CN114335732A - Lithium ion battery electrolyte - Google Patents
Lithium ion battery electrolyte Download PDFInfo
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- CN114335732A CN114335732A CN202210008928.9A CN202210008928A CN114335732A CN 114335732 A CN114335732 A CN 114335732A CN 202210008928 A CN202210008928 A CN 202210008928A CN 114335732 A CN114335732 A CN 114335732A
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- lithium ion
- ion battery
- electrolyte
- battery electrolyte
- bicyclic
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 80
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 68
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 34
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 31
- 229910000077 silane Inorganic materials 0.000 claims abstract description 31
- 239000010452 phosphate Substances 0.000 claims abstract description 30
- 125000002619 bicyclic group Chemical group 0.000 claims abstract description 28
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000011737 fluorine Substances 0.000 claims abstract description 27
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 26
- 239000000654 additive Substances 0.000 claims abstract description 25
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 24
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 24
- 230000000996 additive effect Effects 0.000 claims abstract description 20
- 239000003125 aqueous solvent Substances 0.000 claims abstract description 11
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 6
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 6
- -1 bicyclic fluorosulfonate ester Chemical class 0.000 claims description 31
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 13
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 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
- 125000001153 fluoro group Chemical group F* 0.000 claims description 8
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims description 6
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 6
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 6
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 5
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 4
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 4
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-UHFFFAOYSA-N 0.000 claims description 3
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 claims description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 3
- 229910012265 LiPO2F2 Inorganic materials 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 3
- 229940090181 propyl acetate Drugs 0.000 claims description 3
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910010941 LiFSI Inorganic materials 0.000 claims description 2
- 229910013188 LiBOB Inorganic materials 0.000 claims 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 24
- 229910052759 nickel Inorganic materials 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 11
- 230000002195 synergetic effect Effects 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 description 45
- 230000000052 comparative effect Effects 0.000 description 27
- 235000021317 phosphate Nutrition 0.000 description 25
- 239000007774 positive electrode material Substances 0.000 description 23
- 238000000034 method Methods 0.000 description 18
- 238000002360 preparation method Methods 0.000 description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 14
- 239000010410 layer Substances 0.000 description 14
- 229910052744 lithium Inorganic materials 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 6
- 239000006258 conductive agent Substances 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 5
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 229920003048 styrene butadiene rubber Polymers 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 4
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 4
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 3
- 150000005678 chain carbonates Chemical class 0.000 description 3
- 150000005676 cyclic carbonates Chemical class 0.000 description 3
- 239000011883 electrode binding agent Substances 0.000 description 3
- 239000011267 electrode slurry Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 2
- WHROWQPBDAJSKH-UHFFFAOYSA-N [Mn].[Ni].[Cr] Chemical compound [Mn].[Ni].[Cr] WHROWQPBDAJSKH-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- XGVXNTVBGYLJIR-UHFFFAOYSA-N fluoroiodomethane Chemical compound FCI XGVXNTVBGYLJIR-UHFFFAOYSA-N 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 2
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000002070 nanowire Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920005597 polymer membrane Polymers 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- MGGGFDCMRADCEW-UHFFFAOYSA-N 1,3,5-trioxepane-2,4-dione Chemical compound O=C1OCCOC(=O)O1 MGGGFDCMRADCEW-UHFFFAOYSA-N 0.000 description 1
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- SXAMGRAIZSSWIH-UHFFFAOYSA-N 2-[3-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,2,4-oxadiazol-5-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NOC(=N1)CC(=O)N1CC2=C(CC1)NN=N2 SXAMGRAIZSSWIH-UHFFFAOYSA-N 0.000 description 1
- YJLUBHOZZTYQIP-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=N2 YJLUBHOZZTYQIP-UHFFFAOYSA-N 0.000 description 1
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 1
- 229910014733 LiNiaCobMncO2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003660 carbonate based solvent Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 1
- SBWRUMICILYTAT-UHFFFAOYSA-K lithium;cobalt(2+);phosphate Chemical compound [Li+].[Co+2].[O-]P([O-])([O-])=O SBWRUMICILYTAT-UHFFFAOYSA-K 0.000 description 1
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 description 1
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- KTQDYGVEEFGIIL-UHFFFAOYSA-N n-fluorosulfonylsulfamoyl fluoride Chemical compound FS(=O)(=O)NS(F)(=O)=O KTQDYGVEEFGIIL-UHFFFAOYSA-N 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000004205 trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
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- 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
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- Secondary Cells (AREA)
Abstract
The invention provides a lithium ion battery electrolyte which comprises a non-aqueous solvent, lithium salt and an additive, wherein the additive comprises bicyclic fluorine-containing sulfonate and silane phosphate. The invention combines the bicyclic fluorine-containing sulfonate and the silane phosphate in the lithium ion battery electrolyte to play a synergistic effect of the two, and obtains the effect of improving the high-temperature cycle performance and the rate capability of a high-nickel system and a high-voltage system of the lithium ion battery better than the effect of singly using any one additive.
