary lithium ion battery electrolyte of claim 1, wherein the negative film-forming additive is selected from a mixture of at least two of fluoroethylene carbonate, ethylene sulfate, vinylene carbonate, tris (trimethylsilyl) phosphite, and 1, 3-propane sultone.
6. The high-nickel ternary lithium ion battery electrolyte according to claim 1, wherein the mass percentage of the negative electrode film-forming additive in the high-nickel ternary lithium ion battery electrolyte is 0.5-15%.
7. The high-nickel ternary lithium ion battery electrolyte of claim 1, wherein the lithium salt is selected from a mixture of at least three of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium difluorobis-oxalate phosphate, lithium bis-fluorosulfonylimide, lithium difluorophosphate, lithium bis (nonafluorobutylsulfonyl) imide.
8. The high-nickel ternary lithium ion battery electrolyte according to claim 1, wherein the mass percentage of the lithium salt in the high-nickel ternary lithium ion battery electrolyte is 10-20%.
9. The high-nickel ternary lithium ion battery electrolyte according to claim 1, wherein the non-aqueous organic solvent is a mixture of ethylene carbonate, diethyl carbonate and ethyl methyl carbonate, and the mass ratio of ethylene carbonate, diethyl carbonate and ethyl methyl carbonate in the mixture is 3:1: 6.
10. A lithium ion battery, characterized in that the lithium ion battery contains the high-nickel ternary lithium ion battery electrolyte according to any one of claims 1 to 9.
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