WO2021015264A1 - 非水電解液、非水電解液電池、及び化合物 - Google Patents
非水電解液、非水電解液電池、及び化合物 Download PDFInfo
- Publication number
- WO2021015264A1 WO2021015264A1 PCT/JP2020/028526 JP2020028526W WO2021015264A1 WO 2021015264 A1 WO2021015264 A1 WO 2021015264A1 JP 2020028526 W JP2020028526 W JP 2020028526W WO 2021015264 A1 WO2021015264 A1 WO 2021015264A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- lithium
- carbonate
- aqueous
- general formula
- Prior art date
Links
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 100
- 150000001875 compounds Chemical class 0.000 title claims abstract description 79
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 36
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 23
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 23
- 239000011356 non-aqueous organic solvent Substances 0.000 claims abstract description 21
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 18
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 13
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 11
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- -1 fluorosulfonyl Chemical group 0.000 claims description 79
- 239000008151 electrolyte solution Substances 0.000 claims description 52
- 125000004432 carbon atom Chemical group C* 0.000 claims description 51
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 39
- 229910052744 lithium Inorganic materials 0.000 claims description 39
- 150000003949 imides Chemical class 0.000 claims description 18
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 16
- 229910001415 sodium ion Inorganic materials 0.000 claims description 16
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 10
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052700 potassium Inorganic materials 0.000 claims description 10
- 239000011591 potassium Substances 0.000 claims description 10
- MRDKYAYDMCRFIT-UHFFFAOYSA-N oxalic acid;phosphoric acid Chemical compound OP(O)(O)=O.OC(=O)C(O)=O MRDKYAYDMCRFIT-UHFFFAOYSA-N 0.000 claims description 9
- 229910001414 potassium ion Inorganic materials 0.000 claims description 8
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 7
- 150000005678 chain carbonates Chemical class 0.000 claims description 7
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 7
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 5
- SYRDSFGUUQPYOB-UHFFFAOYSA-N [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O SYRDSFGUUQPYOB-UHFFFAOYSA-N 0.000 claims description 5
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 claims description 5
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims description 5
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 5
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 4
- 239000001294 propane Substances 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 48
- 238000002360 preparation method Methods 0.000 description 19
- 239000000654 additive Substances 0.000 description 17
- 150000003839 salts Chemical class 0.000 description 13
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 12
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 229910052708 sodium Inorganic materials 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- 230000000996 additive effect Effects 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 7
- 150000001768 cations Chemical class 0.000 description 7
- 239000011737 fluorine Substances 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 229910013870 LiPF 6 Inorganic materials 0.000 description 6
- KTQDYGVEEFGIIL-UHFFFAOYSA-N n-fluorosulfonylsulfamoyl fluoride Chemical compound FS(=O)(=O)NS(F)(=O)=O KTQDYGVEEFGIIL-UHFFFAOYSA-N 0.000 description 6
- 229910052723 transition metal Inorganic materials 0.000 description 6
- 150000003624 transition metals Chemical class 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 5
- 229910021383 artificial graphite Inorganic materials 0.000 description 5
- 125000000753 cycloalkyl group Chemical group 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- 125000000304 alkynyl group Chemical group 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 125000000392 cycloalkenyl group Chemical group 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 3
- 125000004778 2,2-difluoroethyl group Chemical group [H]C([H])(*)C([H])(F)F 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910001413 alkali metal ion Inorganic materials 0.000 description 3
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 125000003302 alkenyloxy group Chemical group 0.000 description 3
- 125000005133 alkynyloxy group Chemical group 0.000 description 3
- 125000004104 aryloxy group Chemical group 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 125000004465 cycloalkenyloxy group Chemical group 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002905 metal composite material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 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 2
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 2
- RVEUZXSLRKKPCQ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-yl hydrogen carbonate Chemical compound FC(F)(F)CC(C)OC(O)=O RVEUZXSLRKKPCQ-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- CHHOPPGAFVFXFS-UHFFFAOYSA-M [Li+].[O-]S(F)(=O)=O Chemical compound [Li+].[O-]S(F)(=O)=O CHHOPPGAFVFXFS-UHFFFAOYSA-M 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 125000000000 cycloalkoxy group Chemical group 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- ODMITNOQNBVSQG-UHFFFAOYSA-N ethyl 2-fluoropropanoate Chemical compound CCOC(=O)C(C)F ODMITNOQNBVSQG-UHFFFAOYSA-N 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000002847 impedance measurement Methods 0.000 description 2
- 229940006487 lithium cation Drugs 0.000 description 2
- GBPVMEKUJUKTBA-UHFFFAOYSA-N methyl 2,2,2-trifluoroethyl carbonate Chemical compound COC(=O)OCC(F)(F)F GBPVMEKUJUKTBA-UHFFFAOYSA-N 0.000 description 2
- MHAIQPNJLRLFLO-UHFFFAOYSA-N methyl 2-fluoropropanoate Chemical compound COC(=O)C(C)F MHAIQPNJLRLFLO-UHFFFAOYSA-N 0.000 description 2
- 229940017219 methyl propionate Drugs 0.000 description 2
- RQIMPDXRFCFBGC-UHFFFAOYSA-N n-(oxomethylidene)sulfamoyl fluoride Chemical compound FS(=O)(=O)N=C=O RQIMPDXRFCFBGC-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
- 125000000962 organic group Chemical group 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- DZXBHDRHRFLQCJ-UHFFFAOYSA-M sodium;methyl sulfate Chemical compound [Na+].COS([O-])(=O)=O DZXBHDRHRFLQCJ-UHFFFAOYSA-M 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 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
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- DPDMZACOTSJMOY-UHFFFAOYSA-N 1,1,1-trifluoropentan-3-yl hydrogen carbonate Chemical compound FC(F)(F)CC(CC)OC(O)=O DPDMZACOTSJMOY-UHFFFAOYSA-N 0.000 description 1
- RDOGTTNFVLSBKG-UHFFFAOYSA-N 1,2-difluoro-3-methoxybenzene Chemical compound COC1=CC=CC(F)=C1F RDOGTTNFVLSBKG-UHFFFAOYSA-N 0.000 description 1
- GWAOOGWHPITOEY-UHFFFAOYSA-N 1,5,2,4-dioxadithiane 2,2,4,4-tetraoxide Chemical compound O=S1(=O)CS(=O)(=O)OCO1 GWAOOGWHPITOEY-UHFFFAOYSA-N 0.000 description 1
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 1
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- GUYHXQLLIISBQF-UHFFFAOYSA-N 1-cyclohexyl-2-fluorobenzene Chemical compound FC1=CC=CC=C1C1CCCCC1 GUYHXQLLIISBQF-UHFFFAOYSA-N 0.000 description 1
- MMZYCBHLNZVROM-UHFFFAOYSA-N 1-fluoro-2-methylbenzene Chemical compound CC1=CC=CC=C1F MMZYCBHLNZVROM-UHFFFAOYSA-N 0.000 description 1
- KLECYOQFQXJYBC-UHFFFAOYSA-N 1-fluoro-2-phenylbenzene Chemical group FC1=CC=CC=C1C1=CC=CC=C1 KLECYOQFQXJYBC-UHFFFAOYSA-N 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 125000004793 2,2,2-trifluoroethoxy group Chemical group FC(CO*)(F)F 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- SXAMGRAIZSSWIH-UHFFFAOYSA-N 2-[3-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,2,4-oxadiazol-5-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NOC(=N1)CC(=O)N1CC2=C(CC1)NN=N2 SXAMGRAIZSSWIH-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- YJLUBHOZZTYQIP-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=N2 YJLUBHOZZTYQIP-UHFFFAOYSA-N 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- XNMQEEKYCVKGBD-UHFFFAOYSA-N 2-butyne Chemical group CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 1
- GKFGCJGPBOCQQW-UHFFFAOYSA-N 2-ethoxy-1,2,2,6,6-pentafluoro-1,3,5-triaza-2lambda5,4,6lambda5-triphosphacyclohex-5-ene Chemical compound C(C)OP1(N(P(=NPN1)(F)F)F)(F)F GKFGCJGPBOCQQW-UHFFFAOYSA-N 0.000 description 1
- 125000004777 2-fluoroethyl group Chemical group [H]C([H])(F)C([H])([H])* 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- QHTJSSMHBLGUHV-UHFFFAOYSA-N 2-methylbutan-2-ylbenzene Chemical compound CCC(C)(C)C1=CC=CC=C1 QHTJSSMHBLGUHV-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- DSMUTQTWFHVVGQ-UHFFFAOYSA-N 4,5-difluoro-1,3-dioxolan-2-one Chemical compound FC1OC(=O)OC1F DSMUTQTWFHVVGQ-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
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 1
- YNNVCNXYUGJPKN-UHFFFAOYSA-J C(C(=O)[O-])(=O)F.C(C(=O)[O-])(=O)F.C(C(=O)[O-])(=O)F.C(C(=O)[O-])(=O)F.[K+].[K+].[K+].[K+] Chemical compound C(C(=O)[O-])(=O)F.C(C(=O)[O-])(=O)F.C(C(=O)[O-])(=O)F.C(C(=O)[O-])(=O)F.[K+].[K+].[K+].[K+] YNNVCNXYUGJPKN-UHFFFAOYSA-J 0.000 description 1
- CLODVVCTNPJPIG-UHFFFAOYSA-J C(C(=O)[O-])(=O)F.C(C(=O)[O-])(=O)F.C(C(=O)[O-])(=O)F.C(C(=O)[O-])(=O)F.[Na+].[Na+].[Na+].[Na+] Chemical compound C(C(=O)[O-])(=O)F.C(C(=O)[O-])(=O)F.C(C(=O)[O-])(=O)F.C(C(=O)[O-])(=O)F.[Na+].[Na+].[Na+].[Na+] CLODVVCTNPJPIG-UHFFFAOYSA-J 0.000 description 1
- LTFGXQCYRGEYGB-UHFFFAOYSA-N CCC(C#C)OC(O)=O Chemical compound CCC(C#C)OC(O)=O LTFGXQCYRGEYGB-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
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910011281 LiCoPO 4 Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910011322 LiNi0.6Mn0.2Co0.2O2 Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- UBQYURCVBFRUQT-UHFFFAOYSA-N N-benzoyl-Ferrioxamine B Chemical compound CC(=O)N(O)CCCCCNC(=O)CCC(=O)N(O)CCCCCNC(=O)CCC(=O)N(O)CCCCCN UBQYURCVBFRUQT-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 235000002597 Solanum melongena Nutrition 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910000102 alkali metal hydride Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000005910 alkyl carbonate group Chemical group 0.000 description 1
- 125000005336 allyloxy group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- YRIJPMBUGWOQCC-UHFFFAOYSA-N bis(prop-2-ynyl) carbonate Chemical compound C#CCOC(=O)OCC#C YRIJPMBUGWOQCC-UHFFFAOYSA-N 0.000 description 1
- UQWLFOMXECTXNQ-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)methylsulfonyl-trifluoromethane Chemical compound FC(F)(F)S(=O)(=O)[C-](S(=O)(=O)C(F)(F)F)S(=O)(=O)C(F)(F)F UQWLFOMXECTXNQ-UHFFFAOYSA-N 0.000 description 1
