JP2008098097A - 二次電池 - Google Patents
二次電池 Download PDFInfo
- Publication number
- JP2008098097A JP2008098097A JP2006281529A JP2006281529A JP2008098097A JP 2008098097 A JP2008098097 A JP 2008098097A JP 2006281529 A JP2006281529 A JP 2006281529A JP 2006281529 A JP2006281529 A JP 2006281529A JP 2008098097 A JP2008098097 A JP 2008098097A
- Authority
- JP
- Japan
- Prior art keywords
- group
- secondary battery
- lithium
- positive electrode
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract description 22
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 21
- 239000003792 electrolyte Substances 0.000 claims abstract description 20
- 125000005843 halogen group Chemical group 0.000 claims abstract description 18
- 125000003118 aryl group Chemical group 0.000 claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 57
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 52
- 239000008151 electrolyte solution Substances 0.000 claims description 45
- -1 polyethylene Polymers 0.000 claims description 38
- 150000001875 compounds Chemical class 0.000 claims description 27
- 239000004698 Polyethylene Substances 0.000 claims description 26
- 239000007774 positive electrode material Substances 0.000 claims description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 21
- 239000004743 Polypropylene Substances 0.000 claims description 18
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 239000002131 composite material Substances 0.000 claims description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 12
- 229920000573 polyethylene Polymers 0.000 claims description 11
- 229920001155 polypropylene Polymers 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 8
- 239000002033 PVDF binder Substances 0.000 claims description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 8
- 125000001153 fluoro group Chemical group F* 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 5
- 125000006575 electron-withdrawing group Chemical group 0.000 claims description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 230000000737 periodic effect Effects 0.000 claims description 5
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 125000000732 arylene group Chemical group 0.000 claims description 4
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 3
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- SYRDSFGUUQPYOB-UHFFFAOYSA-N [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O SYRDSFGUUQPYOB-UHFFFAOYSA-N 0.000 claims description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 2
- 125000006551 perfluoro alkylene group Chemical group 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims 1
- 238000009795 derivation Methods 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- 229910052748 manganese Inorganic materials 0.000 claims 1
