EP3834246A1 - Liquid electrolyte comprising organic carbonates and cyclic sulfoxides for applications in lithium secondary batteries - Google Patents
Liquid electrolyte comprising organic carbonates and cyclic sulfoxides for applications in lithium secondary batteriesInfo
- Publication number
- EP3834246A1 EP3834246A1 EP19752077.8A EP19752077A EP3834246A1 EP 3834246 A1 EP3834246 A1 EP 3834246A1 EP 19752077 A EP19752077 A EP 19752077A EP 3834246 A1 EP3834246 A1 EP 3834246A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- lithium
- oxide
- liquid electrolyte
- carbonate
- propylene carbonate
- 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
- 239000011244 liquid electrolyte Substances 0.000 title claims abstract description 42
- -1 cyclic sulfoxides Chemical class 0.000 title claims abstract description 31
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 28
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 15
- 150000005677 organic carbonates Chemical class 0.000 title claims description 9
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims abstract description 107
- 239000003792 electrolyte Substances 0.000 claims abstract description 76
- 239000002904 solvent Substances 0.000 claims abstract description 50
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 23
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 16
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 16
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 16
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 7
- 150000003624 transition metals Chemical class 0.000 claims abstract description 7
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 claims abstract description 6
- ISXOBTBCNRIIQO-UHFFFAOYSA-N tetrahydrothiophene 1-oxide Chemical compound O=S1CCCC1 ISXOBTBCNRIIQO-UHFFFAOYSA-N 0.000 claims description 78
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 34
- 150000003839 salts Chemical class 0.000 claims description 25
- 125000004432 carbon atom Chemical group C* 0.000 claims description 17
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 14
- 238000007363 ring formation reaction Methods 0.000 claims description 13
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 10
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 6
- 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 6
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 229910013872 LiPF Inorganic materials 0.000 claims description 3
- 101150058243 Lipf gene Proteins 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- GFDQTQWMQFSCRF-UHFFFAOYSA-N 3-methylthiolane 1-oxide Chemical compound CC1CCS(=O)C1 GFDQTQWMQFSCRF-UHFFFAOYSA-N 0.000 claims description 2
- LWLOKSXSAUHTJO-UHFFFAOYSA-N 4,5-dimethyl-1,3-dioxolan-2-one Chemical compound CC1OC(=O)OC1C LWLOKSXSAUHTJO-UHFFFAOYSA-N 0.000 claims description 2
- SDROQGXGPRQQON-UHFFFAOYSA-N 4-butyl-1,3-dioxolan-2-one Chemical compound CCCCC1COC(=O)O1 SDROQGXGPRQQON-UHFFFAOYSA-N 0.000 claims description 2
- YZUSKDQJXPRENU-UHFFFAOYSA-N 4-decyl-1,3-dioxolan-2-one Chemical compound CCCCCCCCCCC1COC(=O)O1 YZUSKDQJXPRENU-UHFFFAOYSA-N 0.000 claims description 2
- LSUWCXHZPFTZSF-UHFFFAOYSA-N 4-ethyl-5-methyl-1,3-dioxolan-2-one Chemical compound CCC1OC(=O)OC1C LSUWCXHZPFTZSF-UHFFFAOYSA-N 0.000 claims description 2
- KVOZCZVWECMVDU-UHFFFAOYSA-N 4-hexyl-1,3-dioxolan-2-one Chemical compound CCCCCCC1COC(=O)O1 KVOZCZVWECMVDU-UHFFFAOYSA-N 0.000 claims description 2
- AUXJVUDWWLIGRU-UHFFFAOYSA-N 4-propyl-1,3-dioxolan-2-one Chemical compound CCCC1COC(=O)O1 AUXJVUDWWLIGRU-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910015015 LiAsF 6 Inorganic materials 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 125000004104 aryloxy group Chemical group 0.000 claims description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- OKVJWADVFPXWQD-UHFFFAOYSA-N difluoroborinic acid Chemical compound OB(F)F OKVJWADVFPXWQD-UHFFFAOYSA-N 0.000 claims description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 claims description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Inorganic materials [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 2
- 125000003431 oxalo group Chemical group 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- IVYRWXQWSZFPJZ-UHFFFAOYSA-N 2-methylthiolane 1-oxide Chemical compound CC1CCCS1=O IVYRWXQWSZFPJZ-UHFFFAOYSA-N 0.000 claims 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims 1
- 150000001342 alkaline earth metals Chemical class 0.000 claims 1
- QVXQYMZVJNYDNG-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)methylsulfonyl-trifluoromethane Chemical compound [Li+].FC(F)(F)S(=O)(=O)[C-](S(=O)(=O)C(F)(F)F)S(=O)(=O)C(F)(F)F QVXQYMZVJNYDNG-UHFFFAOYSA-N 0.000 claims 1
- NNLBRYQGMOYARS-UHFFFAOYSA-N thiane 1-oxide Chemical compound O=S1CCCCC1 NNLBRYQGMOYARS-UHFFFAOYSA-N 0.000 claims 1
- GINSRDSEEGBTJO-UHFFFAOYSA-N thietane 1-oxide Chemical compound O=S1CCC1 GINSRDSEEGBTJO-UHFFFAOYSA-N 0.000 claims 1
- 239000011241 protective layer Substances 0.000 abstract description 31
- 239000006184 cosolvent Substances 0.000 abstract description 16
- 150000004649 carbonic acid derivatives Chemical class 0.000 abstract description 11
- 230000002441 reversible effect Effects 0.000 abstract description 8
- 230000002829 reductive effect Effects 0.000 abstract description 7
- 230000001351 cycling effect Effects 0.000 abstract description 6
- 238000010494 dissociation reaction Methods 0.000 abstract description 6
- 230000005593 dissociations Effects 0.000 abstract description 6
