JP5277044B2 - Non-aqueous electrolyte - Google Patents
Non-aqueous electrolyte Download PDFInfo
- Publication number
- JP5277044B2 JP5277044B2 JP2009084794A JP2009084794A JP5277044B2 JP 5277044 B2 JP5277044 B2 JP 5277044B2 JP 2009084794 A JP2009084794 A JP 2009084794A JP 2009084794 A JP2009084794 A JP 2009084794A JP 5277044 B2 JP5277044 B2 JP 5277044B2
- Authority
- JP
- Japan
- Prior art keywords
- lithium
- weight
- aqueous electrolyte
- ion secondary
- lithium ion
- 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
Links
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims description 39
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 45
- 229910001416 lithium ion Inorganic materials 0.000 claims description 45
- 229910052744 lithium Inorganic materials 0.000 claims description 27
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 26
- 239000008151 electrolyte solution Substances 0.000 claims description 14
- 239000003792 electrolyte Substances 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 13
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 12
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 11
- FSIJKGMIQTVTNP-UHFFFAOYSA-N bis(ethenyl)-methyl-trimethylsilyloxysilane Chemical compound C[Si](C)(C)O[Si](C)(C=C)C=C FSIJKGMIQTVTNP-UHFFFAOYSA-N 0.000 claims description 11
- 150000004651 carbonic acid esters Chemical class 0.000 claims description 10
- 125000001153 fluoro group Chemical group F* 0.000 claims description 10
- 239000007773 negative electrode material Substances 0.000 claims description 9
- 239000007774 positive electrode material Substances 0.000 claims description 9
- 239000003125 aqueous solvent Substances 0.000 claims description 6
- DSMUTQTWFHVVGQ-UHFFFAOYSA-N 4,5-difluoro-1,3-dioxolan-2-one Chemical compound FC1OC(=O)OC1F DSMUTQTWFHVVGQ-UHFFFAOYSA-N 0.000 claims description 2
- -1 cyclic carbonate ester Chemical class 0.000 description 13
- 239000002904 solvent Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 239000011230 binding agent Substances 0.000 description 9
- 239000002131 composite material Substances 0.000 description 9
- 239000004020 conductor Substances 0.000 description 9
- 229910052731 fluorine Inorganic materials 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000002033 PVDF binder Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- 150000003624 transition metals Chemical class 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 229920000388 Polyphosphate Polymers 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000001205 polyphosphate Substances 0.000 description 4
- 235000011176 polyphosphates Nutrition 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
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-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
- 239000006230 acetylene black Substances 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000002134 carbon nanofiber Substances 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- MBABOKRGFJTBAE-UHFFFAOYSA-N methyl methanesulfonate Chemical compound COS(C)(=O)=O MBABOKRGFJTBAE-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000003223 protective agent Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 description 2
- WDXYVJKNSMILOQ-UHFFFAOYSA-N 1,3,2-dioxathiolane 2-oxide Chemical compound O=S1OCCO1 WDXYVJKNSMILOQ-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
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 2
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 description 2
- SJHAYVFVKRXMKG-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2-oxide Chemical compound CC1COS(=O)O1 SJHAYVFVKRXMKG-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-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
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 150000005678 chain carbonates Chemical class 0.000 description 2
- 150000005676 cyclic carbonates Chemical class 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 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
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 2
- 150000004862 dioxolanes Chemical class 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
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002905 metal composite material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229940014800 succinic anhydride Drugs 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical class O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- 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
- YAOIFBJJGFYYFI-UHFFFAOYSA-N 1-cyclohexyl-4-fluorobenzene Chemical compound C1=CC(F)=CC=C1C1CCCCC1 YAOIFBJJGFYYFI-UHFFFAOYSA-N 0.000 description 1
- MBDUIEKYVPVZJH-UHFFFAOYSA-N 1-ethylsulfonylethane Chemical compound CCS(=O)(=O)CC MBDUIEKYVPVZJH-UHFFFAOYSA-N 0.000 description 1
- KLECYOQFQXJYBC-UHFFFAOYSA-N 1-fluoro-2-phenylbenzene Chemical group FC1=CC=CC=C1C1=CC=CC=C1 KLECYOQFQXJYBC-UHFFFAOYSA-N 0.000 description 1
- SJMSHBHQMICGBL-UHFFFAOYSA-N 2,2-dimethylpentan-3-yl hydrogen carbonate Chemical compound CCC(C(C)(C)C)OC(O)=O SJMSHBHQMICGBL-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- DZRUNSUYJCQUIG-UHFFFAOYSA-N 2-methylbutan-2-yl hydrogen carbonate Chemical compound CCC(C)(C)OC(O)=O DZRUNSUYJCQUIG-UHFFFAOYSA-N 0.000 description 1
- QHTJSSMHBLGUHV-UHFFFAOYSA-N 2-methylbutan-2-ylbenzene Chemical compound CCC(C)(C)C1=CC=CC=C1 QHTJSSMHBLGUHV-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- COVZYZSDYWQREU-UHFFFAOYSA-N Busulfan Chemical compound CS(=O)(=O)OCCCCOS(C)(=O)=O COVZYZSDYWQREU-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
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- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910011281 LiCoPO 4 Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910014422 LiNi1/3Mn1/3Co1/3O2 Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910012513 LiSbF 6 Inorganic materials 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 0.000 description 1
- 229940063013 borate ion Drugs 0.000 description 1
- 229960002092 busulfan Drugs 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- CCAFPWNGIUBUSD-UHFFFAOYSA-N diethyl sulfoxide Chemical compound CCS(=O)CC CCAFPWNGIUBUSD-UHFFFAOYSA-N 0.000 description 1
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- BDUPRNVPXOHWIL-UHFFFAOYSA-N dimethyl sulfite Chemical compound COS(=O)OC BDUPRNVPXOHWIL-UHFFFAOYSA-N 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
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- 239000003063 flame retardant Substances 0.000 description 1
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- ROCSCYHXUBXLGH-UHFFFAOYSA-N hexan-3-yl hydrogen carbonate Chemical compound CCCC(CC)OC(O)=O ROCSCYHXUBXLGH-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000010220 ion permeability Effects 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- DMEJJWCBIYKVSB-UHFFFAOYSA-N lithium vanadium Chemical compound [Li].[V] DMEJJWCBIYKVSB-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- VUQUOGPMUUJORT-UHFFFAOYSA-N methyl 4-methylbenzenesulfonate Chemical compound COS(=O)(=O)C1=CC=C(C)C=C1 VUQUOGPMUUJORT-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- SWVGZFQJXVPIKM-UHFFFAOYSA-N n,n-bis(methylamino)propan-1-amine Chemical compound CCCN(NC)NC SWVGZFQJXVPIKM-UHFFFAOYSA-N 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- XDLVYYYGCNMREZ-UHFFFAOYSA-N propane-1,2-diol;sulfuric acid Chemical compound CC(O)CO.OS(O)(=O)=O XDLVYYYGCNMREZ-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 150000003459 sulfonic acid esters Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- ISXOBTBCNRIIQO-UHFFFAOYSA-N tetrahydrothiophene 1-oxide Chemical compound O=S1CCCC1 ISXOBTBCNRIIQO-UHFFFAOYSA-N 0.000 description 1
- HNKJADCVZUBCPG-UHFFFAOYSA-N thioanisole Chemical compound CSC1=CC=CC=C1 HNKJADCVZUBCPG-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 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
Description
本発明は、非水電解液及びそれを用いたリチウムイオン二次電池に係り、更には、そのようなリチウムイオン二次電池を電源として備えた電子機器や輸送機器等に関するものである。 The present invention relates to a non-aqueous electrolyte and a lithium ion secondary battery using the same, and further relates to an electronic device, a transport device, and the like equipped with such a lithium ion secondary battery as a power source.
近年、二次電池としてのリチウムイオン電池が、高出力や高エネルギー密度を実現し得る電池として注目され、既に、パソコン、携帯電話、携帯音楽プレイヤー等の小型民生機器用の領域では、その電源として実用化されており、また自動車産業においても、電気自動車やハイブリッド車等の車載用エネルギー源として、小型・軽量であるリチウムイオン二次電池の実用化が期待されている。 In recent years, lithium-ion batteries as secondary batteries have attracted attention as batteries that can achieve high output and high energy density, and have already been used as power sources in the area of small consumer devices such as personal computers, mobile phones, and portable music players. The lithium ion secondary battery, which is small and light, is expected to be put into practical use as an in-vehicle energy source for electric vehicles and hybrid vehicles in the automobile industry.
