CN117652049A - Liquid electrolyte composition and electrochemical cell having the same - Google Patents
Liquid electrolyte composition and electrochemical cell having the same Download PDFInfo
- Publication number
- CN117652049A CN117652049A CN202280048916.7A CN202280048916A CN117652049A CN 117652049 A CN117652049 A CN 117652049A CN 202280048916 A CN202280048916 A CN 202280048916A CN 117652049 A CN117652049 A CN 117652049A
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- formula
- electrolyte composition
- lithium
- group
- salt
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 112
- 239000011244 liquid electrolyte Substances 0.000 title claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 92
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000003446 ligand Substances 0.000 claims abstract description 28
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 27
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 12
- 125000000129 anionic group Chemical group 0.000 claims abstract description 5
- 239000003792 electrolyte Substances 0.000 claims description 107
- -1 Lithium bis (2-fluoro-2-trifluoromethyl-malonate) borate Chemical compound 0.000 claims description 58
- 229910052744 lithium Inorganic materials 0.000 claims description 57
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 56
- 159000000002 lithium salts Chemical class 0.000 claims description 50
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 40
- 229910003002 lithium salt Inorganic materials 0.000 claims description 38
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 35
- 150000002500 ions Chemical class 0.000 claims description 34
- 229910052731 fluorine Inorganic materials 0.000 claims description 25
- 239000011737 fluorine Substances 0.000 claims description 25
- 229910001416 lithium ion Inorganic materials 0.000 claims description 25
- 239000000654 additive Substances 0.000 claims description 20
- 125000004122 cyclic group Chemical group 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- 230000000996 additive effect Effects 0.000 claims description 15
- 230000000737 periodic effect Effects 0.000 claims description 15
- 125000001153 fluoro group Chemical group F* 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 13
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 13
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 229910052796 boron Inorganic materials 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 8
- 150000001768 cations Chemical class 0.000 claims description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 150000002466 imines Chemical class 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 5
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 5
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 5
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- 150000002739 metals Chemical class 0.000 claims description 5
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 5
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 4
- 150000002602 lanthanoids Chemical class 0.000 claims description 4
- GKZFQPGIDVGTLZ-UHFFFAOYSA-N 4-(trifluoromethyl)-1,3-dioxolan-2-one Chemical compound FC(F)(F)C1COC(=O)O1 GKZFQPGIDVGTLZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000006374 C2-C10 alkenyl group Chemical group 0.000 claims description 3
- 125000005865 C2-C10alkynyl group Chemical group 0.000 claims description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000005587 carbonate group Chemical group 0.000 claims description 3
- 150000007942 carboxylates Chemical group 0.000 claims description 3
- 150000001244 carboxylic acid anhydrides Chemical group 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- UQSQSQZYBQSBJZ-UHFFFAOYSA-M fluorosulfonate Chemical group [O-]S(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-M 0.000 claims description 3
- 125000005462 imide group Chemical group 0.000 claims description 3
- 125000000468 ketone group Chemical group 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 125000002827 triflate group Chemical group FC(S(=O)(=O)O*)(F)F 0.000 claims description 3
- WKYGDMSOKGXAAY-UHFFFAOYSA-N 2,3,4,5-tetrafluoro-6-hydroxybenzoic acid Chemical class OC(=O)C1=C(O)C(F)=C(F)C(F)=C1F WKYGDMSOKGXAAY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- GBXQPDCOMJJCMJ-UHFFFAOYSA-M trimethyl-[6-(trimethylazaniumyl)hexyl]azanium;bromide Chemical compound [Br-].C[N+](C)(C)CCCCCC[N+](C)(C)C GBXQPDCOMJJCMJ-UHFFFAOYSA-M 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910010941 LiFSI Inorganic materials 0.000 claims 2
- 235000010269 sulphur dioxide Nutrition 0.000 description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 17
- 238000000034 method Methods 0.000 description 17
- 150000001450 anions Chemical group 0.000 description 14
- 239000002904 solvent Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 11
- LINZKRDXGNYMMB-UHFFFAOYSA-N 2,2-bis(trifluoromethyl)propanedioic acid Chemical compound OC(=O)C(C(O)=O)(C(F)(F)F)C(F)(F)F LINZKRDXGNYMMB-UHFFFAOYSA-N 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 229910001317 nickel manganese cobalt oxide (NMC) Inorganic materials 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 125000002015 acyclic group Chemical group 0.000 description 7
- 150000004645 aluminates Chemical class 0.000 description 7
- 239000006182 cathode active material Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 238000011161 development Methods 0.000 description 6
- 230000018109 developmental process Effects 0.000 description 6
- 150000002009 diols Chemical class 0.000 description 6
- 125000001033 ether group Chemical group 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000004064 recycling Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 239000006183 anode active material Substances 0.000 description 5
- 239000013522 chelant Substances 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 5
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 5
- 125000004430 oxygen atom Chemical group O* 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 3
- CUHCMEDDEGQCHU-UHFFFAOYSA-N 3-oxo-3-(trifluoromethoxy)propanoic acid Chemical compound OC(=O)CC(=O)OC(F)(F)F CUHCMEDDEGQCHU-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 3
- 150000004697 chelate complex Chemical class 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000012453 solvate Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000004291 sulphur dioxide Substances 0.000 description 3
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 2
- CKQSBYDHYWBCJM-UHFFFAOYSA-N 2,3,3-trifluoropropanoic acid Chemical compound OC(=O)C(F)C(F)F CKQSBYDHYWBCJM-UHFFFAOYSA-N 0.000 description 2
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 description 2
- 229910000838 Al alloy Inorganic materials 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
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229910000531 Co alloy Inorganic materials 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910000846 In alloy Inorganic materials 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 229910000676 Si alloy Inorganic materials 0.000 description 2
- 229910001128 Sn alloy Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011883 electrode binding agent Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 229910021385 hard carbon Inorganic materials 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 229910001867 inorganic solvent Inorganic materials 0.000 description 2
- 239000003049 inorganic solvent Substances 0.000 description 2
- 239000010416 ion conductor Substances 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 2
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 description 2
- 229910001537 lithium tetrachloroaluminate Inorganic materials 0.000 description 2
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- MPDOUGUGIVBSGZ-UHFFFAOYSA-N n-(cyclobutylmethyl)-3-(trifluoromethyl)aniline Chemical compound FC(F)(F)C1=CC=CC(NCC2CCC2)=C1 MPDOUGUGIVBSGZ-UHFFFAOYSA-N 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910021382 natural graphite Inorganic materials 0.000 description 2
- 239000005486 organic electrolyte Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229960004624 perflexane Drugs 0.000 description 2
- ZJIJAJXFLBMLCK-UHFFFAOYSA-N perfluorohexane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F ZJIJAJXFLBMLCK-UHFFFAOYSA-N 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 229910021384 soft carbon Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 230000032258 transport Effects 0.000 description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- GKDCWKGUOZVDFX-UHFFFAOYSA-N 1,1,1,4,4,4-hexafluoro-2,3-bis(trifluoromethyl)butane-2,3-diol Chemical compound FC(F)(F)C(C(F)(F)F)(O)C(O)(C(F)(F)F)C(F)(F)F GKDCWKGUOZVDFX-UHFFFAOYSA-N 0.000 description 1
- 125000006039 1-hexenyl group Chemical group 0.000 description 1
- 125000006023 1-pentenyl group Chemical group 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- 125000000530 1-propynyl group Chemical group [H]C([H])([H])C#C* 0.000 description 1
- BWLMKPFFGYWBTQ-UHFFFAOYSA-N 2,3,3,4-tetramethylpentane-2,4-diol Chemical compound CC(C)(O)C(C)(C)C(C)(C)O BWLMKPFFGYWBTQ-UHFFFAOYSA-N 0.000 description 1
- DBTGFWMBFZBBEF-UHFFFAOYSA-N 2,4-dimethylpentane-2,4-diol Chemical compound CC(C)(O)CC(C)(C)O DBTGFWMBFZBBEF-UHFFFAOYSA-N 0.000 description 1
- AZPKQKQYAXOSJX-UHFFFAOYSA-N 2-fluoro-2-(trifluoromethyl)propanedioic acid Chemical compound OC(=O)C(F)(C(O)=O)C(F)(F)F AZPKQKQYAXOSJX-UHFFFAOYSA-N 0.000 description 1
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- AUKCYOUETBBMFV-UHFFFAOYSA-N 3-trimethylsilyl-1,3-oxazolidin-2-one Chemical compound C[Si](C)(C)N1CCOC1=O AUKCYOUETBBMFV-UHFFFAOYSA-N 0.000 description 1
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 description 1
- 125000005915 C6-C14 aryl group Chemical group 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910010082 LiAlH Inorganic materials 0.000 description 1
- 229910013075 LiBF Inorganic materials 0.000 description 1
- 229910015965 LiNi0.8Mn0.1Co0.1O2 Inorganic materials 0.000 description 1
- 229910014422 LiNi1/3Mn1/3Co1/3O2 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical class [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical class [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910000091 aluminium hydride Inorganic materials 0.000 description 1
- NDPGDHBNXZOBJS-UHFFFAOYSA-N aluminum lithium cobalt(2+) nickel(2+) oxygen(2-) Chemical compound [Li+].[O--].[O--].[O--].[O--].[Al+3].[Co++].[Ni++] NDPGDHBNXZOBJS-UHFFFAOYSA-N 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 150000001638 boron Chemical class 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 238000007707 calorimetry Methods 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000006547 cyclononyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 229940043279 diisopropylamine Drugs 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
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- RIFGWPKJUGCATF-UHFFFAOYSA-N ethyl chloroformate Chemical compound CCOC(Cl)=O RIFGWPKJUGCATF-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000001640 fractional crystallisation Methods 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 239000002223 garnet Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- QDYVPYWKJOJPBF-UHFFFAOYSA-M lithium;hydroxide;dihydrate Chemical compound [Li+].O.O.[OH-] QDYVPYWKJOJPBF-UHFFFAOYSA-M 0.000 description 1
- VGYDTVNNDKLMHX-UHFFFAOYSA-N lithium;manganese;nickel;oxocobalt Chemical compound [Li].[Mn].[Ni].[Co]=O VGYDTVNNDKLMHX-UHFFFAOYSA-N 0.000 description 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002895 organic esters Chemical class 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000013014 purified material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000008844 regulatory mechanism Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 125000002088 tosyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])[H])S(*)(=O)=O 0.000 description 1
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 1
- 238000002061 vacuum sublimation Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a liquid electrolyte composition for an electrochemical cell, comprising the following components: (a) sulfur dioxide; (B) At least one salt, wherein the salt comprises an anionic complex having at least one bidentate ligand. The ligand forms together with the central ion Z of the anionic complex a five to eight membered ring, wherein the ring comprises a sequence of 2 to 5 carbon atoms optionally interrupted by heteroatoms.