- 239000010439 graphite Substances 0.000 description 36
- 229910002804 graphite Inorganic materials 0.000 description 36
- 239000000654 additive Substances 0.000 description 35
- 239000000126 substance Substances 0.000 description 20
- 230000009467 reduction Effects 0.000 description 18
- 239000010410 layer Substances 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 11
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 9
- 102100033750 39S ribosomal protein L47, mitochondrial Human genes 0.000 description 9
- 101000733895 Homo sapiens 39S ribosomal protein L47, mitochondrial Proteins 0.000 description 9
- 238000000354 decomposition reaction Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- 230000037427 ion transport Effects 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 239000011593 sulfur Substances 0.000 description 8
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 7
- 238000009792 diffusion process Methods 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000002484 cyclic voltammetry Methods 0.000 description 5
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 5
- 238000007614 solvation Methods 0.000 description 5
- 241000894007 species Species 0.000 description 5
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000011835 investigation Methods 0.000 description 4
- 230000002427 irreversible effect Effects 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000011163 secondary particle Substances 0.000 description 4
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 150000003983 crown ethers Chemical class 0.000 description 3
- 230000002500 effect on skin Effects 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000004299 exfoliation Methods 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000000329 molecular dynamics simulation Methods 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 description 2
- IXWMDGLNJQNMIO-UHFFFAOYSA-N 1-bromo-4-(isocyanatomethyl)benzene Chemical compound BrC1=CC=C(CN=C=O)C=C1 IXWMDGLNJQNMIO-UHFFFAOYSA-N 0.000 description 2
- YXDXXGXWFJCXEB-UHFFFAOYSA-N 2-furonitrile Chemical compound N#CC1=CC=CO1 YXDXXGXWFJCXEB-UHFFFAOYSA-N 0.000 description 2
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 2
- SJHAYVFVKRXMKG-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2-oxide Chemical compound CC1COS(=O)O1 SJHAYVFVKRXMKG-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 101100317222 Borrelia hermsii vsp3 gene Proteins 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 241000283973 Oryctolagus cuniculus Species 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- VPUGDVKSAQVFFS-UHFFFAOYSA-N coronene Chemical compound C1=C(C2=C34)C=CC3=CC=C(C=C3)C4=C4C3=CC=C(C=C3)C4=C2C3=C1 VPUGDVKSAQVFFS-UHFFFAOYSA-N 0.000 description 2
- 150000005676 cyclic carbonates Chemical class 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000002593 electrical impedance tomography Methods 0.000 description 2
- 125000001033 ether group Chemical group 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000016507 interphase Effects 0.000 description 2
- YDNLNVZZTACNJX-UHFFFAOYSA-N isocyanatomethylbenzene Chemical compound O=C=NCC1=CC=CC=C1 YDNLNVZZTACNJX-UHFFFAOYSA-N 0.000 description 2
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- CAWRUEZRLRNISR-UHFFFAOYSA-N methyl 2,3,3,3-tetrafluoro-2-methoxypropanoate Chemical compound COC(=O)C(F)(OC)C(F)(F)F CAWRUEZRLRNISR-UHFFFAOYSA-N 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- YHLVIDQQTOMBGN-UHFFFAOYSA-N methyl prop-2-enyl carbonate Chemical compound COC(=O)OCC=C YHLVIDQQTOMBGN-UHFFFAOYSA-N 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000001472 pulsed field gradient Methods 0.000 description 2
- 238000001469 pulsed-field gradient nuclear magnetic spectroscopy Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 230000032258 transport Effects 0.000 description 2
- YBADLXQNJCMBKR-UHFFFAOYSA-N (4-nitrophenyl)acetic acid Chemical compound OC(=O)CC1=CC=C([N+]([O-])=O)C=C1 YBADLXQNJCMBKR-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- XJYDIOOQMIRSSY-UHFFFAOYSA-N 1,3,2-dioxathiepane 2-oxide Chemical compound O=S1OCCCCO1 XJYDIOOQMIRSSY-UHFFFAOYSA-N 0.000 description 1
- WDXYVJKNSMILOQ-UHFFFAOYSA-N 1,3,2-dioxathiolane 2-oxide Chemical compound O=S1OCCO1 WDXYVJKNSMILOQ-UHFFFAOYSA-N 0.000 description 1
- WTRBJJXKZUJRBA-UHFFFAOYSA-N 1,3-dioxacyclopentadecan-2-one Chemical compound O=C1OCCCCCCCCCCCCO1 WTRBJJXKZUJRBA-UHFFFAOYSA-N 0.000 description 1
- ANLVEXKNRYNLDH-UHFFFAOYSA-N 1,3-dioxonan-2-one Chemical compound O=C1OCCCCCCO1 ANLVEXKNRYNLDH-UHFFFAOYSA-N 0.000 description 1
- QNTPNTFBQZBRCK-UHFFFAOYSA-N 1,5,9,13-tetraoxacyclohexadecane Chemical compound C1COCCCOCCCOCCCOC1 QNTPNTFBQZBRCK-UHFFFAOYSA-N 0.000 description 1
- JLHTVZLEHOQZBM-UHFFFAOYSA-N 1-bromo-2-isocyanatoethane Chemical compound BrCCN=C=O JLHTVZLEHOQZBM-UHFFFAOYSA-N 0.000 description 1
- NAMDIHYPBYVYAP-UHFFFAOYSA-N 1-methoxy-2-(2-methoxyethoxy)ethane Chemical compound COCCOCCOC.COCCOCCOC NAMDIHYPBYVYAP-UHFFFAOYSA-N 0.000 description 1
- PRPINYUDVPFIRX-UHFFFAOYSA-M 1-naphthaleneacetate Chemical compound C1=CC=C2C(CC(=O)[O-])=CC=CC2=C1 PRPINYUDVPFIRX-UHFFFAOYSA-M 0.000 description 1
- AGLWLXYDTLVWKM-UHFFFAOYSA-N 2-isocyanato-1,3,5-trimethoxybenzene Chemical compound COC1=CC(OC)=C(N=C=O)C(OC)=C1 AGLWLXYDTLVWKM-UHFFFAOYSA-N 0.000 description 1
- OYOKPDLAMOMTEE-UHFFFAOYSA-N 4-chloro-1,3-dioxolan-2-one Chemical compound ClC1COC(=O)O1 OYOKPDLAMOMTEE-UHFFFAOYSA-N 0.000 description 1
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 description 1
