JP5482151B2 - 非水電解質二次電池 - Google Patents
非水電解質二次電池 Download PDFInfo
- Publication number
- JP5482151B2 JP5482151B2 JP2009269384A JP2009269384A JP5482151B2 JP 5482151 B2 JP5482151 B2 JP 5482151B2 JP 2009269384 A JP2009269384 A JP 2009269384A JP 2009269384 A JP2009269384 A JP 2009269384A JP 5482151 B2 JP5482151 B2 JP 5482151B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- phosphate
- alkyl group
- nonaqueous electrolyte
- terminal structure
- 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.)
- Expired - Fee Related
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- 239000011255 nonaqueous electrolyte Substances 0.000 title claims description 104
- -1 fluorinated phosphate compound Chemical class 0.000 claims description 141
- 125000000217 alkyl group Chemical group 0.000 claims description 66
- 229910052744 lithium Inorganic materials 0.000 claims description 43
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 39
- 150000001875 compounds Chemical class 0.000 claims description 29
- 239000002905 metal composite material Substances 0.000 claims description 23
- 229920000447 polyanionic polymer Polymers 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 12
- 229910019142 PO4 Inorganic materials 0.000 claims description 10
- 239000010452 phosphate Substances 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 9
- JLEXUIVKURIPFI-UHFFFAOYSA-N tris phosphate Chemical compound OP(O)(O)=O.OCC(N)(CO)CO JLEXUIVKURIPFI-UHFFFAOYSA-N 0.000 claims description 9
- 125000004778 2,2-difluoroethyl group Chemical group [H]C([H])(*)C([H])(F)F 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 7
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 4
- 229910001416 lithium ion Inorganic materials 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 239000011164 primary particle Substances 0.000 claims description 4
- 239000011163 secondary particle Substances 0.000 claims description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 4
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 claims description 3
- AJRAGDKNFYMGMK-UHFFFAOYSA-N OP(OC(F)F)(OC(F)F)=O Chemical compound OP(OC(F)F)(OC(F)F)=O AJRAGDKNFYMGMK-UHFFFAOYSA-N 0.000 claims description 2
- 125000006343 heptafluoro propyl group Chemical group 0.000 claims description 2
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- XBVXBDYWIWPXIV-UHFFFAOYSA-N tris(difluoromethyl) phosphate Chemical compound FC(F)OP(=O)(OC(F)F)OC(F)F XBVXBDYWIWPXIV-UHFFFAOYSA-N 0.000 claims description 2
- XBUGKDHALPQOTH-UHFFFAOYSA-N bis(2,2,2-trifluoroethyl) hydrogen phosphate Chemical compound FC(F)(F)COP(=O)(O)OCC(F)(F)F XBUGKDHALPQOTH-UHFFFAOYSA-N 0.000 claims 1
- XFSPFPFUBRZQFO-UHFFFAOYSA-N trifluoromethyl dihydrogen phosphate Chemical compound OP(O)(=O)OC(F)(F)F XFSPFPFUBRZQFO-UHFFFAOYSA-N 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 56
- 239000003792 electrolyte Substances 0.000 description 27
- 238000007600 charging Methods 0.000 description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 15
- 238000012360 testing method Methods 0.000 description 13