Description
Technical Field
The invention belongs to the field of lithium ion batteries, and particularly relates to a lithium ion battery electrolyte.
Background
The lithium ion battery has the advantages of high energy density, high voltage, small self-discharge, wide working temperature range, no memory effect, environmental friendliness and the like. In recent years, lithium ion batteries have been widely used in the fields of consumer electronics, electric vehicles, electric tools, and the like. With the wide application of lithium ion batteries, the performance requirements of lithium ion batteries are higher and higher. The electrolyte is used as the core blood of the lithium ion battery and has a crucial influence on the performance of the lithium ion battery.
The electrolyte consists of three parts of a solvent, lithium salt and an additive. In the components of the electrolyte, the additive obviously improves the performance of the lithium ion battery. The performance of the lithium ion battery can be greatly improved by adding a small amount of additives with specific functions. The conventional additive Vinylene Carbonate (VC) can be reduced to form an SEI film in a negative electrode in preference to a solvent, and further decomposition of the solvent is inhibited, so that the cycle performance of the lithium ion battery is improved, but the VC negative electrode has high film forming impedance, so that the rate performance of the lithium ion battery is slightly poor, and meanwhile, the VC is easily oxidized and decomposed at the positive electrode under high nickel and high voltage, and the oxidative decomposition product has a deteriorating effect on the battery performance, so that the application of the VC in a high nickel system and a high voltage system is limited.
Patent application No. 201710640474.6 discloses an electrolyte using a cyclic sulfonate and ethylene dicarbonate in combination to improve high-temperature cycle and high-temperature storage performance of a lithium ion battery. Although the electrolyte can improve the high-temperature cycle performance of the lithium ion battery to a certain extent, the electrolyte still has defects in practical application. The stability requirement on the anode interface in a high-nickel system and a high-voltage system is high, and the scheme can not meet the requirements on high-temperature cyclicity and rate capability of the high-nickel system and the high-voltage system in practical application.
Thus, the existing lithium ion battery electrolyte needs to be improved.
Disclosure of Invention
In order to solve the problems, the invention combines and uses the bicyclic fluorine-containing sulfonate and the silane phosphate in the lithium ion battery electrolyte, and plays the synergistic effect of the two, thereby obtaining the effect of improving the high-temperature cycle performance and the rate capability of a high-nickel system and a high-voltage system of the lithium ion battery, which is more excellent than the effect of singly using any one additive.
Specifically, the invention provides a lithium ion battery electrolyte, which comprises a non-aqueous solvent, a lithium salt and an additive, wherein the additive comprises a bicyclic fluorine-containing sulfonate and a silane phosphate.
In one or more embodiments, the bicyclic fluorosulfonate ester has a structure represented by formula I:
in the formula I, R1～R4Each independently selected from a hydrogen atom, a fluorine atom, a C1-C5 alkyl group and a C1-C5 fluoroalkyl group.
In one or more embodiments, the bicyclic fluorosulfonate ester is selected from:
in one or more embodiments, the silane phosphate ester has the structure shown in formula II:
in the formula II, R5～R13Each independently selected from a hydrogen atom, a C1-C5 alkyl group, and a C1-C5 fluoroalkyl group.
In one or more embodiments, the silane phosphate is selected from the group consisting of:
in one or more embodiments, the bicyclic fluorosulfonate ester is present in the electrolyte in an amount of 0.1% to 5% by weight.
In one or more embodiments, the mass fraction of the silane phosphate ester in the electrolyte is 0.05% to 1%.
In one or more embodiments, the non-aqueous solvent is selected from at least two of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, γ -butyrolactone, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl propionate, propyl propionate, and butyl propionate.
In one or more embodiments, the electrolyte salt is selected from LiPF6、LiBF4LiFSI, LiTFSI, LiBOB, LiODFB and LiPO2F2At least one of; preferably, the concentration of the electrolyte salt in the electrolyte is 0.5-2 mol/L.
