WO2014115690A1 - 非水電解液及びそれを用いた蓄電デバイス - Google Patents
非水電解液及びそれを用いた蓄電デバイス Download PDFInfo
- Publication number
- WO2014115690A1 WO2014115690A1 PCT/JP2014/051020 JP2014051020W WO2014115690A1 WO 2014115690 A1 WO2014115690 A1 WO 2014115690A1 JP 2014051020 W JP2014051020 W JP 2014051020W WO 2014115690 A1 WO2014115690 A1 WO 2014115690A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- carbonate
- carbon atoms
- lithium
- trifluoromethyl
- Prior art date
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- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 48
- 238000003860 storage Methods 0.000 title claims abstract description 46
- 230000005611 electricity Effects 0.000 title claims abstract description 36
- -1 phenyl ester compound Chemical class 0.000 claims abstract description 301
- 125000005843 halogen group Chemical group 0.000 claims abstract description 46
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 32
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 31
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 25
- 239000003792 electrolyte Substances 0.000 claims abstract description 22
- 125000000304 alkynyl group Chemical group 0.000 claims abstract description 17
- 125000003118 aryl group Chemical group 0.000 claims abstract description 17
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 16
- 125000004450 alkenylene group Chemical group 0.000 claims abstract description 16
- 125000004419 alkynylene group Chemical group 0.000 claims abstract description 16
- 150000003839 salts Chemical class 0.000 claims abstract description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 97
- 229910052744 lithium Inorganic materials 0.000 claims description 81
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 72
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 43
- 239000002904 solvent Substances 0.000 claims description 39
- 125000001153 fluoro group Chemical group F* 0.000 claims description 35
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 31
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 29
- 239000008151 electrolyte solution Substances 0.000 claims description 27
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 27
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 26
- 229910003002 lithium salt Inorganic materials 0.000 claims description 26
- 159000000002 lithium salts Chemical class 0.000 claims description 26
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 25
- 239000003575 carbonaceous material Substances 0.000 claims description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 19
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 18
- 150000005678 chain carbonates Chemical class 0.000 claims description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 239000011572 manganese Substances 0.000 claims description 9
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 8
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 8
- 229910052718 tin Inorganic materials 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 7
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims description 7
- 150000004706 metal oxides Chemical class 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 150000005687 symmetric chain carbonates Chemical class 0.000 claims description 6
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 4
- 229910013131 LiN Inorganic materials 0.000 claims description 4
- 229910013528 LiN(SO2 CF3)2 Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 229910000733 Li alloy Inorganic materials 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 239000001989 lithium alloy Substances 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- RCIJMMSZBQEWKW-UHFFFAOYSA-N methyl propan-2-yl carbonate Chemical compound COC(=O)OC(C)C RCIJMMSZBQEWKW-UHFFFAOYSA-N 0.000 claims description 3
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims description 3
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 2
- LWLOKSXSAUHTJO-UHFFFAOYSA-N 4,5-dimethyl-1,3-dioxolan-2-one Chemical compound CC1OC(=O)OC1C LWLOKSXSAUHTJO-UHFFFAOYSA-N 0.000 claims description 2
- FOLJHXWWJYUOJV-UHFFFAOYSA-N 4-ethynyl-1,3-dioxolan-2-one Chemical compound O=C1OCC(C#C)O1 FOLJHXWWJYUOJV-UHFFFAOYSA-N 0.000 claims description 2
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 2
- FWBMVXOCTXTBAD-UHFFFAOYSA-N butyl methyl carbonate Chemical compound CCCCOC(=O)OC FWBMVXOCTXTBAD-UHFFFAOYSA-N 0.000 claims description 2
- QLVWOKQMDLQXNN-UHFFFAOYSA-N dibutyl carbonate Chemical compound CCCCOC(=O)OCCCC QLVWOKQMDLQXNN-UHFFFAOYSA-N 0.000 claims description 2
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 claims description 2
- CYEDOLFRAIXARV-UHFFFAOYSA-N ethyl propyl carbonate Chemical compound CCCOC(=O)OCC CYEDOLFRAIXARV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 150000003377 silicon compounds Chemical class 0.000 claims description 2
- 150000003606 tin compounds Chemical class 0.000 claims description 2
- 239000011149 active material Substances 0.000 claims 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 17
- 239000003125 aqueous solvent Substances 0.000 abstract description 12
- 230000014759 maintenance of location Effects 0.000 abstract description 6
- 230000001351 cycling effect Effects 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract 3
- 239000001257 hydrogen Substances 0.000 abstract 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 2
- 239000011737 fluorine Substances 0.000 abstract 2
- 125000002733 (C1-C6) fluoroalkyl group Chemical group 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 150000002431 hydrogen Chemical class 0.000 abstract 1
- 238000000034 method Methods 0.000 description 41
- 238000006243 chemical reaction Methods 0.000 description 39
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 24
- 239000000203 mixture Substances 0.000 description 23
- 150000001875 compounds Chemical class 0.000 description 22
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 18
- 230000000694 effects Effects 0.000 description 18
- 239000000243 solution Substances 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 13
- 125000001424 substituent group Chemical group 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 238000000354 decomposition reaction Methods 0.000 description 12
- 150000002736 metal compounds Chemical class 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 11
- 229910002804 graphite Inorganic materials 0.000 description 11
- 239000010439 graphite Substances 0.000 description 11
- 229910001416 lithium ion Inorganic materials 0.000 description 11
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- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 8
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 8
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- DHPCRFYUUWAGAH-UHFFFAOYSA-N 4-fluoro-3-(trifluoromethyl)phenol Chemical compound OC1=CC=C(F)C(C(F)(F)F)=C1 DHPCRFYUUWAGAH-UHFFFAOYSA-N 0.000 description 5
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 5
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- 101150058243 Lipf gene Proteins 0.000 description 5
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- PFKFTWBEEFSNDU-UHFFFAOYSA-N carbonyldiimidazole Chemical compound C1=CN=CN1C(=O)N1C=CN=C1 PFKFTWBEEFSNDU-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 125000005442 diisocyanate group Chemical group 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
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- 125000006575 electron-withdrawing group Chemical group 0.000 description 4
- 238000010828 elution Methods 0.000 description 4
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- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 3
- 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 3
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- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- IZOLXQKBJBWATB-UHFFFAOYSA-N [2-(trifluoromethyl)phenyl] methanesulfonate Chemical compound CS(=O)(=O)OC1=CC=CC=C1C(F)(F)F IZOLXQKBJBWATB-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- IPBVNPXQWQGGJP-UHFFFAOYSA-N acetic acid phenyl ester Natural products CC(=O)OC1=CC=CC=C1 IPBVNPXQWQGGJP-UHFFFAOYSA-N 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 125000005087 alkynylcarbonyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- URWVQLWOBPHQCH-UHFFFAOYSA-N bis(prop-2-ynyl) oxalate Chemical compound C#CCOC(=O)C(=O)OCC#C URWVQLWOBPHQCH-UHFFFAOYSA-N 0.000 description 1
- YRYKCYXAYPTIIE-AATRIKPKSA-N bis[4-chloro-3-(trifluoromethyl)phenyl] (E)-but-2-enedioate Chemical compound C(\C=C\C(=O)OC1=CC(=C(C=C1)Cl)C(F)(F)F)(=O)OC1=CC(=C(C=C1)Cl)C(F)(F)F YRYKCYXAYPTIIE-AATRIKPKSA-N 0.000 description 1
- MVELPUNEXQCIBI-UHFFFAOYSA-N bis[4-chloro-3-(trifluoromethyl)phenyl] butanedioate Chemical compound C(CCC(=O)OC1=CC(=C(C=C1)Cl)C(F)(F)F)(=O)OC1=CC(=C(C=C1)Cl)C(F)(F)F MVELPUNEXQCIBI-UHFFFAOYSA-N 0.000 description 1
- LEESKJAJGNMEED-UHFFFAOYSA-N bis[4-chloro-3-(trifluoromethyl)phenyl] carbonate Chemical compound ClC1=C(C=C(C=C1)OC(OC1=CC(=C(C=C1)Cl)C(F)(F)F)=O)C(F)(F)F LEESKJAJGNMEED-UHFFFAOYSA-N 0.000 description 1
- UVCQSLHJXOCMJQ-UHFFFAOYSA-N bis[4-chloro-3-(trifluoromethyl)phenyl] hexanedioate Chemical compound ClC1=C(C=C(C=C1)OC(CCCCC(=O)OC1=CC(=C(C=C1)Cl)C(F)(F)F)=O)C(F)(F)F UVCQSLHJXOCMJQ-UHFFFAOYSA-N 0.000 description 1
- MEOPZPLGDYODDZ-UHFFFAOYSA-N bis[4-chloro-3-(trifluoromethyl)phenyl] oxalate Chemical compound C(C(=O)OC1=CC(=C(C=C1)Cl)C(F)(F)F)(=O)OC1=CC(=C(C=C1)Cl)C(F)(F)F MEOPZPLGDYODDZ-UHFFFAOYSA-N 0.000 description 1
- CDCPRHLKESQOMP-UHFFFAOYSA-N bis[4-fluoro-3-(trifluoromethyl)phenyl] carbonate Chemical compound FC1=C(C=C(C=C1)OC(OC1=CC(=C(C=C1)F)C(F)(F)F)=O)C(F)(F)F CDCPRHLKESQOMP-UHFFFAOYSA-N 0.000 description 1
- UVGBEWHUHUEOLZ-UHFFFAOYSA-N bis[4-fluoro-3-(trifluoromethyl)phenyl] hexanedioate Chemical compound C(CCCCC(=O)OC1=CC(=C(C=C1)F)C(F)(F)F)(=O)OC1=CC(=C(C=C1)F)C(F)(F)F UVGBEWHUHUEOLZ-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 125000006251 butylcarbonyl group Chemical group 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001786 chalcogen compounds Chemical class 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- FZFAMSAMCHXGEF-UHFFFAOYSA-N chloro formate Chemical compound ClOC=O FZFAMSAMCHXGEF-UHFFFAOYSA-N 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229920000547 conjugated polymer Polymers 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
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- TXFOLHZMICYNRM-UHFFFAOYSA-N dichlorophosphoryloxybenzene Chemical compound ClP(Cl)(=O)OC1=CC=CC=C1 TXFOLHZMICYNRM-UHFFFAOYSA-N 0.000 description 1
- FAMRKDQNMBBFBR-BQYQJAHWSA-N diethyl azodicarboxylate Substances CCOC(=O)\N=N\C(=O)OCC FAMRKDQNMBBFBR-BQYQJAHWSA-N 0.000 description 1
- LGTLXDJOAJDFLR-UHFFFAOYSA-N diethyl chlorophosphate Chemical compound CCOP(Cl)(=O)OCC LGTLXDJOAJDFLR-UHFFFAOYSA-N 0.000 description 1
- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 description 1
- WHBMWHKJXUBZFV-UHFFFAOYSA-N dimethyl methanedisulfonate Chemical compound COS(=O)(=O)CS(=O)(=O)OC WHBMWHKJXUBZFV-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- PQLFROTZSIMBKR-UHFFFAOYSA-N ethenyl carbonochloridate Chemical compound ClC(=O)OC=C PQLFROTZSIMBKR-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- HHEIMYAXCOIQCJ-UHFFFAOYSA-N ethyl 2,2-dimethylpropanoate Chemical compound CCOC(=O)C(C)(C)C HHEIMYAXCOIQCJ-UHFFFAOYSA-N 0.000 description 1
- RIFGWPKJUGCATF-UHFFFAOYSA-N ethyl chloroformate Chemical compound CCOC(Cl)=O RIFGWPKJUGCATF-UHFFFAOYSA-N 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 1
- 229950004696 flusalan Drugs 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 125000005928 isopropyloxycarbonyl group Chemical group [H]C([H])([H])C([H])(OC(*)=O)C([H])([H])[H] 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000005001 laminate film Substances 0.000 description 1
- 239000006233 lamp black Substances 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- BDKWOJYFHXPPPT-UHFFFAOYSA-N lithium dioxido(dioxo)manganese nickel(2+) Chemical compound [Mn](=O)(=O)([O-])[O-].[Ni+2].[Li+] BDKWOJYFHXPPPT-UHFFFAOYSA-N 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910021470 non-graphitizable carbon Inorganic materials 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
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 description 1
- 125000005003 perfluorobutyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- 125000005009 perfluoropropyl group Chemical group FC(C(C(F)(F)F)(F)F)(F)* 0.000 description 1
- AHWALFGBDFAJAI-UHFFFAOYSA-N phenyl carbonochloridate Chemical compound ClC(=O)OC1=CC=CC=C1 AHWALFGBDFAJAI-UHFFFAOYSA-N 0.000 description 1
- WXVUCMFEGJUVTN-UHFFFAOYSA-N phenyl methanesulfonate Chemical compound CS(=O)(=O)OC1=CC=CC=C1 WXVUCMFEGJUVTN-UHFFFAOYSA-N 0.000 description 1
- 229940049953 phenylacetate Drugs 0.000 description 1
- 125000003170 phenylsulfonyl group Chemical group C1(=CC=CC=C1)S(=O)(=O)* 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical group 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
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- 238000006116 polymerization reaction Methods 0.000 description 1
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- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- CAEWJEXPFKNBQL-UHFFFAOYSA-N prop-2-enyl carbonochloridate Chemical compound ClC(=O)OCC=C CAEWJEXPFKNBQL-UHFFFAOYSA-N 0.000 description 1
- BYXGTJQWDSWRAG-UHFFFAOYSA-N prop-2-ynyl 2-diethoxyphosphorylacetate Chemical compound CCOP(=O)(OCC)CC(=O)OCC#C BYXGTJQWDSWRAG-UHFFFAOYSA-N 0.000 description 1
- PZAWASVJOPLHCJ-UHFFFAOYSA-N prop-2-ynyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC#C PZAWASVJOPLHCJ-UHFFFAOYSA-N 0.000 description 1
- RIZZXCJMFIGMON-UHFFFAOYSA-N prop-2-ynyl acetate Chemical compound CC(=O)OCC#C RIZZXCJMFIGMON-UHFFFAOYSA-N 0.000 description 1
- RAMTXCRMKBFPRG-UHFFFAOYSA-N prop-2-ynyl carbonochloridate Chemical compound ClC(=O)OCC#C RAMTXCRMKBFPRG-UHFFFAOYSA-N 0.000 description 1
- KDIDLLIMHZHOHO-UHFFFAOYSA-N prop-2-ynyl formate Chemical compound O=COCC#C KDIDLLIMHZHOHO-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- QMKUYPGVVVLYSR-UHFFFAOYSA-N propyl 2,2-dimethylpropanoate Chemical compound CCCOC(=O)C(C)(C)C QMKUYPGVVVLYSR-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003230 pyrimidines Chemical class 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 125000005930 sec-butyloxycarbonyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(OC(*)=O)C([H])([H])[H] 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
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- 238000003756 stirring Methods 0.000 description 1
- 125000005017 substituted alkenyl group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 125000006253 t-butylcarbonyl group Chemical group [H]C([H])([H])C(C(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—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
- 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
- H01G11/64—Liquid electrolytes characterised by additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/63—Esters of sulfonic acids
- C07C309/64—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms
- C07C309/65—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms of a saturated carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/63—Esters of sulfonic acids
- C07C309/64—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms
- C07C309/65—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms of a saturated carbon skeleton
- C07C309/66—Methanesulfonates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/63—Esters of sulfonic acids
- C07C309/64—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms
- C07C309/67—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms of an unsaturated carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/63—Esters of sulfonic acids
- C07C309/72—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C309/73—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton to carbon atoms of non-condensed six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
- C07C69/12—Acetic acid esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
- C07C69/22—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/34—Esters of acyclic saturated polycarboxylic acids having an esterified carboxyl group bound to an acyclic carbon atom
- C07C69/36—Oxalic acid esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/34—Esters of acyclic saturated polycarboxylic acids having an esterified carboxyl group bound to an acyclic carbon atom
- C07C69/40—Succinic acid esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/34—Esters of acyclic saturated polycarboxylic acids having an esterified carboxyl group bound to an acyclic carbon atom
- C07C69/44—Adipic acid esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
- C07C69/54—Acrylic acid esters; Methacrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/62—Halogen-containing esters
- C07C69/63—Halogen-containing esters of saturated acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/96—Esters of carbonic or haloformic acids
-
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- C07—ORGANIC CHEMISTRY
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
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- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
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- 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
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- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M2300/00—Electrolytes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
- H01M2300/0037—Mixture of solvents
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- 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
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- 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
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- 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
Definitions
- the present invention relates to a nonaqueous electrolytic solution capable of improving electrochemical characteristics when an electricity storage device is used at a high temperature and an electricity storage device using the same.
- power storage devices in particular lithium secondary batteries
- electronic devices such as mobile phones and laptop computers
- power sources for electric vehicles and power storage In particular, in thin electronic devices such as tablet terminals and ultrabooks, a laminate type battery or a square type battery using an aluminum laminate film, an aluminum alloy or the like as an exterior member is often used. Since these battery exterior members are thin, they are easily deformed, and there is a problem that the influence of the deformation on the electronic device is very large.
