WO2014203912A1 - 非水電解液、それを用いた蓄電デバイス、及びそれに用いられるビフェニル基含有カーボネート化合物 - Google Patents
非水電解液、それを用いた蓄電デバイス、及びそれに用いられるビフェニル基含有カーボネート化合物 Download PDFInfo
- Publication number
- WO2014203912A1 WO2014203912A1 PCT/JP2014/066071 JP2014066071W WO2014203912A1 WO 2014203912 A1 WO2014203912 A1 WO 2014203912A1 JP 2014066071 W JP2014066071 W JP 2014066071W WO 2014203912 A1 WO2014203912 A1 WO 2014203912A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- carbonate
- group
- phenylphenyl
- lithium
- compound
- Prior art date
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- -1 carbonate compound Chemical class 0.000 title claims abstract description 152
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 58
- 238000003860 storage Methods 0.000 title claims abstract description 35
- 125000006267 biphenyl group Chemical group 0.000 title claims abstract description 26
- 230000005611 electricity Effects 0.000 title claims abstract description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 44
- 239000002904 solvent Substances 0.000 claims abstract description 32
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 26
- 239000003792 electrolyte Substances 0.000 claims abstract description 18
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 16
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 14
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 13
- 125000000304 alkynyl group Chemical group 0.000 claims abstract description 13
- 125000003118 aryl group Chemical group 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims description 85
- 229910052744 lithium Inorganic materials 0.000 claims description 80
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 74
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 30
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 26
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 20
- 150000005678 chain carbonates Chemical class 0.000 claims description 18
- 239000008151 electrolyte solution Substances 0.000 claims description 17
- 229910019142 PO4 Inorganic materials 0.000 claims description 13
- 125000005843 halogen group Chemical group 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 239000003125 aqueous solvent Substances 0.000 claims description 12
- 229910003002 lithium salt Inorganic materials 0.000 claims description 12
- 159000000002 lithium salts Chemical class 0.000 claims description 12
- 239000011572 manganese Substances 0.000 claims description 12
- 239000010452 phosphate Substances 0.000 claims description 12
- 229910052731 fluorine Inorganic materials 0.000 claims description 11
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 10
- 239000011203 carbon fibre reinforced carbon Chemical group 0.000 claims description 10
- 239000003575 carbonaceous material Substances 0.000 claims description 10
- 125000001153 fluoro group Chemical group F* 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 229910044991 metal oxide Inorganic materials 0.000 claims description 8
- 150000004706 metal oxides Chemical class 0.000 claims description 8
- 229910052718 tin Inorganic materials 0.000 claims description 8
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 7
- 150000008040 ionic compounds Chemical class 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 239000012948 isocyanate Substances 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-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
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- NLIPFRMVFDIBCS-UHFFFAOYSA-N (2,6-diphenylphenyl) methyl carbonate Chemical compound C(OC1=C(C=CC=C1C1=CC=CC=C1)C1=CC=CC=C1)(OC)=O NLIPFRMVFDIBCS-UHFFFAOYSA-N 0.000 claims description 5
- DNODXRKKYDGUIE-UHFFFAOYSA-N (2-benzyl-6-phenylphenyl) phenyl carbonate Chemical compound C(OC1=C(C=CC=C1C1=CC=CC=C1)CC1=CC=CC=C1)(OC1=CC=CC=C1)=O DNODXRKKYDGUIE-UHFFFAOYSA-N 0.000 claims description 5
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 5
- LCTYQEDRGNZITB-UHFFFAOYSA-N phenyl (2-phenylphenyl) carbonate Chemical compound C=1C=CC=C(C=2C=CC=CC=2)C=1OC(=O)OC1=CC=CC=C1 LCTYQEDRGNZITB-UHFFFAOYSA-N 0.000 claims description 5
- 150000005687 symmetric chain carbonates Chemical class 0.000 claims description 5
- 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
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- RCIJMMSZBQEWKW-UHFFFAOYSA-N methyl propan-2-yl carbonate Chemical compound COC(=O)OC(C)C RCIJMMSZBQEWKW-UHFFFAOYSA-N 0.000 claims description 4
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims description 4
- JAVDFKKWKDXRGP-UHFFFAOYSA-N (2-phenylphenyl) (3-phenylphenyl) carbonate Chemical compound C=1C=CC=C(C=2C=CC=CC=2)C=1OC(=O)OC(C=1)=CC=CC=1C1=CC=CC=C1 JAVDFKKWKDXRGP-UHFFFAOYSA-N 0.000 claims description 3
- XYSBQDLJIHDCNC-UHFFFAOYSA-N (2-phenylphenyl) (4-phenylphenyl) carbonate Chemical compound C=1C=CC=C(C=2C=CC=CC=2)C=1OC(=O)OC(C=C1)=CC=C1C1=CC=CC=C1 XYSBQDLJIHDCNC-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910000733 Li alloy Inorganic materials 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims description 3
- 150000001555 benzenes Chemical group 0.000 claims description 3
- FWBMVXOCTXTBAD-UHFFFAOYSA-N butyl methyl carbonate Chemical compound CCCCOC(=O)OC FWBMVXOCTXTBAD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 239000001989 lithium alloy Substances 0.000 claims description 3
- FSJBDPCMIUVQRY-UHFFFAOYSA-N (2,6-diphenylphenyl) (2-phenylphenyl) carbonate Chemical compound C(OC1=C(C=CC=C1C1=CC=CC=C1)C1=CC=CC=C1)(OC1=C(C=CC=C1)C1=CC=CC=C1)=O FSJBDPCMIUVQRY-UHFFFAOYSA-N 0.000 claims description 2
- FODLEPANZRHIKR-UHFFFAOYSA-N (2,6-diphenylphenyl) (4-phenylphenyl) carbonate Chemical compound C(OC1=C(C=CC=C1C1=CC=CC=C1)C1=CC=CC=C1)(OC1=CC=C(C=C1)C1=CC=CC=C1)=O FODLEPANZRHIKR-UHFFFAOYSA-N 0.000 claims description 2
- NRFFEMDSFYPTNO-UHFFFAOYSA-N (2,6-diphenylphenyl) ethyl carbonate Chemical compound C(OC1=C(C=CC=C1C1=CC=CC=C1)C1=CC=CC=C1)(OCC)=O NRFFEMDSFYPTNO-UHFFFAOYSA-N 0.000 claims description 2
- RFSIIKQMWXKEGS-UHFFFAOYSA-N (2,6-diphenylphenyl) phenyl carbonate Chemical compound C(OC1=C(C=CC=C1C1=CC=CC=C1)C1=CC=CC=C1)(OC1=CC=CC=C1)=O RFSIIKQMWXKEGS-UHFFFAOYSA-N 0.000 claims description 2
- PUWUSBRWELHCPM-UHFFFAOYSA-N (2-benzyl-6-phenylphenyl) (2-phenylphenyl) carbonate Chemical compound C(OC1=C(C=CC=C1C1=CC=CC=C1)CC1=CC=CC=C1)(OC1=C(C=CC=C1)C1=CC=CC=C1)=O PUWUSBRWELHCPM-UHFFFAOYSA-N 0.000 claims description 2
- IKJQDTADOPXXGO-UHFFFAOYSA-N (2-benzyl-6-phenylphenyl) ethyl carbonate Chemical compound C(OC1=C(C=CC=C1C1=CC=CC=C1)CC1=CC=CC=C1)(OCC)=O IKJQDTADOPXXGO-UHFFFAOYSA-N 0.000 claims description 2
- DAEGBAZGIYAVNO-UHFFFAOYSA-N (2-benzyl-6-phenylphenyl) methyl carbonate Chemical compound C(OC1=C(C=CC=C1C1=CC=CC=C1)CC1=CC=CC=C1)(OC)=O DAEGBAZGIYAVNO-UHFFFAOYSA-N 0.000 claims description 2
- 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
- LGXDMAUHWFVPKO-UHFFFAOYSA-N bis(2-phenylphenyl) carbonate Chemical compound C=1C=CC=C(C=2C=CC=CC=2)C=1OC(=O)OC1=CC=CC=C1C1=CC=CC=C1 LGXDMAUHWFVPKO-UHFFFAOYSA-N 0.000 claims description 2
- GGXPTRKVXUZXJF-UHFFFAOYSA-N ethyl (2-phenylphenyl) carbonate Chemical compound CCOC(=O)OC1=CC=CC=C1C1=CC=CC=C1 GGXPTRKVXUZXJF-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
- XELDFVZUWBZRDS-UHFFFAOYSA-N methyl (2-phenylphenyl) carbonate Chemical compound COC(=O)OC1=CC=CC=C1C1=CC=CC=C1 XELDFVZUWBZRDS-UHFFFAOYSA-N 0.000 claims description 2
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical class CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 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
- 238000005868 electrolysis reaction Methods 0.000 claims 3
- 239000011149 active material Substances 0.000 claims 2
- RTQNUUXTJGRGNL-UHFFFAOYSA-N (2,6-diphenylphenyl) (3-phenylphenyl) carbonate Chemical compound C(OC1=C(C=CC=C1C1=CC=CC=C1)C1=CC=CC=C1)(OC1=CC(=CC=C1)C1=CC=CC=C1)=O RTQNUUXTJGRGNL-UHFFFAOYSA-N 0.000 claims 1
- LWOIPYWKSBADRF-UHFFFAOYSA-N (2-benzyl-6-phenylphenyl) (3-phenylphenyl) carbonate Chemical compound C(OC1=C(C=CC=C1C1=CC=CC=C1)CC1=CC=CC=C1)(OC1=CC(=CC=C1)C1=CC=CC=C1)=O LWOIPYWKSBADRF-UHFFFAOYSA-N 0.000 claims 1
- DUIQWOQKBCNESA-UHFFFAOYSA-N (4-phenylphenyl) hydrogen carbonate Chemical compound C1=CC(OC(=O)O)=CC=C1C1=CC=CC=C1 DUIQWOQKBCNESA-UHFFFAOYSA-N 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 26
- LIIRZRQVACDFBI-HOTGVXAUSA-N (4s)-5-amino-4-[[(2s)-4-carboxy-2-[3-(3-phenyl-1,2-oxazol-5-yl)propanoylamino]butanoyl]amino]-5-oxopentanoic acid Chemical compound O1C(CCC(=O)N[C@@H](CCC(O)=O)C(=O)N[C@@H](CCC(O)=O)C(=O)N)=CC(C=2C=CC=CC=2)=N1 LIIRZRQVACDFBI-HOTGVXAUSA-N 0.000 description 24
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 description 19
- 239000000203 mixture Substances 0.000 description 19
- 229910052760 oxygen Inorganic materials 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 16
- 230000000694 effects Effects 0.000 description 15
- 229910001416 lithium ion Inorganic materials 0.000 description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 239000007773 negative electrode material Substances 0.000 description 12
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 235000021317 phosphate Nutrition 0.000 description 11
- 239000007774 positive electrode material Substances 0.000 description 11
- 230000002829 reductive effect Effects 0.000 description 11
- 150000002148 esters Chemical class 0.000 description 10
- 229910002804 graphite Inorganic materials 0.000 description 10
- 239000010439 graphite Substances 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 10
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000000354 decomposition reaction Methods 0.000 description 9
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000006258 conductive agent Substances 0.000 description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 7
- 239000002033 PVDF binder Substances 0.000 description 7
- 229910021383 artificial graphite Inorganic materials 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 7
- 239000003990 capacitor Substances 0.000 description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 239000006230 acetylene black Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 5
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 5
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 5
- 229910013872 LiPF Inorganic materials 0.000 description 5
- 101150058243 Lipf gene Proteins 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910021382 natural graphite Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229940122361 Bisphosphonate Drugs 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 4
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 description 4
- JLEXUIVKURIPFI-UHFFFAOYSA-N tris phosphate Chemical compound OP(O)(O)=O.OCC(N)(CO)CO JLEXUIVKURIPFI-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- VDFVNEFVBPFDSB-UHFFFAOYSA-N 1,3-dioxane Chemical compound C1COCOC1 VDFVNEFVBPFDSB-UHFFFAOYSA-N 0.000 description 3
- OVTAWRRSQQRLIV-UHFFFAOYSA-N 2,2,4,4,6-pentafluoro-6-methoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound COP1(F)=NP(F)(F)=NP(F)(F)=N1 OVTAWRRSQQRLIV-UHFFFAOYSA-N 0.000 description 3
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 3