- DEIXAXKIKOHRED-UHFFFAOYSA-N 5-(4-chlorophenyl)-1,2-thiazole Chemical compound C1=CC(Cl)=CC=C1C1=CC=NS1 DEIXAXKIKOHRED-UHFFFAOYSA-N 0.000 description 1
- KLLQVNFCMHPYGL-UHFFFAOYSA-N 5h-oxathiole 2,2-dioxide Chemical compound O=S1(=O)OCC=C1 KLLQVNFCMHPYGL-UHFFFAOYSA-N 0.000 description 1
- 229910013075 LiBF Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 238000003841 Raman measurement Methods 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 102100030951 Tissue factor pathway inhibitor Human genes 0.000 description 1
- IPBVNPXQWQGGJP-UHFFFAOYSA-N acetic acid phenyl ester Natural products CC(=O)OC1=CC=CC=C1 IPBVNPXQWQGGJP-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- BEIBNZUDHJCOKR-UHFFFAOYSA-N benzyl n-(2-aminoethyl)-n-methylcarbamate Chemical compound NCCN(C)C(=O)OCC1=CC=CC=C1 BEIBNZUDHJCOKR-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- JZQAAQZDDMEFGZ-UHFFFAOYSA-N bis(ethenyl) hexanedioate Chemical compound C=COC(=O)CCCCC(=O)OC=C JZQAAQZDDMEFGZ-UHFFFAOYSA-N 0.000 description 1
- 238000007707 calorimetry Methods 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 150000001793 charged compounds Polymers 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
- WUDNUHPRLBTKOJ-UHFFFAOYSA-N ethyl isocyanate Chemical compound CCN=C=O WUDNUHPRLBTKOJ-UHFFFAOYSA-N 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000002847 impedance measurement Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000007912 intraperitoneal administration Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 108010013555 lipoprotein-associated coagulation inhibitor Proteins 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 1
- 229940049953 phenylacetate Drugs 0.000 description 1
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- QZDWODWEESGPLC-UHFFFAOYSA-N pyridin-3-yl acetate Chemical compound CC(=O)OC1=CC=CN=C1 QZDWODWEESGPLC-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000005838 radical anions Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
-
- 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
- H01M4/58—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
-
- 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
- the invention describes new non-aqueous liquid electrolytes which can be used in lithium-ion, lithium-metal and lithium-sulfur batteries and which comprise non-linear organic carbonates, such as propylene carbonate, as solvents.
- the non-aqueous, aprotic electrolytes that are used today in most commercial rechargeable lithium-ion batteries contain organic carbonates, such as. B. ethylene carbonate (EC) and dimethyl carbonate (DMC), and lithium hexafluorophosphate as the conductive salt.
- organic carbonates such as. B. ethylene carbonate (EC) and dimethyl carbonate (DMC), and lithium hexafluorophosphate as the conductive salt.
- EC-based electrolytes have a decisive disadvantage.
- DMC dimethyl carbonate
- co-solvents since they have low viscosities and therefore facilitate ion transport.
- the high volatility and flammability of the linear carbonates generally lead to a safety risk. It is therefore necessary to look for alternative solvents, especially with regard to larger-scale applications, such as stationary energy storage systems, which are a growing part of the network infrastructure as decentralized energy generation increases.
- the requirements for battery safety are particularly high for private households.
- Alternative solvents should both have high relative permittivities in order to enable high solubility and dissociation of the lithium salt, and should be able to form stable protective layers on the electrodes, an anode protective layer (solid electrolyte interphase, SEI) and a cathode protective layer (cathode electrolyte inter - phase, CEI), both of which are well permeable to unions, but electronically insulating to prevent irreversible oxidation of the solvent on the cathode and irreversible reductions on the anode.
- SEI solid electrolyte interphase
- CEI cathode electrolyte inter - phase
- the electrolytes prefferably have ionic conductivities in the range of at least 5-8 mS cm 1 at 20 ° C., in the absence of linear carbonates, in order to ensure sufficient ion transport guarantee. This is important in order to enable reversible capacities and a long calendar life of a battery due to lower polarization effects.
- PC propylene carbonate
- propylene carbonate has a relatively high viscosity of 2.3 mPa-s, which hinders ion transport.
- DMC has a viscosity of 0.5 mPa s at 30 ° C. 141
- additives are usually substances which make up up to 5% by weight or% by volume of the solvent. 151 At higher proportions one speaks of co-solvents.
- Reduction additives have a higher reduction potential than the solvent. The additives are reduced in the first charging cycle before the solvent is reduced. They form insoluble products that are deposited on the surface of the electrodes and form protective layers. For propylene carbonate, therefore, additives come into question, the reduction potentials of> 0.8 V vs. Have Li / Li + .
- Polymerizing substances have one or more carbon-carbon bonds and form a protective layer through electrochemically induced polymerization. The following molecules with vinyl groups have already been used with propylene carbonate, for example:
- VEC vinyl ethylene carbonate
- NDP N-Vinyl-2-pyrrolidone
- FEC Fluoroethylene carbonate
- CIEC chloroethylene carbonate
- reaction additives have also been successfully used.