Description
Technical Field
The present invention relates to an electrolyte composition and an electrochemical cell having the same.
Background
Electrochemical cells are of great importance in many technical fields. Electrochemical cells are particularly often used in applications requiring low voltages, for example for driving notebook computers or mobile phones. An advantage of electrochemical cells is that a number of individual cells can be connected to each other. The cells can for example provide a high voltage by a series connection, whereas a parallel connection of the cells results in a higher nominal capacity. Such a connection creates a battery with greater energy. Such battery systems are also suitable for high voltage applications and may for example enable electric drive of a vehicle or for stationary energy storage.
In the following, the term "electrochemical cell" is used as a synonym for all names for rechargeable galvanic elements common in the art, such as battery cells, battery cells, accumulators, battery accumulators and secondary batteries.
The electrochemical cell is capable of providing electrons during discharge for use in an external circuit. In contrast, the electrochemical cell is charged by the input electrons during the charging process by means of an external circuit.
The electrochemical cell has at least two different electrodes, namely a positive electrode (cathode) and a negative electrode (anode). The two electrodes are in contact with an electrolyte composition.
The most commonly used electrochemical cells are called lithium ion cells, also called lithium ion batteries.
Lithium ion cells known from the prior art have assembled anodes, which very often comprise a carbon-based anode active material (typically graphite-type carbon) deposited on a metallic copper carrier foil. The cathode typically includes metallic aluminum coated with a cathode active material (e.g., layered oxide). For example LiCoO coated onto a rolled aluminium carrier foil can be used 2 Or LiNi 1/3 Mn 1/3 Co 1/3 O 2 As a layered oxide.
The electrolyte composition plays an important role in the safety and performance of the electrochemical cell. This ensures charge balance between the cathode and the anode during charge-discharge. The current required for this is achieved by ion transport of the conductive salt in the electrolyte composition. In a lithium ion cell, the conductive salt is a lithium conductive salt, and lithium ions are used as ions that transport electric current.
There is therefore the following necessity: suitable conductive salts are selected to maintain an effective charge balance during operation, which are not only sufficiently soluble in the electrolyte composition, but also have suitable ionic conductivity. The most commonly used conductive salt in lithium ion cells is lithium hexafluorophosphate (LiPF 6 )。
In addition to the lithium conductive salt, the electrolyte composition further comprises a solvent that can achieve dissociation of the conductive salt and sufficient mobility of lithium ions. Liquid organic solvents consisting of a series of linear and cyclic dialkyl carbonates are known from the prior art. Generally, a mixture of the following substances is used: ethylene Carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), propylene Carbonate (PC) and Ethyl Methyl Carbonate (EMC).
It is noted herein that each solvent has a specific range of cell voltage stability, also referred to as a "voltage window". In this voltage window, the electrochemical cell can be operated stably during operation. Electrochemical oxidation of the components of the electrolyte composition occurs if the cell voltage approaches the upper voltage limit. Instead, the reduction process is performed at the lower end of the voltage window. These two redox reactions are undesirable, reducing the performance and reliability of the cell and leading to its failure in adverse situations.
The processes mentioned here are in particular relevant for deep discharge and overcharge of lithium-ion cells.
Prior art lithium ion cells with organic electrolyte compositions tend to generate gases during charge-discharge. By "gas generating" (Gasung) is understood that the components of the electrolyte are electrochemically decomposed into volatile and gaseous compounds as a result of the use of an excessively high cell voltage. The generation of gas reduces the proportion of electrolyte and results in the generation of undesirable decomposition products, thereby resulting in lower service life and lower lithium ion cell efficiency.
In order that the cell can operate over as wide a potential range as possible, fluorinated solvents or additives are added to the electrolyte compositions of the prior art. Fluorinated solvents such as fluoroethylene carbonate (FEC) are chemically inert and electrochemically stable with respect to the operating voltage of the lithium ion cell.
A well-known disadvantage of fluorinated electrolytes is that in the event of thermal defects in the cell, it can lead to enhanced exotherms and the formation and emission of unhealthy gases such as Hydrogen Fluoride (HF).
Because of this disadvantage, lithium ion cells possess a number of regulatory mechanisms to maintain the cell within the optimal voltage range for the respective solvent during operation and thereby stabilize the electrolyte composition.
In the prior art, various schemes for stabilizing electrolyte compositions are known.
EP 1 689 756 B1 describes a process for the preparation of the formula X (OR F ) m Wherein X is selected from the group consisting of B, al, ga, in, P, as and Sb, m is 3 or 5, and R F Being linear or branched, partial or completePerfluorinated alkyl or aryl groups. The weakly coordinating anion forms a salt with a monovalent or divalent cation, preferably with an alkali metal ion. Due to the chemical stability, in particular of anions, the disclosed salts are especially proposed for use as inert lithium conducting salts in lithium ion batteries. But does not describe electrolyte compositions having weakly coordinating anions for use in lithium ion batteries.
In addition to the selection of chemically inert conductive salts, the stability of the battery cells can be improved by the selection of suitable solvents. Sulfur dioxide (SO) has been discussed in David Linden, "handbook of batteries (Handbook of Batteries)" (2 nd edition, mcGraw Hill, 1994) 2 ) As an inorganic solvent in the electrolyte composition. The electrolyte composition based on sulfur dioxide has in particular an increased ionic conductivity and thus allows for operation of the battery cell at high discharge currents without negatively affecting the stability of the cell. In addition, sulfur dioxide-based electrolyte compositions are unique in high energy density, low self-discharge rate, and limited overcharge and deep discharge.
Sulfur dioxide has the disadvantage that it only does not dissolve sufficiently many lithium conducting salts, which can dissolve well in organic solvents. Thus, for example, the widely used lithium conducting salt lithium hexafluorophosphate cannot be used in electrolyte compositions containing sulfur dioxide.
EP 1,201,004 B1 discloses a rechargeable electrochemical cell with an electrolyte based on sulfur dioxide. Sulfur dioxide is not added here as an additive, but rather as a main component of the electrolyte composition. It should therefore at least partially ensure the mobility of the ions of the conductive salt, which leads to charge transport between the electrodes. In the proposed cells, lithium tetrachloroaluminate is used as a lithium-containing conductive salt with a cathode active material formed from a metal oxide, such as lithium cobalt oxide (LiCoO), in particular 2 ) Is used in combination. By adding a salt additive, such as an alkali metal halide like lithium fluoride, sodium chloride or lithium chloride, to the sulphur dioxide containing electrolyte composition, a functional and rechargeable cell is obtained.
EP 2534719 B1 shows a rechargeable lithium battery cell with a sulfur dioxide-based electrolyte in combination with lithium iron phosphate as cathode active material. Lithium tetrachloroaluminate is used as a preferred conductive salt in the electrolyte composition. In research on cells based on these components, higher electrochemical resistance of the cells can be demonstrated.