- FWBMVXOCTXTBAD-UHFFFAOYSA-N butyl methyl carbonate Chemical compound CCCCOC(=O)OC FWBMVXOCTXTBAD-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- PMGNOQUKCGLETL-TYYBGVCCSA-N carbonic acid;(e)-1,2-difluoroethene Chemical compound OC(O)=O.F\C=C\F PMGNOQUKCGLETL-TYYBGVCCSA-N 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 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 1
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 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
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 1
- DGTVXEHQMSJRPE-UHFFFAOYSA-N difluorophosphinic acid Chemical class OP(F)(F)=O DGTVXEHQMSJRPE-UHFFFAOYSA-N 0.000 description 1
- YRLQYTUFYPUCAE-UHFFFAOYSA-N difluorophosphoryloxybenzene Chemical compound FP(F)(=O)OC1=CC=CC=C1 YRLQYTUFYPUCAE-UHFFFAOYSA-N 0.000 description 1
- URSLCTBXQMKCFE-UHFFFAOYSA-N dihydrogenborate Chemical compound OB(O)[O-] URSLCTBXQMKCFE-UHFFFAOYSA-N 0.000 description 1
- SXWUDUINABFBMK-UHFFFAOYSA-L dilithium;fluoro-dioxido-oxo-$l^{5}-phosphane Chemical compound [Li+].[Li+].[O-]P([O-])(F)=O SXWUDUINABFBMK-UHFFFAOYSA-L 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- QKBJDEGZZJWPJA-UHFFFAOYSA-N ethyl propyl carbonate Chemical compound [CH2]COC(=O)OCCC QKBJDEGZZJWPJA-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000004991 fluoroalkenyl group Chemical group 0.000 description 1
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-M fluorosulfonate Chemical compound [O-]S(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-M 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910021469 graphitizable carbon Inorganic materials 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- AHKHZLVXUVZTGF-UHFFFAOYSA-M lithium dihydrogen phosphate oxalic acid Chemical compound P(=O)([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] AHKHZLVXUVZTGF-UHFFFAOYSA-M 0.000 description 1
- KGCSOBYKHTVXLK-UHFFFAOYSA-M lithium ethyl fluoro phosphate Chemical compound P(=O)(OF)(OCC)[O-].[Li+] KGCSOBYKHTVXLK-UHFFFAOYSA-M 0.000 description 1
- 229910000103 lithium hydride Inorganic materials 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- RLQOUIUVEQXDPW-UHFFFAOYSA-M lithium;2-methylprop-2-enoate Chemical compound [Li+].CC(=C)C([O-])=O RLQOUIUVEQXDPW-UHFFFAOYSA-M 0.000 description 1
- 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 1
- DCWYVUZDHJMHRQ-UHFFFAOYSA-M lithium;ethyl sulfate Chemical compound [Li+].CCOS([O-])(=O)=O DCWYVUZDHJMHRQ-UHFFFAOYSA-M 0.000 description 1
- ALYPSPRNEZQACK-UHFFFAOYSA-M lithium;methyl sulfate Chemical compound [Li+].COS([O-])(=O)=O ALYPSPRNEZQACK-UHFFFAOYSA-M 0.000 description 1
- XSAOIFHNXYIRGG-UHFFFAOYSA-M lithium;prop-2-enoate Chemical compound [Li+].[O-]C(=O)C=C XSAOIFHNXYIRGG-UHFFFAOYSA-M 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
- 159000000003 magnesium salts Chemical class 0.000 description 1
- BZQRBEVTLZHKEA-UHFFFAOYSA-L magnesium;trifluoromethanesulfonate Chemical compound [Mg+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F BZQRBEVTLZHKEA-UHFFFAOYSA-L 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- MBABOKRGFJTBAE-UHFFFAOYSA-N methyl methanesulfonate Chemical compound COS(C)(=O)=O MBABOKRGFJTBAE-UHFFFAOYSA-N 0.000 description 1
- AUUBCQYRIBDKHO-UHFFFAOYSA-N methyl prop-2-ynyl carbonate Chemical compound COC(=O)OCC#C AUUBCQYRIBDKHO-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 1
- WKBFOPPPPFIKOU-UHFFFAOYSA-N n-methylsulfamoyl fluoride Chemical compound CNS(F)(=O)=O WKBFOPPPPFIKOU-UHFFFAOYSA-N 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
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910021470 non-graphitizable carbon Inorganic materials 0.000 description 1
- 125000006344 nonafluoro n-butyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- GLGXXYFYZWQGEL-UHFFFAOYSA-M potassium;trifluoromethanesulfonate Chemical compound [K+].[O-]S(=O)(=O)C(F)(F)F GLGXXYFYZWQGEL-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- FOWDZVNRQHPXDO-UHFFFAOYSA-N propyl hydrogen carbonate Chemical compound CCCOC(O)=O FOWDZVNRQHPXDO-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 239000013558 reference substance Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 description 1
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 description 1
- KBVUALKOHTZCGR-UHFFFAOYSA-M sodium;difluorophosphinate Chemical compound [Na+].[O-]P(F)(F)=O KBVUALKOHTZCGR-UHFFFAOYSA-M 0.000 description 1
- XGPOMXSYOKFBHS-UHFFFAOYSA-M sodium;trifluoromethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C(F)(F)F XGPOMXSYOKFBHS-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 229910000319 transition metal phosphate Inorganic materials 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- SLVAEVYIJHDKRO-UHFFFAOYSA-N trifluoromethanesulfonyl fluoride Chemical compound FC(F)(F)S(F)(=O)=O SLVAEVYIJHDKRO-UHFFFAOYSA-N 0.000 description 1
- YZYKZHPNRDIPFA-UHFFFAOYSA-N tris(trimethylsilyl) borate Chemical compound C[Si](C)(C)OB(O[Si](C)(C)C)O[Si](C)(C)C YZYKZHPNRDIPFA-UHFFFAOYSA-N 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/086—Compounds containing nitrogen and non-metals and optionally metals containing one or more sulfur atoms
-
- 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
-
- 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
- H01M10/052—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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
-
- 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
- H01M2300/0034—Fluorinated solvents
-
- 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 present invention relates to a non-aqueous electrolyte solution, a non-aqueous electrolyte solution battery, and a compound.
- batteries which are electrochemical devices, information-related equipment and communication equipment, that is, power storage systems for small and high energy density applications such as personal computers, video cameras, digital cameras, mobile phones and smartphones, electric vehicles and hybrid vehicles .
- Fuel cell vehicle auxiliary power supply, power storage system for large-scale, power applications such as power storage are attracting attention.
- non-aqueous electrolyte batteries such as lithium-ion batteries, which have high energy density and voltage and high capacity, and are currently being actively researched and developed.
- Non-aqueous electrolyte solution examples of the non-aqueous electrolyte solution used in the battery include lithium hexafluorophosphate (hereinafter LiPF 6 ) and bis (fluorosulfonylimide) lithium (hereinafter referred to as LiPF 6 ) as solutes in solvents such as cyclic carbonate, chain carbonate, and ester.
- LiPF 6 lithium hexafluorophosphate
- LiPF 6 bis (fluorosulfonylimide) lithium
- a non-aqueous electrolyte solution in which a fluorine-containing electrolyte such as LFSI) or lithium tetrafluoroborate (hereinafter LiBF 4 ) is dissolved is often used because it is suitable for obtaining a battery having a high voltage and a high capacity.
- a non-aqueous electrolyte battery using such a non-aqueous electrolyte is not always satisfactory in terms of battery characteristics such as cycle characteristics and output characteristics.
- the negative electrode and the lithium cation, or the negative electrode and the electrolytic solution solvent react, and lithium oxide, lithium carbonate, or alkylcarbonate is formed on the surface of the negative electrode.
- a film containing lithium as the main component is formed.
- the film on the surface of the electrode is called Solid Electrolyte Interface (SEI), and its properties have a great influence on the battery performance, such as suppressing further reduction decomposition of the solvent and suppressing deterioration of the battery performance.
- SEI Solid Electrolyte Interface
- a film of decomposition products is formed on the surface of the positive electrode, which is also known to play an important role in suppressing oxidative decomposition of the solvent and suppressing gas generation inside the battery.
- Non-aqueous electrolyte-related technology is no exception, and it has been proposed to suppress deterioration due to decomposition of the non-aqueous electrolyte on the surface of an active positive electrode or negative electrode with various additives.
- Patent Document 1 proposes to improve each battery characteristic such as high temperature storage characteristic by adding vinylene carbonate to a non-aqueous electrolytic solution. This method prevents decomposition of the non-aqueous electrolyte solution on the electrode surface by coating the electrode with a polymer film obtained by polymerizing vinylene carbonate, but lithium ions also do not easily pass through this film, so the internal resistance increases. Is an issue.
- Patent Document 2 the addition of lithium difluorophosphate disclosed in Patent Document 2 is effective, and by using vinylene carbonate and lithium difluorophosphate together, the internal resistance is maintained while maintaining high high-temperature storage characteristics. It is known that a battery in which the increase in the amount of phosphorus is suppressed can be obtained.
- Patent Document 3 discloses a method for improving input / output characteristics and impedance characteristics by containing a fluorosulfonate in a non-aqueous electrolytic solution as a single additive rather than a combination of a plurality of additives. There is.
- the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a non-aqueous electrolyte solution having a low initial resistance value and a non-aqueous electrolyte solution battery. Another object of the present invention is to provide a compound that can be suitably used for the non-aqueous electrolytic solution.
- the present inventors have conducted intensive studies and found that the initial resistance value is low due to the non-aqueous electrolytic solution containing the compound represented by the general formula (1), the solute, and the non-aqueous organic solvent. We have found that a non-aqueous electrolyte battery can be obtained, and have completed the present invention.
- a non-aqueous electrolytic solution containing a compound represented by the following general formula (1), a solute, and a non-aqueous organic solvent a compound represented by the following general formula (1), a solute, and a non-aqueous organic solvent.
- R 1 and R 2 independently represent PO (R f ) 2 or SO 2 R f , respectively.
- R f independently represents a fluorine atom or a linear or branched perfluoroalkyl group having 1 to 4 carbon atoms or 3 to 4 carbon atoms.
- R 3 and R 4 independently represent hydrogen atoms, lithium ions, sodium ions, potassium ions, or linear alkyl groups having 1 to 12 carbon atoms or branched alkyl groups having 3 to 12 carbon atoms.
- Oxygen atoms may be contained between the carbon atoms in the alkyl group, or R 3 and R 4 together with the nitrogen atoms to which they are bonded form a cyclic structure.