- AOBBDXYJJKBZJY-UHFFFAOYSA-N 2,2,3,3-tetrafluorobutane-1,4-diamine Chemical compound NCC(F)(F)C(F)(F)CN AOBBDXYJJKBZJY-UHFFFAOYSA-N 0.000 description 11
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 11
- 239000007774 positive electrode material Substances 0.000 description 11
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 10
- 229920001577 copolymer Polymers 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 8
- 239000012046 mixed solvent Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 229910013870 LiPF 6 Inorganic materials 0.000 description 7
- 239000002131 composite material Substances 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 7
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 239000003125 aqueous solvent Substances 0.000 description 6
- 239000003575 carbonaceous material Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229910000314 transition metal oxide Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000012423 maintenance Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000011149 active material Substances 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 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 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000010280 constant potential charging Methods 0.000 description 3
- 150000005676 cyclic carbonates Chemical class 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 239000003223 protective agent Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 3
- YZQXAGZTJRSUJT-UHFFFAOYSA-N tris(2,2,3,3-tetrafluoropropyl) phosphate Chemical compound FC(F)C(F)(F)COP(=O)(OCC(F)(F)C(F)F)OCC(F)(F)C(F)F YZQXAGZTJRSUJT-UHFFFAOYSA-N 0.000 description 3
- HQUQLFOMPYWACS-UHFFFAOYSA-N tris(2-chloroethyl) phosphate Chemical compound ClCCOP(=O)(OCCCl)OCCCl HQUQLFOMPYWACS-UHFFFAOYSA-N 0.000 description 3
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 2
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 2
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 2
- DRVMZMGCPWFDBI-UHFFFAOYSA-N 2,2,2-trifluoroethyl dihydrogen phosphate Chemical compound OP(O)(=O)OCC(F)(F)F DRVMZMGCPWFDBI-UHFFFAOYSA-N 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- XDJQVCIRFIRWKY-UHFFFAOYSA-N C=C.C(=C)(F)F Chemical group C=C.C(=C)(F)F XDJQVCIRFIRWKY-UHFFFAOYSA-N 0.000 description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- GUUVPOWQJOLRAS-UHFFFAOYSA-N Diphenyl disulfide Chemical compound C=1C=CC=CC=1SSC1=CC=CC=C1 GUUVPOWQJOLRAS-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000010277 constant-current charging Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- JQVXMIPNQMYRPE-UHFFFAOYSA-N ethyl dimethyl phosphate Chemical compound CCOP(=O)(OC)OC JQVXMIPNQMYRPE-UHFFFAOYSA-N 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
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- 230000008569 process Effects 0.000 description 2
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- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- MHWAJHABMBTNHS-UHFFFAOYSA-N 1,1-difluoroethene;1,1,2,2-tetrafluoroethene Chemical group FC(F)=C.FC(F)=C(F)F MHWAJHABMBTNHS-UHFFFAOYSA-N 0.000 description 1