- Reaction additives are not reduced throughout the charging cycle, instead they are able to intercept solvent reduction intermediates or to react with the decomposition products of the solvent molecules to form a stable SEI.
- Representatives of the group of reduction additives are, for example, CO 2 and aromatic esters.
- phenylacetate, 4-nitrophenylacetate, 1-naphthylacetate, 3-acetoxypyridine and methylbenzoate were used. used in combination with propylene carbonate.
- These compounds have an extensive aromatic framework (conjugated p-system), which can stabilize the radical anions that occur as an intermediate stage of solvent reduction by charge delocalization.
- Some isocyanates have also been used as additives with propylene carbonate:
- DOPI diethoxyphosphinyl isocyanate
- Lithium bis (oxalato) borate (LiBOB) and lithium difluoro (oxalato) borate (LiDFOB) can be used both as lithium salts and as additives.
- Alkali metal acetates have also been used as additives for propylene carbonate-based electrolytes. It is assumed that a larger ionic radius of the alkali metal ions leads to a reduction in the propylene carbonate reduction and thus to an improvement in the battery performance.
- Bis (2-methoxyethyl) ether (diglyme) was used as a further additive. Lithium ions that are solvated by Diglyme preferentially store in the graphite electrode, decompose within the graphite and form a protective layer.
- Crown ethers as additives such as [12] crown-4, were able to successfully suppress the propylene carbonate reduction. This could be attributed to their extremely strong solvation ability of Li + ions. In the presence of crown ethers, the Li + ion solvation of propylene carbonate molecules is severely weakened, so that propylene carbonate does not become embedded in graphite together with Li + ions. This leads to a reduction in the propylene carbonate reduction.
- DTD ethylene sulfate
- the investigated electrolyte consisting of 1 M LiBF 4 in 10% by weight DTD, 90% by weight propylene carbonate only has an ionic conductivity of ⁇ 3.5 mS cm 1 at 20 ° C, which is no longer in the desired conductivity range for usable electrolytes.
- Methyl tetrafluoro-2- (methoxy) propionate as a co-solvent for propylene carbonate-based electrolytes also leads to higher viscosities than electrolytes based only on propylene carbonate. 191
- linear carbonates such as DEC, DMC and MEC
- linear carbonates were also used in addition to other additives such as VC to reduce the viscosity of the propylene carbonate-based electrolyte.
- the solvents should have high relative permittivities in order to enable high solubility and dissociation of the lithium salt and should be able to form stable protective layers on the electrodes, in particular an anode protective layer (SEI) and a cathode protective layer (CEI), both of which are well permeable to Li + ions and insulating to avoid irreversible oxidation and reduction of the solvent.
- SEI anode protective layer
- CEI cathode protective layer
- liquid mixtures comprising at least one non-linear, organic carbonate as the main solvent and at least one cyclic sulfoxide in combination with at least one conductive salt are suitable liquid electrolytes for lithium-ion batteries.
- the cyclic sulfoxide serves as a co-solvent with a proportion of 10 - 40 mol% based on the solvent of the electrolyte.
- the organic, non-linear carbonate is, in particular, non-linear, ring-shaped carbonates such as, for example, ethylene carbonate (EC), propylene carbonate (PC), 1, 2-butylene carbonate, 2,3-butylene carbonate, 1, 2-pentylene carbonate, 2 , 3-pentylene carbonate, 1, 2-hexylene carbonate, 1, 2-octylene carbonate, 1, 2-dodecylene carbonate and
- liquid electrolyte according to the invention in particular for lithium-ion batteries, the use of linear carbonates is explicitly dispensed with, since their high volatility and flammability in principle lead to a safety risk.
- the cyclic sulfoxide does not contain any further heteroatoms in the ring.
- the ring may have one or more double bonds.
- a typical and particularly advantageous representative of a cyclic sulfoxide is tetrahydrothiophene-1-oxide. It is a five-part cyclic sulfur substance that is structurally similar to additives and cosolvents (ES, 1, 3-PS, sulfolane) previously used in lithium-ion batteries. Tetrahydrothiophene-1-oxide has so far not been regarded as an electrolyte component of lithium-ion, lithium-metal and lithium-sulfur batteries. Tetrahydrothiophene-1-oxide is easy to manufacture (reaction of tetrahydrothiophene with hydrogen peroxide and a catalyst at room temperature) and can therefore be synthesized in principle at low cost.
- Tetrahydrothiophene is already used worldwide as an odorant in natural gas.
- the solvent mixture according to the invention is only a two-component system, with at least one non-linear, organic carbonate as solvent and a cyclic sulfur substance, such as, for. B. tetrahydrothiophene-1-oxide, as a co-solvent, which regularly keeps the price low.
- LiTFSI bis (trifluoromethanesulfonyl) imide
- propylene carbonate / tetrahydrothiophene-1-oxide liquid electrolyte represents - like all other electrolyte mixtures according to the invention - a safe electrolyte for use in lithium-ion batteries.
- Both solvents of the exemplary embodiment and further nonlinear organic carbonates have comparable high flash points (T F ) and boiling points (T 6 ):
- this advantageously enables use in stationary energy storage systems, which can also be used in private households.
- the propylene carbonate / tetrahydrothiophene-1-oxide electrolyte provides - like also all other electrolyte mixtures according to the invention - regularly pose no danger to the human organism.
- Propylene carbonate LD50, rat, oral:> 5,000 mg / kg
- Ethylene carbonate LD50, rat, dermal:> 2,000 mg / kg
- 1, 2-butylene carbonate LD50, rat, oral:> 5,000 mg / kg
- Tetrahydrothiophene-1-oxide LD50, mouse, intraperitoneal: 3,500 mg / kg [14]
- Lithium-ion batteries with liquid electrolytes according to the invention can thus be handled without problems in private households without the electrolyte posing a danger to people in the event of a damaged battery.