- 125000002521 alkyl halide group Chemical group 0.000 abstract 1
- 125000003286 aryl halide group Chemical group 0.000 abstract 1
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 28
- 239000007773 negative electrode material Substances 0.000 description 28
- 239000000654 additive Substances 0.000 description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 18
- 230000000996 additive effect Effects 0.000 description 18
- 238000007600 charging Methods 0.000 description 15
- 239000002904 solvent Substances 0.000 description 13
- 235000002639 sodium chloride Nutrition 0.000 description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
- 229910052718 tin Inorganic materials 0.000 description 10
- YAOIFBJJGFYYFI-UHFFFAOYSA-N 1-cyclohexyl-4-fluorobenzene Chemical compound C1=CC(F)=CC=C1C1CCCCC1 YAOIFBJJGFYYFI-UHFFFAOYSA-N 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 229910052742 iron Inorganic materials 0.000 description 9
- GUYHXQLLIISBQF-UHFFFAOYSA-N 1-cyclohexyl-2-fluorobenzene Chemical compound FC1=CC=CC=C1C1CCCCC1 GUYHXQLLIISBQF-UHFFFAOYSA-N 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 229910052725 zinc Inorganic materials 0.000 description 8
- 239000011701 zinc Substances 0.000 description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 230000007246 mechanism Effects 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 229910052719 titanium Inorganic materials 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 6
- 229910013870 LiPF 6 Inorganic materials 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 229910052796 boron Inorganic materials 0.000 description 6
- 229910052804 chromium Inorganic materials 0.000 description 6
- 239000011651 chromium Substances 0.000 description 6
- 150000005676 cyclic carbonates Chemical class 0.000 description 6
- 239000010419 fine particle Substances 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 229910052752 metalloid Inorganic materials 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 238000004804 winding Methods 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 5
- 239000007771 core particle Substances 0.000 description 5
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052750 molybdenum Inorganic materials 0.000 description 5
- 239000011733 molybdenum Substances 0.000 description 5
- 229910052712 strontium Inorganic materials 0.000 description 5
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 5
- 239000011135 tin Substances 0.000 description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 5
- 229910052721 tungsten Inorganic materials 0.000 description 5
- 239000010937 tungsten Substances 0.000 description 5
- 229910052720 vanadium Inorganic materials 0.000 description 5
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical class O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 4