The invention also provides a lithium ion battery comprising the lithium ion battery electrolyte according to any of the embodiments herein.
Drawings
FIG. 1 is a synthesis scheme of compounds L1 to L5 used in examples and comparative examples.
Detailed Description
To make the features and effects of the present invention obvious to those skilled in the art, the terms and words used in the specification and claims are generally described and defined below. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The theory or mechanism described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, i.e., the present disclosure may be practiced without limitation to any particular theory or mechanism.
All features defined herein as numerical ranges or percentage ranges, such as numbers, amounts, levels and concentrations, are for brevity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to cover and specifically disclose all possible subranges and individual numerical values (including integers and fractions) within the range.
In this context, for the sake of brevity, not all possible combinations of features in the various embodiments or examples are described. Therefore, the respective features in the respective embodiments or examples may be arbitrarily combined as long as there is no contradiction between the combinations of the features, and all the possible combinations should be considered as the scope of the present specification.
The invention provides a lithium ion electrolyte. The electrolyte is applied to the lithium ion battery, and can obviously improve the high-temperature cycle performance and the rate capability of the lithium ion battery. The lithium ion battery electrolyte comprises a non-aqueous solvent, a lithium salt and an additive, wherein the additive comprises a bicyclic fluorine-containing sulfonate and a silane phosphate. According to the invention, through the synergistic effect of the bicyclic fluorine-containing sulfonate and the silane phosphate, the film forming components are optimized, and the effect of improving the high-temperature cycle performance and rate performance of a high-nickel system and a high-voltage system of the lithium ion battery, which is more excellent than the effect of using any one additive alone, is obtained.
The bicyclic fluorine-containing sulfonate has a bicyclic structure and contains a plurality of-RSO3Functional group and contains fluorine. The electron-withdrawing effect of the bicyclic structure of the bicyclic fluorine-containing sulfonate improves the electron-gaining capacity of a central atom, so that the central atom is more easily reduced on the surface of a negative electrode to form a solid electrolyte interface film (SEI film), and a formed passivation film has better stability than that of a monocyclic structure, thereby improving the high-temperature cycle and high-temperature storage performance of the battery. However, the inventor of the invention finds that the impedance of a passivation film formed by the bicyclic fluorine-containing sulfonate is large, the multiplying power performance of the battery is poor, silane phosphate can also form a film on the surfaces of a positive electrode and a negative electrode, the impedance of the passivation film formed by the material is low, when the bicyclic fluorine-containing sulfonate and the silane phosphate are used in combination, the bicyclic fluorine-containing sulfonate and the silane phosphate both form a film on the surface of the negative electrode, and the addition of the silane phosphate optimizes the film forming component of the bicyclic fluorine-containing sulfonate, so that RSO in the component formed by the bicyclic fluorine-containing sulfonate forming the film3Reduced Li content, Li2SO4Increased content relative to RSO3In the case of Li, Li2SO4The electrolyte has better stability and lithium conductivity, and reduces the SEI film impedance, thereby improving the high-temperature cycle performance of the battery and improving the rate performance.
The bicyclic fluorosulfonate ester used in the present invention has a structure represented by formula I:
in the formula I, R1～R4Each independently selected from a hydrogen atom, a fluorine atom, a C1-C5 alkyl group and a C1-C5 fluoroalkyl group. R1～R4May be the same or different.
In the present invention, the "C + number" before a group represents the number of carbon atoms contained in the group. In the present invention, a fluoroalkyl group may be a group in which one or more hydrogen atoms of an alkyl group are replaced with a fluorine atom. In some embodiments, fluoroalkyl is a group formed by all of the hydrogen atoms of an alkyl group being replaced with fluorine atoms, i.e., perfluoroalkyl.
In some embodiments, R1～R4Each independently selected from a hydrogen atom, a fluorine atom, a C1-C3 alkyl group and a C1-C3 fluoroalkyl group. In some embodiments, R1～R4Each independently selected from a hydrogen atom, a fluorine atom, a C1-C2 alkyl group and a C1-C2 fluoroalkyl group. In some embodiments, R1～R4Each independently selected from a hydrogen atom, a fluorine atom, a methyl group and a fluoromethyl group. The fluoromethyl group may be trifluoromethyl.
