JP5308314B2 - 蓄電デバイス用非水溶媒および蓄電デバイス用非水電解液、ならびに、これらを用いた蓄電デバイス、リチウム二次電池および電気二重層キャパシタ - Google Patents
蓄電デバイス用非水溶媒および蓄電デバイス用非水電解液、ならびに、これらを用いた蓄電デバイス、リチウム二次電池および電気二重層キャパシタ Download PDFInfo
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- JP5308314B2 JP5308314B2 JP2009262040A JP2009262040A JP5308314B2 JP 5308314 B2 JP5308314 B2 JP 5308314B2 JP 2009262040 A JP2009262040 A JP 2009262040A JP 2009262040 A JP2009262040 A JP 2009262040A JP 5308314 B2 JP5308314 B2 JP 5308314B2
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- storage device
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- electricity storage
- solvent
- nonaqueous
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- 238000003860 storage Methods 0.000 title claims abstract description 106
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 68
- 239000003990 capacitor Substances 0.000 title claims description 38
- 239000003125 aqueous solvent Substances 0.000 title claims description 25
- 229910052744 lithium Inorganic materials 0.000 title description 24
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title description 23
- 239000002904 solvent Substances 0.000 claims abstract description 80
- -1 sulfone compound Chemical class 0.000 claims abstract description 71
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 63
- 239000011737 fluorine Substances 0.000 claims abstract description 53
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 52
- 229930195734 saturated hydrocarbon Natural products 0.000 claims abstract description 52
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 47
- 125000001424 substituent group Chemical group 0.000 claims abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 4
- 230000005611 electricity Effects 0.000 claims description 77
- 150000003457 sulfones Chemical class 0.000 claims description 40
- 150000003839 salts Chemical class 0.000 claims description 30
- 239000003115 supporting electrolyte Substances 0.000 claims description 28
- 239000008151 electrolyte solution Substances 0.000 claims description 27
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 20
- 229910001416 lithium ion Inorganic materials 0.000 claims description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 229910003002 lithium salt Inorganic materials 0.000 claims description 5
- 159000000002 lithium salts Chemical group 0.000 claims description 5
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 33
- 230000003647 oxidation Effects 0.000 abstract description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 13
- 229910052799 carbon Inorganic materials 0.000 abstract description 10
- 239000010410 layer Substances 0.000 description 52
- 239000000203 mixture Substances 0.000 description 23
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 19
- QXPZOKVSFMRGMQ-UHFFFAOYSA-N trifluoromethylcyclohexane Chemical compound FC(F)(F)C1CCCCC1 QXPZOKVSFMRGMQ-UHFFFAOYSA-N 0.000 description 16