- the lithium secondary battery is mainly composed of a positive electrode and a negative electrode containing a material capable of occluding and releasing lithium, a non-aqueous electrolyte composed of a lithium salt and a non-aqueous solvent, and the non-aqueous solvent includes ethylene carbonate (EC), Carbonates such as propylene carbonate (PC) are used.
- EC ethylene carbonate
- PC propylene carbonate
- negative electrodes of lithium secondary batteries lithium metal, metal compounds capable of inserting and extracting lithium (metal simple substance, oxide, alloy with lithium, etc.) and carbon materials are known.
- non-aqueous electrolyte secondary batteries using carbon materials that can occlude and release lithium such as coke and graphite (artificial graphite, natural graphite), are widely used.
- the above negative electrode materials store and release lithium and electrons at a very low potential equivalent to that of lithium metal, so many solvents may undergo reductive decomposition, regardless of the type of negative electrode material.
- Some of the solvent in the electrolyte solution is reductively decomposed on the negative electrode, and lithium ion migration is hindered by the deposition of decomposition products, gas generation, and swelling of the electrode, especially when the battery is used at high temperatures. There are problems such as deterioration of the battery characteristics and deformation of the battery due to swelling of the electrodes.
- lithium secondary batteries using lithium metal, alloys thereof, simple metals such as tin or silicon, and oxides as negative electrode materials have a high initial capacity, but are finely pulverized during the cycle. In comparison, reductive decomposition of non-aqueous solvents occurs at an accelerated rate, and battery performance such as battery capacity and cycle characteristics is greatly reduced, and problems such as battery deformation due to electrode swelling are known.
- materials capable of occluding and releasing lithium such as LiCoO 2 , LiMn 2 O 4 , LiNiO 2 , LiFePO 4 and the like used as the positive electrode material, store lithium and electrons at a noble voltage of 3.5 V or more on the basis of lithium.
- many solvents may undergo oxidative decomposition, and some of the solvent in the electrolyte on the positive electrode does not depend on the type of positive electrode material. Oxidative decomposition may cause problems such as increase in resistance due to deposition of decomposition products, and generation of gas due to decomposition of the solvent, causing the battery to swell.
- Patent Document 1 when an electrolyte containing a phenyl ester compound such as 4- (trifluoromethyl) phenyl acetate and 3,4-difluorophenyl acetate is used, the overcharge characteristics of the lithium secondary battery are improved. In addition, it is described that storage characteristics and continuous charge characteristics can be improved. Patent Document 2 describes that the use of an electrolyte containing a sulfonic acid phenyl compound such as 2,4-difluorophenyl methanesulfonate can improve the low-temperature cycle characteristics of the battery.
- a sulfonic acid phenyl compound such as 2,4-difluorophenyl methanesulfonate
- Patent Document 3 describes that when an electrolyte containing a sulfonic acid phenyl compound such as 2-trifluoromethylphenyl methanesulfonate is used, a lithium battery having excellent electrochemical characteristics in a wide temperature range can be obtained. ing.
- the present invention improves the electrochemical characteristics when an electricity storage device is used at a high temperature, and further uses not only a discharge capacity maintenance rate after a high voltage cycle but also a gas generation can be suppressed, and a non-aqueous electrolyte used therefor It is an object of the present invention to provide a power storage device.
- the present inventors have examined in detail the performance of the above-described prior art non-aqueous electrolyte.
- the non-aqueous electrolytes of Patent Documents 1 to 3 cannot be said to be sufficiently satisfactory when the operating temperature of the electricity storage device is widened.
- the present inventors have added a phenyl ester compound in which a specific benzene ring is substituted with both a halogen atom and a fluoroalkyl group to a non-aqueous electrolyte.
- the inventors have found that the capacity retention rate after cycling when the electricity storage device is used at a high temperature can be improved and that gas generation can be suppressed, and the present invention has been completed.
- the present invention provides the following (1) to (3).
- R f represents a fluoroalkyl group having 1 to 6 carbon atoms
- X represents a halogen atom
- p and q are integers of 1 to 4, and (p + q) is 5 or less.
- at least one hydrogen atom of each group may be substituted with a halogen atom.
- the nonaqueous electrolytic solution contains the phenyl ester compound represented by the above general formula (I)
- An electricity storage device characterized by that.
- R f 1 represents a fluoroalkyl group having 1 to 6 carbon atoms
- X 1 represents a halogen atom.
- L 4 represents an alkylene group having 1 to 8 carbon atoms
- R 1 represents an alkyl group having 1 to 6 carbon atoms.
- Y that may be fluorine atoms
- Y that may be hydrogen atoms
- Y 1 is a trifluoromethyl group.
- alkyl group alkenyl group, alkynyl group, aryl group, alkylene group, alkenylene group, and alkynylene group
- at least one hydrogen atom of each group may be substituted with a halogen atom.
- a non-aqueous electrolyte that can improve the capacity retention rate after cycling when the power storage device is used at a high temperature and suppresses gas generation, and a power storage device such as a lithium battery using the nonaqueous electrolyte Can be provided.
- the nonaqueous electrolytic solution of the present invention is a nonaqueous electrolytic solution in which an electrolyte is dissolved in a nonaqueous solvent, wherein the benzene ring represented by the general formula (I) is substituted with both a halogen atom and a fluoroalkyl group. It is a non-aqueous electrolyte characterized by containing a phenyl ester compound.
- the reason why the non-aqueous electrolyte of the present invention can greatly improve the electrochemical characteristics when the electricity storage device is used at a high temperature is not clear, but is considered as follows.
- the phenyl ester compound represented by the general formula (I) is a fluoroalkyl group that is an electron-withdrawing group that is not bulky and has a high electrophilic functional group such as an alkanesulfonyl group, an alkylcarbonyl group, and an alkoxycarbonyl group. And a phenyl group having both a halogen atom which is a strong electron-withdrawing group.
- the decomposability of the compound is improved, and benzene rings are polymerized on the negative electrode to form a coating film derived from a highly heat-resistant benzene ring. Furthermore, excessive polymerization is suppressed because the fluoroalkyl group is a substituent that does not leave bulky. Therefore, it cannot be achieved with a compound having only a bulky electron-withdrawing substituent such as 4- (trifluoromethyl) phenyl acetate or a compound having only a strong electron-withdrawing group, such as 2,4-difluorophenyl acetate. It is considered that a significant improvement in high-temperature cycle characteristics was obtained.
- the compound contained in the nonaqueous electrolytic solution of the present invention is represented by the following general formula (I).
- R f represents a fluoroalkyl group having 1 to 6 carbon atoms
- X represents a halogen atom
- p and q are integers of 1 to 4, and (p + q) is 5 or less.
- at least one hydrogen atom of each group may be substituted with a halogen atom.
- X in the general formula (I) represents a halogen atom, and specific examples of X include a fluorine atom, a chlorine atom, and a bromine atom. Among these, a fluorine atom or a chlorine atom is more preferable, and a fluorine atom is still more preferable.
- R f in the general formula (I) represents a fluoroalkyl group having 1 to 6 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, more preferably a fluoroalkyl group having 1 or 2 carbon atoms, More preferred is a fluoroalkyl group.
- fluoroalkyl group represented by R f include fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, perfluoroethyl group, perfluoropropyl group, perfluorobutyl.
- Preferred examples include a group.
- a fluoroalkyl group having 1 or 2 carbon atoms such as a difluoromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, and a perfluoroethyl group is preferable, and a difluoromethyl group, a trifluoromethyl group, More preferred are C1-fluoroalkyl groups such as In the general formula (I), p and q represent an integer of 1 to 4, and (p + q) is 5 or less. p and q are each preferably 1 to 2, and more preferably 1.
- —S ( ⁇ O) 2 —, —C ( ⁇ O) —O—, —C ( ⁇ O) —L 1 —C ( ⁇ O) —, or —C ( ⁇ O) —L 2 —P ( ⁇ O) (OR) —O— is preferable, and —S ( ⁇ O) 2 — or C ( ⁇ O) —O— is more preferable.
- Y in the general formula (I) is a fluorine atom, a hydrogen atom, an alkyl group having 1 to 4 carbon atoms in which at least one hydrogen atom may be substituted with a halogen atom, and at least one hydrogen atom is a halogen atom.
- An aryl group having 6 to 10 carbon atoms, which may be substituted, is preferably a fluorine atom, a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, an alkynyl group having 3 to 5 carbon atoms, or An aryl group having 6 to 8 carbon atoms in which at least one hydrogen atom may be substituted with a halogen atom is more preferable.
- L 1 represents an alkylene group having 2 to 7 carbon atoms in which at least one hydrogen atom may be substituted with a halogen atom, and alkenylene having 2 to 6 carbon atoms in which at least one hydrogen atom may be substituted with a halogen atom.
- an alkynylene group having 2 to 6 carbon atoms in which at least one hydrogen atom may be substituted with a halogen atom, or a direct bond (no substituent) is preferable, an alkylene group having 2 to 7 carbon atoms, More preferred are 6 alkenylene groups, alkynylene groups having 2 to 6 carbon atoms, or direct bonds.
- L 2 is preferably an alkylene group having 1 to 4 carbon atoms in which at least one hydrogen atom may be substituted with a halogen atom, and 1 or 2 carbon atoms in which at least one hydrogen atom may be substituted with a halogen atom.
- the alkylene group is more preferable.
- R is preferably an alkyl group having 1 to 4 carbon atoms in which at least one hydrogen atom may be substituted with a halogen atom, and more preferably an alkyl group having 1 to 3 carbon atoms.
- —AY group of the general formula (I) a formyl group, a fluorosulfonyl group, an alkylsulfonyl group having 1 to 4 carbon atoms in which at least one hydrogen atom may be substituted with a halogen atom, at least one A C2-C4 alkenylsulfonyl group in which a hydrogen atom may be substituted with a halogen atom, a C6-C10 arylsulfonyl group in which at least one hydrogen atom may be substituted with a halogen atom, at least one An alkylcarbonyl group having 1 to 4 carbon atoms, a alkenylcarbonyl group having 2 to 6 carbon atoms, an alkynylcarbonyl group having 3 to 6 carbon atoms, and at least one hydrogen atom in which the hydrogen atom may be substituted with a halogen atom is a halogen atom
- -AY group of the general formula (I) include the following groups (i) to (xvii).
- (I) linear alkanesulfonyl groups such as fluorosulfonyl group, methanesulfonyl group, ethanesulfonyl group, propane-1-sulfonyl group, butane-1-sulfonyl group, pentane-1-sulfonyl group, hexane-1-sulfonyl group, etc.
- fluoromethanesulfonyl groups trifluoromethanesulfonyl groups, 2,2,2-trifluoroethanesulfonyl groups, etc.
- Alkanesulfonyl group in which part of hydrogen atoms is replaced by fluorine atoms (v) Nenesulfonyl group, 2-methylbenzenesulfonyl group, 3-methylbenzenesulfonyl group, 4-methylbenzenesulfonyl group, 4-tert-butylbenzenesulfonyl group, 2,4,6-trimethylbenzenesulfonyl group, 2-fluorobenzenesulfonyl Group, 3-fluorobenzenesulfonyl group, 4-fluorobenzenesulfonyl group, 2,4-difluorobenzenesulfonyl group, 2,6-difluorobenzenesulfonyl group, 3,4-difluorobenzenesulfonyl group, 2,4,6-tri Arylsulfonyl groups such as fluorobenzenesulfonyl group, pentafluorobenzene
- alkoxycarbonyl group in which a part of the hydrogen atom is substituted with a fluorine atom (ix) vinylcarbonyl group, 1-propenylcarbonyl group, 2-propenylcarbonyl group, 1-methyl-2-propenylcarbonyl group, 1,1-dimethyl -2-propenylcarbonyl group, 1 Alkenylcarbonyl groups such as butenylcarbonyl group, 2-butenylcarbonyl group, 3-butenylcarbonyl group, 2-pentenylcarbonyl group, 2-hexenylcarbonyl group, etc.
- (Xii) linear alkoxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, n-butoxycarbonyl group, n-pentyloxycarbonyl group, n-hexyloxycarbonyl group, etc.
- (xiii) isopropoxycarbonyl Group, sec-butoxycarbonyl group, tert-butoxycarbonyl group, tert-amyloxycarbonyl group and the like branched alkoxycarbonyl group (xiv) fluoromethoxycarbonyl group, trifluoromethoxycarbonyl group, 2,2,2-trimethyl Alkoxycarbonyl group (xv) vinyloxycarbonyl group, 1-propenyloxycarbonyl group, 2-propenyloxycarbonyl group, 1-methyl-2-propenyl in which part of hydrogen atoms such as fluoroethoxycarbonyl group are substituted with fluorine atoms Xoxycarbonyl group, 1,1-dimethyl-2-propenyloxycarbonyl group, 1-butenyloxycarbonyl group, 2-butenyloxycarbonyl group, 3-butenyloxycarbonyl group, 2-pentenyloxycarbonyl group, 2- Alkenyloxycarbonyl group such as hex
- More preferred specific examples of the -AY group include a methanesulfonyl group, an ethanesulfonyl group, a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, a 2-propynyloxycarbonyl group, and a 2-butynyloxycarbonyl group.
- the range of the above substituent is preferable because electrochemical characteristics in a wide temperature range can be greatly improved.
- the effect of improving electrochemical characteristics over a wide temperature range depends on the substitution position on the benzene ring of R f and X, and those having R f in at least one of the para and meta positions are preferred. Those having X in at least one of the positions are preferred. In particular, those having R f at the meta position are preferred.
- Specific examples of the compound represented by the general formula (I) include compounds represented by the following [Chemical 6] to [Chemical 12].
- structural formulas A1 to A4, A6, A9 to A11, A13, A15, A16, A23 to A33, A35 to A43, B1 to B4, B8 to B13, B15, B24 to B34, B36 to B42, B44, C1 to C3, C8 to C12, C15 to C26, C28 to C33, C35, C36, D1 to D3, D5 to D8, D11 to D22, D24 to D34, D36 to D42, D44 to D57, E1 to E4, E8 to E22, F1 to F4, F6 to F16, F21 are preferred, and structural formulas A2, A3, A6, A9, A15, A16, A25, A29, A35, A36, A40 to A42, B1 to B3, B9, B12, B26, B30, B36 to B38, B41, C1, C2, C8, C10, C12, C15, C22, C28 to C30, C33, C35, 1,
- More preferable specific examples of the compound represented by the general formula (I) include 4-fluoro-3- (trifluoromethyl) phenyl methanesulfonate (Structural Formula A2), 4-fluoro-3- (trifluoro Methyl) phenyl propane-2-sulfonate (structural formula A6), 4-fluoro-3- (trifluoromethyl) phenyl vinyl phonate (structural formula A9), 4-fluoro-3- (trifluoromethyl) phenyl 4-methylbenzenesulfonate (Structural Formula A16), 2-fluoro-3- (trifluoromethyl) phenyl methanesulfonate (Structural Formula A25), 4-fluoro-2- (trifluoromethyl) phenyl methanesulfonate (Structural Formula A29), 3-chloro- 4- (Trifluoromethyl) phenyl methanesulfonate (structure) A35), 4-
- the content of the phenyl ester compound in which the benzene ring represented by the general formula (I) is substituted with both a halogen atom and a fluoroalkyl group is 0.001 in the nonaqueous electrolytic solution. ⁇ 5% by weight is preferred. If the content is 5% by mass or less, a coating film is excessively formed on the electrode, and there is little risk of deterioration in cycle characteristics when the battery is used at a high temperature. The formation is sufficient, and the effect of improving the cycle characteristics when the battery is used at a high voltage is enhanced.
- the content is preferably 0.01% by mass or more, and more preferably 0.1% by mass or more in the nonaqueous electrolytic solution.
- the upper limit is preferably 4% by mass or less, and more preferably 2% by mass or less.
- a phenyl ester compound in which the benzene ring represented by the general formula (I) is substituted with both a halogen atom and a fluoroalkyl group is combined with a nonaqueous solvent and an electrolyte salt described below.
- the capacity retention rate after the cycle when the electricity storage device is used at a high temperature can be improved, and a unique effect of suppressing gas generation is exhibited.
- Nonaqueous solvent examples of the nonaqueous solvent used in the nonaqueous electrolytic solution of the present invention include cyclic carbonates, chain esters, lactones, ethers, and amides, and it is preferable that both cyclic carbonates and chain esters are included.
- chain ester is used as a concept including chain carbonate and chain carboxylic acid ester.
- the cyclic carbonate include one or more selected from ethylene carbonate (EC), propylene carbonate (PC), 1,2-butylene carbonate, 2,3-butylene carbonate, and a cyclic carbonate having a fluorine atom or an unsaturated bond.
- EC electroactive polymer
- PC polymer containing at least one or more selected from EC, PC, and a cyclic carbonate having a fluorine atom or an unsaturated bond
- the cyclic carbonate having a fluorine atom include 4-fluoro-1,3-dioxolan-2-one (FEC), trans or cis-4,5-difluoro-1,3-dioxolan-2-one (hereinafter, both One or more selected from “DFEC” as a whole is preferable, and FEC is more preferable.