- QQFSIGWYINAJOB-UHFFFAOYSA-N 1,4-dicyclohexylbenzene Chemical compound C1CCCCC1C1=CC=C(C2CCCCC2)C=C1 QQFSIGWYINAJOB-UHFFFAOYSA-N 0.000 description 3
- BXMDAGGQRIDSPA-UHFFFAOYSA-N 1-bromo-2-cyclohexylbenzene Chemical compound BrC1=CC=CC=C1C1CCCCC1 BXMDAGGQRIDSPA-UHFFFAOYSA-N 0.000 description 3
- LVIJLEREXMVRAN-UHFFFAOYSA-N 1-bromo-4-cyclohexylbenzene Chemical compound C1=CC(Br)=CC=C1C1CCCCC1 LVIJLEREXMVRAN-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 3
- 125000001246 bromo group Chemical group Br* 0.000 description 3
- 239000011246 composite particle Substances 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 229910052732 germanium Inorganic materials 0.000 description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 230000020169 heat generation Effects 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 3
- 238000003780 insertion Methods 0.000 description 3
- 230000037431 insertion Effects 0.000 description 3
- 229910021470 non-graphitizable carbon Inorganic materials 0.000 description 3
- 239000011255 nonaqueous electrolyte Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 230000003405 preventing effect Effects 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- HKMLIHLPRGKCQZ-UHFFFAOYSA-N 1-cyclohexyl-3-fluorobenzene Chemical compound FC1=CC=CC(C2CCCCC2)=C1 HKMLIHLPRGKCQZ-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 2
- 239000011245 gel electrolyte Substances 0.000 description 2
- 229910021469 graphitizable carbon Inorganic materials 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- 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 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
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- VWIIJDNADIEEDB-UHFFFAOYSA-N 3-methyl-1,3-oxazolidin-2-one Chemical compound CN1CCOC1=O VWIIJDNADIEEDB-UHFFFAOYSA-N 0.000 description 1
- FAOBFWHWLCQTSN-UHFFFAOYSA-N 4-cyclohexyl-1,2-difluorobenzene Chemical compound C1=C(F)C(F)=CC=C1C1CCCCC1 FAOBFWHWLCQTSN-UHFFFAOYSA-N 0.000 description 1
- SBUOHGKIOVRDKY-UHFFFAOYSA-N 4-methyl-1,3-dioxolane Chemical compound CC1COCO1 SBUOHGKIOVRDKY-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910018871 CoO 2 Inorganic materials 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910010238 LiAlCl 4 Inorganic materials 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910015044 LiB Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910010935 LiFOB Inorganic materials 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical class COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
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- 229910052733 gallium Inorganic materials 0.000 description 1
- ZTOMUSMDRMJOTH-UHFFFAOYSA-N glutaronitrile Chemical compound N#CCCCC#N ZTOMUSMDRMJOTH-UHFFFAOYSA-N 0.000 description 1