- CBTAIOOTRCAMBD-UHFFFAOYSA-N 2-ethoxy-2,4,4,6,6-pentafluoro-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound CCOP1(F)=NP(F)(F)=NP(F)(F)=N1 CBTAIOOTRCAMBD-UHFFFAOYSA-N 0.000 description 3
- QHTJSSMHBLGUHV-UHFFFAOYSA-N 2-methylbutan-2-ylbenzene Chemical compound CCC(C)(C)C1=CC=CC=C1 QHTJSSMHBLGUHV-UHFFFAOYSA-N 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- WUMMIJWEUDHZCL-UHFFFAOYSA-N 3-prop-2-enyloxolane-2,5-dione Chemical compound C=CCC1CC(=O)OC1=O WUMMIJWEUDHZCL-UHFFFAOYSA-N 0.000 description 3
- FOLJHXWWJYUOJV-UHFFFAOYSA-N 4-ethynyl-1,3-dioxolan-2-one Chemical compound O=C1OCC(C#C)O1 FOLJHXWWJYUOJV-UHFFFAOYSA-N 0.000 description 3
- HXMJIIPXEYHZSK-UHFFFAOYSA-N 4-formyloxybut-2-ynyl formate Chemical compound O=COCC#CCOC=O HXMJIIPXEYHZSK-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- 229910013733 LiCo Inorganic materials 0.000 description 3
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- CAEWJEXPFKNBQL-UHFFFAOYSA-N prop-2-enyl carbonochloridate Chemical compound ClC(=O)OCC=C CAEWJEXPFKNBQL-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
- KDIDLLIMHZHOHO-UHFFFAOYSA-N prop-2-ynyl formate Chemical compound O=COCC#C KDIDLLIMHZHOHO-UHFFFAOYSA-N 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-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
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 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
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 125000005270 trialkylamine group Chemical group 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
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- ZMQDTYVODWKHNT-UHFFFAOYSA-N tris(2,2,2-trifluoroethyl) phosphate Chemical compound FC(F)(F)COP(=O)(OCC(F)(F)F)OCC(F)(F)F ZMQDTYVODWKHNT-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—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
-
- 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Definitions
- the present invention relates to a non-aqueous electrolyte that can improve electrochemical characteristics over a wide temperature range, and in particular, can improve electrochemical characteristics under high temperature, an electricity storage device using the same, and a biphenyl group-containing carbonate compound used therefor.
- power storage devices particularly lithium secondary batteries
- small electronic devices such as mobile phones and laptop computers, electric vehicles, and power storage sources.
- these electronic devices and automobiles may be used in a wide temperature range such as a high temperature in midsummer or a low temperature of extremely cold, it is required to improve electrochemical characteristics in a wide range of temperatures.
- laminated batteries and square batteries used in thin electronic devices such as tablet terminals and ultrabooks are used at high temperatures, they are thin and easily deformed due to a slight expansion of the exterior member. The problem is that it has a very large impact.
- hybrid electric vehicles are among the environmentally friendly vehicles equipped with power storage devices consisting of power storage devices such as lithium secondary batteries and capacitors.
- HEV high-voltage battery
- PHEV plug-in hybrid electric vehicles
- BEV battery electric vehicles Due to the long travel distance of automobiles, automobiles may be used in areas with a wide temperature range from extremely hot areas in the tropics to extremely cold areas. Therefore, in particular, these in-vehicle power storage devices are required not to deteriorate in electrochemical characteristics even when used in a wide temperature range from high temperature to low temperature.
- the term lithium secondary battery is used as a concept including a so-called lithium ion secondary battery.
- 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
- metal lithium metal compounds that can occlude and release lithium (metal simple substance, oxide, alloy with lithium, etc.) and carbon materials are known, and in particular, lithium can be occluded and released.
- Lithium secondary batteries using carbon materials such as coke, artificial graphite and natural graphite have been widely put into practical use.
- a lithium secondary battery using a highly crystallized carbon material such as natural graphite or artificial graphite as a negative electrode material is a decomposition product generated by reductive decomposition of a solvent in a non-aqueous electrolyte on the negative electrode surface during charging. It has been found that the gas interferes with the desired electrochemical reaction of the battery, resulting in poor cycle characteristics. Moreover, if the decomposition product of the nonaqueous solvent accumulates, the insertion and extraction of lithium into the negative electrode cannot be performed smoothly, and the electrochemical characteristics when used in a wide temperature range are liable to deteriorate.
- the above negative electrode material absorbs and releases lithium and electrons at a very low potential equivalent to that of lithium metal, so that many solvents may undergo reductive decomposition, particularly at high temperatures.
- the deposition, gas generation, and electrode swelling hindered lithium ion movement, resulting in problems such as not only deterioration of cycle characteristics but also deformation of the battery.
- lithium secondary batteries using lithium metal, alloys thereof, simple metals such as tin or silicon, and oxides as negative electrode materials have high initial capacities, but fine powders progress during the cycle.
- reductive decomposition of a non-aqueous solvent occurs at an accelerated rate, and battery performance such as battery capacity and cycle characteristics is greatly reduced.
- a positive electrode material for example, a lithium secondary battery using LiCoO 2 , LiMn 2 O 4 , LiNiO 2 , LiFePO 4, etc.
- the nonaqueous solvent in the nonaqueous electrolyte is charged and the positive electrode material and the nonaqueous electrolyte
- the migration of lithium ions is hindered by the decomposition products and gas generated when the non-aqueous electrolyte is decomposed on the positive electrode and the negative electrode, and the battery is swollen or the battery performance is deteriorated.
- electronic devices equipped with lithium secondary batteries are becoming more and more multifunctional and power consumption is increasing.
- the capacity of lithium secondary batteries has been increasing, and the volume occupied by non-aqueous electrolyte in the battery has become smaller, such as increasing the electrode density and reducing the useless space volume in the battery. .
- Patent Document 1 proposes a non-aqueous electrolyte containing an aromatic carbonate such as bis (4-phenylphenyl) carbonate, and a non-aqueous electrolyte secondary battery using the same. It has been suggested that safety is improved.
- the present invention provides a non-aqueous electrolyte capable of improving electrochemical characteristics over a wide temperature range, particularly at high temperatures, and further reducing the rate of increase in electrode thickness after a high-temperature cycle, an electricity storage device using the same, and It is an object to provide a biphenyl group-containing carbonate compound to be used.
- the present inventors can improve the safety during overcharge to some extent in the non-aqueous electrolyte secondary battery of Patent Document 1.
- the present inventors have included a specific biphenyl group-containing carbonate compound in the non-aqueous electrolyte solution, thereby increasing the rate of increase in electrode thickness after a high-temperature cycle.
- the present invention has been completed.
- R 1 is an alkyl group optionally substituted with a halogen atom having 1 to 12 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 3 to 6 carbon atoms, or 6 to 20 carbon atoms
- An electricity storage device including the positive electrode, the negative electrode, and the nonaqueous electrolytic solution according to (1).
- R 2 is an alkyl group optionally substituted with a halogen atom having 1 to 12 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 3 to 6 carbon atoms, or 6 to 20 carbon atoms
- Y 1 to Y 4 each independently represents a hydrogen atom, a phenyl group, or a benzyl group, provided that all of Y 1 to Y 4 are hydrogen. In the case of an atom, R 2 is a phenyl group.
- a non-aqueous electrolyte that can improve electrochemical characteristics over a wide temperature range, particularly a non-aqueous electrolyte that can reduce the rate of increase in electrode thickness after a high-temperature cycle, a lithium battery using the non-aqueous electrolyte, and the like
- An electricity storage device and a biphenyl group-containing carbonate compound used therefor can be provided.
- the nonaqueous electrolytic solution of the present invention includes a biphenyl group-containing carbonate compound represented by the following general formula (I) in the nonaqueous electrolytic solution in which an electrolyte salt is dissolved in a nonaqueous solvent. It is characterized by.
- R 1 is an alkyl group optionally substituted with a halogen atom having 1 to 12 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 3 to 6 carbon atoms, or 6 to 20 carbon atoms
- the nonaqueous electrolytic solution of the present invention can improve the electrochemical characteristics in a wide temperature range, particularly under high temperature, and further reduce the increase rate of the electrode thickness after the high temperature cycle is not necessarily clear, but as follows Conceivable.
- the nonaqueous electrolytic solution of the present invention is considered to form a mixed film composed of at least three kinds of characteristic groups. That is, (i) in the compound represented by the general formula (I), when at least one of X 1 to X 4 is substituted with a phenyl group or a benzyl group, the compound represented by the general formula (I) is oxidized.
- the polymerization reaction proceeds rapidly, and the mixture contains at least three characteristic groups of “biphenyl group”, “phenyl group or benzyl group”, and “—O—C ( ⁇ O) —O— group”. It is easy to form a film.
- (ii) in the compound represented by the general formula (I) when all of X 1 to X 4 are hydrogen atoms, it is used in combination with a fluorine atom or an unsaturated bond-containing cyclic carbonate at the electrode interface. It is easy to form a mixed film (SEI film) containing at least three characteristic groups of “biphenyl group”, “—O—C ( ⁇ O) —O— group”, and “fluorine atom or unsaturated bond”.
- These mixed coatings are considered to be strong when the substitution position of the benzene ring in the general formula (I) is ortho to the carbonate skeleton, and have an appropriate flexibility that does not prevent the permeation of lithium ions. It is considered that the decomposition of the resulting solvent can be suppressed, and the increase in the electrode thickness after the high temperature cycle can be further suppressed. In addition, it is thought that the mixed film containing these characteristic groups is formed from 1 type or multiple types of compounds.