In some embodiments, the bicyclic fluorosulfonate ester used in the present invention is selected from one or more of compound L1, compound L2, compound L3, compound L4, and compound L5 having the structure shown below:
the bicyclic fluorosulfonate ester used in the present invention can be synthesized by a known method. In some embodiments, the bicyclic fluorine-containing sulfonate is prepared by reacting a silver disulfonate compound with iodofluoromethane, phosphorus pentoxide can be used as a reaction catalyst, and the bicyclic fluorine-containing sulfonate obtained by the reaction can be fluorinated to prepare other bicyclic fluorine-containing sulfonates. In some embodiments, compounds L1-L5 were synthesized using the following reaction:
compound L1:
compound L2:
compounds L3, L4:
compound L5:
the silane phosphate used in the present invention has a structure represented by formula II:
in the formula II, R5～R13Each independently selected from a hydrogen atom, a C1-C5 alkyl group, and a C1-C5 fluoroalkyl group. R5～R13May be the same or different. In some embodiments, R5～R13The same is true.
In some embodiments, R5～R13Each independently selected from a hydrogen atom, a C1-C3 alkyl group, and a C1-C3 fluoroalkyl group. In some embodiments, R1～R4Each independently selected from a hydrogen atom, a C1-C2 alkyl group, and a C1-C2 fluoroalkyl group. In some embodiments, R1～R4Each independently selected from C1-C2 alkyl and C1-C2 fluoromethyl. C1-C2 fluoromethyl groups including trifluoromethyl andand (3) trifluoroethyl.
In some embodiments, the silane phosphate used in the present invention is selected from one or more of compound P1, compound P2, and compound P3 having the structure shown below:
the silane phosphates suitable for use in the present invention are commercially available and can also be synthesized by known methods.
The invention discovers that the combination of the bicyclic fluorine-containing sulfonate and the silane phosphate with the structure in the electrolyte of the lithium ion battery can obtain a particularly excellent synergistic effect on improving the high-temperature cycle performance and the rate capability of a high-nickel system and a high-voltage system of the lithium ion battery.
In the present invention, the mass fraction of the bicyclic fluorine-containing sulfonate in the electrolyte is preferably 0.1% to 5%, for example, 0.5%, 0.8%, 1%, 3%, 5%, and the mass fraction of the silane phosphate in the electrolyte is preferably 0.05% to 1%, for example, 0.05%, 0.1%, 0.3%, 0.5%, 1%, based on the total mass of the lithium ion battery electrolyte. The dosage of the dicyclic fluorine-containing sulfonate and the silane phosphate is controlled in the range, which is beneficial to the dicyclic fluorine-containing sulfonate and the silane phosphate to play a synergistic effect in improving the high-temperature cycle performance and the rate capability of a high-nickel system and a high-voltage system of the lithium ion battery.
The non-aqueous solvent in the lithium ion battery electrolyte of the present invention may be a non-aqueous solvent commonly used in the art, including, but not limited to, one or more, preferably two or more, selected from the group consisting of Ethylene Carbonate (EC), Propylene Carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), Ethyl Methyl Carbonate (EMC), γ -butyrolactone, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl propionate, propyl propionate, and butyl propionate. In some embodiments, the non-aqueous solvent is a carbonate-based solvent. Preferably, the nonaqueous solvent includes at least one cyclic carbonate and at least one chain carbonate. Examples of the cyclic carbonate include ethylene carbonate and propylene carbonate. Examples of the chain carbonate include dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate. The mass ratio of the cyclic carbonate to the chain carbonate may be 1:1 to 1:5, for example, 1: 2. In some embodiments, the non-aqueous solvent comprises ethylene carbonate, ethyl methyl carbonate and diethyl carbonate, and the mass ratio of the ethylene carbonate, the ethyl methyl carbonate and the diethyl carbonate can be 1 (0.5-2) to (0.5-2), such as 1:1: 1.
The electrolyte salt in the lithium ion battery electrolyte of the present invention may be an electrolyte salt commonly used in the art, for example, may be a lithium salt, including but not limited to, one selected from LiPF6、LiBF4Lithium bis (fluorosulfonyl) imide (LiFSI), lithium bis (trifluoromethylsulfonyl) imide (LiTFSI), lithium bis (oxalato) borate (LiBOB), lithium difluoro (oxalato) borate (LiODFB) and LiPO2F2One or more of (a). In some embodiments, the electrolyte salt is LiPF6. The concentration of the electrolyte salt in the electrolyte solution may be 0.5 to 2mol/L, for example, 0.8 to 1.2mol/L, 1 mol/L.