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- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical class [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical class [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 1
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 description 1
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- 229910052758 niobium Inorganic materials 0.000 description 1
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- MCSAJNNLRCFZED-UHFFFAOYSA-N nitroethane Chemical compound CC[N+]([O-])=O MCSAJNNLRCFZED-UHFFFAOYSA-N 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 125000005151 nonafluorobutanesulfonyl group Chemical group FC(C(C(S(=O)(=O)*)(F)F)(F)F)(C(F)(F)F)F 0.000 description 1
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- 239000010450 olivine Substances 0.000 description 1
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- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 125000005062 perfluorophenyl group Chemical group FC1=C(C(=C(C(=C1F)F)F)F)* 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
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- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
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- 239000002296 pyrolytic carbon Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
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- 150000003377 silicon compounds Chemical class 0.000 description 1
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- 229910052596 spinel Inorganic materials 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 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
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 125000006510 trifluorobenzyl group Chemical group 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 125000004360 trifluorophenyl group Chemical group 0.000 description 1
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
図2は図1に示した巻回電極体20の一部を拡大して表すものである。図2に示すように、正極21は、例えば、対向する一対の面を有する正極集電体21Aの両面に正極活物質層21Bが設けられた構造を有している。なお、図示はしないが、正極集電体21Aの片面のみに正極活物質層21Bを設けるようにしてもよい。正極集電体21Aは、例えば、アルミニウム箔などの金属箔により構成されている。正極活物質層21Bは、例えば、正極活物質として、リチウムを吸蔵および放出することが可能な正極材料を1種または複数種含んでおり、必要に応じてグラファイトなどの導電剤およびポリフッ化ビニリデンなどの結着剤を含んで構成されている。
上記式(8)中、M1は、ニッケル、マンガン、マグネシウム、アルミニウム、ホウ素、チタン、バナジウム、クロム、鉄、銅、亜鉛、モリブデン、スズ、カルシウム、ストロンチウムおよびタングステンからなる群のうちの少なくとも1種を表す。r、s、tおよびuは、0.8≦r≦1.2、0≦s<0.5、−0.1≦t≦0.2、0≦u≦0.1の範囲内の値である。なお、リチウムの組成は充放電の状態によって異なり、rの値は完全放電状態における値を表している。
上記式(9)中、M2は、コバルト、マグネシウム、アルミニウム、ホウ素、チタン、バナジウム、クロム、鉄、銅,亜鉛、ジルコニウム、モリブデン、スズ、カルシウム、ストロンチウムおよびタングステンからなる群のうちの少なくとも1種を表す。f、g、h、jおよびkは、0.8≦f≦1.2、0<g<0.5、0≦h≦0.5、g+h<1、−0.1≦j≦0.2、0≦k≦0.1の範囲内の値である。なお、リチウムの組成は充放電の状態によって異なり、fの値は完全放電状態における値を表している。
上記式(10)中、M3は、コバルト、マンガン、マグネシウム、アルミニウム、ホウ素、チタン、バナジウム、クロム、鉄、銅、亜鉛、モリブデン、スズ、カルシウム、ストロンチウムおよびタングステンからなる群のうちの少なくとも1種を表す。m、n、pおよびqは、0.8≦m≦1.2、0.005≦n≦0.5、−0.1≦p≦0.2、0≦q≦0.1の範囲内の値である。なお、リチウムの組成は充放電の状態によって異なり、mの値は完全放電状態における値を表している。