- 238000007600 charging Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 15
- 125000001153 fluoro group Chemical group F* 0.000 description 15
- 150000002430 hydrocarbons Chemical class 0.000 description 15
- 239000007789 gas Substances 0.000 description 14
- 239000007774 positive electrode material Substances 0.000 description 14
- 239000000126 substance Substances 0.000 description 14
- VTWYQAQIXXAXOR-UHFFFAOYSA-N 2-methylsulfonylpropane Chemical compound CC(C)S(C)(=O)=O VTWYQAQIXXAXOR-UHFFFAOYSA-N 0.000 description 13
- CMJLMPKFQPJDKP-UHFFFAOYSA-N 3-methylthiolane 1,1-dioxide Chemical compound CC1CCS(=O)(=O)C1 CMJLMPKFQPJDKP-UHFFFAOYSA-N 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 10
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- YBJCDTIWNDBNTM-UHFFFAOYSA-N 1-methylsulfonylethane Chemical compound CCS(C)(=O)=O YBJCDTIWNDBNTM-UHFFFAOYSA-N 0.000 description 8
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 8
- 150000005676 cyclic carbonates Chemical class 0.000 description 8
- 238000004817 gas chromatography Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000012044 organic layer Substances 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 239000006258 conductive agent Substances 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 6
- XAXBJEMVFBTTKF-UHFFFAOYSA-N 1,2-bis(trifluoromethyl)cyclohexane Chemical compound FC(F)(F)C1CCCCC1C(F)(F)F XAXBJEMVFBTTKF-UHFFFAOYSA-N 0.000 description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 150000005678 chain carbonates Chemical class 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 5
- 239000002798 polar solvent Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- RDKKQZIFDSEMNU-UHFFFAOYSA-N 2-ethylsulfonylpropane Chemical compound CCS(=O)(=O)C(C)C RDKKQZIFDSEMNU-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- SGJDSXRTGWZIMH-UHFFFAOYSA-N 1,1-bis(trifluoromethyl)cyclohexane Chemical compound FC(F)(F)C1(C(F)(F)F)CCCCC1 SGJDSXRTGWZIMH-UHFFFAOYSA-N 0.000 description 3
- XIJLJFDFDZSWDG-UHFFFAOYSA-N 1,3-bis(trifluoromethyl)cyclohexane Chemical compound FC(F)(F)C1CCCC(C(F)(F)F)C1 XIJLJFDFDZSWDG-UHFFFAOYSA-N 0.000 description 3
- RCJZROJZUKPMTD-UHFFFAOYSA-N 1-(1,1,2,2,2-pentafluoroethyl)-1-(trifluoromethyl)cyclohexane Chemical compound FC(F)(F)C(F)(F)C1(C(F)(F)F)CCCCC1 RCJZROJZUKPMTD-UHFFFAOYSA-N 0.000 description 3
- UEUGALWLUYPXSZ-UHFFFAOYSA-N 2-cyclohexylethyl methanesulfonate Chemical compound CS(=O)(=O)OCCC1CCCCC1 UEUGALWLUYPXSZ-UHFFFAOYSA-N 0.000 description 3
- BRRLJOYGNUNENI-UHFFFAOYSA-N 2-fluoroethylcyclohexane Chemical compound FCCC1CCCCC1 BRRLJOYGNUNENI-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 230000002238 attenuated effect Effects 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000010280 constant potential charging Methods 0.000 description 3