- R 3 and R 4 together form an alkylene group, and an oxygen atom may be contained between carbon atoms in the alkylene group, and the side chain thereof may contain an oxygen atom.
- any hydrogen atom of the alkyl group and the alkylene group may be substituted with a fluorine atom, where R 3 represents a lithium ion, a sodium ion or a potassium ion.
- R 3 represents a lithium ion, a sodium ion or a potassium ion.
- the bond between the nitrogen atom and R 3 in the general formula (1) represents an ionic bond
- R 4 represents a lithium ion, a sodium ion or a potassium ion
- the bond with R 4 represents an ionic bond.
- R 3 and R 4 in the general formula (1) are independently hydrogen atoms, lithium ions, sodium ions, or linear alkyl having 1 to 4 carbon atoms or branched alkyl having 3 to 4 carbon atoms.
- the cyclic carbonate is at least one selected from the group consisting of ethylene carbonate, propylene carbonate, and fluoroethylene carbonate
- the chain carbonate is a group consisting of ethylmethyl carbonate, dimethyl carbonate, diethyl carbonate, and methylpropyl carbonate.
- the content of the compound represented by the general formula (1) with respect to the total amount of the compound represented by the general formula (1), the solute, and the non-aqueous organic solvent is 0.01% by mass to 10.0.
- vinylene carbonate lithium bis (oxalate) borate, lithium difluorooxalat borate, lithium difluorobis (oxalat) phosphate, lithium tetrafluorooxalatrate, bis (fluorosulfonyl) imidelithium, (difluorophosphonyl) Contains at least one selected from (fluorosulfonyl) imide lithium, 1,3-propensulton and 1,3-propane sulton in an amount of 0.01% by mass to 5.0% by mass based on the total amount of the non-aqueous electrolyte solution.
- the non-aqueous electrolyte solution according to any one of [1] to [8].
- a non-aqueous electrolyte battery comprising a positive electrode, a negative electrode, and the non-aqueous electrolytic solution according to any one of [1] to [9].
- non-aqueous electrolyte solution and a non-aqueous electrolyte battery having a low initial resistance value.
- a compound that can be suitably used for the non-aqueous electrolytic solution can be provided.
- ⁇ is used to mean that the numerical values before and after it are included as the lower limit value and the upper limit value.
- the initial resistance value represents the resistance value of the non-aqueous electrolyte battery immediately after the first charge / discharge operation for stabilizing the battery. Specifically, it refers to the resistance value measured by impedance measurement immediately after the three-cycle charge / discharge operation for stabilizing the battery.
- the non-aqueous electrolytic solution of the present invention is a non-aqueous electrolytic solution containing the compound represented by the above general formula (1), a solute, and a non-aqueous organic solvent.
- the non-aqueous electrolytic solution of the present invention contains a compound represented by the general formula (1).
- a non-aqueous electrolyte solution containing the compound represented by the general formula (1) is used in a non-aqueous electrolyte battery (for example, a lithium ion secondary battery)
- the compound represented by the general formula (1) is on the positive electrode and the negative electrode.
- a film having good ionic conductivity is formed on the surfaces of the positive electrode and the negative electrode. It is considered that this film suppresses direct contact between the non-aqueous organic solvent or solute and the electrode active material, and reduces the Li ion dissociation energy of the solute.
- the present inventors presume that the effect of lowering the initial resistance of the non-aqueous electrolyte battery is exerted.
- R 1 and R 2 independently represent PO (R f ) 2 or SO 2 R f , respectively.
- R f represents a fluorine atom or a linear or branched perfluoroalkyl group having 1 to 4 carbon atoms or 3 to 4 carbon atoms.
- R f represents a linear perfluoroalkyl group having 1 to 4 carbon atoms or a branched perfluoroalkyl group having 3 to 4 carbon atoms
- R f represents a linear perfluoroalkyl group having 1 to 4 carbon atoms or a branched perfluoroalkyl group having 3 to 4 carbon atoms
- R f represents a linear perfluoroalkyl group having 1 to 4 carbon atoms or a branched perfluoroalkyl group having 3 to 4 carbon atoms.
- examples thereof include a propyl group, a heptafluoroisopropyl group and a nonafluoro-n-butyl group.
- R f is preferably a fluorine atom.
- R 1 and R 2 each independently preferably an POF 2 or SO 2 F, R 1 and R 2 are preferably both a SO 2 F.
- R 3 and R 4 are independently hydrogen atoms, lithium ions, sodium ions, potassium ions, linear atoms having 1 to 12 carbon atoms, or branched forms having 3 to 12 carbon atoms. Represents the alkyl group of.
- R 3 and R 4 represent a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms include, for example, a methyl group, an ethyl group, and an n-propyl group. Examples thereof include isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group and n-pentyl group.
- An oxygen atom may be contained between the carbon atoms and the carbon atom bonds in the alkyl group.
- Specific examples of the case where an oxygen atom is contained between the carbon atoms and the carbon atom bonds in the alkyl group include 2-methoxyethyl group and 2-ethoxyethyl group.
- Any hydrogen atom of the above alkyl group may be substituted with a fluorine atom.
- the alkyl group in which any hydrogen atom is replaced with a fluorine atom include a trifluoromethyl group, a difluoromethyl group, a fluoromethyl group, a 2,2,2-trifluoroethyl group, and a 2,2-difluoroethyl group.
- the alkyl group is an alkyl group having 6 or less carbon atoms because the resistance when a film is formed on the electrode can be reduced.
- the alkyl group is more preferably an alkyl group having 4 or less carbon atoms, and particularly preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, or a tert-butyl group. ..
- R 3 and R 4 are preferably hydrogen atoms, lithium ions, sodium ions, or alkyl groups having 1 to 4 carbon atoms, respectively, and are hydrogen atoms, lithium ions, sodium ions, or methyl groups. Is more preferable, and it is further preferable that both R 3 and R 4 are lithium ions.
- R 3 and R 4 may form a cyclic structure together with the nitrogen atom to which they are bonded. In this case, R 3 and R 4 together form an alkylene group having 2 to 4 carbon atoms, and an oxygen atom is contained between the carbon atoms in the alkylene group. Also, it may have an alkyl group in its side chain. Further, any hydrogen atom of the alkyl group and the alkylene group may be substituted with a fluorine atom. Examples of the alkylene group include an ethylene group and a propylene group, and an ethylene group is particularly preferable.
- the compound represented by the general formula (1) is preferably at least one selected from the group consisting of the compounds represented by the following formulas (1a) to (1y). More preferably, the compound represented by the formula (1a) (also referred to as the compound (1a)), the compound represented by the formula (1b) (also referred to as the compound (1b)), and the formula (1c) are represented. Compound (also referred to as compound (1c)), compound represented by formula (1e) (also referred to as compound (1e)), compound represented by formula (1p) (also referred to as compound (1p)), and It is at least one selected from the group consisting of the compound represented by the formula (1w) (also referred to as compound (1w)), and more preferably composed of compound (1a), compound (1e), and compound (1w). It is at least one selected from the group, and is particularly preferably compound (1a).
- the present invention also relates to the above compound (1a).
- the compound represented by the above general formula (1) is preferably used as an additive.
- the total amount of the compound represented by the general formula (1) with respect to the total amount (100% by mass) of the compound, the solute, and the non-aqueous organic solvent represented by the general formula (1) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and further. It is preferably 0.1% by mass or more.
- the upper limit of the concentration of the compound represented by the general formula (1) is preferably 10.0% by mass or less, more preferably 5.0% by mass or less, still more preferably 2.0% by mass or less. is there.
- the concentration of the compound represented by the general formula (1) By setting the concentration of the compound represented by the general formula (1) to 0.01% by mass or more, the effect of suppressing an increase in the initial resistance of the non-aqueous electrolyte battery using the non-aqueous electrolyte can be easily obtained.
- the concentration of the compound represented by the general formula (1) by setting the concentration of the compound represented by the general formula (1) to 10.0% by mass or less, an increase in the viscosity of the non-aqueous electrolytic solution can be suppressed, and the non-aqueous electrolytic solution battery using the non-aqueous electrolytic solution can be used. The effect of improving high temperature cycle characteristics can be easily obtained.
- one kind of compound may be used alone as long as the concentration of the compound represented by the general formula (1) does not exceed 10.0% by mass.
- Two or more kinds of compounds may be mixed and used in any combination and ratio according to the application.
- the method for synthesizing the compound represented by the general formula (1) is not particularly limited, and for example, Chemische Berichte (1968), 101 (1), 162-73, Journal of Chemical Research, Synopses (1977), (10). ), 237, it can be synthesized by the reaction of fluorosulfonyl isocyanate with water or the reaction of phosgene with methylsulfamoyl fluoride. Further, by reacting with an inorganic base such as an alkali metal hydride ion, a compound represented by the above general formula (1) in which R 3 and R 4 are lithium ion, sodium ion, or potassium ion is synthesized. Can be done.
- the non-aqueous electrolytic solution of the present invention contains a solute.
- the solute is not particularly limited, but is preferably an ionic salt, and more preferably an ionic salt containing fluorine.
- the solutes include, for example, at least one cation selected from the group consisting of alkali metal ions such as lithium ion and sodium ion, alkaline earth metal ions, and quaternary ammonium, hexafluorophosphate anion, and tetrafluoro.
- solutes may be used alone, or two or more types may be mixed and used in any combination and ratio according to the intended use.
- the cation is at least one selected from the group consisting of lithium, sodium, magnesium, and quaternary ammonium, and the anion is hexafluorophosphoric acid.
- Anions tetrafluoroborate anions, bis (trifluoromethanesulfonyl) imide anions, bis (fluorosulfonyl) imide anions, bis (difluorophosphonyl) imide anions, (difluorophosphonyl) (fluorosulfonyl) imide anions, and difluorophosphoric acids At least one selected from the group consisting of anions is preferred.
- the total amount of solutes in the non-aqueous electrolytic solution of the present invention (hereinafter, also referred to as “solute concentration”) is not particularly limited, but the lower limit is preferably 0.5 mol / L or more, more preferably 0.7 mol. It is / L or more, and more preferably 0.9 mol / L or more.
- the upper limit of the solute concentration is preferably 5.0 mol / L or less, more preferably 4.0 mol / L or less, and further preferably 2.0 mol / L or less.
- solute concentration By setting the solute concentration to 0.5 mol / L or more, it is possible to suppress the deterioration of the cycle characteristics and output characteristics of the non-aqueous electrolyte battery due to the decrease in ionic conductivity, and by setting it to 5.0 mol / L or less, it is non-water. It is possible to suppress a decrease in ionic conductivity due to an increase in the viscosity of the electrolytic solution, and a decrease in cycle characteristics and output characteristics of a non-aqueous electrolytic solution battery.
