EP4374446A1 - Composition d'électrolyte liquide et cellule électrochimique comprenant ladite composition d'électrolyte - Google Patents
Composition d'électrolyte liquide et cellule électrochimique comprenant ladite composition d'électrolyteInfo
- Publication number
- EP4374446A1 EP4374446A1 EP22754786.6A EP22754786A EP4374446A1 EP 4374446 A1 EP4374446 A1 EP 4374446A1 EP 22754786 A EP22754786 A EP 22754786A EP 4374446 A1 EP4374446 A1 EP 4374446A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- electrolyte composition
- formula
- group
- lithium
- salt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 115
- 239000011244 liquid electrolyte Substances 0.000 title claims abstract description 7
- 239000003792 electrolyte Substances 0.000 title claims description 110
- 150000003839 salts Chemical class 0.000 claims abstract description 89
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 56
- 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
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 81
- 229910052744 lithium Inorganic materials 0.000 claims description 66
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 55
- 159000000002 lithium salts Chemical class 0.000 claims description 46
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 38
- 150000002500 ions Chemical class 0.000 claims description 36
- 229910003002 lithium salt Inorganic materials 0.000 claims description 35
- 229910001416 lithium ion Inorganic materials 0.000 claims description 25
- 239000000654 additive Substances 0.000 claims description 20
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 18
- 125000004122 cyclic group Chemical group 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- 239000004215 Carbon black (E152) Substances 0.000 claims description 16
- 229930195733 hydrocarbon Natural products 0.000 claims description 16
- 230000000737 periodic effect Effects 0.000 claims description 15
- 150000001875 compounds Chemical class 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
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- 230000000996 additive effect Effects 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 229910052796 boron Inorganic materials 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000001301 oxygen Substances 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
- 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
- 229910052698 phosphorus Inorganic materials 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
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 229910052799 carbon 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
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 4
- 150000002602 lanthanoids Chemical class 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 claims description 3
- 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
- 229910019142 PO4 Inorganic materials 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
- 150000001642 boronic acid derivatives Chemical class 0.000 claims description 3
- 150000004651 carbonic acid esters 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
- 125000003262 carboxylic acid ester group Chemical group [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 claims description 3
- 229910052733 gallium Inorganic materials 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
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- KTQDYGVEEFGIIL-UHFFFAOYSA-N n-fluorosulfonylsulfamoyl fluoride Chemical compound FS(=O)(=O)NS(F)(=O)=O KTQDYGVEEFGIIL-UHFFFAOYSA-N 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 239000007983 Tris buffer Substances 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229910010941 LiFSI Inorganic materials 0.000 claims 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-M fluorosulfonate Chemical group [O-]S(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-M 0.000 claims 1
- 125000002827 triflate group Chemical group FC(S(=O)(=O)O*)(F)F 0.000 claims 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 claims 1
- 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 1
- 150000003254 radicals Chemical group 0.000 description 21
- 230000015572 biosynthetic process Effects 0.000 description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- 150000001450 anions Chemical class 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- 239000013522 chelant Substances 0.000 description 12
- 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
- 229910052731 fluorine Inorganic materials 0.000 description 11
- 239000011737 fluorine Substances 0.000 description 11
- 229910001317 nickel manganese cobalt oxide (NMC) Inorganic materials 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 150000002009 diols Chemical class 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000006182 cathode active material Substances 0.000 description 7
- 230000002829 reductive effect Effects 0.000 description 7
- 238000011161 development Methods 0.000 description 6
- 230000018109 developmental process Effects 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- 238000004064 recycling Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- RAEAYTICAPHWJW-UHFFFAOYSA-N 3,3,3-trifluoro-2-(trifluoromethyl)propanoic acid Chemical compound OC(=O)C(C(F)(F)F)C(F)(F)F RAEAYTICAPHWJW-UHFFFAOYSA-N 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 230000032683 aging Effects 0.000 description 5
- 150000004645 aluminates Chemical class 0.000 description 5
- 239000006183 anode active material Substances 0.000 description 5
- 125000001033 ether group Chemical group 0.000 description 5
- 239000007789 gas 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
- 125000004430 oxygen atom Chemical group O* 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 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 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- 125000002015 acyclic group Chemical group 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000007599 discharging Methods 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
- 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
- 239000010406 cathode material Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 3
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 3
- 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 description 3
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 229930195734 saturated hydrocarbon Natural products 0.000 description 3
- 239000012453 solvate Substances 0.000 description 3
- 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 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
- 239000004593 Epoxy Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 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
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 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
- 239000002253 acid Substances 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 238000013459 approach Methods 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
- 150000004697 chelate complex Chemical class 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
- 238000001035 drying Methods 0.000 description 2
- 239000011883 electrode binding agent Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 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
- 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
- 229910052748 manganese Inorganic materials 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
- 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
- 239000000047 product Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000010992 reflux Methods 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
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 2
- 125000004209 (C1-C8) 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
- GPKYZQLMEPJAGJ-UHFFFAOYSA-N 2,3,3,3-tetrafluoropropanoic acid Chemical compound OC(=O)C(F)C(F)(F)F GPKYZQLMEPJAGJ-UHFFFAOYSA-N 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
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound 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
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 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
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910014422 LiNi1/3Mn1/3Co1/3O2 Inorganic materials 0.000 description 1
- 229910012223 LiPFe Inorganic materials 0.000 description 1
- XUPPQJDFIBRQKT-UHFFFAOYSA-N OC(C(C(C(F)(F)F)(C(F)(F)F)O)(C(F)(F)F)C(F)(F)F)(C(F)(F)F)C(F)(F)F Chemical compound OC(C(C(C(F)(F)F)(C(F)(F)F)O)(C(F)(F)F)C(F)(F)F)(C(F)(F)F)C(F)(F)F XUPPQJDFIBRQKT-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-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
- 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
- 125000000217 alkyl 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- 125000004429 atom Chemical group 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
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000002131 composite 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
- 238000000113 differential scanning calorimetry Methods 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
- 150000002170 ethers Chemical class 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
- 238000002474 experimental method 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
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical class OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 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
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 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
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation 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
- 238000011068 loading method Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000007246 mechanism Effects 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 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
- 230000001473 noxious effect Effects 0.000 description 1
- 150000002895 organic esters Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 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
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 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
- 238000002407 reforming Methods 0.000 description 1
- 230000001105 regulatory effect Effects 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
- 239000007858 starting material Substances 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
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000032258 transport Effects 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
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0563—Liquid materials, e.g. for Li-SOCl2 cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/002—Inorganic electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/387—Tin or alloys based on tin
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/46—Alloys based on magnesium or aluminium
- H01M4/463—Aluminium based
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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
Definitions
- Liquid electrolyte composition and an electrochemical cell containing the electrolyte composition Liquid electrolyte composition and an electrochemical cell containing the electrolyte composition
- the present invention relates to an electrolyte composition and an electrochemical cell with the electrolyte composition.