In WO 2021/019042 A1 rechargeable battery cells with an active metal, a layered oxide as cathode active material and an electrolyte containing sulfur dioxide are described. The use of formula M in these cells is due to the poor solubility of many common lithium conducting salts in sulfur dioxide + [Z(OR) 4 ] - Wherein M is a metal selected from the group consisting of alkali metals, alkaline earth metals and metals of group 12 of the periodic table, and R is a hydrocarbon group. The alkoxy groups-OR are each singly bonded to a central atom Z, which may be aluminum OR boron. In a preferred embodiment, the cell comprises formula Li + [Al(OC(CF 3 ) 3 ) 4 ] - Is a perfluorinated conductive salt of (2). The cells composed of the described components show stable electrochemical performance in experimental studies. In addition, the conductive salts, especially perfluorinated anions, have an unexpected hydrolytic stability. In addition, the electrolyte should be stable to oxidation up to an upper potential of 5.0V. It is further shown that the cells with the disclosed electrolytes can be discharged or charged at low temperatures up to-41 ℃. However, electrochemical performance measurements were not made at high temperatures.
The thermal stability of lithium perfluorinated aluminate at high temperatures was investigated in the specialized publication by Malinowski et al (Dalton Trans.,2020,49,7766). The authors characterized in the study [ Al (OC (CF) 3 ) 3 ) 4 ]Various properties of the salts, especially the temperature stability of the lithium derivatives. Thermogravimetric studies showed that the compound Li [ Al (OC (CF) 3 ) 3 ) 4 ]There is already a mass loss at 105 c, which is caused by the onset of decomposition of the fluorinated anions.
Disclosure of Invention
Summary of The Invention
The present invention is based on the object of providing an electrolyte composition for an electrochemical cell and in particular a rechargeable battery, which is inexpensive and can be operated safely at different operating voltages.
According to the invention, this object is achieved by a liquid electrolyte composition for an electrochemical cell according to claim 1.
Advantageous embodiments of the electrolyte composition according to the invention are given in the dependent claims, which may optionally be combined with each other.
According to the invention, this object is achieved by a liquid electrolyte composition for an electrochemical cell. The electrolyte composition comprises the following components:
(A) Sulfur dioxide;
(B) At least one salt, wherein the salt comprises an anionic complex having at least one bidentate ligand and the salt corresponds to formula (I)
Formula (II)
Or (III)
M is a metal cation selected from the group consisting of alkali metals, alkaline earth metals and metals of group 12 of the periodic Table. m is an integer from 1 to 2, and Z represents a central ion selected from the group consisting of elements of groups 2 to 16 of the periodic table, including lanthanides. A is that 1 To A 12 Each being a coordinating element bonded to the central ion Z, wherein A 1 And A 12 Each independently of the other is selected from the group consisting of elements of groups 15 and 16 of the periodic table. R is R 1 And R is 2 Each representing a single bond and being terminal and independently of each other selected from the group consisting of hydrocarbon groups optionally substituted by fluorine, trifluoromethanesulfonyl groups, trifluoromethanesulfonate groups and fluorosulfonate groups. L (L) 1 To L 6 Each independently of the others is an aliphatic or aromatic bridging group. The bridging group forms a five to eight membered ring with the central ion Z and with two coordinating elements bonded to the central ion Z and the bridging group, wherein the ring comprises a sequence of 2 to 5 carbon atoms optionally interrupted by heteroatoms.
The salts proposed according to the invention have anions comprising at least one bidentate ligand. Bidentate ligands in the sense of the present invention are understood as molecules: the molecule has at least two coordinating elements, and the molecule is linked to the central ion Z via the at least two coordinating elements. It is also conceivable to use other multidentate ligands having other numbers of teeth, such as three, four, five or six teeth.
Bidentate or multidentate ligands are also commonly referred to as chelating ligands and complexes formed by their combination are referred to as chelating complexes. The anions of the salts of the formulae (I), (II) and (III) are therefore chelate complexes. Within the scope of the present invention, chelate complexes and salts formed therefrom have various advantages over single bond complexes and salts formed therefrom.
The chelate complex is chemically more stable than its single bond derivative. The bond between the chelating ligand and the central ion is difficult to break off, and thus the chelating complexes according to the invention are chemically inert with respect to external chemical and physical influences.
According to the invention, the chelating complex is an anion of at least one salt of formula (I), (II) or (III), wherein the salt is used as a conducting salt of the electrolyte composition. The electrolyte composition thus achieves charge balance between the two electrodes with which it is in contact.
Another advantage is the high affinity of the chelating ligand for the central ion. The chelate complexes used according to the invention are chemically and electrochemically stable compounds which, owing to the strongly coordinating nature of the ligands to the central ion, have a relatively low affinity for the bond with the positively charged ion. Thus, the chelate complex itself is a weakly coordinating anion. Thus, the chelate complex itself is a weakly coordinating anion. Thus, the conductive salt can dissociate in the electrolyte composition with little or no reversion to the original salt, and form ions in solution with high mobility and correspondingly high ionic conductivity. This in turn improves the electrochemical performance of the electrochemical cell.
Owing to these properties, the chelate complexes used according to the invention, in particular the salts composed of the same, are temperature-resistant and hydrolysis-resistant.
According to the invention, the described salts are sufficiently soluble in liquid sulfur dioxide, which is an inorganic solvent for the electrolyte composition. Within the scope of the present invention, sulfur dioxide is not only contained as an additive in the electrolyte composition in low concentrations, but is also present to such an extent that it can act as a solvent to ensure ion mobility of the conductive salt.
Sulfur dioxide is gaseous at room temperature and forms stable liquid solvate complexes with lithium conducting salts with a significantly reduced vapor pressure relative to sulfur dioxide as a pure substance. The gaseous sulphur dioxide is thus combined in liquid form and can be handled safely and relatively simply. Sulfur dioxide itself and the incombustibility of the solvate complexes are particular advantages, such incombustibility improving the operational safety of electrolyte compositions based on such solvate complexes and improving the operational safety of cells prepared with electrolyte compositions.
The described salts of chelate complexes of the formulae (I), (II) and (III) are nonflammable. Thus, the electrolyte composition of the present invention is also non-flammable and safer operation of the electrochemical cell comprising the disclosed components of the electrolyte composition can be achieved. If sulfur dioxide escapes from the cell in the event of mechanical damage, sulfur dioxide cannot ignite outside the cell.
In addition, the electrolyte composition of the invention is also low cost relative to conventional organic electrolytes. The improved temperature stability and hydrolysis resistance allow for direct and almost complete recycling of the electrolyte composition from the old battery without increased costs. In order to recycle the old cells, hydrothermal methods at high pressure and high temperature are used in most cases. Conventional electrolyte compositions are mostly not hydrolysis-resistant and therefore have to be worked up in other ways. For this purpose, the electrolyte composition is extracted from the cell in a costly manner, for example by flushing the cell with supercritical carbon dioxide. In contrast, newer electrolyte formulations based on aluminates, borates or gallates, as described in the prior art, often do not have sufficient temperature stability.
The electrolyte compositions proposed here have a temperature stability and hydrolysis resistance and can therefore be recycled directly from the electrochemical cells using water-based extraction processes at low cost. The electrolyte compositions presented herein have high recycling potential and high recycling ratio due to the water solubility of the proposed components.
Recycling not only reduces the consumption of the main raw materials and energy requirements of the electrolyte composition that must be spent producing the freshly prepared electrolyte composition, but thereby also reduces carbon dioxide emissions caused during the manufacturing process. Thus, the manufacturing costs of the electrolyte composition of the present invention and the manufacturing costs of the electrochemical cells manufactured using the electrolyte composition are kept low.
According to the invention, the electrolyte composition comprises at least one salt of formula (I), (II) or (III), wherein the salt comprises an anionic complex with at least one bidentate ligand.
In the formula, the charge of the anion is balanced by a positively charged metal cation M selected from the group consisting of alkali metals, alkaline earth metals and metals of group 12 of the periodic table in stoichiometric proportions. The metal cation is preferably a lithium ion, and the salt is preferably a lithium salt. Accordingly, m is an integer from 1 to 2, where m is determined by the oxidation number of the metal cation used in accordance with the stoichiometric ratio.
In formula (I), (II) or (III), Z represents a central ion selected from the group consisting of elements of groups 2 to 16 and the lanthanide series of the periodic table. The central ion Z is preferably selected from the group consisting of elements B, al, ga, in, P, ti, nb, zn, V and La. Z is particularly preferably selected from the group consisting of aluminum, boron and phosphorus.
If the central ion corresponds to one of the elements aluminum, boron or phosphorus, the corresponding salt thus formed is an aluminate, borate or phosphate. The anions of the salts of the formulae (I), (II) or (III) are correspondingly singly negatively charged.