- FEC 4-fluoro-1,3-dioxolan-2-one
- DFEC trans or cis-4,5-difluoro-1,3-dioxolan-2-one
- cyclic carbonates having unsaturated bonds such as carbon-carbon double bonds and carbon-carbon triple bonds
- ON (EEC) and the like can be mentioned, and one or more selected from VC, VEC, and EEC are preferable.
- the content of the cyclic carbonate having an unsaturated bond is preferably 0.07% by volume or more, more preferably 0.2% by volume or more, further preferably 0.7% by volume, based on the total volume of the nonaqueous solvent. Further, the upper limit thereof is preferably 7% by volume or less, more preferably 4% by volume or less, and still more preferably 2.5% by volume or less. This is preferable because the cycle characteristics when used in the above are improved.
- the content of the cyclic carbonate having a fluorine atom is preferably 0.07% by volume or more, more preferably 4% by volume or more, still more preferably 7% by volume or more, based on the total volume of the nonaqueous solvent.
- the upper limit is preferably 35% by volume or less, more preferably 25% by volume or less, and even more preferably 15% by volume or less. This increases the stability of the coating, and improves the cycle characteristics when the electricity storage device is used at a high temperature. This is preferable.
- the non-aqueous solvent contains both the cyclic carbonate having an unsaturated bond and the cyclic carbonate having a fluorine atom
- the content ratio of the cyclic carbonate having an unsaturated bond to the content of the cyclic carbonate having a fluorine atom is preferably 0.2% or more, more preferably 3% or more, further preferably 7% or more
- the upper limit thereof is preferably 40% or less, more preferably 30% or less, still more preferably 15% or less.
- the stability of the coating is increased, and the cycle characteristics when the electricity storage device is used at a high temperature is improved, which is particularly preferable.
- the non-aqueous solvent contains ethylene carbonate and / or propylene carbonate
- the resistance of the film formed on the electrode is reduced, and the content of ethylene carbonate and / or propylene carbonate is preferably equal to the total volume of the non-aqueous solvent.
- it is preferably 3% by volume or more, more preferably 5% by volume or more, further preferably 7% by volume or more, and the upper limit thereof is preferably 45% by volume or less, more preferably 35% by volume or less, further Preferably it is 25 volume% or less.
- these solvents may be used alone, and when two or more types are used in combination, it is preferable because the electrochemical characteristics when the electricity storage device is used at a high temperature is further improved, and three or more types are combined. It is particularly preferred to use it.
- Preferred combinations of these cyclic carbonates include EC and PC, EC and VC, PC and VC, VC and FEC, EC and FEC, PC and FEC, FEC and DFEC, EC and DFEC, PC and DFEC, VC and DFEC , VEC and DFEC, VC and EEC, EC and EEC, EC and PC and VC, EC and PC and FEC, EC and VC and FEC, EC and VC and VEC, EC and VC and EEC, EC and EEC and FEC, PC And VC and FEC, EC and VC and DFEC, PC and VC and DFEC, EC and PC and VC and FEC, EC and PC and VC and FEC,
- EC and PC EC and VC
- EC and FEC PC and FEC
- EC and PC and VC EC and PC and VC
- EC and PC and FEC EC and VC and FEC
- EC and VC and EEC EC and EEC
- EC and EEC A combination of FEC, PC / VC / FEC, EC / PC / VC / FEC, or the like is more preferable.
- the cyclic carbonate containing EC or PC and the cyclic carbonate which has a fluorine atom or an unsaturated bond is preferable, and the cyclic carbonate containing EC or PC and FEC or VC is still more preferable.
- chain ester examples include one or more asymmetric chain carbonates selected from methyl ethyl carbonate (MEC), methyl propyl carbonate (MPC), methyl isopropyl carbonate (MIPC), methyl butyl carbonate, ethyl propyl carbonate, and the like, dimethyl carbonate ( One or more symmetrical chain carbonates selected from DMC), diethyl carbonate (DEC), dipropyl carbonate, dibutyl carbonate, and the like, pivalate esters (MPV) such as methyl pivalate, ethyl pivalate, propyl pivalate, and propionic acid
- Preferred examples include chain carboxylic acid esters such as methyl (MP), ethyl propionate (EP), methyl acetate (MA), ethyl acetate (EA), and n-propyl acetate (PA).
- an asymmetric chain carbonate because the cycle characteristics when the electricity storage device is used at a high voltage is improved and the amount of gas generation tends to be reduced.
- These solvents may be used singly or in combination of two or more, since the cycle characteristics when the electricity storage device is used at a high temperature is improved and the amount of gas generated is reduced.
- the content of the chain ester is not particularly limited, but it is preferably used in the range of 60 to 90% by volume with respect to the total volume of the nonaqueous solvent. If the content is 60% by volume or more, preferably 65% by volume or more, the effect of lowering the viscosity of the non-aqueous electrolyte can be sufficiently obtained. % Or less, the electrical conductivity of the non-aqueous electrolyte is sufficiently increased, and the electrochemical characteristics when the electricity storage device is used at a high temperature is improved.
- chain carbonate when using chain carbonate, it is preferable to use 2 or more types. Further, it is more preferable that both a symmetric chain carbonate and an asymmetric chain carbonate are included, and it is more preferable that the symmetric chain carbonate includes diethyl carbonate (DEC), and the asymmetric chain carbonate includes methyl ethyl carbonate (MEC). More preferably, both diethyl carbonate (DEC) and methyl ethyl carbonate (MEC) are included.
- the content of the symmetric chain carbonate is preferably larger than the content of the asymmetric chain carbonate.
- the volume ratio of the symmetric chain carbonate in the chain carbonate is preferably 51% by volume or more, more preferably 55% by volume or more, still more preferably 60% by volume or more, and still more preferably 65% by volume or more.
- the upper limit is preferably 95% by volume or less, more preferably 90% by volume or less, still more preferably 85% by volume or less, and still more preferably 80% by volume or less. In the above case, it is preferable because cycle characteristics when the electricity storage device is used at a higher temperature are improved.
- the ratio between the cyclic carbonate and the chain carbonate is preferably 10:90 to 45:55 in terms of the cyclic carbonate: chain carbonate (volume ratio) from the viewpoint of improving the electrochemical characteristics when the electricity storage device is used at a high temperature. 85 to 40:60 is more preferable, and 20:80 to 35:65 is particularly preferable.
- additives for the purpose of improving electrochemical characteristics when the electricity storage device is used at a higher temperature, it is preferable to add other additives to the non-aqueous electrolyte.
- other additives include phosphate esters, nitriles, triple bond-containing compounds, S ⁇ O bond-containing compounds, acid anhydrides, cyclic phosphazene compounds, diisocyanate compounds, cyclic acetals, and aromatics having branched alkyl groups. Examples thereof include compounds and aromatic compounds.
- the phosphate ester include trimethyl phosphate, triethyl phosphate, tributyl phosphate, and trioctyl phosphate.
- nitrile examples include acetonitrile, propionitrile, succinonitrile, 2-ethylsuccinonitrile, glutaronitrile, 2-methylglutaronitrile, 3-methylglutaronitrile, adiponitrile, and pimelonitrile.
- triple bond-containing compound examples include methyl 2-propynyl carbonate, 2-propynyl acetate, 2-propynyl formate, 2-propynyl methacrylate, 2-propynyl methanesulfonate, 2-propynyl vinyl sulfonate, di (2-propynyl) oxalate Glutaric acid di (2-propynyl), 2-butyne-1,4-diyl dimethanesulfonate, and 2-butyne-1,4-diyl diformate, 2-propynyl 2- (diethoxyphosphoryl) acetate, 2-propynyl And 2-((methanesulfonyl) oxy) propanoate.
- S ⁇ O bond-containing compound examples include sultone compounds, cyclic sulfite compounds, sulfonic acid ester compounds, and the like.
- sultone compounds include 1,3-propane sultone, 1,3-butane sultone, 1,4-butane sultone, 2,4-butane sultone, 1,3-propene sultone, 2,2-dioxide-1,2-oxathiolane-4 -Yl acetate, 5,5-dimethyl-1,2-oxathiolan-4-one 2,2-dioxide, methylene methane disulfonate and the like.
- cyclic sulfite compounds include ethylene sulfite, hexahydrobenzo [1,3,2] dioxathiolane-2-oxide (also referred to as 1,2-cyclohexanediol cyclic sulfite), 5-vinyl-hexahydro1,3, And 2-benzodioxathiol-2-oxide.
- the sulfonic acid ester compound include butane-2,3-diyl dimethanesulfonate, butane-1,4-diyl dimethanesulfonate, methylenemethane disulfonate, dimethylmethane disulfonate, and the like.
- vinyl sulfone compound examples include divinyl sulfone, 1,2-bis (vinylsulfonyl) ethane, bis (2-vinylsulfonylethyl) ether, vinylsulfonyl fluoride, and the like.
- acid anhydride examples include chain carboxylic acid anhydrides such as acetic anhydride and propionic anhydride, succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, 3-sulfo-propionic anhydride, and the like.
- cyclic phosphazene compound examples include methoxypentafluorocyclotriphosphazene, ethoxypentafluorocyclotriphosphazene, phenoxypentafluorocyclotriphosphazene, ethoxyheptafluorocyclotetraphosphazene, and the like.
- diisocyanate compound examples include 1,4-diisocyanatobutane, 1,5-diisocyanatopentane, 1,6-diisocyanatohexane, 1,7-diisocyanatoheptane, etc. , 3-dioxolane, 1,3-dioxane and the like.
- aromatic compounds having a branched alkyl group examples include cyclohexylbenzene, fluorocyclohexylbenzene compounds (1-fluoro-2-cyclohexylbenzene, 1-fluoro-3-cyclohexylbenzene, 1-fluoro-4-cyclohexylbenzene), tert- Examples thereof include butylbenzene, tert-amylbenzene, 1-fluoro-4-tert-butylbenzene.
- Aromatic compounds include biphenyl, terphenyl (o-, m-, p-isomer), diphenyl ether, fluorobenzene, difluorobenzene (o-, m-, p-isomer), anisole, 2,4-difluoroanisole, Terphenyl partially hydride (1,2-dicyclohexylbenzene, 2-phenylbicyclohexyl, 1,2-diphenylcyclohexane, o-cyclohexylbiphenyl) and the like.
- nitriles one or more selected from nitriles, diisocyanate compounds, cyclic acetals, and aromatic compounds, since the electrochemical characteristics when the electricity storage device is used at a high temperature are further improved.
- nitriles one or more selected from succinonitrile, 2-ethylsuccinonitrile, glutaronitrile, 2-methylglutaronitrile, 3-methylglutaronitrile, adiponitrile, and pimelonitrile are more preferable.
- diisocyanate compounds one or more selected from 1,5-diisocyanatopentane, 1,6-diisocyanatohexane, and 1,7-diisocyanatoheptane is more preferable.
- cyclic acetal compounds 1,3-dioxane is preferred.
- aromatic compounds at least one selected from biphenyl, terphenyl (o-, m-, p-isomer), fluorobenzene, cyclohexylbenzene, tert-butylbenzene, and tert-amylbenzene is more preferable.
- the content of one or more selected from nitriles, diisocyanate compounds, cyclic acetals, and aromatic compounds is preferably 0.001 to 5% by mass in the non-aqueous electrolyte. In this range, the film is sufficiently formed without becoming too thick, and the effect of improving the electrochemical characteristics when the electricity storage device is used at a high temperature is enhanced.
- the content is more preferably 0.005% by mass or more, more preferably 0.01% by mass or more, particularly preferably 0.03% by mass or more in the non-aqueous electrolyte, and the upper limit is 3% by mass or less. More preferred is 2% by mass or less, and particularly preferred is 1.5% by mass or less.
- the inclusion of one or more selected from a triple bond-containing compound, a sultone compound, and a vinyl sulfone compound is preferable because the electrochemical characteristics when the battery is used at a higher temperature are further improved.
- the triple bond-containing compounds 2-propynyl methanesulfonate, 2-propynyl vinylsulfonate, di (2-propynyl) oxalate, 2-butyne-1,4-diyl dimethanesulfonate, 2-propynyl 2- (di-)
- One or more selected from ethoxyphosphoryl) acetate and 2-propynyl 2-((methanesulfonyl) oxy) propanoate are more preferable.
- sultone compounds 1,3-propane sultone, 1,3-propene sultone, 2,2-dioxide-1,2-oxathiolan-4-yl acetate, 5,5-dimethyl-1,2-oxathiolane-4
- sultone compounds 1,3-propane sultone, 1,3-propene sultone, 2,2-dioxide-1,2-oxathiolan-4-yl acetate, 5,5-dimethyl-1,2-oxathiolane-4
- vinyl sulfone compounds one or more selected from divinyl sulfone, bis (2-vinylsulfonylethyl) ether, and vinylsulfonyl fluoride are more preferable.
- the content of one or more selected from triple bond-containing compounds, sultone compounds, and vinylsulfone compounds is preferably 0.001 to 5% by mass in the non-aqueous electrolyte. In this range, the film is sufficiently formed without becoming too thick, and the effect of improving the electrochemical characteristics when the electricity storage device is used at a high temperature is enhanced.
- the content is more preferably 0.005% by mass or more, more preferably 0.01% by mass or more, particularly preferably 0.03% by mass or more in the non-aqueous electrolyte, and the upper limit is 3% by mass or less. More preferred is 2% by mass or less, and particularly preferred is 1.5% by mass or less.
- lithium salt having an oxalic acid skeleton, a lithium salt having a phosphoric acid skeleton, and a sulfonic acid skeleton in a non-aqueous electrolyte It is preferable to include one or more lithium salts selected from lithium salts having the following.
- Specific examples of lithium salts include lithium bis (oxalato) borate (LiBOB), lithium difluoro (oxalato) borate (LiDFOB), lithium tetrafluoro (oxalato) phosphate (LiTFOP), and lithium difluorobis (oxalato) phosphate (LiDFOP).
- the total content of lithium salts such as LiTFMSB and FSO 3 Li is preferably 0.001 to 10% by mass in the non-aqueous electrolyte. If the content is 10% by mass or less, there is little possibility that a film is excessively formed on the electrode and the cycle characteristics are lowered, and if it is 0.001% by mass or more, the formation of the film is sufficient. The effect of improving the characteristics when used at a high voltage is increased.
- the content is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.3% by mass or more, and the upper limit is preferably 5% by mass or less in the non-aqueous electrolyte. 3 mass% or less is more preferable, and 2 mass% or less is still more preferable.
- Electrode salt Preferred examples of the electrolyte salt used in the present invention include the following lithium salts.
- Examples of the lithium salt include inorganic lithium salts such as LiPF 6 , LiBF 4 , LiN (SO 2 F) 2 , LiClO 4 , LiN (SO 2 CF 3 ) 2 , LiN (SO 2 C 2 F 5 ) 2 , LiCF 3 SO 3 , LiC (SO 2 CF 3 ) 3 , LiPF 4 (CF 3 ) 2 , LiPF 3 (C 2 F 5 ) 3 , LiPF 3 (CF 3 ) 3 , LiPF 3 (iso-C 3 F 7 ) 3 , LiPF 5 Lithium salts containing a chain-like fluorinated alkyl group such as (iso-C 3 F 7 ), (CF 2 ) 2 (SO 2 ) 2 NLi, (CF 2 ) 3 (SO 2 ) 2 NLi, etc.
- One or more lithium salts selected from lithium salts having a cyclic fluorinated alkylene chain are preferred.
- at least one selected from LiPF 6 , LiBF 4 , LiN (SO 2 CF 3 ) 2 , LiN (SO 2 C 2 F 5 ) 2 , and LiN (SO 2 F) 2 is preferable, and LiPF 6 is used. It is more preferable.
- the concentration of the lithium salt that is an electrolyte salt is usually preferably 0.3 M or more, more preferably 0.7 M or more, and even more preferably 1.1 M or more with respect to the non-aqueous solvent.
- the upper limit is preferably 2.5M or less, more preferably 2.0M or less, and still more preferably 1.6M or less.
- a preferable combination of these lithium salts includes LiPF 6 , and one or more lithium salts selected from LiBF 4 , LiN (SO 2 CF 3 ) 2 , and LiN (SO 2 F) 2 are non-aqueous.
- the proportion of the lithium salt other than LiPF 6 is preferably 0.01 M or more, more preferably 0.03 M or more, and further preferably 0.04 M or more.
- the upper limit is preferably 0.4 M or less, more preferably 0. .2M or less.
- the non-aqueous electrolyte of the present invention is prepared, for example, by mixing the non-aqueous solvent described above with the benzene ring represented by the general formula (I) with respect to the electrolyte salt and the non-aqueous electrolyte. It can be obtained by adding a phenyl ester compound substituted with both alkyl groups. At this time, it is preferable that the compound added to the non-aqueous solvent and the non-aqueous electrolyte to be used is one that is purified in advance and has as few impurities as possible within a range that does not significantly reduce the productivity.
- the non-aqueous electrolyte of the present invention can be used in the following first and second electricity storage devices, and as the non-aqueous electrolyte, not only a liquid but also a gelled one can be used. Furthermore, the non-aqueous electrolyte of the present invention can be used for a solid polymer electrolyte. In particular, it is preferably used for a first electricity storage device (ie, for a lithium battery) or a second electricity storage device (ie, for a lithium ion capacitor) using a lithium salt as an electrolyte salt, and is used for a lithium battery. More preferably, it is most suitable for use as a lithium secondary battery.