- the biphenyl group-containing carbonate compound contained in the nonaqueous electrolytic solution of the present invention is represented by the following general formula (I).
- R 1 is an alkyl group optionally substituted with a halogen atom having 1 to 12 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 3 to 6 carbon atoms, or 6 to 20 carbon atoms
- R 1 in the general formula (I) is preferably an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 to 3 carbon atoms, an alkynyl group having 3 to 4 carbon atoms, or an aryl group having 6 to 18 carbon atoms. More preferably, an alkyl group having 1 or 2 carbon atoms, an alkenyl group having 3 carbon atoms, an alkynyl group having 3 carbon atoms, or an aryl group having 6 to 12 carbon atom
- R 1 examples include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-decyl group, Or a branched alkyl group such as an n-dodecyl group, an iso-propyl group, a sec-butyl group, a tert-butyl group, a tert-amyl group, or a 2-ethylhexyl group, a cyclopentyl group, or a cyclohexyl group
- a cycloalkyl group such as a vinyl group, a 2-propenyl group, a 2-butenyl group, or a linear alkenyl group such as a 3-butenyl group, a branched alkenyl group of a 2-methyl-2-propenyl group,
- X 1 to X 4 each independently represents a hydrogen atom, a phenyl group, or a benzyl group, preferably X 2 is a hydrogen atom, and all of X 1 to X 3 Is more preferably a hydrogen atom.
- X 1 to X 4 when at least one of X 1 to X 4 is a phenyl group or a benzyl group, the following compounds are specifically preferred.
- X 1 to X 4 in the general formula (I) such as compounds A1 to A45 and A52 to A73 is a phenyl group or a benzyl group are preferable, and X 4 is a phenyl group Or a compound having a structure which is a benzyl group is more preferable, and 2,6-diphenylphenyl methyl carbonate (Compound A1), 2,6-diphenylphenyl ethyl carbonate (Compound A2), 2,6-diphenylphenyl allyl carbonate (Compound A18) ), 2,6-diphenylphenyl 2-propynyl carbonate (compound A22), 2,6-diphenylphenyl phenyl carbonate (compound A27), 2,6-diphenylphenyl 2-phenylphenyl carbonate (compound A40), 2,6- Diphenylphenyl 3-ph Nylphenyl carbon
- compounds having the structures of compounds B1 to B4, B17 to B18, B22, B27, and B39 to B42 are preferable, and methyl 2-phenylphenyl carbonate (compound B1), ethyl 2-phenylphenyl carbonate (compound B2), Allyl 2-phenylphenyl carbonate (compound B18), 2-phenylphenyl 2-propynyl carbonate (compound B22), phenyl 2-phenylphenyl carbonate (compound B27), bis (2-phenylphenyl) carbonate (compound B40), 2- One or more selected from phenylphenyl 3-phenylphenyl carbonate (compound B41) and 2-phenylphenyl 4-phenylphenyl carbonate (compound B42) Masui.
- these compounds are used, it is easy to form a coating film that is strong and has an appropriate flexibility that does not impede permeation of lithium ions, and an increase in electrode thickness can be suppressed
- the content of the biphenyl group-containing carbonate compound represented by the general formula (I) contained in the non-aqueous electrolyte is 0.001 to 5% by mass in the non-aqueous electrolyte. It is preferable that If the content is 5% by mass or less, there is little possibility that the film is excessively formed on the electrode and the thickness of the electrode increases, and if it is 0.001% by mass or more, the film is sufficiently formed, and the high temperature cycle Since the characteristics are enhanced, the above range is preferable.
- the content is more preferably 0.05% by mass or more, and further preferably 0.1% by mass or more in the non-aqueous electrolyte.
- the upper limit is more preferably 3% by mass or less, and further preferably 2% by mass or less.
- the fluorine atom-containing or unsaturated bond-containing cyclic carbonate that can be used in combination with the biphenyl group-containing carbonate compound represented by the general formula (I) includes 4-fluoro-1,3-dioxolane- Fluorine atom-containing cyclic carbonates such as 2-one (FEC), trans or cis-4,5-difluoro-1,3-dioxolan-2-one (hereinafter collectively referred to as “DFEC”), vinylene carbonate ( VC), vinyl ethylene carbonate (VEC), and carbon carbonate-carbon double bonds such as 4-ethynyl-1,3-dioxolan-2-one (EEC), or cyclic carbonates having a carbon-carbon triple bond 1 Species or two or more are preferably mentioned, such as 4-fluoro-1,3-dioxolan-2-one (FEC), One or more selected from two alkylene carbonate (VC) or 4-ethynyl-1,3
- fluorine atom-containing or unsaturated bond-containing cyclic carbonates may be used singly or in combination of two or more, which is preferable because electrochemical characteristics in a wide temperature range are further improved. . Moreover, it is preferable to use together a fluorine atom-containing cyclic carbonate and an unsaturated bond-containing cyclic carbonate. Suitable combinations of these fluorine-containing or unsaturated bond-containing cyclic carbonates include FEC and DFEC, FEC and VC, FEC and VEC, FEC and EEC, DFEC and VC, DFEC and VEC, DFEC and EEC, VC and VEC.
- VC and EEC VEC and EEC, VEC and EEC, FEC and DFEC and VC, FEC and DFEC and VEC, FEC and DFEC and EEC, FEC and VC and VEC, FEC and VC and EEC, FEC and VEC and EEC, DFEC and VC and VEC DFEC and VC and EEC, DFEC and VEC and EEC, or VC and VEC and EEC are preferable.
- the content of the fluorine atom-containing cyclic carbonate is preferably 0.07% by volume or more, more preferably 1% by volume or more, still more preferably 2% by volume or more with respect to the total volume of the nonaqueous solvent, and the upper limit thereof. Is preferably 35% by volume or less, more preferably 25% by volume or less, still more preferably 15% by volume or less, and even more preferably 10% by volume or less, and the rate of increase in electrode thickness without impairing Li ion permeability. Can be reduced, which is preferable.
- the content of an unsaturated bond-containing cyclic carbonate such as a carbon-carbon double bond or carbon-carbon triple bond is preferably 0.07% by volume or more, more preferably 0.2%, based on the total volume of the nonaqueous solvent. Volume% or more, more preferably 0.7% by volume or more, and the upper limit thereof is preferably 7% by volume or less, more preferably 4% by volume or less, still more preferably 2.5% by volume or less. This is preferable because the increase rate of the electrode thickness can be reduced without impairing the Li ion permeability.
- the biphenyl group-containing carbonate compound represented by the general formula (I) is combined with a non-aqueous solvent, an electrolyte salt, and other additives described below, and a wide temperature range, particularly
- the electrochemical characteristics at high temperatures are synergistically improved, and a unique effect of reducing the increase rate of the electrode thickness is exhibited.
- Nonaqueous solvent As the non-aqueous solvent used in the non-aqueous electrolyte solution of the present invention, one or more selected from cyclic carbonates, chain esters, ethers, lactones, amides, and sulfones are preferably exemplified. From the viewpoint of synergistically improving electrochemical properties over a wide temperature range, it is preferable that a chain ester is included, more preferably a chain carbonate is included, and both a cyclic carbonate and a chain carbonate are included. Most preferred. In the present specification, the term “chain ester” is used as a concept including a chain carbonate and a chain carboxylic acid ester.
- cyclic carbonate one or two kinds selected from the fluorine atom or unsaturated bond-containing cyclic carbonate, ethylene carbonate (EC), propylene carbonate (PC), 1,2-butylene carbonate, and 2,3-butylene carbonate.
- EC ethylene carbonate
- PC propylene carbonate
- 1,2-butylene carbonate 1,2-butylene carbonate
- 2,3-butylene carbonate 1,2-butylene carbonate
- 1 type or 2 types chosen from ethylene carbonate and propylene carbonate are more suitable.
- the non-aqueous solvent contains ethylene carbonate and / or propylene carbonate
- the resistance of the film formed on the electrode is preferably reduced.
- the content of ethylene carbonate and / or propylene carbonate is based on the total volume of the non-aqueous solvent.
- Preferably it is at least 3% by volume, more preferably at least 5% by volume, even more preferably at least 7% by volume, and the upper limit is preferably at most 50% by volume, more preferably at most 45% by volume, still more preferably 35% by volume or less.
- solvents may be used alone, and when used in combination with two or more fluorine atoms or unsaturated bond-containing cyclic carbonates, the electrochemical properties are further improved over a wide temperature range, particularly at high temperatures. Therefore, it is preferable to use a combination of three or more.
- 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 and VC and DFEC, and the like are preferable.
- one or more asymmetric chain carbonates selected from methyl ethyl carbonate (MEC), methyl propyl carbonate (MPC), methyl isopropyl carbonate (MIPC), methyl butyl carbonate, and ethyl propyl carbonate
- MEC methyl ethyl carbonate
- MPC methyl propyl carbonate
- MIPC methyl isopropyl carbonate
- DMC dimethyl carbonate
- DEC diethyl carbonate
- dipropyl carbonate dibutyl carbonate
- pivalate esters such as methyl pivalate, ethyl pivalate, and propyl pivalate
- Preferable examples include one or two or more chain carboxylic acid esters selected from methyl propionate, ethyl propionate, methyl acetate, and ethyl acetate.
- chain esters having a methyl group selected from dimethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, methyl isopropyl carbonate, methyl butyl carbonate, methyl propionate, methyl acetate, and ethyl acetate are preferable, particularly methyl.
- a chain carbonate having a group is preferred.
- 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 contained, and it is further more preferable that the content of the symmetric chain carbonate is more than that of the asymmetric chain carbonate.
- 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, the viscosity of the non-aqueous electrolyte does not become too high, and if it is 90% by volume or less, the electrical conductivity of the non-aqueous electrolyte is lowered and the temperature is wide, particularly at high temperatures. Since there is little possibility that an electrochemical characteristic will fall, it is preferable that it is the said range.
- the volume ratio of the symmetric chain carbonate in the chain carbonate is preferably 51% by volume or more, and more preferably 55% by volume or more.
- the upper limit is more preferably 95% by volume or less, and still more preferably 90% by volume or less.
- the symmetric chain carbonate contains dimethyl carbonate.
- the asymmetric chain carbonate preferably has a methyl group, and methyl ethyl carbonate is particularly preferable. The above-described case is preferable because electrochemical characteristics at a wider temperature range, particularly at a high temperature, are improved and the rate of increase in electrode thickness is reduced.
- the ratio between the cyclic carbonate and the chain ester is preferably 10:90 to 45:55, and 15:85 from the viewpoint of improving electrochemical characteristics over a wide temperature range, particularly at high temperatures. ⁇ 40: 60 is more preferred, and 20:80 to 35:65 is particularly preferred.
- nonaqueous solvents include cyclic ethers such as tetrahydrofuran, 2-methyltetrahydrofuran and 1,4-dioxane, chains such as 1,2-dimethoxyethane, 1,2-diethoxyethane and 1,2-dibutoxyethane.
- cyclic ethers such as tetrahydrofuran, 2-methyltetrahydrofuran and 1,4-dioxane
- chains such as 1,2-dimethoxyethane, 1,2-diethoxyethane and 1,2-dibutoxyethane.