Coordination element A 1 To A 12 Each bonded to a central ion Z and a bridging group, wherein the coordinating element A 1 And A 12 Each independently of the other is selected from the group consisting of elements of groups 15 and 16 of the periodic table.
If the coordinating element is an element selected from the group consisting of elements of group 15 of the periodic table, the relevant coordinating element bears a fluorine-containing group. In other words, the relevant coordinating element thus has a total of three bonds, a bond to the central ion Z, a bond to the bridging group and a bond to the fluorine-containing group.
The fluorine-containing groups are selected in particular from the group consisting of trifluoromethanesulfonyl groups, trifluoromethanesulfonate groups, tosyl groups, fluorosulfonate groups and perfluorinated C 1 -C 8 Alkyl groups.
In a preferred embodiment of the invention, the at least one coordinating element comprises oxygen. Particularly preferably, all coordinating elements are oxygen.
According to another aspect, the salt corresponds to formula (I), wherein R 1 And R is 2 Each independently of the others comprises hydrocarbon groups optionally substituted by fluorine. Hydrocarbon group R 1 And R is 2 Each being singly bound and independently of one another selected from the group consisting of C 1 -C 8 Alkyl, C 2 -C 10 Alkenyl, C 2 -C 10 Alkynyl, C 6 -C 12 Cycloalkyl and C 6 -C 12 Aryl groups.
In the sense of the present invention, single bond means a hydrocarbon radical R 1 And R is 2 Each bonded to the central atom Z via a single coordinating element.
In the sense of the present invention, the term C 1 -C 8 Alkyl groups include straight or branched saturated hydrocarbon groups having one to eight carbon atoms. Preferred hydrocarbon groups include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, 2-dimethylpropyl, n-hexyl, isohexyl, 2-ethylhexyl, n-heptyl, isoheptyl, n-octyl and isooctyl.
In the sense of the present invention, the term C 2 -C 10 Alkenyl groups include straight or branched chain, at least partially unsaturated hydrocarbon groups having from two to ten carbon atoms, wherein the hydrocarbon group has at least one c—c double bond. Preferred hydrocarbon groups include, for example, vinyl, 1-propenyl, 2-propenyl, 1-n-butenyl, 2-n-butenyl, isobutenyl, 1-pentenyl, 1-hexenyl, 1-heptenyl, 1-octenyl, 1-nonenyl and 1-decenyl.
In the sense of the present invention, the term C 2 -C 10 Alkynyl groups include linear or branched, at least partially linear, unsaturated hydrocarbon groups having from two to ten carbon atoms, wherein the hydrocarbon group has at least one c—c triple bond. Preferred hydrocarbon groups include, for example, ethynyl, 1-propynyl, 2-propynyl, 1-n-butynyl, 2-n-butynyl, isobutynyl, 1-pentynyl, 1-hexynyl, 1-heptynyl, 1-octynyl, 1-nonynyl and 1-decynyl.
In the sense of the present invention, the term C 6 -C 12 Cycloalkyl includes cyclic saturated hydrocarbon groups having six to twelve carbon atoms. Preferred hydrocarbon groups include, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclohexyl, cyclononyl, and cyclodecyl.
In the sense of the present invention, the term C 6 -C 14 Aryl groups include aromatic hydrocarbon groups having six to twelve carbon atoms. Preferred hydrocarbon groups include, for example, phenyl, naphthyl and anthracenyl.
In a preferred embodiment, the hydrocarbon group R 1 And/or R 2 At least partially substituted with fluorine.
In a particularly preferred embodiment, the hydrocarbon radicals R 1 And/or R 2 Completely substituted by fluorine.
The bidentate chelating ligand has at least two coordinating elements and one bridging group L bonded to the two coordinating elements 1 To L 6 。
L 1 To L 6 Each independently of the others is an aliphatic or aromatic bridging group.
The bridging group forms a five to eight membered ring with the central ion Z and with two coordinating atoms bonded to the central ion Z and the bridging group.
The ring comprises a sequence of 2 to 5 carbon atoms optionally interrupted by heteroatoms.
According to another aspect of the invention, the ring comprises a continuous sequence of 2 to 5 carbon atoms, preferably 2 to 3 carbon atoms.
Another aspect proposes that the ring has a sequence of 2 to 5 carbon atoms interrupted by heteroatoms. In this case, heteroatoms are enclosed in the bridging group.
The heteroatom may be selected from the group consisting of elements of main groups 15 and 16 of the periodic table.
The heteroatom may in particular be oxygen. In other words, the ring or bridge group has in particular at least one ether group.
Advantageously, the ring has a sequence of 2 to 4 carbon atoms interrupted by oxygen.
The fluorine content of the ring can advantageously be reduced by the addition of ether groups. Thereby also reducing the fluorine content of the ligand as a whole. Fluorinated compounds, while having good electrochemical resistance, the synthesis of such compounds is costly and cost intensive. The inventors herein have recognized that by adding heteroatoms to the ring, the fluorine content in the ring and thus also the ligand can be reduced without compromising the electrochemical stability of the ligand.
Suitable ether groups for this are, in particular, those which are likewise stable to oxidation potential, so that the ligands are electrochemically stable even if the fluorine content is reduced.
The ring may include at least one carbonyl group selected from the group consisting of an imide group, a carboxylate group, a ketone group, a carboxylic anhydride group, a carbonate group, and a carbamate group.
The presence of at least one carbonyl advantageously results in a reduced fluorine content in the ring. The proportion of fluorine in the ligand can thus also be reduced overall. In addition, the carbonyl has higher electrochemical stability.
In a development of the invention, the bridging group L 1 To L 6 Each having a linear, branched or cyclic saturated hydrocarbon backbone optionally substituted with fluorine.
The bridging group L 1 To L 6 Preferably having 3 to 16 carbon atoms, preferably 6 to 9 carbon atoms. Hydrocarbon backbones having a number of carbon atoms (kohlenwasssto atoms) within the mentioned range give rise to anions which form particularly stable salts of the formulae (I), (II) or (III).
In a preferred embodiment, the bridging group L 1 To L 6 Each comprising a hydrocarbon backbone at least partially substituted with fluorine.
In a particularly preferred embodiment, the hydrocarbon backbone is fully fluorinated. The present embodiments therefore preferably do not contain a hydrogen atom.
The bridging group L 1 To L 6 The hydrocarbon backbone of (2) may comprise at least one carbonyl group selected from the group consisting of imide groups, carboxylate groups, ketone groups, carboxylic anhydride groups, carbonate groups, and carbamate groups.
In addition, the bridging group L 1 To L 6 The hydrocarbon backbone of (2) may include at least one heteroatom selected from the group consisting of elements of main groups 15 and 16 of the periodic table.
The heteroatoms may in particular comprise oxygen, which is incorporated in the form of ether functions in the bridging group L 1 To L 6 Is a hydrocarbon skeleton of (2).
Oxygen may also be present as an epoxy bridge at the bridging group L 1 To L 6 Is a hydrocarbon skeleton of (2). In this case, oxygen is bound to the bridging group L in a cyclic manner 1 To L 6 Is a hydrocarbon skeleton of (2).
According to another aspect, component (B) of the electrolyte composition comprises at least one lithium salt of formula (II) comprising at least one ether function in the ring and/or an epoxy bridge in the hydrocarbon backbone. Such lithium salts are preferably selected from the group consisting of:
lithium bis [3, 4, 5-hexafluoro-2, 6-bis (trifluoromethyl) tetrahydro-2H-pyran-2, 6-diolato ] borate of formula (IV)
Lithium bis [1, 3-hexafluoro-2- (2, 2-trifluoro-1-alkoxide- (trifluoromethyl) ethoxy) -2-propoxide ] borate of formula (V), and
Lithium bis [3, 4-tetrafluoro-2, 5-bis (trifluoromethyl) tetrahydro-2, 5-furandiolato ] borate of formula (VI)
And combinations thereof.
According to another aspect, component (B) of the electrolyte composition comprises at least one lithium salt of formula (II), said lithium salt having at least one carbonyl function. Such lithium salts are preferably selected from the group consisting of:
lithium bis [2, 5-tetrafluoro-3, 4-diolato-3, 4-bis (trifluoromethyl) cyclopentanone ] borate of formula (VII)
Lithium bis (2, 3,4, 5-octafluoro-1, 1-cyclopentane-dicarboxy-late) of formula (VIII)
Lithium bis (2, 3,4, 5, 6-decafluoro-1, 1-cyclohexane-dicarboxylate) borate of formula (IX)
Lithium bis (2-fluoro-2-trifluoromethyl-malonate) borate of formula (X)
Lithium bis (5, 5-difluoro-2-oxo-1, 3-dioxolane-4, 4-dicarboxy-lato) borate of formula (XI)
Lithium bis (perfluoromalonate) borate of formula (XII)
Lithium bis [3, 3-trifluoro-2-alkoxide-2- (trifluoromethyl) -propionate ] borate of formula (XIII)
Lithium bis [2, 2-bis (trifluoromethyl) malonate ] borate of formula (XIV), and
lithium bis (perfluorosalicylates) borate of formula (XV)
And combinations thereof.