- Non-aqueous organic solvent used in the non-aqueous electrolytic solution of the present invention is not particularly limited, and any non-aqueous organic solvent can be used. Specifically, ethyl methyl carbonate (hereinafter, also referred to as "EMC”), dimethyl carbonate (hereinafter, also referred to as “DMC”), diethyl carbonate (hereinafter, also referred to as "DEC”), methylpropyl carbonate, ethyl.
- EMC ethyl methyl carbonate
- DMC dimethyl carbonate
- DEC diethyl carbonate
- methylpropyl carbonate ethyl.
- the non-aqueous organic solvent is at least one selected from the group consisting of cyclic carbonate and chain carbonate because it is excellent in cycle characteristics at high temperature. Further, it is preferable that the non-aqueous organic solvent is at least one selected from the group consisting of esters because it is excellent in input / output characteristics at low temperatures.
- cyclic carbonate examples include EC, PC, butylene carbonate, FEC and the like, and at least one selected from the group consisting of EC, PC and FEC is preferable.
- chain carbonate examples include EMC, DMC, DEC, methylpropyl carbonate, ethylpropyl carbonate, 2,2,2-trifluoroethylmethyl carbonate, 2,2,2-trifluoroethylethyl carbonate, 1,1, Examples thereof include 1,3,3,3-hexafluoro-1-propylmethyl carbonate and 1,1,1,3,3,3-hexafluoro-1-propylethyl carbonate, among which EMC, DMC, DEC, etc. And at least one selected from the group consisting of methylpropyl carbonate.
- ester examples include methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, methyl 2-fluoropropionate, ethyl 2-fluoropropionate and the like.
- the additive components generally used in the non-aqueous electrolytic solution of the present invention may be further added at an arbitrary ratio.
- specific examples of other additives include cyclohexylbenzene, cyclohexylfluorobenzene, fluorobenzene, biphenyl, difluoroanisole, tert-butylbenzene, tert-amylbenzene, 2-fluorotoluene, 2-fluorobiphenyl, vinylene carbonate, and dimethylvinylene.
- the non-aqueous electrolytic solution of the present invention may contain a compound represented by the following general formula (2) as another additive.
- R 5 to R 7 are independently a fluorine atom, a linear or branched alkyl group having 1 to 10 carbon atoms, and a linear or branched alkyl group having 1 to 10 carbon atoms.
- at least one of R 5 to R 7 is a fluorine atom.
- M m + is an alkali metal cation, an alkaline earth metal cation, or an onium cation, and m represents an integer having the same number as the valence of the corresponding cation. ]
- the compound represented by the general formula (2) salt having an imide anion
- excellent low temperature characteristics can be obtained.
- R 5 to R 7 are all fluorine atoms, which is more preferable.
- At least one of R 5 to R 7 is a fluorine atom, It is preferable that at least one of R 5 to R 7 is a compound selected from hydrocarbon groups having 6 or less carbon atoms which may contain fluorine atoms.
- At least one of R 5 to R 7 is a fluorine atom
- At least one of R 5 to R 7 is methyl group, methoxy group, ethyl group, ethoxy group, propyl group, propoxyl group, vinyl group, allyl group, allyloxy group, ethynyl group, 2-propynyl group, 2-propynyloxy.
- the counter cation M m + of the salt having an imide anion represented by the general formula (2) is selected from the group consisting of lithium ion, sodium ion, potassium ion, and tetraalkylammonium ion.
- the alkyl group and the alkoxyl group represented by R 5 to R 7 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a second butyl group, and a third group.
- alkenyl group and the alkenyloxy group examples include an alkenyl group having 2 to 10 carbon atoms such as a vinyl group, an allyl group, a 1-propenyl group, an isopropenyl group, a 2-butenyl group, and a 1,3-budazienyl group. Fluoroalkenyl groups and alkenyloxy groups derived from these groups can be mentioned.
- the alkynyl group and the alkynyloxy group include an alkynyl group having 2 to 10 carbon atoms, a fluorine-containing alkynyl group such as an ethynyl group, a 2-propynyl group, and a 1,1 dimethyl-2-propynyl group, and these groups. Included are alkynyloxy groups that are induced.
- Examples of the cycloalkyl group and the cycloalkoxy group include a cyclopentyl group, a cycloalkyl group having 3 to 10 carbon atoms such as a cyclohexyl group, a fluorine-containing cycloalkyl group, and a cycloalkoxy group derived from these groups. ..
- Examples of the cycloalkenyl group and the cycloalkenyloxy group include a cycloalkenyl group having 3 to 10 carbon atoms such as a cyclopentenyl group and a cyclohexenyl group, a fluorine-containing cycloalkenyl group, and a cycloalkenyloxy derived from these groups. The group is mentioned.
- aryl group and the aryloxy group examples include an aryl group having 6 to 10 carbon atoms such as a phenyl group, a tolyl group, and a xylyl group, a fluorine-containing aryl group, and an aryloxy group derived from these groups. ..
- the content of the other additive in the non-aqueous electrolytic solution is preferably 0.01% by mass or more and 8.0% by mass or less with respect to the total amount of the non-aqueous electrolytic solution.
- the ionic salt listed as the solute has a negative electrode coating as "other additives" when the content in the non-aqueous electrolyte solution is smaller than the lower limit of 0.5 mol / L, which is the lower limit of the suitable concentration of the solute. It can exert a forming effect and a positive electrode protection effect.
- the content in the non-aqueous electrolytic solution is preferably 0.01% by mass to 5.0% by mass.
- Examples of the ionic salt in this case include lithium trifluoromethanesulfonate, sodium trifluoromethanesulfonate, potassium trifluoromethanesulfonate, magnesium trifluoromethanesulfonate, bis (trifluoromethanesulfonyl) imidelithium, and bis (trifluoromethanesulfonyl).
- an alkali metal salt other than the above solutes may be used as an additive.
- carboxylates such as lithium acrylate, sodium acrylate, lithium methacrylate and sodium methacrylate
- sulfates such as lithium methyl sulfate, sodium methyl sulfate, lithium ethyl sulfate and sodium methyl sulfate. ..
- the non-aqueous electrolytic solution of the present invention contains vinylene carbonate, lithium bis (oxalate) borate, lithium difluorooxalat borate, lithium difluorobis (oxalate) phosphate, and tetrafluorooxalatric acid.
- At least one selected from lithium difluorooxalate borate, lithium (difluorophosphonyl) (fluorosulfonyl) imide lithium and lithium difluorobis (oxalate) phosphate is more preferable.
- non-aqueous electrolyte solution of the present invention may contain a polymer, and the non-aqueous electrolyte solution is pseudo-solidified by a gelling agent or a crosslinked polymer as in the case of being used in a non-aqueous electrolyte battery called a polymer battery. It is also possible to use it.
- Polymer solid electrolytes also include those containing a non-aqueous organic solvent as a plasticizer.
- the polymer is not particularly limited as long as it is an aprotic polymer capable of dissolving the compound represented by the general formula (1), the solute and other additives.
- examples thereof include polymers having a polyethylene oxide in the main chain or side chains, homopolymers or copolymers of polyvinylidene fluoride, methacrylic acid ester polymers, polyacrylonitrile and the like.
- the aprotic non-aqueous organic solvent among the above-mentioned non-aqueous organic solvents is preferable.
- the non-aqueous electrolyte battery of the present invention includes at least the above-mentioned non-aqueous electrolyte battery of the present invention, a negative electrode, and a positive electrode. Further, it is preferable to include a separator, an exterior body and the like.
- the negative electrode is not particularly limited, but it is preferable to use a material capable of reversibly inserting and removing alkali metal ions such as lithium ions and sodium ions, or alkaline earth metal ions.
- the positive electrode is not particularly limited, but it is preferable to use a material capable of reversibly inserting and removing alkali metal ions such as lithium ions and sodium ions, or alkaline earth metal ions.
- the negative electrode material is lithium metal, an alloy of lithium and other metals, an intermetal compound, various carbon materials capable of occluding and releasing lithium, metal oxides, metal nitrides, and activated carbon.
- Conductive polymer and the like are used.
- the above-mentioned carbon material include graphitizable carbon, non-graphitizable carbon (also called hard carbon) having a (002) plane spacing of 0.37 nm or more, and (002) plane spacing of 0. Examples thereof include graphite having a diameter of 37 nm or less, and artificial graphite, natural graphite and the like are used as the latter.
- the positive electrode materials include lithium-containing transition metal composite oxides such as LiCoO 2 , LiNiO 2 , LiMnO 2 , LiMn 2 O 4 , and the lithium-containing transition metal composite oxides Co, Mn, Ni, etc.
- LiCoO 2 , LiNiO 2 , LiMnO 2 , LiMn 2 O 4 lithium-containing transition metal composite oxides
- LiMnO 2 , LiMn 2 O 4 lithium-containing transition metal composite oxides
- Co, Mn, Ni etc.
- Transition metal phosphate compounds oxides such as TiO 2 , V 2 O 5 , MoO 3 , sulfides such as TiS 2 , FeS, or conductive polymers such as polyacetylene, polyparaphenylene, polyaniline, and polypyrrole, activated carbon. , Polymers that generate radicals, carbon materials, etc. are used.
- Acetylene black, Ketjen black, carbon fiber, or graphite is added as a conductive material to the positive electrode and negative electrode materials, and polytetrafluoroethylene, polyvinylidene fluoride, SBR resin, etc. are added as a binder, and the material is further molded into a sheet.
- An electrode sheet can be used.
- a separator for preventing contact between the positive electrode and the negative electrode a non-woven fabric or a porous sheet made of polypropylene, polyethylene, paper, glass fiber or the like is used.
- a coin-shaped, cylindrical, square, or aluminum laminated sheet type electrochemical device can be assembled.
- Examples 1-2 to 1-7, Comparative examples 1-2 to 1-5> (Preparation of non-aqueous electrolytes 1-2 to 1-7 and comparative non-aqueous electrolytes 1-2 to 1-5)
- the non-aqueous electrolytic solution is the same as the preparation of the non-aqueous electrolytic solution 1-1, except that the type and the amount of the compound (and the comparative compound) represented by the general formula (1) are changed as shown in Table 1. 1-2 to 1-7 and comparative non-aqueous electrolytes 1-2 to 1-5 were obtained.
- Examples 2-1 to 2-3, Comparative Examples 2-1 to 2-3> (Preparation of non-aqueous electrolytes 2-1 to 2-3 and comparative non-aqueous electrolytes 2-1 to 2-3) Further, as other additives, vinylene carbonate was added to the total amount of the non-aqueous electrolytic solution at the concentration shown in Table 2 and dissolved, except that the non-aqueous electrolytic solution 1-2, 1-5. , 1-7, Comparative non-aqueous electrolytes 1-1, 1-3, 1-5, Non-aqueous electrolytes 2-1 to 2-3, Comparative non-aqueous electrolytes 2-1 to 2 I got -3 respectively.