- the conductivities are a direct consequence of the viscosities, which also have a minimum ( ⁇ 6.4 mPa-s at 25 ° C) in the system with 30 mol% tetrahydrothiophene-1-oxide and LiPF 6 .
- Table 1 shows the concentrations of propylene carbonate (PC) and tetrahydrothiophene-1-oxide (abbreviated here as THHoxide) in the 1 M LiPF 6 -based electrolytes and Coordination numbers of Li-PC and Li-tetrahydrothiophene-1-oxide complexes from molecular dynamics simulations. The possible solvation complexes that result from this are also listed.
- PC propylene carbonate
- THHoxide tetrahydrothiophene-1-oxide
- the molecular dynamics simulations confirm that tetrahydrothiophene-1-oxide replaces PC in the complex as soon as there is enough tetrahydrothiophene-1-oxide in the solution, ie at least 1 mol of tetrahydrothiophene-1-oxide for 1 mol of Li + .
- propylene carbonate / tetrahydrothiophene-1-oxide electrolyte also shows a remarkable physicochemical behavior at low temperatures. The difference in conductivity and viscosity is much larger for low temperatures. Electrolytes with 30 mol% tetrahydrothiophene-1-oxide have about 1.5 times higher conductivities at -20 ° C than electrolytes based solely on propylene carbonate. In addition, the mixtures crystallize down to temperatures of -150 ° C not.
- liquid electrolyte is still liquid even at low temperatures and has an increased ionic conductivity, could also be confirmed for most of the liquid electrolytes claimed according to the invention.
- Electrolyte decomposition at high temperatures is only limited by the lithium salt.
- the exemplary embodiment according to the invention comprising propylene carbonate / tetrahydro-thiophene-1-oxide mixtures in combination with a conductive salt also enables regularly stable cycling in lithium-ion batteries with carbon-based anodes and transition metal oxide-based cathodes, although propylene carbonate and tetrahydrothiophene -1-oxide as the sole solvent is not compatible with the electrodes, ie both solvents decompose at ⁇ 0.8 V vs. Li / Li + , which leads to exfoliation of graphite in the case of propylene carbonate, while the tetrahydrothiophene-1-oxide molecules and / or their decomposition products suppress the de- / intercalation of lithium.
- anode protection layer typically has a thickness ( ⁇ 5 nm) that it is visible under the scanning electron microscope.
- electrolytes based on ethylene carbonate (EC) and vinylene carbonate (VC) regularly only lead to layers of a maximum of 3.3 nm.
- the examination with the scanning electron microscope was difficult because the sample was hardly electrically conductive and therefore a high secondary electron current could not be obtained.
- the protective layer on the carbon-based electrode therefore shows a low electrical conductivity, which advantageously protects against further electrolyte reduction and thus increases the life of the battery.
- the anode protective layer is formed almost completely in the first three formation cycles and initially covers the entire electrode in terms of area, while it continues to nestle around the individual secondary particles of the active material.
- Secondary particles consist of primary particles on the order of 1 pm and usually have sizes of less than 1 to 100 pm. 1161
- the cathode protective layer is regularly significantly thinner ( ⁇ 1 nm), but is also formed almost completely after the formation.
- the organic fraction of both layers, consisting of a polymer with ether groups, is around 66 at%, which is excellent in terms of the permeability of the solvated Li + cations, since inorganic films are less permeable.
- the sulfur compounds are not part of the anode protective layer, but only form part of the inorganic part of the cathode protective layer, in which metal sulfites and sulfates can be detected.
- These salts have a positive impact on the battery. They are well-known electronic isolators and can effectively prevent the continued oxidation of solvent molecules.
- propylene carbonate / tetrahydrothiophene-1-oxide electrolyte comprises at least one lithium salt.
- lithium salts are particularly suitable as conductive salts for use in the liquid electrolyte according to the invention individually or as any mixtures:
- LiPF 6 lithium hexafluorophosphate
- Lithium tetrafluoroborate LiBF 4
- Lithium perchlorate LiCI0 4
- Lithium hexafluoroarsenate (V) LiAsF 6
- Lithium trifluoromethanesulfonate LiCF 3 S0 3
- Li-TFSM lithium tris (trifluoromethylsulfonyl) methanide
- LiBOB Lithium bis (oxalato) borate
- Lithium oxalyl difluoroborate LiBF 2 C 2 0 4
- LiPF 3 (CF 2 CF 3 ) 3 lithium fluoroalkyl phosphate
- LiBETI Lithium bisperfluoroethysulfonylimide
- salts such as lithium bis (trifluoromethanesulfonyl) imide (LiTFSI) and lithium bis (fluorosulfonyl) imide (LiFSI) is disadvantageously not possible without additional additives, since it is known that they dissolve aluminum from which the cathode current collector is made , promote at high potentials (> 3 V vs. Li / Li + ).
- Tetrahydrothiophene-1-oxide as the preferred cyclic sulfoxide has a high relative permittivity of 44.1 at 20 ° C.
- Propylene carbonate shows a very high relative permittivity of 66.2 at 20 ° C.
- this enables high solubility and dissociation of the lithium salt.
- Salt concentrations of 0.01-22 mol / L, based on the liquid electrolytes, are generally proposed as being suitable not only for the preferred exemplary embodiment but also for all the liquid electrolytes claimed, preferably salt concentrations in the range from 0.1 to 10 mol / l.
- cyclic sulfoxides Although tetrahydrothiophene-1-oxide is a preferred example of cyclic sulfoxides, it was found in the context of the invention that other compounds, individually or as mixtures, are also suitable for being able to further improve the properties already present.
- the modifications of the cyclic sulfoxide encompassed by the invention can be represented as follows, starting from the general formula (1).