The carbonyl functionality may be present in the ring and/or in the hydrocarbon backbone of the bridging group.
According to another aspect, component (B) of the electrolyte composition comprises at least one lithium salt of formula (II), the lithium salt comprising an ether function and a carbonyl group. Such lithium salts are preferably selected from the group consisting of:
lithium bis (2,2,4,4,5,5-hexafluorotetrahydro-3, 3-furandicarboxy-late) of formula (XVI), and
lithium bis (2, 5-tetrafluoro-3-alkoxide-4-oxotetrahydro-3-furanoate) borate of formula (XVII)
And combinations thereof.
In one development of the invention, component (B) of the electrolyte composition comprises at least one lithium salt of formula (II) or (III), wherein the lithium salt has an aromatic bridging group optionally substituted by fluorine and the lithium salt is preferably selected from the group consisting of:
lithium tris (2, 3,4, 5-tetrafluorobenzene-1, 2-diol) phosphate of formula (XVIII)
Lithium bis (2, 3,4, 5-tetrafluorobenzene-1, 2-diolato) borate of formula (XIX), and
lithium bis (2, 3,4,5,6, 7-hexafluoronaphthalene-1, 8-diol) borate of formula (XX)
And combinations thereof.
In principle, the salts of formulae (IV) - (XX) set forth above fall into formula (II) or (III). However, it is also conceivable to use two ligands R according to formula (I) in the case of salts of the formulae (IV) - (XX) 1 A 1 R 2 A 3 To replace the chelating ligand. In the case of the salts of the formula (XVIII), it is also possible to replace two chelating ligands.
In a further development of the invention, the salt of component (B) is a salt of the formula (XXI)
Or formula (XXII)
Wherein Z represents a central ion selected from the group consisting of aluminum and boron. In the salts of formulas (XXI) and (XXII), the coordinating element includes oxygen. In principle, formula (XXI) is only one particular variant of formula (II), and formula (XXII) is only one variant of formula (I).
In the sense of the present invention, in the salts of the formulae (XXI) and (XXII), the bonding of the bridging group to the central ion via an oxygen atom is understood to be a coordinate bond. By the binding of the ligand to the central ion, a ring is formed consisting of a bridging group, two oxygen atoms bound to the bridging group and a central ion Z. The ring here has at least one continuous sequence of 2 to 5 carbon atoms, preferably 2, 3 or 5 carbon atoms.
In a further development of the invention, such rings form salts of the formula (XXIII)
Wherein n=0, 1, 2 or 3 and R is a group. M is a metal cation selected from the group consisting of alkali metals, alkaline earth metals and metals of group 12 of the periodic Table. m is 1 or 2 and Z represents a central ion selected from the group consisting of aluminum and boron. The anion of the salt of the formula (XXIII) has two polycyclic rings according to the bonding conditions of the formula (XXI) OR one polycyclic ring according to the bonding conditions of the formula (XXII) and the group OR 1 And OR 2 。
The radicals R may be identical or different and are selected, independently of one another, from the group consisting of C 1 -C 4 Alkyl, hydrogen and fluorine.
In the sense of the present invention, the term C 1 -C 4 Alkyl groups include straight or branched saturated hydrocarbon groups having one to four carbon atoms. Preferred hydrocarbon groups include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, and tert-butyl.
In another embodiment, the hydrocarbon group R may be at least partially fluorinated. Preferred fluorinated hydrocarbon groups include, for example, trifluoromethyl or pentafluoroethyl.
If n in formula (XXIII) is equal to 0, the ring formed by the central ion Z, the bridging group and the two oxygen atoms bonded to the bridging group is pentacyclic and has a continuous sequence of 2 carbon atoms.
If n in formula (XXIII) is equal to 1, the ring formed by the central ion Z, the bridging group and the two oxygen atoms bonded to the bridging group is six-membered and has a continuous sequence of 3 carbon atoms.
If n in formula (XXIII) is equal to 3, the ring formed by the central ion Z, the bridging group and the two oxygen atoms bonded to the bridging group is eight membered and has a continuous sequence of 5 carbon atoms.
In one embodiment, n in formula (XXIII) is equal to 0 and the radicals R are identical and correspond to methyl radicals optionally substituted by fluorine. As the simplest representative, such chelating ligands are derived from pinacol.
In an advantageous development of the invention, component (B) of the electrolyte composition comprises at least one lithium salt of formula (XXI). Lithium salts are particularly suitable for use as lithium conductive salts in lithium ion batteries.
The lithium salt may preferably be selected from the group consisting of: having the general formula Li [ B (O) 2 C 2 (CF 3 ) 4 ) 2 ]Lithium bis- (1, 4-hexafluoro-2, 3-bis- (trifluoromethyl) -2, 3-butanediolato) borate of formula (XXIV), herein abbreviated as lithium bis (perfluoropinacolato) borate (LiBPFPB),
has the general formula Li [ Al (O) 2 C 2 (CF 3 ) 4 CF 2 ) 2 ]Lithium bis- (1,1,1,3,3,5,5,5-octafluoro-2, 4-bis-trifluoromethylpentane-2, 4-diolato) aluminate of formula (XXV), herein abbreviated as LiOTA
/>
And has the general formula Li [ Al (O) 2 C 3 (CF 3 ) 6 ) 2 ]Abbreviated herein as LiHTTDA, lithium bis- (1, 5-hexafluoro-2,3,3,4-tetra-trifluoromethylpentane-2, 4-diolato) aluminate of formula (XXVI)
And combinations thereof.
Lithium salts LiBPFPB (XXIV), liOTA (XXV) and LiHTTDA (XXVI) can be prepared by means of examples 1, 2 and 3 described below.
The proposed lithium salts (IV) - (XX), (XXIV) - (XXVI) dissolve well in liquid sulphur dioxide as solvent. The electrolyte composition thus prepared is nonflammable and has excellent ionic conductivity over a wide temperature range.
The conductivity of lithium salts can be determined by conductivity measurements. Lithium salts (IV) - (XX), (XXIV) - (XXVI) were prepared in different concentrations in sulfur dioxide. The conductivity of the solution was then determined by means of a two-electrode sensor immersed in the solution at constant room temperature. For this purpose, the conductivity of the solutions with lithium salts (IV) - (XX), (XXIV) - (XXVI) was measured in the range of 0-100 mS/cm.
Due to the high electrochemical resistance of lithium salts, lithium salts do not participate in the cyclic and daily aging processes in battery cells.
In addition, the proposed lithium salts have improved thermal, chemical and electrochemical resistance and particularly excellent hydrolysis resistance. Thermal resistance can be studied, for example, by thermogravimetric analysis (TGA) and dynamic differential calorimetry (DSC).
The service life of the lithium ion battery is improved due to the improved thermal, chemical and electrochemical stability of the proposed conductive salts. Thus, electrolyte compositions prepared from lithium salts are also less costly to operate.
In addition, the mentioned characteristics of lithium conductive salts can enable a series of suitable recycling processes. Preferably, a recycling process based on water as solvent can be used. Whereby the lithium conductive salt can be completely recovered again from the used battery.
The cost of preparing the electrolyte salt can be accounted for by the better recyclability of the electrolyte, which saves costs in the battery preparation process.
In another embodiment, the electrolyte composition comprises the component (B) in a concentration of 0.01 to 15mol/L, preferably 0.1 to 10mol/L, particularly preferably 0.5 to 5mol/L, relative to the total volume of the electrolyte composition.
The electrolyte composition may further comprise at least one further additive in a proportion of 0-10 wt.%, preferably 0.1-2 wt.%, relative to the total weight of the electrolyte composition.
In one embodiment, the additional additive comprises a compound selected from the group consisting of: 2-vinylpyridine, 4-vinylpyridine, cyclic exomethylene carbonates, sulfones, cyclic and acyclic sulfonates, acyclic sulfinates, cyclic and acyclic sulfinates, organic esters of inorganic acids, acyclic and cyclic alkanes, aromatic compounds, halogenated cyclic and acyclic sulfonylimines, halogenated cyclic and acyclic phosphates, halogenated cyclic and acyclic phosphines, halogenated cyclic and acyclic phosphites, halogenated cyclic and acyclic phosphazenes, halogenated cyclic and acyclic silalkylamines, halogenated cyclic and acyclic halogenated esters, halogenated cyclic and acyclic amides, halogenated cyclic and acyclic anhydrides, and halogenated organic heterocycles.