- Examples 3-1 to 3-3 Comparative examples 3-1 to 3-3> (Preparation of non-aqueous electrolytes 3-1 to 3-3 and comparative non-aqueous electrolytes 3-1 to 3-3) Non-electrolyzed in the same manner as the preparation of non-aqueous electrolytes 2-1 to 2-3 and comparative non-aqueous electrolytes 2-1 to 2-3, except that vinylene carbonate was changed to lithium bis (oxalate) borate. Liquids 3-1 to 3-3 and comparative non-aqueous electrolytic solutions 3-1 to 3-3 were obtained, respectively.
- Examples 4-1 to 4-3, Comparative Examples 4-1 to 4-3> (Preparation of non-aqueous electrolytes 4-1 to 4-3 and comparative non-aqueous electrolytes 4-1 to 4-3)
- 4-1 to 4-3 and comparative non-aqueous electrolytic solutions 4-1 to 4-3 were obtained, respectively.
- Examples 5-1 to 5-3, Comparative Examples 5-1 to 5-3> (Preparation of non-aqueous electrolytes 5-1 to 5-3 and comparative non-aqueous electrolytes 5-1 to 5-3)
- Electrolyte 5-1 to 5-3 and comparative non-aqueous electrolytic solution 5-1 to 5-3 were obtained, respectively.
- Examples 6-1 to 6-3, Comparative Examples 6-1 to 6-3> Preparation of non-aqueous electrolytes 6-1 to 6-3 and comparative non-aqueous electrolytes 6-1 to 6-3
- Liquids 6-1 to 6-3 and comparative non-aqueous electrolytic solutions 6-1 to 6-3 were obtained, respectively.
- Examples 7-1 to 7-3, Comparative Examples 7-1 to 7-3> (Preparation of non-aqueous electrolytes 7-1 to 7-3 and comparative non-aqueous electrolytes 7-1 to 7-3)
- Liquids 7-1 to 7-3 and comparative non-aqueous electrolytic solutions 7-1 to 7-3 were obtained, respectively.
- Examples 8-1 to 8-3, Comparative Examples 8-1 to 8-3> (Preparation of non-aqueous electrolytes 8-1 to 8-3 and comparative non-aqueous electrolytes 8-1 to 8-3)
- 8-1 to 8-3 and comparative non-aqueous electrolytic solutions 8-1 to 8-3 were obtained, respectively.
- DFP lithium difluorophosphate
- FS lithium fluorosulfonate
- VC vinylene carbonate
- BOB lithium bis (oxalate) borate
- DFOB lithium difluorooxalate borate
- DFBOP means lithium difluorobis (oxalat) phosphate
- TFOP means lithium tetrafluorooxalatrate
- FSI means bis (fluorosulfonyl) imide lithium
- PRS means 1,3-propensulton.
- the addition amount of the compound represented by the general formula (1) represents the concentration of the non-aqueous solvent, the solute, and the compound with respect to the total amount.
- the addition amount of the other additive represents the concentration of the non-aqueous solvent, the solute, the compound and the other additive with respect to the total amount.
- Comparative Examples using a comparative non-aqueous electrolytic solution to which neither the compound represented by the general formula (1) nor the comparative compound was added Comparative Examples 1-1 and 1-1 in Table 1). Comparative Example 2-1 in Table 2, Comparative Example 3-1 in Table 3, Comparative Example 4-1 in Table 4, Comparative Example 5-1 in Table 5, and Comparative Example 6-1 in Table 6.
- Table 7 the value of the initial resistance of Comparative Example 7-1 and in Table 8 was set to 100, and the evaluation results of the initial resistance of each Example and Comparative Example are shown as relative values.
- the non-aqueous electrolyte battery using the non-aqueous electrolyte containing the compound represented by the general formula (1) of the present invention has a low initial resistance and is excellent. ..
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
Description
[1]
下記一般式(1)で表される化合物、溶質、及び非水有機溶媒を含有する非水電解液。
R1及びR2は、それぞれ独立に、PO(Rf)2又はSO2Rfを表し、
Rfは、それぞれ独立に、フッ素原子、又は炭素原子数1~4の直鎖若しくは炭素原子数3~4の分岐状のパーフルオロアルキル基を表し、
R3及びR4は、それぞれ独立に、水素原子、リチウムイオン、ナトリウムイオン、カリウムイオン、又は炭素原子数1~12の直鎖若しくは炭素原子数3~12の分岐状のアルキル基を表し、前記アルキル基中の炭素原子-炭素原子結合間には、酸素原子が含まれていてもよく、又は、R3及びR4は、それらが結合する窒素原子と一緒になって、環状構造を形成し、この場合、R3及びR4は、一緒になってアルキレン基を形成し、当該アルキレン基中の炭素原子-炭素原子結合間には、酸素原子が含まれていてもよく、その側鎖にアルキル基を有していてもよく、また、前記アルキル基及びアルキレン基の任意の水素原子はフッ素原子に置換されていても良く、但し、R3が、リチウムイオン、ナトリウムイオン又はカリウムイオンを表す場合、一般式(1)中の窒素原子とR3との結合はイオン結合を表し、また、R4がリチウムイオン、ナトリウムイオン又はカリウムイオンを表す場合、一般式(1)中の窒素原子とR4との結合はイオン結合を表す。]
前記一般式(1)中のR1及びR2が、それぞれ独立に、POF2又はSO2Fである[1]に記載の非水電解液。
前記一般式(1)中のR1及びR2が、いずれもSO2Fである[1]又は[2]に記載の非水電解液。
前記一般式(1)中のR3及びR4が、それぞれ独立に、水素原子、リチウムイオン、ナトリウムイオン、又は炭素原子数1~4の直鎖若しくは炭素原子数3~4の分岐状のアルキル基を表す[1]~[3]のいずれか1項に記載の非水電解液。
前記一般式(1)で表される化合物が、下記式(1a)で表される化合物である、[1]~[4]のいずれか1項に記載の非水電解液。
前記非水有機溶媒が、環状カーボネート及び鎖状カーボネートからなる群から選ばれる少なくとも1種を含有する、[1]~[5]のいずれか1項に記載の非水電解液。
前記環状カーボネートが、エチレンカーボネート、プロピレンカーボネート、及びフルオロエチレンカーボネートからなる群から選ばれる少なくとも1種であり、前記鎖状カーボネートが、エチルメチルカーボネート、ジメチルカーボネート、ジエチルカーボネート、及びメチルプロピルカーボネートからなる群から選ばれる少なくとも1種である、[6]に記載の非水電解液。
前記一般式(1)で表される化合物、前記溶質、及び前記非水有機溶媒の総量に対する、前記一般式(1)で表される化合物の含有量が、0.01質量%~10.0質量%である、[1]~[7]のいずれか1項に記載の非水電解液。
更に、ビニレンカーボネート、ビス(オキサラト)ホウ酸リチウム、ジフルオロオキサラトホウ酸リチウム、ジフルオロビス(オキサラト)リン酸リチウム、テトラフルオロオキサラトリン酸リチウム、ビス(フルオロスルホニル)イミドリチウム、(ジフルオロホスホニル)(フルオロスルホニル)イミドリチウム、1,3-プロペンスルトン及び1,3-プロパンスルトンから選ばれる少なくとも1種を、前記非水電解液の総量に対して0.01質量%~5.0質量%含有する、[1]~[8]のいずれか1項に記載の非水電解液。
正極と、負極と、[1]~[9]のいずれか1項に記載の非水電解液とを含む、非水電解液電池。
下記式(1a)で表される化合物。
本発明の非水電解液は、上記一般式(1)で表される化合物、溶質、及び非水有機溶媒を含有する非水電解液である。
本発明の非水電解液は、一般式(1)で表される化合物を含む。