- the lithium battery of the present invention is a generic term for a lithium primary battery and a lithium secondary battery.
- the term lithium secondary battery is used as a concept including a so-called lithium ion secondary battery.
- the lithium battery of the present invention comprises the nonaqueous electrolyte solution in which an electrolyte salt is dissolved in a positive electrode, a negative electrode, and a nonaqueous solvent.
- Components other than the non-aqueous electrolyte, such as a positive electrode and a negative electrode can be used without particular limitation.
- a positive electrode active material for a lithium secondary battery a composite metal oxide with lithium containing one or more selected from cobalt, manganese, and nickel is used.
- lithium composite metal oxides include LiCoO 2 , LiMn 2 O 4 , LiNiO 2 , LiCo 1-x Ni x O 2 (0.01 ⁇ x ⁇ 1), LiCo 1/3 Ni 1/3.
- LiCoO 2 and LiMn 2 O 4 , LiCoO 2 and LiNiO 2 , LiMn 2 O 4 and LiNiO 2 may be used in combination.
- a part of the lithium composite metal oxide may be substituted with another element.
- a part of cobalt, manganese, and nickel is replaced with one or more elements selected from Sn, Mg, Fe, Ti, Al, Zr, Cr, V, Ga, Zn, Cu, Bi, Mo, La, and the like.
- O can be partially substituted with S or F, or can be coated with a compound containing these other elements.
- lithium composite metal oxides such as LiCoO 2 , LiMn 2 O 4 , and LiNiO 2 that can be used at a charged potential of the positive electrode in a fully charged state of 4.3 V or more on the basis of Li are preferable, and LiCo 1-x M x O 2 (where M is one or more elements selected from Sn, Mg, Fe, Ti, Al, Zr, Cr, V, Ga, Zn, Cu, 0.001 ⁇ x ⁇ 0.05), LiCo 1/3 Ni 1/3 Mn 1/3 O 2 , LiNi 1/2 Mn 3/2 O 4 , Li 2 MnO 3 and LiMO 2 (M is a transition metal such as Co, Ni, Mn, Fe)
- M is a transition metal such as Co, Ni, Mn, Fe
- the electrochemical characteristics particularly when the battery is used at a high voltage are likely to deteriorate due to the reaction with the electrolyte during charging. In the battery, it is possible to suppress a decrease in these electrochemical characteristics.
- lithium-containing olivine-type phosphate can also be used as the positive electrode active material.
- a lithium-containing olivine-type phosphate containing one or more selected from iron, cobalt, nickel, and manganese is preferable. Specific examples thereof include LiFePO 4 , LiCoPO 4 , LiNiPO 4 , LiMnPO 4 and the like. Some of these lithium-containing olivine-type phosphates may be substituted with other elements, and some of iron, cobalt, nickel, and manganese are replaced with Co, Mn, Ni, Mg, Al, B, Ti, V, and Nb.
- Cu, Zn, Mo, Ca, Sr, W and Zr can be substituted with one or more elements selected from these, or can be coated with a compound or carbon material containing these other elements.
- a lithium-containing olivine-type phosphate containing at least Co, Ni, Mn such as LiCoPO 4 , LiNiPO 4 , LiMnPO 4, etc.
- the battery voltage becomes higher potential, It is preferable because the effect is likely to appear.
- mold phosphate can also be mixed with the said positive electrode active material, for example, and can be used.
- the positive electrode for lithium primary battery CuO, Cu 2 O, Ag 2 O, Ag 2 CrO 4, CuS, CuSO 4, TiO 2, TiS 2, SiO 2, SnO, V 2 O 5, V 6 O 12 , VO x , Nb 2 O 5 , Bi 2 O 3 , Bi 2 Pb 2 O 5 , Sb 2 O 3 , CrO 3 , Cr 2 O 3 , MoO 3 , WO 3 , SeO 2 , MnO 2 , Mn 2 O 3 , Fe 2 O 3 , FeO, Fe 3 O 4 , Ni 2 O 3 , NiO, CoO 3 , CoO, oxides of one or more metal elements, or chalcogen compounds, sulfur compounds such as SO 2 , SOCl 2, etc. And fluorinated carbon (fluorinated graphite) represented by the general formula (CF x ) n . Of these, MnO 2 , V 2 O 5 , graphite fluoride and the like are preferable.
- the positive electrode conductive agent is not particularly limited as long as it is an electron conductive material that does not cause a chemical change.
- Examples thereof include graphite such as natural graphite (flaky graphite and the like) and artificial graphite, carbon black such as acetylene black, ketjen black, channel black, furnace black, lamp black and thermal black. Further, graphite and carbon black may be appropriately mixed and used.
- the addition amount of the conductive agent to the positive electrode mixture is preferably 1 to 10% by mass, and particularly preferably 2 to 5% by mass.
- the positive electrode is composed of a conductive agent such as acetylene black and carbon black, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), a copolymer of styrene and butadiene (SBR), acrylonitrile and butadiene.
- a conductive agent such as acetylene black and carbon black, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), a copolymer of styrene and butadiene (SBR), acrylonitrile and butadiene.
- PTFE polytetrafluoroethylene
- PVDF polyvinylidene fluoride
- SBR styrene and butadiene
- SBR styrene and butadiene
- acrylonitrile and butadiene acrylonitrile and butadiene.
- binder such as copolymer (NBR), carb
- this positive electrode mixture was applied to a current collector aluminum foil, a stainless steel lath plate, etc., dried and pressure-molded, and then subjected to vacuum at a temperature of about 50 ° C. to 250 ° C. for about 2 hours. It can be manufactured by heat treatment.
- the density of the part except the collector of the positive electrode is usually at 1.5 g / cm 3 or more, to further enhance the capacity of the battery, is preferably 2 g / cm 3 or more, more preferably, 3 g / cm 3 It is above, More preferably, it is 3.6 g / cm 3 or more. In addition, as an upper limit, 4 g / cm ⁇ 3 > or less is preferable.
- Examples of the negative electrode active material for a lithium secondary battery include lithium metal, lithium alloy, and a carbon material capable of occluding and releasing lithium (easily graphitized carbon and a (002) plane spacing of 0.37 nm or more).
- One or more selected from lithium compounds and the like can be used in combination.
- a highly crystalline carbon material such as artificial graphite and natural graphite
- the lattice spacing (002) of the lattice plane ( 002 ) is 0.00.
- a carbon material having a graphite type crystal structure of 340 nm (nanometer) or less, particularly 0.335 to 0.337 nm.
- a mechanical action such as compression force, friction force, shear force, etc.
- the density of the portion excluding the current collector of the negative electrode can be obtained from X-ray diffraction measurement of the negative electrode sheet when pressure-molded to a density of 1.5 g / cm 3 or more.
- the ratio I (110) / I (004) of the peak intensity I (110) of the (110) plane of the graphite crystal and the peak intensity I (004) of the (004) plane is 0.01 or more, the temperature becomes even wider.
- electrochemical characteristics are improved, more preferably 0.05 or more, and still more preferably 0.1 or more.
- an upper limit is preferable 0.5 or less, and 0.3 or less is more preferable.
- the highly crystalline carbon material is covered with a carbon material that is less crystalline than the core material, because the electrochemical characteristics when the battery is used at a high voltage are further improved.
- the crystallinity of the coating carbon material can be confirmed by TEM.
- the lithium secondary battery according to the present invention When a highly crystalline carbon material is used, it reacts with the non-aqueous electrolyte during charging and tends to lower the electrochemical characteristics at low or high temperatures due to an increase in interface resistance. However, in the lithium secondary battery according to the present invention, The electrochemical characteristics when the battery is used at a high temperature are improved.
- Examples of the metal compound capable of inserting and extracting lithium as the negative electrode active material include Si, Ge, Sn, Pb, P, Sb, Bi, Al, Ga, In, Ti, Mn, Fe, Co, Ni, and Cu. , Zn, Ag, Mg, Sr, Ba, and other compounds containing at least one metal element.
- These metal compounds may be used in any form such as a simple substance, an alloy, an oxide, a nitride, a sulfide, a boride, and an alloy with lithium, but any of a simple substance, an alloy, an oxide, and an alloy with lithium. Is preferable because the capacity can be increased.
- those containing at least one element selected from Si, Ge and Sn are preferable, and those containing one or more elements selected from Si and Sn are particularly preferable because the capacity of the battery can be increased.
- the ratio of the metal compound capable of occluding and releasing lithium and the carbon material is a mixture of the carbon material and the carbon material.
- the carbon material is preferably 10% by mass or more based on the total mass of the metal compound capable of occluding and releasing lithium in the negative electrode mixture, 30 More preferably, it is at least mass%.
- the carbon material is preferably 98% by mass or less, and more preferably 90% by mass or less based on the total mass of the metal compound capable of inserting and extracting lithium.
- the nonaqueous electrolytic solution of the present invention containing a phenyl ester compound in which the benzene ring represented by the general formula (I) is substituted with both a halogen atom and a fluoroalkyl group, and lithium as a negative electrode active material as described above.
- the phenyl ester compound represented by the general formula (I) generally acts on both the metal compound and the carbon material, so It is considered that the electrical contact between the metal compound and the carbon material having a large volume change due to occlusion and release is reinforced, and the cycle characteristics are further improved.
- the negative electrode is kneaded using the same conductive agent, binder, and high-boiling solvent as in the production of the positive electrode, and then the negative electrode mixture is applied to the copper foil of the current collector. After being dried and pressure-molded, it can be produced by heat treatment under vacuum at a temperature of about 50 ° C. to 250 ° C. for about 2 hours.
- the density of the portion excluding the current collector of the negative electrode is usually 1.1 g / cm 3 or more, and is preferably 1.5 g / cm 3 or more, particularly preferably 1.7 g in order to further increase the capacity of the battery. / Cm 3 or more.
- 2 g / cm ⁇ 3 > or less is preferable.
- examples of the negative electrode active material for a lithium primary battery include lithium metal and lithium alloy.
- the structure of the lithium battery is not particularly limited, and a coin-type battery, a cylindrical battery, a square battery, a laminated battery, or the like having a single-layer or multi-layer separator can be applied. Although it does not restrict
- the lithium secondary battery according to the present invention has excellent electrochemical characteristics even when the end-of-charge voltage of the positive electrode with respect to lithium metal is 4.2 V or higher, particularly 4.3 V or higher, and further has excellent characteristics even at 4.4 V or higher. is there.
- the current value is not particularly limited, but is usually used in the range of 0.1 to 30C.
- the lithium battery in the present invention can be charged / discharged at ⁇ 40 to 100 ° C., preferably ⁇ 10 to 80 ° C.
- a method of providing a safety valve on the battery lid or cutting a member such as a battery can or a gasket can be employed.
- the battery lid can be provided with a current interruption mechanism that senses the internal pressure of the battery and interrupts the current.
- LiPF 6 LiPF 6
- the nonaqueous electrolytic solution of the present invention can improve the charge / discharge characteristics of a lithium ion capacitor used at a high voltage.
- the phenyl ester compound in which the benzene ring, which is a novel compound of the present invention, is substituted with both a halogen atom and a fluoroalkyl group is represented by the following general formula (II).
- R f 1 represents a fluoroalkyl group having 1 to 6 carbon atoms
- X 1 represents a halogen atom.
- L 4 represents an alkylene group having 1 to 8 carbon atoms
- R 1 represents an alkyl group having 1 to 6 carbon atoms.
- Y that may be fluorine atoms
- Y that may be hydrogen atoms
- Y 1 is a trifluoromethyl group.
- alkyl group alkenyl group, alkynyl group, aryl group, alkylene group, alkenylene group, and alkynylene group
- at least one hydrogen atom of each group may be substituted with a halogen atom.
- the halogen atom as the substituent X 1 is preferably a fluorine atom or a bromine atom, more preferably a fluorine atom.
- Substituent R f 1 , Substituent A 1 , Substituent Y 1 , Substituent L 3 , Substituent L 4 , and Substituent R 1 are the same as in the description of Formula (I), and the preferred examples are also the same. Therefore, in this column, the description is omitted to avoid duplication.
- the phenyl ester compound of the present invention can be synthesized by the following methods (a) to (c), but is not limited to these methods.
- Method (a) is a method in which the phenol compound and the halide compound are reacted in the presence or absence of a solvent and in the presence or absence of a base.
- the said phenol compound and the said halide compound can also use a commercial item, or can also synthesize
- the amount of the halide compound used is preferably 0.8 to 20 mol, more preferably 0.9 to 10 mol, still more preferably 1 to 5 mol, relative to 1 mol of the phenol compound. It is.
- Examples of the halide compound used in the method (a) include methanesulfonyl chloride, 4-methylbenzenesulfonyl chloride, methyl chloroformate, ethyl chloroformate, vinyl chloroformate, 2-propenyl chloroformate, 2-propynyl chloroformate, chloroformate
- Examples include phenyl acid, 4-methylphenyl chloroformate, 4-fluorophenyl chloroformate, 2- (dimethoxyphosphoryl) acetyl chloride, 2- (diethoxyphosphoryl) acetyl chloride and the like.
- the reaction proceeds without solvent, but a solvent can be used if it is inert to the reaction.
- Solvents used are aliphatic hydrocarbons such as heptane and cyclohexane, halogenated hydrocarbons such as dichloromethane and dichloroethane, aromatic hydrocarbons such as toluene and xylene, halogenated aromatic hydrocarbons such as chlorobenzene and fluorobenzene, diisopropyl Ethers such as ether, dioxane and dimethoxyethane, esters such as ethyl acetate, butyl acetate, dimethyl carbonate and diethyl carbonate, nitriles such as acetonitrile and propionitrile, sulfoxides such as dimethyl sulfoxide and sulfolane, N, N-dimethylformamide, N , N-dimethylacetamide and the like, or a mixture thereof.
- aliphatic or aromatic hydrocarbons such as heptane, cyclohexane, toluene, ethyl acetate, dimethyl carbonate, and esters are preferable.
- the amount of the solvent used is preferably 0 to 30 parts by mass, more preferably 1 to 10 parts by mass with respect to 1 part by mass of the phenol compound.
- the reaction proceeds in the absence of a base, but the presence of a base is preferable because the reaction is promoted.
- a base both inorganic bases and organic bases can be used.
- the inorganic base include potassium carbonate, sodium carbonate, calcium hydroxide, and calcium oxide.
- Organic bases include linear or branched aliphatic tertiary amines, unsubstituted or substituted imidazoles, pyridines, pyrimidines, among which trimethylamine, triethylamine, tripropylamine, tributylamine, diisopropyl Trialkylamines such as pluethylamine and pyridines such as pyridine and N, N-dimethylaminopyridine are preferred.
- the amount of the base used is preferably 0.8 to 5 mol, more preferably 1 to 3 mol, and still more preferably 1 to 1.5 mol, with respect to 1 mol of the phenol compound.
- the lower limit of the reaction temperature is preferably ⁇ 20 ° C.
- the upper limit of the reaction temperature is preferably 80 ° C. or less, and more preferably 50 ° C. or less.
- the reaction time can be appropriately changed depending on the reaction temperature and scale, but if the reaction time is too short, unreacted substances remain, and conversely if the reaction time is too long, there is a risk of decomposition of the reaction product or side reaction. Is 0.1 to 12 hours, more preferably 0.2 to 6 hours.
- Method (b) is a method in which the phenol compound and the carbonylating agent are reacted in the presence or absence of a solvent.
- the amount of the carbonylating agent used is preferably 0.4 to 5 mol, more preferably 0.5 to 3 mol, still more preferably 0.5 mol, per 1 mol of the phenol compound. ⁇ 1 mole.
- the carbonylating agent used in the method (b) include N, N′-carbonyldiimidazole, phenyl chloroformate, and triphosgene.
- the reaction proceeds without solvent, but a solvent can be used if it is inert to the reaction.
- the solvent used is an aliphatic hydrocarbon, halogenated hydrocarbon, aromatic hydrocarbon, halogenated aromatic hydrocarbon, ether, ester, nitrile, sulfoxide, amide, or a mixture thereof described in the method (a). Can be mentioned. Among these, aliphatic or aromatic hydrocarbons such as heptane, cyclohexane, and toluene that are difficult to mix with water are preferable.
- the amount of the solvent used is preferably 0 to 30 parts by mass, more preferably 1 to 10 parts by mass with respect to 1 part by mass of the phenol compound.
- the reaction proceeds in the absence of a base, but the presence of a base is preferable because the reaction is promoted.
- a base both inorganic bases and organic bases can be used.
- an inorganic base and an organic base the same thing as what was demonstrated by the (a) method is mentioned preferably.
- the amount of the base used is preferably 0.8 to 5 mol, more preferably 1 to 3 mol, and still more preferably 1 to 1.5 mol, with respect to 1 mol of the phenol compound.
- the lower limit of the reaction temperature is preferably ⁇ 20 ° C. or higher, and more preferably 0 ° C. or higher from the viewpoint of not reducing the reactivity.
- the upper limit of the reaction temperature is preferably 80 ° C. or less, and more preferably 50 ° C. or less.