- 238000010277 constant-current charging Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- CSJLBAMHHLJAAS-UHFFFAOYSA-N diethylaminosulfur trifluoride Chemical compound CCN(CC)S(F)(F)F CSJLBAMHHLJAAS-UHFFFAOYSA-N 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
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- 229920000573 polyethylene Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 125000006850 spacer group Chemical group 0.000 description 3
- IIZKNKHOOPBVEG-UHFFFAOYSA-N 1,1,2,2,2-pentafluoroethylcyclohexane Chemical compound FC(F)(F)C(F)(F)C1CCCCC1 IIZKNKHOOPBVEG-UHFFFAOYSA-N 0.000 description 2
- GBAPQIKKEVNMLC-UHFFFAOYSA-N 1,1-bis(1,1,2,2,2-pentafluoroethyl)cyclohexane Chemical compound FC(F)(F)C(F)(F)C1(C(F)(F)C(F)(F)F)CCCCC1 GBAPQIKKEVNMLC-UHFFFAOYSA-N 0.000 description 2
- XXZOEDQFGXTEAD-UHFFFAOYSA-N 1,2-bis(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1C(F)(F)F XXZOEDQFGXTEAD-UHFFFAOYSA-N 0.000 description 2
- RIUQAPDKVUDMLI-UHFFFAOYSA-N 1-fluoroethylcyclohexane Chemical compound CC(F)C1CCCCC1 RIUQAPDKVUDMLI-UHFFFAOYSA-N 0.000 description 2
- QJQZRLXDLORINA-UHFFFAOYSA-N 2-cyclohexylethanol Chemical compound OCCC1CCCCC1 QJQZRLXDLORINA-UHFFFAOYSA-N 0.000 description 2
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical group [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229920006026 co-polymeric resin Polymers 0.000 description 2
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- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethyl cyclohexane Natural products CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000000806 fluorine-19 nuclear magnetic resonance spectrum Methods 0.000 description 2
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229940017219 methyl propionate Drugs 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
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- 238000006864 oxidative decomposition reaction Methods 0.000 description 2
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- IDBYQQQHBYGLEQ-UHFFFAOYSA-N 1,1,2,2,3,3,4-heptafluorocyclopentane Chemical compound FC1CC(F)(F)C(F)(F)C1(F)F IDBYQQQHBYGLEQ-UHFFFAOYSA-N 0.000 description 1
- FPPBYJBOHUMXJN-UHFFFAOYSA-N 1,1,2-trifluorocyclohexane Chemical compound FC1CCCCC1(F)F FPPBYJBOHUMXJN-UHFFFAOYSA-N 0.000 description 1
- PCBXUDQFZHWMKH-UHFFFAOYSA-N 1,1,2-trifluoroethylcyclohexane Chemical compound FCC(F)(F)C1CCCCC1 PCBXUDQFZHWMKH-UHFFFAOYSA-N 0.000 description 1
- DBVMRQUISHFOFA-UHFFFAOYSA-N 1,1-difluoroethylcyclohexane Chemical compound CC(F)(F)C1CCCCC1 DBVMRQUISHFOFA-UHFFFAOYSA-N 0.000 description 1
- BQSOVTVFDGMJNB-UHFFFAOYSA-N 1,2,2,2-tetrafluoroethylcyclohexane Chemical compound FC(F)(F)C(F)C1CCCCC1 BQSOVTVFDGMJNB-UHFFFAOYSA-N 0.000 description 1
- RKURYFJWZRPRGW-UHFFFAOYSA-N 1,2,2-trifluoroethylcyclohexane Chemical compound FC(F)C(F)C1CCCCC1 RKURYFJWZRPRGW-UHFFFAOYSA-N 0.000 description 1