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
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- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 description 1
- WDXYVJKNSMILOQ-UHFFFAOYSA-N 1,3,2-dioxathiolane 2-oxide Chemical compound O=S1OCCO1 WDXYVJKNSMILOQ-UHFFFAOYSA-N 0.000 description 1
- NZPSDGIEKAQVEZ-UHFFFAOYSA-N 1,3-benzodioxol-2-one Chemical compound C1=CC=CC2=C1OC(=O)O2 NZPSDGIEKAQVEZ-UHFFFAOYSA-N 0.000 description 1
- IOBWAHRFIPQEQL-UHFFFAOYSA-N 1,3-difluoro-2-methoxybenzene Chemical compound COC1=C(F)C=CC=C1F IOBWAHRFIPQEQL-UHFFFAOYSA-N 0.000 description 1
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- GUYHXQLLIISBQF-UHFFFAOYSA-N 1-cyclohexyl-2-fluorobenzene Chemical compound FC1=CC=CC=C1C1CCCCC1 GUYHXQLLIISBQF-UHFFFAOYSA-N 0.000 description 1
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- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
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- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 description 1
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- OYOKPDLAMOMTEE-UHFFFAOYSA-N 4-chloro-1,3-dioxolan-2-one Chemical compound ClC1COC(=O)O1 OYOKPDLAMOMTEE-UHFFFAOYSA-N 0.000 description 1
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- SJHAYVFVKRXMKG-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2-oxide Chemical compound CC1COS(=O)O1 SJHAYVFVKRXMKG-UHFFFAOYSA-N 0.000 description 1
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- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910012425 Li3Fe2 (PO4)3 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910011281 LiCoPO 4 Inorganic materials 0.000 description 1
- 229910011993 LiFe0.5Co0.5PO4 Inorganic materials 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
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- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
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- 239000004645 polyester resin Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
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- 229910052718 tin Inorganic materials 0.000 description 1
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- 150000003624 transition metals Chemical class 0.000 description 1
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Classifications
-
- 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
Landscapes
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
非水電解質二次電池を構成する正極活物質としてはリチウム含有遷移金属酸化物が、負極活物質としてはグラファイトに代表される炭素材料が、非水電解質としては、エチレンカーボネートを主構成成分とする非水溶媒に六フッ化リン酸リチウム(LiPF6)等の電解質を溶解したものが広く知られている。
なお、前記リチウム含有ポリアニオン金属複合化合物の二次粒子の平均粒子径及び一次粒子の平均粒子径は、透過型電子顕微鏡(TEM)観察の結果を画像解析することにより求める。
例えば、プロピレンカーボネート、エチレンカーボネート、ブチレンカーボネート、クロロエチレンカーボネート、スチレンカーボネート、カテコールカーボネート、1−フェニルビニレンカーボネート、1,2−ジフェニルビニレンカーボネート等の環状カーボネート、γ−ブチロラクトン、γ−バレロラクトン、プロピオラクトン等の環状カルボン酸エステル、ジメチルカーボネート、ジエチルカーボネート、エチルメチルカーボネート、ジフェニルカーボネート等の鎖状カーボネート、酢酸メチル、酪酸メチル等の鎖状カルボン酸エステル、テトラヒドロフランまたはその誘導体、1,3−ジオキサン、ジメトキシエタン、ジエトキシエタン、メトキシエトキシエタン、メチルジグライム等のエーテル類、アセトニトリル、ベンゾニトリル等のニトリル類、ジオキサランまたはその誘導体等の単独またはそれら2種以上の混合物等を挙げることができるが、これらに限定されるものではない。
