JP4770118B2 - Non-aqueous electrolyte and lithium secondary battery - Google Patents
Non-aqueous electrolyte and lithium secondary battery Download PDFInfo
- Publication number
- JP4770118B2 JP4770118B2 JP2004029425A JP2004029425A JP4770118B2 JP 4770118 B2 JP4770118 B2 JP 4770118B2 JP 2004029425 A JP2004029425 A JP 2004029425A JP 2004029425 A JP2004029425 A JP 2004029425A JP 4770118 B2 JP4770118 B2 JP 4770118B2
- Authority
- JP
- Japan
- Prior art keywords
- carbonate
- aqueous electrolyte
- mass
- lithium
- battery
- 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
- 229910052744 lithium Inorganic materials 0.000 title claims description 39
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 37
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims description 33
- 239000008151 electrolyte solution Substances 0.000 claims description 42
- -1 cyclic carbonate compound Chemical class 0.000 claims description 33
- 150000001875 compounds Chemical class 0.000 claims description 24
- 229910003002 lithium salt Inorganic materials 0.000 claims description 23
- 159000000002 lithium salts Chemical class 0.000 claims description 22
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- 239000003575 carbonaceous material Substances 0.000 claims description 14
- 239000003125 aqueous solvent Substances 0.000 claims description 12
- 229910052731 fluorine Inorganic materials 0.000 claims description 11
- 125000001153 fluoro group Chemical group F* 0.000 claims description 11
- 238000002441 X-ray diffraction Methods 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 33
- 238000003860 storage Methods 0.000 description 33
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 20
- 239000007789 gas Substances 0.000 description 17
- 238000011156 evaluation Methods 0.000 description 15
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 14
- 229910013870 LiPF 6 Inorganic materials 0.000 description 14
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical class O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 13
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 12
- 229940021013 electrolyte solution Drugs 0.000 description 12
- 238000007600 charging Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 229910002804 graphite Inorganic materials 0.000 description 9
- 239000010439 graphite Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 7
- 239000000956 alloy Substances 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 150000005676 cyclic carbonates Chemical class 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- WCFDSGHAIGTEKL-UHFFFAOYSA-N n,n-dimethylmethanesulfonamide Chemical compound CN(C)S(C)(=O)=O WCFDSGHAIGTEKL-UHFFFAOYSA-N 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910013075 LiBF Inorganic materials 0.000 description 4
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- 101150058243 Lipf gene Proteins 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
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- 239000007773 negative electrode material Substances 0.000 description 4
- 229910052718 tin Inorganic materials 0.000 description 4
- ZLKNPIVTWNMMMH-UHFFFAOYSA-N 1-imidazol-1-ylsulfonylimidazole Chemical compound C1=CN=CN1S(=O)(=O)N1C=CN=C1 ZLKNPIVTWNMMMH-UHFFFAOYSA-N 0.000 description 3
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 229910014211 My O Inorganic materials 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 150000001491 aromatic compounds Chemical class 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 3
- 150000001733 carboxylic acid esters Chemical class 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 239000011572 manganese Substances 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- MORLSCQKZAPYFM-UHFFFAOYSA-N n,n-dimethylethanesulfonamide Chemical compound CCS(=O)(=O)N(C)C MORLSCQKZAPYFM-UHFFFAOYSA-N 0.000 description 3
- 229910021382 natural graphite Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000004438 BET method Methods 0.000 description 2
- 229910000733 Li alloy Inorganic materials 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
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- 239000004743 Polypropylene Substances 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
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- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical compound C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- ZCRZCMUDOWDGOB-UHFFFAOYSA-N ethanesulfonimidic acid Chemical compound CCS(N)(=O)=O ZCRZCMUDOWDGOB-UHFFFAOYSA-N 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
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- 239000001989 lithium alloy Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
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- YKXINVWHNNYQMA-UHFFFAOYSA-N n,n-dibutylbenzenesulfonamide Chemical compound CCCCN(CCCC)S(=O)(=O)C1=CC=CC=C1 YKXINVWHNNYQMA-UHFFFAOYSA-N 0.000 description 2
- PJKYCCUNKLHUMZ-UHFFFAOYSA-N n,n-diethylethanesulfonamide Chemical class CCN(CC)S(=O)(=O)CC PJKYCCUNKLHUMZ-UHFFFAOYSA-N 0.000 description 2
- KSEMETYAQIUBQB-UHFFFAOYSA-N n,n-diethylmethanesulfonamide Chemical compound CCN(CC)S(C)(=O)=O KSEMETYAQIUBQB-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
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- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
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- COVZYZSDYWQREU-UHFFFAOYSA-N Busulfan Chemical compound CS(=O)(=O)OCCCCOS(C)(=O)=O COVZYZSDYWQREU-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229910018871 CoO 2 Inorganic materials 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