The further additive contributes to the stability of the electrolyte composition during operation of the electrochemical cell.
The further additive may also provide at least one further lithium-containing conductive salt into the electrolyte composition. In one embodiment, the additional lithium-containing conductive salt may help adapt the conductivity of the electrolyte composition to the requirements of the respective cell or to increase the corrosion resistance of the metal carrier foil of the cathode.
Preferred lithium-containing conductive salts include lithium tetrafluoroborate (LiBF) 4 ) Lithium trifluoromethane sulfonate, lithium fluoride, lithium bromide, lithium sulfate, lithium oxalate, (bis) oxalato) borate, lithium difluoro (oxalato) borate, lithium tetrahalo aluminate, lithium hexafluorophosphate, lithium bis- (trifluoromethane sulfonyl) imide (LiTFSI) and lithium bis- (fluoro sulfonyl) imide (LiFSI).
The further additive may likewise comprise a further solvent. Additional solvents may help to adjust the solubility of the electrolyte composition relative to the polar or non-polar components therein.
The additional solvent preferably includes Vinyl Ethylene Carbonate (VEC), ethyl Methyl Carbonate (EMC), vinyl Carbonate (VC) and 4-fluoro-1, 3-dioxolan-2-one (FEC).
In another embodiment, the further additive may further comprise at least one solid inorganic lithium ion conductor (solid electrolyte). Suitable examples of solid inorganic lithium ion conductors include perovskite, garnet, sulfide and amorphous compounds such as glass and combinations thereof.
In a particularly preferred embodiment, the electrolyte composition comprises the following components:
(A) Sulfur dioxide;
(B) At least one salt of the above formula (I), formula (II) or formula (III) in a concentration of 0.01 to 15mol/L, preferably 0.1 to 10mol/L, relative to the total volume of the electrolyte composition, wherein the salt is preferably a lithium salt, particularly preferably selected from the group consisting of compounds of formulae (IV) - (XX) and formulae (XXIV) - (XXVI) and combinations thereof;
(C) 0 to 10 wt%, preferably 0.1 to 2 wt% of at least one additive, relative to the total weight of the electrolyte composition, wherein the additive is preferably selected from the group consisting of: vinylene Carbonate (VC), 4-fluoro-1, 3-dioxolan-2-one (FEC), lithium hexafluorophosphate, cis-4, 5-difluoro-1, 3-dioxolan-2-one (ctfec), 4- (trifluoromethyl) -1, 3-dioxolan-2-one, bis- (trifluoromethanesulfonyl) imine (LiTFSI) and bis- (fluorosulfonyl) imine (LiFSI), and combinations thereof.
The invention also relates to an electrochemical cell having a cathode, an anode and the described electrolyte composition in contact with the cathode and the anode.
In an advantageous development of the invention, the electrochemical cell is a lithium ion cell, wherein the electrolyte composition comprises the following components:
(A) Sulfur dioxide;
(B) 0.5-2mol/L, preferably 0.4-1.5mol/L, of a salt selected from the group consisting of compounds of formulae (IV) - (XX) and formulae (XXIV) - (XXVI), relative to the total volume of the electrolyte composition;
(C) 0.1-2 wt% lithium hexafluorophosphate and 0.1-2 wt% 4-fluoro-1, 3-dioxolan-2-one (FEC), each relative to the total weight of the electrolyte composition.
The proposed lithium ion cell is low cost and can be operated safely at different operating voltages. The electrochemical properties associated therewith can be determined by measuring the test cells.
The cyclic aging resistance of the test cells can be determined by the number of cycles. The test cells are first charged with a constant charging current strength up to the maximum allowed cell voltage. The upper limit of the off-voltage is kept constant until the charging current has been reduced to the input value or the maximum charging time is reached. This is also referred to as I/U charging. The test cells are then discharged with a constant discharge current intensity up to a given off-voltage. The charging is repeated depending on the number of cycles sought to be achieved. The upper and lower breaking voltage limits and the given charge or discharge current strength must be selected experimentally. This also applies to the value to which the charging current is reduced.
The daily aging resistance and the degree of self-discharge can be determined by storing fully charged battery cells, in particular at elevated temperatures.
For this purpose, the battery cells are charged up to an upper permissible voltage limit and held at this voltage until the charging current drops to a previously determined limit value. The cell is then disconnected from the power source and stored in the temperature chamber for a period of time, e.g., one month, at an elevated temperature, e.g., 45 c (variant 1). The cells are then removed again from the temperature chamber and the residual capacity present is determined under defined conditions. For this purpose, a discharge current is selected, which corresponds in value to, for example, one third of the nominal capacity, and the cells are thereby discharged up to a lower discharge limit. This process may be repeated any number of times, for example, until the detectable residual capacity is reduced to a previously determined value, such as 70% of the nominal capacity.
In the second variant of the storage (variant 2), the storage is carried out in the temperature chamber with the power supply connected, the voltage corresponding to the upper voltage limit and this voltage being to be maintained. Experiments were performed according to both storage variants. The actual daily aging and self-discharge of the battery cells were then determined from these experiments: daily aging corresponds to the capacity loss produced by storing according to variant 2 and is calculated by subtracting the resulting residual capacity 2 from the nominal capacity. The self-discharge rate is determined from the difference between the measured residual capacities 1 and 2 relative to the nominal capacity of the battery cells by storing the measured residual capacities according to variants 1 and 2.
The cathode of the lithium ion cell preferably has a cathode active material.
Preferred cathode active materials for electrochemical cells include: lithium Cobalt Oxide (LCO), lithium Nickel Oxide (LNO), lithium nickel cobalt aluminum oxide (NCA), lithium nickel manganese cobalt oxide (NMC), lithium Manganese Oxide (LMO), lithium iron phosphate (LFP), lithium nickel manganese oxide (LMR), lithium nickel manganese oxide spinel (LNMO), and combinations thereof.
Lithium nickel manganese cobalt compounds are also known under the abbreviation NMC, sometimes the technical abbreviation NCM is also used instead. NMC-based cathode materials are particularly useful in lithium ion batteries for vehicles. NMC has as cathode material an advantageous combination of desirable properties, such as a high specific capacity, a reduced cobalt fraction, a large high current capacity and a high intrinsic safety, which for example is manifested by a sufficiently high stability upon overcharging.
NMC can be prepared with the unit of formula Li α Ni x Mn y Co z O 2 Where x+y+z=1, where α represents the value of the stoichiometric ratio of lithium and is typically between 0.8 and 1.15. Specific stoichiometric ratios are given in the literature as three digits, for example NMC 811, NMC 622, NMC 532 and NMC 111. These three digits give the relative contents of nickel to manganese to cobalt, respectively. In other words, NMC 811 is, for example, a unit of the formula LiNi 0.8 Mn 0.1 Co 0.1 O 2 I.e. where α=1. In addition, compounds of the general formulaCell Li 1+ε (Ni x Mn y Co z ) 1-ε O 2 In particular, epsilon is between 0.1 and 0.6, preferably between 0.2 and 0.4. Such lithium-rich layered oxides are also known as over-lithiated (layered) oxides (OLO).
In addition to the cathode active material, the cathode may also have further components and additives, for example foil carriers (rolled metal foil) or polymer films coated with metal, electrode binders and/or conductivity improvers (for example conductive carbon black). All the usual compounds and materials known in the art can be used as further components and additives.
The anode of the lithium ion cell preferably has an anode active material.
The anode active material may in particular be selected from the group consisting of: carbonaceous materials, soft carbon, hard carbon, natural graphite, synthetic graphite, silicon suboxide, silicon alloy, lithium alloy, aluminum alloy, indium alloy, tin alloy, cobalt alloy, niobium pentoxide, titanium dioxide, titanates such as lithium titanate (Li) 4 Ti 5 O 12 Or Li (lithium) 2 Ti 3 O 7 ) Tin dioxide and mixtures thereof.
The anode active material is preferably selected from the group consisting of: synthetic graphite, natural graphite, graphene, mesophase carbon, doped carbon, hard carbon, soft carbon, fullerenes, silicon carbon composites, silicon, surface coated silicon, suboxide of silicon, silicon alloys, lithium, aluminum alloys, indium alloys, tin alloys, cobalt alloys, and mixtures thereof.
In addition to the anode active material, the anode may have further components and additives, such as foil carriers, electrode binders and/or conductivity improvers (e.g. conductive carbon black, conductive graphite, so-called "carbon nanotubes" (CNTs), carbon fibers and/or graphene). All the usual compounds and materials known in the art can be used as further components and additives.
Detailed Description
Examples:
some synthetic routes for the salts of formulas (IV) - (XX), (XXIV) - (XXVI) are given by way of example in the examples. The remaining salts can likewise be synthesized by means of the procedure given, using variants common in the art.