- the cyclic sulfoxide has at least 3 or more ring carbon atoms x.
- R 1 , R 2 , R 3 up to a maximum of R 10 arranged on the ring carbon atoms x are in each case selected identically or independently of one another from the group consisting of:
- Alkoxy groups with 1 to 12 carbon atoms in particular (poly) alkoxy groups with up to 5 ethoxy units
- a ring carbon atom does not form a double bond, it is saturated with a hydrogen atom in addition to the radical R x .
- cyclic sulfoxides listed below have been found to be particularly suitable as cosolvents in the electrolyte mixture according to the invention, since they are regularly liquid between -20 and 80 ° C., are comparatively highly conductive and also have an improved ion transport and good cyclization properties exhibit:
- the liquid electrolytes according to the invention have very good resistance to carbon-based electrodes. This was found in cyclic voltammetry experiments and in the galvanostatic cycling of the liquid electrolytes in combination with a carbon-based anode and a transition metal-based cathode.
- the protective layers (SEI and CEI) formed on the respective electrodes proved to be well permeable to Li + ions, but at the same time brought about adequate electronic insulation.
- liquid electrolytes optimized according to the invention for use in lithium-ion batteries are shown, which combine the advantages of previous SEI additives and viscosity-reducing co-solvents and thereby dispense entirely with volatile, highly flammable substances. In this case, no further additives are advantageously necessary and also not provided.
- the increased safety makes the liquid electrolytes according to the invention particularly interesting for applications on a larger scale and for private households.
- the following positive properties were regularly recorded with the liquid electrolytes according to the invention:
- Figure 1 Ionic conductivities (s) and viscosities (h) of an embodiment of the invention
- FIG. 1 Heat flow of electrolytes comprising 1 M LiPF 6 in propylene carbonate, 1 M
- FIG. 3 Raman spectra of the propylene carbonate / tetrahydro-thiophene-1-oxide electrolyte according to the invention with LiPF 6 as the conductive salt with different solvent fractions.
- Figure 4 Cyclic voltammograms of Li / graphite cells, which a) 1 M LiPF 6 in propylene carbonate, b) 1 M LiPF 6 in tetrahydrothiophene-1-oxide and c) 1 M LiPF 6 in 15 mol% tetrahydrothiophene 1-oxide and 85 mol% propylene carbonate.
- Figure 5 Cyclic voltammograms of U / NCM1 1 1 cells, the a) 1 M LiPF 6 in propylene carbonate, b) 1 M LiPF 6 in tetrahydrothiophene-1-oxide and c) 1 M LiPF 6 in 15 mol% Tetrahydrothiophene-1-oxide and 85 mol% propylene carbonate.
- Figure 6 Galvanostatic cyclization of propylene carbonate / tetra-hydrothiophene-1-oxide electrolytes according to the invention with LiPF 6 as the conductive salt with different solvent fractions in graphite / NCM1 1 1 cells.
- Figure 10 X-ray photoelectron spectroscopy measurements to determine the composition and the layer thickness of protective layers on the electrodes, a) for a graphite anode and b) for an NCM1 1 1 cathode.
- FIG. 1 Thermogravimetric analyzes (TGA) of LiPF 6 in PC, LiPF 6 in PC / tetrahydrothiophene-1-oxide and LiPF 6 in tetrahydrothiophene-1-oxide.
- Electrolytes with LiBF 4 as conductive salt with different solvent proportions are Electrolytes with LiBF 4 as conductive salt with different solvent proportions.
- Figure 13 Galvanostatic cyclization of propylene carbonate / tetra-hydrothiophene-1-oxide electrolytes according to the invention with LiBF 4 as the conductive salt with different solvent fractions in graphite / NCM11 1 cells.
- Figure 14 Structural formulas of selected cyclic sulfoxides as co-solvents.
- Tetrahydrothiophene-1-oxide was dried over molecular sieves before use (water content ⁇ 80 ppm).
- the electrolytes with 1 M LiPF 6 or 1 M LiBF 4 , x mol% tetrahydrothiophene-1 oxide and (100-x) mol% propylene carbonate (x 0, 5, 10, 15, 20, 30, 40, 50, 70, 100) were produced with the exclusion of air and water.
- DSC Dynamic differential calorimetry
- buttons cells with graphite and LiNi 1 / 3Co 1/3 Mn 1 / with the Inventions according tetrahydrothiophene-1 oxide / propylene carbonate electrolyte in the potential region 3 302 were built in a drying room (water content ⁇ 30 ppm), which contained Separion ® as a separator and 100 ml electrolyte. After 3 formation cycles at 0.2 C, the cells were cycled for 100 cycles at 1 C.
- the specific discharge capacities for 1 M LiPF 6 (FIG. 6) and for 1 M LiBF 4 (FIG. 13) are shown as a function of the number of cycles.
- the self-diffusion coefficients of the species present in the electrolyte were determined with field gradient NMR spectroscopy (pulsed field gradient nuclear magnetic resonance, PFG-NMR).
- the measurements were carried out with stimulated echo sequences on a Bruker AVANCE III 200 spectrometer, using a Bruker Diff50 probe head, Equipped with a 7 Li / 1 H and 19 F coil (5 mm), at 25 ° C (stabilized at ⁇ 0.1 ° C).
- the gradient strengths were varied from 5 to 1800 G / cm.
- the gradient pulse length was 1 ms, the diffusion time 40 ms. The results are shown in Figure 8.
- Propylene carbonate molecules have the highest self-diffusion coefficients and show the same trend as the ionic conductivities, ie with LiPF 6 a maximum value of 1.95-10 1 ° m 2 s 1 with 30 mol% tetrahydrothiophene-1- oxide and decreasing self-diffusion coefficients if more or less tetrahydrothiophene-1-oxide or propylene carbonate is contained.