- Preferable examples include one or more selected from lactones such as cyclic ether, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -angelicalactone, amides such as dimethylformamide, and sulfones such as sulfolane.
- the above non-aqueous solvents are usually used as a mixture in order to achieve appropriate physical properties.
- the combination includes, for example, a combination of a cyclic carbonate and a chain carbonate, a combination of a cyclic carbonate and a chain carboxylic acid ester, a combination of a cyclic carbonate, a chain carbonate and a lactone, and a combination of a cyclic carbonate, a chain carbonate and an ether.
- a combination, a combination of a cyclic carbonate, a chain carbonate, and a chain carboxylate, and the like are preferable.
- non-aqueous electrolyte of the present invention as an additive that can be used in combination with the biphenyl group-containing carbonate compound represented by the general formula (I), (a) SO 2 group-containing compound, (b) fluorinated benzene Compound, (c) phosphate compound, (d) carbon-carbon triple bond-containing compound, (e) carboxylic acid anhydride, (f) isocyanate compound, (g) lithium-containing ionic compound, (h) nitrile compound, Examples thereof include at least one selected from (i) a benzene compound, (j) a cyclic acetal compound, and (k) a phosphazene compound.
- the biphenyl group-containing carbonate compound represented by the general formula (I) (a) SO 2 group-containing compound, (b) fluorinated benzene Compound, (c) phosphate compound, (d) carbon-carbon triple bond-containing compound, (e) carboxylic acid anhydride, (f) isocyan
- a mixed SEI film is formed by four or five or more functional groups or characteristic groups, and the rate of increase in electrode thickness after high-temperature cycling is increased. The effect of reducing can be further enhanced.
- the (a) SO 2 group-containing compound is not particularly limited as long as it is a compound having an “SO 2 group” in the molecule.
- Specific examples thereof include 1,3-propane sultone, 1,3-butane sultone, 2,4-butane sultone, 1,4-butane sultone, 1,3-propene sultone, 2,2-dioxide-1,2-oxathiolane- Sultone such as 4-yl acetate or 5,5-dimethyl-1,2-oxathiolane-4-one 2,2-dioxide, ethylene sulfite, butane-2,3-diyl dimethanesulfonate, butane-1,4 Preferred examples include one or more selected from diyl dimethanesulfonate, pentane-1,5-diyl dimethanesulfonate, methylenemethane disulfonate, divinylsulfone, and the like.
- 1,3-propane sultone, 1,4-butane sultone, 2,4-butane sultone, 2,2-dioxido-1,2-oxathiolan-4-yl acetate, 5,5-dimethyl -1,2-oxathiolane-4-one One or more selected from 2,2-dioxide, butane-2,3-diyl dimethanesulfonate, and divinylsulfone are more preferable.
- the type of (b) fluorinated benzene compound is not particularly limited as long as it is a compound having a “phenyl group in which at least a part of the benzene ring is substituted with fluorine” in the molecule.
- Specific examples thereof include fluorobenzene, difluorobenzene (o, m, p isomer), 2,4-difluoroanisole, 1-fluoro-2-cyclohexylbenzene, 1-fluoro-3-cyclohexylbenzene, 1-fluoro-4.
- fluorinated benzene compound examples include fluorobenzene, 2,4-difluoroaniol, 1-fluoro-4-cyclohexylbenzene, pantafluorophenylmethanesulfonate, 2-fluorophenylmethanesulfonate, 2,4-difluorophenylmethanesulfonate, And one or more selected from 4-fluoro-3-trifluoromethylphenylmethanesulfonate.
- the type of (c) phosphate ester compound is not particularly limited as long as it is a compound having a “P ( ⁇ O) group” in the molecule.
- Specific examples thereof include trimethyl phosphate, tributyl phosphate, and trioctyl phosphate, tris (2,2,2-trifluoroethyl) phosphate, bis (2,2,2-trifluoroethyl) methyl phosphate, Bis (2,2,2-trifluoroethyl) phosphate, bis (2,2,2-trifluoroethyl) phosphate, 2,2-difluoroethyl phosphate, bis (2,2,2-trifluoroethyl phosphate) ) 2,2,3,3-tetrafluoropropyl, bis (2,2-difluoroethyl) phosphate 2,2,2-trifluoroethyl, bis (2,2,3,3-tetrafluoropropyl) phosphate 2,2,2-trifluoroethy
- tris phosphate (2,2,2-trifluoroethyl), tris phosphate (1,1,1,3,3,3-hexafluoropropan-2-yl), methyl 2 -(Dimethoxyphosphoryl) acetate, ethyl 2- (dimethoxyphosphoryl) acetate, methyl 2- (diethoxyphosphoryl) acetate, ethyl 2- (diethoxyphosphoryl) acetate, 2-propynyl 2- (dimethoxyphosphoryl) acetate, 2-propynyl 2- (Diethoxyphosphoryl) acetate is preferred
- One or more selected from diethoxyphosphoryl) acetate is more preferable.
- the carbon-carbon triple bond-containing compound is not particularly limited as long as it is a compound having a “carbon-carbon triple bond” in the molecule.
- the type of (e) carboxylic acid anhydride is not particularly limited as long as it is a compound having a “C ( ⁇ O) —O—C ( ⁇ O) group” in the molecule.
- chain carboxylic anhydrides such as acetic anhydride and propionic anhydride, succinic anhydride, maleic anhydride, allyl succinic anhydride, glutaric anhydride, itaconic anhydride, 3-sulfo-propionic anhydride
- One type or two or more types selected from cyclic acid anhydrides and the like are preferable.
- carboxylic anhydrides one or more selected from succinic anhydride, maleic anhydride, and allyl succinic anhydride are preferable, and one or two selected from succinic anhydride and allyl succinic anhydride are preferable. More preferred.
- the type of isocyanate compound is not particularly limited as long as it is a compound having “N ⁇ C ⁇ O group”. Specific examples thereof include methyl isocyanate, ethyl isocyanate, butyl isocyanate, phenyl isocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, 1,4-phenylene diisocyanate, 2-isocyanatoethyl acrylate, and 2-isocyanatoethyl. One or more kinds selected from methacrylate and the like are preferably mentioned.
- isocyanate compounds one or more selected from hexamethylene diisocyanate, octamethylene diisocyanate, 2-isocyanatoethyl acrylate, and 2-isocyanatoethyl methacrylate are preferable.
- Hexamethylene diisocyanate, 2-isocyanatoethyl One or more selected from acrylate and 2-isocyanatoethyl methacrylate are more preferable.
- the lithium-containing ionic compound is not particularly limited as long as it is a compound having “lithium” as a cation species. Specific examples thereof include lithium difluorophosphate, lithium fluorophosphate, lithium fluorosulfonate, difluorobis [oxalate-O, O ′] lithium phosphate (LiPFO), and tetrafluoro [oxalate-O, O ′] phosphate.
- lithium borate LiBOB
- difluoro [oxalate-O, O ′] lithium borate lithium methyl sulfate, lithium ethyl sulfate, lithium propyl sulfate, and the like Two or more are preferably mentioned.
- lithium-containing ionic compounds lithium difluorophosphate, lithium fluorosulfonate, difluorobis [oxalate-O, O ′] lithium phosphate (LiPFO), lithium tetrafluoro [oxalate-O, O ′] lithium phosphate,
- LiPFO difluorobis [oxalate-O, O ′] lithium phosphate
- Li tetrafluoro [oxalate-O, O ′] lithium phosphate lithium tetrafluoro [oxalate-O, O ′] lithium phosphate
- LiBOB lithium borate
- difluoro [oxalate-O, O ′] lithium borate lithium methyl sulfate, lithium ethyl sulfate, and lithium propyl sulfate Is more preferable.
- the type of (h) nitrile compound is not particularly limited as long as it is a compound having a “nitrile group”. Specific examples thereof include one or more selected from acetonitrile, propionitrile, succinonitrile, glutaronitrile, adiponitrile, pimelonitrile, suberonitrile, and sebaconitrile. Among the nitrile compounds, one or more selected from succinonitrile, glutaronitrile, adiponitrile, and pimelonitrile are more preferable.
- the type of benzene compound is not particularly limited as long as it is a compound having a “phenyl group” in the molecule. Specific examples thereof include aromatic compounds having a branched alkyl group such as cyclohexylbenzene, tert-butylbenzene, tert-amylbenzene, biphenyl, terphenyl (o-, m-, p-isomer), diphenyl ether, anisole.
- Terphenyl hydrides (1,2-dicyclohexylbenzene, 2-phenylbicyclohexyl, 1,2-diphenylcyclohexane, o-cyclohexylbiphenyl), and phenyl carbonates such as methylphenyl carbonate, ethylphenyl carbonate, or diphenyl carbonate
- phenyl carbonates such as methylphenyl carbonate, ethylphenyl carbonate, or diphenyl carbonate
- One type or two or more types selected from compounds are preferred.
- benzene compounds one selected from cyclohexylbenzene, tert-butylbenzene, tert-amylbenzene, biphenyl, terphenyl (o-, m-, p-isomer), methylphenyl carbonate, ethylphenyl carbonate, and diphenyl carbonate Alternatively, two or more are more preferable, and one or more selected from cyclohexylbenzene, tert-amylbenzene, biphenyl, o-terphenyl, methylphenyl carbonate, ethylphenyl carbonate, and diphenyl carbonate are particularly preferable.
- the type of the cyclic acetal compound is not particularly limited as long as it is a compound having an “acetal group” in the molecule. Specific examples thereof include one or more selected from 1,3-dioxolane, 1,3-dioxane, 1,3,5-trioxane, and the like. Among the cyclic acetal compounds, 1,3-dioxolane or 1,3-dioxane is preferable, and 1,3-dioxane is more preferable.
- the type of (k) phosphazene compound is not particularly limited as long as it is a compound having “N ⁇ PN group” in the molecule. Specific examples thereof include one or more selected from methoxypentafluorocyclotriphosphazene, ethoxypentafluorocyclotriphosphazene, phenoxypentafluorocyclotriphosphazene, ethoxyheptafluorocyclotetraphosphazene, and the like.
- phosphazene compounds such as methoxypentafluorocyclotriphosphazene, ethoxypentafluorocyclotriphosphazene, or phenoxypentafluorocyclotriphosphazene are preferable, and are selected from methoxypentafluorocyclotriphosphazene and ethoxypentafluorocyclotriphosphazene. 1 type or 2 types or more are still more preferable.
- A SO 2 group-containing compound, (b) fluorinated benzene compound, (c) phosphate ester compound, (d) carbon-carbon triple bond-containing compound, (e) carboxylic acid anhydride, (f) isocyanate compound , (G) lithium-containing ionic compound, (h) nitrile compound, (i) benzene compound, (j) cyclic acetal compound, or (k) phosphazene compound content is 0.001 in the non-aqueous electrolyte, respectively. ⁇ 5% by weight is preferred.