Example 1: preparation of LiOTA (XXV)
2, 4-dimethylpentane-2, 4-diol (1) was dissolved in carbon tetrachloride and reacted with phosgene (COCl) 2 ) The reaction was converted to the corresponding 4,4,6,6-tetramethyl-1, 3-dioxolan-2-dione (2). The carbonate compound (2) obtained was purified by fractional crystallization from diethyl ether and dried in vacuo. In the next step, the dried carbonate compound (2) is dissolved in dried acetonitrile. A gas stream is directed through the resulting solution, wherein the gas stream consists of a fluorine to nitrogen mixture (10% by volume: 90% by volume). 4,4,6,6-tetramethyl-1, 3-dioxolan-2-dione (2) is thus converted into a perfluorinated carbonate compound (3), which can be isolated by drying under vacuum. Then using aqueous alcohol solution (H) 2 O/etoh=1:1; the sodium hydroxide in the volume%/volume%) hydrolyzes the perfluorinated carbonate to 1, 5-hexafluoro-2,3,3,4-tetra-trifluoromethylpentane-2, 4-diol (4). The aqueous solution was then covered with diethyl ether and the diol (4) was transferred from the aqueous solution to the covered diethyl ether phase by acidification with hydrochloric acid. By means of an aqueous alcoholic solution (H 2 O/etoh=1:1; the diol (4) was purified by multiple crystallization in% by volume/vol-%). In the last step, aluminium hydride (LiAlH) is used at 70-80 DEG C 4 ) In perfluorohexane (C) 6 F 14 ) Is converted into lithium bis- {1,1,1,3,3,5,5,5-octafluoro-2, 4-bis-trifluoromethylpentane-2, 4-diolato } aluminate (LiOTA) (5).
Example 2: preparation of LiHTTDA (XXVI)
The salt, lithium bis- (1, 5-hexafluoro-2,3,3,4-tetra-trifluoromethylpentane-2, 4-diolato) aluminate (LiHTTDA) can be prepared in accordance with the synthetic procedure of example 1. 2,3,3,4-tetramethylpentane-2, 4-diol was used as starting product.
Example 3: preparation of lithium bis (perfluoropinacolato) borate (XXIV)
Lithium bis (perfluoropinacolato) borate can be synthesized according to the synthesis procedure of Wu Xu and c.austen Angell (2000 electrochem. Solid-State lett.3, 366).
Hexafluoro-2, 3-bis- (trifluoromethyl) -2, 3-butanediol, lithium hydroxide dihydrate and boric acid are dissolved in stoichiometric proportions in distilled water. The resulting solution was heated at reflux overnight. The solution was then cooled down to room temperature and the residual water was removed under vacuum. The resulting reaction product lithium bis (perfluoropinacolato) borate was dried in a drying oven at 100 ℃ for 48 hours. The reaction product was purified by vacuum sublimation at 130 ℃ to form colorless crystals.
Example 4:
ligands for the conducting salts (IV) and (VI) can be synthesized according to the synthetic procedure of J.D.O. Anderson et al (1996 Inorg. Chem.35, 3191).
The conductive salts (IV) and (VI) can be prepared as follows:
all work was done in an argon stream: from commercially available LiBH by decantation with diethyl ether 4 (95%) of the insoluble foreign components were removed by purification. The solvent was then pumped away in vacuo and the purified material was dried at 80 ℃. LiBH thus purified 4 Placed in a flask in advance in 1, 2-Dimethoxyethane (DME) and boiled as a clear solution under reflux. A 5% excess of the ligand of the conducting salt (IV) or (VI) in DME was placed in advance in the dropping funnel and slowly added dropwise over a period of 1 hour. Gas is generated during ligand addition, which rapidly subsides once the addition is completed. After complete addition, boiling was continued for 15 minutes under reflux, wherein a clear solution was produced. The DME was then distilled off and the semi-dried residue was dried overnight in vacuo at 80 ℃. The yield was 90%. The insoluble components can be separated from the product by purification by extraction with perfluorohexane.
Example 5:
the conductive salt (XVIII) can be synthesized according to the synthetic procedure of M.Eberwein et al (2003J. Electrochem. Soc.150, A994).
Example 6:
the conductive salt (XIV) may be prepared as described below.
a) Synthesis of the ligand 2, 2-bis (trifluoromethyl) malonic acid:
the desired 2, 2-bis (trifluoromethyl) malonic acid was first prepared from 2- (trifluoromethyl) -3, 3-trifluoropropionic acid and lithium diisopropylamide according to the general synthetic procedure of A.P. Krapcho et al (1974 Tetrahedron Letters 32,2721) described below.
To a solution of 20mmol of diisopropylamine in 50ml of THF (in N 2 Next, -40 ℃ C.) 10ml of n-butyllithium (2M in hexane) was added. The reaction mixture was stirred for 15 minutes. 10mmol of 2- (trifluoromethyl) -3, 3-trifluoropropionic acid (1) was then added and the mixture was heated to 50℃and maintained at this temperature for 1 hour, thereby obtaining tertiary carbanion intermediate (2). The mixture was then cooled to-70 ℃ and 10mmol of ethyl chloroformate was added. The reaction mixture was allowed to slowly reach room temperature with stirring and then poured onto 100g of ice. Subsequently, 30 mmole of HCl was added to obtain monoethyl 2, 2-bis (trifluoromethyl) malonate (3), and the mixture was extracted with 25ml portions of diethyl ether. The ether phase was collected and concentrated. Oily monoethyl 2, 2-bis (trifluoromethyl) malonate was then distilled in vacuo.
The ester (3) was then converted to 2, 2-bis (trifluoromethyl) malonic acid (5) via intermediate (4) in analogy to the procedure in chem.
b) Synthesis of lithium bis (2, 2-bis (trifluoromethyl) malonate):
the synthesis of the boron salt proceeds similarly to the procedure disclosed by Liao et al (2014 Adv.Energy Mater.4 1301368).
By reacting bis (trifluoromethyl) malonic acid (1) with 3-trimethylsilyl-2-Oxazolidinone reaction to obtain bis (trifluoromethyl) -bis (trimethylsilyl) malonate (2). By subsequent addition of lithium tetramethylborate, bis [2, 2-bis (trifluoromethyl) malonate can be isolated]Lithium borate (3).
Example 7:
the conductive salt (X) may be prepared as follows:
a) Synthesis of 2-fluoro-2-trifluoromethylmalonic acid:
2, 3-tetrafluoropropionic acid was used as the starting base for the synthesis. The synthesis procedure was performed similarly to that described above for the XIV number-conducting salt.
b) Synthesis of lithium bis (2-fluoro-2-trifluoromethylmalonate) borate:
synthesis was performed in analogy to the procedure disclosed by Liao et al in 2014 Adv.Energy Mater.4 1301368.
Example 8:
the conducting salts (XIX) can be synthesized according to the synthetic procedure of J.Barthel et al (1996 J.Electrochem Soc.143,3572).
Claims (20)
1. A liquid electrolyte composition for an electrochemical cell, wherein the electrolyte composition comprises the following components:
(A) Sulfur dioxide;
(B) At least one salt, wherein the salt comprises an anionic complex having at least one bidentate ligand and the salt corresponds to formula (I)
Formula (II)
Or (III)
And combinations thereof, wherein
-M is a metal cation selected from the group consisting of alkali metals, alkaline earth metals and metals of group 12 of the periodic table;
-m is 1 or 2;
-Z represents a central ion selected from the group consisting of elements of groups 2 to 16 of the periodic table, including lanthanides;
-A 1 to A 12 Each being a coordinating element bonded to the central ion Z, wherein A 1 And A 12 Each independently of the other selected from the group consisting of elements of groups 15 and 16 of the periodic table;
-R 1 and R is 2 Each being a single bond and being terminal and independently of each other selected from the group consisting of hydrocarbon groups optionally substituted by fluorine, trifluoromethanesulfonyl groups, trifluoromethanesulfonate groups and fluorosulfonate groups; and
-L 1 to L 6 Each independently of the others, is an aliphatic or aromatic bridging group, wherein the bridging group forms a five-to eight-membered ring with the central ion Z and with two coordinating elements bonded to the central ion Z and the bridging group, and wherein the ring comprises a sequence of 2 to 5 carbon atoms that are optionally interrupted by heteroatoms.
2. The electrolyte composition of claim 1 wherein the metal cation M is lithium and the component (B) is a lithium salt.
3. Electrolyte composition according to claim 1 or 2, characterized in that the central ion is selected from the group consisting of elements of groups 2 to 16 and the lanthanide series of the periodic table, preferably from the group consisting of elements B, al, ga, in, P, ti, nb, zn, V and La, further preferably from the group consisting of aluminum, boron and phosphorus.
4. Electrolyte composition according to any one of the preceding claims, characterized in that at least one coordinating element comprises oxygen, preferably all coordinating elements are oxygen.