また、これらの有機溶媒は、任意の割合で混合して用いることができる。
正極活物質として、一次粒子径200nm、二次粒子径11μm、BET比表面積12m2/gのリン酸鉄リチウムを用い、リン酸鉄リチウム90質量%と導電助剤であるアセチレンブラック5質量%と結着剤であるポリフッ化ビニリデン5質量%を含有し、N−メチルピロリドンを溶剤とするペーストを厚さ20μmのアルミニウム箔集電体両面に塗布、乾燥し、プレスすることによって、正極を作製した。
ECとDECとを体積比30:70で混合し、前記混合溶媒とTFEPとを体積比70:30となるように混合した。得られたEC、DEC及びTFEPを含む混合溶媒に、LiPF6を1mol/lとなるように溶解した。この非水電解質を比較電解質bとする。
ECとDECとを体積比30:70で混合し、前記混合溶媒とTFPPとを体積比70:30となるように混合した。得られたEC、DEC及びTFPPを含む混合溶媒に、LiPF6を1mol/lとなるように溶解した。この非水電解質を比較電解質cとする。
ECとDECとを体積比30:70で混合した非水溶媒に、LiPF6を1mol/lとなるように溶解することによって非水電解質を作製した。この非水電解質を比較電解質dとする。
正極活物質であるコバルト酸リチウム94質量%と導電助剤であるアセチレンブラック2質量%と結着剤であるポリフッ化ビニリデン4質量%を含有し、N−メチルピロリドンを溶剤とするペーストを厚さ20μmのアルミニウム箔集電体両面に塗布、乾燥し、プレスすることによって、正極を作製した。
非水電解質に比較電解質cを用いたこと以外は、比較例4と同様の方法で、非水電解質二次電池を作製した。この非水電解質二次電池を比較電池Fとする。
非水電解質に比較電解質dを用いたこと以外は、比較例4と同様の方法で、非水電解質二次電池を作製した。この非水電解質二次電池を比較電池Gとする。
全ての実施例電池及び比較例電池は、評価試験に先立ち、20℃環境下にて初期充放電工程に供した。
続いて、20℃環境下にて、高率放電性能評価試験を行った。
放電電流10ItmAにおける放電容量の値を放電電流1.0ItmAにおける放電容量の値で除することによって、高率放電容量維持率を算出した。
放電電流10ItmAにおける放電容量の値を放電電流1.0ItmAにおける放電容量の値で除することによって、高率放電容量維持率を算出した。
さらに、45℃環境下にて、サイクル性能評価試験を行った。
250サイクル目の放電容量を当該サイクル性能評価試験の1サイクル目の放電容量で除した値をサイクル容量維持率として算出した。
250サイクル目の放電容量を当該サイクル性能評価試験の1サイクル目の放電容量で除した値をサイクル容量維持率として算出した。
TFPP:リン酸トリス(2,2,3,3−テトラフルオロプロピル)
Claims (7)
- 負極と、正極と、セパレータと、有機溶媒及びリチウムイオンを含有する非水電解質と、を備えた非水電解質電池において、前記正極は、平均粒子サイズ100μm以下の粉体であるリチウム含有ポリアニオン金属複合化合物を含有し、前記非水電解質は、アルキル基の末端構造がCF3で表されるフッ素化リン酸エステル化合物と、アルキル基の末端構造がCF2Hで表されるフッ素化リン酸エステル化合物とをそれぞれ一種類以上含有することを特徴とする非水電解質二次電池。
- 前記リチウム含有ポリアニオン金属複合化合物は、二次粒子の平均粒子径は0.5〜20μmであり、一次粒子の粒径は50〜500nmである請求項1に記載の非水電解質二次電池。
- 前記リチウム含有ポリアニオン金属複合化合物は、リン酸鉄リチウムであることを特徴とする請求項1又は2記載の非水電解質二次電池。
- 前記「アルキル基の末端構造がCF 3 で表されるフッ素化リン酸エステル化合物」の有する3つのアルキル基の炭素数がそれぞれ4以下であり、かつ、前記「アルキル基の末端構造がCF 2 Hで表されるフッ素化リン酸エステル化合物」の有する3つのアルキル基の炭素数がそれぞれ4以下であることを特徴とする請求項1乃至3のいずれかに記載の非水電解質電池。
- 前記アルキル基の末端構造がCF 3 で表されるフッ素化リン酸エステル化合物及び/又は前記アルキル基の末端構造がCF 2 Hで表されるフッ素化リン酸エステル化合物の沸点が60℃以上300℃以下であることを特徴とする請求項1乃至4のいずれかに記載の非水電解質電池。
- 前記「アルキル基の末端構造がCF 3 で表されるフッ素化リン酸エステル化合物」の有するアルキル基はトリフルオロメチル基、2,2,2−トリフルオロエチル基、1,2,2,2−テトラフルオロエチル基、ペンタフルオロエチル基、3,3,3−トリフルオロプロピル基、1,3,3,3−テトラフルオロプロピル基、2,3,3,3−テトラフルオロプロピル基、1,2,3,3,3−ペンタフルオロプロピル基、ヘプタフルオロプロピル基、4,4,4−トリフルオロノルマルブチル基、又は2,2,2,2’,2’,2’−ヘキサフルオロイソプロピル基のいずれかであり、
前記「アルキル基の末端構造がCF 2 Hで表されるフッ素化リン酸エステル化合物」の有するアルキル基は、ジフルオロメチル基、2,2−ジフルオロエチル基、1,2,2−トリフルオロエチル基、1,1,2,2−テトラフルオロエチル基、3,3−ジフルオロプロピル基、1,3,3−トリフルオロプロピル基、2,3,3−トリフルオロプロピル基、2,2,3,3−テトラフルオロプロピル基、1,2,3,3−テトラフルオロプロピル基、4,4−ジフルオロノルマルブチル基、3,3,4,4−テトラフルオロノルマルブチル基、又は2,2,2’,2’−テトラフルオロイソプロピル基のいずれかであることを特徴とする請求項1乃至5のいずれかに記載の非水電解質電池。 - 前記「アルキル基の末端構造がCF 3 で表されるフッ素化リン酸エステル化合物」は、リン酸トリス(トリフルオロメチル)、リン酸ビス(トリフルオロメチル)(2,2,2−トリフルオロエチル)、リン酸トリス(2,2,2−トリフルオロエチル)、リン酸ビス(2,2,2−トリフルオロエチル)(1,2,2,2−テトラフルオロエチル)、リン酸(トリフルオロメチル)(2,2,2−トリフルオロエチル)(1,2,2,2−テトラフルオロエチル)又は、リン酸トリス(1,3,3,3−テトラフルオロプロピル)のいずれかであり、
前記「アルキル基の末端構造がCF 2 Hで表されるフッ素化リン酸エステル化合物」は、リン酸トリス(ジフルオロメチル)、リン酸ビス(ジフルオロメチル)(2,2−ジフルオロエチル)、リン酸トリス(2,2−ジフルオロエチル)、リン酸(ジフルオロメチル)(2,2−ジフルオロエチル)(1,2,2−トリフルオロエチル)、リン酸トリス(2,2,3,3−テトラフルオロプロピル)、リン酸ビス(2,2,3,3−テトラフルオロプロピル)(2,2−ジフルオロエチル)、又は、リン酸ビス(1,3,3−トリフルオロプロピル)(ジフルオロメチル)のいずれかであることを特徴とする請求項1乃至6のいずれかに記載の非水電解質電池。
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