- Electrochemical cells are of great importance in many technical fields.
- electrochemical cells are often used for applications in which low voltages are required, such as for the operation of laptops or mobile phones.
- An advantage of electrochemical cells is that many individual cells can be connected together. For example, cells connected in series can deliver a high voltage, while connecting cells in parallel results in a high nominal capacity. Such interconnections result in higher energy batteries.
- Such battery systems are also suitable for high-voltage applications and can, for example, enable vehicles to be driven electrically or be used for stationary energy storage.
- electrochemical cell is used synonymously for all designations customary in the prior art for rechargeable galvanic elements, such as cell, battery, battery cell, accumulator, battery accumulator and secondary battery.
- An electrochemical cell is able to provide electrons for an external circuit during the discharge process. Conversely, an electrochemical cell can be charged during the charging process by means of an external circuit by supplying electrons.
- An electrochemical cell has at least two different electrodes, a positive (cathode) and a negative (anode) electrode. Both electrodes are in contact with an electrolyte composition.
- the most commonly used electrochemical cell is the lithium ion cell, also called lithium ion battery.
- Lithium ion cells known from the prior art have a composite anode, which very often comprises a carbon-based anode active material, typically graphitic carbon, which is deposited on a metallic copper carrier foil.
- the cathode generally comprises metallic aluminum which is coated with an active cathode material, for example a layered oxide.
- LiCoO 2 or LiNi 1/3 Mn 1/3 Co 1/3 O 2 can be used as layer oxide, for example, which is coated onto a rolled aluminum carrier foil.
- Electrolyte composition plays a key role in the safety and performance of an electrochemical cell. This ensures the charge balance between the cathode and anode during the charging and discharging process. The flow of current required for this is achieved by the ion transport of a conductive salt in the electrolyte composition.
- the conductive salt is a lithium conductive salt, and lithium ions serve as the current-carrying ions.
- LiPFe lithium hexafluorophosphate
- electrolyte compositions contain a solvent which enables dissociation of the conductive salt and sufficient mobility of the lithium ions.
- Liquid organic solvents are known in the art and consist of a variety of linear and cyclic dialkyl carbonates. Typically, mixtures of ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), propylene carbonate (PC), and ethyl methyl carbonate (EMC) are used.
- each solvent has a specific stability range for the cell voltage, also called the "voltage window".
- the electrochemical cell can run stably during operation. If the cell voltage approaches the upper voltage limit, an electrochemical oxidation of the components of the electrolyte composition takes place. At the bottom of the voltage window on the other hand, reductive processes take place. Both redox reactions are unwanted, reduce the performance and reliability of the cell and, in the worst case, lead to its failure.
- Gassing means an electrochemical decomposition of the components of the electrolyte into volatile and gaseous compounds due to the use of too high a cell voltage. Gassing reduces the proportion of electrolyte and leads to the formation of unwanted decomposition products, resulting in a shorter service life and lower performance of the lithium-ion cell.
- fluorinated solvents or additives are added to the electrolyte compositions in the prior art.
- Fluorinated solvents such as fluoroethylene carbonate (FEC) are chemically inert and electrochemically stable to the operating voltages of the lithium ion cell.
- a widespread disadvantage of fluorinated electrolytes is that in the event of a thermal defect in the cell, increased heat release and the formation and emission of noxious gases such as hydrogen fluoride (HF) can occur.
- HF hydrogen fluoride
- lithium-ion cells have a large number of regulating and control mechanisms in order to keep the cells in a voltage range that is optimal for the respective solvent during operation and thus to stabilize the electrolyte composition.
- EP 1 689 756 B1 describes a process for preparing weakly coordinating anions of the formula X(OR F ) m , in which X is selected from the group consisting of B, Al, Ga, In, P, As and Sb, m 3 or 5 is and R F one straight-chain or branched-chain, partially or fully fluorinated alkyl or aryl radical.
- the weakly coordinating anions form salts with mono- or divalent cations, preferably with alkali metal ions. Due to the chemical stability, in particular of the anion, the salts disclosed were proposed, inter alia, for use as inert lithium conductive salts in lithium ion batteries. However, an electrolyte composition with the weakly coordinating anions for use in lithium-ion batteries has not been demonstrated.
- the stability of the battery cells can also be increased by selecting a suitable solvent.
- Sulfur dioxide SO2 was already discussed as an inorganic solvent in electrolyte compositions in David Linden's "Handbook of Batteries” (2nd edition, McGraw Hill, 1994).
- Electrolyte compositions based on sulfur dioxide have, in particular, increased ionic conductivity and thus enable battery cells to be operated at high discharge currents without adversely affecting the stability of the cells.
- electrolyte compositions based on sulfur dioxide are characterized by a high energy density, a low self-discharge rate, and limited overcharging and deep discharging.
- a disadvantage of sulfur dioxide is that it only insufficiently dissolves many lithium conductive salts, which are readily soluble in organic solvents. Therefore, for example, the widely used lithium conducting salt lithium hexafluorophosphate cannot be used for 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 as an additive, but represents the main component of the electrolyte composition. It should therefore at least partially ensure the mobility of the ions of the conducting salt, which bring about the charge transport between the electrodes.