- the reaction time of the method (b) can be appropriately changed depending on the reaction temperature and scale, but if the reaction time is too short, unreacted substances remain. Conversely, if the reaction time is too long, there is a risk of decomposition of the reaction product or side reaction. Therefore, it is preferably 0.1 to 24 hours, more preferably 0.2 to 12 hours.
- the phenol compound and the carboxylic acid compound corresponding to the —A 1 —Y 1 group of the general formula (II) are added in the presence or absence of a solvent, in the presence of an acid catalyst or a dehydrating agent. And the condensation method.
- the amount of the carboxylic acid compound used is preferably 0.8 to 20 mol, more preferably 0.9 to 10 mol, still more preferably 1 to 5 mol, relative to 1 mol of the phenol compound. It is.
- the carboxylic acid compound used in the method (c) include formic acid, acetic acid, 2- (diethoxyphosphoryl) acetic acid and the like.
- the reaction proceeds without solvent, but a solvent can be used if it is inert to the reaction.
- the solvent used is an aliphatic hydrocarbon, halogenated hydrocarbon, aromatic hydrocarbon, halogenated aromatic hydrocarbon, ether, ester, nitrile, sulfoxide, amide, or a mixture thereof described in the method (a). Can be mentioned. Of these, aliphatic or aromatic hydrocarbons such as heptane, cyclohexane and toluene are preferred.
- the amount of the solvent used is preferably 0 to 30 parts by mass, more preferably 1 to 10 parts by mass with respect to 1 part by mass of the phenol compound.
- the acid catalyst that can be used includes mineral acids such as sulfuric acid and phosphoric acid, sulfonic acids such as paratoluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, and trifluoro Examples include boric acid, Lewis acids such as tetraisopropoxytitanium, solid acids such as zeolite and acidic resin, or mixed acids thereof. Among these, paratoluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, etc. Lewis acids such as sulfonic acid and tetraisopropoxy titanium are preferred.
- the amount of the catalyst used is preferably 0.001 to 5 mol, more preferably 0.01 to 1 mol, still more preferably 0.01 to 1 mol of the phenol compound from the viewpoint of suppressing side reactions. ⁇ 0.3 mol.
- usable dehydrating agents are dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (WSC), N, N′-carbonyldiimidazole, di-2- Examples thereof include one or more selected from pyridyl carbonate, phenyl dichlorophosphate, ethyl diethylazodicarboxylate and a mixture of triphenylphosphine.
- the amount of the dehydrating agent to be used is preferably 0.8 to 10 mol, more preferably 0.9 to 5 mol, and still more preferably 1 to 3 mol with respect to 1 mol of the phenol compound.
- the lower limit of the reaction temperature when using an acid catalyst is preferably 0 ° C. or higher, and more preferably 20 ° C. or higher from the viewpoint of not reducing the reactivity.
- the upper limit of the reaction temperature is preferably 200 ° C. or less, and more preferably 150 ° C. or less.
- the lower limit of the reaction temperature when using the dehydrating agent is preferably ⁇ 20 ° C. or higher, and more preferably 0 ° C. or higher from the viewpoint of not reducing the reactivity.
- the upper limit of the reaction temperature is preferably 100 ° C.
- reaction time of the method (c) can be appropriately changed depending on the reaction temperature and scale. However, if the reaction time is too short, unreacted substances remain. Therefore, it is preferably 0.1 to 24 hours, more preferably 0.2 to 12 hours.
- Examples 1 to 40, Comparative Examples 1 to 3 [Production of lithium ion secondary battery] 94% by mass of LiNi 1/3 Mn 1/3 Co 1/3 O 2 and 3% by mass of acetylene black (conductive agent) are mixed, and 3% by mass of polyvinylidene fluoride (binder) is previously added to 1-methyl-2-
- a positive electrode mixture paste was prepared by adding to and mixing with the solution dissolved in pyrrolidone. This positive electrode mixture paste was applied to one side of an aluminum foil (current collector), dried and pressurized, and cut into a predetermined size to produce a belt-like positive electrode sheet. The density of the portion excluding the current collector of the positive electrode was 3.6 g / cm 3 .
- the ratio of the peak intensity I (110) of the (110) plane of the graphite crystal to the peak intensity I (004) of the (004) plane [I (110) / I (004)] was 0.1.
- the positive electrode sheet obtained above, a separator made of a microporous polyethylene film, and the negative electrode sheet obtained above are laminated in this order, and a non-aqueous electrolyte solution having the composition shown in Tables 1 and 2 is added to obtain a laminate type battery. Produced.
- Example 41 and Comparative Example 4 In place of the positive electrode active material used in Example 1 and Comparative Example 1, a positive electrode sheet was prepared using LiNi 1/2 Mn 3/2 O 4 (positive electrode active material). 94% by mass of LiNi 1/2 Mn 3/2 O 4 coated with amorphous carbon and 3% by mass of acetylene black (conductive agent) are mixed, and 3% by mass of polyvinylidene fluoride (binder) is previously added to 1- A positive electrode mixture paste was prepared by adding to and mixing with the solution dissolved in methyl-2-pyrrolidone.
- LiNi 1/2 Mn 3/2 O 4 positive electrode active material
- 94% by mass of LiNi 1/2 Mn 3/2 O 4 coated with amorphous carbon and 3% by mass of acetylene black (conductive agent) are mixed, and 3% by mass of polyvinylidene fluoride (binder) is previously added to 1-
- a positive electrode mixture paste was prepared by adding to and mixing with the solution dissolved in methyl-2-pyrrolidone.
- This positive electrode mixture paste was applied to one side of an aluminum foil (current collector), dried, pressurized and cut into a predetermined size to produce a positive electrode sheet, and the end-of-charge voltage during battery evaluation
- a laminate type battery was prepared and evaluated in the same manner as in Example 1 and Comparative Example 1 except that 4.8 V and discharge end voltage were set to 2.7 V. The results are shown in Table 4.
- a negative electrode sheet was prepared using lithium titanate Li 4 Ti 5 O 12 (negative electrode active material) instead of the negative electrode active material used in Example 1 and Comparative Example 1. 80% by mass of lithium titanate Li 4 Ti 5 O 12 and 15% by mass of acetylene black (conductive agent) are mixed, and 5% by mass of polyvinylidene fluoride (binder) is previously dissolved in 1-methyl-2-pyrrolidone.
- a negative electrode mixture paste was prepared by adding to the solution and mixing. This negative electrode mixture paste was applied to one side of a copper foil (current collector), dried, pressurized and cut into a predetermined size to produce a negative electrode sheet, and a charge termination voltage during battery evaluation.
- a laminated battery was prepared in the same manner as in Example 1 and Comparative Example 1, except that the discharge end voltage was 1.2 V and the composition of the non-aqueous electrolyte was changed to a predetermined one. The battery was evaluated. The results are shown in Table 5.
- the non-aqueous electrolyte of the present invention also has an effect of improving the discharge characteristics when the lithium primary battery is used at a high temperature and the charge / discharge characteristics of the lithium ion capacitor.
- the electricity storage device using the non-aqueous electrolyte of the present invention is useful as an electricity storage device such as a lithium secondary battery and a lithium ion capacitor having excellent electrochemical characteristics when the battery is used at a high temperature.
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Abstract
Description
また、リチウム二次電池の負極としては、リチウム金属、リチウムを吸蔵及び放出可能な金属化合物(金属単体、酸化物、リチウムとの合金等)、炭素材料が知られている。特に、炭素材料のうち、例えばコークス、黒鉛(人造黒鉛、天然黒鉛)等のリチウムを吸蔵及び放出することが可能な炭素材料を用いた非水系電解液二次電池が広く実用化されている。上記の負極材料はリチウム金属と同等の極めて卑な電位でリチウムと電子を貯蔵・放出するために、多くの溶媒が還元分解を受ける可能性を有しており、負極材料の種類に拠らず負極上で電解液中の溶媒が一部還元分解してしまい、分解物の沈着、ガス発生、電極の膨れにより、リチウムイオンの移動が妨げられ、特に電池を高温で使用した場合のサイクル特性等の電池特性を低下させる問題や、電極の膨れにより電池が変形する等の問題があった。更に、リチウム金属やその合金、スズ又はケイ素等の金属単体や酸化物を負極材料として用いたリチウム二次電池は、初期の容量は高いもののサイクル中に微粉化が進むため、炭素材料の負極に比べて非水溶媒の還元分解が加速的に起こり、電池容量やサイクル特性のような電池性能が大きく低下することや、電極の膨れにより電池が変形する等の問題が知られている。
特許文献2には、2,4-ジフルオロフェニル メタンスルホネートのようなスルホン酸フェニル化合物を含む電解液を用いると、電池の低温サイクル特性を向上させることができることが記載されている。
特許文献3には、2-トリフルオロメチルフェニル メタンスルホネートのようなスルホン酸フェニル化合物を含有する電解液を用いると、広い温度範囲での電気化学特性に優れたリチウム電池が得られることが記載されている。