- the film is sufficiently formed without becoming too thick, and not only the effect of improving the electrochemical characteristics in a wide temperature range, particularly at a high temperature, but also the increase rate of the electrode thickness can be further reduced.
- the content is more preferably 0.01% by mass or more, more preferably 0.1% by mass or more in the non-aqueous electrolyte, and the upper limit is more preferably 3.5% by mass or less, and 2.5% by mass. The following is more preferable.
- a lithium-containing ionic compound (a) a SO 2 group-containing compound, (b) a fluorinated benzene compound, (c) a phosphate ester compound, (d) a carbon-carbon triple bond-containing compound , (E) carboxylic acid anhydride, (f) isocyanate compound, (h) nitrile compound, (i) benzene compound, (j) cyclic acetal compound, and (k) phosphazene compound.
- a preferable example of the electrolyte salt used in the present invention is a lithium salt.
- the lithium salt include inorganic lithium salts such as LiPF 6 , LiBF 4 , LiClO 4 , LiN (SO 2 F) 2 , 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 , or LiPF 3 (iso-C 3 F 7 ) 3 , Alternatively, a lithium salt containing a chain-like fluorinated alkyl group such as LiPF 5 (iso-C 3 F 7 ), (CF 2 ) 2 (SO 2 ) 2 NLi, or (CF 2 ) 3 (SO 2 ) 2 One or two or more lithium salts having a cyclic fluorinated alkyl group such as LiPF
- LiPF 6 LiBF 4 , LiN (SO 2 F) 2 , LiN (SO 2 CF 3 ) 2 , and LiN (SO 2 C 2 F 5 ) 2 are preferable, LiPF 6, LiBF 4, LiN ( SO 2 CF 3) 2, and LiN (SO 2 F) 1, two or more more preferably selected from 2, it is most preferable to use LiPF 6.
- the concentration of the lithium salt is usually preferably 0.3 M or more, more preferably 0.7 M or more, and further 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.
- lithium salts include LiPF 6, further, LiN (SO 2 F) 1, two or more more preferably selected from 2, lithium salt other than LiPF 6 nonaqueous solvent
- LiPF 6 LiN (SO 2 F) 1, two or more preferably selected from 2, lithium salt other than LiPF 6 nonaqueous solvent
- the proportion of the content is 0.001M or more, the effect of improving the electrochemical characteristics at high temperature is easily exhibited, and if it is 0.5M or less, the effect of improving the electrochemical characteristics at high temperature is less likely to be reduced. Therefore, it is preferable.
- it is 0.01M or more, Especially preferably, it is 0.03M or more, Most preferably, it is 0.04M or more.
- the upper limit is preferably 0.4M or less, particularly preferably 0.2M or less.
- the ratio of the molar concentration of the biphenyl group-containing carbonate compound represented by the general formula (I) to LiPF 6 is 0.0005 or more to improve the electrochemical characteristics at high temperature.
- the effect is easily exhibited, and it is preferable that it is 0.3 or less because the effect of improving electrochemical properties at high temperatures is less likely to be lowered.
- the lower limit is more preferably 0.001 or more, and still more preferably 0.005 or more.
- the upper limit is more preferably 0.2 or less, and still more preferably 0.1 or less.
- the non-aqueous electrolyte of the present invention is prepared, for example, by mixing the non-aqueous solvent with the biphenyl group-containing carbonate compound represented by the general formula (I) with respect to the electrolyte salt and the non-aqueous electrolyte. It can be obtained by adding. 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 to fourth power 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 the first electricity storage device (that is, for a lithium battery) or the fourth electricity storage device (that is, for a lithium ion capacitor) that uses a lithium salt as an electrolyte salt, and is used for a lithium battery. More preferably, it is more preferably used for a lithium secondary battery.
- the lithium battery is a general 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 composite metal oxide with lithium containing one or more selected from cobalt, manganese, and nickel is used as the positive electrode active material for a lithium secondary battery.
- 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. Examples thereof include one or more selected from Mn 1/3 O 2 , LiNi 1/2 Mn 3/2 O 4 , and LiCo 0.98 Mg 0.02 O 2 . Further, 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, nickel is replaced with at least one element such as Sn, Mg, Fe, Ti, Al, Zr, Cr, V, Ga, Zn, Cu, Bi, Mo, La, etc.
- a part of O may be substituted with S or F, or a compound containing these other elements may be coated.
- 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, and Cu, 0.001 ⁇ x ⁇ 0) .05), LiNi 1/3 Mn 1/3 Co 1/3 O 2 , LiNi 1/2 Mn 3/2 O 4 , Li 2 MnO 3 and LiMO 2 (M is Co, Ni, Mn, Fe, etc.
- a lithium composite metal oxide that operates at a high charging voltage When a lithium composite metal oxide that operates at a high charging voltage is used, the electrochemical characteristics when used in a wide temperature range are liable to deteriorate due to a reaction with the electrolyte during charging, but the lithium secondary battery according to the present invention Then, the deterioration of these electrochemical characteristics can be suppressed.
- the resistance of the battery tends to increase with the elution of Mn ions from the positive electrode, so that the electrochemical characteristics when used in a wide temperature range tend to be lowered.
- the lithium secondary battery according to the invention is preferable because it can 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 one or more selected from LiFePO 4 , LiCoPO 4 , LiNiPO 4 , LiMnPO 4 , and LiFe 1-x Mn x PO 4 (0.1 ⁇ x ⁇ 0.9). .
- LiFePO 4 or LiMnPO 4 is more preferable, and LiFePO 4 is more preferable.
- 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 two or more elements selected from these, or can be coated with a compound or carbon material containing these other elements.
- LiFePO 4 or LiMnPO 4 is preferable.
- mold phosphate can also be mixed with the said positive electrode active material, for example, and can be used.
- the lithium-containing olivine-type phosphate forms a stable phosphate skeleton (PO 4 ) structure and is excellent in thermal stability during charging, so that the rate of increase in electrode thickness after a high-temperature cycle can be further reduced.
- positive electrodes for lithium primary batteries 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 3 , one or more metal element oxides or chalcogen compounds, SO 2 , SOCl 2, etc.
- Examples thereof include compounds, and fluorocarbons (fluorinated graphite) represented by the general formula (CF x ) n .
- fluorocarbons fluorinated graphite
- CF x fluorinated graphite
- MnO 2 , V 2 O 5 , graphite fluoride and the like are preferable.
- the pH of the supernatant liquid when 10.0 g of the positive electrode active material is dispersed in 100 ml of distilled water is 10.0 to 12.5, the effect of improving the electrochemical characteristics in a wider temperature range can be easily obtained.
- the case of 10.5 to 12.0 is more preferable.
- impurities such as LiOH in the positive electrode active material tend to increase, an effect of improving electrochemical characteristics in a wider temperature range is easily obtained, which is preferable.
- the case where the atomic concentration of Ni in the substance is 5 to 25 atomic% is more preferable, and the case where it is 8 to 21 atomic% is particularly 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.
- graphite such as natural graphite (flaky graphite, etc.), graphite such as artificial graphite, acetylene black, ketjen black, channel black, furnace black, lamp black, and one or more carbon blacks selected from thermal black, etc. Can be mentioned. Further, graphite and carbon black may be mixed as appropriate.
- 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.
- a binder such as copolymer (NBR), carboxymethyl cellulose (CMC), or ethylene propylene diene terpolymer, add high boiling point solvent such as 1-methyl-2-pyrrolidone and knead to mix the positive electrode.
- this positive electrode mixture is 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 produce by heat-processing with.
- the density of the part except the collector of the positive electrode is usually at 1.5 g / cm 3 or more, for further increasing the capacity of the battery, it 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.
- the upper limit is preferably 4 g / cm 3 or less.
- 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 two or more selected from compounds and the like can be used in combination.
- a highly crystalline carbon material such as artificial graphite and natural graphite
- the lattice spacing (d 002 ) of the lattice plane ( 002 ) is 0.
- a carbon material having a graphite type crystal structure of 340 nm (nanometer) or less, particularly 0.335 to 0.337 nm.
- artificial graphite particles having a massive structure in which a plurality of flat graphite fine particles are assembled or bonded non-parallel to each other, and mechanical actions such as compressive force, frictional force, shearing force, etc. are repeatedly applied, and scaly natural graphite is spherical. It is preferable to use particles that have been treated.
- the (004) plane peak intensity I (004) ratio I (110) / I (004) is preferably 0.01 or more because the electrochemical characteristics in a wider temperature range are further improved, and 0.05 or more. More preferably, it is more preferably 0.1 or more.
- the upper limit of the peak intensity ratio I (110) / I (004) is preferably 0.5 or less. 3 or less is more preferable.
- the highly crystalline carbon material (core material) is covered with a carbon material having lower crystallinity than the core material because electrochemical characteristics in a wide temperature range are further improved.
- the crystallinity of the carbon material of the coating can be confirmed by TEM.
- metal compounds 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, Cu, and Zn.
- Preferred examples include compounds containing at least one metal element such as Ag, Mg, Sr and Ba. These metal compounds may be used in any form such as simple substance, alloy, oxide, nitride, sulfide, boride, or alloy with lithium. Any one is preferable because the capacity can be increased. Among these, those containing at least one element selected from Si, Ge and Sn are preferable, and those containing at least one element selected from Si and Sn are more preferable because the capacity of the battery can be increased.
- 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 in order to further increase the capacity of the battery.
- the upper limit is preferably 2 g / cm 3 or less.
- examples of the negative electrode active material for a lithium primary battery include lithium metal and lithium alloy.
- the lithium battery there is no particular limitation on the structure of the lithium battery, 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.
- a separator for batteries The single layer or laminated microporous film of polyolefin, such as a polypropylene and polyethylene, a woven fabric, a nonwoven fabric, etc. can be used.
- the lithium secondary battery according to the present invention has excellent electrochemical characteristics in a wide temperature range even when the end-of-charge voltage is 4.2 V or more, particularly 4.3 V or more, and the characteristics are also good at 4.4 V or more. is there.
- the end-of-discharge voltage is usually 2.8 V or more, and further 2.5 V or more, but the lithium secondary battery in the present invention can be 2.0 V or more.
- 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 as a safety measure for preventing overcharge.
- the battery lid can be provided with a current interruption mechanism that senses the internal pressure of the battery and interrupts the current.
- the 2nd electrical storage device of this invention is an electrical storage device which stores the energy using the electric double layer capacity
- An example of the present invention is an electric double layer capacitor.
- the most typical electrode active material used for this electricity storage device is activated carbon. Double layer capacity increases roughly in proportion to surface area.
- the 3rd electrical storage device of this invention is an electrical storage device which stores the energy using the dope / dedope reaction of an electrode including the non-aqueous electrolyte of this invention.
- the electrode active material used in this power storage device include metal oxides such as ruthenium oxide, iridium oxide, tungsten oxide, molybdenum oxide, and copper oxide, and ⁇ -conjugated polymers such as polyacene and polythiophene derivatives. Capacitors using these electrode active materials can store energy associated with electrode doping / dedoping reactions.