- lithium tetrachloroaluminate is used as a lithium-containing conducting salt in combination with a cathode active material made of a metal oxide, in particular one Intercalation compound such as lithium cobalt oxide (UC0O2).
- a salt additive for example an alkali metal halide such as lithium fluoride, sodium chloride or lithium chloride
- EP 2534719 B1 shows a rechargeable lithium battery cell with an electrolyte based on sulfur dioxide in combination with lithium iron phosphate as cathode active material. Lithium tetrachloroaluminate was used as the preferred conductive salt in the electrolyte composition. In experiments with cells based on these components, a high electrochemical resistance of the cells could be demonstrated.
- WO 2021/019042 A1 describes rechargeable battery cells with an active metal, a layered oxide as cathode active material and an electrolyte containing sulfur dioxide. Due to the poor solubility of many common lithium conductive salts in sulfur dioxide, a conductive salt of the formula M + [Z(OR) 4 ] ' was used in the cells, where M represents a metal selected from the group consisting of alkali metal, alkaline earth metal and a metal of group 12 of the periodic table, and R is a hydrocarbyl radical.
- the alkoxy groups -OR are each monovalently bonded to the central atom Z, which can be aluminum or boron.
- the cells contain a perfluorinated conductive salt of the formula Li + [AI(OC(CF 3 ) 3 ) 4 ] ' .
- a perfluorinated conductive salt of the formula Li + [AI(OC(CF 3 ) 3 ) 4 ] ' Cells consisting of the described components show a stable electrochemical performance in experimental studies.
- the conductive salts, in particular the perfluorinated anion have a surprising hydrolytic stability.
- the electrolytes should be oxidation-stable up to an upper potential of 5.0 V. It was further shown that cells with the disclosed electrolytes can be discharged or charged at low temperatures of down to -41°C. However, no measurements of the electrochemical performance at high temperatures have been made.
- Electrolyte composition are specified in the subclaims, which can optionally be combined with each other.
- the object is achieved by a liquid electrolyte composition for an electrochemical cell.
- the electrolyte composition includes the following components:
- M is a metal cation selected from the group consisting of alkali metals, alkaline earth metals and Group 12 metals of the Periodic Table
- m represents an integer from 1 to 2
- Z represents a central ion selected from the group consisting of elements from Groups 2 to 16th group of the periodic table, including the group of lanthanides.
- a 1 to A 12 each represent a coordination element which binds to the central ion Z, wherein A 1 to A 12 are each independently selected from the group consisting of elements of groups 15 and 16 of the periodic table.
- R 1 and R 2 each represents a monovalent and terminal radical and are independently selected from the group consisting of optionally fluoro-substituted hydrocarbon radicals, triflyl radical, triflate radical and fluorosulfonate radical.
- L 1 to L 6 each independently represent an aliphatic or aromatic bridging group.
- the bridging group forms a five- to eight-membered ring with the central ion Z and with two coordination elements bonded to the central ion Z and the bridging group, the ring having a optionally punctuated by a heteroatom, sequence of 2 to 5 carbon atoms.
- the salts proposed according to the invention have an anion which contains at least one bidentate ligand.
- a bidentate ligand is a molecule which has at least two coordination elements and which binds to a central ion Z via the at least two coordination elements. It would also be conceivable to use other multidentate ligands which have a different denticity, such as, for example, tridentate, tetradentate, pentadentate or hexadentate.
- Bidentate or multidentate ligands are also generally known as chelate ligands and the complexes composed of them as chelate complexes.
- the anion of the salt of formula (I), formula (II) and formula (III) is thus a chelate complex.
- chelate complexes and the salts formed therefrom have various advantages over monovalent complexes and the salts formed therefrom.
- Chelate complexes are chemically more stable than their monovalent derivatives.
- the bonds between the chelate ligand and the central ion are difficult to break, which is why the chelate complexes according to the invention are chemically inert to external chemical and physical influences.
- a chelate complex represents the anion of the at least one salt of the formula (I), (II) or (III), the salt serving as the conducting salt of the electrolyte composition.
- the electrolyte composition thus enables charge balancing between the two electrodes with which it is in contact.
- the chelate complexes used according to the invention are chemically and electrochemically stable compounds which, due to the strongly coordinating properties of the ligand to the central ion, have a low affinity for binding to positively charged ions.
- the chelate complexes themselves are therefore weakly coordinating anions. Therefore, the conductive salt in the Electrolyte composition dissociate almost completely without reforming back to the starting salt and forms ions with a high mobility and a correspondingly high ionic conductivity in solution. This in turn increases the electrochemical performance of the electrochemical cell.
- the chelate complexes used according to the invention are resistant to both temperature and hydrolysis.
- the salts described are sufficiently soluble in liquid sulfur dioxide, which is the inorganic solvent of the electrolyte composition.
- sulfur dioxide is not only as an additive in low concentrations in the
- Contain electrolyte composition is present to an extent that it can ensure the mobility of the ions of the conductive salt as a solvent.
- Sulfur dioxide is gaseous at room temperature under atmospheric pressure and forms stable liquid solvate complexes with lithium conductive salts, which have a noticeably reduced vapor pressure compared to sulfur dioxide as a pure substance.
- the gaseous sulfur dioxide is thus bound in liquid form and can be handled safely and comparatively easily.
- a particular advantage is the non-combustibility of sulfur dioxide itself and of the solvate complexes, which increases the operational safety of the electrolyte compositions based on such solvate complexes and of the cells produced using the electrolyte composition.
- the salts described with the chelate complexes of the formula (I), (II) and (III) are non-flammable.
- the electrolyte compositions according to the invention are therefore also non-flammable and enable safe operation of an electrochemical cell which comprises the disclosed components of the electrolyte composition. If sulfur dioxide escapes from the cell due to mechanical damage, it cannot ignite outside the cell.
- the electrolyte composition according to the invention is also inexpensive compared to conventional organic electrolytes.
- the elevated Temperature stability and resistance to hydrolysis enable direct and almost complete recycling of the electrolyte composition from old batteries without increased effort. Hydrothermal processes under high pressure and at high temperatures are usually used to recycle old batteries.