上記式(11)中、M4は、コバルト、ニッケル、マグネシウム、アルミニウム、ホウ素、チタン、バナジウム、クロム、鉄、銅、亜鉛、モリブデン、スズ、カルシウム、ストロンチウムおよびタングステンからなる群のうちの少なくとも1種を表す。v、w、xおよびyは、0.9≦v≦1.1、0≦w≦0.6、3.7≦x≦4.1、0≦y≦0.1の範囲内の値である。なお、リチウムの組成は充放電の状態によって異なり、vの値は完全放電状態における値を表している。
上記式(12)中、M5は、コバルト、マンガン、鉄、ニッケル、マグネシウム、アルミニウム、ホウ素、チタン、バナジウム、ニオブ、銅、亜鉛、モリブデン、カルシウム、ストロンチウム、タングステンおよびジルコニウムからなる群のうちの少なくとも1種を表す。zは、0.9≦z≦1.1の範囲内の値である。なお、リチウムの組成は充放電の状態によって異なり、zの値は完全放電状態における値を表している。
負極22は、例えば、対向する一対の面を有する負極集電体22Aの両面に負極活物質層22Bが設けられた構造を有している。なお、図示はしないが、負極集電体22Aの片面のみに負極活物質層22Bを設けるようにしてもよい。負極集電体22Aは、例えば、銅箔などの金属箔により構成されている。
この二次電池では、リチウムを吸蔵および放出することが可能な負極材料の電気化学当量が、正極21の電気化学当量よりも大きくなっており、充電の途中において負極22にリチウム金属が析出しないようになっている。
セパレータ23は、正極21と負極22とを隔離し、両極の接触による電流の短絡を防止しつつ、リチウムイオンを通過させるものである。このセパレータ23は、例えばポリエチレンと、ポリプロピレン、ポリフッ化ビニリデン、ポリテトラフルオロエチレン、Al2O3、およびSiO2の少なくとも1種とを含む、合成樹脂製またはセラミック製の多孔質膜により構成されることが好ましい。これにより、連続充電時における正極と物理的に接触するセパレータの酸化分解を抑制し、急激な電流立ち上がりを阻止することが出来る。セパレータ23は、ポリエチレン並びに、ポリプロピレンおよびポリテトラフルオロエチレンの少なくとも1種を混合して多孔質膜としてもよく、ポリエチレン、ポリプロピレン、ポリテトラフルオロエチレンの多孔質膜にAl2O3、ポリフッ化ビニリデン、SiO2を表面に塗布してもよい。また、ポリエチレン、ポリプロピレン、ポリテトラフルオロエチレンの複数種の多孔質膜を積層した構造としてもよい。これらの多孔質膜はショート防止効果に優れ、かつシャットダウン効果による電池の安全性向上を図ることができるので好ましい。
電解液は、溶媒、この溶媒に溶解された電解質塩、および添加剤を含んでいる。電解液は、添加剤として、下記式(1)で表される芳香族化合物のうち少なくとも1種を含んでいる。過充電状態となった際にこれらの芳香族化合物が酸化重合し、活物質表面に高抵抗の皮膜を形成して過充電電流を抑制し、その結果として電池が危険な状態に至る前に過充電の進行を阻止することが出来るからである。
式(1)において、ハロゲン基としては、フッ素基、臭素基、ヨウ素基、塩素基のいずれであってもよいが、フッ素基であることが好ましい。フッ素基を有することにより酸化還元電位を高くすることができる。アルキル基としては、メチル基、エチル基、t−ブチル基、t−ペンチル基が好ましい。ハロゲン化アルキル基としては、トリフルオロメチル基、ペンタフルオロエチル基、ヘキサフルオロプロピル基が好ましい。アリール基としては、フェニル基、ベンジル基が好ましい。ハロゲン化アリール基としては、モノフルオロフェニル基、ジフルオロフェニル基、トリフルオロフェニル基、テトラフルオロフェニル基、パーフルオロフェニル基、モノフルオロベンジル基、ジフルオロベンジル基、トリフルオロベンジル基、テトラフルオロベンジル基、パーフルオロベンジル基が好ましい。
式(4)で表される化合物の具体例としては、炭酸エチレン、炭酸プロピレン、4−フルオロエチレンカーボネート、4,5−ジフルオロエチレンカーボネートなどが挙げられる。
他の電解質塩としては、下記式(5)で表される化合物が挙げられる。
R11は−C(=O)−R21−C(=O)−基(R21はアルキレン基、ハロゲン化アルキレン基、アリーレン基もしくはハロゲン化アリーレン基を表す。)、または−C(=O)−C(R23)(R24)−基(R23、R24は、アルキル基、ハロゲン化アルキル基、アリール基もしくはハロゲン化アリール基を表す。)、または−C(=O)−C(=O)−基を表し、
R12はハロゲン基、アルキル基、ハロゲン化アルキル基、アリール基またはハロゲン化アリール基を表し、
X11およびX12は酸素または硫黄をそれぞれ表し、
M11は遷移金属元素または短周期型周期表における3B族元素、4B族元素もしくは5B族元素を表し、
M21は短周期型周期表における1A族元素もしくは2A族元素、またはアルミニウムを表し、
aは1〜4の整数であり、bは0〜8の整数であり、c、d、eおよびfはそれぞれ1〜3の整数である。
LiN(CmF2m+1SO2 )(Cn F2n+1SO2 ) (6)
式(6)中、mおよびnは1以上の整数である。
式(6)で表される化合物の含有量としては、電解液に対して0.1質量%以上30質量%以下の範囲内であることが好ましく、0.3質量%以上20質量%の範囲内であることがより好ましい。
式(7)で表される化合物の含有量としては、電解液に対して0.1質量%以上30質量%以下の範囲内であることが好ましく、0.3質量%以上20質量%以下の範囲内であることがより好ましい。
これら他の電解質塩は、1種を単独で混合して用いてもよく、複数種を混合して用いてもよい。
本発明の二次電池は、例えば、次のようにして製造することができる。
図1に示した二次電池を作製した。まず、正極活物質として、リチウム複合酸化物94質量%と、導電剤としてケッチェンブラック(アモルファス性炭素粉)3質量%と、結着剤としてポリフッ化ビニリデン3質量%とを混合し、溶剤であるN−メチル−2−ピロリドンに分散させて正極合剤スラリーとした。次いで、該正極合剤スラリーを厚み20μmの帯状のアルミニウム箔よりなる正極集電体21Aの両面に均一に塗布して乾燥させ、圧縮成型して正極活物質層21Bを形成し正極21を作製した。その後、正極集電体21Aの一端にアルミニウム製の正極リード25を取り付けた。