The additive in the lithium ion battery electrolyte of the invention can optionally comprise other known additives which can be used in the lithium ion battery electrolyte, such as a desolvation agent, a cosolvent, a film-forming additive and the like, besides the bicyclic fluorine-containing sulfonate and the silane phosphate. The total mass fraction of the additives other than the bicyclic fluorosulfonate ester and the silane phosphate ester in the electrolyte may be 0.1% to 10%, for example 1% to 5%, based on the total mass of the lithium ion battery electrolyte. In some embodiments, the lithium ion battery electrolyte of the present invention is comprised of an electrolyte salt, a non-aqueous solvent, and an additive. In some embodiments, the additive consists of a bicyclic fluorosulfonate ester and a phosphorosilicate ester.
The lithium ion battery electrolyte is suitable for various lithium ion batteries known in the field, in particular to the lithium ion battery with a high nickel system. Herein, the high nickel system refers to that the percentage of the amount of nickel element substances in the positive active substances contained in the positive pole piece of the lithium ion battery to the amount of metal elements except lithium is more than or equal to 80%. The present invention provides a lithium ion battery, such as a high nickel system lithium ion battery, in which the electrolyte is the lithium ion battery electrolyte of the present invention.
In addition to the electrolyte, the lithium ion battery further comprises a positive electrode plate, a negative electrode plate and a diaphragm arranged between the positive electrode and the negative electrode.
The positive pole piece comprises a positive current collector and a positive material layer arranged on the surface of the positive current collector. The positive electrode collector may be an aluminum foil. The positive electrode material layer includes a positive electrode active material, a conductive agent, and a binder. The positive electrode active material may be one or more selected from a nickel-cobalt binary positive electrode material, a nickel-manganese binary positive electrode material, a cobalt-manganese binary positive electrode material, a nickel-cobalt-manganese ternary positive electrode material, a nickel-cobalt-aluminum ternary positive electrode material, a nickel-chromium-manganese ternary positive electrode material, a nickel-cobalt-manganese-aluminum quaternary positive electrode material, lithium iron phosphate, cobalt lithium phosphate, manganese lithium phosphate, lithium manganese iron phosphate, lithium manganate, and lithium titanate, for example, one or more selected from a nickel-cobalt binary positive electrode material of a high nickel system, a nickel-manganese binary positive electrode material, a nickel-cobalt-manganese ternary positive electrode material, a nickel-cobalt-aluminum ternary positive electrode material, a nickel-chromium-manganese ternary positive electrode material, and a nickel-cobalt-manganese-aluminum quaternary positive electrode material. In some embodiments, the positive active material is a nickel-cobalt-manganese ternary positive electrode material of a high nickel system, which has the chemical formula LiNiaCobMncO2Wherein a is more than or equal to 0.8 and less than 1, b is more than 0 and less than 1, c is more than 0 and less than 1, and a + b + c is 1. The positive electrode conductive agent may be one or more selected from the group consisting of graphite, carbon black, acetylene black, carbon nanotubes, carbon nanowires, carbon microspheres, carbon fibers, and graphene. The positive electrode binder may be one or more selected from polyvinylidene fluoride (PVDF), Polytetrafluoroethylene (PTFE), acrylonitrile multipolymer, polybutyl acrylate, polyacrylonitrile, Styrene Butadiene Rubber (SBR), and carboxymethyl cellulose (CMC). The mass ratio of each component in the positive electrode material layer may be conventional, for example, the mass fraction of the positive electrode active material may be 90% to 98%, for example, 92%, 94%, 96%, the mass fraction of the conductive agent may be 1% to 5%, for example, 2%, 3%, 3.5%, 4%, and the mass fraction of the binder may be 1% to 5%, for example, 2%, 96%, based on the total mass of the positive electrode material layer%, 2.5%, 3% and 4%. For example, the positive electrode material layer may include a positive electrode material layer having a mass ratio of 94: 3.5: 2.5 LiNi0.8Co0.1Mn0.1O2Carbon black and PVDF.