また、それらの用途の中で、小型民生機器に用いられる電池では、常温近傍で用いられることが多く、その寿命にあっても、車載用に求められるような長期に亘る信頼性は、必ずしも必要とはされていないのであるが、電気自動車或いはハイブリッド自動車用電池では、−４０℃に近い極低温から６０℃以上の高温に至る領域において、正常に作動することが求められ、民生用に比べると、非常に幅広い温度領域での使用が可能であることが要請され、更に、その寿命においても、民生用に比べて、遥かに長期に亘って機能するものであることが要請されている。例えば、米国先進バッテリー・コンソーシアム（ＵＳＡＢＣ）の目標においては、１５年、２４万ｋｍ走行相当において、車載用リチウムイオン電池として機能することが求められているのである。 In addition, among these applications, batteries used in small consumer devices are often used near room temperature, and even in their lifetime, long-term reliability required for in-vehicle use is always necessary. However, batteries for electric vehicles or hybrid vehicles are required to operate normally in the region from extremely low temperatures close to −40 ° C. to high temperatures of 60 ° C. or more, compared to consumer use. Therefore, it is required that it can be used in a very wide temperature range, and further, its life is required to function much longer than that for consumer use. For example, the goal of the US Advanced Battery Consortium (USABC) is to function as an in-vehicle lithium-ion battery for 15 years, equivalent to 240,000 km travel.
このため、従来から、かかるリチウムイオン二次電池については、活発な研究が行なわれてきており、それに用いられる非水電解液、即ち、リチウムを含む電解質塩を非水溶媒に溶解せしめてなる電解液についても、各種の提案が為されているのであって、例えば、特許文献１においては、特定の構造を有するケイ素化合物を電解液に含有せしめることにより、充放電の繰り返し時に電気容量の変化率が小さく、且つ低温時にも高い電気容量を維持するという、サイクル特性及び低温特性に優れたものが、提案されている。 For this reason, active research has been conducted on such lithium ion secondary batteries, and the non-aqueous electrolyte used in the lithium-ion secondary battery, that is, an electrolytic solution obtained by dissolving an electrolyte salt containing lithium in a non-aqueous solvent. Various proposals have also been made for liquids. For example, in Patent Document 1, the rate of change in capacitance at the time of repeated charge and discharge is obtained by including a silicon compound having a specific structure in an electrolytic solution. Have been proposed that have excellent cycle characteristics and low-temperature characteristics, such that they are small and maintain high electric capacity even at low temperatures.
しかしながら、かかる特許文献１に明らかにされた非水電解液にあっては、そこで規定されるケイ素化合物を、環状炭酸エステルや鎖状炭酸エステル等と共に、添加せしめることによって、二次電池としてのサイクル特性や低温特性の改善が、ある程度は図られ得るものではあるが、それは未だ充分ではなく、このため、より高いサイクル特性や低温特性を発揮し得るものが、望まれている。 However, in the non-aqueous electrolyte disclosed in Patent Document 1, the silicon compound specified therein is added together with a cyclic carbonate ester, a chain carbonate ester, etc., so that a cycle as a secondary battery is achieved. Although improvement of characteristics and low temperature characteristics can be achieved to some extent, it is still not sufficient, and therefore, what can exhibit higher cycle characteristics and low temperature characteristics is desired.
また、特許文献２においては、リチウムイオン二次電池の非水電解液として、４−フルオロエチレンカーボネートの如きハロゲン原子を有する炭酸エステルの誘導体を含む溶媒に、２種のアニオンを組み合わせて、添加することによって構成したものが提案され、そこでは、アニオンとして、例えばビス（オキサラト）ボレートイオンと、それ以外のアニオン（ＰＦ6 -等）とを組み合わせて、それらを共存させ、被膜形成を行なうことにより、電極と非水系電解液との余分な副反応が抑制され、出力特性を向上させながら、高温保存特性やサイクル特性を改善し得ることが、明らかにされている。しかしながら、このような対策にあっても、それなりの効果は認められるものの、今後の高度なニーズに充分に応え得るリチウムイオン二次電池を得るには至っていないのである。 In Patent Document 2, a combination of two types of anions is added to a solvent containing a derivative of a carbonic ester having a halogen atom such as 4-fluoroethylene carbonate as a non-aqueous electrolyte for a lithium ion secondary battery. those configuration is proposed by, where, as the anion, for example, a bis (oxalato) borate ion, and the other anion - in combination with (PF 6, etc.), the coexistence of them, by performing film formation It has been clarified that the excessive side reaction between the electrode and the non-aqueous electrolyte is suppressed, and the high-temperature storage characteristics and cycle characteristics can be improved while improving the output characteristics. However, even if such measures are taken, a reasonable effect is recognized, but a lithium ion secondary battery that can fully meet future advanced needs has not yet been obtained.
ここにおいて、本発明は、かかる事情を背景にして為されたものであって、その解決課題とするところは、リチウムイオン二次電池における電池特性をより一層改善せしめ得る非水電解液を提供することにあり、また、そのような非水電解液を用いて、優れた電池特性を有するリチウムイオン二次電池を実現し、更には、かかるリチウムイオン二次電池を備えた電子機器や輸送機器等を提供することにある。 Here, the present invention has been made in the background of such circumstances, and the problem to be solved is to provide a non-aqueous electrolyte that can further improve the battery characteristics of the lithium ion secondary battery. In particular, by using such a non-aqueous electrolyte, a lithium ion secondary battery having excellent battery characteristics is realized, and further, an electronic device, a transportation device, etc. provided with such a lithium ion secondary battery Is to provide.
そして、本発明は、上記した課題又は明細書全体の記載から把握される課題を解決するために、以下に列挙せる如き各種の態様において、好適に実施され得るものであるが、また、以下に記載の各態様は、任意の組合せにおいても採用可能である。なお、本発明の態様乃至は技術的特徴は、以下に記載のものに何等限定されることなく、明細書全体の記載乃至はそこに開示の発明思想に基づいて、認識され得るものであることが、理解されるべきである。 The present invention can be suitably implemented in various modes as listed below in order to solve the problems described above or the problems grasped from the description of the entire specification. Each described aspect can be employed in any combination. It should be noted that aspects or technical features of the present invention are not limited to those described below, and can be recognized based on the description of the entire specification or the inventive idea disclosed therein. Should be understood.
（１） リチウムを含む電解質塩［但し、リチウムビス（オキサラト）ボレートを除く］を１ｍｏｌ／Ｌ〜３ｍｏｌ／Ｌの濃度で非水系溶媒に溶解せしめてなる、リチウムイオン二次電池に用いられる非水電解液にして、リチウムビス（オキサラト）ボレートと、ジビニルテトラメチルジシロキサンと、４−フルオロエチレンカーボネート、ジフルオロエチレンカーボネート、４−フルオロメチル−エチレンカーボネート並びにこれらの誘導体よりなる群から選ばれる１種以上のフッ素原子を有する炭酸エステルとを、それぞれ０．０１重量％以上の割合において含有していることを特徴とする非水電解液。
(1) Nonaqueous used for lithium ion secondary batteries, wherein an electrolyte salt containing lithium [excluding lithium bis (oxalato) borate] is dissolved in a nonaqueous solvent at a concentration of 1 mol / L to 3 mol / L One or more selected from the group consisting of lithium bis (oxalato) borate, divinyltetramethyldisiloxane, 4-fluoroethylene carbonate, difluoroethylene carbonate, 4-fluoromethyl-ethylene carbonate, and derivatives thereof as an electrolytic solution The non-aqueous electrolyte characterized by containing the carbonic acid ester which has the said fluorine atom in the ratio of 0.01 weight% or more , respectively .
（２） 正極活物質を有する正極と、負極活物質を有する負極と、それら正極及び負極の間に介在せしめられて、リチウムイオンを伝導する電解液とを備えたリチウムイオン二次電池において、該電解液として、上記態様（１）に記載の非水電解液が用いられていることを特徴とするリチウムイオン二次電池。
( 2 ) In a lithium ion secondary battery comprising a positive electrode having a positive electrode active material, a negative electrode having a negative electrode active material, and an electrolyte that is interposed between the positive electrode and the negative electrode and conducts lithium ions, A lithium ion secondary battery characterized in that the non-aqueous electrolyte described in the above aspect ( 1) is used as the electrolyte.
このように、本発明に従う、リチウムイオン二次電池に用いられる非水電解液にあっては、リチウムビス（オキサラト）ボレートと、ジビニルテトラメチルジシロキサンと、フッ素原子を有する炭酸エステルとが含有せしめられていることによって、そのようなリチウムイオン二次電池の充放電の繰り返しにおけるサイクル特性が、より一層向上せしめられ得ると共に、内部抵抗の上昇を効果的に抑制することが出来るのである。 Thus, the non-aqueous electrolyte used in the lithium ion secondary battery according to the present invention contains lithium bis (oxalato) borate, divinyltetramethyldisiloxane, and a carbonate ester having a fluorine atom. As a result, the cycle characteristics in the repeated charge / discharge of such a lithium ion secondary battery can be further improved, and an increase in internal resistance can be effectively suppressed.
なお、本発明において、そのような効果が得られる理由については、未だ充分に解明されてはいないが、現在までのところ、以下のように推測されている。即ち、リチウムビス（オキサラト）ボレートと、ジビニルテトラメチルジシロキサンと、フッ素原子を有する炭酸エステルとが、負極及び正極で適度に反応して、リチウムイオン透過性に優れる安定な複合被膜を形成し、そして、この複合被膜により、活性の高い電極と非水系電解液との余分な副反応が抑制され、またリチウムイオンの脱挿入に係わる反応抵抗を低下させて、結果として抵抗上昇を抑制し、出力特性を向上させながら、高温保存特性やサイクル特性が改善されることとなるものと、推定されている。 The reason why such an effect can be obtained in the present invention has not yet been fully elucidated, but has been estimated as follows so far. That is, lithium bis (oxalato) borate, divinyltetramethyldisiloxane, and a carbonic acid ester having a fluorine atom react appropriately at the negative electrode and the positive electrode to form a stable composite film excellent in lithium ion permeability, This composite coating suppresses an extra side reaction between the highly active electrode and the non-aqueous electrolyte, and lowers the reaction resistance related to lithium ion desorption, thereby suppressing the increase in resistance and output. It is estimated that the high-temperature storage characteristics and cycle characteristics will be improved while improving the characteristics.
ところで、リチウムイオン二次電池に用いられる非水電解液は、一般に、リチウムを含む電解質塩を所定の非水系溶媒に溶解せしめて、調製され得るものであって、そこで用いられる電解質塩としては、よく知られているように、例えばＬｉＰＦ6、ＬｉＢＦ4、ＬｉＡｓＦ6、ＬｉＣＦ3ＳＯ3、ＬｉＮ（ＣＦ3ＳＯ2）2、ＬｉＮ（Ｃ2Ｆ5ＳＯ2）2、ＬｉＣ（ＣＦ3ＳＯ2）3 、ＬｉＳｂＦ6、ＬｉＳｉＦ6、ＬｉＡｌＦ4、ＬｉＳＣＮ、ＬｉＣｌＯ4等の無機塩や有機塩を挙げることが出来る。なお、この電解質塩は、非水電解液中の濃度において、一般に、１ｍｏｌ／Ｌ〜３．０ｍｏｌ／Ｌ程度において、好ましくは１ｍｏｌ／Ｌ〜２．０ｍｏｌ／Ｌ程度、更に好ましくは１ｍｏｌ／Ｌ〜１．６ｍｏｌ／Ｌ程度において、含有せしめられることとなる。なお、この電解質塩の濃度が低くなり過ぎると、非水電解液のイオン伝導度が低くなり、また、その濃度が高くなり過ぎると、逆に粘度が上昇するようになり、電池性能が低下することとなる。 By the way, the non-aqueous electrolyte used in the lithium ion secondary battery is generally one that can be prepared by dissolving an electrolyte salt containing lithium in a predetermined non-aqueous solvent. As is well known, for example, LiPF 6 , LiBF 4 , LiAsF 6 , LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 2 ) 2 , LiC (CF 3 SO 2 ) 3 , Inorganic salts and organic salts such as LiSbF 6 , LiSiF 6 , LiAlF 4 , LiSCN, and LiClO 4 can be mentioned. The electrolyte salt generally has a concentration in the non-aqueous electrolyte of about 1 mol / L to 3.0 mol / L, preferably about 1 mol / L to 2.0 mol / L, and more preferably 1 mol. / L to about 1.6 mol / L. If the concentration of the electrolyte salt is too low, the ionic conductivity of the non-aqueous electrolyte is lowered, and if the concentration is too high, the viscosity increases and the battery performance is lowered. It will be.
また、かかるリチウムを含む電解質塩を溶解せしめる非水系溶媒としては、公知の各種の有機溶媒が用いられ得、例えば、カーボネート類、ラクトン類、エーテル類、スルホラン類、ジオキソラン類、イオン液体等を用いることが出来る。具体的には、カーボネート類としては、エチレンカーボネート、プロピレンカーボネート、ブチレンカーボネート等の環状カーボネート類や、ジメチルカーボネート、エチルメチルカーボネート、ジエチルカーボネート、エチル−ｎ−ブチルカーボネート、メチル−ｔ−ブチルカーボネート、ジ−ｉ−プロピルカーボネート、ｔ−ブチル−ｉ−プロピルカーボネート等の鎖状カーボネート類を挙げることが出来、また、ラクトン類としては、γ−ブチルラクトン、γ−バレロラクトン等を、そして、エーテル類としては、テトラヒドロフラン、２−メチルテトラヒドロフラン、テトラヒドロピラン等の環状エーテルや、ジメトキシエタン、ジメトキシメタン等の鎖状エーテルを挙げることが出来、また、スルホラン類としては、スルホラン、テトラメチルスルホラン等を、更に、ジオキソラン類としては、１，３−ジオキソラン等を挙げることが出来る。 As the non-aqueous solvent for dissolving the electrolyte salt containing lithium, various known organic solvents can be used, for example, carbonates, lactones, ethers, sulfolanes, dioxolanes, ionic liquids, etc. I can do it. Specifically, as carbonates, cyclic carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, ethyl-n-butyl carbonate, methyl-t-butyl carbonate, di-carbonate, Examples include chain carbonates such as -i-propyl carbonate and t-butyl-i-propyl carbonate, and examples of lactones include γ-butyl lactone and γ-valerolactone, and ethers. Can include cyclic ethers such as tetrahydrofuran, 2-methyltetrahydrofuran and tetrahydropyran, and chain ethers such as dimethoxyethane and dimethoxymethane. Examples of tramethylsulfolane and the like, and examples of dioxolanes include 1,3-dioxolane.
これらの中でも、高誘電率溶媒である環状カーボネート類の少なくとも１種と、低粘度溶媒である鎖状カーボネート類、エーテル類のうちの少なくとも１種との組合せが、有利に用いられることとなる。それは、非水電解液中にＬｉ含有電解質塩を共存させる場合は、かかるＬｉ含有電解質塩の電離を促進させないと、そのイオン伝導度が大きく変わってしまうものであるところ、電解質塩の電離と溶媒の誘電率とは強い関係があり、より電離を促進させるためには、高い誘電率を持った溶媒を用いることが望ましいからである。また、高誘電率溶媒は粘性が高く、そのままでは充分なイオンの移動度を得ることが困難であるため、リチウムイオン電池の電位窓において分解しない低粘度溶媒を、更に混合せしめることで、リチウムイオンが移動し易くなるからである。 Among these, a combination of at least one cyclic carbonate that is a high dielectric constant solvent and at least one chain carbonate or ether that is a low viscosity solvent is advantageously used. That is, when Li-containing electrolyte salt coexists in a non-aqueous electrolyte solution, unless ionization of the Li-containing electrolyte salt is promoted, its ionic conductivity changes greatly. This is because it is desirable to use a solvent having a high dielectric constant in order to further promote ionization. In addition, since the high dielectric constant solvent has a high viscosity and it is difficult to obtain sufficient ion mobility as it is, a low-viscosity solvent that does not decompose in the potential window of the lithium ion battery is further mixed with lithium ions. This is because it becomes easy to move.
そして、本発明にあっては、かくの如きリチウムを含む電解質塩を所定の非水系溶媒に溶解せしめてなる非水電解液に、更に、リチウムビス（オキサラト）ボレートと、ジビニルテトラメチルジシロキサンと、フッ素原子を有する炭酸エステルとを組み合わせて、含有せしめることによって、リチウムイオン二次電池における電池特性をより一層向上せしめ得たのである。 In the present invention, a non-aqueous electrolyte obtained by dissolving an electrolyte salt containing lithium in such a non-aqueous solvent, lithium bis (oxalato) borate, divinyltetramethyldisiloxane, Thus, the battery characteristics in the lithium ion secondary battery could be further improved by combining the carbonic acid ester having a fluorine atom with the lithium ester secondary battery.
そこで、リチウムビス（オキサラト）ボレートは、非水電解液中に、一般に、０．０１重量％以上の割合において含有せしめられ、中でも、０．０５重量％以上１０重量％以下であることが好ましく、特に、０．１重量％以上５重量％以下であることが、より一層好ましい。その含有量が０．０１重量％以上であれば、充放電を繰り返した際の電池容量の低下を充分に抑制することが出来ることとなるのであり、更に、１０重量％以下の含有量として、オキサラト錯体をアニオンとするリチウム塩の含有量を抑えることによって、電極に生成する被膜による抵抗の増加を有利に抑制することが出来ることとなる。特に、その含有量を０．１重量％以上５重量％以下とすることにより、上記の効果をより一層大きく得ることが出来るのである。 Therefore, lithium bis (oxalato) borate is generally contained in the non-aqueous electrolyte at a ratio of 0.01% by weight or more, and preferably 0.05% by weight or more and 10% by weight or less, In particular, the content is more preferably 0.1% by weight or more and 5% by weight or less. If the content is 0.01% by weight or more, it is possible to sufficiently suppress the decrease in battery capacity when repeated charging and discharging, and further, as a content of 10% by weight or less, By suppressing the content of the lithium salt having an oxalato complex as an anion, an increase in resistance due to the coating film formed on the electrode can be advantageously suppressed. In particular, when the content is 0.1% by weight or more and 5% by weight or less, the above effect can be further enhanced.
また、本発明に従って非水電解液に更に添加含有せしめられる、ジビニルテトラメチルジシロキサンは、非水電解液中において、一般に、０．０１重量％以上の割合において含有せしめられ、中でも、０．０５重量％以上５重量％以下であることが好ましく、特に、０．１重量％以上２重量％以下であることが、より一層好ましい。その含有量が０．０１重量％以上であれば、充放電を繰り返した際の電池抵抗の増加を充分に抑制することが出来るのであり、また、５重量％以下の含有量として、その含有量を抑えることによって、電極に生成する被膜による抵抗の増加を、有利に抑制することが出来ることとなる。なお、かかる含有量を、０．１重量％以上２重量％以下とすることによって、より一層大きな上記の効果を得ることが出来るのである。 Further, divinyltetramethyldisiloxane, which is further added to the non-aqueous electrolyte according to the present invention, is generally contained in the non-aqueous electrolyte at a ratio of 0.01% by weight or more. The content is preferably from 5% by weight to 5% by weight, and more preferably from 0.1% by weight to 2% by weight. If the content is 0.01% by weight or more, an increase in battery resistance when charging and discharging is repeated can be sufficiently suppressed, and the content is 5% by weight or less. By suppressing the increase in resistance, an increase in resistance due to the coating formed on the electrode can be advantageously suppressed. In addition, the said effect can be acquired much larger by making this content into 0.1 to 2 weight%.
さらに、本発明に従って非水電解液に更に添加含有せしめられる、フッ素原子を有する炭酸エステルとしては、４−フルオロエチレンカーボネート、４，４−ジ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、４−フルオロメチル−エチレンカーボネート、４−トリフルオロメチル−エチレンカーボネート等を挙げることが出来る。その中でも、特に、本発明にあっては、４−フルオロエチレンカーボネートが有利に用いられることとなる。また、それらハロゲンを有する炭酸エステルを、２種以上組み合わせて、用いることも可能である。 Further, the carbonic acid ester having a fluorine atom, which is further added to the non-aqueous electrolyte according to the present invention, includes 4-fluoroethylene carbonate, 4,4-difluoroethylene carbonate, 4,5-difluoroethylene carbonate, 4-fluoro Examples thereof include methyl-ethylene carbonate and 4-trifluoromethyl-ethylene carbonate. Among them, particularly in the present invention, 4-fluoroethylene carbonate is advantageously used. Moreover, it is also possible to use these carbonic acid esters having halogen in combination of two or more.
そして、かかるフッ素原子を有する炭酸エステルは、非水電解液中において、一般に、０．０１重量％以上の割合において含有せしめられ、中でも、０．０５重量％以上１０重量％以下であることが好ましく、特に、０．１重量％以上５重量％以下であることが、より一層好ましい。その含有量が０．０１重量％以上であれば、充放電を繰り返した際の電池抵抗の増加を充分に抑制することが出来るのであり、また、１０重量％以下の含有量として、その含有量を抑えることによって、電極に生成する被膜による抵抗の増加を、有利に抑制することが出来ることとなる。なお、かかる含有量を、０．１重量％以上５重量％以下とすることによって、より一層大きな上記の効果を得ることが出来るのである。 Such a carbonic acid ester having a fluorine atom is generally contained in a non-aqueous electrolyte at a ratio of 0.01% by weight or more, preferably 0.05% by weight or more and 10% by weight or less. In particular, the content is more preferably 0.1% by weight or more and 5% by weight or less. If the content is 0.01% by weight or more, an increase in battery resistance when charging and discharging is repeated can be sufficiently suppressed, and the content is 10% by weight or less. By suppressing this, an increase in resistance due to the coating film formed on the electrode can be advantageously suppressed. In addition, the said effect can be acquired much larger by making this content into 0.1 weight% or more and 5 weight% or less.
このように、本発明にあっては、リチウムビス（オキサラト）ボレートと、ジビニルテトラメチルジシロキサンと、フッ素原子を有する炭酸エステルとは、それぞれ、上述の如き割合において含有せしめられることとなるのであるが、特に、それら３成分は、その合計含有量において、非水電解液中において１０重量％以下となるように調整されることが望ましく、中でも、５重量％以下とすることが、より好ましく、更に３重量％以下とすることが、より一層好ましい。そして、それら三つの成分の含有量と、得られる効果の関係や、コスト面を考慮すると、それら３成分の合計含有量を、０．１重量％以上２重量％以下の割合となるように調整することが、より一層好ましいということが出来る。 Thus, in the present invention, lithium bis (oxalato) borate, divinyltetramethyldisiloxane, and a carbonic acid ester having a fluorine atom are contained in the proportions as described above. However, in particular, the three components are desirably adjusted so that the total content thereof is 10% by weight or less in the non-aqueous electrolyte, and more preferably 5% by weight or less. Furthermore, it is still more preferable to set it as 3 weight% or less. And considering the relationship between the content of these three components, the effect obtained, and the cost, the total content of these three components is adjusted to a ratio of 0.1 wt% to 2 wt%. It can be said that it is even more preferable.
なお、本発明に従うリチウムイオン二次電池の非水電解液には、上記した必須の添加成分の他にも、更に必要に応じて、公知の各種の添加成分を、本発明の効果を損なわない範囲で、任意の量で含有させることが出来る。そのような任意の添加成分となる他の化合物としては、具体的には、例えば、
（１）ビフェニル、アルキルビフェニル、ターフェニル、ターフェニルの部分水素化体、シクロヘキシルベンゼン、ｔ−ブチルベンゼン、ｔ−アミルベンゼン、ジフェニルエーテル、ジベンゾフラン等の芳香族化合物；２−フルオロビフェニル、ｏ−シクロヘキシルフルオロベンゼン、ｐ−シクロヘキシルフルオロベンゼン等の前記芳香族化合物の部分フッ素化物等の過充電防止剤；
（２）ビニレンカーボネート、ビニルエチレンカーボネート等の不飽和結合含有カーボネート；無水コハク酸、無水グルタル酸、無水マレイン酸、無水シトラコン酸等の酸無水物等の負極被膜形成剤；
（３）亜硫酸エチレン、亜硫酸プロピレン、亜硫酸ジメチル、プロパンスルトン、ブタンスルトン、プロペンスルトン、メタンスルホン酸メチル、ブスルファン、トルエンスルホン酸メチル、硫酸ジメチル、硫酸エチレン、スルホラン、ジメチルスルホン、ジエチルスルホン、ジメチルスルホキシド、ジエチルスルホキシド、テトラメチレンスルホキシド、ジフェニルスルフィド、チオアニソール、ジフェニルジスルフィド、グリコールサルフェートやプロピレングリコールサルフェート等の硫酸エステル類；メタンスルホン酸トリメチルシリル、エタンスルホン酸トリメチルシリル、メタンスルホン酸トリエチルシリル、フルオロメタンスルホン酸トリメチルシリル、フルオロメタンスルホン酸メチル等のスルホン酸エステル類等の正極保護剤；
（４）トリメチルホスフェートやトリエチルホスフェート等のリン酸エステル類；ポリリン酸メラミン塩やポリリン酸アンモニウム塩、ポリリン酸エチレンジアミン塩、ポリリン酸ヘキサメチレンジアミン塩、ポリリン酸ピペラジン塩等のポリリン酸塩類等の難燃化剤；
等が挙げられる。
The non-aqueous electrolyte of the lithium ion secondary battery according to the present invention may contain various known additive components in addition to the above-described essential additive components without impairing the effects of the present invention. It can be contained in any amount within the range. Specific examples of such other compounds that are optional components include, for example,
(1) Aromatic compounds such as biphenyl, alkylbiphenyl, terphenyl, partially hydrogenated terphenyl, cyclohexylbenzene, t-butylbenzene, t-amylbenzene, diphenyl ether, dibenzofuran; 2-fluorobiphenyl, o-cyclohexylfluoro Overcharge inhibitors such as partially fluorinated compounds of the aromatic compounds such as benzene and p-cyclohexylfluorobenzene;
(2) Unsaturated bond-containing carbonates such as vinylene carbonate and vinyl ethylene carbonate; negative electrode film forming agents such as acid anhydrides such as succinic anhydride, glutaric anhydride, maleic anhydride, and citraconic anhydride;
(3) Ethylene sulfite, propylene sulfite, dimethyl sulfite, propane sultone, butane sultone, propene sultone, methyl methanesulfonate, busulfan, methyl toluenesulfonate, dimethyl sulfate, ethylene sulfate, sulfolane, dimethyl sulfone, diethyl sulfone, dimethyl sulfoxide, diethyl Sulfoxide, tetramethylene sulfoxide, diphenyl sulfide, thioanisole, diphenyl disulfide, sulfate esters such as glycol sulfate and propylene glycol sulfate; Cathode protection of sulfonic acid esters such as methyl methanesulfonate Agent;
(4) Phosphate esters such as trimethyl phosphate and triethyl phosphate; Flame retardants such as polyphosphates such as melamine polyphosphate, ammonium polyphosphate, ethylenediamine diamine phosphate, hexamethylenediamine polyphosphate, piperazine polyphosphate Agent;
Etc.
そして、上記した各種の任意の添加成分の中で、過充電防止剤としては、ビフェニル、ターフェニル（又はその部分水素化体）、シクロヘキシルベンゼン、ｔ−ブチルベンゼンが、好ましく用いられる。これらは、２種類以上組み合わせて用いられても、何等差し支えない。 Of the various optional additives described above, biphenyl, terphenyl (or a partially hydrogenated product thereof), cyclohexylbenzene, and t-butylbenzene are preferably used as the overcharge inhibitor. These may be used in combination of two or more.
また、負極被膜形成剤としては、上記の中でも、ビニレンカーボネート、ビニルエチレンカーボネート、無水コハク酸、無水マレイン酸が、好ましく用いられる。これらは、２種類以上併用して、用いられてもよい。更に、正極保護剤としては、亜硫酸エチレン、亜硫酸プロピレン、プロパンスルトン、ブタンスルトン、メタンスルホン酸メチルが、好ましく用いられる。これらは、２種類以上併用して、用いられてもよい。そして、負極被膜形成剤と正極保護剤との併用や、過充電防止剤と負極被膜形成剤と正極保護剤との併用が、特に好ましく採用される。 Of the above, vinylene carbonate, vinyl ethylene carbonate, succinic anhydride, and maleic anhydride are preferably used as the negative electrode film forming agent. Two or more of these may be used in combination. Furthermore, as the positive electrode protective agent, ethylene sulfite, propylene sulfite, propane sultone, butane sultone, or methyl methanesulfonate is preferably used. Two or more of these may be used in combination. And combined use with a negative electrode film formation agent and a positive electrode protective agent, and combined use with an overcharge inhibitor, a negative electrode film formation agent, and a positive electrode protective agent are employ | adopted especially preferably.
さらに、非水電解液中における、これら他の化合物の含有割合は、特に限定されるものではないが、非水系電解液全体に対し、それぞれ、０．０１重量％以上１０重量％以下が望ましく、より好ましくは０．１重量％以上５重量％以下、特に好ましくは０．２重量％以上２重量％以下である。これらの化合物を添加することにより、過充電による異常時に電池の破裂・発火を抑制したり、高温保存後の容量維持率やサイクル特性を向上させたりすることが出来る。 Furthermore, the content ratio of these other compounds in the non-aqueous electrolyte solution is not particularly limited, but is preferably 0.01% by weight or more and 10% by weight or less, respectively, with respect to the entire non-aqueous electrolyte solution. More preferably, they are 0.1 weight% or more and 5 weight% or less, Most preferably, they are 0.2 weight% or more and 2 weight% or less. By adding these compounds, it is possible to suppress rupture / ignition of the battery at the time of abnormality due to overcharge, and to improve the capacity retention rate and cycle characteristics after high temperature storage.
ところで、かくの如き本発明に従う非水電解液を用いたリチウムイオン二次電池は、よく知られているように、正極活物質を有する正極と、負極活物質を有する負極と、それら正極及び負極の間に介在せしめられた、本発明に従う非水電解液とを含んでなる構造において、基本的に構成されることとなる。 By the way, as is well known, a lithium ion secondary battery using a non-aqueous electrolyte according to the present invention as described above includes a positive electrode having a positive electrode active material, a negative electrode having a negative electrode active material, and these positive and negative electrodes. In the structure containing the nonaqueous electrolyte solution according to the present invention interposed between the two, it is basically configured.
そこにおいて、正極は、一般に、正極活物質と導電材と結着材とを含んで構成されている。具体的には、それら正極活物質と導電材と結着材とを適当な溶媒にて混合して得られた正極スラリーを用い、それを、適当な塗工装置にて所定の正極集電箔上に塗工することにより、正極シートを形成して、目的とする正極として用いられるのである。 In this regard, the positive electrode is generally configured to include a positive electrode active material, a conductive material, and a binder. Specifically, a positive electrode slurry obtained by mixing the positive electrode active material, the conductive material, and the binder with an appropriate solvent is used, and this is applied to a predetermined positive electrode current collector foil with an appropriate coating device. By coating on top, a positive electrode sheet is formed and used as a target positive electrode.
そして、そのような正極を与える構成成分の一つたる正極活物質は、リチウムイオンを吸蔵・放出可能なリチウム含有遷移金属複合酸化物、リチウム含有遷移金属リン酸化物が挙げられる。リチウム含有遷移金属酸化物としては、例えば、リチウムコバルト系複合酸化物（典型的にはＬｉＣｏＯ2 ）、リチウムニッケル系複合酸化物（典型的にはＬｉＮｉＯ2 ）、リチウムマンガン系複合酸化物（典型的にはＬｉＭｎ2Ｏ4）、リチウムバナジウム系複合酸化物（典型的にはＬｉＶ2Ｏ3）や、更に、遷移金属を２種以上含む複合酸化物等が挙げられる。リチウム含有遷移金属リン酸化物としては、例えば、鉄リン酸化物（典型的にはＬｉＦｅＰＯ4）、コバルトリン酸化物（典型的にはＬｉＣｏＰＯ4）や、遷移金属を２種以上含む複合リン酸化物等が挙げられる。 Examples of the positive electrode active material that is one of the components that provide such a positive electrode include lithium-containing transition metal composite oxides and lithium-containing transition metal phosphorous oxides that can occlude and release lithium ions. Examples of the lithium-containing transition metal oxide include lithium cobalt-based composite oxide (typically LiCoO 2 ), lithium nickel-based composite oxide (typically LiNiO 2 ), lithium manganese-based composite oxide (typical Include LiMn 2 O 4 ), lithium vanadium-based composite oxides (typically LiV 2 O 3 ), and composite oxides containing two or more transition metals. Examples of the lithium-containing transition metal phosphorous oxide include iron phosphorous oxide (typically LiFePO 4 ), cobalt phosphorous oxide (typically LiCoPO 4 ), and composite phosphorous oxide containing two or more transition metals. Etc.
また、導電材は、正極の電気伝導性を確保するためのものであり、一般に、公知の各種の炭素粉末材料が用いられ、例えば、非水電解液との反応がなく且つ良好な体積固有抵抗（１００Ω・ｃｍ未満）を有しているために、アセチレンブラック等のカーボンブラックや炭素繊維等の炭素微粉が用いられることとなる。更に、結着材は、活物質粒子及び導電材粒子を繋ぎ止める役割を果たすものであり、一般に、リチウムイオン二次電池の電位において分解反応がなく且つ非水電解液に対して不溶であるポリマー、例えば、ポリフッ化ビニリデン、ポリエチレンオキサイド、ポリプロピレンオキサイド等が、好適に用いられる。なお、正極活物質、導電材及び結着材を分散させる溶媒としては、例えば、Ｎ−メチル−２−ピロリドン、ジメチルホルムアミド、ジメチルアセトアミド、メチルエチルケトン、シクロヘキサノン、酢酸メチル、アクリル酸メチル、ジエチルトリアミン、Ｎ，Ｎ−ジメチルアミノプロピルアミン、エチレンオキシド、テトラヒドロフラン等が用いられ、更に、集電体となる集電箔の材質としては、アルミニウム、ステンレス、ニッケルメッキ鋼等が採用されることとなる。 In addition, the conductive material is for ensuring the electrical conductivity of the positive electrode, and generally, various known carbon powder materials are used. For example, there is no reaction with a non-aqueous electrolyte and a good volume resistivity. Therefore, carbon black such as acetylene black or carbon fine powder such as carbon fiber is used. Furthermore, the binder serves to bind the active material particles and the conductive material particles, and is generally a polymer that has no decomposition reaction at the potential of the lithium ion secondary battery and is insoluble in the non-aqueous electrolyte. For example, polyvinylidene fluoride, polyethylene oxide, polypropylene oxide and the like are preferably used. Examples of the solvent in which the positive electrode active material, the conductive material, and the binder are dispersed include, for example, N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, methyl ethyl ketone, cyclohexanone, methyl acetate, methyl acrylate, diethyltriamine, N , N-dimethylaminopropylamine, ethylene oxide, tetrahydrofuran, and the like are used, and aluminum, stainless steel, nickel-plated steel, and the like are employed as the material of the current collector foil that becomes the current collector.
さらに、リチウムイオン二次電池における負極は、一般に、負極活物質と結着材とを含んで構成され、そして、その電気抵抗を下げるために、適宜に導電材が配合されて用いられることとなる。なお、それら負極活物質と結着材と更に必要に応じて配合される導電材には、上記した正極の場合と同様にして、適当な溶媒が加えられて、ペースト状の負極材として、所定の集電体の表面に塗工することにより、負極シートとして用いられるのである。 Furthermore, the negative electrode in the lithium ion secondary battery is generally configured to include a negative electrode active material and a binder, and a conductive material is appropriately mixed and used in order to reduce the electric resistance. . In addition, an appropriate solvent is added to the conductive material blended as necessary with the negative electrode active material and the binder, as in the case of the positive electrode described above, and a predetermined negative paste material is obtained as a paste-like negative electrode material. It is used as a negative electrode sheet by coating on the surface of the current collector.
なお、そのような負極を構成する成分の一つである負極活物質は、電気化学的にリチウムイオンを吸蔵・放出可能なものであれば、特に制限はなく、天然黒鉛や人造炭素物質、コークス等の炭素質材料、酸化錫や酸化ケイ素等の金属酸化物、金属複合酸化物、リチウム単体やリチウムアルミニウム合金等のリチウム合金、ＳｎやＳｉ等のリチウムと合金形成可能な金属等が挙げられる。これらは、１種類を単独で用いても、２種以上を任意の組み合わせ及び比率で併用してもよい。中でも、炭素質材料又はリチウム複合酸化物が安全性の点から好適に用いられることとなる。また、結着材としては、上記した正極の場合と同様に、ポリフッ化ビニリデン、ポリエチレンオキサイド、ポリプロピレンオキサイド等が好適に用いられ、更に導電材としては、非水電解液との反応がなく且つ良好な体積固有抵抗（１００Ω・ｃｍ未満）を有しているところから、アセチレンブラック等のカーボンブラックや、気相成長させた炭素繊維等の微粉体が、有利に用いられることとなる。更に、負極の集電体には、銅、ニッケル、ステンレス鋼、ニッケルメッキ鋼等の箔を用いることが出来る。 The negative electrode active material, which is one of the components constituting such a negative electrode, is not particularly limited as long as it can electrochemically occlude and release lithium ions. Natural graphite, artificial carbon materials, coke Examples thereof include carbonaceous materials such as tin oxide, metal oxides such as tin oxide and silicon oxide, metal composite oxides, lithium alloys such as lithium alone and lithium aluminum alloys, and metals that can form alloys with lithium such as Sn and Si. These may be used alone or in combination of two or more in any combination and ratio. Among these, carbonaceous materials or lithium composite oxides are preferably used from the viewpoint of safety. As the binder, polyvinylidene fluoride, polyethylene oxide, polypropylene oxide, and the like are preferably used as in the case of the positive electrode described above, and the conductive material has no reaction with the non-aqueous electrolyte and is good. Therefore, carbon black such as acetylene black and fine powder such as vapor grown carbon fiber are advantageously used because of having a large volume resistivity (less than 100 Ω · cm). Furthermore, foils of copper, nickel, stainless steel, nickel-plated steel, etc. can be used for the negative electrode current collector.
また、本発明に従って構成されるリチウムイオン二次電池においても、従来と同様に、負極と正極との間に、適当なセパレータを配設することが可能である。このセパレータとしては、小型民生機器用リチウムイオン電池で従来から用いられているもので良く、特に限定されるものではない。尤も、正極と負極とを隔てることが可能であり且つ電解液を保持することが出来るものであることが望ましく、そのために、不織布や、ポリエチレン、ポリプロピレン等のポリオレフィン系微多孔膜（フィルム）が、好適に用いられることとなる。 Also in the lithium ion secondary battery constructed according to the present invention, an appropriate separator can be disposed between the negative electrode and the positive electrode, as in the prior art. As this separator, what is conventionally used with the lithium ion battery for small consumer devices may be used, and it is not specifically limited. However, it is desirable that the positive electrode and the negative electrode can be separated and the electrolyte solution can be held. For that purpose, a non-woven fabric, a polyolefin microporous film (film) such as polyethylene, polypropylene, etc. It will be used suitably.
加えて、本発明が適用されるリチウムイオン二次電池の形状としては、特に限定されるものではなく、従来から公知の各種の形状乃至は構造において、本発明が適用され得るものであって、例えば、コイン型、ボタン型、シート型、積層型、円筒型、扁平型、角型等の形状を採用することが可能である。また、電気自動車等の輸送機器に用いる大型のもの等にも、有利に適用することが可能である。 In addition, the shape of the lithium ion secondary battery to which the present invention is applied is not particularly limited, and the present invention can be applied to various conventionally known shapes or structures, For example, a coin shape, a button shape, a sheet shape, a stacked shape, a cylindrical shape, a flat shape, a square shape, or the like can be employed. In addition, the present invention can be advantageously applied to large-sized ones used for transportation equipment such as electric vehicles.
以上、本発明の実施形態について詳述してきたが、それは、あくまでも、例示に過ぎないものであって、本発明は、そのような実施形態に係る具体的な記述によって、何等限定的に解釈されるものではないことが、理解されるべきである。本発明は、当業者の知識に基づいて、種々なる変更、修正、改良等を加えた態様において実施され得るものであり、そしてそのような実施態様が、本発明の趣旨を逸脱しない限りにおいて、何れも、本発明の範疇に属するものであることは、言うまでもないところである。 The embodiment of the present invention has been described in detail above, but it is merely an example, and the present invention is interpreted in a limited manner by a specific description according to such an embodiment. It should be understood that it is not. The present invention can be implemented in variously modified, modified, improved, and other forms based on the knowledge of those skilled in the art, and such embodiments do not depart from the spirit of the present invention. It goes without saying that both belong to the category of the present invention.
以下に、本発明の代表的な実施例を示し、本発明を更に具体的に明らかにすることとするが、本発明が、そのような実施例の記載によって、何等の制約をも受けるものでないことも、また、理解されるべきである。 Hereinafter, representative examples of the present invention will be shown to clarify the present invention more specifically, but the present invention is not limited by the description of such examples. That should also be understood.
−非水電解液の調製−
エチレンカーボネート、ジメチルカーボネート、エチルメチルカーボネート及びジメチルカーボネートを、体積比で、１：１：１：１となるように混合してなる混合溶媒に、ＬｉＰＦ6 を、１ｍｏｌ／Ｌの濃度となるように溶解せしめ、更に、リチウムビス（オキサラト）ボレート（ＬｉＢＯＢ）を０．２重量％、ジビニルテトラメチルジシロキサンを０．１０〜２．００重量％の各種割合において、また、フッ素原子を有する炭酸エステルとして、４−フルオロエチレンカーボネート（ＦＥＣ）を１．０重量％の割合となるように配合して、溶解・含有せしめ、実験例１〜５に係る各種の非水電解液を調製した。
-Preparation of non-aqueous electrolyte-
In a mixed solvent obtained by mixing ethylene carbonate, dimethyl carbonate, ethyl methyl carbonate and dimethyl carbonate in a volume ratio of 1: 1: 1: 1, LiPF 6 is adjusted to a concentration of 1 mol / L. Furthermore, lithium bis (oxalato) borate (LiBOB) is 0.2% by weight, divinyltetramethyldisiloxane is 0.10 to 2.00% by weight, and a carbonic acid ester having a fluorine atom. 4-fluoroethylene carbonate (FEC) was blended at a ratio of 1.0% by weight, dissolved and contained, and various nonaqueous electrolytes according to Experimental Examples 1 to 5 were prepared.
また、ＦＥＣの電解液中の含有濃度を、０．１重量％、０．５重量％又は２．０重量％とすること以外は、上記した実験例１の場合と同様にして、実験例６，７又は８に係る非水電解液を調製した。 Further, Experimental Example 6 was performed in the same manner as in Experimental Example 1 except that the concentration of FEC in the electrolytic solution was 0.1% by weight, 0.5% by weight, or 2.0% by weight. , 7 or 8 was prepared.
さらに、ＬｉＢＯＢの電解液中の含有濃度を、１．０重量％とすること以外は、上記した実験例１の場合と同様にして、実験例９に係る非水電解液を調製した。 Furthermore, a nonaqueous electrolytic solution according to Experimental Example 9 was prepared in the same manner as in Experimental Example 1 except that the concentration of LiBOB in the electrolytic solution was 1.0% by weight.
加えて、実験例１におけるＦＥＣに代えて、４−フルオロメチル−エチレンカーボネートを用いたこと以外は、実験例１の場合と同様にして、実験例１０に係る非水電解液を調製した。 In addition, a nonaqueous electrolytic solution according to Experimental Example 10 was prepared in the same manner as in Experimental Example 1 except that 4-fluoromethyl-ethylene carbonate was used instead of FEC in Experimental Example 1.
一方、比較のために、実験例１におけるＬｉＢＯＢ、ジビニルテトラメチルジシロキサン及びＦＥＣを添加含有せしめないこと以外は、実験例１の場合と同様にして、非水電解液を調製し、比較例１に係る非水電解液とした。 On the other hand, for comparison, a nonaqueous electrolytic solution was prepared in the same manner as in Experimental Example 1 except that LiBOB, divinyltetramethyldisiloxane and FEC in Experimental Example 1 were not added and contained. It was set as the non-aqueous electrolyte concerning.
また、実験例１において、ＦＥＣのみを添加含有せしめないこと、又はジビニルテトラメチルジシロキサンのみを添加含有せしめないこと以外は、実験例１の場合と同様にして非水電解液を調製し、それぞれ、比較例２又は比較例３に係る非水電解液とした。 Further, in Experimental Example 1, a nonaqueous electrolytic solution was prepared in the same manner as in Experimental Example 1, except that only FEC was not added or only divinyltetramethyldisiloxane was not added. The nonaqueous electrolyte solution according to Comparative Example 2 or Comparative Example 3 was obtained.
さらに、実験例１０におけるＬｉＢＯＢとジビニルテトラメチルジシロキサンを添加含有せしめないこと以外は、実験例１０の場合と同様にして、非水電解液を調製し、比較例４に係る非水電解液とした。 Further, a nonaqueous electrolytic solution was prepared in the same manner as in Experimental Example 10 except that LiBOB and divinyltetramethyldisiloxane in Experimental Example 10 were not added, and the nonaqueous electrolytic solution according to Comparative Example 4 was did.
−リチウムイオン二次電池の作製−
［正極の作製］
正極活物質としてのＬｉＮｉ1/3Ｍｎ1/3Ｃｏ1/3Ｏ2の９０質量％と、導電剤としてのアセチレンブラックの５質量％と、結着材としてのポリフッ化ビニリデン（ＰＶｄＦ）の５質量％とを、Ｎ−メチルピロリドン溶媒中で混合して、スラリー化した。次いで、その得られたスラリーを厚さ２０μｍのアルミ箔の両面に塗布して乾燥し、そしてそれをプレス機で厚さ６４μｍに圧延したものを、活物質層として幅：８０ｍｍ、長さ：１２０ｍｍのサイズを有し且つ幅：１５ｍｍの未塗工部を有する形状に切り出し、正極とした。
-Fabrication of lithium ion secondary battery-
[Production of positive electrode]
90% by mass of LiNi 1/3 Mn 1/3 Co 1/3 O 2 as the positive electrode active material, 5% by mass of acetylene black as the conductive agent, and 5% of polyvinylidene fluoride (PVdF) as the binder % By mass was mixed in N-methylpyrrolidone solvent to make a slurry. Next, the obtained slurry was applied to both sides of an aluminum foil having a thickness of 20 μm, dried, and rolled into a thickness of 64 μm by a press machine, and the active material layer had a width of 80 mm and a length of 120 mm. And was cut out into a shape having an uncoated part with a width of 15 mm.
［負極の作製］
また、負極活物質としてのハードカーボンの９０質量％に、導電材としてのカーボンナノファイバ（昭和電工株式会社製ＶＧＣＦ）の５質量％と、結着材としてのポリフッ化ビニリデン（ＰＶｄＦ）の５質量％とを、Ｎ−メチルピロリドン溶媒中で混合して、スラリー化した。次いで、その得られたスラリーを厚さ１４μｍの銅箔の両面に塗布して乾燥し、そしてそれをプレス機で厚さ１０８μｍに圧延したものを、活物質層として幅：８３ｍｍ、長さ：１２４ｍｍのサイズを有し且つ幅：１３ｍｍの未塗工部を有する形状に切り出し、負極とした。
[Production of negative electrode]
Also, 90% by mass of hard carbon as the negative electrode active material, 5% by mass of carbon nanofiber (VGCF manufactured by Showa Denko KK) as the conductive material, and 5% by mass of polyvinylidene fluoride (PVdF) as the binder. % In an N-methylpyrrolidone solvent and slurried. Subsequently, the obtained slurry was applied to both sides of a copper foil having a thickness of 14 μm, dried, and rolled to a thickness of 108 μm with a press machine, and the active material layer had a width of 83 mm and a length of 124 mm. A negative electrode was cut into a shape having an uncoated part with a size of 13 mm and a width of 13 mm.
［電池の組立］
かくして得られた正極の２０枚と負極の２１枚とが交互となるように配置すると共に、各電極の間に、多孔性ポリプロピレンシートのセパレータ（厚さ２５μｍ）が挟まれるようにして、積層した。この際、正極活物質面が負極活物質面内から外れないよう対面させた。この正極と負極のそれぞれにおける未塗工部同士と金属集電体とを溶接して集電タブを作製し、電極群としたものを、ラミネート状の外装体（外寸：１６０×９０×６ｍｍ）に封入した。その後、かかる電極群を装填した電池に、先に調製した実験例１〜１０及び比較例１〜４に係る非水系電解液を、それぞれ、１８ｍＬ注入して、電極に充分に浸透させ、そして密閉することにより、それぞれ、実験例１〜１０及び比較例１〜４に係るリチウムイオン二次電池を作製した。この二次電池の１個の電池外装に収納される電池要素の持つ電気容量、即ち、かかる電池の定格放電容量は、約２アンペアーアワー（Ａｈ）であり、１０ｋＨｚ交流法で測定される直流抵抗成分は、約１ミリオーム（ｍΩ）であった。
[Battery assembly]
The 20 positive electrodes and 21 negative electrodes thus obtained were alternately arranged, and a porous polypropylene sheet separator (thickness 25 μm) was sandwiched between the electrodes, and the layers were laminated. . At this time, the positive electrode active material surface was faced so as not to deviate from the negative electrode active material surface. A current collector tab is prepared by welding uncoated portions of each of the positive electrode and the negative electrode to a metal current collector, and an electrode group is formed as a laminated outer package (outside dimension: 160 × 90 × 6 mm). ). Thereafter, 18 mL of the non-aqueous electrolytes according to Experimental Examples 1 to 10 and Comparative Examples 1 to 4 prepared above were respectively injected into the battery loaded with such an electrode group, and the electrodes were sufficiently infiltrated and sealed. As a result, lithium ion secondary batteries according to Experimental Examples 1 to 10 and Comparative Examples 1 to 4 were produced. The electric capacity of the battery element housed in one battery exterior of the secondary battery, that is, the rated discharge capacity of the battery is about 2 ampere hours (Ah), and the DC resistance measured by the 10 kHz AC method. The component was about 1 milliohm (mΩ).
《電池の評価》
−容量測定−
上記で作製した実験例１〜１０及び比較例１〜４のリチウムイオン二次電池を用いて、２５℃で、電圧範囲：４．２Ｖ〜２．７Ｖ、電流値：０．２Ｃ（１時間率の放電容量による定格容量を１時間で放電する電流値を１Ｃとする、以下同様）にて、６サイクル初期充放電を行なった。そして、この時の６サイクル目の１Ｃ放電容量を、初期容量とした。
<Battery evaluation>
-Capacity measurement-
Using the lithium ion secondary batteries of Experimental Examples 1 to 10 and Comparative Examples 1 to 4 prepared above, at 25 ° C., voltage range: 4.2 V to 2.7 V, current value: 0.2 C (1 hour rate 6 cycles initial charge / discharge was performed at a current value of 1 C for the rated capacity due to the discharge capacity of 1 C, and so on. And the 1C discharge capacity of the 6th cycle at this time was made into the initial stage capacity.
−サイクル試験−
上記で得られた実験例１〜１０及び比較例１〜４のリチウムイオン二次電池を用いて、リチウム二次電池の実使用上限温度と目される６５℃の高温環境下にて、サイクル試験を行なった。このサイクル試験は、電池のＳＯＣ（state of charge ：充電率）を６０％まで定電流定電圧で充電した後、下記の充放電モードを３サイクル繰り返し、続いてＳＯＣを７０％まで定電流定電圧で充電した後、下記の充放電モードを３サイクル繰り返し、更に続いてＳＯＣを８０％まで定電流定電圧で充電した後、下記の充放電モードを３サイクル繰り返し、更に続いてＳＯＣ６０％まで定電流定電圧で放電してスタート時のＳＯＣ６０％に合わせる、という合計９サイクルの充放電モードの繰返しを１セットとして、繰り返すこととした。なお、充放電のモードの１サイクルは、放電が１００Ｃで６．７秒、回生は５０Ｃで１〜２秒を６回連続して実施し、そしてそれら放電・回生間の休止時間を５秒とすることにより、構成した。また、充電上限電圧を４．２Ｖ、放電下限電圧を２．７Ｖとし、万が一上下限電圧に達した場合は、当該電圧を保持する様に電流調整を行なった。そして、上記のセットを、４０００セットまで、繰り返した。
-Cycle test-
Using the lithium ion secondary batteries of Experimental Examples 1 to 10 and Comparative Examples 1 to 4 obtained above, a cycle test was performed under a high temperature environment of 65 ° C. that is regarded as the actual upper limit temperature of the lithium secondary battery. Was done. In this cycle test, after charging the battery SOC (state of charge) to 60% at a constant current and constant voltage, the following charge / discharge mode was repeated for 3 cycles, and then the SOC was constant current and constant voltage to 70%. After charging the battery, the following charge / discharge mode is repeated for 3 cycles, and then the SOC is charged at a constant current / constant voltage up to 80%. Then, the following charge / discharge mode is repeated for 3 cycles, followed by a constant current until the SOC reaches 60%. It was decided to repeat the charge / discharge mode for a total of 9 cycles of discharging at a constant voltage and adjusting to SOC 60% at the start as one set. In one cycle of the charge / discharge mode, the discharge is 6.7 seconds at 100C, the regeneration is 6 times continuously at 1-2 seconds at 50C, and the rest time between the discharge and regeneration is 5 seconds. To make up. Moreover, the charge upper limit voltage was set to 4.2 V, the discharge lower limit voltage was set to 2.7 V, and in the event that the upper limit voltage was reached, current adjustment was performed so as to maintain the voltage. The above set was repeated up to 4000 sets.
−初期抵抗測定及びサイクル試験後の抵抗測定−
２５℃の環境下で、ＳＯＣ２０％から８０％まで各１０％毎に充電状態を調整して、各充電状態の下で、１０Ｃ、１５Ｃ、２０Ｃ、２５Ｃで１２秒間放電させ、その１０秒目の電圧を測定した。そして、電流−電圧直線と下限電圧（２．４Ｖ）とで囲まれる３角形の面積を放電出力（Ｗ）、電流−電圧直線と上限電圧（４．２Ｖ）とで囲まれる３角形の面積を回生出力（Ｗ）とした。なお、抵抗に関する比較には、ＳＯＣ５０％における放電出力を用いている。
-Initial resistance measurement and resistance measurement after cycle test-
Under the environment of 25 ° C, the state of charge is adjusted every 10% from SOC 20% to 80%, and discharged under 10C, 15C, 20C, 25C for 12 seconds under each state of charge. The voltage was measured. The area of the triangle surrounded by the current-voltage straight line and the lower limit voltage (2.4V) is the discharge output (W), and the area of the triangle surrounded by the current-voltage straight line and the upper limit voltage (4.2V) is Regenerative output (W). In addition, the discharge output in SOC50% is used for the comparison regarding resistance.
−容量維持率の測定−
上記４０００セットの繰返しからなるサイクル試験終了後の１Ｃ放電容量を、初期の１Ｃ放電容量で除した値を、容量維持率とした。
-Measurement of capacity retention rate-
The value obtained by dividing the 1C discharge capacity after the end of the cycle test consisting of the above 4000 sets by the initial 1C discharge capacity was defined as the capacity retention rate.
−抵抗増加率の測定−
上記４０００セットの繰返しからなるサイクル試験終了後のＳＯＣ５０％における放電出力を、初期のＳＯＣ５０％における放電出力で除した値を、抵抗増加率とした。
-Measurement of resistance increase rate-
The value obtained by dividing the discharge output at 50% SOC after the end of the cycle test consisting of the above 4000 sets by the discharge output at 50% of the initial SOC was defined as the resistance increase rate.
かくして得られた実験例１〜９及び比較例１〜３に係るリチウムイオン二次電池についての放電容量維持率、初期抵抗特性及び電池抵抗増加率に係る測定の結果を、下記表１に示し、また実験例１０及び比較例４に係るリチウムイオン二次電池についての結果を、それぞれ、下記表２に示した。 The results of the measurement relating to the discharge capacity maintenance rate, the initial resistance characteristics, and the battery resistance increase rate for the lithium ion secondary batteries according to Experimental Examples 1 to 9 and Comparative Examples 1 to 3 thus obtained are shown in Table 1 below. The results for the lithium ion secondary batteries according to Experimental Example 10 and Comparative Example 4 are shown in Table 2 below.
かかる表１，２の結果から明らかなように、本発明に従って、非水系溶媒にリチウムを含む電解質塩を溶解させてなる非水電解液に対して、更に、リチウムビス（オキサラト）ボレートと、ジビニルテトラメチルジシロキサン及びフッ素原子を含有する炭酸エステルを添加配合せしめてなる非水電解液を用いたリチウムイオン二次電池（実験例１〜１０）にあっては、その何れか一つを少なくとも含有していない比較例１〜４に係るリチウムイオン電池に比べて、初期抵抗及びサイクル試験後の容量維持率、抵抗増加率が有利に改善せしめられていることが、認められた。 As is apparent from the results of Tables 1 and 2, according to the present invention, lithium bis (oxalato) borate and divinyl were further added to the non-aqueous electrolyte obtained by dissolving an electrolyte salt containing lithium in a non-aqueous solvent. In the lithium ion secondary battery (Experimental Examples 1 to 10) using a non-aqueous electrolyte obtained by adding and blending tetramethyldisiloxane and a carbonic acid ester containing a fluorine atom, at least one of them is contained. It was recognized that the initial resistance, the capacity retention rate after the cycle test, and the resistance increase rate were advantageously improved as compared with the lithium ion batteries according to Comparative Examples 1 to 4 that were not performed.
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