作製した二次電池について、連続充電特性、過充電特性、高温サイクル特性を以下のようにして測定した。
(1)連続充電特性
60℃に設定された恒温槽中において、1000mAの定電流で所定電圧に達するまで定電流充電を行なった後、所定電圧で定電圧充電を行った際に充電電流の変動が見られる(漏れ電流が発生する)時間を求めた。
(2)過充電特性
所定電圧、1000mAで定電流定電圧充電を行い、満充電状態にしたセルを2400mAで18Vになるまで充電し、その際のセルの表面温度の最高到達温度を求めた。
(3)高温サイクル特性
40度の高温槽内で、所定電圧、1000mAで定電流定電圧充電を行い、引き続き2000mAの定電流で電池電圧が3Vに達するまで定電流放電を行い、この充放電を繰り返して1サイクル目の放電容量に対する300サイクルにおける放電容量維持率(100サイクルにおける放電容量/1サイクル目の放電容量)×100%として求めた。
実施例1−1−1〜1−4−6においては、正極におけるリチウム複合酸化物は、LiCoO2を100%用い、セパレータにポリプロピレン/ポリエチレン/ポリプロピレンと3層重なったセパレータ(PP/PE/PP三層セパレータ)を用い、電解液に表1に示す添加剤を加えた。充電上限電圧は4.25〜4.60Vとした。
実施例1−5−1〜1−8−6として、セパレータにポリエチレンセパレータ(PEセパレータ)を用いたことを除き、他は実施例1−1−1〜1−4−6と同様にして二次電池を作製した。
実施例1−9−1〜1−9−6として、添加剤にシクロヘキシルベンゼンを用いたことを除き、他は実施例1−1−1〜1−4−6と同様にして二次電池を作製した。
比較例1−1−1〜1−1−6として、電解液に添加剤を加えなかったことを除き、他は実施例1−1−1〜1−4−6と同様にして二次電池を作製した。
比較例1−2−1〜1−2−6として、電解液に添加剤を加えなかったことを除き、他は実施例1−5−1〜1−8−6と同様にして二次電池を作製した。
比較例1−3−1〜1−3−8として、正極活物質および負極活物質の量を調整して、完全充電時における開回路電圧が4.20Vとなるようにしたことを除き、他は実施例1−1−1〜1−4−6と同様にして二次電池を作製した。比較例1−3−9は正極活物質および負極活物質の量を調整して、完全充電時における開回路電圧が4.20Vとなるようにしたことを除き、他は比較例1−1−1〜1−1−6と同様にして二次電池を作製した。
使用するセパレータを表2に示すように変化させたことを除き、他は実施例1−5−3および実施例1−7−3と同様にして二次電池を作製した。実施例2−1−1〜2−1−8の各二次電池の特性を評価した結果を表2に示す。
電解液に添加する添加剤の量と種類を表3に示すように変化させたことを除き、他は実施例1−1−3と同様にして二次電池を作製した。実施例3−1−1〜3−3−5の各二次電池の特性を評価した結果を表3に示す。
表4に示す化合物をさらに添加したことを除き、他は実施例1−1−3、実施例1−3−3と同様にして二次電池を作製した。実施例4−1−1〜4−2−5の各二次電池の特性を評価した結果を表4に示す。
正極におけるリチウム複合酸化物の組成を表5に示すリチウム複合酸化物の混合組成としたことを除き、他は実施例1−1−3と同様にして二次電池を作製した。実施例5−1−1〜5−1−5の各二次電池の特性を評価した結果を表5に示す。
表6に示すように、添加剤の種類を1,4−ジシクロヘキシルベンゼン、1−ブロモ−2−シクロヘキシルベンゼンまたは1−ブロモ−4−シクロヘキシルベンゼンに変化させたことを除き、他は実施例1−1−3、1−3−3と同様にして二次電池を作製した。実施例6−1−1〜6−1−3の各二次電池の特性を評価した結果を表6に示す。
Claims (13)
- 前記セパレータがポリエチレンと、ポリプロピレン、ポリフッ化ビニリデン、ポリテトラフルオロエチレン、Al2O3およびSiO2の少なくとも1種とを含むことを特徴とする請求項1に記載の二次電池。
- 前記式(1)で表される芳香族化合物のR1からR10の少なくとも1つがハロゲン基であることを特徴とする請求項1に記載の二次電池。
- 前記ハロゲン基がフッ素基である請求項1に記載の二次電池。
- 前記電解液は、前記式(1)で表される芳香族化合物のうち少なくとも1種を0.1質量%以上20質量%以下の範囲で含むことを特徴とする請求項1に記載の二次電池。
- 前記正極は、正極活物質として、リチウム、コバルト、酸素を含むリチウム複合酸化物を含有することを特徴とする請求項1に記載の二次電池。
- 前記正極は、正極活物質として、リチウムと、ニッケルおよびマンガンの少なくとも1つを含むリチウム複合酸化物とをさらに含有することを特徴とする請求項7記載の二次電池。
- 前記式(3)で表される化合物が炭酸ビニレンであり、前記式(4)で表される化合物が、4−フルオロエチレンカーボネートまたは4,5−ジフルオロエチレンカーボネートである請求項9に記載の二次電池。
- 前記電解液はさらに下記式(5)〜(7)で表される化合物の少なくとも1種を含むことを特徴とする請求項1に記載の二次電池。
R11は−C(=O)−R21−C(=O)−基(R21はアルキレン基、ハロゲン化アルキレン基、アリーレン基もしくはハロゲン化アリーレン基を表す。)、または−C(=O)−C(R23)(R24)−基(R23、R24は、アルキル基、ハロゲン化アルキル基、アリール基もしくはハロゲン化アリール基を表す。)、または−C(=O)−C(=O)−基を表し、
R12はハロゲン基、アルキル基、ハロゲン化アルキル基、アリール基またはハロゲン化アリール基を表し、
X11およびX12は酸素または硫黄をそれぞれ表し、
M11は遷移金属元素または短周期型周期表における3B族元素、4B族元素もしくは5B族元素を表し、
M21は短周期型周期表における1A族元素もしくは2A族元素またはアルミニウムを表し、aは1〜4の整数であり、bは0〜8の整数であり、c、d、eおよびfはそれぞれ1〜3の整数である。]
LiN(CmF2m+1SO2)(CnF2n+1SO2) (6)
[上記式(6)中、mおよびnは1以上の整数である。]
- 前記電解液はリチウムビスオキサレートボレート、リチウムジフルオロオキサレートボレート、リチウムビストリフルオロメタンスルホンイミド、リチウムビスパーフルオロエチレンスルホニルイミド、リチウムパーフルオロプロパン−1,3−ジスルホニルイミドのうち少なくとも1種を含むことを特徴とする請求項1に記載の二次電池。