The negative pole piece comprises a negative pole current collector and a negative pole material layer arranged on the surface of the negative pole current collector. The negative electrode current collector may be a copper foil. The negative electrode material layer includes a negative electrode active material, a conductive agent, and a binder. The negative active material may be graphite. The negative electrode conductive agent may be one or more of carbon black, acetylene black, carbon nanotubes, carbon nanowires, carbon microspheres, carbon fibers, and graphene. The negative electrode binder may be one or more selected from polyvinylidene fluoride, polytetrafluoroethylene, acrylonitrile multipolymer, polybutyl acrylate, polyacrylonitrile, styrene butadiene rubber, and carboxymethyl cellulose, for example, the negative electrode binder may be carboxymethyl cellulose and styrene butadiene rubber. The mass ratio of each component in the anode material layer may be conventional, for example, the mass fraction of the anode active material may be 90% to 98%, for example, 93%, 95.5%, 97%, the mass fraction of the conductive agent may be 1% to 5%, for example, 2%, 1.5%, 3%, 4%, and the mass fraction of the binder may be 1% to 5%, for example, 2%, 3%, 4%, based on the total mass of the anode material layer. For example, the negative electrode material layer may include graphite, carbon black, carboxymethyl cellulose, and styrene-butadiene rubber in a mass ratio of 95.5:1.5:1.2: 1.8.
The membrane may be a polymer membrane, a ceramic membrane or a polymer/ceramic composite membrane. The polymer separator includes a single-layer polymer separator and a multi-layer polymer separator. Monolayer polymer membranes include Polyethylene (PE) membranes and polypropylene (PP) membranes. Each layer in the multilayer polymeric separator may independently be polyethylene or polypropylene. For example, the multilayer separator may be a PE/PP trilayer polymer separator. The thickness of the separator may be 5 to 50 μm, for example 20 μm.
The lithium ion battery of the present invention can be prepared using a method that is conventional in the art. For example, the positive electrode plate, the negative electrode plate and the separator are placed in the order of positive electrode plate/separator/negative electrode plate/separator from top to bottom, and are wound to form a battery electrode core, and then the battery assembly process is completed through the processes of electrolyte injection, sealing and the like, so as to form the finished battery.
The invention creatively combines the bicyclic fluorine-containing sulfonate and the silane phosphate to play the synergistic effect of the two, and obtains the effect of improving the high-temperature cycle performance and the rate capability of a high-nickel system and a high-voltage system of the lithium ion battery better than the effect of singly using any one additive.
The present invention will be illustrated below by way of specific examples. It should be understood that these examples are illustrative only and are not intended to limit the scope of the present invention. The methods, reagents and materials used in the examples and comparative examples are those conventional in the art unless otherwise indicated.
The compounds P1 to P3 used in the examples and comparative examples were purchased from Jiangsu Huasheng lithium battery materials, Inc. The compounds L1 to L5 used in the examples and comparative examples were prepared using silver disulfonate and iodofluoromethane as raw materials, and the synthetic routes are shown in fig. 1.
Example 1
Step 1: in a glove box with the moisture content less than 1ppm, mixing ethylene carbonate, methyl ethyl carbonate and diethyl carbonate according to the mass ratio of 1:1:1 to obtain a mixed solvent, after uniformly mixing, adding 1mol/L lithium hexafluorophosphate to completely dissolve the mixed solvent, uniformly stirring to obtain a basic electrolyte sample, and then adding a compound L1 accounting for 1 wt% of the basic electrolyte sample into the basic electrolyte sample
And 0.3% by weight of a compound P1
Obtaining electrolyte;
step 2: according to a formula of 94: 3.5: 2.5 mass ratio LiNi0.8Co0.1Mn0.1O2Mixing and dispersing carbon black and PVDF in NMP, and uniformly dispersing to obtain anode slurry; coating the positive electrode slurry on an aluminum foil current collector, drying, rolling and cutting to obtain a positive electrode plate;
and step 3: mixing graphite, carbon black, carboxymethyl cellulose and styrene butadiene rubber according to the mass ratio of 95.5:1.5:1.2:1.8, dispersing in solvent water, and uniformly dispersing to obtain negative electrode slurry; coating the negative electrode slurry on a copper foil current collector, drying, rolling and cutting to obtain a negative electrode plate;
and 4, step 4: selecting a PE/PE/PP three-layer polymer diaphragm with the thickness of 20 mu m as a battery diaphragm, putting the diaphragm, a positive pole piece and a negative pole piece in the order of positive pole piece/diaphragm/negative pole piece/diaphragm from top to bottom, winding to prepare a battery pole core, injecting the electrolyte obtained in the step (1), sealing and other technological processes, and finishing the assembly process of the battery to prepare the finished battery.
Example 2
Except that 0.3 wt% of the compound P1 was changed to 0.3 wt% of the compound P2 in the preparation of the electrolyte
Otherwise, the same as example 1.