- Conventional electrolyte compositions are usually not resistant to hydrolysis and therefore have to be worked up in some other way.
- the electrolyte compositions are extracted from batteries in a laborious process, for example by rinsing the cells with supercritical carbon dioxide.
- more recent electrolyte formulations based on aluminate, borate or gallate salts, as are described in the prior art are usually not sufficiently thermally stable.
- the electrolyte composition proposed here is thermally stable and resistant to hydrolysis and can therefore be recycled directly from the electrochemical cells at low cost using water-based extraction methods. Due to the water solubility of the proposed components, the electrolyte composition proposed here has a high recycling potential with a high recycling rate.
- the electrolyte composition comprises at least one salt of the formula (I), (II) or (III), the salt containing an anionic complex with at least one bidentate ligand.
- the charge of the anion is stoichiometrically 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.
- 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.
- the metal cation is a lithium ion and the salt is a lithium salt.
- m is an integer from 1 to 2, where m is stoichiometrically determined by the oxidation number of the metal cation used.
- Z in the formula (I), (II) or (III) is a central ion which is selected from the group consisting of the elements of groups 2 to 16 and the group of lanthanides of the periodic table.
- the central ion Z is preferably selected from the group consisting of the 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.
- the central ion corresponds to one of the elements aluminum, boron or phosphorus
- the respective salts formed from them are either aluminates, borates or phosphates. Accordingly, the anion of the salt of formula (I), (II) or (III) has a single negative charge.
- the coordination elements A 1 to A 12 each bond to the central ion Z and to the bridge moiety, the coordination elements A 1 to A 12 each being independently selected from the group consisting of elements from groups 15 and 16 of the periodic table.
- the coordination element is an element selected from the group consisting of the elements of group 15 of the periodic table, then the coordination element in question is provided with a fluorine-containing radical.
- the coordination element in question thus has a total of three bonds, a bond to the central ion Z, a bond to the bridge residue and a bond to the fluorine-containing residue.
- the fluorine-containing radical is in particular selected from the group consisting of triflyl radical, triflate radical, tosyl radical, fluorosulfonate radical and perfluorinated C1-C8 alkyl radical.
- the at least one coordination element comprises oxygen. All of the coordination elements are particularly preferably oxygen.
- the salt is of formula (I) wherein Ri and R2 each independently comprise an optionally fluoro-substituted hydrocarbyl group.
- the hydrocarbon radicals R 1 and R 2 are each monovalent and independently selected from the group consisting of C1-C8 alkyl, C2 -C10 alkenyl, C2 -C10 alkynyl , C6 -C12 cycloalkyl and C6 -C12 aryl .
- monovalent means that the hydrocarbon radicals R 1 and R 2 each bond to the central ion Z via a single coordination element.
- C 1 -C 8 -alkyl encompasses linear or branched saturated hydrocarbon radicals having one to eight carbon atoms.
- Preferred hydrocarbon radicals include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n-pentyl, isopentyl, 2,2-dimethylpropyl, n-hexyl, iso- hexyl, 2-ethylhexyl, n-heptyl, iso-heptyl, n-octyl and iso-octyl.
- C 2 -C 10 -alkenyl encompasses linear or branched, at least partially unsaturated hydrocarbon radicals having two to ten carbon atoms, the hydrocarbon radicals having at least one CC double bond.
- Preferred hydrocarbon radicals include, for example, ethenyl, 1-propenyl, 2-propenyl, 1-n-butenyl, 2-n-butenyl, isobutenyl, 1-pentenyl, 1-hexenyl, 1-heptenyl, 1-octenyl, and 1-nonenyl 1-decenyl.
- C 2 -C 10 -alkynyl encompasses linear or branched, at least partially linear, unsaturated hydrocarbon radicals having two to ten carbon atoms, the hydrocarbon radicals having at least one CC triple bond.
- Preferred hydrocarbon radicals include, for example, ethynyl, 1-propynyl, 2-propynyl, 1-n-butynyl, 2-n-butynyl, isobutynyl, 1-pentynyl, 1-hexynyl, 1-heptynyl, 1-octynyl, and 1-nonynyl 1-decynyl.
- C 6 -C 12 -cycloalkyl encompasses cyclic, saturated hydrocarbon radicals having six to twelve carbon atoms.
- Preferred hydrocarbon radicals include, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclohexyl, cyclononyl and cyclodecanyl.
- C 6 -C 14 -aryl encompasses aromatic hydrocarbon radicals having six to twelve carbon atoms.
- Preferred hydrocarbon radicals include, for example, phenyl, naphthyl and anthracyl.
- the hydrocarbon radicals Ri and/or R 2 are at least partially fluorine-substituted.
- the hydrocarbon radicals R 1 and/or R 2 are fully fluorinated.
- the bidentate chelate ligand has at least two coordination elements and a bridging moiety L 1 to L 6 that binds to both coordination elements.
- L 1 to L 6 each independently represent an aliphatic or aromatic bridging group.
- the bridging group forms a five- to eight-membered ring with the central ion Z and two coordination elements bonded to the central ion Z and the bridging group.
- the ring contains a sequence of 2 to 5 carbon atoms, optionally interrupted by a heteroatom.
- the ring contains a continuous sequence of 2 to 5 carbon atoms, preferably 2 to 3 carbon atoms.
- the ring has a heteroatom-interrupted sequence of 2 to 5 carbon atoms.
- a heteroatom is enclosed in the bridge residue.
- the heteroatom can be selected from the group consisting of elements of main groups 15 and 16 of the periodic table.
- the heteroatom can in particular be oxygen.
- the ring or the bridge residue has in particular at least one ether group.
- the ring has an oxygen-interrupted sequence of 2 to 4 carbon atoms.
- an ether group can advantageously reduce the fluorine content of the ring. This also reduces the fluorine content of the ligand overall.
- fluorinated compounds have a good electrochemical resistance, but the synthesis of such compounds is complicated and expensive.
- the inventors here have recognized that the fluorine content in the ring and thus also in the ligand can be reduced without impairing the electrochemical stability of the ligand by adding heteroatoms to the ring.