- the self-diffusion coefficients of the PF 6 ⁇ anions show comparable behavior, but with a less pronounced increase for 0-30 mol% tetrahydro-thiophene-1-oxide.
- the LF ions represent the slowest species in the electrolyte. The contributions of the Li + and PF 6 ions lead to the observed behavior of the ionic conductivities.
- Electrochemical impedance measurements were also carried out with a VMP3 (BioLogic Science Instruments) to investigate the resistances of the protective layers.
- VMP3 BioLogic Science Instruments
- symmetrical graphite / graphite (a) and NCM111 / NCM111- (b) button cells as well as graphite NCM111 (c) cells were manufactured, which were measured in a frequency range from 100 kHz to 10 mHz.
- the graphite and NCM111 electrodes were removed from cells after 24 hours of open circuit voltage (OCV), after three formation cycles at 0.2 C, or after a further 100 cycles at 1 C.
- OCV open circuit voltage
- the resistances were obtained by fitting the impedance curves in the Nyquist graph.
- FIG. 9a makes it clear that there are no protective layers on the graphite electrodes after the open circuit voltage.
- an anode protective layer SEI
- the sheet resistance increases slightly in the further 100 cycles.
- the SEI is therefore only formed by galvanostatic cycling and not chemically.
- the high charge transfer resistances indicate that the layers are electronically insulating and therefore have a high organic content.
- the sharp increase in charge transfer resistances can be attributed not only to an increasing layer thickness, but also to a change in the surface morphology or the layer composition.
- FIG. 9b makes it clear that the cathode protective layer (CEI) is also formed by galvanostatic cyclization and that the layer thickness slowly increases with an increasing number of cycles.
- the resistance of the CEI is less than that of the SEI.
- the charge transfer resistance also increases.
- the results of the impedance measurements with graphite / NCM111 cells show the influence of both layers on the overall resistance.
- X-ray photoelectron spectroscopy measurements were carried out to determine the composition and layer thickness of the protective layers on the electrodes. The electrodes were inserted into the XPS device (Axis Ultra DLD, Kratos, UK) and kept under vacuum for 12 hours. AI K Q radiation with an energy of 1486.3 eV and an emission angle of 0 ° (cathode) or 45 ° (anode) was used.
- the sputter depth profile for the anodes was carried out with a polyatomic ion source (coronene) with a sputter crater ten times as large as the measuring range. Sputtering was carried out for 60 s, 120 s and 600 s. Two or three data points with a lateral resolution of 700 x 300 mm were recorded for each sample and arithmetically averaged. The spectra generated were adapted with the CasaXPS software (version 2.3.16 PR 1.6, Casa Software Ltd., U.K.). The C 1 s C-H / C-C peak (284.5 eV) was used as the internal standard for the calibration of the binding energies. FIG.
- the 10 shows the determined compositions a) for the graphite anode and b) for the NCM1 1 1 cathode and the layer thicknesses.
- the SEI is ⁇ 5 nm thick (5.5 ⁇ 0.6 nm after 3 cycles, 4.9 ⁇ 0.1 nm after 103 cycles), whereas the CEI is ⁇ 1 nm (1.0 ⁇ 0.3 nm after 3 cycles, 1, 4 ⁇ 0.1 nm after 103 cycles) is significantly thinner.
- the layers were almost completely formed during the formation cycles since no significant change in the layer thickness between 3 and 103 cycles could be observed.
- the organic content of both layers is approximately 66 at%, which indicates a good permeability for Li + ions. It consists of a polymer with ether groups.
- the SEI does not include any sulfur substances, whereas the inorganic part of the CEI contains metal sulfites and sulfates, among others, which are electronically insulating.
- Thermogravimetric analyzes were carried out with a TGA Q5000 measuring device. The samples were weighed in closed aluminum crucibles. The temperature was increased from 30 ° C to 600 ° C at 10 ° C per minute and the weight of the samples was measured. Nitrogen was used as the ambient gas.
- Figure 1 1 shows that the decomposition of all electrolytes (1 M LiPF 6 in PC, 1 M LiPF 6 in tetrahydrothiophene-1-oxide and 1 M LiPF 6 in 15 mol% tetrahydrothiophene-1 oxide and 85 mol% PC) at about 120 ° C.