- SZZVRXGIUHCXFW-UHFFFAOYSA-N 1,2-bis(1,1,2,2,2-pentafluoroethyl)cyclohexane Chemical compound FC(F)(F)C(F)(F)C1CCCCC1C(F)(F)C(F)(F)F SZZVRXGIUHCXFW-UHFFFAOYSA-N 0.000 description 1
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- JKSIJLIVHIGTNW-UHFFFAOYSA-N 1,3-bis(1,1,2,2,2-pentafluoroethyl)cyclohexane Chemical compound FC(F)(F)C(F)(F)C1CCCC(C(F)(F)C(F)(F)F)C1 JKSIJLIVHIGTNW-UHFFFAOYSA-N 0.000 description 1
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- YQBZQARTKCPGBH-UHFFFAOYSA-N 1,4-bis(trifluoromethyl)cyclohexane Chemical compound FC(F)(F)C1CCC(C(F)(F)F)CC1 YQBZQARTKCPGBH-UHFFFAOYSA-N 0.000 description 1
- URDYJNJREUFXGD-UHFFFAOYSA-N 1-ethylsulfonylpropane Chemical compound CCCS(=O)(=O)CC URDYJNJREUFXGD-UHFFFAOYSA-N 0.000 description 1
- QAPSIUMUNHNUPW-UHFFFAOYSA-N 1-methylsulfonylpropane Chemical compound CCCS(C)(=O)=O QAPSIUMUNHNUPW-UHFFFAOYSA-N 0.000 description 1
- KRYBGIIKAMJTRV-UHFFFAOYSA-N 2,2,2-trifluoroethylcyclohexane Chemical compound FC(F)(F)CC1CCCCC1 KRYBGIIKAMJTRV-UHFFFAOYSA-N 0.000 description 1
- DKCLBVYFGUVPAG-UHFFFAOYSA-N 2,2-difluoroethylcyclohexane Chemical compound FC(F)CC1CCCCC1 DKCLBVYFGUVPAG-UHFFFAOYSA-N 0.000 description 1
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- PPDFQRAASCRJAH-UHFFFAOYSA-N 2-methylthiolane 1,1-dioxide Chemical compound CC1CCCS1(=O)=O PPDFQRAASCRJAH-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
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- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 1
- 229910018871 CoO 2 Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000004057 DFT-B3LYP calculation Methods 0.000 description 1
- 208000005156 Dehydration Diseases 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- XJCNIFKXBRJJEN-UHFFFAOYSA-N FCCC1CCCCC1.FCCC1CCCCC1 Chemical compound FCCC1CCCCC1.FCCC1CCCCC1 XJCNIFKXBRJJEN-UHFFFAOYSA-N 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910012513 LiSbF 6 Inorganic materials 0.000 description 1
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/04—Hybrid capacitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
-
- 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
- Y02E60/13—Energy storage using capacitors
-
- 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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Secondary Cells (AREA)
Description
以下、本発明による蓄電デバイス用非水溶媒の実施形態を説明する。本実施形態の非水溶媒は、リチウムイオン二次電池や電気二重層キャパシタなどの蓄電デバイスに用いられる。
以下、本発明による蓄電デバイス用非水電解液の実施形態を説明する。本実施形態の非水電解液は、リチウムイオン二次電池や電気二重層キャパシタなどの蓄電デバイスに用いられる。
以下、本発明による蓄電デバイスの実施形態を説明する。本実施形態の蓄電デバイスは、リチウムイオン二次電池である。
以下、本発明による蓄電デバイスの実施形態を説明する。本実施形態の蓄電デバイスは、電気二重層キャパシタである。
<非水電解液の調製>
(実施例1)
一般式(2)で表される鎖状スルホンとしてエチルメチルスルホン(EtMeSF)、イソプロピルメチルスルホン(iPrMeSF)、イソプロピルエチルスルホン(iPrEtSF)、一般式(3)で表される環状スルホンとして、スルホラン(SLF)、3−メチルスルホラン(3MeSLF)および一般式(1)で表されるフッ素含有環状飽和炭化水素として、トリフルオロメチルシクロヘキサン(TFMCH)、1,2−ビス(トリフルオロメチル)シクロヘキサン(12BTFMCH)、(2−フルオロエチル)シクロヘキサン(2FECH)を用い、支持電解質塩として六フッ化リン酸リチウム(LiPF6)を溶解させた非水電解液AからIを調製した。