- ether groups which are also stable to oxidative potentials, so that the ligand is electrochemically stable despite the reduced fluorine content.
- the ring may include at least one carbonyl group selected from the group consisting of imide group, carboxylic acid ester group, carboxylate group, ketone group, carboxylic acid anhydride group,
- the presence of at least one carbonyl group advantageously leads to a reduced fluorine content in the ring. In this way, the proportion of fluorine in the ligand can also be reduced overall.
- the carbonyl groups mentioned above also have high electrochemical stability.
- the bridging radicals L 1 to L 6 each have a linear, branched or cyclic, saturated, optionally fluorine-substituted hydrocarbon skeleton.
- the hydrocarbon skeleton of the bridge radicals L 1 to L 6 preferably has 3 to 16 carbon atoms, preferably 6 to 9 carbon atoms. Hydrocarbon skeletons having a number of carbon atoms in the range mentioned yield anions which form particularly stable salts of formula (I), formula (II) or (III).
- the bridging radicals L 1 to L 6 each comprise an at least partially fluorine-substituted hydrocarbon skeleton.
- the hydrocarbon backbone is fully fluorinated.
- the previous embodiments therefore preferably contain no hydrogen atoms.
- the hydrocarbon skeleton of the bridging radicals L 1 to L 6 can comprise at least one carbonyl group selected from the group consisting of imide group, carboxylic acid ester group, carboxylate group, ketone group, carboxylic acid anhydride group, carbonic acid ester group and carbamate ester group.
- hydrocarbon skeleton of the bridge radicals L 1 to L 6 can comprise at least one heteroatom selected from the group consisting of elements from main groups 15 and 16 of the periodic table.
- the heteroatom can in particular comprise oxygen which is integrated in the form of an ether functionality in the hydrocarbon skeleton of the bridging radicals L 1 to L 6 .
- the oxygen can also be present as an epoxy bridge in the hydrocarbon backbone of the bridge radicals L 1 to L 6 .
- the oxygen is bound in the form of a ring in the hydrocarbon structure of the bridge radicals L 1 to L 6 .
- component (B) of the electrolyte composition comprises at least one lithium salt of formula (II) containing at least one ether functionality in the ring and/or an epoxy bridge in the hydrocarbon backbone.
- a lithium salt is preferably selected from the group consisting of
- component (B) of the electrolyte composition comprises at least one lithium salt of formula (II) having at least one carbonyl function.
- a lithium salt is preferably selected from the group consisting of
- the carbonyl function can be present in the ring and/or in the hydrocarbon backbone of the bridging group.
- component (B) of the electrolyte composition comprises at least one lithium salt of formula (II) containing both an ether functionality and a carbonyl group.
- a lithium salt is preferably selected from the group consisting of
- component (B) of the electrolyte composition comprises at least one lithium salt of the formula (II) or (III), the lithium salt having an optionally fluorine-substituted aromatic bridge radical and the lithium salt preferably being selected from the group consisting of
- the salts of the formulas (IV) - (XX) proposed above fall under the general formulas (II) or (III).
- a chelating ligand is replaced by two ligands R 1 A 1 R 2 A 3 according to the formula (I).
- two chelating ligands can also be substituted.
- the salt of component (B) is a salt of the following formula (XXI)
- the binding of the bridging radicals via the oxygen atoms to the central ion in the salts of the formulas (XXI) and (XXII) can be interpreted as a coordinate bond for the purposes of the invention.
- the binding of the ligand to the central ion forms a ring consisting of a bridging residue, the two oxygen atoms bound to the bridging residue and the central ion Z.
- the ring 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
- n 0, 1, 2 or 3 and R represents a radical.
- 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 formula (XXIII ) has either two polycyclic rings according to the bonding situation according to formula (XXI) or one polycyclic ring and the radicals OR 1 and OR 2 according to the bonding situation according to formula (XXII).
- the radicals R can be identical or different and independently selected from the group consisting of C 1 -C 4 -alkyl, hydrogen and fluorine.
- C 1 -C 4 -alkyl includes linear or branched saturated hydrocarbon radicals having one to four carbon atoms.
- Preferred hydrocarbon radicals include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl and tert-butyl.
- hydrocarbon radicals R can be at least partially fluorinated.
- Preferred fluorinated hydrocarbon radicals include, for example, trifluoromethyl or pentafluoroethyl.
- the ring formed with 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.
- n in formula (XXIII) is 1, the ring formed with the central ion Z, the bridging moiety and the two oxygen atoms bonded to the bridging moiety is hexacyclic and has a continuous sequence of 3 carbon atoms.
- the ring formed with the central ion Z, the bridging moiety and the two oxygen atoms bonded to the bridging moiety is eight-membered and has a continuous sequence of 5 carbon atoms.
- component (B) of the electrolyte composition comprises at least one lithium salt of the formula (XXI). Lithium salts are particularly suitable for use as lithium conducting salts in lithium ion batteries.
- the lithium salt can preferably be selected from the group consisting of lithium bis (1, 1, 1, 4, 4, 4-hexafluoro-2, 3-bis (trifluoromethyl) -2, 3-butanediolato) borate with the Molecular formula here abbreviated as Lithium bis(perfluoropinacolato)borate (LiBPFPB) of formula (XXIV)
- LiOTA LiOTA of formula (XXV)
- LiHTTDA LiHTTDA of formula (XXVI)
- the lithium salts LiBPFPB (XXIV), LiOTA (XXV), and Li H TT DA (XXVI) can be prepared using Examples 1, 2 and 3 described below.
- the proposed lithium salts (IV) - (XX), (XXIV) - (XXVI) dissolve well in liquid sulfur dioxide as a solvent.
- the electrolyte compositions produced therefrom are non-flammable and have extremely good ionic conductivity over a wide temperature range.
- the conductivity of the lithium salts can be determined by conductive measurement methods. For this purpose, different concentrations of the lithium salts (IV) - (XX), (XXIV) - (XXVI) are prepared in sulfur dioxide. The conductivities of the solutions are then determined using a two-electrode sensor immersed in the solution at constant room temperature. For this purpose, the conductivity of the solution with the lithium salts (IV) - (XX), (XXIV) - (XXVI) is measured in a range of 0-100 mS/cm. Due to the high electrochemical stability of the lithium salts, they do not participate in cyclical and calendar aging processes in the battery cell.