そこで、本発明者らは、上記課題を解決するために鋭意研究を重ねた結果、特定のベンゼン環がハロゲン原子とフルオロアルキル基の両方で置換されたフェニルエステル化合物を非水電解液に添加することにより、蓄電デバイスを高温で使用した場合のサイクル後の容量維持率を向上させることができ、かつガス発生を抑制させることができることを見出し、本発明を完成した。
前記アルキル基、アルケニル基、アルキニル基、アリール基、アルキレン基、アルケニレン基、及びアルキニレン基は、各々の基の少なくとも一つの水素原子がハロゲン原子で置換されていてもよい。)
前記アルキル基、アルケニル基、アルキニル基、アリール基、アルキレン基、アルケニレン基、及びアルキニレン基は、各々の基の少なくとも一つの水素原子がハロゲン原子で置換されていてもよい。)
本発明の非水電解液は、非水溶媒に電解質が溶解されている非水電解液において、前記一般式(I)で表されるベンゼン環がハロゲン原子とフルオロアルキル基の両方で置換されたフェニルエステル化合物を含有することを特徴とする非水電解液である。
前記一般式(I)で表されるフェニルエステル化合物は、求電子性の高いアルカンスルホニル基、アルキルカルボニル基、アルコキシカルボニル基等の官能基と、かさ高く脱離しない電子吸引基であるフルオロアルキル基、及び強力な電子吸引基であるハロゲン原子の両方を持つフェニル基を有する。求電子性の高い官能基と電子吸引基を持つことで化合物の分解性が向上し、負極上でベンゼン環同士が重合し、耐熱性の高いベンゼン環由来の被膜を形成する。更にフルオロアルキル基がかさ高く脱離しない置換基であるため過度の重合が抑制される。したがって、かさ高く電子引性の置換基のみを持つ化合物、例えば4-(トリフルオロメチル)フェニル アセテートや強力な電子吸引基のみを持つ化合物、例えば2,4-ジフルオロフェニル アセテートでは達成し得ない、著しい高温サイクル特性の改善が得られたものと考えられる。
前記アルキル基、アルケニル基、アルキニル基、アリール基、アルキレン基、アルケニレン基、及びアルキニレン基は、各々の基の少なくとも一つの水素原子がハロゲン原子で置換されていてもよい。)
前記一般式(I)のRfは少なくとも1つの水素原子がフッ素原子で置換された炭素数1~6のフルオロアルキル基を示し、炭素数1又は2のフルオロアルキル基がより好ましく、炭素数1のフルオロアルキル基が更に好ましい。
前記Rfであるフルオロアルキル基の具体例としてはフルオロメチル基、ジフルオロメチル基、トリフルオロメチル基、2,2,2-トリフルオロエチル基、パーフルオロエチル基、パーフルオロプロピル基、パーフルオロブチル基等が好適に挙げられる。これらの中でも、ジフルオロメチル基、トリフルオロメチル基、2,2,2-トリフルオロエチル基、パーフルオロエチル基等の炭素数1又は2のフルオロアルキル基が好ましく、ジフルオロメチル基、トリフルオロメチル基等の炭素数1のフルオロアルキル基が更に好ましい。
前記一般式(I)のp及びqは1~4の整数を示し、(p+q)は5以下である。p及びqは、それぞれ1~2がより好ましく、1が更に好ましい。
特にAが-C(=O)-L2-P(=O)(OR)-O-、又は-P(=O)(OR)-O-の場合は、炭素数1~3のアルキル基が好ましい。
L1は、少なくとも一つの水素原子がハロゲン原子で置換されていてもよい炭素数2~7のアルキレン基、少なくとも一つの水素原子がハロゲン原子で置換されていてもよい炭素数2~6のアルケニレン基、少なくとも一つの水素原子がハロゲン原子で置換されていてもよい炭素数2~6のアルキニレン基、又は直接結合(置換基なし)が好ましく、炭素数2~7のアルキレン基、炭素数2~6のアルケニレン基、炭素数2~6のアルキニレン基、又は直接結合がより好ましい。
L2は、少なくとも一つの水素原子がハロゲン原子で置換されていてもよい炭素数1~4のアルキレン基が好ましく、少なくとも一つの水素原子がハロゲン原子で置換されていてもよい炭素数1又は2のアルキレン基がより好ましい。
Rは、少なくとも一つの水素原子がハロゲン原子で置換されていてもよい炭素数1~4のアルキル基が好ましく、炭素数1~3のアルキル基がより好ましい。
(i)フルオロスルホニル基、メタンスルホニル基、エタンスルホニル基、プロパン-1-スルホニル基、ブタン-1-スルホニル基、ペンタン-1-スルホニル基、ヘキサン-1-スルホニル基等の直鎖のアルカンスルホニル基
(ii)プロパン-2-スルホニル基、ブタン-2-スルホニルスルホニル基、2-メチルプロパン-2-スルホニル基、2-メチルブタン-2-スルホニル基等の分枝鎖のアルカンスルホニル基
(iii)ビニルスルホニル基、2-プロペン-1-スルホニル基、2-プロペン-2-スルホニル基等のアルケニルスルホニル基
(iv)フルオロメタンスルホニル基、トリフルオロメタンスルホニル基、2,2,2-トリフルオロエタンスルホニル基等の水素原子の一部がフッ素原子で置換されたアルカンスルホニル基
(v)ベンゼンスルホニル基、2-メチルベンゼンスルホニル基、3-メチルベンゼンスルホニル基、4-メチルベンゼンスルホニル基、4-tert-ブチルベンゼンスルホニル基、2,4,6-トリメチルベンゼンスルホニル基、2-フルオロベンゼンスルホニル基、3-フルオロベンゼンスルホニル基、4-フルオロベンゼンスルホニル基、2,4-ジフルオロベンゼンスルホニル基、2,6-ジフルオロベンゼンスルホニル基、3,4-ジフルオロベンゼンスルホニル基、2,4,6-トリフルオロベンゼンスルホニル基、ペンタフルオロベンゼンスルホニル基、4-(トリフルオロメチル)ベンゼンスルホニル基等のアリールスルホニル基
(vii)イソプロピルカルボニル基、sec-ブチルカルボニル基、tert-ブチルカルボニル基、tert-アミルカルボニル基等の分枝鎖のアルコキシカルボニル基
(viii)フルオロメチルカルボニル基、トリフルオロメチルカルボニル基、2,2,2-トリフルオロエチルカルボニル基等の水素原子の一部がフッ素原子で置換されたアルコキシカルボニル基
(ix)ビニルカルボニル基、1-プロペニルカルボニル基、2-プロペニルカルボニル基、1-メチル-2-プロペニルカルボニル基、1,1-ジメチル-2-プロペニルカルボニル基、1-ブテニルカルボニル基、2-ブテニルカルボニル基、3-ブテニルカルボニル基、2-ペンテニルカルボニル基、2-ヘキセニルカルボニル基等のアルケニルカルボニル基
(x)2-プロピニルカルボニル基、2-ブチニルカルボニル基、3-ブチニルカルボニル基、4-ペンチニルカルボニル基、5-ヘキシニルカルボニル基、1-メチル-2-プロピニルカルボニル基、1-メチル-2-ブチニルカルボニル基、1,1-ジメチル-2-プロピニルカルボニル基等のアルキニルカルボニル基
(xi)フェニルカルボニル基、2-メチルフェニルカルボニル基、3-メチルフェニルカルボニル基、4-メチルフェニルカルボニル基、4-tert-ブチルフェニルカルボニル基、2,4,6-トリメチルフェニルカルボニル基、2-フルオロフェニルカルボニル基、3-フルオロフェニルカルボニル基、4-フルオロフェニルカルボニル基、2,4-ジフルオロフェニルカルボニル基、2,6-ジフルオロフェニルカルボニル基、3,4-ジフルオロフェニルカルボニル基、2,4,6-トリフルオロフェニルカルボニル基、ペンタフルオロフェニルカルボニル基、2-(トリフルオロメチル)フェニルカルボニル基、3-(トリフルオロメチル)フェニルカルボニル基等のアリールカルボニル基
(xiii)イソプロポキシカルボニル基、sec-ブトキシカルボニル基、tert-ブトキシカルボニル基、tert-アミルオキシカルボニル基等の分枝鎖のアルコキシカルボニル基
(xiv)フルオロメトキシカルボニル基、トリフルオロメトキシカルボニル基、2,2,2-トリフルオロエトキシカルボニル基等の水素原子の一部がフッ素原子で置換されたアルコキシカルボニル基
(xv)ビニルオキシカルボニル基、1-プロペニルオキシカルボニル基、2-プロペニルオキシカルボニル基、1-メチル-2-プロペニルオキシカルボニル基、1,1-ジメチル-2-プロペニルオキシカルボニル基、1-ブテニルオキシカルボニル基、2-ブテニルオキシカルボニル基、3-ブテニルオキシカルボニル基、2-ペンテニルオキシカルボニル基、2-ヘキセニルオキシカルボニル基等のアルケニルオキシカルボニル基
(xvi)2-プロピニルオキシカルボニル基、2-ブチニルオキシカルボニル基、3-ブチニルオキシカルボニル基、4-ペンチニルオキシカルボニル基、5-ヘキシニルオキシカルボニル基、1-メチル-2-プロピニルオキシカルボニル基、1-メチル-2-ブチニルオキシカルボニル基、1,1ジメチル-2-プロピニルオキシカルボニル基等のアルキニルオキシカルボニル基、
(xvii)フェニルオキシカルボニル基、2-メチルフェニルオキシカルボニル基、3-メチルフェニルオキシカルボニル基、4-メチルフェニルオキシカルボニル基、4-tert-ブチルフェニルオキシカルボニル基、2,4,6-トリメチルフェニルオキシカルボニル基、2-フルオロフェニルオキシカルボニル基、3-フルオロフェニルオキシカルボニル基、4-フルオロフェニルオキシカルボニル基、2,4-ジフルオロフェニルオキシカルボニル基、2,6-ジフルオロフェニルオキシカルボニル基、3,4-ジフルオロフェニルオキシカルボニル基、2,4,6-トリフルオロフェニルオキシカルボニル基、ペンタフルオロフェニルオキシカルボニル基、2-(トリフルオロメチル)フェニルオキシカルボニル基、3-トリフルオロメチルフェニルオキシカルボニル基、4-(トリフルオロメチル)フェニルオキシカルボニル基、4-フルオロ-3-(トリフルオロメチル)フェニルオキシカルボニル基、4-クロロ-3-(トリフルオロメチル)フェニルオキシカルボニル基等のアリールオキシカルボニル基
広い温度範囲での電気化学特性の改善効果は、RfやXのベンゼン環上の置換位置にも依存し、パラ位及びメタ位の少なくとも一方にRfを有するものが好ましく、オルト位及びパラ位の少なくとも一方にXを有するものが好ましい。特に、メタ位にRfを有するものが好ましい。
本発明の非水電解液に使用される非水溶媒としては、環状カーボネート、鎖状エステル、ラクトン、エーテル、アミドが挙げられ、環状カーボネートと鎖状エステルの両方が含まれることが好ましい。
なお、鎖状エステルなる用語は、鎖状カーボネート及び鎖状カルボン酸エステルを含む概念として用いる。
環状カーボネートとしては、エチレンカーボネート(EC)、プロピレンカーボネート(PC)、1,2-ブチレンカーボネート、2,3-ブチレンカーボネート、及びフッ素原子又は不飽和結合を有する環状カーボネート等から選ばれる一種以上が挙げられ、EC、PC、及びフッ素原子又は不飽和結合を有する環状カーボネートから選ばれる一種以上が好ましい。
フッ素原子を有する環状カーボネートとしては、4-フルオロ-1,3-ジオキソラン-2-オン(FEC)、トランス又はシス-4,5-ジフルオロ-1,3-ジオキソラン-2-オン(以下、両者を総称して「DFEC」という)から選ばれる一種以上が好ましく、FECがより好ましい。
炭素-炭素二重結合、炭素-炭素三重結合等の不飽和結合を有する環状カーボネートとしては、ビニレンカーボネート(VC)、ビニルエチレンカーボネート(VEC)、及び4-エチニル-1,3-ジオキソラン-2-オン(EEC)等から選ばれる一種以上が挙げられ、VC、VEC、及びEECから選ばれる一種以上が好ましい。
前記フッ素原子又は不飽和結合を有する環状カーボネートのうち少なくとも一種を使用すると蓄電デバイスを高温で使用した場合のサイクル後のガス発生を一段と抑制できるので好ましく、前記フッ素原子を含む環状カーボネートと不飽和結合を有する環状カーボネートを両方含むことがより好ましい。
フッ素原子を有する環状カーボネートの含有量は、非水溶媒の総体積に対して好ましくは0.07体積%以上、より好ましくは4体積%以上、更に好ましくは7体積%以上であり、また、その上限としては、好ましくは35体積%以下、より好ましくは25体積%以下、更に好ましくは15体積%以下であると、被膜の安定性が増し、蓄電デバイスを高温で使用した場合のサイクル特性が向上するので好ましい。
非水溶媒が前記不飽和結合を有する環状カーボネートとフッ素原子を有する環状カーボネートの両方を含む場合、フッ素原子を有する環状カーボネートの含有量に対する前記不飽和結合を有する環状カーボネートの含有割合は、好ましくは0.2%以上、より好ましくは3%以上、更に好ましくは7%以上であり、その上限としては、好ましくは40%以下、より好ましくは30%以下、更に好ましくは15%以下であると、被膜の安定性が増し、蓄電デバイスを高温で使用した場合のサイクル特性が向上するので特に好ましい。
また、非水溶媒がエチレンカーボネート及び/又はプロピレンカーボネートを含むと電極上に形成される被膜の抵抗が小さくなるので好ましく、エチレンカーボネート及び/又はプロピレンカーボネートの含有量は、非水溶媒の総体積に対し、好ましくは3体積%以上、より好ましくは5体積%以上、更に好ましくは7体積%以上であり、また、その上限としては、好ましくは45体積%以下、より好ましくは35体積%以下、更に好ましくは25体積%以下である。
これらの環状カーボネートの好適な組合せとしては、ECとPC、ECとVC、PCとVC、VCとFEC、ECとFEC、PCとFEC、FECとDFEC、ECとDFEC、PCとDFEC、VCとDFEC、VECとDFEC、VCとEEC、ECとEEC、ECとPCとVC、ECとPCとFEC、ECとVCとFEC、ECとVCとVEC、ECとVCとEEC、ECとEECとFEC、PCとVCとFEC、ECとVCとDFEC、PCとVCとDFEC、ECとPCとVCとFEC、ECとPCとVCとDFEC等が好ましい。前記の組合せのうち、ECとPC、ECとVC、ECとFEC、PCとFEC、ECとPCとVC、ECとPCとFEC、ECとVCとFEC、ECとVCとEEC、ECとEECとFEC、PCとVCとFEC、ECとPCとVCとFEC等の組合せがより好ましい。
また、EC又はPCと、フッ素原子又は不飽和結合を有する環状カーボネートとを含有する環状カーボネートが好ましく、EC又はPCと、FEC又はVCとを含有する環状カーボネートが更に好ましい。
これらの溶媒は一種単独で使用してもよく、また二種以上を組み合わせて使用した場合は、蓄電デバイスを高温で使用した場合のサイクル特性が向上し、ガス発生量が減少するので好ましい。
対称鎖状カーボネートの含有量は、非対称鎖状カーボネートの含有量より多い方が好ましい。
鎖状カーボネート中に対称鎖状カーボネートが占める体積の割合は、51体積%以上が好ましく、55体積%以上がより好ましく、60体積%以上が更に好ましく、65体積%以上が更に好ましい。その上限としては、95体積%以下が好ましく、90体積%以下がより好ましく、85体積%以下であると更に好ましく、80体積%以下が更に好ましい。
上記の場合に一段と蓄電デバイスを高温で使用した場合のサイクル特性が向上するので好ましい。
その他の添加剤の具体例としては、リン酸エステル、ニトリル、三重結合含有化合物、S=O結合含有化合物、酸無水物、環状ホスファゼン化合物、ジイソシアナト化合物、環状アセタール、分枝アルキル基を有する芳香族化合物、芳香族化合物等が挙げられる。
リン酸エステルとしては、リン酸トリメチル、リン酸トリエチル、リン酸トリブチル、及びリン酸トリオクチル等が挙げられる。
ニトリルとしては、アセトニトリル、プロピオニトリル、スクシノニトリル、2-エチルスクシノニトリル、グルタロニトリル、2-メチルグルタロニトリル、3-メチルグルタロニトリル、アジポニトリル、及びピメロニトリル等が挙げられる。
三重結合含有化合物としては、メチル 2-プロピニル カーボネート、酢酸 2-プロピニル、ギ酸 2-プロピニル、メタクリル酸 2-プロピニル、メタンスルホン酸 2-プロピニル、ビニルスルホン酸 2-プロピニル、ジ(2-プロピニル)オギザレート、グルタル酸 ジ(2-プロピニル)、2-ブチン-1,4-ジイル ジメタンスルホネート、及び2-ブチン-1,4-ジイル ジホルメート、2-プロピニル 2-(ジエトキシホスホリル)アセテート、2-プロピニル 2-((メタンスルホニル)オキシ)プロパノエート等が挙げられる。
スルトン化合物としては、1,3-プロパンスルトン、1,3-ブタンスルトン、1,4-ブタンスルトン、2,4-ブタンスルトン、1,3-プロペンスルトン、2,2-ジオキシド-1,2-オキサチオラン-4-イル アセテート、5,5-ジメチル-1,2-オキサチオラン-4-オン 2,2-ジオキシド、メチレン メタンジスルホネート等が挙げられる。
環状サルファイト化合物としては、エチレンサルファイト、ヘキサヒドロベンゾ[1,3,2]ジオキサチオラン-2-オキシド(1,2-シクロヘキサンジオールサイクリックサルファイトともいう)、5-ビニル-ヘキサヒドロ1,3,2-ベンゾジオキサチオール-2-オキシド等が挙げられる。
スルホン酸エステル化合物としては、ブタン-2,3-ジイル ジメタンスルホネート、ブタン-1,4-ジイル ジメタンスルホネート、メチレンメタンジスルホネート、ジメチルメタンジスルホネート等が挙げられる。
ビニルスルホン化合物としては、ジビニルスルホン、1,2-ビス(ビニルスルホニル)エタン、ビス(2-ビニルスルホニルエチル)エーテル、ビニルスルホニルフルオリド等が挙げられる。
酸無水物としては、無水酢酸、無水プロピオン酸等の鎖状のカルボン酸無水物、無水コハク酸、無水マレイン酸、無水グルタル酸、無水イタコン酸、3-スルホ-プロピオン酸無水物等が挙げられる。
環状ホスファゼン化合物としては、メトキシペンタフルオロシクロトリホスファゼン、エトキシペンタフルオロシクロトリホスファゼン、フェノキシペンタフルオロシクロトリホスファゼン、エトキシヘプタフルオロシクロテトラホスファゼン等が挙げられる。
環状アセタールとしては、1,3-ジオキソラン、1,3-ジオキサン等が挙げられる。
分枝アルキル基を有する芳香族化合物としては、シクロヘキシルベンゼン、フルオロシクロヘキシルベンゼン化合物(1-フルオロ-2-シクロヘキシルベンゼン、1-フルオロ-3-シクロヘキシルベンゼン、1-フルオロ-4-シクロヘキシルベンゼン)、tert-ブチルベンゼン、tert-アミルベンゼン、1-フルオロ-4-tert-ブチルベンゼン等が挙げられる。
芳香族化合物としては、ビフェニル、ターフェニル(o-、m-、p-体)、ジフェニルエーテル、フルオロベンゼン、ジフルオロベンゼン(o-、m-、p-体)、アニソール、2,4-ジフルオロアニソール、ターフェニルの部分水素化物(1,2-ジシクロヘキシルベンゼン、2-フェニルビシクロヘキシル、1,2-ジフェニルシクロヘキサン、o-シクロヘキシルビフェニル)等が挙げられる。
ニトリルの中では、スクシノニトリル、2-エチルスクシノニトリル、グルタロニトリル、2-メチルグルタロニトリル、3-メチルグルタロニトリル、アジポニトリル、及びピメロニトリルから選ばれる一種以上がより好ましい。
ジイソシアナト化合物の中では、1,5-ジイソシアナトペンタン、1,6-ジイソシアナトヘキサン、及び1,7-ジイソシアナトヘプタンから選ばれる一種以上がより好ましい。
環状アセタール化合物の中では、1,3-ジオキサンが好ましい。
また、芳香族化合物の中では、ビフェニル、ターフェニル(o-、m-、p-体)、フルオロベンゼン、シクロヘキシルベンゼン、tert-ブチルベンゼン、及びtert-アミルベンゼンから選ばれる一種以上がより好ましい。
ニトリル、ジイソシアナト化合物、環状アセタール、芳香族化合物から選ばれる一種以上の含有量は、非水電解液中に0.001~5質量%が好ましい。この範囲では、被膜が厚くなり過ぎずに十分に形成され、蓄電デバイスを高温で使用した場合の電気化学特性の改善効果が高まる。該含有量は、非水電解液中に0.005質量%以上がより好ましく、0.01質量%以上が更に好ましく、0.03質量%以上が特に好ましく、その上限は、3質量%以下がより好ましく、2質量%以下が更に好ましく、1.5質量%以下が特に好ましい。