Example 3
Except that 0.3 wt% of the compound P1 was changed to 0.3 wt% of the compound P3 in the preparation of the electrolyte
Otherwise, the same as example 1.
Example 4
Except that 1% by weight of compound L1 was replaced by 1% by weight of compound L2 in the preparation of the electrolyte
Otherwise, the same as example 1.
Example 5
Except that 1% by weight of compound L1 was replaced by 1% by weight of compound L3 in the preparation of the electrolyte
Otherwise, the same as example 1.
Example 6
The procedure of example 1 was repeated, except that 1% by weight of the compound L1 was changed to 3% by weight of the compound L1 in the preparation of the electrolyte.
Example 7
The same procedure as in example 1 was repeated, except that 0.3% by weight of the compound P1 was changed to 0.05% by weight of the compound P1 in the preparation of the electrolyte.
Example 8
The procedure of example 1 was repeated, except that 1% by weight of the compound L1 was changed to 5% by weight of the compound L1 in the preparation of the electrolyte.
Example 9
The same as example 1 except that 0.3 wt% of the compound P1 was changed to 1 wt% of the compound P1 in the preparation of the electrolyte.
Comparative example 1
The same procedure as in example 1 was repeated, except that 0.3% by weight of the compound P1 was not added in the preparation of the electrolyte.
Comparative example 2
The same procedure as in example 1 was repeated, except that 1% by weight of Compound L1 was not added in the preparation of the electrolyte.
Comparative example 3
The procedure of example 1 was repeated, except that 1% by weight of the compound L1 was changed to 6% by weight of the compound L1 in the preparation of the electrolyte.
Comparative example 4
The same as example 1 except that 0.3 wt% of the compound P1 was changed to 2 wt% of the compound P1 in the preparation of the electrolyte.
Comparative example 5
The procedure of example 1 was repeated, except that 1% by weight of the compound L1 was changed to 0.05% by weight of the compound L1 in the preparation of the electrolyte.
Comparative example 6
The same procedure as in example 1 was repeated, except that 0.3% by weight of the compound P1 was changed to 0.01% by weight of the compound P1 in the preparation of the electrolyte.
The types and contents of the additives added during the preparation of the electrolytes in examples 1 to 9 and comparative examples 1 to 4 are shown in Table 1.
TABLE 1
| L1(％) | L2(％) | L3(％) | P1(％) | P2(％) | P3(％) | |
| Example 1 | 1 | 0.3 | ||||
| Example 2 | 1 | 0.3 | ||||
| Example 3 | 1 | 0.3 | ||||
| Example 4 | 1 | 0.3 | ||||
| Example 5 | 1 | 0.3 | ||||
| Example 6 | 3 | 0.3 | ||||
| Example 7 | 1 | 0.05 | ||||
| Example 8 | 5 | 0.3 | ||||
| Example 9 | 1 | 1 | ||||
| Comparative example 1 | 1 | |||||
| Comparative example 2 | 0.3 | |||||
| Comparative example 3 | 6 | 0.3 | ||||
| Comparative example 4 | 1 | 2 | ||||
| Comparative example 5 | 0.05 | 0.3 | ||||
| Comparative example 6 | 1 | 0.01 |
Test example
The batteries obtained in examples 1 to 9 and comparative examples 1 to 4 were subjected to high-temperature cycle performance and rate performance tests, the results of which are shown in table 2, and the test methods were as follows:
the high-temperature cycle performance test method comprises the following steps: at 45 ℃, the lithium ion battery is charged to 4.25V at a constant current of 1C, then is charged at a constant voltage until the current is 0.05C, and then is discharged to 2.75V at a constant current of 1C, and the first cycle is carried out, and the cyclic charge/discharge is carried out according to the conditions. Capacity retention rate of lithium ion battery (discharge capacity corresponding to cycle number/discharge capacity of first cycle) x 100%
The method for testing the rate capability comprises the following steps: charging the lithium ion battery to 4.25V at a constant current of 1C at the normal temperature of 25 ℃, then charging at a constant voltage until the current is 0.05C, then discharging at a constant current of 0.33C to 2.75V, and recording the discharge capacity; and then charging to 4.25V at a constant current of 1C, then charging to 0.05C at a constant voltage, then discharging to 2.75V at a constant current of 3C, and recording the discharge capacity. The 3C rate discharge retention rate (3C discharge capacity/0.33C discharge capacity) × 100%
TABLE 2