- the proposed lithium salts have an increased thermal, chemical and electrochemical stability and a particularly pronounced resistance to hydrolysis.
- the thermal stability can be examined, for example, by means of a thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC).
- the electrolyte compositions made from the lithium salts are also less expensive to operate.
- the properties of the lithium conductive salts mentioned enable the selection of a suitable recycling process.
- a recycling process based on water as a solvent can preferably be used.
- the lithium conducting salts can thus be completely recovered from the used batteries.
- the improved recyclability of the electrolyte saves costs in the battery manufacturing process, which can be offset against the manufacturing costs of the electrolyte salts.
- the electrolyte composition contains component (B) in a concentration of 0.01 to 15 mol/L, preferably 0.1 to 10 mol/L, particularly preferably 0.5 to 5 mol/L, based on the total volume of the electrolyte composition .
- the electrolyte composition may further comprise at least one other additive in a proportion of 0-10% by weight, preferably 0.1-2% by weight, based on the total weight of the electrolyte composition.
- the other additives include compounds selected from the group consisting of 2-vinylpyridine, 4-vinylpyridine, cyclic exomethylene carbonates, sulfones, cyclic and acyclic sulfonates, acyclic sulfites, cyclic and acyclic sulfinates, organic esters of inorganic Acids, acyclic and cyclic alkanes, aromatic compounds, halogenated cyclic and acyclic sulfonylimides, halogenated cyclic and acyclic phosphate esters, halogenated cyclic and acyclic phosphines, halogenated cyclic and acyclic phosphites, halogenated cyclic and acyclic phosphazenes, halogenated cyclic and acyclic silylamines, halogenated cyclic and acyclic halogenated esters, halogenated cyclic and acycl
- the other additives contribute to the stability of the electrolyte composition during operation in an electrochemical cell.
- the further additives can also make at least one further lithium-containing conductive salt available to the electrolyte composition.
- the further lithium-containing conducting salt can contribute to adapting the conductivity of the electrolyte composition to the requirements of the respective cell or to increasing the corrosion resistance of the cathodic metal carrier foil.
- Preferred lithium-containing conductive salts include lithium tetrafluoroborate (L1BF4), lithium trifluoromethanesulfonate, lithium fluoride, lithium bromide, lithium sulfate, lithium oxalate, lithium (bisoxalato)borate, lithium difluoro(oxalato)borate,
- lithium tetrahaloaluminate lithium hexafluorophosphate
- lithium bis(trifluoromethanesulfonyl)imide LiTFSI
- lithium bis(fluorosulfonyl)imide LiFSI
- the other additives can also include other solvents.
- Other solvents can contribute to adjusting the solubility of the electrolyte composition with respect to polar or non-polar components in the same.
- the other solvents preferably include vinyl ethylene carbonate (VEC), ethyl methyl carbonate (EMC), vinylene carbonate (VC) and 4-fluoro-1,3-dioxolane-2-one (FEC).
- VEC vinyl ethylene carbonate
- EMC ethyl methyl carbonate
- VC vinylene carbonate
- FEC 4-fluoro-1,3-dioxolane-2-one
- the further additives can also include at least one solid inorganic lithium ion conductor (solid electrolyte).
- solid inorganic lithium ion conductors include perovskites, garnets, sulfides, and amorphous compounds such as glasses, and combinations thereof.
- the electrolyte composition comprises the following components:
- the salt in a concentration of 0.01-15 mol/L, preferably 0.1-10 mol/L, based on the total volume of the electrolyte composition, the salt preferably being a lithium salt, particularly preferably selected from the group consisting of the compounds of the formula
- (C) 0-10% by weight, preferably 0.1-2% by weight, of at least one additive, the additive preferably being 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 (cDFEC), 4-(trifluoromethyl)-1,3-dioxolan-2-one, bis- (trifluoromethanesulfonyl)imide (LiTFSI) and bis(fluorosulfonyl)imide (LiFSI), and combinations thereof, based on the total weight of the electrolyte composition.
- VC vinylene carbonate
- FEC 4-fluoro-1,3- dioxolan-2-one
- cDFEC lithium hexafluorophosphate
- cDFEC cis-4,5-difluoro-1,
- the invention relates to an electrochemical cell with a cathode, an anode and the described electrolyte composition, which is in contact with the cathode and the anode.
- the electrochemical cell is a lithium-ion cell, with the electrolyte composition comprising the following components:
- the proposed lithium-ion cells are inexpensive and can be safely operated at different working voltages.
- the associated electrochemical properties can be determined by measurements on test cells.
- the cyclic aging resistance of the test cells can be determined via the number of cycles.
- the test cells are initially charged with a constant charging current up to a maximum permissible cell voltage.
- the upper switch-off voltage is kept constant until a charging current has fallen to a specified value or the maximum charging time has been reached. This is also known as I/U loading.
- the test cells are then discharged with a constant discharge current intensity up to a given switch-off voltage. Depending on the desired number of cycles, charging can be repeated.
- the upper cut-off voltage and the lower cut-off voltage as well as the given charging or discharging current strengths must be chosen experimentally. This also applies to the value to which the charging current has dropped.
- the calendrical aging resistance and the extent of self-discharge can be determined by storing a fully charged battery cell, in particular at elevated temperature.
- the battery cell is charged up to the permissible upper voltage limit and maintained at this voltage until the charging current has dropped to a previously specified limit value.
- the cell is then disconnected from the power supply and stored in a temperature chamber at an elevated temperature, for example at 45 °C, for a specific time, for example one month (variant 1).
- the cell is then removed from the temperature chamber and the remaining capacity is determined under defined conditions.
- a discharge current is selected which, for example, numerically corresponds to one third of the nominal capacity, and the cell is thus discharged down to the lower discharge limit.
- This process can be repeated any number of times, for example until the detectable residual capacity a predetermined value, for example 70% of the rated capacity.