三重結合含有化合物の中では、メタンスルホン酸 2-プロピニル、ビニルスルホン酸 2-プロピニル、ジ(2-プロピニル)オギザレート、2-ブチン-1,4-ジイル ジメタンスルホネート、2-プロピニル 2-(ジエトキシホスホリル)アセテート、及び2-プロピニル 2-((メタンスルホニル)オキシ)プロパノエートから選ばれる一種以上がより好ましい。
スルトン化合物の中では、1,3-プロパンスルトン、1,3-プロペンスルトン、2,2-ジオキシド-1,2-オキサチオラン-4-イル アセテート、5,5-ジメチル-1,2-オキサチオラン-4-オン 2,2-ジオキシド、メチレン メタンジスルホネートから選ばれる一種以上がより好ましい。
ビニルスルホン化合物の中では、ジビニルスルホン、ビス(2-ビニルスルホニルエチル)エーテル、ビニルスルホニルフルオリドから選ばれる一種以上がより好ましい。
三重結合含有化合物、スルトン化合物、及びビニルスルホン化合物から選ばれる一種以上の含有量は、非水電解液中に0.001~5質量%が好ましい。この範囲では、被膜が厚くなり過ぎずに十分に形成され、蓄電デバイスを高温で使用した場合の電気化学特性の改善効果が高まる。該含有量は、非水電解液中に0.005質量%以上がより好ましく、0.01質量%以上が更に好ましく、0.03質量%以上が特に好ましく、その上限は、3質量%以下がより好ましく、2質量%以下が更に好ましく、1.5質量%以下が特に好ましい。
リチウム塩の具体例としては、リチウム ビス(オキサラト)ボレート(LiBOB)、リチウム ジフルオロ(オキサラト)ボレート(LiDFOB)、リチウム テトラフルオロ(オキサラト)ホスフェート(LiTFOP)、及びリチウム ジフルオロビス(オキサラト)ホスフェート(LiDFOP)から選ばれる一種以上のシュウ酸骨格を有するリチウム塩、LiPO2F2やLi2PO3F等のリン酸骨格を有するリチウム塩、リチウム トリフルオロ((メタンスルホニル)オキシ)ボレート(LiTFMSB)、リチウム ペンタフルオロ((メタンスルホニル)オキシ)ホスフェート(LiPFMSP)、及びFSO3Liから選ばれる一種以上のスルホン酸骨格を有するリチウム塩が好適に挙げられ、LiBOB、LiDFOB、LiTFOP、LiDFOP、LiPO2F2、LiTFMSB、LiPFMSP、及びFSO3Liから選ばれる一種以上のリチウム塩がより好ましく、LiTFMSBが更に好ましい。
前記LiTFMSB、FSO3Li等のリチウム塩の総含有量は、非水電解液中に0.001~10質量%が好ましい。該含有量が10質量%以下であれば、電極上に過度に被膜が形成されサイクル特性が低下するおそれが少なく、また0.001質量%以上であれば被膜の形成が十分であり、電池を高電圧で使用した場合の特性の改善効果が高まる。該含有量は、非水電解液中に0.05質量%以上が好ましく、0.1質量%以上がより好ましく、0.3質量%以上が更に好ましく、その上限は、5質量%以下が好ましく、3質量%以下がより好ましく、2質量%以下が更に好ましい。
本発明に使用される電解質塩としては、下記のリチウム塩が好適に挙げられる。
(リチウム塩)
リチウム塩としては、LiPF6、LiBF4、LiN(SO2F)2、LiClO4等の無機リチウム塩、LiN(SO2CF3)2、LiN(SO2C2F5)2、LiCF3SO3、LiC(SO2CF3)3、LiPF4(CF3)2、LiPF3(C2F5)3、LiPF3(CF3)3、LiPF3(iso-C3F7)3、LiPF5(iso-C3F7)等の鎖状のフッ化アルキル基を含有するリチウム塩や、(CF2)2(SO2)2NLi、(CF2)3(SO2)2NLi等の環状のフッ化アルキレン鎖を有するリチウム塩等から選ばれる一種以上のリチウム塩が好適に挙げられる。
これらの中でも、LiPF6、LiBF4、LiN(SO2CF3)2、LiN(SO2C2F5)2、及びLiN(SO2F)2から選ばれる一種以上が好ましく、LiPF6を用いることがより好ましい。
電解質塩であるリチウム塩の濃度は、前記の非水溶媒に対して、通常0.3M以上が好ましく、0.7M以上がより好ましく、1.1M以上が更に好ましい。またその上限は、2.5M以下が好ましく、2.0M以下がより好ましく、1.6M以下が更に好ましい。
また、これらのリチウム塩の好適な組み合わせとしては、LiPF6を含み、更にLiBF4、LiN(SO2CF3)2、及びLiN(SO2F)2から選ばれる一種以上のリチウム塩が非水電解液中に含まれている場合が好ましく、LiPF6以外のリチウム塩が非水溶媒中に占める割合は、0.001M以上であると、電池を高温で使用した場合の電気化学特性の向上効果が発揮されやすく、0.005M以下であると電池を高温で使用した場合の電気化学特性の向上効果が低下する懸念が少ないので好ましい。LiPF6以外のリチウム塩の割合は、好ましくは0.01M以上、より好ましくは0.03M以上、更に好ましくは0.04M以上であり、その上限は、好ましくは0.4M以下、より好ましくは0.2M以下である。
本発明の非水電解液は、例えば、前記の非水溶媒を混合し、これに前記の電解質塩及び該非水電解液に対して一般式(I)で表されるベンゼン環がハロゲン原子とフルオロアルキル基の両方で置換されたフェニルエステル化合物を添加することにより得ることができる。
この際、用いる非水溶媒及び非水電解液に加える化合物は、生産性を著しく低下させない範囲内で、予め精製して、不純物が極力少ないものを用いることが好ましい。
本発明のリチウム電池は、リチウム一次電池及びリチウム二次電池を総称する。また、本明細書において、リチウム二次電池という用語は、いわゆるリチウムイオン二次電池も含む概念として用いる。本発明のリチウム電池は、正極、負極及び非水溶媒に電解質塩が溶解されている前記非水電解液からなる。非水電解液以外の正極、負極等の構成部材は特に制限なく使用できる。
例えば、リチウム二次電池用正極活物質としては、コバルト、マンガン、及びニッケルから選ばれる一種以上を含有するリチウムとの複合金属酸化物が使用される。これらの正極活物質は、1種単独又は2種以上を組み合わせて用いることができる。
このようなリチウム複合金属酸化物としては、例えば、LiCoO2、LiMn2O4、LiNiO2、LiCo1-xNixO2(0.01<x<1)、LiCo1/3Ni1/3Mn1/3O2、LiNi1/2Mn3/2O4、LiCo0.98Mg0.02O2等から選ばれる一種以上が挙げられる。また、LiCoO2とLiMn2O4、LiCoO2とLiNiO2、LiMn2O4とLiNiO2のように併用してもよい。
これらの中では、LiCoO2、LiMn2O4、LiNiO2のような満充電状態における正極の充電電位がLi基準で4.3V以上で使用可能なリチウム複合金属酸化物が好ましく、LiCo1-xMxO2(但し、MはSn、Mg、Fe、Ti、Al、Zr、Cr、V、Ga、Zn、Cuから選ばれる一種以上の元素、0.001≦x≦0.05)、LiCo1/3Ni1/3Mn1/3O2、LiNi1/2Mn3/2O4、Li2MnO3とLiMO2(Mは、Co、Ni、Mn、Fe等の遷移金属)との固溶体のような4.4V以上で使用可能なリチウム複合金属酸化物がより好ましい。高充電電圧で動作するリチウム複合金属酸化物を使用すると、充電時における電解液との反応により特に電池を高電圧で使用した場合の電気化学特性が低下しやすいが、本発明に係るリチウム二次電池ではこれらの電気化学特性の低下を抑制することができる。
これらのリチウム含有オリビン型リン酸塩の一部は他元素で置換してもよく、鉄、コバルト、ニッケル、マンガンの一部をCo、Mn、Ni、Mg、Al、B、Ti、V、Nb、Cu、Zn、Mo、Ca、Sr、W及びZr等から選ばれる1種以上の元素で置換したり、又はこれらの他元素を含有する化合物や炭素材料で被覆することもできる。これらの中では、LiCoPO4、LiNiPO4、LiMnPO4等のように少なくともCo、Ni、Mnを含むリチウム含有オリビン型リン酸塩を使用した場合、電池電圧がより高電位となるので、本願発明の効果が現れやすいため好ましい。
また、リチウム含有オリビン型リン酸塩は、例えば前記の正極活物質と混合して用いることもできる。
正極の集電体を除く部分の密度は、通常は1.5g/cm3以上であり、電池の容量を更に高めるため、好ましくは2g/cm3以上であり、より好ましくは、3g/cm3以上であり、更に好ましくは、3.6g/cm3以上である。なお、上限としては、4g/cm3以下が好ましい。
これらの中では、リチウムイオンの吸蔵及び放出能力において、人造黒鉛や天然黒鉛等の高結晶性の炭素材料を使用することが更に好ましく、格子面(002)の面間隔(d002)が0.340nm(ナノメータ)以下、特に0.335~0.337nmである黒鉛型結晶構造を有する炭素材料を使用することが特に好ましい。
複数の扁平状の黒鉛質微粒子が互いに非平行に集合或いは結合した塊状構造を有する人造黒鉛粒子や、例えば鱗片状天然黒鉛粒子に圧縮力、摩擦力、剪断力等の機械的作用を繰り返し与え、球形化処理を施した黒鉛粒子を用いることにより、負極の集電体を除く部分の密度を1.5g/cm3以上の密度に加圧成形したときの負極シートのX線回折測定から得られる黒鉛結晶の(110)面のピーク強度I(110)と(004)面のピーク強度I(004)の比I(110)/I(004)が0.01以上となると一段と広い温度範囲での電気化学特性が向上するので好ましく、0.05以上となることがより好ましく、0.1以上となることが更に好ましい。また、過度に処理し過ぎて結晶性が低下し電池の放電容量が低下する場合があるので、上限は0.5以下が好ましく、0.3以下がより好ましい。
また、高結晶性の炭素材料(コア材)はコア材よりも低結晶性の炭素材料によって被覆されていると、電池を高電圧で使用した場合の電気化学特性が一段と良好となるので好ましい。被覆の炭素材料の結晶性は、TEMにより確認することが出来る。
高結晶性の炭素材料を使用すると、充電時において非水電解液と反応し、界面抵抗の増加によって低温もしくは高温における電気化学特性を低下させる傾向があるが、本発明に係るリチウム二次電池では電池を高温で使用した場合の電気化学特性が良好となる。
一般式(I)で表されるベンゼン環がハロゲン原子とフルオロアルキル基の両方で置換されたフェニルエステル化合物を含有する本願発明の非水電解液と上記のように負極活物質としてリチウムを吸蔵及び放出可能な金属化合物と炭素材料を混合した負極を組み合わせて用いた場合、一般式(I)で表されるフェニルエステル化合物が金属化合物と炭素材料の両方に作用することにより、一般的にリチウムの吸蔵及び放出に伴う体積変化が大きい金属化合物と炭素材料の電気的な接触が補強され、一段とサイクル特性が向上すると考えられる。
負極の集電体を除く部分の密度は、通常は1.1g/cm3以上であり、電池の容量を更に高めるため、好ましくは1.5g/cm3以上であり、特に好ましくは1.7g/cm3以上である。なお、上限としては、2g/cm3以下が好ましい。
電池用セパレータとしては、特に制限はされないが、ポリプロピレン、ポリエチレン等のポリオレフィンの単層又は積層の微多孔性フィルム、織布、不織布等を使用できる。
負極であるグラファイト等の炭素材料へのリチウムイオンのインターカレーションを利用してエネルギーを貯蔵する蓄電デバイスである。リチウムイオンキャパシタ(LIC)と呼ばれる。正極は、例えば活性炭電極と電解液との間の電気二重層を利用したものや、π共役高分子電極のドープ/脱ドープ反応を利用したもの等が挙げられる。電解液には少なくともLiPF6等のリチウム塩が含まれる。
本発明の非水電解液は、高電圧で使用するリチウムイオンキャパシタの充放電特性を改善することができる。
前記アルキル基、アルケニル基、アルキニル基、アリール基、アルキレン基、アルケニレン基、及びアルキニレン基は、各々の基の少なくとも一つの水素原子がハロゲン原子で置換されていてもよい。)
置換基Rf 1、置換基A1、置換基Y1、置換基L3、置換基L4、置換基R1については、前記一般式(I)の説明と同じであり、好適例も同じであるので、この欄では重複をさけるためそれらの説明を省略する。この場合において一般式(I)の置換基Rf、A、Y、L1、L2及びRは、それぞれ一般式(II)の置換基Rf 1、A1、Y1、L3、L4及びR1と読み替える。
(a)ベンゼン環がハロゲン原子とフルオロアルキル基の両方で置換されたフェノール化合物(以下、単に「フェノール化合物」という)と、一般式(II)の-A1-Y1基に対応するアルキルスルホニルハライド、アルケニルスルホハライド、アルキニルスルホハライド、アリールスルホハライド、アルキルカルボニルハライド、アルケニルカルボニルハライド、アルキニルカルボニルハライド、アリールカルボニルハライド、アルコキシカルボニルハライド、アルケニルオキシカルボニルハライド、アルキニルオキシカルボニルハライド、アリールオキシカルボニルハライド、オギザリルジハライド、及びジアルコキシホスホリルアルキルカルボニルハライドから選ばれる一種以上(以下、「ハライド化合物」という)とを、溶媒の存在下又は不存在下、塩基の存在下又は不存在下で反応させる方法(以下「(a)法」ともいう)。
(b)前記フェノール化合物とカルボニル化剤とを、溶媒の存在下又は不存在下で反応させる方法(以下「(b)法」ともいう)。
(c)前記フェノール化合物と、一般式(II)の-A1-Y1基に対応するカルボン酸化合物とを、溶媒の存在下又は不存在下、酸触媒又は脱水剤の存在下で縮合させる方法(以下「(c)法」ともいう)。
(a)法は、前記フェノール化合物と、前記ハライド化合物とを、溶媒の存在下又は不存在下、塩基の存在下又は不存在下で反応させる方法である。なお、前記フェノール化合物及び前記ハライド化合物は市販品を使用することもできるし、又は既存の方法により合成することもできる。
(a)法の反応において、前記ハライド化合物の使用量は前記フェノール化合物1モルに対して、好ましくは0.8~20モル、より好ましくは0.9~10モル、更に好ましくは1~5モルである。
(a)法として使用される前記ハライド化合物としては、メタンスルホニルクロリド、4-メチルベンゼンスルホニルクロリド、クロロギ酸メチル、クロロギ酸エチル、クロロギ酸ビニル、クロロギ酸2-プロペニル、クロロギ酸2-プロピニル、クロロギ酸フェニル、クロロギ酸4-メチルフェニル、クロロギ酸4-フルオロフェニル、2-(ジメトキシホスホリル)アセチルクロリド、2-(ジエトキシホスホリル)アセチルクロリド等が挙げられる。
前記溶媒の使用量は、前記フェノール化合物1質量部に対して、好ましくは0~30質量部、より好ましくは1~10質量部である。
無機塩基としては、炭酸カリウム、炭酸ナトリウム、水酸化カルシウム、及び酸化カルシウム等が挙げられる。有機塩基としては、直鎖又は分枝した脂肪族3級アミン、無置換又は置換されたイミダゾール、ピリジン、ピリミジンが挙げられ、これらの中では、トリメチルアミン、トリエチルアミン、トリプロピルアミン、トリブチルアミン、ジイソプロプルエチルアミン等のトリアルキルアミン類、ピリジン、N,N-ジメチルアミノピリジン等のピリジン類が好ましい。
前記塩基の使用量は、前記フェノール化合物1モルに対して、好ましくは0.8~5モル、より好ましくは1~3モル、更に好ましくは1~1.5モルである。
(a)法の反応において、反応温度の下限は、反応性を低下させない観点から、-20℃以上が好ましく、-10℃以上がより好ましい。また副反応や生成物の分解を抑制する観点から、反応温度の上限は80℃以下が好ましく、50℃以下がより好ましい。
反応時間は前記反応温度やスケールにより適宜変更しうるが、反応時間が短すぎると未反応物が残り、逆に反応時間が長すぎると反応生成物の分解や副反応のおそれが生じるため、好ましくは0.1~12時間、より好ましくは0.2~6時間である。
(b)法は、前記フェノール化合物とカルボニル化剤とを、溶媒の存在下又は不存在下で反応させる方法である。
(b)法の反応において、カルボニル化剤の使用量は、前記フェノール化合物1モルに対して、好ましくは0.4~5モル、より好ましくは0.5~3モル、更に好ましくは0.5~1モルである。
(b)法として使用されるカルボニル化剤としては、N,N’-カルボニルジイミダゾール、クロロギ酸フェニル、トリホスゲン等が挙げられる。
(b)法の反応においては、無溶媒で反応は進行するが、反応に不活性であれば、溶媒を使用することができる。使用される溶媒は、(a)法において記述した脂肪族炭化水素、ハロゲン化炭化水素、芳香族炭化水素、ハロゲン化芳香族炭化水素、エーテル、エステル、ニトリル、スルホキシド、アミド、又はこれらの混合物が挙げられる。これらの中では、水と混和しにくい、ヘプタン、シクロヘキサン、トルエン等の脂肪族又は芳香族炭化水素が好ましい。
前記溶媒の使用量は、前記フェノール化合物1質量部に対して、好ましくは0~30質量部、より好ましくは1~10質量部である。
無機塩基、有機塩基としては、(a)法で説明したものと同じものが好ましく挙げられる。
前記塩基の使用量は、前記フェノール化合物1モルに対して、好ましくは0.8~5モル、より好ましくは1~3モル、更に好ましくは1~1.5モルである。
(b)法の反応において、反応温度の下限は、-20℃以上が好ましく、反応性を低下させない観点から、0℃以上がより好ましい。また副反応や生成物の分解を抑制する観点から、反応温度の上限は80℃以下が好ましく、50℃以下がより好ましい。
(b)法の反応時間は反応温度やスケールにより適宜変更しうるが、反応時間が短すぎると未反応物が残り、逆に反応時間が長すぎると反応生成物の分解や副反応のおそれが生じるため、好ましくは0.1~24時間、より好ましくは0.2~12時間である。
(c)法は、前記フェノール化合物と、一般式(II)の-A1-Y1基に対応するカルボン酸化合物とを、溶媒の存在下又は不存在下、酸触媒又は脱水剤の存在下で、縮合させる方法である。
(c)法の反応において、カルボン酸化合物の使用量は前記フェノール化合物1モルに対して、好ましくは0.8~20モル、より好ましくは0.9~10モル、更に好ましくは1~5モルである。
(c)法として使用されるカルボン酸化合物としては、ギ酸、酢酸、2-(ジエトキシホスホリル)酢酸等が挙げられる。
(c)法の反応においては、無溶媒で反応は進行するが、反応に不活性であれば、溶媒を使用することができる。使用される溶媒は、(a)法において記述した脂肪族炭化水素、ハロゲン化炭化水素、芳香族炭化水素、ハロゲン化芳香族炭化水素、エーテル、エステル、ニトリル、スルホキシド、アミド、又はこれらの混合物が挙げられる。これらの中では、ヘプタン、シクロヘキサン、トルエン等の脂肪族又は芳香族炭化水素が好ましい。
前記溶媒の使用量は、前記フェノール化合物1質量部に対して、好ましくは0~30質量部、より好ましくは1~10質量部である。
前記触媒の使用量は、副反応を抑制する観点から、前記フェノール化合物1モルに対し、好ましくは0.001~5モル、より好ましくは0.01~1モルであり、更に好ましくは0.01~0.3モルである。
また、脱水剤を使用する場合、使用できる脱水剤はジシクロヘキシルカルボジイミド、1-エチル-3-(3-ジメチルアミノプロピル)カルボジイミド塩酸塩(WSC)、N,N’-カルボニルジイミダゾール、ジ-2-ピリジルカーボネート、フェニルジクロロホスフェート、ジエチルアゾジカルボン酸エチルをトリフェニルホスフィンの混合物等から選ばれる1種以上が挙げられる。