- a fourth electricity storage device of the present invention is an electricity storage device that contains the non-aqueous electrolyte of the present invention and stores energy using lithium ion intercalation into a carbon material such as graphite as a negative electrode. It is called an ion capacitor (LIC).
- the positive electrode include those using an electric double layer between an activated carbon electrode and an electrolytic solution, and those using a ⁇ -conjugated polymer electrode doping / dedoping reaction.
- the electrolyte contains at least a lithium salt such as LiPF 6 .
- R 2 is an alkyl group optionally substituted with a halogen atom having 1 to 12 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 3 to 6 carbon atoms, or 6 to 20 carbon atoms
- Y 1 to Y 4 each independently represents a hydrogen atom, a phenyl group, or a benzyl group, provided that all of Y 1 to Y 4 are hydrogen. In the case of an atom, R 2 is a phenyl group.
- the aryl group which may be substituted with a halogen atom having 6 to 20 carbon atoms has the same meaning as R 1 in the general formula (I), and description thereof is omitted in this column to avoid duplication.
- the compound represented by the general formula (II) can be synthesized by the methods described in the following (a) to (c), but is not limited to these methods.
- A A method in which a phenol compound is reacted with a carbonylating agent such as triphosgene or carbonyldiimidazole in a solvent or in the absence of a solvent in the presence or absence of a base.
- B A method in which a phenol compound is reacted with a chloroformate in the presence or absence of a base in a solvent or in the absence of a solvent.
- C A method in which a phenol compound is transesterified with a carbonate ester in the presence of an acid or a base catalyst in a solvent or without a solvent.
- the amount of triphosgene and carbonyldiimidazole to be reacted with the phenol compound for (a) when synthesizing a symmetrical carbonate, it is preferably 0.1 to 10 per mol of the phenol compound. Mol, more preferably 0.3 to 5 mol, still more preferably 0.5 to 1.5 mol. When synthesizing an asymmetric carbonate, it is preferably 0.8 to 10 mol, more preferably 1 to 5 mol, and still more preferably 1 to 3 mol.
- chloroformate to be reacted with the phenol compound for (b) commercially available products such as methyl chloroformate, ethyl chloroformate, vinyl chloroformate, allyl chloroformate, phenyl chloroformate and the like can be used.
- Various chloroformates can be prepared and used by reacting triphosgene with alcohol or a phenol compound. The amount to be used is preferably 0.8 to 10 mol, more preferably 1 to 5 mol, and still more preferably 1 to 3 mol with respect to 1 mol of the phenol compound.
- the base used in the methods (a) to (c) may be either an inorganic base or an organic base, and these may be used alone or in combination.
- Inorganic bases used include potassium carbonate, sodium carbonate, calcium hydroxide, and calcium oxide.
- Organic bases used include linear or branched aliphatic tertiary amines, unsubstituted or substituted imidazoles, pyridines, pyrimidines, especially trimethylamine, triethylamine, tripropylamine, tributylamine, or ethyldiisopropyl. More preferred are trialkylamines such as amines, pyridines, and pyridines such as N, N-dimethylaminopyridine.
- the amount of the base used is 0.8 to 5 mol, more preferably 1 to 3 mol, and particularly preferably 1 to 1.5 mol, with respect to 1 mol of the phenolic compound, and is particularly preferably 1 to 1.5 mol since the formation of by-products can be suppressed.
- the solvent used in the methods (a) to (c) is not particularly limited as long as it is inert to the reaction. Suitable examples of the solvent that can be used include aliphatic hydrocarbons, halogenated hydrocarbons, aromatic hydrocarbons, halogenated aromatic hydrocarbons, ethers, esters, and carbonates.
- aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as methylene chloride and 1,2-dichloroethane, ethers such as diethyl ether and tetrahydrofuran, esters such as ethyl acetate and butyl acetate, or Carbonic acid esters such as dimethyl carbonate and diethyl carbonate can be suitably used.
- the amount of the solvent used is preferably 0 to 30 parts by mass, more preferably 1 to 15 parts by mass with respect to 1 part by mass of the phenol compound.
- Examples of the effect of the compound represented by the general formula (II) include, but are not limited to, the effect as an additive for an electricity storage device shown in the following examples.
- the compound represented by the general formula (II) is a novel biphenyl group-containing carbonate compound, and due to its special structure, it can be used as an electrolyte in the fields of chemistry in general, especially organic chemistry, electrochemistry, biochemistry and polymer chemistry. In addition, it can be used as a material for heat-resistant applications. Therefore, the compound represented by the general formula (II) is a compound useful as an intermediate raw material such as pharmaceuticals, agricultural chemicals, electronic materials, polymer materials, or battery materials.
- the obtained 2-benzyl-6-phenylphenyl carbonate was measured by 1 H-NMR and CI-MS to confirm its structure. The results are shown below.
- Examples 1-1 to 1-18, 2-1 to 2-20, Comparative Example 1-1 [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 to 5 is added to produce a laminate type battery. did.
- Discharge capacity retention ratio (%) (discharge capacity at the 100th cycle / discharge capacity at the first cycle) ⁇ 100 ⁇ Initial anode thickness>
- the battery cycled by the above method was disassembled and the initial negative electrode thickness was measured.
- ⁇ Negative thickness after cycle> The battery that had been subjected to 100 cycles by the above method was disassembled, and the negative electrode thickness after the high temperature cycle was measured.
- Negative electrode thickness increase value negative electrode thickness after cycle ⁇ initial negative electrode thickness
- Negative electrode thickness increase rate (%) was determined based on the negative electrode thickness increase value of Comparative Example 1-1 as 100%.
- Example 1-2 was compared with Example 1-2, except that this negative electrode mixture paste was applied to one side of a copper foil (current collector), dried and pressurized to produce a negative electrode sheet cut into a predetermined size.
- a laminated battery was produced in the same manner as in Example 1-1, and the battery was evaluated. The results are shown in Table 6.
- Example 1-20 and Comparative Example 1-3 A positive electrode sheet was produced using LiFePO 4 (positive electrode active material) coated with amorphous carbon instead of the positive electrode active material used in Example 1-2 and Comparative Example 1-1. 90% by mass of LiFePO 4 coated with amorphous carbon and 5% by mass of acetylene black (conductive agent) are mixed, and 5% by mass of polyvinylidene fluoride (binder) is dissolved in 1-methyl-2-pyrrolidone in advance.
- a positive electrode mixture paste was prepared by adding to and mixing with the previously prepared solution. This positive electrode mixture paste was applied to one side of an aluminum foil (current collector), dried, pressurized, cut into a predetermined size, and a positive electrode sheet was produced.
- Example 1-2 and Comparative Example 1 except that the voltage was 3.6 V, the end-of-discharge voltage was 2.0 V, and the compound of the general formula (1) was not added in Comparative Example 1-3.
- a laminate type battery was produced in the same manner as in Example 1, and the battery was evaluated. The results are shown in Table 7.
- Example 1-21 and Comparative Example 1-4 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 1-2 and Comparative Example 1-1. 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. Of Example 1-2 and Comparative Example 1 except that the compound of formula (1) was not added in Comparative Example 1-4. A laminate type battery was produced in the same manner as in Example 1, and the battery was evaluated. The results are shown in Table 8.
- the thickness of the negative electrode after the high temperature cycle was increased as compared with Comparative Example 1-1. Is suppressed.
- the effect of reducing the increase rate of the electrode thickness of the present invention is a unique effect when the specific compound of the present invention is contained in the nonaqueous electrolytic solution in which the electrolyte salt is dissolved in the nonaqueous solvent. It turned out to be.
- silicon was used for the negative electrode.
- LiFePO 4 is used for the positive electrode, the same effect is obtained when lithium titanate is used for the negative electrode.
- the non-aqueous electrolyte of the present invention has an effect of improving the discharge characteristics in a wide temperature range of the lithium primary battery.
- non-aqueous electrolyte of the present invention an electricity storage device having excellent electrochemical characteristics over a wide temperature range, particularly at high temperatures, and further suppressing an increase in electrode thickness after a high temperature cycle can be obtained.
- non-aqueous electrolytes for power storage devices such as lithium secondary batteries mounted on devices that are likely to be used at high temperatures such as hybrid electric vehicles, plug-in hybrid electric vehicles, battery electric vehicles, tablet terminals and ultrabooks
- novel biphenyl group-containing carbonate compound of the present invention from its special structure, in general chemistry, particularly in the fields of organic chemistry, electrochemistry, biochemistry and polymer chemistry, as a material for electrolyte use, heat resistance use, etc. It is useful as an intermediate material for medicines, agricultural chemicals, electronic materials, polymer materials, etc., or battery materials.