| Capacity retention rate of 500 weeks at 1C 45 ℃ cycle | 3C rate discharge | |
| Example 1 | 92.3％ | 96.2％ |
| Example 2 | 91.8％ | 95.9％ |
| Example 3 | 91.1％ | 95.3％ |
| Example 4 | 92％ | 96％ |
| Example 5 | 91.6％ | 94.9％ |
| Example 6 | 90.3％ | 94.5％ |
| Example 7 | 89.3％ | 94.1％ |
| Example 8 | 90.5％ | 95.2％ |
| Example 9 | 88.7％ | 94％ |
| Comparative example 1 | 84.3％ | 88.1％ |
| Comparative example 2 | 85.6％ | 89.4％ |
| Comparative example 3 | 87.1％ | 90.2％ |
| Comparative example 4 | 86.4％ | 89.3％ |
| Comparative example 5 | 85.2％ | 89.1％ |
| Comparative example 6 | 84.4％ | 88.5％ |
Comparing examples 1-5 with comparative examples 1-2, according to the data in table 2, it can be seen that: the dicyclic fluorine-containing sulfonate and the silane phosphate are used as additives in a combined mode, and due to the synergistic effect of the dicyclic fluorine-containing sulfonate and the silane phosphate, the effect of improving high-temperature cycle performance and rate performance better than that of a single additive can be achieved.
According to the data in table 2, it can be seen that examples 1, 6, 8 are compared with comparative examples 3, 5: the content of the bicyclic fluorine-containing sulfonate is too high or too low, so that great influence is generated, and when the content is too low, the function of improving the performance of the lithium ion battery cannot be realized; when the content is too high, the impedance is increased due to the too high content, and the high-temperature cycle and rate performance of the lithium ion battery are deteriorated.
According to the data in table 2, it can be seen that examples 1, 7, 9 are compared with comparative examples 4, 6: the silane phosphate ester content is too high or too low, which can generate great influence, and when the content is too low, the silane phosphate ester can not improve the performance of the lithium ion battery; when the content is too high, the impedance is increased due to the too high content, and the high-temperature cycle and rate performance of the lithium ion battery are deteriorated.
Claims (10)
1. The lithium ion battery electrolyte is characterized by comprising a non-aqueous solvent, lithium salt and an additive, wherein the additive comprises bicyclic fluorine-containing sulfonate and silane phosphate.
2. The lithium ion battery electrolyte of claim 1, wherein the bicyclic fluorosulfonate ester has a structure represented by formula I:
in the formula I, R1～R4Each independently selected from a hydrogen atom, a fluorine atom, a C1-C5 alkyl group and a C1-C5 fluoroalkyl group.
3. The lithium ion battery electrolyte of claim 1 wherein the bicyclic fluorosulfonate ester is selected from the group consisting of:
4. the lithium ion battery electrolyte of claim 1 wherein the silane phosphate has a structure represented by formula II:
in the formula II, R5～R13Each independently selected from a hydrogen atom, a C1-C5 alkyl group, and a C1-C5 fluoroalkyl group.
5. The lithium ion battery electrolyte of claim 1 wherein the silane phosphate is selected from the group consisting of:
6. the lithium ion battery electrolyte of claim 1, wherein the bicyclic fluorosulfonate ester is present in the electrolyte at a mass fraction of 0.1% to 5%.
7. The lithium ion battery electrolyte of claim 1 wherein the mass fraction of the silane phosphate ester in the electrolyte is 0.05% to 1%.
8. The lithium ion battery electrolyte of claim 1 wherein the non-aqueous solvent is selected from at least two of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, gamma-butyrolactone, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl propionate, propyl propionate, and butyl propionate.
9. The lithium ion battery electrolyte of claim 1 wherein the electrolyte salt is selected from LiPF6、LiBF4LiFSI, LiTFSI, LiBOB, LiODFB and LiPO2F2At least one of; preferably, the concentration of the electrolyte salt in the electrolyte is 0.5-2 mol/L.
10. A lithium ion battery comprising the lithium ion battery electrolyte of any one of claims 1-9.
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| CN113346140A (en) * | 2021-06-01 | 2021-09-03 | 昆山宝创新能源科技有限公司 | Electrolyte and application thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114824486A (en) * | 2022-06-29 | 2022-07-29 | 天鹏锂能技术(淮安)有限公司 | Electrolyte for lithium ion battery, preparation method of electrolyte and lithium ion battery |
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