脱水剤の使用量は、前記フェノール化合物1モルに対して、好ましくは0.8~10モル、よりは好ましくは0.9~5モル、更に好ましくは1~3モルである。
また、脱水剤を使用する場合の反応温度の下限は、-20℃以上が好ましく、反応性を低下させない観点から、0℃以上がより好ましい。また副反応や生成物の分解を抑制する観点から、反応温度の上限は100℃以下が好ましく、50℃以下がより好ましい。
(c)法の反応時間は反応温度やスケールにより適宜変更しうるが、反応時間が短すぎると未反応物が残り、逆に反応時間が長すぎると反応生成物の分解や副反応のおそれが生じるため、好ましくは0.1~24時間、より好ましくは0.2~12時間である。
4-フルオロ-3-(トリフルオロメチル)フェノール10.00g(55.5mmol)とメタンスルホニルクロリド6.87g(60.0mmol)とをジメチルカーボネート50mLに溶解し、2℃に冷却した。この溶液にトリエチルアミン6.07g(60.0mmol)を、2~11℃で15分かけて滴下し、室温で1時間撹拌した。ガスクロマトグラフィーで原料の消失を確認した後、反応液を水洗、分液した後に有機層を濃縮した。残渣を減圧蒸留で精製し、無色液体である目的の4-フルオロ-3-(トリフルオロメチル)フェニル メタンスルホネート6.87g(収率48%)を得た。
得られた4-フルオロ-3-(トリフルオロメチル)フェニル メタンスルホネートについて、1H-NMRの測定を行い、その構造を確認した。結果を以下に示す。
1H-NMR(300MHz,CDCl3):δ= 7.58 - 7.46(m, 2H), 7.33 - 7.23(m, 1H), 3.22(s, 3H)
4-フルオロ-3-(トリフルオロメチル)フェノール5.00g(27.8mmol)とトリエチルアミン3.09g(30.5mmol)とをジメチルカーボネート30mLに溶解し、5℃に冷却した。この溶液に塩化アセチル2.39g(30.5mmol)を、5~16℃で10分かけて滴下し、室温で1時間撹拌した。ガスクロマトグラフィーで原料の消失を確認した後、反応液を水洗、分液した後に有機層を濃縮した。得られた濃縮液を、シリカゲルカラムクロマトグラフィー(ワコーゲルC-200、ヘキサン/酢酸エチル=9/1溶出)で精製し、無色液体である目的の4-フルオロ-3-(トリフルオロメチル)フェニル アセテート5.77g(収率93%)を得た。
得られた4-フルオロ-3-(トリフルオロメチル)フェニル アセテートについて、1H-NMRの測定を行い、その構造を確認した。結果を以下に示す。
1H-NMR(300MHz,CDCl3):δ= 7.38 - 7.26(m, 2H), 7.23 - 7.18(m, 1H), 2.31(s, 3H)
4-フルオロ-3-(トリフルオロメチル)フェノール5.00g(27.8mmol)とトリエチルアミン3.09g(30.5mmol)とをジメチルカーボネート30mLに溶解し、5℃に冷却した。この溶液にクロロギ酸メチル2.88g(30.5mmol)を、5~14℃で10分かけて滴下し、室温で1時間撹拌した。ガスクロマトグラフィーで原料の消失を確認した後、反応液を水洗、分液した後に有機層を濃縮した。得られた濃縮液を、シリカゲルカラムクロマトグラフィー(ワコーゲルC-200、ヘキサン/酢酸エチル=9/1溶出)で精製し、無色液体である目的の4-フルオロ-3-(トリフルオロメチル)フェニル メチル カーボネート6.28g(収率95%)を得た。
得られた4-フルオロ-3-(トリフルオロメチル)フェニル メチル カーボネートについて、1H-NMRの測定を行い、その構造を確認した。結果を以下に示す。
1H-NMR(300MHz,CDCl3):δ= 7.46 - 7.35(m, 2H), 7.26 - 7.20(m, 1H), 3.93(s, 3H)
4-フルオロ-3-(トリフルオロメチル)フェノール5.00g(27.8mmol)とトリエチルアミン3.09g(30.5mmol)とをジメチルカーボネート30mLに溶解し、5℃に冷却した。この溶液に塩化オギザリル1.76g(13.9mmol)を、5~18℃で10分かけて滴下し、室温で1時間撹拌した。ガスクロマトグラフィーで原料の消失を確認した後、反応液を水洗、分液した後に有機層を濃縮した。得られた濃縮液を、シリカゲルカラムクロマトグラフィー(ワコーゲルC-200、ヘキサン/酢酸エチル=9/1溶出)で精製し、無色液体である目的のビス(4-フルオロ-3-(トリフルオロメチル)フェニル) オキサレート0.96g(収率17%)を得た。
得られたビス(4-フルオロ-3-(トリフルオロメチル)フェニル) オキサレートについて、1H-NMRの測定を行い、その構造を確認した。結果を以下に示す。
1H-NMR(300MHz,CDCl3):δ= 7.40 - 7.27(m, 2H), 7.25 - 7.20(m, 1H)
4-フルオロ-3-(トリフルオロメチル)フェノール8.54g(47.4mmol)とトリエチルアミン5.28g(52.1mmol)とをジメチルカーボネート50mLに溶解し、5℃に冷却した。この溶液にクロロリン酸ジエチル9.00g(52.1mmol)を、5~13℃で15分かけて滴下し、室温で3時間撹拌した。ガスクロマトグラフィーで原料の消失を確認した後、反応液を水洗、分液した後に有機層を濃縮した。得られた濃縮液を、シリカゲルカラムクロマトグラフィー(ワコーゲルC-200、ヘキサン/酢酸エチル=4/1溶出)で精製し、淡黄色液体である目的の4-フルオロ-3-(トリフルオロメチル)フェニル ジエチルホスフェート13.80g(収率92%)を得た。
得られた4-フルオロ-3-(トリフルオロメチル)フェニル ジエチルホスフェートについて、1H-NMRの測定を行い、その構造を確認した。結果を以下に示す。
1H-NMR(300MHz,CDCl3):δ= 7.47 - 7.42(m, 2H), 7.21 - 7.15(m, 1H), 4.29 - 4.19(m, 2H), 1.44 - 1.33(m, 3H)
〔リチウムイオン二次電池の作製〕
LiNi1/3Mn1/3Co1/3O2 94質量%、アセチレンブラック(導電剤)3質量%を混合し、予めポリフッ化ビニリデン(結着剤)3質量%を1-メチル-2-ピロリドンに溶解させておいた溶液に加えて混合し、正極合剤ペーストを調製した。この正極合剤ペーストをアルミニウム箔(集電体)上の片面に塗布し、乾燥、加圧処理して所定の大きさに裁断し、帯状の正極シートを作製した。正極の集電体を除く部分の密度は3.6g/cm3であった。また、ケイ素(単体)10質量%、人造黒鉛(d002=0.335nm、負極活物質)80質量%、アセチレンブラック(導電剤)5質量%を混合し、予めポリフッ化ビニリデン(結着剤)5質量%を1-メチル-2-ピロリドンに溶解させておいた溶液に加えて混合し、負極合剤ペーストを調製した。この負極合剤ペーストを銅箔(集電体)上の片面に塗布し、乾燥、加圧処理して所定の大きさに裁断し、負極シートを作製した。負極の集電体を除く部分の密度は1.5g/cm3であった。また、この電極シートを用いてX線回折測定した結果、黒鉛結晶の(110)面のピーク強度I(110)と(004)面のピーク強度I(004)の比〔I(110)/I(004)〕は0.1であった。
上記で得られた正極シート、微多孔性ポリエチレンフィルム製セパレータ、上記で得られた負極シートの順に積層し、表1及び表2に記載の組成の非水電解液を加えて、ラミネート型電池を作製した。
上記の方法で作製した電池を用いて60℃の恒温槽中、1Cの定電流及び定電圧で、終止電圧4.3Vまで3時間充電し、次に1Cの定電流下、放電電圧3.0Vまで放電することを1サイクルとし、これを100サイクルに達するまで繰り返した。そして、以下の式により放電容量維持率を求めた。
放電容量維持率(%)=(100サイクル後の放電容量/1サイクル目の放電容量)×100
〔100サイクル後のガス発生量の評価〕
100サイクル後のガス発生量はアルキメデス法により測定した。ガス発生量は、比較例1のガス発生量を100%としたときを基準とし、相対的なガス発生量を調べた。
また、電池の作製条件及び電池特性を表1~表3に示す。
実施例1及び比較例1で用いた正極活物質に変えて、LiNi1/2Mn3/2O4(正極活物質)を用いて、正極シートを作製した。非晶質炭素で被覆されたLiNi1/2Mn3/2O4 94質量%、アセチレンブラック(導電剤)3質量%を混合し、予めポリフッ化ビニリデン(結着剤)3質量%を1-メチル-2-ピロリドンに溶解させておいた溶液に加えて混合し、正極合剤ペーストを調製した。この正極合剤ペーストをアルミニウム箔(集電体)上の片面に塗布し、乾燥、加圧処理して所定の大きさに裁断し、正極シートを作製したこと、電池評価の際の充電終止電圧を4.8V、放電終止電圧を2.7Vとしたことの他は、実施例1及び比較例1と同様にラミネート型電池を作製し、電池評価を行った。結果を表4に示す。
実施例1及び比較例1で用いた負極活物質に代えて、チタン酸リチウムLi4Ti5O12(負極活物質)を用いて、負極シートを作製した。チタン酸リチウムLi4Ti5O12 80質量%、アセチレンブラック(導電剤)15質量%を混合し、予めポリフッ化ビニリデン(結着剤)5質量%を1-メチル-2-ピロリドンに溶解させておいた溶液に加えて混合し、負極合剤ペーストを調製した。この負極合剤ペーストを銅箔(集電体)上の片面に塗布し、乾燥、加圧処理して所定の大きさに裁断し、負極シートを作製したこと、電池評価の際の充電終止電圧を2.7V、放電終止電圧を1.2Vとしたこと、非水電解液の組成を所定のものに変えたことの他は、実施例1及び比較例1と同様にラミネート型電池を作製し、電池評価を行った。結果を表5に示す。
また、実施例41と比較例4の対比から、正極にニッケルマンガン酸リチウム塩(LiNi1/2Mn3/2O4)を用いた場合や、実施例42、43と比較例5の対比から、負極にチタン酸リチウム(Li4Ti5O12)を用いた場合にも同様な効果がみられることが分かる。従って、本発明の効果は、特定の正極や負極に依存した効果でないことは明らかである。
Claims (14)
- 非水溶媒に電解質塩が溶解されている非水電解液において、下記一般式(I)で表されるベンゼン環がハロゲン原子とフルオロアルキル基の両方で置換されたフェニルエステル化合物を含有することを特徴とする非水電解液。
前記アルキル基、アルケニル基、アルキニル基、アリール基、アルキレン基、アルケニレン基、及びアルキニレン基は、各々の基の少なくとも一つの水素原子がハロゲン原子で置換されていてもよい。) - 非水電解液中における前記一般式(I)で表されるフェニルエステル化合物の含有量が合わせて0.01~5質量%である、請求項1に記載の非水電解液。
- 非水溶媒が、環状カーボネート及び鎖状カーボネートを含み、該鎖状カーボネートとして、対称鎖状カーボネートと非対称鎖状カーボネートの両方を含む、請求項1又は2に記載の非水電解液。
- 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、1,2-ブチレンカーボネート、2,3-ブチレンカーボネート、及びフッ素原子又は不飽和結合を有する環状カーボネートから選ばれる一種以上を含有する、請求項3に記載の非水電解液。
- フッ素原子を有する環状カーボネートが、4-フルオロ-1,3-ジオキソラン-2-オン、及びトランス又はシス-4,5-ジフルオロ-1,3-ジオキソラン-2-オンから選ばれる一種以上を含有する、請求項3又は4に記載の非水電解液。
- 不飽和結合を有する環状カーボネートが、ビニレンカーボネート、ビニルエチレンカーボネート、及び4-エチニル-1,3-ジオキソラン-2-オンから選ばれる一種以上を含有する、請求項4に記載の非水電解液。
- 環状カーボネートが、エチレンカーボネート又はプロピレンカーボネートと、ビニレンカーボネート又はフッ素原子を有する環状カーボネートとを含有する、請求項3~6のいずれかに記載の非水電解液。
- 非対称鎖状カーボネートが、メチルエチルカーボネート、メチルプロピルカーボネート、メチルイソプロピルカーボネート、メチルブチルカーボネート、及びエチルプロピルカーボネートから選ばれる一種以上である、請求項3~7のいずれかに記載の非水電解液。
- 対称鎖状カーボネートが、ジメチルカーボネート、ジエチルカーボネート、ジプロピルカーボネート、及びジブチルカーボネートから選ばれる一種以上である、請求項3~8のいずれかに記載の非水電解液。
- 電解質塩が、LiPF6、LiBF4、LiN(SO2CF3)2、及びLiN(SO2F)2から選ばれる一種以上のリチウム塩を含む、請求項1~9のいずれかに記載の非水電解液。
- 正極、負極及び非水溶媒に電解質塩が溶解されている非水電解液を備えた蓄電デバイスにおいて、非水電解液中に上記一般式(I)で表されるベンゼン環がハロゲン原子とフルオロアルキル基の両方で置換されたフェニルエステル化合物を含有することを特徴とする蓄電デバイス。
- 正極の活物質が、コバルト、マンガン、及びニッケルから選ばれる一種以上を含有するリチウムとの複合金属酸化物、又は鉄、コバルト、ニッケル、及びマンガンから選ばれる一種以上を含有するリチウム含有オリビン型リン酸塩である、請求項11に記載の蓄電デバイス。
- 負極の活物質が、リチウム金属、リチウム合金、リチウムを吸蔵及び放出することが可能な炭素材料、スズ、スズ化合物、ケイ素、ケイ素化合物、及びチタン酸リチウム化合物から選ばれる一種以上を含有する、請求項11又は12に記載の蓄電デバイス。
- 下記一般式(II)で表されるベンゼン環がハロゲン原子とフルオロアルキル基の両方で置換されたフェニルエステル化合物。
前記アルキル基、アルケニル基、アルキニル基、アリール基、アルキレン基、アルケニレン基、及びアルキニレン基は、各々の基の少なくとも一つの水素原子がハロゲン原子で置換されていてもよい。)
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Cited By (4)
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JPWO2016060038A1 (ja) * | 2014-10-16 | 2017-07-27 | 株式会社Adeka | 非水電解液及び非水電解液二次電池 |
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000106209A (ja) * | 1998-09-30 | 2000-04-11 | Mitsui Chemicals Inc | 非水電解液および非水電解液二次電池 |
WO2009107786A1 (ja) * | 2008-02-29 | 2009-09-03 | 三菱化学株式会社 | 非水系電解液および非水系電解液電池 |
WO2011025016A1 (ja) * | 2009-08-31 | 2011-03-03 | 三菱化学株式会社 | 非水系電解液及びそれを用いた非水系電解液電池 |
JP2011165583A (ja) * | 2010-02-12 | 2011-08-25 | Mitsubishi Chemicals Corp | 非水系電解液およびそれを用いた非水系電解液二次電池 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4333862A1 (de) * | 1993-10-05 | 1995-04-13 | Hoechst Ag | 4-Fluor-3-trifluormethylbenzole und ihre Verwendung in Flüssigkristallmischungen |
US6369279B1 (en) * | 1999-09-08 | 2002-04-09 | Shin-Etsu Chemical Co., Ltd. | Styrene derivatives |
JP5514608B2 (ja) * | 2010-03-31 | 2014-06-04 | 富士フイルム株式会社 | 感活性光線性又は感放射線性樹脂組成物、及びそれを用いたパターン形成方法 |
GB201012587D0 (en) * | 2010-07-27 | 2010-09-08 | Syngenta Ltd | Formulations |
-
2014
- 2014-01-20 CN CN201480004471.8A patent/CN104919641A/zh active Pending
- 2014-01-20 US US14/760,825 patent/US20150372349A1/en not_active Abandoned
- 2014-01-20 KR KR1020157020005A patent/KR20150108370A/ko not_active Application Discontinuation
- 2014-01-20 WO PCT/JP2014/051020 patent/WO2014115690A1/ja active Application Filing
- 2014-01-20 JP JP2014558559A patent/JP6225923B2/ja active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000106209A (ja) * | 1998-09-30 | 2000-04-11 | Mitsui Chemicals Inc | 非水電解液および非水電解液二次電池 |
WO2009107786A1 (ja) * | 2008-02-29 | 2009-09-03 | 三菱化学株式会社 | 非水系電解液および非水系電解液電池 |
WO2011025016A1 (ja) * | 2009-08-31 | 2011-03-03 | 三菱化学株式会社 | 非水系電解液及びそれを用いた非水系電解液電池 |
JP2011165583A (ja) * | 2010-02-12 | 2011-08-25 | Mitsubishi Chemicals Corp | 非水系電解液およびそれを用いた非水系電解液二次電池 |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPWO2016060038A1 (ja) * | 2014-10-16 | 2017-07-27 | 株式会社Adeka | 非水電解液及び非水電解液二次電池 |
WO2017055282A1 (en) * | 2015-10-02 | 2017-04-06 | Basf Se | Non-aqueous electrolytes for high energy lithium-ion batteries |
WO2019093313A1 (ja) * | 2017-11-08 | 2019-05-16 | 株式会社Gsユアサ | 正極、非水電解質蓄電素子、正極の製造方法、及び非水電解質蓄電素子の製造方法 |
JPWO2019093313A1 (ja) * | 2017-11-08 | 2020-12-03 | 株式会社Gsユアサ | 正極、非水電解質蓄電素子、正極の製造方法、及び非水電解質蓄電素子の製造方法 |
JP7205484B2 (ja) | 2017-11-08 | 2023-01-17 | 株式会社Gsユアサ | 正極、非水電解質蓄電素子、正極の製造方法、及び非水電解質蓄電素子の製造方法 |
WO2023017685A1 (ja) * | 2021-08-12 | 2023-02-16 | 株式会社村田製作所 | 二次電池用電解液および二次電池 |
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