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Abstract
Description
また、地球温暖化防止のため、CO2排出量を削減することが急務となっており、リチウム二次電池やキャパシタ等の蓄電デバイスからなる蓄電装置を搭載した環境対応車の中でも、ハイブリッド電気自動車(HEV)、プラグインハイブリッド電気自動車(PHEV)、バッテリー電気自動車(BEV)の早期普及が求められている。
自動車は移動距離が長いため、熱帯の非常に暑い地域から極寒の地域まで幅広い温度範囲の地域で使用される可能性がある。従って、特にこれらの車載用の蓄電デバイスは、高温から低温まで幅広い温度範囲で使用しても電気化学特性が低下しないことが要求されている。
なお、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。
また、負極としては、金属リチウム、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)や炭素材料が知られており、特にリチウムを吸蔵及び放出することが可能なコークス、人造黒鉛、天然黒鉛等の炭素材料を用いたリチウム二次電池が広く実用化されている。
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が知られている。また、これらの負極材料の微粉化や非水溶媒の分解物が蓄積すると、負極へのリチウムの吸蔵及び放出がスムーズにできなくなり、広い温度範囲で使用した場合における電気化学特性が低下しやすくなる。特に高温下において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1には、ビス(4-フェニルフェニル)カーボネート等の芳香族炭酸エステルを含有する非水電解液、及びそれを用いた非水電解液二次電池が提案されており、過充電時の安全性が向上することが示唆されている。
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、特定のビフェニル基含有カーボネート化合物を非水電解液中に含有することにより、高温サイクル後の電極厚みの増加率を低減させることができることを見出し、本発明を完成した。
(1)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)で表されるビフェニル基含有カーボネート化合物を含むことを特徴とする非水電解液。
(3)下記一般式(II)で表されるビフェニル基含有カーボネート化合物。
本発明の非水電解液は、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、非水電解液中に下記一般式(I)で表されるビフェニル基含有カーボネート化合物を含むことを特徴とする。
本発明の非水電解液は、少なくとも3種の特性基からなる混合被膜を形成すると考えられる。即ち、(i)一般式(I)で表される化合物において、X1~X4の少なくとも1つがフェニル基又はベンジル基で置換されている場合、一般式(I)で表される化合物が酸化還元を受け、速やかに重合反応が進行し、「ビフェニル基」、「フェニル基又はベンジル基」、及び「-O-C(=O)-O-基」の少なくとも3種の特性基を含む混合被膜を形成しやすい。また、(ii)一般式(I)で表される化合物において、X1~X4の全てが水素原子である場合、フッ素原子又は不飽和結合含有環状カーボネートと併用することで、電極界面に「ビフェニル基」、「-O-C(=O)-O-基」、及び「フッ素原子又は不飽和結合」の少なくとも3種の特性基を含む混合被膜(SEI被膜)を形成しやすい。これらの混合被膜は、一般式(I)におけるベンゼン環の置換位置がカーボネート骨格に対してオルト位の場合に強固となり、かつリチウムイオンの透過を妨げない適度な柔軟性を有すると考えられ、更なる溶媒の分解を抑制し、高温サイクル後の電極厚みの増加をより一層抑制することができると考えられる。なお、これらの特性基を含む混合被膜は、1種又は複数種の化合物から形成されていると考えられる。
前記一般式(I)のR1としては、炭素数1~3のアルキル基、炭素数2~3のアルケニル基、炭素数3~4のアルキニル基、又は炭素数6~18のアリール基が好ましく、炭素数1又は2のアルキル基、炭素数3のアルケニル基、炭素数3のアルキニル基、又は炭素数6~12のアリールがより好ましい。
これらの中でも、メチル基、エチル基、n-プロピル基、iso-プロピル基、ビニル基、2-プロペニル基、2-プロピニル基、2-ブチニル基、3-ブチニル基、フェニル基、2-フェニルフェニル基、3-フェニルフェニル基、4-フェニルフェニル基、2,6-ジフェニルフェニル基、2,4-ジメチルフェニル基、2-フルオロフェニル基、又はパーフルオロフェニル基が好ましく、メチル基、エチル基、2-プロペニル基、2-プロピニル基、フェニル基、2-フェニルフェニル基、3-フェニルフェニル基、4-フェニルフェニル基、又は2,6-ジフェニルフェニル基がより好ましい。
前記一般式(I)において、X1~X4のうち、少なくとも1つがフェニル基、又はベンジル基の場合、具体的に以下の化合物が好適に挙げられる。
これらのフッ素原子含有又は不飽和結合含有環状カーボネートの好適な組合せとしては、FECとDFEC、FECとVC、FECとVEC、FECとEEC、DFECとVC、DFECとVEC、DFECとEEC、VCとVEC、VCとEEC、VECとEEC、FECとDFECとVC、FECとDFECとVEC、FECとDFECとEEC、FECとVCとVEC、FECとVCとEEC、FECとVECとEEC、DFECとVCとVEC、DFECとVCとEEC、DFECとVECとEEC、又はVCとVECとEEC等が好適に挙げられる。前記組み合わせのうち、FECとVC、FECとEEC、VCとVEC、VCとEEC、VECとEEC、FECとVCとVEC、FECとVCとEEC、FECとVECとEEC、又はVCとVECとEECがより好ましい。
炭素-炭素二重結合又は炭素-炭素三重結合等の不飽和結合含有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0.2体積%以上、更に好ましくは0.7体積%以上であり、また、その上限が、好ましくは7体積%以下、より好ましくは4体積%以下、更に好ましくは2.5体積%以下であると、Liイオン透過性を損なうことなく電極厚みの増加率を低減することができるので好ましい。
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、エーテル、ラクトン、アミド、及びスルホンから選ばれる1種又は2種以上が好適に挙げられる。広い温度範囲で電気化学特性を相乗的に向上させる観点から、鎖状エステルが含まれることが好ましく、鎖状カーボネートが含まれることが更に好ましく、環状カーボネートと鎖状カーボネートの両方が含まれることがもっとも好ましい。
なお、本明細書において「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。
前記鎖状エステルの中でも、ジメチルカーボネート、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、プロピオン酸メチル、酢酸メチル及び酢酸エチルから選ばれるメチル基を有する鎖状エステルが好ましく、特にメチル基を有する鎖状カーボネートが好ましい。
鎖状エステルの含有量は、特に制限されないが、非水溶媒の総体積に対して、60~90体積%の範囲で用いるのが好ましい。該含有量が60体積%以上であれば非水電解液の粘度が高くなりすぎず、90体積%以下であれば非水電解液の電気伝導度が低下して広い温度範囲、特に高温での電気化学特性が低下するおそれが少ないので上記範囲であることが好ましい。
環状カーボネートと鎖状エステルの割合は、広い温度範囲、特に高温での電気化学特性向上の観点から、環状カーボネート:鎖状エステル(体積比)が10:90~45:55が好ましく、15:85~40:60がより好ましく、20:80~35:65が特に好ましい。
前記SO2基含有化合物の中でも、1,3-プロパンスルトン、1,4-ブタンスルトン、2,4-ブタンスルトン、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、ブタン-2,3-ジイル ジメタンスルホネート、及びジビニルスルホンから選ばれる1種又は2種以上が更に好ましい。
前記フッ素化ベンゼン化合物としては、フルオロベンゼン、2,4-ジフルオロアニオール、1-フルオロ-4-シクロヘキシルベンゼン、パンタフルオロフェニルメタンスルホネート、2-フルオロフェニルメタンスルホネート、2,4-ジフルオロフェニルメタンスルホネート、及び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から選ばれる1種又は2種以上が更に好ましい。
前記三重結合化合物の中でも、2-プロピニル メチル カーボネート、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、2-(メタンスルホニルオキシ)プロピオン酸 2-プロピニル、ジ(2-プロピニル)オギザレート、メチル 2-プロピニル オギザレート、エチル 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、及び2-ブチン-1,4-ジイル ジホルメートから選ばれる1種又は2種以上が好ましく、2-プロピニル メチル カーボネート、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、2-(メタンスルホニルオキシ)プロピオン酸 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、及び2-ブチン-1,4-ジイル ジホルメートから選ばれる1種又は2種以上が更に好ましい。
前記カルボン酸無水物の中でも、無水コハク酸、無水マレイン酸、及びアリル無水コハク酸から選ばれる1種又は2種以上が好ましく、無水コハク酸及びアリル無水コハク酸から選ばれる1種又は2種がより好ましい。
前記、イソシアネート化合物の中でも、ヘキサメチレンジイソシアネート、オクタメチレンジイソシアネート、2-イソシアナトエチル アクリレート、及び2-イソシアナトエチル メタクリレートから選ばれる1種又は2種以上が好ましく、ヘキサメチレンジイソシアネート、2-イソシアナトエチル アクリレート、及び2-イソシアナトエチル メタクリレートから選ばれる1種又は2種以上がより好ましい。
前記リチウム含有イオン性化合物の中でも、ジフルオロリン酸リチウム、フルオロスルホン酸リチウム、ジフルオロビス[オキサレート-O,O’]リン酸リチウム(LiPFO)、テトラフルオロ[オキサレート-O,O’]リン酸リチウム、ビス[オキサレート-O,O’]ホウ酸リチウム(LiBOB)やジフルオロ[オキサレート-O,O’]ホウ酸リチウム、リチウム メチルサルフェート、リチウム エチルサルフェート、及びリチウム プロピルサルフェートから選ばれる1種又は2種以上がより好ましい。
前記ニトリル化合物の中でも、スクシノニトリル、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1種又は2種以上がより好ましい。
前記ベンゼン化合物の中でも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、ビフェニル、ターフェニル(o-、m-、p-体)、メチルフェニルカーボネート、エチルフェニルカーボネート、及びジフェニルカーボネートから選ばれる1種又は2種以上がより好ましく、シクロヘキシルベンゼン、tert-アミルベンゼン、ビフェニル、o-ターフェニル、メチルフェニルカーボネート、エチルフェニルカーボネート、及びジフェニルカーボネートから選ばれる1種又は2種以上が特に好ましい。
前記環状アセタール化合物の中でも1,3-ジオキソラン又は1,3-ジオキサンが好ましく、1,3-ジオキサンが更に好ましい。
前記ホスファゼン化合物の中でも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、又はフェノキシペンタフルオロシクロトリホスファゼン等の環状ホスファゼン化合物が好ましく、メトキシペンタフルオロシクロトリホスファゼン及びエトキシペンタフルオロシクロトリホスファゼンから選ばれる1種又は2種以上が更に好ましい。
本発明に使用される電解質塩としては、リチウム塩が好適に挙げられる。
リチウム塩としては、LiPF6、LiBF4、LiClO4、LiN(SO2F)2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、もしくはLiPF3(iso-C3F7)3、もしくは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、もしくは(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の1種又は2種以上を混合して使用することができる。
これらの中でも、LiPF6、LiBF4、LiN(SO2F)2、LiN(SO2CF3)2、及びLiN(SO2C2F5)2から選ばれる1種又は2種以上が好ましく、LiPF6、LiBF4、LiN(SO2CF3)2、及びLiN(SO2F)2から選ばれる1種又は2種以上が更に好ましく、LiPF6を用いることが最も好ましい。
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。
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前記一般式(I)で表されるビフェニル基含有カーボネート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。
本明細書においてリチウム電池とは、リチウム一次電池及びリチウム二次電池の総称である。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1種又は2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種単独で又は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、及びLiCo0.98Mg0.02O2から選ばれる1種又は2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、及びCuから選ばれる1種又は2種以上の元素、0.001≦x≦0.05)、LiNi1/3Mn1/3Co1/3O2、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広い温度範囲で使用した場合における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。特にMnを含む正極の場合に正極からのMnイオンの溶出に伴い電池の抵抗が増加しやすい傾向にあるため、広い温度範囲で使用した場合における電気化学特性が低下しやすい傾向にあるが、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ので好ましい。
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種又は2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、LiFePO4又はLiMnPO4が好ましい。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。