[イソプロピルエチルスルホン]
エチルメチルスルホン(EtMeSF)[CAS RN:594−43−4]、イソプロピルエチルスルホン(iPrEtSF)[CAS RN:4853−75−2]には市販品を用い、回転バンド式精密分留装置(大科工業製)により精製を行った。得られた精製物の純度をガスクロマトグラフィー(島津製作所製)により測定したところ、いずれも純度は99.5%以上であった。さらに、電解液調製の直前に、真空中200℃で12時間処理したモレキュラーシーブ[4A]を用いて脱水処理を行った。処理後の水分量は、いずれも20ppm以下であった。
トリフルオロシクロへキサン(TFMCH)[CAS RN:401−75−2]には市販品を用い、回転バンド式精密分留装置(大科工業製)により精製を行った。得られた精製物の純度をガスクロマトグラフィー(島津製作所製)により測定したところ、純度は99.5%であった。
1,2−ビス(トリフルオロメチル)シクロへキサン(12BTFMCH)は、以下に示す合成法により得た。
(2−フルオロエチル)シクロへキサン(2FECH)は、以下に示す合成法により得た。
比較例1として、3−メチルスルホラン(3MeSLF)、またはイソプロピルメチルスルホン(iPrMeSF)とトリフルオロメチルシクロヘキサン(TFMCH)を溶媒として含む非水電解液JからNを調製した。
従来例として、プロピレンカーボネート(PC)とジメチルカーボネート(DMC)を75:25の重量比率で混合した混合溶媒を含む非水電解液Oを調整した。表3に調製した非水電解液のサンプル名と支持電解質塩の濃度をmol/Lで示す。なお、用いた溶媒および支持電解質塩の純度はいずれも市販のバッテリーグレードである。
まず、正極活物質としてLiCoO2(平均粒径10μm、BET法による比表面積0.38m2/g)を準備した。100重量部の活物質に、導電剤であるアセチレンブラックを3重量部、結着剤であるポリフッ化ビニリデンを4重量部、および適量のN−メチル−2−ピロリドンを加え、攪拌・混合して、スラリー状の正極合剤を得た。なお、ポリフッ化ビニリデンは、あらかじめN−メチル−2−ピロリドンに溶解した状態で用いた。
まず、ステンレス(SUS304)製メッシュを図4に示す寸法に打ち抜いて負極集電体2a、(図1(c))を形成した。負極集電体2aは、31mm×41mmの長方形状を有する電極部と、7mm×7mmの正方形状を有するリード取り付け部とを有する。負極集電体2aのうちの電極部の上に、厚さ150μmの金属リチウム2bを圧着して、負極2を得た。
得られた正極1および負極2を、セパレータ3を介して積層し、図1(c)に示すような電極群13を作製した。セパレータとしては、厚さ20μmのポリエチレン製微多孔質シートを用いた。
<高率放電特性>
作製した実施例1の電池AからI、比較例1の電池K、M、N、従来例1の電池Oを用いて高率放電特性の評価を行った。
作成した実施例1の電池AからI、比較例1の電池K、M、N、従来例1の電池Oを用いて高温保存試験を行った。
1.電気二重層キャパシタの作製
<非水電解液の調製>
(実施例2)
溶媒として3−メチルスルホラン(3MeSLF)、イソプロピルメチルスルホン(iPrMeSF)およびトリフルオロメチルシクロヘキサン(TFMCH)を用い、支持電解質塩として(C2H5)4NBF4を用いて非水電解液Pを調製した。
プロピレンカーボネート(PC)のみを溶媒として含む非水電解液を調製して、(C2H5)4NBF4を0.2mol/Lの濃度で溶解することにより、非水電解液Qを調製した。
電極は活性炭粉末(比表面積1700m2/g、平均粒子径2μm)を用いて作成した。活性炭粉末100mgとアセチレンブラック20mgとを均一に混合し、ポリビニルピロリドン20mg、メタノール800mgを加えてスラリーを得た。このスラリー状の電極合剤をアルミニウム箔からなる集電体上に塗布し、真空乾燥を行った。電極合剤の塗布重量は、集電体の単位面積あたり2.2mg/cm2であった。得られた極板を、直径12.5mmの円盤状に打ち抜いて電極とした。
円盤状に打ち抜いた電極を用いて、図2に示すようなコイン形電気二重層キャパシタを組み立てた。まず、直径15mmの円形に打ち抜いたポリプロピレン製不織布シートからなるセパレータ17を介して電極22a、22bを互いに対向させて配置させ、電極群とした。電極群をケース20の内部に収容し、所定量の各種非水電解液を含浸させた後、ガスケット20を装着した封口板19により、キャパシタ内部を密封した。これにより、実施例2、および従来例2の非水電解液を用いた電気二重層キャパシタP、Qを作製した。
<充放電試験>
作製した電気二重層キャパシタに対して、25℃の環境下において、0.1mAの定電流で0Vから2.0Vの電圧範囲での充放電試験を行った。図5(a)に実施例2の電気二重層キャパシタ、図5(b)に比較例2の電気二重層キャパシタの充放電試験結果を示す。
1a 正極集電体
1b 正極合剤
2 負極
2a 負極集電体
2b 金属リチウム
3 セパレータ
11 正極リード
12 負極リード
13 電極群
14 電池ケース
15、24 非水電解液
16a、16b 集電体
17 セパレータ
18 スペーサ
19 封口板
20 ガスケット
21 ケース
22a、22b 電極合剤
23a、23b 電極
Claims (9)
- 前記一般式(1)において、nは1または2である請求項1に記載の蓄電デバイス用非水溶媒。
- 前記鎖状スルホンが非対称の鎖状スルホンである請求項1または2に記載の蓄電デバイス用非水溶媒。
- 請求項1から3のいずれかに記載の蓄電デバイス用非水溶媒と、支持電解質塩とを備える蓄電デバイス用非水電解液。
- 前記支持電解質塩はリチウム塩である請求項4に記載の蓄電デバイス用非水電解液。
- 前記支持電解質塩は四級アンモニウム塩である請求項4に記載の蓄電デバイス用非水電解液。
- 請求項1から3のいずれかに記載の蓄電デバイス用非水溶媒または請求項4から6のいずれかに記載の蓄電デバイス用非水電解液を含む蓄電デバイス。
- 請求項1から3のいずれかに記載の蓄電デバイス用非水溶媒または請求項4から6いずれかに記載の蓄電デバイス用非水電解液を含むリチウムイオン二次電池。
- 請求項1から3のいずれかに記載の蓄電デバイス用非水溶媒または請求項4から6のいずれかに記載の蓄電デバイス用非水電解液を含む電気二重層キャパシタ。
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