一般式(1)で表される化合物を含む非水電解液を、非水電解液電池(例えばリチウムイオン二次電池)に用いると、一般式(1)で表される化合物は正極及び負極上で分解し、イオン伝導性の良い被膜を正極及び負極表面に形成する。この被膜は、非水有機溶媒や溶質と電極活物質との間の直接の接触を抑制し、溶質のLiイオン乖離エネルギーを低下させると考えられる。その結果、非水電解液電池の初期抵抗の低下効果を奏するものであると本発明者らは推定している。
一般式(1)中、R1及びR2は、それぞれ独立に、PO(Rf)2又はSO2Rfを表す。
Rfが炭素原子数1~4の直鎖若しくは炭素原子数3~4の分岐状のパーフルオロアルキル基を表す場合の具体例としては、例えば、トリフルオロメチル基、ペンタフルオロエチル基、ヘプタフルオロプロピル基、ヘプタフルオロイソプロピル基、ノナフルオロ-n-ブチル基等が挙げられる。その中でも、トリフルオロメチル基が好ましい。
Rfは、フッ素原子であることが好ましい。
PO(Rf)2における2つのRfは同一でも異なっていてもよい。
また、R3及びR4は、それらが結合する窒素原子と一緒になって、環状構造を形成してもよい。この場合、R3及びR4は、一緒になって、炭素原子数2~4のアルキレン基を形成し、該アルキレン基中の炭素原子-炭素原子結合間には、酸素原子が含まれていてもよく、その側鎖にアルキル基を有していてもよい。また、前記アルキル基及びアルキレン基の任意の水素原子はフッ素原子に置換されていても良い。
アルキレン基としては、例えば、エチレン基や、プロピレン基などが挙げられ、特に好ましいのは、エチレン基である。
より好ましくは、式(1a)で表される化合物(化合物(1a)とも呼ぶ。)、式(1b)で表される化合物(化合物(1b)とも呼ぶ。)、式(1c)で表される化合物(化合物(1c)とも呼ぶ。)、式(1e)で表される化合物(化合物(1e)とも呼ぶ。)、式(1p)で表される化合物(化合物(1p)とも呼ぶ。)、及び式(1w)で表される化合物(化合物(1w)とも呼ぶ。)からなる群から選ばれる少なくとも1種であり、更に好ましくは化合物(1a)、化合物(1e)、及び化合物(1w)からなる群から選ばれる少なくとも1種であり、特に好ましくは化合物(1a)である。
一般式(1)で表される化合物の濃度を0.01質量%以上とすることで、該非水電解液を用いた非水電解液電池の初期抵抗上昇を抑制する効果が得られやすい。一方、一般式(1)で表される化合物の濃度を10.0質量%以下とすることで、該非水電解液の粘度上昇を抑制でき、該非水電解液を用いた非水電解液電池の高温サイクル特性向上効果が得られ易くなる。
更に、水素化アルカリ金属イオンなどの無機塩基と反応させることで、R3及びR4が、リチウムイオン、ナトリウムイオン、又はカリウムイオンである上記一般式(1)で表される化合物を合成することができる。
本発明の非水電解液は、溶質を含有する。
溶質としては特に限定されないが、イオン性塩であることが好ましく、フッ素を含むイオン性塩であることがより好ましい。
中でも、非水電解液電池としてのエネルギー密度、出力特性、寿命等から考えると、カチオンはリチウム、ナトリウム、マグネシウム、及び四級アンモニウムからなる群から選ばれる少なくとも1種が、アニオンはヘキサフルオロリン酸アニオン、テトラフルオロホウ酸アニオン、ビス(トリフルオロメタンスルホニル)イミドアニオン、ビス(フルオロスルホニル)イミドアニオン、ビス(ジフルオロホスホニル)イミドアニオン、(ジフルオロホスホニル)(フルオロスルホニル)イミドアニオン、及びジフルオロリン酸アニオンからなる群から選ばれる少なくとも1種が好ましい。
本発明の非水電解液に用いる非水有機溶媒の種類は、特に限定されず、任意の非水有機溶媒を用いることができる。
具体的には、エチルメチルカーボネート(以降「EMC」とも記載する。)、ジメチルカーボネート(以降「DMC」とも記載する。)、ジエチルカーボネート(以降「DEC」とも記載する。)、メチルプロピルカーボネート、エチルプロピルカーボネート、メチルブチルカーボネート、2,2,2-トリフルオロエチルメチルカーボネート、2,2,2-トリフルオロエチルエチルカーボネート、2,2,2-トリフルオロエチルプロピルカーボネート、ビス(2,2,2-トリフルオロエチル)カーボネート、1,1,1,3,3,3-ヘキサフルオロ-1-プロピルメチルカーボネート、1,1,1,3,3,3-ヘキサフルオロ-1-プロピルエチルカーボネート、1,1,1,3,3,3-ヘキサフルオロ-1-プロピルプロピルカーボネート、ビス(1,1,1,3,3,3-ヘキサフルオロ-1-プロピル)カーボネート、エチレンカーボネート(以降「EC」とも記載する。)、プロピレンカーボネート(以降「PC」とも記載する。)、ブチレンカーボネート、フルオロエチレンカーボネート(以降「FEC」とも記載する。)、ジフルオロエチレンカーボネート、酢酸メチル、酢酸エチル、プロピオン酸メチル、プロピオン酸エチル、2-フルオロプロピオン酸メチル、2-フルオロプロピオン酸エチル、ジエチルエーテル、ジブチルエーテル、ジイソプロピルエーテル、1,2-ジメトキシエタン、テトラヒドロフラン、2-メチルテトラヒドロフラン、フラン、テトラヒドロピラン、1,3-ジオキサン、1,4-ジオキサン、N,N-ジメチルホルムアミド、アセトニトリル、プロピオニトリル、ジメチルスルホキシド、スルホラン、γ-ブチロラクトン、及びγ-バレロラクトンからなる群から選ばれる少なくとも1種であることが好ましい。
また、本発明においては、非水有機溶媒として、塩構造を採るイオン液体を用いても良い。
本発明の要旨を損なわない限りにおいて、本発明の非水電解液に一般に用いられる添加成分を任意の比率で更に添加しても良い。
その他の添加剤の具体例としては、シクロヘキシルベンゼン、シクロヘキシルフルオロベンゼン、フルオロベンゼン、ビフェニル、ジフルオロアニソール、tert-ブチルベンゼン、tert-アミルベンゼン、2-フルオロトルエン、2-フルオロビフェニル、ビニレンカーボネート、ジメチルビニレンカーボネート、ビニルエチレンカーボネート、フルオロエチレンカーボネート、trans-ジフルオロエチレンカーボネート、メチルプロパルギルカーボネート、エチルプロパルギルカーボネート、ジプロパルギルカーボネート、無水マレイン酸、無水コハク酸、プロパンスルトン、1,3-プロパンスルトン、1,3-プロペンスルトン、ブタンスルトン、メチレンメタンジスルホネート、ジメチレンメタンジスルホネート、トリメチレンメタンジスルホネート、メタンスルホン酸メチル、1,6-ジイソシアナトヘキサン、トリス(トリメチルシリル)ボレート、スクシノニトリル、(エトキシ)ペンタフルオロシクロトリホスファゼン、ジフルオロビス(オキサラト)リン酸リチウム、ジフルオロビス(オキサラト)リン酸ナトリウム、ジフルオロビス(オキサラト)リン酸カリウム、ジフルオロオキサラトホウ酸リチウム、ジフルオロオキサラトホウ酸ナトリウム、ジフルオロオキサラトホウ酸カリウム、ビス(オキサラト)ホウ酸リチウム、ビス(オキサラト)ホウ酸ナトリウム、ビス(オキサラト)ホウ酸カリウム、テトラフルオロオキサラトリン酸リチウム、テトラフルオロオキサラトリン酸ナトリウム、テトラフルオロオキサラトリン酸カリウム、トリス(オキサラト)リン酸リチウム、エチルフルオロリン酸リチウム、フルオロリン酸リチウム、エテンスルホニルフルオリド、フルオロスルホン酸リチウム、トリフルオロメタンスルホニルフルオリド、メタンスルホニルフルオリド、ジフルオロリン酸フェニル等の過充電防止効果、負極被膜形成効果や正極保護効果を有する化合物が挙げられる。
Mm+は、アルカリ金属カチオン、アルカリ土類金属カチオン、又はオニウムカチオンであり、mは該当するカチオンの価数と同数の整数を表す。]
R5~R7の少なくとも1つがフッ素原子であり、
R5~R7の少なくとも1つがフッ素原子を含んでいてもよい炭素原子数6以下の炭化水素基から選ばれる化合物であることが好ましい。
R5~R7の少なくとも1つがフッ素原子であり、
R5~R7の少なくとも1つが、メチル基、メトキシ基、エチル基、エトキシ基、プロピル基、プロポキシル基、ビニル基、アリル基、アリルオキシ基、エチニル基、2-プロピニル基、2-プロピニルオキシ基、フェニル基、フェニルオキシ基、2,2-ジフルオロエチル基、2,2-ジフルオロエチルオキシ基、2,2,2-トリフルオロエチル基、2,2,2-トリフルオロエチルオキシ基、2,2,3,3-テトラフルオロプロピル基、2,2,3,3-テトラフルオロプロピルオキシ基、1,1,1,3,3,3-ヘキサフルオロイソプロピル基、及び1,1,1,3,3,3-ヘキサフルオロイソプロピルオキシ基から選ばれる化合物であることが好ましい。
この場合のイオン性塩としては、例えば、トリフルオロメタンスルホン酸リチウム、トリフルオロメタンスルホン酸ナトリウム、トリフルオロメタンスルホン酸カリウム、トリフルオロメタンスルホン酸マグネシウム、ビス(トリフルオロメタンスルホニル)イミドリチウム、ビス(トリフルオロメタンスルホニル)イミドナトリウム、ビス(トリフルオロメタンスルホニル)イミドカリウム、ビス(トリフルオロメタンスルホニル)イミドマグネシウム、ビス(フルオロスルホニル)イミドリチウム、ビス(フルオロスルホニル)イミドナトリウム、ビス(フルオロスルホニル)イミドカリウム、ビス(フルオロスルホニル)イミドマグネシウム、(トリフルオロメタンスルホニル)(フルオロスルホニル)イミドリチウム、(トリフルオロメタンスルホニル)(フルオロスルホニル)イミドナトリウム、(トリフルオロメタンスルホニル)(フルオロスルホニル)イミドカリウム、(トリフルオロメタンスルホニル)(フルオロスルホニル)イミドマグネシウム、ビス(ジフルオロホスホニル)イミドリチウム、ビス(ジフルオロホスホニル)イミドナトリウム、ビス(ジフルオロホスホニル)イミドカリウム、ビス(ジフルオロホスホニル)イミドマグネシウム、(ジフルオロホスホニル)(フルオロスルホニル)イミドリチウム、(ジフルオロホスホニル)(フルオロスルホニル)イミドナトリウム、(ジフルオロホスホニル)(フルオロスルホニル)イミドカリウム、(ジフルオロホスホニル)(フルオロスルホニル)イミドマグネシウム、(ジフルオロホスホニル)(トリフルオロメタンスルホニル)イミドリチウム、(ジフルオロホスホニル)(トリフルオロメタンスルホニル)イミドナトリウム、(ジフルオロホスホニル)(トリフルオロメタンスルホニル)イミドカリウム、(ジフルオロホスホニル)(トリフルオロメタンスルホニル)イミドマグネシウム、ジフルオロリン酸リチウム、ジフルオロリン酸ナトリウム等が挙げられる。
具体的には、アクリル酸リチウム、アクリル酸ナトリウム、メタクリル酸リチウム、メタクリル酸ナトリウムなどのカルボン酸塩、リチウムメチルサルフェート、ナトリウムメチルサルフェート、リチウムエチルサルフェート、ナトリウムメチルサルフェートなどの硫酸エステル塩などが挙げられる。
初期抵抗値上昇抑制の観点から、ジフルオロオキサラトホウ酸リチウム、(ジフルオロホスホニル)(フルオロスルホニル)イミドリチウム及びジフルオロビス(オキサラト)リン酸リチウムから選ばれる少なくとも1種であることが更に好ましい。
本発明の非水電解液電池は、少なくとも、上記の本発明の非水電解液と、負極と、正極とを含む。更には、セパレータや外装体等を含むことが好ましい。
50mlナスフラスコにEMC7.0g 、水0.07gを入れた後、フルオロスルホ
ニルイソシアネート1.00gをゆっくりと加えた。発泡が終息した後、水素化リチウム0.07gを加え、一晩攪拌した。反応液を濾過することにより、目的物が14.7質量%溶解した、EMC溶液7.8g(目的物0.8g、回収率86%)を得た。
化合物(1a):
19F-NMR[基準物質;CFCl3、重溶媒CD3CN]、δppm;50.46
(s、2F).