- a second variant of the storage (variant 2), the storage takes place in a temperature chamber with the power supply connected, the voltage corresponding to the upper voltage limit and this voltage being maintained. Tests are carried out according to the two storage variants. The actual calendrical aging and the self-discharge of the battery cell is then determined from these tests: The calendrical aging corresponds to the capacity loss due to storage according to variant 2 and is calculated by subtracting the determined residual capacity 2 from the nominal capacity. The self-discharge rate is determined from the difference between the residual capacities 1 and 2 determined by storage according to variants 1 and 2 in relation to the nominal capacity of the battery cell.
- the cathode of the lithium ion cell preferably comprises a cathode active material.
- Preferred cathode active materials for the electrochemical cell include lithium cobalt oxide (LCO), lithium nickel oxide (LNO), lithium nickel cobalt alumina (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.
- LCO lithium cobalt oxide
- LNO lithium nickel oxide
- NCA lithium nickel cobalt alumina
- NMC lithium nickel manganese cobalt oxide
- LMO lithium manganese oxide
- LFP lithium iron phosphate
- LMR lithium nickel manganese oxide spinel
- LNMO lithium nickel manganese oxide spinel
- NMC Lithium-nickel-manganese-cobalt compounds
- NCM Lithium-nickel-manganese-cobalt compounds
- NMC-based cathode materials are used in particular in lithium-ion batteries for vehicles.
- NMC as a cathode material has an advantageous combination of desirable properties, for example a high specific capacity, a reduced cobalt content, high current capability and high intrinsic safety, which is reflected, for example, in sufficient stability in the event of overcharging.
- Certain stoichiometries are given in the literature as triples of numbers, for example NMC 811, NMC 622, NMC 532 and NMC 111.
- the triple number indicates the relative nickel : manganese : cobalt content.
- lithium and manganese-rich NMCs having the general formula unit are used, where ⁇ is in particular between 0.1 and 0.6, preferably between 0.2 and 0.4.
- These lithium-rich layered oxides are also known as Overlithitated (Layered) Oxides (OLO).
- the cathode can have other components and additives, such as a foil carrier (rolled metal foil) or a metal-coated polymer foil, an electrode binder and/or an electrical conductivity improver, for example conductive carbon black. All customary compounds and materials known in the prior 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 can be selected from the group consisting of carbonaceous materials, soft carbon, hard carbon, natural graphite, synthetic graphite, silicon, silicon suboxide, silicon alloys, lithium, lithium alloys, aluminum alloys, indium,
- the anode active material is preferably selected from the group consisting of synthetic graphite, natural graphite, graphene, mesocarbon, doped
- the anode can have other components and additives, such as a film carrier, an electrode binder and/or an electrical conductivity improver, for example Conductive carbon black, conductive graphite, so-called "Carbon Nano Tubes" (CNT), carbon fibers and/or graphene. All customary compounds and materials known in the prior art can be used as further components and additives.
- Example 1 Production of LiOTA (XXV) 2,4-dimethylpentane-2,4-diol (1) is dissolved in carbon tetrachloride and reacted with phosgene (COCl 2 ) to give the corresponding 4,4,6,6-tetramethyl-1,3-dioxolane-2-dione (2). .
- the obtained carbonate compound (2) is purified by fractional crystallization in diethyl ether and dried under vacuum. In the next step, the dried carbonate compound (2) is dissolved in dry acetonitrile. A gas stream is passed through the resulting solution, the gas stream consisting of a fluorine:nitrogen mixture (10% by volume:90% by volume).
- the diol (4) is converted to lithium-bis- ⁇ 1,1,1,3,3,5,5,5-octafluoro-2) with aluminum hydride (LiAlhL) in perfluorohexane (CeFn) at 70-80°C ,4-bis-trifluoromethylpentane-2,4-diolato ⁇ aluminate (LiOTA) (5).
- the salt lithium bis (1, 1, 1, 5, 5, 5-hexafluoro-2, 3, 3, 4-tetrakis- trifluoromethylpentane-2, 4-diolato) aluminate can according to the synthesis instructions of Example 1 being represented. 2,3,3,4-Tetramethylpentane-2,4-diol is used as the starting material.
- Lithium bis(perfluoropinacolato)borate can be synthesized according to a synthesis procedure by Wu Xu and C. Austen Angell (2000 Electrochem. Solid-State Lett. 3, 366).
- the ligands for the conductive salts (IV) and (VI) can be synthesized by J.D.O. Anderson et al. (1996 Inorg. Chem. 35, 3191).
- the conducting salts (IV) and (VI) can be produced as follows: All work is done under suspicion: commercially available LiBFU (95%) is cleaned of the insoluble foreign matter by decantation with diethyl ether. The solvent is then removed in vacuo and the purified material dried at 80°C. The sc cleaned LiBH 4 is dissolved in a flask in 1,2-
- DME Dimethoxyethane
- a 5% excess of the ligands of the conductive salts (IV) or (VI) is placed in DME in a dropping funnel and slowly added dropwise over a period of 1 h. Gas evolution occurs during the addition of the ligands, which quickly subsides as soon as the addition is stopped. After the addition is complete, the mixture is boiled under reflux for a further 15 minutes, giving a clear solution. The DME is then distilled off and the semi-dry residue is dried in vacuo at 80° C. overnight. The yield is 90%. The purification takes place via extraction with perfluorohexane, which allows the insoluble components to be separated from the product.
- the conducting salt (XVIII) can be synthesized by M. Eberwein et al. (2003 J. Electrochem. Soc. 150, A994).
- the conducting salt (XIV) can be prepared as described below.
- a) Synthesis of the ligand 2,2-ditrifluoromethylmaleic acid First, the required 2,2-ditrifluoromethylmalonic acid is synthesized from 2-(trifluoromethyl)-3,3,3-trifluoropropionic acid and lithium diisopropylamide according to the general synthesis procedure of AP Krapcho et al. (1974 Tetrahedron Leiters 32, 2721) which is described below. To a solution of 20 mmol of diisopropylamine in 50 mL of THF (under N 2 , -40°C) is added 10 mL of n-butyllithium (2 M in hexane).