- 過電流が流れることにより抵抗値が増大するPTC素子と、電池内部のガス圧力が上昇して所定の圧力以上になることにより変形し前記PTC素子への通電を遮断する電力導出板とを備えたことを特徴とする請求項1に記載の二次電池。
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JP4433833B2 (ja) * | 2003-05-13 | 2010-03-17 | 三菱化学株式会社 | 非水系電解液及び非水系電解液二次電池 |
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KR100657225B1 (ko) * | 2003-09-05 | 2006-12-14 | 주식회사 엘지화학 | 전지의 안전성을 향상시키기 위한 전해액 용매 및 이를포함하는 리튬 이차 전지 |
DE10347566A1 (de) * | 2003-10-14 | 2005-05-12 | Degussa | Keramischer Separator für elektrochemische Zellen mit verbesserter Leitfähigkeit |
EP2472638A3 (en) * | 2003-12-15 | 2013-09-11 | Mitsubishi Chemical Corporation | Nonaqueous-Electrolyte Secondary Battery |
JP4811697B2 (ja) * | 2003-12-26 | 2011-11-09 | 株式会社Gsユアサ | リチウム二次電池及びその初期活性化方法 |
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2006
- 2006-10-16 JP JP2006281529A patent/JP5298419B2/ja active Active
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2007
- 2007-10-03 US US11/866,875 patent/US20080152998A1/en not_active Abandoned
- 2007-10-04 TW TW096137316A patent/TWI449232B/zh active
- 2007-10-12 KR KR1020070103068A patent/KR101502894B1/ko active IP Right Grant
- 2007-10-16 CN CNA2007101628855A patent/CN101165962A/zh active Pending
- 2007-10-16 CN CN201510967749.8A patent/CN105406122A/zh active Pending
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JP2004349131A (ja) * | 2003-05-22 | 2004-12-09 | Mitsubishi Chemicals Corp | 非水系電解液及びそれを用いた非水系電解液二次電池 |
JP2004349132A (ja) * | 2003-05-22 | 2004-12-09 | Mitsubishi Chemicals Corp | 非水系電解液及びそれを用いた非水系電解液二次電池 |
WO2005048391A1 (ja) * | 2003-11-13 | 2005-05-26 | Ube Industries, Ltd. | 非水電解液およびリチウム二次電池 |
WO2005074067A1 (ja) * | 2004-02-02 | 2005-08-11 | Ube Industries, Ltd. | 非水電解液およびリチウム二次電池 |
JP2006173099A (ja) * | 2004-11-19 | 2006-06-29 | Matsushita Electric Ind Co Ltd | 非水電解質二次電池 |
WO2006077763A1 (ja) * | 2005-01-20 | 2006-07-27 | Ube Industries, Ltd. | 非水電解液及びそれを用いたリチウム二次電池 |
JP2006236725A (ja) * | 2005-02-24 | 2006-09-07 | Sanyo Electric Co Ltd | 非水電解質二次電池 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2008262901A (ja) * | 2007-03-19 | 2008-10-30 | Mitsubishi Chemicals Corp | 非水系電解液および非水系電解液電池 |
JP2012109219A (ja) * | 2010-10-28 | 2012-06-07 | Sanyo Electric Co Ltd | 非水電解液二次電池及びその製造方法 |
JP2013165049A (ja) * | 2012-02-13 | 2013-08-22 | Toyota Motor Corp | 非水電解質二次電池 |
Also Published As
Publication number | Publication date |
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KR101502894B1 (ko) | 2015-03-16 |
JP5298419B2 (ja) | 2013-09-25 |
TW200832780A (en) | 2008-08-01 |
CN101165962A (zh) | 2008-04-23 |
KR20080034400A (ko) | 2008-04-21 |
US20080152998A1 (en) | 2008-06-26 |
TWI449232B (zh) | 2014-08-11 |
CN105406122A (zh) | 2016-03-16 |
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