リチウム含有オリビン型リン酸塩は、安定したリン酸骨格(PO4)構造を形成し、充電時の熱安定性に優れるため、高温サイクル後の電極厚みの増加率を更に低減することができる。
また、正極中に元素としてNiが含まれる場合、正極活物質中のLiOH等の不純物が増える傾向があるため、一段と広い温度範囲での電気化学特性の改善効果が得られやすいので好ましく、正極活物質中のNiの原子濃度が5~25atomic%である場合が更に好ましく、8~21atomic%である場合が特に好ましい。
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、電池の容量をさらに高めるため、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、その上限としては、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より好ましく、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更に好ましい。特に複数の扁平状の黒鉛質微粒子が互いに非平行に集合又は結合した塊状構造を有する人造黒鉛粒子や、圧縮力、摩擦力、剪断力等の機械的作用を繰り返し与え、鱗片状天然黒鉛を球形化処理した粒子を用いることが好ましい。
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広い温度範囲での電気化学特性が良好となる。
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、電池の容量をさらに高めるため、好ましくは1.5g/cm3以上である。なお、その上限としては、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。
本発明におけるリチウム二次電池は、充電終止電圧が4.2V以上、特に4.3V以上の場合にも広い温度範囲での電気化学特性に優れ、更に、4.4V以上においても特性は良好である。放電終止電圧は、通常2.8V以上、更には2.5V以上とすることができるが、本発明におけるリチウム二次電池は、2.0V以上とすることができる。電流値については特に限定されないが、通常0.1~30Cの範囲で使用される。また、本発明におけるリチウム電池は、-40~100℃、好ましくは-10~80℃で充放電することができる。
本発明においては、リチウム電池の内圧上昇の対策として、電池蓋に安全弁を設けたり、電池缶やガスケット等の部材に切り込みを入れる方法も採用することができる。また、過充電防止の安全対策として、電池の内圧を感知して電流を遮断する電流遮断機構を電池蓋に設けることができる。
本発明の第2の蓄電デバイスは、本発明の非水電解液を含み、電解液と電極界面の電気二重層容量を利用してエネルギーを貯蔵する蓄電デバイスである。本発明の一例は、電気二重層キャパシタである。この蓄電デバイスに用いられる最も典型的な電極活物質は、活性炭である。二重層容量は概ね表面積に比例して増加する。
本発明の第3の蓄電デバイスは、本発明の非水電解液を含み、電極のドープ/脱ドープ反応を利用してエネルギーを貯蔵する蓄電デバイスである。この蓄電デバイスに用いられる電極活物質として、酸化ルテニウム、酸化イリジウム、酸化タングステン、酸化モリブデン、酸化銅等の金属酸化物や、ポリアセン、ポリチオフェン誘導体等のπ共役高分子が挙げられる。これらの電極活物質を用いたキャパシタは、電極のドープ/脱ドープ反応に伴うエネルギー貯蔵が可能である。
本発明の第4の蓄電デバイスは、本発明の非水電解液を含み、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り、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。
(a)フェノール化合物を溶媒中又は無溶媒中で、塩基の存在下、又は非存在下トリホスゲンやカルボニルジイミダゾール等のカルボニル化剤と反応させる方法が挙げられる。
(b)フェノール化合物を溶媒中又は無溶媒中で、塩基の存在下、又は非存在下クロロギ酸エステルと反応させる方法が挙げられる。
(c)フェノール化合物を溶媒中又は無溶媒中で、酸もしくは塩基触媒の存在下、炭酸エステルとエステル交換させる方法が挙げられる。
前記塩基の使用量はフェノール化合物1モルに対して0.8~5モル、より好ましくは1~3モルであり、特に1~1.5モルが、副生物の生成が抑さえられ好ましい。
前記溶媒の使用量は、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1~15質量部である。
一般式(II)で表される化合物は新規なビフェニル基含有カーボネート化合物であり、その特殊な構造から、化学一般、特に有機化学、電気化学、生化学および高分子化学の分野において、電解質としての用途があり、その他にも耐熱用途等の材料としても用いることができる。
したがって、一般式(II)で表される化合物は医薬、農薬、電子材料、高分子材料等の中間原料、又は電池材料として有用な化合物である。
2-ベンジル-6-フェニルフェノール5.00g(19.2mmol)、クロロギ酸メチル1.99g(21.1mmol)、酢酸エチル20mlにトリエチルアミン2.14g(21.1mmol)を内温2℃~10℃で10分間かけ滴下した後、室温で1時間攪拌した。その後、反応液を水洗、分液し有機層を濃縮した。得られた残渣をシリカゲルカラムクロマトグラフィー(酢酸エチル/ヘキサン=1/20溶出)で精製し、目的の2-ベンジル-6-フェニルフェニル フェニル カーボネート5.91g(97%)を得た。
得られた2-ベンジル-6-フェニルフェニル フェニル カーボネートについて、1H-NMR及びCI-MSの測定を行い、その構造を確認した。結果を以下に示す。
(1)1H-NMR(400 MHz, CDCl3):δ= 7.45-7.14(m, 13H), 3.99(s, 2H), 3.51(s, 3H)
(2)融点:86-88℃
(3)質量分析:MS(CI)m/z = 319[M+1]+
2-フェニルフェノール10.00g(58.8mmol)、クロロギ酸フェニル9.66g(61.7mmol)、酢酸エチル50mlにトリエチルアミン6.24g(61.7mmol)を内温2℃~10℃で20分かけ滴下した後、室温で1時間攪拌した。その後、反応液を水洗、分液し有機層を濃縮した。得られた残渣にジメチルカーボネート40mlを加え、晶析精製し、目的のフェニル 2-フェニルフェニル カーボネート4.25g(25%)を得た。
得られたフェニル 2-フェニルフェニル カーボネートについて、1H-NMR及びCI-MSの測定を行い、その構造を確認した。結果を以下に示す。
(1)1H-NMR(400 MHz, CDCl3):δ= 7.53-6.87(m, 14H)
(2)融点:99-100℃
(3)質量分析:MS(CI)m/z = 291[M+1]+
2,6-ジフェニルフェノール5.00g(20.3mmol)、クロロギ酸メチル2.12g(22.4mmol)、酢酸エチル20mlにトリエチルアミン2.27g(22.4mmol)を内温2℃~10℃で10分かけ滴下した後、室温で1時間攪拌した。その後、反応液を水洗、分液し有機層を濃縮した。得られた残渣にジメチルカーボネート10mlを加え晶析精製し、目的の2,6-ジフェニルフェニル メチル カーボネート2.25g(36%)を得た。
得られた2,6-ジフェニルフェニル メチル カーボネートについて、1H-NMR及びCI-MSの測定を行い、その構造を確認した。結果を以下に示す。
(1)1H-NMR(400 MHz, CDCl3):δ= 7.60-7.33(m, 13H)
(2)融点:110-111℃
(3)質量分析:MS(CI)m/z = 305[M+1]+
〔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、人造黒鉛(d002=0.335nm、負極活物質)95質量%を、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切り抜き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1~5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。
〔高温サイクル特性の評価〕
上記の方法で作製した電池を用いて65℃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、以下の式によりサイクル後の放電容量維持率を求めた。
放電容量維持率(%)=(100サイクル目の放電容量/1サイクル目の放電容量)×100
<初期負極厚み>
上記の方法で1サイクルさせた電池を解体し、初期の負極厚みを測定した。
<サイクル後の負極厚み>
上記の方法で100サイクルさせた電池を解体し、高温サイクル後の負極厚みを測定した。
<負極厚み増加率>
負極厚み増加値を以下の式により求めた。
負極厚み増加値=サイクル後の負極厚み-初期負極厚み
負極厚み増加率(%)は比較例1-1の負極厚み増加値を100%としたときを基準として求めた。
実施例1-2及び比較例1-1で用いた負極活物質に変えて、ケイ素(単体)(負極活物質)を用いて、負極シートを作製した。ケイ素(単体)40質量%、人造黒鉛(d002=0.335nm、負極活物質)50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切り抜き負極シートを作製したことの他は、実施例1-2、比較例1-1と同様にしてラミネート型電池を作製し、電池評価を行った。結果を表6に示す。
実施例1-2及び比較例1-1で用いた正極活物質に変えて、非晶質炭素で被覆されたLiFePO4(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LiFePO4 90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、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切り抜き、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3.6V、放電終止電圧を2.0Vとしたこと、及び比較例1-3においては一般式(1)の化合物を添加しなかったことの他は、実施例1-2及び比較例1-1と同様にしてラミネート型電池を作製し、電池評価を行った。結果を表7に示す。
実施例1-2及び比較例1-1で用いた負極活物質に変えて、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、比較例1-4においては一般式(1)の化合物を添加しなかったことの他は、実施例1-2及び比較例1-1と同様にしてラミネート型電池を作製し、電池評価を行った。結果を表8に示す。
また、本発明の新規なビフェニル基含有カーボネート化合物は、その特殊な構造から、化学一般、特に有機化学、電気化学、生化学および高分子化学の分野において、電解質用途、耐熱用途等の材料として、医薬、農薬、電子材料、高分子材料等の中間原料、又は電池材料として有用である。
Claims (15)
- 前記一般式(I)において、X1~X4のうち、少なくとも1つがフェニル基又はベンジル基である、請求項1に記載の非水電解液。
- 前記一般式(I)で表される化合物が、2,6-ジフェニルフェニル メチル カーボネート、2,6-ジフェニルフェニル エチル カーボネート、2,6-ジフェニルフェニル アリル カーボネート、2,6-ジフェニルフェニル 2-プロピニル カーボネート、2,6-ジフェニルフェニル フェニル カーボネート、2,6-ジフェニルフェニル 2-フェニルフェニル カーボネート、2,6-ジフェニルフェニル 3-フェニルフェニル カーボネート、2,6-ジフェニルフェニル 4-フェニルフェニル カーボネート、2-ベンジル-6-フェニルフェニル メチル カーボネート、2-ベンジル-6-フェニルフェニル エチル カーボネート、2-ベンジル-6-フェニルフェニル アリル カーボネート、2-ベンジル-6-フェニルフェニル 2-プロピニル カーボネート、2-ベンジル-6-フェニルフェニル フェニル カーボネート、2-ベンジル-6-フェニルフェニル 2-フェニルフェニル カーボネート、2-ベンジル-6-フェニルフェニル 3-フェニルフェニル カーボネート、及び2-ベンジル-6-フェニルフェニル 4-フェニルフェニル カーボネートから選ばれる1種又は2種以上である、請求項2に記載の非水電解液。
- 前記一般式(I)において、X1~X4の全てが水素原子である、請求項1に記載の非水電解液。
- 前記一般式(I)で表される化合物が、メチル 2-フェニルフェニル カーボネート、エチル 2-フェニルフェニル カーボネート、アリル 2-フェニルフェニル カーボネート、2-フェニルフェニル 2-プロピニル カーボネート、フェニル 2-フェニルフェニル カーボネート、ビス(2-フェニルフェニル) カーボネート、2-フェニルフェニル 3-フェニルフェニル カーボネート、及び2-フェニルフェニル 4-フェニルフェニル カーボネートから選ばれる1種又は2種以上である、請求項4に記載の非水電解液。
- 前記非水溶媒が、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1~5のいずれかに記載の非水電解液。
- 前記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少なくとも1種である、請求項6に記載の非水電解液。
- 前記環状カーボネートとして、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、及び2,3-ブチレンカーボネートから選ばれる少なくとも2種以上を含む、請求項6又は7に記載の非水電解液。
- 更に、フッ素原子含有環状カーボネート又は不飽和結合含有環状カーボネートを含む、請求項8に記載の非水電解液。
- 更に、SO2基含有化合物、フッ素化ベンゼン化合物、リン酸エステル化合物、炭素-炭素三重結合含有化合物、カルボン酸無水物、イソシアネート化合物、リチウム含有イオン性化合物、ニトリル化合物、ベンゼン化合物、環状アセタール化合物、及びホスファゼン化合物から選ばれる少なくとも1種を含む、請求項1~9のいずれかに記載の非水電解液。
- 前記電解質塩が、LiPF6、LiBF4、LiN(SO2CF3)2、及びLiN(SO2F)2から選ばれる1種又は2種以上のリチウム塩である、請求項1~10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であって、前記非水電解液が請求項1~11のいずれかに記載の非水電解液であ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1種又は2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1種又は2種以上を含むリチウム含有オリビン型リン酸塩である、請求項12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、及び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1種又は2種以上を含有する、請求項12又は13に記載の蓄電デバイス。
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