13C-NMR[基準物質;CD3CN、重溶媒CD3CN]、δppm;166.36 (s、1C)
<比較例1-1>
(LiPF6溶液の調製)
露点-60℃以下のグローブボックス内において、EC、FEC、EMC及びDMCを、EC:FEC:EMC:DMC=2:1:3:4の体積比率で混合させた。その後、内温を40℃以下に保ちながら非水電解液の総量に対して1.0mol/Lの濃度となる量のLiPF6を添加し、攪拌して完全に溶解させる事でLiPF6溶液を得た。これを比較非水電解液1-1とした。
(非水電解液1-1の調製)
露点-60℃以下のグローブボックス内において、EC、FEC、EMC及びDMCを、EC:FEC:EMC:DMC=2:1:3:4の体積比率で混合させた。その後、内温を40℃以下に保ちながら非水電解液の総量に対して1.0mol/Lの濃度となる量のLiPF6を加え、一般式(1)で表される化合物に該当する化合物(1a)を、非水有機溶媒と溶質と当該化合物(1a)の総量に対して0.5質量%の濃度となるように加え、1時間攪拌して溶解させることで実施例1-1の非水電解液1-1を調製した。
(非水電解液1-2~1-7、及び比較非水電解液1-2~1-5の調製)
一般式(1)で表される化合物(及び比較化合物)の種類や添加量を表1に記載のように変更した以外は非水電解液1-1の調製と同様にして、非水電解液1-2~1-7、及び比較非水電解液1-2~1-5を得た。
(非水電解液2-1~2-3、及び比較非水電解液2-1~2-3の調製)
更に、その他の添加剤として、ビニレンカーボネートを非水電解液の総量に対して表2に記載の濃度となるように添加し、溶解させた以外は、非水電解液1-2、1-5、1-7、比較非水電解液1-1、1-3、1-5の調製と同様にして、非水電解液2-1~2-3、比較非水電解液2-1~2-3をそれぞれ得た。
(非水電解液3-1~3-3、及び比較非水電解液3-1~3-3の調製)
ビニレンカーボネートをビス(オキサラト)ホウ酸リチウムに変更した以外は、非水電解液2-1~2-3、比較非水電解液2-1~2-3の調製と同様にして、非水電解液3-1~3-3、比較非水電解液3-1~3-3をそれぞれ得た。
(非水電解液4-1~4-3、及び比較非水電解液4-1~4-3の調製)
ビニレンカーボネートをジフルオロオキサラトホウ酸リチウムに変更した以外は、非水電解液2-1~2-3、比較非水電解液2-1~2-3の調製と同様にして、非水電解液4-1~4-3、比較非水電解液4-1~4-3をそれぞれ得た。
(非水電解液5-1~5-3、及び比較非水電解液5-1~5-3の調製)
ビニレンカーボネートをジフルオロビス(オキサラト)リン酸リチウムに変更した以外は、非水電解液2-1~2-3、比較非水電解液2-1~2-3の調製と同様にして、非水電解液5-1~5-3、比較非水電解液5-1~5-3をそれぞれ得た。
(非水電解液6-1~6-3、及び比較非水電解液6-1~6-3の調製)
ビニレンカーボネートをテトラフルオロオキサラトリン酸リチウムに変更した以外は、非水電解液2-1~2-3、比較非水電解液2-1~2-3の調製と同様にして、非水電解液6-1~6-3、比較非水電解液6-1~6-3をそれぞれ得た。
(非水電解液7-1~7-3、及び比較非水電解液7-1~7-3の調製)
ビニレンカーボネートをビス(フルオロスルホニル)イミドリチウムに変更した以外は、非水電解液2-1~2-3、比較非水電解液2-1~2-3の調製と同様にして、非水電解液7-1~7-3、比較非水電解液7-1~7-3をそれぞれ得た。
(非水電解液8-1~8-3、及び比較非水電解液8-1~8-3の調製)
ビニレンカーボネートを1,3-プロペンスルトンに変更した以外は、非水電解液2-1~2-3、比較非水電解液2-1~2-3の調製と同様にして、非水電解液8-1~8-3、比較非水電解液8-1~8-3をそれぞれ得た。
(NCM622正極の作製)
LiNi0.6Mn0.2Co0.2O2粉末90質量%に、バインダーとしてポリフッ化ビニリデン(以下、PVDFとも記載する)を5質量%、導電材としてアセチレンブラックを5質量%混合し、更にN-メチル-2-ピロリドンを添加し、正極合材ペーストを作製した。このペーストをアルミニウム箔(A1085)の両面に塗布して、乾燥、加圧を行った後に、4×5cmに打ち抜くことで試験用NCM622正極を得た。
人造黒鉛粉末90質量%、バインダーとしてPVDFを5質量%、導電材としてアセチレンブラックを5質量%混合し、負極合材ペーストを作製した。このペーストを銅箔の片面に塗布して、乾燥、加圧を行った後に、4×5cmに打ち抜くことで試験用人造黒鉛負極を得た。
露点-50℃以下のアルゴン雰囲気で、上述のNCM622正極に端子を溶接した後に、その両側をポリエチレン製セパレータ(5×6cm)2枚で挟み、更にその外側を予め端子を溶接した人造黒鉛負極2枚で、負極活物質面が正極活物質面と対向するように挟み込んだ。そして、それらを一辺の開口部が残されたアルミラミネートの袋に入れ、非水電解液を真空注液した後に、開口部を熱で封止する事によって、実施例及び比較例のアルミラミネート型の非水電解液電池を作製した。なお、非水電解液として表1~8に記載のものを用いた。
-初期充放電-
非水電解液電池を25℃恒温槽に入れその状態で充放電装置と接続した。3mAで4.3Vまで充電を行った。4.3Vを1時間維持した後に、6mAで3.0Vまで放電を行った。これを充放電1サイクルとし、計3サイクルの充放電を行って電池を安定化させた。
<初期抵抗測定>
初期充放電後25℃、6mAで4.3Vまで充電し、そのままインピーダンス測定により抵抗値を測定した。
Claims (11)
- 下記一般式(1)で表される化合物、溶質、及び非水有機溶媒を含有する非水電解液。
R1及びR2は、それぞれ独立に、PO(Rf)2又はSO2Rfを表し、
Rfは、それぞれ独立に、フッ素原子又は炭素原子数1~4の直鎖若しくは炭素原子数3~4の分岐状のパーフルオロアルキル基を表し、
R3及びR4は、それぞれ独立に、水素原子、リチウムイオン、ナトリウムイオン、カリウムイオン、又は炭素原子数1~12の直鎖若しくは炭素原子数3~12の分岐状のアルキル基を表し、前記アルキル基中の炭素原子-炭素原子結合間には、酸素原子が含まれていてもよく、又は、R3及びR4は、それぞれが結合する窒素原子と一緒になって、環状構造を形成し、この場合、R3及びR4は、一緒になってアルキレン基を形成し、当該アルキレン基中の炭素原子-炭素原子結合間には、酸素原子が含まれていてもよいし、側鎖にアルキル基を有していてもよく、前記アルキル基及びアルキレン基の任意の水素原子はフッ素原子に置換されていてもよく、
但し、R3がリチウムイオン、ナトリウムイオン又はカリウムイオンを表す場合、一般式(1)中の窒素原子とR3との結合はイオン結合を表し、また、R4がリチウムイオン、ナトリウムイオン又はカリウムイオンを表す場合、一般式(1)中の窒素原子とR4との結合はイオン結合を表す。] - 前記一般式(1)中のR1及びR2が、それぞれ独立に、POF2又はSO2Fである請求項1に記載の非水電解液。
- 前記一般式(1)中のR1及びR2が、いずれもSO2Fである請求項1又は2に記載の非水電解液。
- 前記一般式(1)中のR3及びR4が、それぞれ独立に、水素原子、リチウムイオン、ナトリウムイオン、又は炭素原子数1~4の直鎖若しくは炭素原子数3~4の分岐状のアルキル基を表す請求項1~3のいずれか1項に記載の非水電解液。
- 前記非水有機溶媒が、環状カーボネート及び鎖状カーボネートからなる群から選ばれる少なくとも1種を含有する、請求項1~5のいずれか1項に記載の非水電解液。
- 前記環状カーボネートが、エチレンカーボネート、プロピレンカーボネート、及びフルオロエチレンカーボネートからなる群から選ばれる少なくとも1種であり、前記鎖状カーボネートが、エチルメチルカーボネート、ジメチルカーボネート、ジエチルカーボネート、及びメチルプロピルカーボネートからなる群から選ばれる少なくとも1種である、請求項6に記載の非水電解液。
- 前記一般式(1)で表される化合物、前記溶質、及び前記非水有機溶媒の総量に対する、前記一般式(1)で表される化合物の含有量が、0.01質量%~10.0質量%である、請求項1~7のいずれか1項に記載の非水電解液。
- 更に、ビニレンカーボネート、ビス(オキサラト)ホウ酸リチウム、ジフルオロオキサラトホウ酸リチウム、ジフルオロビス(オキサラト)リン酸リチウム、テトラフルオロオキサラトリン酸リチウム、ビス(フルオロスルホニル)イミドリチウム、(ジフルオロホスホニル)(フルオロスルホニル)イミドリチウム、1,3-プロペンスルトン及び1,3-プロパンスルトンから選ばれる少なくとも1種を、前記非水電解液の総量に対して0.01質量%~5.0質量%含有する、請求項1~8のいずれか1項に記載の非水電解液。
- 正極と、負極と、請求項1~9のいずれか1項に記載の非水電解液とを含む、非水電解液電池。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP20843677.4A EP4016686A4 (en) | 2019-07-24 | 2020-07-22 | NONAQUEOUS ELECTROLYTE SOLUTION, NONAQUEOUS ELECTROLYTE BATTERY AND COMPOUND |
JP2021534082A JPWO2021015264A1 (ja) | 2019-07-24 | 2020-07-22 | |
US17/629,085 US20220271340A1 (en) | 2019-07-24 | 2020-07-22 | Nonaqueous electrolyte solution, nonaqueous electrolyte battery and compound |
CN202080053117.XA CN114175340B (zh) | 2019-07-24 | 2020-07-22 | 非水电解液、非水电解液电池及化合物 |
KR1020227003500A KR20220039726A (ko) | 2019-07-24 | 2020-07-22 | 비수전해액, 비수전해액 전지 및 화합물 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2019-136223 | 2019-07-24 | ||
JP2019136223 | 2019-07-24 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2021015264A1 true WO2021015264A1 (ja) | 2021-01-28 |
Family
ID=74194250
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2020/028526 WO2021015264A1 (ja) | 2019-07-24 | 2020-07-22 | 非水電解液、非水電解液電池、及び化合物 |
Country Status (6)
Country | Link |
---|---|
US (1) | US20220271340A1 (ja) |
EP (1) | EP4016686A4 (ja) |
JP (1) | JPWO2021015264A1 (ja) |
KR (1) | KR20220039726A (ja) |
CN (1) | CN114175340B (ja) |
WO (1) | WO2021015264A1 (ja) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2022158398A1 (ja) * | 2021-01-22 | 2022-07-28 | セントラル硝子株式会社 | 非水電解液及び非水電解液電池 |
WO2022158400A1 (ja) * | 2021-01-22 | 2022-07-28 | セントラル硝子株式会社 | 非水電解液及び非水電解液電池 |
WO2022158399A1 (ja) * | 2021-01-22 | 2022-07-28 | セントラル硝子株式会社 | 非水電解液、非水電解液電池、及び化合物 |
KR20230015289A (ko) * | 2021-07-22 | 2023-01-31 | 주식회사 천보 | 설페이트 또는 설포네이트 용제 중의 비스(플루오로설포닐)이미드 알칼리금속염의 제조방법 |
WO2023063317A1 (ja) | 2021-10-12 | 2023-04-20 | セントラル硝子株式会社 | 非水電解液、非水電解液電池、及び化合物 |
WO2023119948A1 (ja) * | 2021-12-24 | 2023-06-29 | 株式会社村田製作所 | 二次電池 |
WO2023162431A1 (ja) * | 2022-02-25 | 2023-08-31 | 株式会社村田製作所 | 二次電池用電解液および二次電池 |
WO2023162430A1 (ja) * | 2022-02-25 | 2023-08-31 | 株式会社村田製作所 | 二次電池用電解液および二次電池 |
WO2023162429A1 (ja) * | 2022-02-25 | 2023-08-31 | 株式会社村田製作所 | 二次電池用電解液および二次電池 |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3438636B2 (ja) | 1998-08-27 | 2003-08-18 | 宇部興産株式会社 | 非水電解液およびそれを用いたリチウム二次電池 |
JP3439085B2 (ja) | 1997-08-21 | 2003-08-25 | 三洋電機株式会社 | 非水系電解液二次電池 |