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102018006379.9A DE102018006379A1 (en) | 2018-08-11 | 2018-08-11 | Liquid electrolytes comprising organic carbonates for applications in lithium-ion, lithium-metal and lithium-sulfur batteries |
PCT/DE2019/000195 WO2020035098A1 (en) | 2018-08-11 | 2019-07-20 | Liquid electrolyte comprising organic carbonates and cyclic sulfoxides for applications in lithium secondary batteries |
Publications (1)
Publication Number | Publication Date |
---|---|
EP3834246A1 true EP3834246A1 (en) | 2021-06-16 |
Family
ID=67543971
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19752077.8A Pending EP3834246A1 (en) | 2018-08-11 | 2019-07-20 | Liquid electrolyte comprising organic carbonates and cyclic sulfoxides for applications in lithium secondary batteries |
Country Status (6)
Country | Link |
---|---|
US (1) | US20210313623A1 (en) |
EP (1) | EP3834246A1 (en) |
JP (1) | JP7427650B2 (en) |
CN (1) | CN112585794A (en) |
DE (1) | DE102018006379A1 (en) |
WO (1) | WO2020035098A1 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115602911B (en) * | 2022-11-07 | 2023-03-03 | 中创新航科技股份有限公司 | Lithium ion battery |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3229757B2 (en) * | 1994-09-05 | 2001-11-19 | 三洋電機株式会社 | Lithium secondary battery |
US6265109B1 (en) * | 1998-06-02 | 2001-07-24 | Matsushita Electric Industrial Co., Ltd. | Magnesium alloy battery |
WO2002101869A1 (en) * | 2001-06-07 | 2002-12-19 | Mitsubishi Chemical Corporation | Lithium secondary cell |
JP4635407B2 (en) * | 2003-03-25 | 2011-02-23 | 三洋電機株式会社 | Non-aqueous electrolyte for secondary battery and non-aqueous electrolyte secondary battery |
KR100515332B1 (en) * | 2003-04-28 | 2005-09-15 | 삼성에스디아이 주식회사 | An electrolyte for a lithium battery and a lithium battery comprising the same |
US7968235B2 (en) * | 2003-07-17 | 2011-06-28 | Uchicago Argonne Llc | Long life lithium batteries with stabilized electrodes |
JP2005327566A (en) * | 2004-05-13 | 2005-11-24 | Daiso Co Ltd | Battery using cross-linked polymer electrolyte |
US8758946B2 (en) * | 2006-10-04 | 2014-06-24 | Giner, Inc. | Electrolyte suitable for use in a lithium ion cell or battery |
EP2206189B1 (en) * | 2007-09-19 | 2014-10-22 | Lg Chem, Ltd. | Non-aqueous electrolyte lithium secondary battery |
JP2010140737A (en) * | 2008-12-11 | 2010-06-24 | Sanyo Electric Co Ltd | Nonaqueous electrolyte secondary battery |
EP2772981B1 (en) * | 2011-10-28 | 2020-10-21 | Asahi Kasei Kabushiki Kaisha | Non-aqueous secondary battery |
JP5955629B2 (en) * | 2011-11-01 | 2016-07-20 | 株式会社Adeka | Non-aqueous electrolyte secondary battery |
CN103367801B (en) * | 2012-04-09 | 2016-08-31 | 张家港市国泰华荣化工新材料有限公司 | The electrolyte of high-temperature lithium ion battery performance can be improved |
CN105449279B (en) * | 2015-12-30 | 2018-08-24 | 东莞新能源科技有限公司 | Nonaqueous electrolytic solution and the lithium ion battery for using the nonaqueous electrolytic solution |
-
2018
- 2018-08-11 DE DE102018006379.9A patent/DE102018006379A1/en active Pending
-
2019
- 2019-07-20 WO PCT/DE2019/000195 patent/WO2020035098A1/en active Application Filing
- 2019-07-20 CN CN201980046446.9A patent/CN112585794A/en active Pending
- 2019-07-20 EP EP19752077.8A patent/EP3834246A1/en active Pending
- 2019-07-20 US US17/259,958 patent/US20210313623A1/en active Pending
- 2019-07-20 JP JP2021500381A patent/JP7427650B2/en active Active
Also Published As
Publication number | Publication date |
---|---|
JP7427650B2 (en) | 2024-02-05 |
US20210313623A1 (en) | 2021-10-07 |
DE102018006379A1 (en) | 2020-02-13 |
WO2020035098A1 (en) | 2020-02-20 |
JP2021533527A (en) | 2021-12-02 |
CN112585794A (en) | 2021-03-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP3794663B1 (en) | Rechargeable battery cell | |
EP3118917A1 (en) | Lithium metal battery and electrolyte | |
DE112016004508T5 (en) | A nonaqueous electrolyte solution for a lithium secondary battery or a lithium ion capacitor, and a lithium secondary battery or a lithium ion capacitor using the same | |
WO2000055935A1 (en) | Use of additives in electrolytes for electrochemical cells | |
DE102005029124A1 (en) | Electrolyte/separator system, useful for producing electro-chemical energy-storage systems e.g. lithium metal batteries, comprises electrolytes comprising base component, ionic liquid, water, additive, lead salt and ceramic separator | |
DE102011052156A1 (en) | Lithium 2-methoxy-1,1,2,2-tetrafluoroethanesulfonate and its use as a conductive salt in lithium-based energy storage | |
EP3155686B1 (en) | Electrolyte, cell and battery comprising the electrolyte, and use of the electrolyte | |
WO2022162005A1 (en) | So2-based electrolyte for a rechargeable battery cell, and rechargeable battery cell | |
EP2937918A1 (en) | Hindered glymes for electrolyte compositions | |
EP3834246A1 (en) | Liquid electrolyte comprising organic carbonates and cyclic sulfoxides for applications in lithium secondary batteries | |
EP3639317A1 (en) | Electrolyte for lithium ion batteries | |
DE102006055770A1 (en) | Electrolyte with lithium bis(oxalato)borate, dissolved in solvent from carbonate or ester and at least an additive, useful e.g. in electro-chemical cells, preferably in lithium cells, lithium ion cells and lithium ion polymer cells | |
WO2013064530A1 (en) | Electrolyte additive for a lithium-based energy storage device | |
DE102014108012B4 (en) | Substituted pyrazoles and their use as conductive salts for lithium-based energy storage devices | |
DE10154912B4 (en) | Rechargeable lithium battery | |
WO2008110558A1 (en) | Electrolytes for electrochemical components | |
WO2017153349A1 (en) | Use of trialkylsiloxy-based metal complexes as an additive in lithium ion batteries | |
EP3560023B1 (en) | Electrolyte for lithium-ion-batteries | |
DE102016125323A1 (en) | Electrolyte for lithium-ion batteries | |
DE102017107253A1 (en) | Electrolyte for lithium-ion batteries | |
WO2022161996A1 (en) | Rechargeable battery cell | |
EP4037036A1 (en) | Rechargeable battery cell | |
DE102018114146A1 (en) | Hybrid electrolyte for aqueous lithium-ion batteries |
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 |
|
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: 20210225 |
|
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 |
|
DAV | Request for validation of the european patent (deleted) | ||
DAX | Request for extension of the european patent (deleted) | ||
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
17Q | First examination report despatched |
Effective date: 20231122 |