5. The electrolyte composition of any one of the preceding claims wherein the salt corresponds to formula (I) wherein R 1 And R is 2 Each independently of the others comprises a hydrocarbon group optionally substituted by fluorine, said hydrocarbon group being selected from the group consisting of C 1 -C 8 Alkyl, C 2 -C 10 Alkenyl, C 2 -C 10 Alkynyl, C 6 -C 12 Cycloalkyl and C 6 -C 12 Aryl groups, wherein the hydrocarbon groups are preferably at least partially substituted with fluorine, further preferably the hydrocarbon groups are fully fluorinated.
6. Electrolyte composition according to any one of the preceding claims, characterized in that the ring comprises a continuous sequence of 2 to 5 carbon atoms, preferably 2 to 3 carbon atoms.
7. Electrolyte composition according to any one of the preceding claims, characterized in that the ring has a sequence of 2 to 5 carbon atoms interrupted by heteroatoms, preferably oxygen.
8. The electrolyte composition of any one of the preceding claims wherein the ring comprises at least one carbonyl group selected from the group consisting of imide groups, carboxylate groups, ketone groups, carboxylic anhydride groups, carbonate groups, and carbamate groups.
9. The electrolyte composition according to any of the preceding claims, wherein L 1 To L 6 Each independently of the others comprises a linear, branched or cyclic saturated hydrocarbon skeleton, optionally substituted by fluorine, wherein the hydrocarbon skeleton has preferably 3 to 16 carbon atoms, preferably 6 to 9 carbon atoms, and further preferably the hydrocarbon skeleton is at least partially substituted by fluorine, and still further preferably the hydrocarbon skeleton is fully fluorinated.
10. Electrolyte composition according to any one of the preceding claims, characterized in that component (B) of the electrolyte composition comprises at least one lithium salt of formula (II), wherein the lithium salt is preferably selected from the group consisting of:
Lithium bis [3, 4, 5-hexafluoro-2, 6-bis (trifluoromethyl) tetrahydro-2H-pyran-2, 6-diolato ] borate of formula (IV)
Lithium bis [1, 3-hexafluoro-2- (2, 2-trifluoro-1-alkoxide- (trifluoromethyl) ethoxy) -2-propoxide ] borate of formula (V), and
lithium bis [3, 4-tetrafluoro-2, 5-bis (trifluoromethyl) tetrahydro-2, 5-furandiol ] borate of formula (VI)
And combinations thereof.
11. Electrolyte composition according to any one of the preceding claims, characterized in that component (B) of the electrolyte composition comprises at least one lithium salt of formula (II), wherein the lithium salt is preferably selected from the group consisting of:
lithium bis [2, 5-tetrafluoro-3, 4-diolato-3, 4-bis (trifluoromethyl) cyclopentanone ] borate of formula (VII)
Lithium bis (2, 3,4, 5-octafluoro-1, 1-cyclopentane-dicarboxy-late) of formula (VIII)
Lithium bis (2, 3,4, 5, 6-decafluoro-1, 1-cyclohexane-dicarboxylate) borate of formula (IX)
Lithium bis (2-fluoro-2-trifluoromethyl-malonate) borate of formula (X)
Lithium bis (5, 5-difluoro-2-oxo-1, 3-dioxolane-4, 4-dicarboxy-lato) borate of formula (XI)
Lithium bis (perfluoromalonate) borate of formula (XII)
Lithium bis [3, 3-trifluoro-2-alkoxide-2- (trifluoromethyl) -propionate ] borate of formula (XIII)
Lithium bis [2, 2-bis (trifluoromethyl) malonate ] borate of formula (XIV), and
lithium bis (perfluorosalicylates) borate of formula (XV)
And combinations thereof.
12. Electrolyte composition according to any one of the preceding claims, characterized in that component (B) of the electrolyte composition comprises at least one lithium salt of formula (II), wherein the lithium salt is preferably selected from the group consisting of:
lithium bis (2,2,4,4,5,5-hexafluorotetrahydro-3, 3-furandicarboxy-late) of formula (XVI), and
lithium bis (2, 5-tetrafluoro-3-alkoxide-4-oxotetrahydro-3-furanato) borate of formula (XVII)
And combinations thereof.
13. Electrolyte composition according to any one of the preceding claims, characterized in that component (B) of the electrolyte composition comprises at least one lithium salt of formula (II) or (III), wherein the lithium salt has an aromatic bridge group optionally substituted by fluorine and the lithium salt is preferably selected from the group consisting of:
lithium tris (2, 3,4, 5-tetrafluorobenzene-1, 2-diol) phosphate of formula (XVIII)
Lithium bis (2, 3,4, 5-tetrafluorobenzene-1, 2-diolato) borate of formula (XIX), and
lithium bis (2, 3,4,5,6, 7-hexafluoronaphthalene-1, 8-diol) borate of formula (XX)
And combinations thereof.
14. The electrolyte composition according to any one of the preceding claims, wherein the salt of component (B) is a salt of formula (XXI)
Or a salt of formula (XXII)
Wherein Z represents a central ion selected from the group consisting of aluminum and boron.
15. The electrolyte composition of claim 14 wherein component (B) of the electrolyte composition comprises at least one lithium salt of formula (XXII), wherein the lithium salt is preferably selected from the group consisting of: b (O) of formula (XXIV) 2 C 2 (CF 3 ) 4 ) 2 (LiBPFPB)
Al (O) of the formula (XXV) 2 C 2 (CF 3 ) 4 CF 2 ) 2 (LiOTA)
And Al (O) of the formula (XXVI) 2 C 3 (CF 3 ) 6 ) 2 (LiHTTDA)
And combinations thereof.
16. Electrolyte composition according to any one of the preceding claims, characterized in that the electrolyte composition comprises the component (B) in a concentration of 0.01 to 15mol/L, preferably 0.1 to 10mol/L, particularly preferably 0.5 to 5mol/L, relative to the total volume of the electrolyte composition.
17. Electrolyte composition according to any one of the preceding claims, characterized in that the electrolyte composition comprises at least one further additive in a proportion of 0-10 wt%, preferably 0.1-2 wt%, relative to the total weight of the electrolyte composition, wherein the further additive is preferably selected from the group consisting of: vinylene Carbonate (VC), 4-fluoro-1, 3-dioxolan-2-one (FEC), lithium hexafluorophosphate, cis-4, 5-difluoro-1, 3-dioxolan-2-one (ctfec), 4- (trifluoromethyl) -1, 3-dioxolan-2-one, bis- (trifluoromethanesulfonyl) imine (LiTFSI) and bis- (fluorosulfonyl) imine (LiFSI), and combinations thereof.
18. The liquid electrolyte composition of any one of the preceding claims, wherein the electrolyte composition comprises the following components:
(A) Sulfur dioxide;
(B) At least one salt of formula (I), formula (II) or formula (III) in a concentration of 0.01 to 15mol/L, preferably 0.1 to 10mol/L, relative to the total volume of the electrolyte composition, wherein the salt is preferably a lithium salt, particularly preferably selected from the group consisting of compounds of formulae (IV-XX) and (XXIV-XXVI), and combinations thereof;
(C) 0 to 10 wt%, preferably 0.1 to 2 wt%, relative to the total weight of the electrolyte composition, of at least one additive, wherein the additive is preferably selected from the group consisting of: vinylene Carbonate (VC), 4-fluoro-1, 3-dioxolan-2-one (FEC), lithium hexafluorophosphate, cis-4, 5-difluoro-1, 3-dioxolan-2-one (ctfec), 4- (trifluoromethyl) -1, 3-dioxolan-2-one, bis- (trifluoromethanesulfonyl) imine (LiTFSI) and bis- (fluorosulfonyl) imine (LiFSI), and combinations thereof.
19. An electrochemical cell having a cathode, an anode, and the electrolyte composition of any one of claims 1 to 18 in contact with the cathode and the anode.
20. The electrochemical cell of claim 19, wherein the electrochemical cell is a lithium ion cell, and wherein the electrolyte composition comprises the following components:
(A) Sulfur dioxide;
(B) 0.5 to 2mol/L, preferably 0.4 to 1.5mol/L of a salt of formula (XXV), relative to the total volume of the electrolyte composition;
(C) 0.1-2 wt% lithium hexafluorophosphate and 0.1-2 wt% 4-fluoro-1, 3-dioxolan-2-one (FEC), each relative to the total weight of the electrolyte composition.
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| DE102021118811.3A DE102021118811A1 (en) | 2021-07-21 | 2021-07-21 | Liquid electrolyte composition and an electrochemical cell containing the electrolyte composition |
| DE102021118811.3 | 2021-07-21 | ||
| PCT/EP2022/069660 WO2023001671A1 (en) | 2021-07-21 | 2022-07-13 | Liquid electrolyte composition, and electrochemical cell comprising said electrolyte composition |
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