WO2013051634A1 (ja) * | 2011-10-04 | 2013-04-11 | ダイキン工業株式会社 | 非水電解液及び電池 |
JP2013152956A (ja) | 2010-02-12 | 2013-08-08 | Mitsubishi Chemicals Corp | 非水系電解液及び非水系電解液二次電池 |
JP2016157679A (ja) * | 2015-02-19 | 2016-09-01 | セントラル硝子株式会社 | 非水電解液電池用電解液、及びこれを用いた非水電解液電池 |
WO2017111143A1 (ja) | 2015-12-22 | 2017-06-29 | セントラル硝子株式会社 | 非水電解液電池用電解液、及びこれを用いた非水電解液電池 |
JP2018172357A (ja) * | 2017-03-31 | 2018-11-08 | 三井化学株式会社 | リチウム塩錯化合物、電池用添加剤、電池用非水電解液、及びリチウム二次電池 |
JP2019106362A (ja) * | 2017-12-12 | 2019-06-27 | セントラル硝子株式会社 | 非水電解液電池用電解液及びそれを用いた非水電解液電池 |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1282590C2 (de) | 1963-10-25 | 1975-02-13 | Lutravil Spinnvlies GmbH & Co., 8750 Kaiserslautern | Vorrichtung zur herstellung von wirrvliesen aus endlosen polymeren fasern |
US3438636A (en) | 1966-09-23 | 1969-04-15 | Marvco Tool & Mfg | Repeating phonograph record changer |
US7709157B2 (en) * | 2002-10-23 | 2010-05-04 | Panasonic Corporation | Non-aqueous electrolyte secondary battery and electrolyte for the same |
US20090023054A1 (en) * | 2007-07-16 | 2009-01-22 | Zhiping Jiang | Lithium cell |
JP2013166698A (ja) * | 2010-05-26 | 2013-08-29 | Mitsubishi Materials Corp | イミド化合物の製造方法 |
CN104995784A (zh) * | 2013-02-27 | 2015-10-21 | 三菱化学株式会社 | 非水电解液及使用该非水电解液的非水电解质电池 |
JP6219635B2 (ja) * | 2013-08-09 | 2017-10-25 | 株式会社日本触媒 | リチウムイオン二次電池 |
CN103935970A (zh) * | 2014-03-24 | 2014-07-23 | 深圳新宙邦科技股份有限公司 | 双氟磺酰亚胺及其碱金属盐的制备方法 |
US10829377B2 (en) * | 2016-05-27 | 2020-11-10 | Nippon Shokubai Co., Ltd. | Method for producing bis(fluorosulfonyl)imide alkali metal salt and method for producing non aqueous electrolytic solution |
KR101955452B1 (ko) * | 2017-04-28 | 2019-03-11 | 주식회사 천보 | 비스(플루오로술포닐)이미드염의 제조방법 |
-
2020
- 2020-07-22 JP JP2021534082A patent/JPWO2021015264A1/ja active Pending
- 2020-07-22 CN CN202080053117.XA patent/CN114175340B/zh active Active
- 2020-07-22 KR KR1020227003500A patent/KR20220039726A/ko active Search and Examination
- 2020-07-22 EP EP20843677.4A patent/EP4016686A4/en active Pending
- 2020-07-22 US US17/629,085 patent/US20220271340A1/en active Pending
- 2020-07-22 WO PCT/JP2020/028526 patent/WO2021015264A1/ja unknown
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3439085B2 (ja) | 1997-08-21 | 2003-08-25 | 三洋電機株式会社 | 非水系電解液二次電池 |
JP3438636B2 (ja) | 1998-08-27 | 2003-08-18 | 宇部興産株式会社 | 非水電解液およびそれを用いたリチウム二次電池 |
JP2013152956A (ja) | 2010-02-12 | 2013-08-08 | Mitsubishi Chemicals Corp | 非水系電解液及び非水系電解液二次電池 |
WO2013051634A1 (ja) * | 2011-10-04 | 2013-04-11 | ダイキン工業株式会社 | 非水電解液及び電池 |
JP2016157679A (ja) * | 2015-02-19 | 2016-09-01 | セントラル硝子株式会社 | 非水電解液電池用電解液、及びこれを用いた非水電解液電池 |
WO2017111143A1 (ja) | 2015-12-22 | 2017-06-29 | セントラル硝子株式会社 | 非水電解液電池用電解液、及びこれを用いた非水電解液電池 |
JP2018172357A (ja) * | 2017-03-31 | 2018-11-08 | 三井化学株式会社 | リチウム塩錯化合物、電池用添加剤、電池用非水電解液、及びリチウム二次電池 |
JP2019106362A (ja) * | 2017-12-12 | 2019-06-27 | セントラル硝子株式会社 | 非水電解液電池用電解液及びそれを用いた非水電解液電池 |
Non-Patent Citations (3)
Title |
---|
CHEMISCHE BERICHTE, vol. 101, no. 1, 1968, pages 162 - 73 |
JOURNAL OF CHEMICAL RESEARCH, SYNOPSES, no. 10, 1977, pages 237 |
See also references of EP4016686A4 |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2022158398A1 (ja) * | 2021-01-22 | 2022-07-28 | セントラル硝子株式会社 | 非水電解液及び非水電解液電池 |
WO2022158400A1 (ja) * | 2021-01-22 | 2022-07-28 | セントラル硝子株式会社 | 非水電解液及び非水電解液電池 |
WO2022158399A1 (ja) * | 2021-01-22 | 2022-07-28 | セントラル硝子株式会社 | 非水電解液、非水電解液電池、及び化合物 |
KR20230015289A (ko) * | 2021-07-22 | 2023-01-31 | 주식회사 천보 | 설페이트 또는 설포네이트 용제 중의 비스(플루오로설포닐)이미드 알칼리금속염의 제조방법 |
KR102639468B1 (ko) | 2021-07-22 | 2024-02-22 | 주식회사 천보 | 설페이트 또는 설포네이트 용제 중의 비스(플루오로설포닐)이미드 알칼리금속염의 제조방법 |
WO2023063317A1 (ja) | 2021-10-12 | 2023-04-20 | セントラル硝子株式会社 | 非水電解液、非水電解液電池、及び化合物 |
KR20240073897A (ko) | 2021-10-12 | 2024-05-27 | 샌트랄 글래스 컴퍼니 리미티드 | 비수전해액, 비수전해액 전지 및 화합물 |
WO2023119948A1 (ja) * | 2021-12-24 | 2023-06-29 | 株式会社村田製作所 | 二次電池 |
WO2023162431A1 (ja) * | 2022-02-25 | 2023-08-31 | 株式会社村田製作所 | 二次電池用電解液および二次電池 |
WO2023162430A1 (ja) * | 2022-02-25 | 2023-08-31 | 株式会社村田製作所 | 二次電池用電解液および二次電池 |
WO2023162429A1 (ja) * | 2022-02-25 | 2023-08-31 | 株式会社村田製作所 | 二次電池用電解液および二次電池 |
Also Published As
Publication number | Publication date |
---|---|
US20220271340A1 (en) | 2022-08-25 |
EP4016686A4 (en) | 2023-11-01 |
CN114175340B (zh) | 2024-09-06 |
KR20220039726A (ko) | 2022-03-29 |
CN114175340A (zh) | 2022-03-11 |
EP4016686A1 (en) | 2022-06-22 |
JPWO2021015264A1 (ja) | 2021-01-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP7016019B2 (ja) | 非水電解液電池用電解液、及びこれを用いた非水電解液電池 | |
JP6770243B2 (ja) | イオン性錯体、非水電解液電池用電解液、非水電解液電池及びイオン性錯体の合成法 | |
CN114175340B (zh) | 非水电解液、非水电解液电池及化合物 | |
JP6255722B2 (ja) | 非水電解液電池用電解液、及びこれを用いた非水電解液電池 | |
KR101363442B1 (ko) | 전기 화학 디바이스용 전해질, 이것을 사용하는 전해액 및 비수 전해액 전지 | |
JP5573313B2 (ja) | 非水電解液電池用電解液及びこれを用いる非水電解液電池 | |
CA3069973A1 (en) | Phosphorus containing electrolytes | |
KR20170021335A (ko) | 이온성 착체, 비수전해액 전지용 전해액, 비수전해액 전지 및 이온성 착체의 합성법 | |
US20150171476A1 (en) | Non-aqueous electrolyte solution for secondary batteries, and lithium ion secondary battery | |
KR20110102818A (ko) | 비수 전해액 및 이것을 시용한 리튬 2차 전지 | |
JP2023169234A (ja) | 非水系電解液及びそれを用いたエネルギーデバイス | |
JPWO2020175522A1 (ja) | 電解液、電気化学デバイス、リチウムイオン二次電池、モジュール及び化合物 | |
JP2016131059A (ja) | 非水電解液電池用電解液、及びこれを用いた非水電解液電池 | |
JP6785148B2 (ja) | 非水電解液およびそれを用いた非水電解液二次電池 | |
WO2016208738A1 (ja) | 非水系電解液用添加剤及びその製法、非水系電解液、非水系電解液二次電池 | |
JP7076527B2 (ja) | リチウム電池用の電解質組成物のための複素環式スルホニルフルオリド添加剤 | |
WO2016133169A1 (ja) | 非水電解液電池用電解液、及びこれを用いた非水電解液電池 | |
WO2022158397A1 (ja) | 非水電解液、非水電解液電池、及び化合物 | |
WO2022158400A1 (ja) | 非水電解液及び非水電解液電池 | |
CN116918123A (zh) | 非水电解液、非水电解液电池、及化合物 | |
JP2022042755A (ja) | 非水電解液、及びこれを用いた非水電解液電池 | |
WO2022158399A1 (ja) | 非水電解液、非水電解液電池、及び化合物 | |
WO2022158398A1 (ja) | 非水電解液及び非水電解液電池 | |
CN117121254A (zh) | 非水电解液、非水电解液电池、及非水电解液电池的制造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 20843677 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2021534082 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20227003500 Country of ref document: KR Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 2020843677 Country of ref document: EP Effective date: 20220222 |