- reaction mixture is stirred for 15 minutes. Then 10 mmol of 2-(trifluoromethyl)-3,3,3-trifluoropropionic acid (1) are added and the mixture is heated to 50°C and kept at this temperature for 1 hour to obtain a tertiary carbanion intermediate (2). The mixture is then cooled to -70° C. and 10 mmol of ethyl chloroformate are added. The reaction mixture is slowly brought to room temperature with stirring and then poured onto 100 g of ice. Then 30 mmol of HCl is added to obtain a 2,2-ditrifluoromethylmalonic acid monoethyl ester (3) and extracted with several 25 ml portions of diethyl ether. The ethereal phases are collected and concentrated. The oily monoethyl 2,2-ditrifluoromethylmalonate is then distilled in vacuo.
- the boron salt is synthesized analogously to the procedure published by Liao et al (2014 Adv. Energy Mater. 4, 1301368).
- the conductive salt (X) can be prepared as follows: a) Synthesis of 2-fluoro-2-trifluoromethylmalonic acid:
- Example 8 The conductive salt (XIX) can be synthesized by J. Barthel et al. (1996 J. Electrochem Soc. 143 , 3572).
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
L'invention concerne une composition d'électrolyte liquide pour une cellule électrochimique, comprenant les composants suivants : (A) du dioxyde de soufre ; (B) au moins un sel, ledit sel contenant un complexe anionique avec au moins un ligand bidenté. Le ligand ainsi que l'ion central Z du complexe anionique forment un cycle à cinq jusqu'à huit chaînons contenant une séquence de 2 à 5 atomes de carbone, ladite séquence étant éventuellement interrompue par un hétéroatome.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102021118811.3A DE102021118811A1 (de) | 2021-07-21 | 2021-07-21 | Flüssige Elektrolytzusammensetzung sowie eine elektrochemische Zelle mit der Elektrolytzusammensetzung |
PCT/EP2022/069660 WO2023001671A1 (fr) | 2021-07-21 | 2022-07-13 | Composition d'électrolyte liquide et cellule électrochimique comprenant ladite composition d'électrolyte |
Publications (1)
Publication Number | Publication Date |
---|---|
EP4374446A1 true EP4374446A1 (fr) | 2024-05-29 |
Family
ID=90048227
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP22754786.6A Pending EP4374446A1 (fr) | 2021-07-21 | 2022-07-13 | Composition d'électrolyte liquide et cellule électrochimique comprenant ladite composition d'électrolyte |
Country Status (2)
Country | Link |
---|---|
EP (1) | EP4374446A1 (fr) |
CN (1) | CN117652049A (fr) |
-
2022
- 2022-07-13 EP EP22754786.6A patent/EP4374446A1/fr active Pending
- 2022-07-13 CN CN202280048916.7A patent/CN117652049A/zh active Pending
Also Published As
Publication number | Publication date |
---|---|
CN117652049A (zh) | 2024-03-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2023001671A1 (fr) | Composition d'électrolyte liquide et cellule électrochimique comprenant ladite composition d'électrolyte | |
EP3794666B9 (fr) | Cellule de batterie rechargeable | |
US20180301759A1 (en) | Additives to improve electrolyte performance in lithium ion battery | |
EP1162682A1 (fr) | Composés de silane comme additives dans l'électrolyte de piles électrochimiques | |
EP1088814A1 (fr) | Sulphonamides fluorés comme solvants ignifuges pour utilisation dans des cellules électrochimiques | |
DE10026565A1 (de) | Ionische Flüssigkeiten | |
EP1178050B1 (fr) | Phosphates de fluoroalkyl pour cellules électrochimiques | |
WO2014060077A2 (fr) | Additifs pour cellules galvaniques | |
DE10103189A1 (de) | Boratsalze zur Anwendung in elektrochemischen Zellen | |
EP1106617A2 (fr) | Sels d'alkyl-spiroborate et leur utilisation dans des cellules électrochimiques | |
DE10055811A1 (de) | Tetrakisfluoroalkylborat-Salze und deren Verwendung als Leitsalze | |
EP4037056A1 (fr) | Électrolyte à base de so2 pour un élément de batterie rechargeable et élément de batterie rechargeable | |
EP1187244A2 (fr) | Amines organiques pour piles électrochimiques | |
EP1236732B1 (fr) | Sels de Phosphates de fluoroalkyl ET PREPARATION DE CEUX-CI | |
DE10016801A1 (de) | Lithiumsalze, Verfahren zu deren Herstellung, nichtwässriger Elektrolyt sowie elektrochemische Zelle | |
EP2399318B1 (fr) | Cellule galvanique comprenant du lithium métal ou un alliage contenant du lithium métal comme matériau d'anode et un électrolyte contenant du lithium-bis(oxalato)borate ainsi qu'au moins un autre sel complexe de lithium | |
DE10119278C1 (de) | Verfahren zur Herstellung von Fluoralkylphosphaten | |
EP1081129A2 (fr) | Sels d'amine de formule (CF3)2N stables, procédé de préparation des mêmes sels et leurs utilisations avec la préparation des composées de cristaux liquides | |
EP3604276A1 (fr) | Nouveaux composants pour compositions d'électrolyte | |
EP4374446A1 (fr) | Composition d'électrolyte liquide et cellule électrochimique comprenant ladite composition d'électrolyte | |
EP1095942A2 (fr) | Sels complexes pour les cellules eletrochimiques | |
WO2024012974A1 (fr) | Composition d'électrolyte liquide comprenant un sel, cellule électrochimique comprenant la composition d'électrolyte, sel et utilisation du sel dans la cellule électrochimique | |
WO2024012973A1 (fr) | Composition d'électrolyte liquide comprenant un sel, cellule électrochimique comprenant la composition d'électrolyte, sel et utilisation du sel dans la cellule électrochimique | |
EP3605698A1 (fr) | Nouveaux composants pour compositions d'électrolyte | |
EP4037036A1 (fr) | Élément de batterie rechargeable |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: UNKNOWN |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
17P | Request for examination filed |
Effective date: 20231124 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |