JP4187959B2 - Non-aqueous electrolyte and secondary battery using the same - Google Patents
Non-aqueous electrolyte and secondary battery using the same Download PDFInfo
- Publication number
- JP4187959B2 JP4187959B2 JP2001326630A JP2001326630A JP4187959B2 JP 4187959 B2 JP4187959 B2 JP 4187959B2 JP 2001326630 A JP2001326630 A JP 2001326630A JP 2001326630 A JP2001326630 A JP 2001326630A JP 4187959 B2 JP4187959 B2 JP 4187959B2
- Authority
- JP
- Japan
- Prior art keywords
- carbonate
- borate
- electrolytic solution
- lithium
- aqueous electrolyte
- 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 - Lifetime
Links
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims description 57
- -1 dimethyl monolithium borate Chemical compound 0.000 claims description 47
- 239000008151 electrolyte solution Substances 0.000 claims description 43
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 29
- 239000003792 electrolyte Substances 0.000 claims description 28
- 229910001416 lithium ion Inorganic materials 0.000 claims description 27
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 25
- 239000000010 aprotic solvent Substances 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 20
- 229910052744 lithium Inorganic materials 0.000 claims description 19
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 19
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 18
- 239000003125 aqueous solvent Substances 0.000 claims description 17
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 16
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical class O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 15
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 15
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 14
- 239000003575 carbonaceous material Substances 0.000 claims description 14
- 125000004122 cyclic group Chemical group 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 239000004327 boric acid Substances 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 10
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 10
- 150000005678 chain carbonates Chemical class 0.000 claims description 9
- 229910003002 lithium salt Inorganic materials 0.000 claims description 9
- 159000000002 lithium salts Chemical class 0.000 claims description 9
- 239000007773 negative electrode material Substances 0.000 claims description 8
- 229910052723 transition metal Inorganic materials 0.000 claims description 7
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 239000007774 positive electrode material Substances 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 3
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 3
- IFDLFCDWOFLKEB-UHFFFAOYSA-N 2-methylbutylbenzene Chemical compound CCC(C)CC1=CC=CC=C1 IFDLFCDWOFLKEB-UHFFFAOYSA-N 0.000 claims description 3
- QYIOFABFKUOIBV-UHFFFAOYSA-N 4,5-dimethyl-1,3-dioxol-2-one Chemical compound CC=1OC(=O)OC=1C QYIOFABFKUOIBV-UHFFFAOYSA-N 0.000 claims description 3
- CTLXBMDFBWAXQB-UHFFFAOYSA-N B(OC(C(C(F)(F)F)F)(F)F)(OC(C(C(F)(F)F)F)(F)F)OC(C(C(F)(F)F)F)(F)F Chemical compound B(OC(C(C(F)(F)F)F)(F)F)(OC(C(C(F)(F)F)F)(F)F)OC(C(C(F)(F)F)F)(F)F CTLXBMDFBWAXQB-UHFFFAOYSA-N 0.000 claims description 3
- ZIDZGLYBOIGPGZ-UHFFFAOYSA-N B(OC(C(F)(F)F)(C(F)(F)F)C)(OC(C(F)(F)F)(C(F)(F)F)C)OC(C(F)(F)F)(C(F)(F)F)C Chemical compound B(OC(C(F)(F)F)(C(F)(F)F)C)(OC(C(F)(F)F)(C(F)(F)F)C)OC(C(F)(F)F)(C(F)(F)F)C ZIDZGLYBOIGPGZ-UHFFFAOYSA-N 0.000 claims description 3
- OYTZKDRUOXLKRE-UHFFFAOYSA-N B(OC(C(F)(F)F)F)(OC(C(F)(F)F)F)OC(C(F)(F)F)F Chemical compound B(OC(C(F)(F)F)F)(OC(C(F)(F)F)F)OC(C(F)(F)F)F OYTZKDRUOXLKRE-UHFFFAOYSA-N 0.000 claims description 3
- VWIBWXQYSWPRRI-UHFFFAOYSA-N B(OC)(OCC(F)(F)F)OCC(F)(F)F Chemical compound B(OC)(OCC(F)(F)F)OCC(F)(F)F VWIBWXQYSWPRRI-UHFFFAOYSA-N 0.000 claims description 3
- DHOHKUULWWCWOR-UHFFFAOYSA-N B(OCC(Cl)(Cl)Cl)(OCC(Cl)(Cl)Cl)OCC(Cl)(Cl)Cl Chemical compound B(OCC(Cl)(Cl)Cl)(OCC(Cl)(Cl)Cl)OCC(Cl)(Cl)Cl DHOHKUULWWCWOR-UHFFFAOYSA-N 0.000 claims description 3
- 101150058243 Lipf gene Proteins 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000002441 X-ray diffraction Methods 0.000 claims description 3
- ZTCLFSRIWSZUHZ-UHFFFAOYSA-N but-1-yne;carbonic acid Chemical compound CCC#C.OC(O)=O ZTCLFSRIWSZUHZ-UHFFFAOYSA-N 0.000 claims description 3
- BPTOPBBYWGYDGS-UHFFFAOYSA-N carbonic acid;3,3,3-trifluoroprop-1-yne Chemical compound OC(O)=O.FC(F)(F)C#C BPTOPBBYWGYDGS-UHFFFAOYSA-N 0.000 claims description 3
- ZNNZFUYGJVHLGX-UHFFFAOYSA-N carbonic acid;fluoroethyne Chemical compound FC#C.OC(O)=O ZNNZFUYGJVHLGX-UHFFFAOYSA-N 0.000 claims description 3
- DOAYJNMCHKRFLA-UHFFFAOYSA-N carbonic acid;hex-3-yne Chemical compound OC(O)=O.CCC#CCC DOAYJNMCHKRFLA-UHFFFAOYSA-N 0.000 claims description 3
- DYCIODWFEIGZLV-UHFFFAOYSA-N carbonic acid;oct-4-yne Chemical compound OC(O)=O.CCCC#CCCC DYCIODWFEIGZLV-UHFFFAOYSA-N 0.000 claims description 3
- ANTVXUWVWRKHPP-UHFFFAOYSA-N carbonic acid;pent-1-ene Chemical compound OC(O)=O.CCCC=C ANTVXUWVWRKHPP-UHFFFAOYSA-N 0.000 claims description 3
- SYLNJGIBLUVXCG-UHFFFAOYSA-N carbonic acid;prop-1-yne Chemical compound CC#C.OC(O)=O SYLNJGIBLUVXCG-UHFFFAOYSA-N 0.000 claims description 3
- AVPJLIXBXNQRPA-UHFFFAOYSA-N diethyl methyl borate Chemical compound CCOB(OC)OCC AVPJLIXBXNQRPA-UHFFFAOYSA-N 0.000 claims description 3
- OUVUDMURERSZSE-UHFFFAOYSA-N dimethyl benzene-1,2-disulfonate Chemical compound COS(=O)(=O)C1=CC=CC=C1S(=O)(=O)OC OUVUDMURERSZSE-UHFFFAOYSA-N 0.000 claims description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000003784 fluoroethyl group Chemical group [H]C([H])(F)C([H])([H])* 0.000 claims description 3
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 3
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 150000008053 sultones Chemical class 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 3
- 229910001887 tin oxide Inorganic materials 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 claims description 3
- AJSTXXYNEIHPMD-UHFFFAOYSA-N triethyl borate Chemical compound CCOB(OCC)OCC AJSTXXYNEIHPMD-UHFFFAOYSA-N 0.000 claims description 3
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 claims description 3
- JLPJTCGUKOBWRJ-UHFFFAOYSA-N tripentyl borate Chemical compound CCCCCOB(OCCCCC)OCCCCC JLPJTCGUKOBWRJ-UHFFFAOYSA-N 0.000 claims description 3
- LTEHWCSSIHAVOQ-UHFFFAOYSA-N tripropyl borate Chemical compound CCCOB(OCCC)OCCC LTEHWCSSIHAVOQ-UHFFFAOYSA-N 0.000 claims description 3
- DIEXQJFSUBBIRP-UHFFFAOYSA-N tris(2,2,2-trifluoroethyl) borate Chemical compound FC(F)(F)COB(OCC(F)(F)F)OCC(F)(F)F DIEXQJFSUBBIRP-UHFFFAOYSA-N 0.000 claims description 3
- MHUUWQSRUNMMHR-UHFFFAOYSA-N tris(2,2,3,3,3-pentafluoropropyl) borate Chemical compound FC(F)(F)C(F)(F)COB(OCC(F)(F)C(F)(F)F)OCC(F)(F)C(F)(F)F MHUUWQSRUNMMHR-UHFFFAOYSA-N 0.000 claims description 3
- IYGPXXORQKFXCZ-UHFFFAOYSA-N tris(2-methoxyethyl) borate Chemical compound COCCOB(OCCOC)OCCOC IYGPXXORQKFXCZ-UHFFFAOYSA-N 0.000 claims description 3
- YISHWCPSPGRKND-UHFFFAOYSA-N B(OC)(OCCOCC(F)(F)F)OCCOCC(F)(F)F Chemical compound B(OC)(OCCOCC(F)(F)F)OCCOCC(F)(F)F YISHWCPSPGRKND-UHFFFAOYSA-N 0.000 claims description 2
- 229910013131 LiN Inorganic materials 0.000 claims description 2
- 229910013872 LiPF Inorganic materials 0.000 claims description 2
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 229920001940 conductive polymer Polymers 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 claims description 2
- 229940017219 methyl propionate Drugs 0.000 claims description 2
- 239000002861 polymer material Substances 0.000 claims description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 2
- 229910015015 LiAsF 6 Inorganic materials 0.000 claims 1
- 229910013063 LiBF 4 Inorganic materials 0.000 claims 1
- 229910013684 LiClO 4 Inorganic materials 0.000 claims 1
- 229910013870 LiPF 6 Inorganic materials 0.000 claims 1
- 244000062793 Sorghum vulgare Species 0.000 claims 1
- 235000019713 millet Nutrition 0.000 claims 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims 1
- 229940090181 propyl acetate Drugs 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims 1
- 238000003860 storage Methods 0.000 description 22
- 150000002430 hydrocarbons Chemical group 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- 229910032387 LiCoO2 Inorganic materials 0.000 description 8
- 229910002804 graphite Inorganic materials 0.000 description 8
- 239000010439 graphite Substances 0.000 description 8
- 238000000354 decomposition reaction Methods 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 229910021382 natural graphite Inorganic materials 0.000 description 7
- 230000002829 reductive effect Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000000654 additive Substances 0.000 description 6
- 229910001290 LiPF6 Inorganic materials 0.000 description 5
- 125000005842 heteroatom Chemical group 0.000 description 5
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical compound [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 5
- 125000000962 organic group Chemical group 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical class OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical class F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 3
- 229910013833 LiOSO2 Inorganic materials 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-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
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 150000008282 halocarbons Chemical group 0.000 description 3
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000005518 polymer electrolyte Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910000733 Li alloy Inorganic materials 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- FWBMVXOCTXTBAD-UHFFFAOYSA-N butyl methyl carbonate Chemical compound CCCCOC(=O)OC FWBMVXOCTXTBAD-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- QLVWOKQMDLQXNN-UHFFFAOYSA-N dibutyl carbonate Chemical compound CCCCOC(=O)OCCCC QLVWOKQMDLQXNN-UHFFFAOYSA-N 0.000 description 2
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001989 lithium alloy Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 2
- BIGYLAKFCGVRAN-UHFFFAOYSA-N 1,3,4-thiadiazolidine-2,5-dithione Chemical compound S=C1NNC(=S)S1 BIGYLAKFCGVRAN-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- XUKLTPZEKXTPBT-UHFFFAOYSA-N 3-oxatricyclo[5.2.1.01,5]dec-5-ene-2,4-dione Chemical compound C1CC2C=C3C(=O)OC(=O)C13C2 XUKLTPZEKXTPBT-UHFFFAOYSA-N 0.000 description 1
- LWLOKSXSAUHTJO-UHFFFAOYSA-N 4,5-dimethyl-1,3-dioxolan-2-one Chemical compound CC1OC(=O)OC1C LWLOKSXSAUHTJO-UHFFFAOYSA-N 0.000 description 1
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 description 1
- LSUWCXHZPFTZSF-UHFFFAOYSA-N 4-ethyl-5-methyl-1,3-dioxolan-2-one Chemical compound CCC1OC(=O)OC1C LSUWCXHZPFTZSF-UHFFFAOYSA-N 0.000 description 1
- VUKVVXBCZIPVSE-UHFFFAOYSA-N 4-methyl-5h-1,3-oxazol-2-one Chemical compound CC1=NC(=O)OC1 VUKVVXBCZIPVSE-UHFFFAOYSA-N 0.000 description 1
- AUXJVUDWWLIGRU-UHFFFAOYSA-N 4-propyl-1,3-dioxolan-2-one Chemical compound CCCC1COC(=O)O1 AUXJVUDWWLIGRU-UHFFFAOYSA-N 0.000 description 1
- 229920003026 Acene Polymers 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- HBJICDATLIMQTJ-UHFFFAOYSA-N C(O)(O)=O.C(=C)C=CC=C Chemical compound C(O)(O)=O.C(=C)C=CC=C HBJICDATLIMQTJ-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- QEVGZEDELICMKH-UHFFFAOYSA-N Diglycolic acid Chemical compound OC(=O)COCC(O)=O QEVGZEDELICMKH-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910007549 Li2SiF6 Inorganic materials 0.000 description 1
- 229910013075 LiBF Inorganic materials 0.000 description 1
- 229910001559 LiC4F9SO3 Inorganic materials 0.000 description 1
- 229910000552 LiCF3SO3 Inorganic materials 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910002993 LiMnO2 Inorganic materials 0.000 description 1
- 229910003005 LiNiO2 Inorganic materials 0.000 description 1
- 229910013100 LiNix Inorganic materials 0.000 description 1
- 229910013138 LiNixCo(1-x)O2 Inorganic materials 0.000 description 1
- 229910013141 LiNixCo(1−x)O2 Inorganic materials 0.000 description 1
- 229910012227 LiPFn Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229910004074 SiF6 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910003092 TiS2 Inorganic materials 0.000 description 1
- GNTDGMZSJNCJKK-UHFFFAOYSA-N Vanadium(V) oxide Inorganic materials O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 239000002180 crystalline carbon material Substances 0.000 description 1
- 150000003950 cyclic amides Chemical class 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- ZYKOICDLSSOLAN-UHFFFAOYSA-N diheptyl carbonate Chemical compound CCCCCCCOC(=O)OCCCCCCC ZYKOICDLSSOLAN-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- CYEDOLFRAIXARV-UHFFFAOYSA-N ethyl propyl carbonate Chemical compound CCCOC(=O)OCC CYEDOLFRAIXARV-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- IBTAFYOTPNVGLR-UHFFFAOYSA-N heptyl methyl carbonate Chemical compound CCCCCCCOC(=O)OC IBTAFYOTPNVGLR-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- GBPVMEKUJUKTBA-UHFFFAOYSA-N methyl 2,2,2-trifluoroethyl carbonate Chemical compound COC(=O)OCC(F)(F)F GBPVMEKUJUKTBA-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- RCIJMMSZBQEWKW-UHFFFAOYSA-N methyl propan-2-yl carbonate Chemical compound COC(=O)OC(C)C RCIJMMSZBQEWKW-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 125000004205 trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- YFHICDDUDORKJB-UHFFFAOYSA-N trimethylene carbonate Chemical group O=C1OCCCO1 YFHICDDUDORKJB-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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
【０００１】
【発明の属する技術分野】
本発明は、充放電特性に優れた非水電解液、およびそれを用いた二次電池に関する。より詳細には、ホウ酸エステルを含むリチウム二次電池に適した非水電解液、およびそれを用いた二次電池に関する。
【０００２】
【発明の技術的背景】
非水電解液を用いた電池は、高電圧でかつ高エネルギー密度を有しており、また貯蔵性などの信頼性も高いので、民生用電子機器の電源として広く用いられている。
【０００３】
このような電池として非水電解液二次電池があり、その代表的存在は、リチウムイオン二次電池である。リチウムイオン二次電池の電解質材料には、非水電解液が広く使用されており、それに用いられる非水溶媒として、誘電率の高いカーボネート化合物が知られている。非水電解液として、より具体的には、プロピレンカーボネート、エチレンカーボネートなどの誘電率の高いカーボネート化合物溶媒と、炭酸ジメチル、炭酸ジエチルなどの粘度の低いカーボネート溶媒との混合溶媒に、ＬｉＢＦ４、ＬｉＰＦ６、ＬｉＣlＯ４、ＬｉＡｓＦ６、ＬｉＣＦ３ＳＯ３、ＬI２ＳｉＦ６などの電解質を混合した溶液が提案されている。
【０００４】
一方で、電池の高容量化を目指して電極の研究も進められており、リチウムイオン二次電池の負極として、リチウムの吸蔵、放出が可能な炭素材料が用いられている。特に黒鉛などの高結晶性炭素は、放電電位が平坦であるなどの特徴を有していることから、現在市販されているリチウムイオン二次電池の多くで負極材料として採用されている。
【０００５】
しかしながら、黒鉛などの高結晶性炭素を負極に用いる場合、電解液用の非水溶媒として、凝固点の低い高誘電率溶媒であるプロピレンカーボネートや１,２‐ブチレンカーボネートを用いると、初回充電時に溶媒の還元分解反応が起こり、活物質であるリチウムイオンの黒鉛への挿入反応が進行しにくくなり、その結果、初回の充放電効率の低下や、電解液の分解物による電解液のＬｉイオン伝導性の低下や、電極界面抵抗の増大による電池の負荷特性の低下が起こる。
【０００６】
このため、電解液に使用される高誘電率の非水溶媒として、常温で固体ではあるものの、還元分解反応が継続的に起こりにくいエチレンカーボネートをプロピレンカーボネ−トに代えて使用したり、混合したりすることにより、非水溶媒の還元分解反応を抑える試みがなされているが、必ずしも十分ではない。また、非晶質炭素を負極に用いた場合でも、溶媒の微少な還元分解反応が起こり、電解液の分解物による電解液のＬｉイオン伝導性の低下や、電極界面抵抗の増大による電池の負荷特性の低下が起こる。
【０００７】
このため、還元分解反応をさらに抑制するために、様々な添加剤を加えることが提案されている。（特開平５−１３０８８、特開平６−５２８８７、特開昭６３−１０２１７３、特開平１１−１６２５１１、特開平１１−３７２８）
【０００８】
また、電池の負荷特性を改善する試みとしては、電解液のイオン伝導性を向上するために、低粘度の鎖状溶媒を混合すること（特開平１０−２７６２５）なども提案されている。
【０００９】
【発明が解決しようとする課題】
本発明は、電極の界面抵抗の増大を抑制し、電池にすぐれた負荷特性および低温特性を与え、さらに優れた寿命特性を与える非水電解液の提供を目的とする。
また本発明は、この非水電解液を用いた寿命特性にすぐれた二次電池の提供を目的とする。
【００１０】
【課題を解決するための手段】
本発明は、ホウ酸トリメチル、ホウ酸トリエチル、ホウ酸トリプロピル、ホウ酸トリブチル、ホウ酸トリペンチル、ホウ酸ジエチルメチル、ホウ酸トリ（メトキシエチル）、ヒドロキシホウ酸ジメチル、ホウ酸ジメチルモノリチウム塩およびホウ酸モノメチルジリチウム塩から選ばれるアルキルホウ酸エステル類ならびにホウ酸トリ（トリフルオロエチル）、ホウ酸メチルジ（トリフルオロエチル）、ホウ酸トリ（トリクロロエチル）、ホウ酸トリ（テトラフルオロエチル）、ホウ酸トリ（モノフルオロエチル）、ホウ酸トリ（ペンタフルオロプロピル）、ホウ酸トリ（ヘキサフルオロプロピル）、ホウ酸トリ（２−メチル−１，１，１，３，３，３−ヘキサフルオロプロピル）、ホウ酸トリ（２−フェニル−１，１，１，３，３，３−ヘキサフルオロプロピル）、ホウ酸トリ（トリフルオロエトキシエチル）及びホウ酸メチルジ（トリフルオロエトキシエチル）から選ばれるハロゲン含有ホウ酸エステルなる群から選ばれたホウ酸エステルと、１，３―プロパンスルトン、１，４―ブタンスルトン、１，３―プロペンスルトン、１，４―ブテンスルトンおよび１，５―ペンテンスルトンから選ばれたスルトン並びにベンゼンジスルホン酸ジメチルなる群から選ばれたスルホニル基含有化合物と、非水溶媒と電解質を含むリチウム二次電池用非水電解液を提供する。
【００１１】
前記の非水電解液がさらに、ビニレンカーボネート、メチルビニレンカーボネート、エチルビニレンカーボネート、プロピルエチレンカーボネート、ジメチルビニレンカーボネート、ジエチルビニレンカーボネート、ジプロピルビニレンカーボネート、フルオロビニレンカーボネートおよびトリフルオロメチルビニレンカーボネートから選ばれたビニレンカーボネート誘導体を含む前記の非水電解液は、本発明の好ましい態様である。
【００１２】
前記非水溶媒が環状非プロトン性溶媒および／または鎖状非プロトン性溶媒からなる溶媒である前記の非水電解液は、本発明の好ましい態様である。
【００１３】
前記環状非プロトン性溶媒が、環状カーボネートおよび環状エステルから選ばれた少なくとも１種の溶媒である前記の非水電解液は、本発明の好ましい態様である。
【００１４】
前記鎖状非プロトン性溶媒が、鎖状カーボネートおよび鎖状エステルから選ばれた少なくとも１種の溶媒である前記の非水電解液は、本発明の好ましい態様である。
【００１５】
前記電解質が、ＬｉＰＦ６、ＬｉＢＦ４、ＬｉＯＳＯ２ＣｋＦ（２ｋ＋１）（ｋ＝１〜８の整数）、ＬｉＣｌＯ４、ＬｉＡｓＦ６、ＬｉＮ（ＳＯ２ＣｋＦ（２ｋ＋１））２（ｋ＝１〜８の整数）、ＬｉＰＦｎ（ＣｋＦ（２ｋ＋１））（６−ｎ）（n＝１〜５、ｋ＝１〜８の整数）から選ばれた少なくとも１種である前記の非水電解液は、本発明の好ましい態様である。
【００１６】
また本発明は、前記の非水電解液を含むリチウム二次電池を提供する。
【００１７】
さらに本発明は、負極活物質として金属リチウム、リチウム含有合金、リチウムイオンのドープ・脱ドープが可能な炭素材料、リチウムイオンのドープ・脱ドープが可能な酸化スズ、リチウムイオンのドープ・脱ドープが可能な酸化チタン、酸化ニオブもしくは酸化バナジウム、またはリチウムイオンのドープ・脱ドープが可能なシリコンもしくはスズのいずれかを含む負極と、正極活物質として遷移金属酸化物、遷移金属硫化物、リチウムと遷移金属の複合酸化物、導電性高分子材料、炭素材料またはこれらの混合物のいずれかを含む正極と、前記の非水電解液とを含むリチウム二次電池を提供する。
【００１８】
前記リチウムイオンのドープ・脱ドープが可能な炭素材料が、Ｘ線解析で測定した（００２）面における面間隔距離（ｄ００２）が、０．３４０ｎｍ以下である前記のリチウムイオン二次電池は、本発明の好ましい態様である。
【００１９】
【発明の実施の形態】
本発明に係る非水電解液およびこの非水電解液を用いた非水電解液二次電池について具体的に説明する。
【００２０】
本発明に係る非水電解液は、ホウ酸エステルと非水溶媒と電解質を含む非水電解液である。
本発明の電解液において、ホウ酸エステル類を含有すると、初期充電時の電極界面抵抗の上昇が抑制されるために望ましい非水電解液が得られる。この非水電解液を用いた非水電解液二次電池はすぐれた負荷特性を示す。
【００２１】
ホウ酸エステル
本発明で使用されるホウ酸エステル類は、ホウ酸トリメチル、ホウ酸トリエチル、ホウ酸トリプロピル、ホウ酸トリブチル、ホウ酸トリペンチル、ホウ酸ジエチルメチル、ホウ酸トリ（メトキシエチル）、ヒドロキシホウ酸ジメチル、ホウ酸ジメチルモノリチウム塩およびホウ酸モノメチルジリチウム塩から選ばれるアルキルホウ酸エステル類ならびにホウ酸トリ（トリフルオロエチル）、ホウ酸メチルジ（トリフルオロエチル）、ホウ酸トリ（トリクロロエチル）、ホウ酸トリ（テトラフルオロエチル）、ホウ酸トリ（モノフルオロエチル）、ホウ酸トリ（ペンタフルオロプロピル）、ホウ酸トリ（ヘキサフルオロプロピル）、ホウ酸トリ（２−メチル−１，１，１，３，３，３−ヘキサフルオロプロピル）、ホウ酸トリ（２−フェニル−１，１，１，３，３，３−ヘキサフルオロプロピル）、ホウ酸トリ（トリフルオロエトキシエチル）及びホウ酸メチルジ（トリフルオロエトキシエチル）から選ばれるハロゲン含有ホウ酸エステルなる群から選ばれたホウ酸エステルである。
【００２２】
本発明の非水電解液は、前記ホウ酸エステルと、非水溶媒と電解質に加えて、さらに１，３―プロパンスルトン、１，４―ブタンスルトン、１，３―プロペンスルトン、１，４―ブテンスルトンおよび１，５―ペンテンスルトンから選ばれたスルトン並びにベンゼンジスルホン酸ジメチルなる群から選ばれたスルホニル基含有化合物を含有することができる。
非水電解液が、さらにスルホニル基含有化合物を含むと、初期充電時の界面抵抗の上昇が抑制する効果が高められる。また、初期充電時のみならず、繰返し使用後や高温保存後の界面抵抗の上昇が抑制されるため望ましい。
【００２３】
スルホニル基含有化合物の非水電解液への添加量は、０．０１〜１０重量％が望ましく、さらには０．０５〜５重量％が望ましい。
【００２４】
ビニレンカーボネート誘導体
本発明の非水電解液は、さらに下記一般式（３）で表わされるビニレンカーボネート誘導体をさらに含有してもよい。
【００２５】
本発明の非水電解液が、下記一般式（３）で表わされるビニレンカーボネート誘導体を含有すると、初期充電時の界面抵抗の上昇が抑制される効果がさらに高められることに加えて、サイクル試験や高温保存試験時の電池容量の維持率が向上する。
【００２６】
【化１】
式中Ｒ７およびＲ８は、同一でも異なってもよく、水素または炭素数１〜１０の有機基である。
有機基の好ましい例としては、炭化水素基、ヘテロ原子含有炭化水素基が挙げられる。
【００２８】
炭化水素基としては、メチル基、エチル基、プロピル基、ブチル基、オクチル基のような飽和炭化水素基、ビニル基、アリル基などの二重結合含有炭化水素基、エチニル基、プロパルギル基などの三重結合含有炭化水素基のような不飽和炭化水素基などを挙げることができる。
【００２９】
ヘテロ原子含有炭化水素基の、ヘテロ原子としては、酸素、窒素、イオウ、リン、ホウ素などが挙げられる。ヘテロ原子含有炭化水素基の好ましい例として、メトキシエチル基やメトキシカルボニルエチル基のようにエーテル結合、エステル結合、カーボネート結合などを含む酸素含有炭化水素基や、アミノ基などを含む窒素含有炭化水素基を挙げることができる。
【００３０】
有機基は、ハロゲン原子で置換されていてもよい。ハロゲン元素としては、フッ素、塩素、臭素などが挙げられるが、フッ素が好適である。ハロゲン原子で置換された有機基としては、トリフルオロエチル基のようなハロゲン化炭化水素基、ハロゲン含有基で置換された炭化水素基、ハロゲン化ヘテロ原子含有炭化水素基などを挙げることができる。特にはハロゲン化炭化水素基が好ましい。
【００３１】
有機基としては、中でも炭素数１〜１０の炭化水素基または炭素数１〜１０のハロゲン化炭化水素基が好ましい。
【００３２】
前記一般式（３）で表わされるビニレンカーボネート誘導体の具体例としては、ビニレンカーボネート、メチルビニレンカーボネート、エチルビニレンカーボネート、プロピルエチレンカーボネート、ジメチルビニレンカーボネート、ジエチルビニレンカーボネート、ジプロピルビニレンカーボネート、フルオロビニレンカーボネート、トリフルオロメチルビニレンカーボネートなどを挙げることができる。これらのうち、ビニレンカーボネートが好ましい。
【００３３】
ビニレンカーボネート誘導体の電解液への添加量は、非水電解液全体に対して、０．０５〜５重量％が好ましい。
【００３４】
前記一般式（１）で表わされるホウ酸エステル類、前記一般式（２）で表わされる化合物および前記一般式（３）で表わされるビニレンカーボネート誘導体を含む非水電解液は、本発明の非水電解液の好ましい態様である。
前記一般式（１）で表わされるホウ酸エステル類および前記一般式（３）で表わされるビニレンカーボネート誘導体を含む非水電解液もまた、本発明の非水電解液の好ましい態様である。
【００３５】
これらの中では前記一般式（１）で表わされるホウ酸エステル類、前記一般式（２）で表わされる化合物を含む非水電解液、および前記一般式（３）で表わされるビニレンカーボネート誘導体を含む非水電解液がより好ましい態様である。
【００３６】
非水溶媒
本発明の非水電解液は、非水溶媒に電解質を溶解した溶液に、これまで説明してきた化合物を含有させた構成になっている。
【００３７】
本発明では、非水溶媒として環状非プロトン性溶媒および／または鎖状非プロトン性溶媒からなることが望ましい。
環状非プロトン性溶媒としては、エチレンカーボネートのような環状カーボネート、γ−ブチロラクトンのような環状エステル、ジオキソランのような環状エーテルが例示され、鎖状非プロトン性溶媒としては、ジメチルカーボネートのような鎖状カーボネート、プロピオン酸メチルのような鎖状カルボン酸エステル、ジメトキシエタンのような鎖状エーテル、リン酸トリメチルのような鎖状リン酸エステルが例示される。
【００３８】
電池の負荷特性、低温特性の向上を特に意図した場合は、非水溶媒を環状非プロトン性溶媒および鎖状非プロトン性溶媒の組み合わせにすることが好ましい。 さらに、電解液の電気化学的安定性から、環状非プロトン性溶媒には環状カーボネートを、鎖状非プロトン性溶媒には鎖状カーボネートを適用することが好ましい。
【００３９】
環状カーボネートの具体例としては、エチレンカーボネート、プロピレンカーボネート、１,２‐ブチレンカーボネート、２,３‐ブチレンカーボネート、１,２‐ペンチレンカーボネート、２,３‐ペンチレンカーボネートなどを挙げることができる。中でも誘電率が高いエチレンカーボネートとプロピレンカーボネートが好適に使用される。負極活物質に黒鉛を使用した電池の場合は、エチレンカーボネートが好ましい。これら環状カーボネートは２種以上混合して使用してもよい。
【００４０】
鎖状カーボネートの具体例としては、ジメチルカーボネート、メチルエチルカーボネート、ジエチルカーボネート、メチルプロピルカーボネート、メチルイソプロピルカーボネート、ジプロピルカーボネート、メチルブチルカーボネート、ジブチルカーボネート、エチルプロピルカーボネート、メチルトリフルオロエチルカーボネートなどを挙ることができる。中でも粘度が低いジメチルカーボネート、メチルエチルカーボネート、ジエチルカーボネートが好適に使用される。これら鎖状カーボネートは２種以上混合して使用してもよい。
【００４１】
環状カーボネートと鎖状カーボネートの組合せとして具体的には、エチレンカーボネートとジメチルカーボネート、エチレンカーボネートとメチルエチルカーボネート、エチレンカーボネートとジエチルカーボネート、プロピレンカーボネートとジメチルカーボネート、プロピレンカーボネートとメチルエチルカーボネート、プロピレンカーボネートとジエチルカーボネート、エチレンカーボネートとプロピレンカーボネートとジメチルカーボネート、エチレンカーボネートとプロピレンカーボネートとメチルエチルカーボネート、エチレンカーボネートとプロピレンカーボネートとジエチルカーボネート、エチレンカーボネートとジメチルカーボネートとメチルエチルカーボネート、エチレンカーボネートとジメチルカーボネートとジエチルカーボネート、エチレンカーボネートとメチルエチルカーボネートとジエチルカーボネート、エチレンカーボネートとジメチルカーボネートとメチルエチルカーボネートとジエチルカーボネート、エチレンカーボネートとプロピレンカーボネートとジメチルカーボネートとメチルエチルカーボネート、エチレンカーボネートとプロピレンカーボネートとジメチルカーボネートとジエチルカーボネート、エチレンカーボネートとプロピレンカーボネートとメチルエチルカーボネートとジエチルカーボネート、エチレンカーボネートとプロピレンカーボネートとジメチルカーボネートとメチルエチルカーボネートとジエチルカーボネートなどが挙げられる。
【００４２】
環状カーボネートと鎖状カーボネートの混合割合は、重量比で表して、環状カーボネート：鎖状カーボネートが、５：９５〜８０：２０、さらに好ましくは１０：９０〜７０：３０、特に好ましくは１５：８５〜５５：４５である。
【００４３】
このような比率にすることによって、電解液の粘度上昇を抑制し、電解質の解離度を高めることができるため、電池の充放電特性に関わる電解液の伝導度を高めることができ、電解質の溶解度をさらに高めることができる。それによって、常温から低温での電気伝導性に優れた電解液とすることできるので、常温から低温での電池の負荷特性を改善することができる。
【００４４】
また、電池の安全性向上のために、溶媒の引火点の向上を指向する場合は、非水溶媒として、環状の非プロトン性溶媒を単独で使用するか、鎖状の非プロトン性溶媒の混合量を、非水溶媒全体に対して重量比で２０％未満に制限することが望ましい。
【００４５】
この場合の環状の非プロトン性溶媒としては、特に、エチレンカーボネート、プロピレンカーボネート、γ−ブチロラクトン、メチルオキサゾリノンから選ばれる１種またはこれらの混合物を混合することが望ましい。具体的な溶媒の組み合わせとしては、エチレンカーボネートとスルホラン、エチレンカーボネートとγ−ブチロラクトン、エチレンカーボネートとプロピレンカーボネート、エチレンカーボネートとプロピレンカーボネートとガンマブチロラクトンなどが例示される。
【００４６】
鎖状の非プロトン性溶媒の混合量を、非水溶媒全体に対して重量比で２０％以下混合する場合は、鎖状の非プロトン性溶媒として、鎖状カーボネート、鎖状カルボン酸エステル、鎖状リン酸エステルが例示され、特に、ジメチルカーボネート、ジエチルカーボネート、ジプロピルカーボネート、ジブチルカーボネート、ジヘプチルカーボネート、メチルエチルカーボネート、メチルプロピルカーボネート、メチルブチルカーボネート、メチルヘプチルカーボネートなどの鎖状カーボネートが望ましい。
【００４７】
本発明に係る非水電解液では、非水溶媒として、上記以外の他の溶媒を含んでいてもよく、他の溶媒としては、具体的には、ジメチルホルムアミドなどのアミド、メチル‐Ｎ，Ｎ‐ジメチルカーバメートなどの鎖状カーバメート、Ｎ‐メチルピロリドンなどの環状アミド、Ｎ，Ｎ‐ジメチルイミダゾリジノンなどの環状ウレア、および下記一般式で表わされるエチレングリコール誘導体などを挙げることができる。
ＨＯ（ＣＨ２ＣＨ２Ｏ）ａＨ、ＨＯ｛ＣＨ２ＣＨ（ＣＨ３）Ｏ｝ｂＨ、ＣＨ３Ｏ（ＣＨ２ＣＨ２Ｏ）ｃＨ、ＣＨ３Ｏ｛ＣＨ２ＣＨ（ＣＨ３）Ｏ｝ｄＨ、ＣＨ３Ｏ（ＣＨ２ＣＨ２Ｏ）ｅＣＨ３、ＣＨ３Ｏ｛ＣＨ２ＣＨ（ＣＨ３）Ｏ｝ｆＣＨ３、Ｃ９Ｈ１９ＰｈＯ（ＣＨ２ＣＨ２Ｏ）ｇ｛ＣＨ（ＣＨ３）Ｏ｝ｈＣＨ３（Ｐｈはフェニル基）、ＣＨ３Ｏ｛ＣＨ２ＣＨ（ＣＨ３）Ｏ｝ｉＣＯ｛Ｏ（ＣＨ３）ＣＨＣＨ２｝ｊＯＣＨ３（式中、ａ〜ｆは５〜２５０の整数、ｇ〜ｊは２〜２４９の整数、５≦ｇ＋ｈ≦２５０、５≦ｉ＋ｊ≦２５０である。）
非水電解液
本発明の非水電解液は、非水溶媒に電解質を溶解し、さらに前述の化合物類を含有するものである。使用される電解質としては、通常、非水電解液用電解質として使用されているものであれば、いずれをも使用することができる。
【００４８】
電解質の具体例としては、ＬｉＰＦ６、ＬｉＢＦ４、ＬｉＣlＯ４、ＬｉＡｓＦ６、Ｌｉ２ＳｉＦ６、ＬｉＣ４Ｆ９ＳＯ３、ＬｉＣ８Ｆ１７ＳＯ３などのリチウム塩が挙げられる。また、次の一般式で示されるリチウム塩も使用することができる。ＬｉＯＳＯ２Ｒ８、ＬｉＮ（ＳＯ２Ｒ９）（ＳＯ２Ｒ１０）、ＬｉＣ（ＳＯ２Ｒ１１）（ＳＯ２Ｒ１２）（ＳＯ２Ｒ１３）、ＬｉＮ（ＳＯ２ＯＲ１４）（ＳＯ２ＯＲ１５）（ここで、Ｒ８〜Ｒ１５は、互いに同一であっても異なっていてもよく、炭素数１〜６のパーフルオロアルキル基である）。これらのリチウム塩は単独で使用してもよく、また２種以上を混合して使用してもよい。
【００４９】
これらのうち、特に、ＬｉＰＦ６、ＬｉＢＦ４、ＬｉＯＳＯ２Ｒ８、ＬｉＮ（ＳＯ２Ｒ９）（ＳＯ２Ｒ１０）、ＬｉＣ（ＳＯ２Ｒ１１）（ＳＯ２Ｒ１２）（ＳＯ２Ｒ１３）、ＬｉＮ（ＳＯ２ＯＲ１４）（ＳＯ２ＯＲ１５）が好ましい。
【００５０】
このような電解質は、０．１〜３モル／リットル、好ましくは０．５〜２モル／リットルの濃度で非水電解液中に含まれていることが望ましい。
【００５１】
本発明における非水電解液は、前述の化合物類と非水溶媒と電解質とを必須構成成分として含むが、必要に応じて他の添加剤などを加えてもよい。
【００５２】
他の添加剤としては、無水マレイン酸、ノルボルネンジカルボン酸無水物、ジグリコール酸などのカルボン酸無水物類；ビニルエチレンカーボネート、ジビニルエチレンカーボネート、メチレン−１，２−エチレンカーボネートなどの不飽和炭化水素置換環状カーボネート類；フッ化水素などが挙げられる。
【００５３】
フッ化水素を添加剤に使用する場合、電解液への添加方法は、直接、電解液にフッ化水素ガスを所定量吹き込むことが挙げられる。また、本発明で使用するリチウム塩がＬｉＰＦ６やＬｉＢＦ４などのフッ素を含有するリチウム塩である場合は、下記に示した水のような活性プロトン化合物と電解質の反応を利用して、水を電解液に添加し、電解液中で発生させても良い。
【００５４】
ＬｉＭＦｎ ＋ Ｈ２Ｏ → ＬｉＰＦ（ｎ−２）Ｏ ＋ ２ＨＦ
（ただし、ＭはＰ、Ｂなどを表わし、 Ｍ＝Ｐのときｎ＝６、Ｍ＝Ｂのときｎ＝４である。）
【００５５】
水を電解液に添加し、間接的にＨＦを電解液中に生成させる場合、水１分子からＨＦがほぼ定量的に２分子生成するので、水の添加量は、所望のＨＦ添加濃度にあわせて計算し添加する。具体的には、所望のＨＦ量の０．４５倍（重量比）の水を添加するのが好ましい。
【００５６】
他のプロトン性化合物の具体例としては、トリフルオロ酢酸、メタノール、エタノール、エチレングリコール、プロピレングリコールなどを挙げることができる。
【００５７】
フッ化水素としての添加量は０．０００１〜０．７ｗｔ％、好ましくは０．００１〜０．３ｗｔ％、より好ましくは０．００１〜０．１ｗｔ％である。
【００５８】
本発明に係る非水電解液は、リチウムイオン二次電池用の非水電解液として好適であるばかりでなく、一次電池用の非水電解液としても用いることができる。
【００５９】
二次電池
本発明に係る非水電解液二次電池は、負極と、正極と、前記の非水電解液とを基本的に含んで構成されており、通常、負極と正極との間にセパレータが設けられている。
【００６０】
負極を構成する負極活物質としては、金属リチウム、リチウム合金、リチウムイオンをドーブ・脱ドーブすることが可能な炭素材料、リチウムイオンをドープ・脱ドープすることが可能な酸化スズ、酸化ニオブもしくは酸化バナジウム、リチウムイオンをドープ・脱ドープすることが可能な酸化チタン、またはリチウムイオンをドープ・脱ドープすることが可能なシリコンもしくはスズのいずれも用いることができる。これらの中でもリチウムイオンをドーブ・脱ドーブすることが可能な炭素材料が好ましい。このような炭素材料は、グラファイトであっても非晶質炭素であってもよく、活性炭、炭素繊維、カーボンブラック、メソカーボンマイクロビーズ、天然黒鉛などが用いられる。
【００６１】
負極活物質として、特にＸ線解析で測定した（００２）面の面間隔（ｄ００２）が０．３４０ｎｍ以下の炭素材料が好ましく、密度が１．７０ｇ／ｃｍ３以上である黒鉛またはそれに近い性質を有する高結晶性炭素材料が望ましい。このような炭素材料を使用すると、電池のエネルギー密度を高くすることができる。
【００６２】
正極を構成する正極活物質としては、ＭｏＳ２、ＴｉＳ２、ＭｎＯ２、Ｖ２Ｏ５などの遷移金属酸化物または遷移金属硫化物、ＬｉＣｏＯ２、ＬｉＭｎＯ２、ＬｉＭｎ２Ｏ４、ＬｉＮｉＯ２、ＬｉＮｉｘＣｏ（１−ｘ）Ｏ２、ＬｉＮｉｘＭｎｙＣｏ（１−ｘ−ｙ）Ｏ２などのリチウムと遷移金属とからなる複合酸化物、ポリアニリン、ポリチオフェン、ポリピロール、ポリアセチレン、ポリアセン、ジメルカプトチアジアゾール／ポリアニリン複合体などの導電性高分子材料などが挙げられる。これらの中でも、特にリチウムと遷移金属とからなる複合酸化物が好ましい。負極がリチウム金属またはリチウム合金である場合は、正極として炭素材料を用いることもできる。また、正極として、リチウムと遷移金属の複合酸化物と炭素材料との混合物を用いることもできる。
【００６３】
セパレータは正極と負極を電気的に絶縁しかつリチウムイオンを透過する膜であって、多孔性膜や高分子電解質が例示される。多孔性膜としては微多孔性ポリマーフィルムが好適に使用され、材質としてポリオレフィンやポリイミド、ポリフッ化ビニリデンが例示される。特に、多孔性ポリオレフィンフィルムが好ましく、具体的には多孔性ポリエチレンフィルム、多孔性ポリプロピレンフィルム、または多孔性のポリエチレンフィルムとポリプロピレンとの多層フィルムを例示することができる。高分子電解質としては、リチウム塩を溶解した高分子や、電解液で膨潤させた高分子などが挙げられる。本発明の電解液は、高分子を膨潤させて高分子電解質を得る目的で使用しても良い。
【００６４】
このような非水電解液二次電池は、円筒型、コイン型、角型、フィルム型その他任意の形状に形成することができる。しかし、電池の基本構造は形状によらず同じであり、目的に応じて設計変更を施すことができる。次に、円筒型およびコイン型電池の構造について説明するが、各電池を構成する負極活物質、正極活物質およびセパレータは、前記したものが共通して使用される。
【００６５】
例えば、円筒型非水電解液二次電池の場合には、負極集電体に負極活物質を塗布してなる負極と、正極集電体に正極活物質を塗布してなる正極とを、非水電解液を注入したセパレータを介して巻回し、巻回体の上下に絶縁板を載置した状態で電池缶に収納されている。
【００６６】
また、本発明に係る非水電解液二次電池は、コイン型非水電解液二次電池にも適用することができる。コイン型電池では、円盤状負極、セパレータ、円盤状正極、およびステンレス、またはアルミニウムの板が、この順序に積層された状態でコイン型電池缶に収納されている。
【００６７】
【実施例】
以下、実施例によって本発明をより具体的に説明するが、本発明はこれら実施例によって何ら制限されるものではない。
【００６８】
（実施例１〜７、参考例１〜３）
１．電池の作製
＜非水電解液の調製＞
エチレンカーボネート（ＥＣ）とメチルエチルカーボネート（ＭＥＣ）を、ＥＣ：ＭＥＣ＝４：６（重量比）の割合で混合し、次に電解質であるＬｉＰＦ６を非水溶媒に溶解し、電解質濃度が１．０モル／リットルとなるように非水電解液を調製した。次にこの非水電解液（１００重量％とする）に対して、表１に示す添加剤を、表１に示す割合で添加した。
【００６９】
＜負極の作製＞
天然黒鉛（中越黒鉛製ＬＦ−１８Ａ）８７重量部と結着剤のポリフッ化ビニリデン（ＰＶＤＦ）１３重量部を混合し、溶剤のＮ−メチルピロリジノンに分散させ、天然黒鉛合剤スラリーを調製した。次に、この負極合剤スラリーを厚さ１８μｍの帯状銅箔製の負極集電体に塗布し、乾燥させた後、圧縮成型し、これを１４ｍｍの円盤状に打ち抜いて、コイン状の天然黒鉛電極を得た。この天然黒鉛電極合剤の厚さは１１０μｍ、重量は直径１４ｍｍの円の面積あたり２０ｍｇであった。
【００７０】
＜ＬｉＣｏＯ２電極の作製＞
ＬｉＣｏＯ２（本荘ＦＭＣエナジーシステムズ（株）製 ＨＬＣ−２１）９０重量部と、導電剤の黒鉛６重量部及びアセチレンブラック１重量部と結着剤のポリフッ化ビニリデン３重量部を混合し、溶剤のＮ−メチルピロリドンに分散させ、ＬｉＣｏＯ２合剤スラリーを調製した。
このＬｉＣｏＯ２合剤スラリーを厚さ２０μｍのアルミ箔に塗布、乾燥させ、圧縮成型し、これを直径１３ｍｍにうちぬき、ＬｉＣｏＯ２電極を作製した。
このＬｉＣｏＯ２合剤の厚さは９０μｍ、重量は直径１３ｍｍの円の面積あたり３５ｍｇであった。
【００７１】
＜電池の作製＞
直径１４ｍｍの天然黒鉛電極、直径１３ｍｍのＬｉＣｏＯ２電極、厚さ２５μｍ、直径１６ｍｍの微多孔性ポリプロピレンフィルムからできたセパレータを、ステンレス製の２０３２サイズの電池缶内に、天然黒鉛電極、セパレーター、ＬｉＣｏＯ２電極の順序で積層した。その後、セパレータに前記非水電解液０．０３ｍｌを注入し、アルミニウム製の板（厚さ１．２ｍｍ、直径１６ｍｍ、およびバネを収納した。最後に、ポリプロピレン製のガスケットを介して、電池缶蓋をかしめることにより、電池内の気密性を保持し、直径２０ｍｍ、高さ３．２ｍｍのコイン型電池を作製した。
【００７２】
２．電池特性の評価
＜電池の初期特性の測定＞
（１）初期低負荷放電容量の測定
前述のように作製したコイン型電池を使用し、この電池を０．５ｍＡ定電流４．２Ｖ定電圧の条件で、４．２Ｖ定電圧の時の電流値が０．０５ｍＡになるまで充電し、その後、０．５ｍＡ定電流３．０Ｖ定電圧の条件で、３．０Ｖ定電圧の時の電流値が０．０５ｍＡになるまで放電した。この時のコイン型電池の放電容量を、「初期低負荷放電容量」と呼ぶこととする。初期低負荷放電容量は、いずれの電池でも、４．５ｍＡｈ前後であった。
【００７３】
（２）初期中負荷放電容量の測定
次に、この電池を３ｍＡ定電流４．２Ｖ定電圧の条件で、４．２Ｖ定電圧の時の電流値が０．０５ｍＡになるまで充電し、その後５ｍＡの電流で電池の電圧が３．０Ｖになるまで放電した。この時のコイン型電池の放電容量を「初期中負荷放電容量」と呼ぶこととする。
【００７４】
＜電極の界面抵抗の測定＞
コイン型電池を４．２Ｖに充電した後、０．２Ｈｚおよび２５００Ｈｚでのインピーダンスを測定し、０．２Ｈｚでのインピーダンス値から２５００Ｈｚでのインピーダンス値を差し引いたインピーダンス値を「電極界面抵抗」とした。
【００７５】
＜電池の保存特性の測定＞
（１）放電容量の測定
電池を一旦３Ｖに放電した後、３ｍＡ定電流４．１Ｖ定電圧の条件で、４．１Ｖ定電圧の時の電流値が０．０５ｍＡになるまで充電した。この時の充電量を「保存前充電容量」とした。
この電池を、５０℃で１週間保存した後、０．５ｍＡ定電流３．０Ｖ定電圧の条件で、３．０Ｖ定電圧の時の電流値が０．０５ｍＡになるまで放電した。この時の放電量を、「保存後放電容量」とした。
「保存後放電容量」と「保存前充電容量」の差を「高温保存自己放電容量」とした（「保存後放電容量」−「保存前充電容量」＝「高温保存自己放電容量」）。
【００７６】
（２）保存後中負荷放電容量の測定
次に、この電池を３ｍＡ定電流４．２Ｖ定電圧の条件で、４．２Ｖ定電圧の時の電流値が０．０５ｍＡになるまで充電し、その後５ｍＡの電流で電池の電圧が３．０Ｖになるまで放電した。この時のコイン型電池の放電容量を「保存後中負荷放電容量」と呼ぶこととする。
【００７７】
実施例１〜７、参考例１〜３の電池特性の評価結果を表２に示した。
【００７８】
（比較例１）
実施例１の＜非水電解液の調製＞において、添加剤の添加を省略するほかは同様にして非水電解液の調製を行ない、得られた非水電解液を用いて、実施例１と同様にして電池を作製し、電池特性の評価を行なった。
比較例１で測定された「電極界面抵抗」および「高温保存自己放電容量」をそれぞれ「ブランクでの電極界面抵抗」および「ブランクでの高温保存自己放電容量」とする。
電池特性の評価の結果を表２に示した。
【００７９】
表２に示した電池特性の評価は、実施例１〜１０および比較例１における実験結果から、以下の指標を用いて行った。いずれも単位は％である。
「電極界面抵抗比」＝｛「試験電解液使用電池の電極界面抵抗」／「ブランクでの電極界面抵抗」｝×１００
「初期負荷特性指標」＝｛「初期中負荷放電容量」／「初期低負荷放電容量」｝×１００
「負荷特性維持率」＝｛「保存後中負荷放電容量」／「初期中負荷放電容量」｝×１００
「自己放電比」＝｛「試験電解液の高温保存自己放電容量」／「ブランクでの高温保存自己放電容量」｝×１００
【００８０】
【表１】
【表２】
表２より、実施例１〜７のいずれの電解液を使用しても、初期の界面抵抗がブランク（比較例１）よりも小さくなっており、優れた負荷特性を示す電池が得られることが分かった。
【００８３】
また、表２より本願発明の電解液によって、高温保存後の負荷特性の劣化が少ない電池が得られることが分かる。電解液がさらに前記一般式（３）で表わされるビニレンカーボネート誘導体を含有すると、高温保存後の負荷特性の劣化および自己放電が抑制され、さらに優れた特性を示す電池が得られることが分かる。
【００８４】
【発明の効果】
本発明により、リチウムイオン二次電池用の電解液として特に好適な非水電解液が提供される。
本発明の非水電解液を使用することによって、初期特性、または初期特性および高温保存後の特性において、電極の界面抵抗が小さく、負荷特性に優れた非水電解液二次電池を得ることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a non-aqueous electrolyte excellent in charge / discharge characteristics and a secondary battery using the same. More specifically, the present invention relates to a nonaqueous electrolytic solution suitable for a lithium secondary battery containing a borate ester, and a secondary battery using the same.
[0002]
TECHNICAL BACKGROUND OF THE INVENTION
A battery using a non-aqueous electrolyte is widely used as a power source for consumer electronic devices because of its high voltage and high energy density and high reliability such as storage.
[0003]
As such a battery, there is a nonaqueous electrolyte secondary battery, and a typical example thereof is a lithium ion secondary battery. Non-aqueous electrolytes are widely used as electrolyte materials for lithium ion secondary batteries, and carbonate compounds having a high dielectric constant are known as non-aqueous solvents used therefor. More specifically, as a non-aqueous electrolyte, LiBF is mixed with a mixed solvent of a carbonate compound solvent having a high dielectric constant such as propylene carbonate or ethylene carbonate and a carbonate solvent having a low viscosity such as dimethyl carbonate or diethyl carbonate.4, LiPF6, LiClO4, LiAsF6, LiCF3SO3, LI2SiF6A solution in which an electrolyte such as the above is mixed has been proposed.
[0004]
On the other hand, research on electrodes has been conducted with the aim of increasing the capacity of batteries, and carbon materials capable of inserting and extracting lithium are used as negative electrodes of lithium ion secondary batteries. In particular, highly crystalline carbon such as graphite has features such as a flat discharge potential, and is therefore adopted as a negative electrode material in many of the lithium ion secondary batteries currently on the market.
[0005]
However, when highly crystalline carbon such as graphite is used for the negative electrode, if non-aqueous solvent for the electrolyte is propylene carbonate or 1,2-butylene carbonate, which is a high dielectric constant having a low freezing point, As a result, reductive decomposition reaction of lithium ion, which is the active material, becomes difficult to proceed into the graphite, resulting in a decrease in the initial charge / discharge efficiency and the Li ion conductivity of the electrolyte solution due to the decomposition product of the electrolyte solution. Or the load characteristics of the battery are reduced due to an increase in electrode interface resistance.
[0006]
Therefore, as a non-aqueous solvent having a high dielectric constant used for the electrolyte, ethylene carbonate, which is solid at room temperature but hardly undergoes reductive decomposition reaction, can be used instead of propylene carbonate or mixed. Although attempts have been made to suppress the reductive decomposition reaction of non-aqueous solvents by doing so, it is not always sufficient. In addition, even when amorphous carbon is used for the negative electrode, a slight reductive decomposition reaction of the solvent occurs, and the battery load is reduced due to a decrease in Li ion conductivity of the electrolytic solution due to the decomposition product of the electrolytic solution and an increase in electrode interface resistance. Degradation of characteristics occurs.
[0007]
For this reason, in order to further suppress the reductive decomposition reaction, it has been proposed to add various additives. (JP-A-5-13088, JP-A-6-52887, JP-A-63-102173, JP-A-11-162511, JP-A-11-3728)
[0008]
Further, as an attempt to improve the load characteristics of the battery, mixing a low-viscosity chain solvent (Japanese Patent Laid-Open No. 10-27625) has been proposed in order to improve the ionic conductivity of the electrolytic solution.
[0009]
[Problems to be solved by the invention]
An object of the present invention is to provide a nonaqueous electrolytic solution that suppresses an increase in interfacial resistance of an electrode, gives excellent load characteristics and low temperature characteristics to a battery, and gives excellent life characteristics.
It is another object of the present invention to provide a secondary battery having excellent life characteristics using this non-aqueous electrolyte.
[0010]
[Means for Solving the Problems]
The present inventionTrimethyl borate, triethyl borate, tripropyl borate, tributyl borate, tripentyl borate, diethyl methyl borate, tri (methoxyethyl) borate, dimethyl hydroxyborate, dimethyl monolithium borate and monomethyl diborate Alkyl borate esters selected from lithium salts and tri (trifluoroethyl) borate, methyl di (trifluoroethyl) borate, tri (trichloroethyl) borate, tri (tetrafluoroethyl) borate, tri (monofluoroborate) Fluoroethyl), tri (pentafluoropropyl) borate, tri (hexafluoropropyl) borate, tri (2-methyl-1,1,1,3,3,3-hexafluoropropyl) borate, triborate (2-Phenyl-1,1,1,3,3,3-hexafluoro Boric acid ester selected from the group consisting of halogen-containing boric acid ester selected from tripropyl (trifluoroethoxyethyl) borate and methyl di (trifluoroethoxyethyl) borate, 1,3-propane sultone, A sulfonyl group-containing compound selected from the group consisting of sultone selected from 4-butane sultone, 1,3-propene sultone, 1,4-butene sultone and 1,5-pentene sultone, and dimethyl benzenedisulfonate, Including non-aqueous solvent and electrolyteLithium secondary batteryProvide non-aqueous electrolyte.
[0011]
The non-aqueous electrolyte is furtherSelected from vinylene carbonate, methyl vinylene carbonate, ethyl vinylene carbonate, propyl ethylene carbonate, dimethyl vinylene carbonate, diethyl vinylene carbonate, dipropyl vinylene carbonate, fluoro vinylene carbonate and trifluoromethyl vinylene carbonateThe non-aqueous electrolyte containing a vinylene carbonate derivative is a preferred embodiment of the present invention..
[0012]
in frontThe above-mentioned non-aqueous electrolytic solution in which the non-aqueous solvent is a solvent comprising a cyclic aprotic solvent and / or a chain aprotic solvent is a preferred embodiment of the present invention.
[0013]
The non-aqueous electrolyte solution in which the cyclic aprotic solvent is at least one solvent selected from cyclic carbonates and cyclic esters is a preferred embodiment of the present invention.
[0014]
The non-aqueous electrolyte solution in which the chain aprotic solvent is at least one solvent selected from a chain carbonate and a chain ester is a preferred embodiment of the present invention.
[0015]
The electrolyte is LiPF6, LiBF4, LiOSO2CkF(2k + 1)(K = integer from 1 to 8), LiClO4, LiAsF6, LiN (SO2CkF(2k + 1))2(K = integer from 1 to 8), LiPFn(CkF(2k + 1))(6-n)The nonaqueous electrolytic solution which is at least one selected from (n = 1 to 5, k = 1 to 8) is a preferred embodiment of the present invention.
[0016]
The present invention also includes the above non-aqueous electrolyte.lithiumA secondary battery is provided.
[0017]
Furthermore, the present invention includes metallic lithium as a negative electrode active material, a lithium-containing alloy, a carbon material that can be doped / undoped with lithium ions, a tin oxide that can be doped / undoped with lithium ions, and a doped / undoped lithium ion. Transitions with possible negative electrode containing titanium oxide, niobium oxide or vanadium oxide, or silicon or tin that can be doped / undoped with lithium ion, and transition metal oxide, transition metal sulfide, lithium as positive electrode active material Provided is a lithium secondary battery comprising a positive electrode including any one of a metal complex oxide, a conductive polymer material, a carbon material, or a mixture thereof, and the non-aqueous electrolyte.
[0018]
The lithium ion secondary battery in which the intercalation distance (d002) on the (002) plane measured by X-ray analysis is 0.340 nm or less is the carbon material that can be doped / undoped with lithium ions. This is a preferred embodiment of the invention.
[0019]
DETAILED DESCRIPTION OF THE INVENTION
The nonaqueous electrolyte solution according to the present invention and the nonaqueous electrolyte secondary battery using the nonaqueous electrolyte solution will be specifically described.
[0020]
The nonaqueous electrolytic solution according to the present invention is a nonaqueous electrolytic solution containing a boric acid ester, a nonaqueous solvent, and an electrolyte.
When the boric acid ester is contained in the electrolytic solution of the present invention, an increase in electrode interface resistance during initial charging is suppressed, and thus a desirable nonaqueous electrolytic solution is obtained. A non-aqueous electrolyte secondary battery using this non-aqueous electrolyte exhibits excellent load characteristics.
[0021]
Borate ester
The borate esters used in the present invention are:Trimethyl borate, triethyl borate, tripropyl borate, tributyl borate, tripentyl borate, diethyl methyl borate, tri (methoxyethyl) borate, dimethyl hydroxyborate, dimethyl monolithium borate and monomethyl diborate Alkyl borate esters selected from lithium salts and tri (trifluoroethyl) borate, methyl di (trifluoroethyl) borate, tri (trichloroethyl) borate, tri (tetrafluoroethyl) borate, tri (monofluoroborate) Fluoroethyl), tri (pentafluoropropyl) borate, tri (hexafluoropropyl) borate, tri (2-methyl-1,1,1,3,3,3-hexafluoropropyl) borate, triborate (2-Phenyl-1,1,1,3,3,3-hexafluoro Propyl), tri borate (trifluoroethoxy ethyl) and halogen-containing borate ester comprising a boric acid ester selected from the group selected from boric acid methyl di (trifluoroethoxy ethyl)Is.
[0022]
BookThe non-aqueous electrolyte of the inventionRecordIn addition to oxalate, non-aqueous solvent and electrolyte,Sultone selected from the group consisting of 1,3-propane sultone, 1,4-butane sultone, 1,3-propene sultone, 1,4-butene sultone and 1,5-pentene sultone, and a sulfonyl group selected from the group consisting of dimethyl benzenedisulfonate ContainsCompounds can be included.
Non-aqueous electrolyteContains sulfonyl groupWhen the compound is contained, an effect of suppressing an increase in interface resistance at the time of initial charge is enhanced. In addition, it is desirable not only during initial charging, but also because the increase in interface resistance after repeated use and storage at high temperatures is suppressed..
[0023]
Contains sulfonyl groupThe amount of the compound added to the non-aqueous electrolyte is preferably 0.01 to 10% by weight, more preferably 0.05 to 5% by weight.
[0024]
Vinylene carbonate derivative
The nonaqueous electrolytic solution of the present invention may further contain a vinylene carbonate derivative represented by the following general formula (3).
[0025]
When the nonaqueous electrolytic solution of the present invention contains a vinylene carbonate derivative represented by the following general formula (3), in addition to further enhancing the effect of suppressing an increase in interface resistance during initial charging, a cycle test or The maintenance rate of the battery capacity during the high temperature storage test is improved.
[0026]
[Chemical 1]
Where R7And R8May be the same or different and are hydrogen or an organic group having 1 to 10 carbon atoms.
Preferable examples of the organic group include a hydrocarbon group and a hetero atom-containing hydrocarbon group.
[0028]
Examples of the hydrocarbon group include a saturated hydrocarbon group such as a methyl group, an ethyl group, a propyl group, a butyl group, and an octyl group, a double bond-containing hydrocarbon group such as a vinyl group and an allyl group, an ethynyl group, and a propargyl group. Examples thereof include unsaturated hydrocarbon groups such as a triple bond-containing hydrocarbon group.
[0029]
Examples of the hetero atom of the hetero atom-containing hydrocarbon group include oxygen, nitrogen, sulfur, phosphorus and boron. Preferred examples of heteroatom-containing hydrocarbon groups include oxygen-containing hydrocarbon groups containing ether bonds, ester bonds, carbonate bonds, etc., such as methoxyethyl groups and methoxycarbonylethyl groups, and nitrogen-containing hydrocarbon groups containing amino groups, etc. Can be mentioned.
[0030]
The organic group may be substituted with a halogen atom. Examples of the halogen element include fluorine, chlorine, bromine and the like, with fluorine being preferred. Examples of the organic group substituted with a halogen atom include a halogenated hydrocarbon group such as a trifluoroethyl group, a hydrocarbon group substituted with a halogen-containing group, and a halogenated heteroatom-containing hydrocarbon group. In particular, a halogenated hydrocarbon group is preferable.
[0031]
As the organic group, a hydrocarbon group having 1 to 10 carbon atoms or a halogenated hydrocarbon group having 1 to 10 carbon atoms is preferable.
[0032]
Specific examples of the vinylene carbonate derivative represented by the general formula (3) include vinylene carbonate, methyl vinylene carbonate, ethyl vinylene carbonate, propyl ethylene carbonate, dimethyl vinylene carbonate, diethyl vinylene carbonate, dipropyl vinylene carbonate, fluoro vinylene carbonate, Examples thereof include trifluoromethyl vinylene carbonate. Of these, vinylene carbonate is preferred.
[0033]
The amount of vinylene carbonate derivative added to the electrolytic solution is preferably 0.05 to 5% by weight with respect to the entire non-aqueous electrolytic solution.
[0034]
The non-aqueous electrolyte containing the boric acid ester represented by the general formula (1), the compound represented by the general formula (2) and the vinylene carbonate derivative represented by the general formula (3) is a non-aqueous electrolyte of the present invention. This is a preferred embodiment of the electrolytic solution.
A nonaqueous electrolytic solution containing the boric acid ester represented by the general formula (1) and the vinylene carbonate derivative represented by the general formula (3) is also a preferred embodiment of the nonaqueous electrolytic solution of the present invention.
[0035]
Among these, a boric acid ester represented by the general formula (1), a non-aqueous electrolyte containing a compound represented by the general formula (2), and a vinylene carbonate derivative represented by the general formula (3) are included. A non-aqueous electrolyte is a more preferred embodiment.
[0036]
Non-aqueous solvent
The nonaqueous electrolytic solution of the present invention has a configuration in which the compound described so far is contained in a solution obtained by dissolving an electrolyte in a nonaqueous solvent.
[0037]
In the present invention, the non-aqueous solvent is preferably composed of a cyclic aprotic solvent and / or a chain aprotic solvent.
Examples of the cyclic aprotic solvent include a cyclic carbonate such as ethylene carbonate, a cyclic ester such as γ-butyrolactone, and a cyclic ether such as dioxolane. The chain aprotic solvent includes a chain such as dimethyl carbonate. Examples thereof include chain carbonates, chain carboxylic acid esters such as methyl propionate, chain ethers such as dimethoxyethane, and chain phosphate esters such as trimethyl phosphate.
[0038]
In the case where the load characteristics and low temperature characteristics of the battery are particularly intended to be improved, the non-aqueous solvent is preferably a combination of a cyclic aprotic solvent and a chain aprotic solvent. Furthermore, it is preferable to apply a cyclic carbonate to the cyclic aprotic solvent and a chain carbonate to the chain aprotic solvent from the electrochemical stability of the electrolytic solution.
[0039]
Specific examples of the cyclic carbonate include ethylene carbonate, propylene carbonate, 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, 2,3-pentylene carbonate and the like. Among them, ethylene carbonate and propylene carbonate having a high dielectric constant are preferably used. In the case of a battery using graphite as the negative electrode active material, ethylene carbonate is preferable. Two or more of these cyclic carbonates may be used as a mixture.
[0040]
Specific examples of the chain carbonate include dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, methyl propyl carbonate, methyl isopropyl carbonate, dipropyl carbonate, methyl butyl carbonate, dibutyl carbonate, ethyl propyl carbonate, methyl trifluoroethyl carbonate, and the like. Can be. Among them, dimethyl carbonate, methyl ethyl carbonate, and diethyl carbonate having a low viscosity are preferably used. These chain carbonates may be used as a mixture of two or more.
[0041]
Specific combinations of cyclic carbonate and chain carbonate include ethylene carbonate and dimethyl carbonate, ethylene carbonate and methyl ethyl carbonate, ethylene carbonate and diethyl carbonate, propylene carbonate and dimethyl carbonate, propylene carbonate and methyl ethyl carbonate, propylene carbonate and diethyl Carbonate, ethylene carbonate and propylene carbonate and dimethyl carbonate, ethylene carbonate and propylene carbonate and methyl ethyl carbonate, ethylene carbonate and propylene carbonate and diethyl carbonate, ethylene carbonate and dimethyl carbonate and methyl ethyl carbonate, ethylene carbonate and dimethyl carbonate and diethyl Carbonate, ethylene carbonate and methyl ethyl carbonate and diethyl carbonate, ethylene carbonate and dimethyl carbonate and methyl ethyl carbonate and diethyl carbonate, ethylene carbonate and propylene carbonate and dimethyl carbonate and methyl ethyl carbonate, ethylene carbonate and propylene carbonate, dimethyl carbonate and diethyl carbonate, Examples thereof include ethylene carbonate, propylene carbonate, methyl ethyl carbonate and diethyl carbonate, ethylene carbonate, propylene carbonate, dimethyl carbonate, methyl ethyl carbonate and diethyl carbonate.
[0042]
The mixing ratio of the cyclic carbonate and the chain carbonate is expressed by weight ratio, and the cyclic carbonate: chain carbonate is 5:95 to 80:20, more preferably 10:90 to 70:30, and particularly preferably 15:85. ~ 55: 45.
[0043]
By setting such a ratio, an increase in the viscosity of the electrolytic solution can be suppressed and the degree of dissociation of the electrolyte can be increased, so that the conductivity of the electrolytic solution related to the charge / discharge characteristics of the battery can be increased, and the solubility of the electrolyte Can be further enhanced. As a result, an electrolytic solution having excellent electrical conductivity from room temperature to low temperature can be obtained, so that the load characteristics of the battery from room temperature to low temperature can be improved.
[0044]
In addition, to improve the flash point of the solvent to improve battery safety, use a cyclic aprotic solvent alone as the non-aqueous solvent, or mix a chain of aprotic solvents. It is desirable to limit the amount to less than 20% by weight with respect to the total non-aqueous solvent.
[0045]
As the cyclic aprotic solvent in this case, it is particularly desirable to mix one kind or a mixture selected from ethylene carbonate, propylene carbonate, γ-butyrolactone, and methyloxazolinone. Specific examples of the solvent combination include ethylene carbonate and sulfolane, ethylene carbonate and γ-butyrolactone, ethylene carbonate and propylene carbonate, ethylene carbonate, propylene carbonate, and gamma butyrolactone.
[0046]
When the amount of the chain aprotic solvent mixed is 20% or less by weight with respect to the total amount of the nonaqueous solvent, the chain aprotic solvent may be a chain carbonate, a chain carboxylate ester, a chain In particular, chain phosphates such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, diheptyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, methyl butyl carbonate, and methyl heptyl carbonate are preferable.
[0047]
In the non-aqueous electrolyte solution according to the present invention, as the non-aqueous solvent, a solvent other than the above may be included. Specifically, as the other solvent, an amide such as dimethylformamide, methyl-N, N And chain carbamates such as -dimethylcarbamate, cyclic amides such as N-methylpyrrolidone, cyclic ureas such as N, N-dimethylimidazolidinone, and ethylene glycol derivatives represented by the following general formula.
HO (CH2CH2O)aH, HO {CH2CH (CH3) O}bH, CH3O (CH2CH2O)cH, CH3O {CH2CH (CH3) O}dH, CH3O (CH2CH2O)eCH3, CH3O {CH2CH (CH3) O}fCH3, C9H19PhO (CH2CH2O)g{CH (CH3) O}hCH3(Ph is a phenyl group), CH3O {CH2CH (CH3) O}iCO {O (CH3) CHCH2}jOCH3(In the formula, a to f are integers of 5 to 250, g to j are integers of 2 to 249, 5 ≦ g + h ≦ 250, 5 ≦ i + j ≦ 250.)
Non-aqueous electrolyte
The non-aqueous electrolyte solution of the present invention dissolves an electrolyte in a non-aqueous solvent and further contains the aforementioned compounds. Any electrolyte can be used as long as it is normally used as an electrolyte for a non-aqueous electrolyte.
[0048]
As a specific example of the electrolyte, LiPF6, LiBF4, LiClO4, LiAsF6, Li2SiF6, LiC4F9SO3, LiC8F17SO3And lithium salts. Moreover, the lithium salt shown by the following general formula can also be used. LiOSO2R8, LiN (SO2R9) (SO2R10), LiC (SO2R11) (SO2R12) (SO2R13), LiN (SO2OR14) (SO2OR15) (Where R8~ R15May be the same as or different from each other, and are perfluoroalkyl groups having 1 to 6 carbon atoms). These lithium salts may be used alone or in combination of two or more.
[0049]
Of these, in particular, LiPF6, LiBF4, LiOSO2R8, LiN (SO2R9) (SO2R10), LiC (SO2R11) (SO2R12) (SO2R13), LiN (SO2OR14) (SO2OR15) Is preferred.
[0050]
Such an electrolyte is desirably contained in the non-aqueous electrolyte at a concentration of 0.1 to 3 mol / liter, preferably 0.5 to 2 mol / liter.
[0051]
The non-aqueous electrolyte in the present invention contains the aforementioned compounds, a non-aqueous solvent and an electrolyte as essential components, but other additives may be added as necessary.
[0052]
Other additives include carboxylic anhydrides such as maleic anhydride, norbornene dicarboxylic anhydride, diglycolic acid; unsaturated hydrocarbons such as vinyl ethylene carbonate, divinyl ethylene carbonate, methylene-1,2-ethylene carbonate Substituted cyclic carbonates; hydrogen fluoride and the like.
[0053]
In the case of using hydrogen fluoride as an additive, the method of adding to the electrolytic solution includes blowing a predetermined amount of hydrogen fluoride gas directly into the electrolytic solution. The lithium salt used in the present invention is LiPF.6And LiBF4In the case of a lithium salt containing fluorine, etc., water may be added to the electrolytic solution using the reaction of an active proton compound such as water and an electrolyte shown below, and may be generated in the electrolytic solution. .
[0054]
LiMFn + H2O → LiPF(N-2)O + 2HF
(However, M represents P, B, etc., n = 6 when M = P, and n = 4 when M = B.)
[0055]
When water is added to the electrolyte and HF is indirectly generated in the electrolyte, two molecules of HF are generated almost quantitatively from one molecule of water, so the amount of water added matches the desired concentration of HF added. Calculate and add. Specifically, it is preferable to add 0.45 times (weight ratio) water as desired.
[0056]
Specific examples of other protic compounds include trifluoroacetic acid, methanol, ethanol, ethylene glycol, propylene glycol and the like.
[0057]
The addition amount as hydrogen fluoride is 0.0001 to 0.7 wt%, preferably 0.001 to 0.3 wt%, more preferably 0.001 to 0.1 wt%.
[0058]
The non-aqueous electrolyte according to the present invention is not only suitable as a non-aqueous electrolyte for a lithium ion secondary battery, but can also be used as a non-aqueous electrolyte for a primary battery.
[0059]
Secondary battery
The non-aqueous electrolyte secondary battery according to the present invention basically includes a negative electrode, a positive electrode, and the non-aqueous electrolyte, and usually includes a separator between the negative electrode and the positive electrode. ing.
[0060]
Examples of the negative electrode active material constituting the negative electrode include metallic lithium, lithium alloy, carbon material capable of doping / dedoing lithium ions, tin oxide, niobium oxide or oxidation capable of doping / dedoping lithium ions. Vanadium, titanium oxide that can be doped / undoped with lithium ions, or silicon or tin that can be doped / undoped with lithium ions can be used. Among these, a carbon material that can dope / dedope lithium ions is preferable. Such a carbon material may be graphite or amorphous carbon, and activated carbon, carbon fiber, carbon black, mesocarbon microbeads, natural graphite and the like are used.
[0061]
As the negative electrode active material, a carbon material having a (002) plane distance (d002) of 0.340 nm or less measured by X-ray analysis is particularly preferable, and the density is 1.70 g / cm.3The above-described graphite or a highly crystalline carbon material having properties close thereto is desirable. When such a carbon material is used, the energy density of the battery can be increased.
[0062]
As the positive electrode active material constituting the positive electrode, MoS2TiS2, MnO2, V2O5Transition metal oxides or transition metal sulfides such as LiCoO2LiMnO2, LiMn2O4, LiNiO2, LiNixCo(1-x)O2, LiNixMnyCo(1-xy)O2Examples thereof include composite oxides composed of lithium and a transition metal such as polyaniline, polythiophene, polypyrrole, polyacetylene, polyacene, and dimercaptothiadiazole / polyaniline composite. Among these, a composite oxide composed of lithium and a transition metal is particularly preferable. When the negative electrode is lithium metal or a lithium alloy, a carbon material can also be used as the positive electrode. As the positive electrode, a mixture of lithium and transition metal composite oxide and a carbon material can be used.
[0063]
The separator is a film that electrically insulates the positive electrode and the negative electrode and transmits lithium ions, and examples thereof include a porous film and a polymer electrolyte. As the porous film, a microporous polymer film is preferably used, and examples of the material include polyolefin, polyimide, and polyvinylidene fluoride. In particular, a porous polyolefin film is preferable, and specifically, a porous polyethylene film, a porous polypropylene film, or a multilayer film of a porous polyethylene film and polypropylene can be exemplified. Examples of the polymer electrolyte include a polymer in which a lithium salt is dissolved, a polymer swollen with an electrolytic solution, and the like. The electrolytic solution of the present invention may be used for the purpose of obtaining a polymer electrolyte by swelling a polymer.
[0064]
Such a nonaqueous electrolyte secondary battery can be formed in a cylindrical shape, a coin shape, a square shape, a film shape, or any other shape. However, the basic structure of the battery is the same regardless of the shape, and the design can be changed according to the purpose. Next, the structures of the cylindrical and coin-type batteries will be described. The negative electrode active material, the positive electrode active material, and the separator constituting each battery are commonly used.
[0065]
For example, in the case of a cylindrical non-aqueous electrolyte secondary battery, a negative electrode formed by applying a negative electrode active material to a negative electrode current collector and a positive electrode formed by applying a positive electrode active material to a positive electrode current collector are It winds through the separator which inject | poured the water electrolyte solution, and is accommodated in the battery can in the state which mounted the insulating board on the upper and lower sides of the wound body.
[0066]
The non-aqueous electrolyte secondary battery according to the present invention can also be applied to a coin-type non-aqueous electrolyte secondary battery. In a coin-type battery, a disk-shaped negative electrode, a separator, a disk-shaped positive electrode, and a stainless steel or aluminum plate are stored in a coin-type battery can in a state of being laminated in this order.
[0067]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not restrict | limited at all by these Examples.
[0068]
(Example 17, Reference Examples 1-3)
1. Battery fabrication
<Preparation of non-aqueous electrolyte>
Ethylene carbonate (EC) and methyl ethyl carbonate (MEC) are mixed in a ratio of EC: MEC = 4: 6 (weight ratio), and then the electrolyte LiPF6Was dissolved in a non-aqueous solvent to prepare a non-aqueous electrolyte so that the electrolyte concentration was 1.0 mol / liter. Next, the additives shown in Table 1 were added to the non-aqueous electrolyte solution (100% by weight) at the ratio shown in Table 1.
[0069]
<Production of negative electrode>
87 parts by weight of natural graphite (LF-18A made by Chuetsu Graphite) and 13 parts by weight of polyvinylidene fluoride (PVDF) as a binder were mixed and dispersed in N-methylpyrrolidinone as a solvent to prepare a natural graphite mixture slurry. Next, this negative electrode mixture slurry was applied to a negative electrode current collector made of a strip-shaped copper foil having a thickness of 18 μm, dried, compression-molded, punched into a 14 mm disk, and coin-shaped natural graphite. An electrode was obtained. The natural graphite electrode mixture had a thickness of 110 μm and a weight of 20 mg per area of a circle having a diameter of 14 mm.
[0070]
<LiCoO2Production of electrodes>
LiCoO290 parts by weight (HLC-21 manufactured by Honjo FMC Energy Systems Co., Ltd.), 6 parts by weight of graphite as a conductive agent and 1 part by weight of acetylene black and 3 parts by weight of polyvinylidene fluoride as a binder were mixed. Dispersed in methylpyrrolidone and LiCoO2A mixture slurry was prepared.
This LiCoO2The mixture slurry was applied to an aluminum foil with a thickness of 20 μm, dried, compression molded, and punched out to a diameter of 13 mm, and LiCoO2An electrode was produced.
This LiCoO2The thickness of the mixture was 90 μm, and the weight was 35 mg per area of a circle having a diameter of 13 mm.
[0071]
<Production of battery>
Natural graphite electrode with a diameter of 14 mm, LiCoO with a diameter of 13 mm2A separator made of an electrode and a microporous polypropylene film having a thickness of 25 μm and a diameter of 16 mm is placed in a 2032 size battery can made of stainless steel, a natural graphite electrode, a separator, LiCoO2Laminated in the order of electrodes. Thereafter, 0.03 ml of the non-aqueous electrolyte was poured into the separator, and an aluminum plate (thickness 1.2 mm, diameter 16 mm, and spring was accommodated. Finally, the battery can lid was passed through a polypropylene gasket. By crimping, a coin-type battery having a diameter of 20 mm and a height of 3.2 mm was produced while maintaining the airtightness in the battery.
[0072]
2. Evaluation of battery characteristics
<Measurement of initial battery characteristics>
(1) Measurement of initial low-load discharge capacity
Using the coin-type battery produced as described above, this battery was charged under the condition of a constant current of 0.5 mA and a constant voltage of 4.2 V until the current value at a constant voltage of 4.2 V was 0.05 mA, Thereafter, discharging was performed under a condition of a constant current of 0.5 mA and a constant voltage of 3.0 V until the current value at a constant voltage of 3.0 V was 0.05 mA. The discharge capacity of the coin-type battery at this time is referred to as “initial low-load discharge capacity”. The initial low load discharge capacity was around 4.5 mAh in any of the batteries.
[0073]
(2) Measurement of initial medium load discharge capacity
Next, this battery was charged under the condition of a constant current of 3 mA and a constant voltage of 4.2 V until the current value at a constant voltage of 4.2 V reached 0.05 mA, and then the battery voltage was 3.0 V at a current of 5 mA. Discharged until The discharge capacity of the coin-type battery at this time is referred to as “initial medium load discharge capacity”.
[0074]
<Measurement of electrode interface resistance>
After charging the coin-type battery to 4.2 V, the impedance at 0.2 Hz and 2500 Hz was measured, and the impedance value obtained by subtracting the impedance value at 2500 Hz from the impedance value at 0.2 Hz was defined as “electrode interface resistance”. .
[0075]
<Measurement of battery storage characteristics>
(1) Measurement of discharge capacity
The battery was once discharged to 3 V, and charged under the condition of a 3 mA constant current of 4.1 V constant voltage until the current value at the time of 4.1 V constant voltage was 0.05 mA. The charge amount at this time was defined as “charge capacity before storage”.
This battery was stored at 50 ° C. for 1 week, and then discharged under a condition of a constant current of 0.5 mA and a constant voltage of 3.0 V until the current value at a constant voltage of 3.0 V was 0.05 mA. The discharge amount at this time was defined as “discharge capacity after storage”.
The difference between “discharge capacity after storage” and “charge capacity before storage” was defined as “high-temperature storage self-discharge capacity” (“discharge capacity after storage” − “charge capacity before storage” = “high-temperature storage self-discharge capacity”).
[0076]
(2) Measurement of medium load discharge capacity after storage
Next, this battery was charged under the condition of a constant current of 3 mA and a constant voltage of 4.2 V until the current value at a constant voltage of 4.2 V reached 0.05 mA, and then the battery voltage was 3.0 V at a current of 5 mA. Discharged until The discharge capacity of the coin-type battery at this time is referred to as “medium-load discharge capacity after storage”.
[0077]
Example 17, Reference Examples 1-3The evaluation results of the battery characteristics are shown in Table 2.
[0078]
(Comparative Example 1)
In <Preparation of Nonaqueous Electrolyte> in Example 1, a nonaqueous electrolyte was prepared in the same manner except that the addition of the additive was omitted. Using the obtained nonaqueous electrolyte, Example 1 and Similarly, batteries were prepared and battery characteristics were evaluated.
The “electrode interface resistance” and “high temperature storage self-discharge capacity” measured in Comparative Example 1 are defined as “electrode interface resistance in blank” and “high temperature storage self-discharge capacity in blank”, respectively.
The evaluation results of the battery characteristics are shown in Table 2.
[0079]
The battery characteristics shown in Table 2 were evaluated using the following indices from the experimental results in Examples 1 to 10 and Comparative Example 1. In both cases, the unit is%.
“Electrode interface resistance ratio” = {“electrode interface resistance of battery using test electrolyte” / “electrode interface resistance in blank”} × 100
“Initial load characteristic index” = {“Initial load discharge capacity” / “Initial low load discharge capacity”} × 100
“Load characteristic maintenance ratio” = {“Medium load discharge capacity after storage” / “Initial medium load discharge capacity”} × 100
“Self-discharge ratio” = {“High-temperature storage self-discharge capacity of test electrolyte” / “High-temperature storage self-discharge capacity in blank”} × 100
[0080]
[Table 1]
[Table 2]
From Table 2, Examples 1 to7It was found that even when any of these electrolytes was used, the initial interface resistance was smaller than that of the blank (Comparative Example 1), and a battery exhibiting excellent load characteristics was obtained.
[0083]
From Table 2With the electrolyte of the present invention, highIt can be seen that a battery with little deterioration in load characteristics after storage at a high temperature can be obtained. It can be seen that when the electrolytic solution further contains a vinylene carbonate derivative represented by the general formula (3), deterioration of load characteristics and self-discharge after high-temperature storage are suppressed, and a battery exhibiting superior characteristics can be obtained.
[0084]
【The invention's effect】
The present invention provides a non-aqueous electrolyte that is particularly suitable as an electrolyte for a lithium ion secondary battery.
By using the non-aqueous electrolyte of the present invention, it is possible to obtain a non-aqueous electrolyte secondary battery with low initial electrode interface resistance and excellent load characteristics in initial characteristics or characteristics after storage at high temperature. it can.
Claims (14)
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