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- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
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- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 241001417524 Pomacanthidae Species 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
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- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical class COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 150000008331 benzenesulfonamides Chemical class 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
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- 229910052797 bismuth Inorganic materials 0.000 description 1
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- UAEWCWCMYQAIDR-UHFFFAOYSA-N diethyl methyl phosphate Chemical compound CCOP(=O)(OC)OCC UAEWCWCMYQAIDR-UHFFFAOYSA-N 0.000 description 1
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 1
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- JOXWSDNHLSQKCC-UHFFFAOYSA-N ethenesulfonamide Chemical class NS(=O)(=O)C=C JOXWSDNHLSQKCC-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
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- JQVXMIPNQMYRPE-UHFFFAOYSA-N ethyl dimethyl phosphate Chemical compound CCOP(=O)(OC)OC JQVXMIPNQMYRPE-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
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- 239000011229 interlayer Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
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- 239000005001 laminate film Substances 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- HNQIVZYLYMDVSB-UHFFFAOYSA-N methanesulfonimidic acid Chemical class CS(N)(=O)=O HNQIVZYLYMDVSB-UHFFFAOYSA-N 0.000 description 1
- 125000005525 methide group Chemical group 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- MBABOKRGFJTBAE-UHFFFAOYSA-N methyl methanesulfonate Chemical compound COS(C)(=O)=O MBABOKRGFJTBAE-UHFFFAOYSA-N 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 1
- AHWCSMDATLBAOR-UHFFFAOYSA-N n,n-bis(trifluoromethyl)methanesulfonamide Chemical compound CS(=O)(=O)N(C(F)(F)F)C(F)(F)F AHWCSMDATLBAOR-UHFFFAOYSA-N 0.000 description 1
- BVSPJPNNLDIUFE-UHFFFAOYSA-N n,n-dimethylbenzenesulfonamide Chemical compound CN(C)S(=O)(=O)C1=CC=CC=C1 BVSPJPNNLDIUFE-UHFFFAOYSA-N 0.000 description 1
- AYRRJFSXEOEOOA-UHFFFAOYSA-N n,n-dimethylethenesulfonamide Chemical compound CN(C)S(=O)(=O)C=C AYRRJFSXEOEOOA-UHFFFAOYSA-N 0.000 description 1
- VFSXTIZTYPMMBS-UHFFFAOYSA-N n,n-dipropylbenzenesulfonamide Chemical compound CCCN(CCC)S(=O)(=O)C1=CC=CC=C1 VFSXTIZTYPMMBS-UHFFFAOYSA-N 0.000 description 1
- MDNOAUDSYKTKJH-UHFFFAOYSA-N n,n-dipropylmethanesulfonamide Chemical compound CCCN(S(C)(=O)=O)CCC MDNOAUDSYKTKJH-UHFFFAOYSA-N 0.000 description 1
- DRSHSWDGJPLMDW-UHFFFAOYSA-N n-benzyl-n-methylmethanesulfonamide Chemical compound CS(=O)(=O)N(C)CC1=CC=CC=C1 DRSHSWDGJPLMDW-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 description 1
- CIHXCFDKVVKCSJ-UHFFFAOYSA-N n-ethyl-n-methylethanesulfonamide Chemical compound CCN(C)S(=O)(=O)CC CIHXCFDKVVKCSJ-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000011356 non-aqueous organic solvent Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 description 1
- 239000001254 oxidized starch Substances 0.000 description 1
- 235000013808 oxidized starch Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- DROIHSMGGKKIJT-UHFFFAOYSA-N propane-1-sulfonamide Chemical compound CCCS(N)(=O)=O DROIHSMGGKKIJT-UHFFFAOYSA-N 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- MBDNRNMVTZADMQ-UHFFFAOYSA-N sulfolene Chemical compound O=S1(=O)CC=CC1 MBDNRNMVTZADMQ-UHFFFAOYSA-N 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- KAKQVSNHTBLJCH-UHFFFAOYSA-N trifluoromethanesulfonimidic acid Chemical class NS(=O)(=O)C(F)(F)F KAKQVSNHTBLJCH-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 239000011701 zinc Substances 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
本発明は、非水系電解液電池、およびそれに用いる非水系電解液に関するものである。詳しくは、高容量で、保存特性、負荷特性および二次電池の場合にはサイクル特性に優れる非水系電解液電池に関するものである。また、ガス発生量の少ない非水系電解液電池に関するものである。 The present invention relates to a non-aqueous electrolyte battery and a non-aqueous electrolyte used therein. Specifically, the present invention relates to a non-aqueous electrolyte battery having a high capacity and excellent storage characteristics, load characteristics and cycle characteristics in the case of a secondary battery. The present invention also relates to a non-aqueous electrolyte battery that generates a small amount of gas.
近年の電気製品の軽量化、小型化にともない、高いエネルギ−密度を持つリチウム電池の開発が進められている。また、リチウム電池の適用分野が拡大するにつれて、その電池特性の改善が要望されている。リチウム電池の負極としては、金属リチウム、リチウムを吸蔵及び放出可能な金属化合物（金属単体、酸化物、リチウムとの合金など）、炭素質材料が用いられている。
特に、炭素質材料について、例えば、コークス、人造黒鉛、天然黒鉛等のリチウムを吸蔵・放出することが可能な炭素質材料を用いた非水系電解液二次電池が提案されている。このような非水系電解液二次電池では、リチウムが金属状態で存在しないためデンドライトの形成が抑制され、電池寿命と安全性を向上することができる。特に人造黒鉛、天然黒鉛等の黒鉛系炭素質材料を用いた非水系電解液二次電池は、高容量化の要求に応えるものとして注目されている。
With the recent reduction in weight and size of electrical products, development of lithium batteries having high energy density is in progress. In addition, as the application field of lithium batteries expands, improvements in battery characteristics are desired. As a negative electrode of a lithium battery, metallic lithium, a metallic compound capable of occluding and releasing lithium (metal simple substance, oxide, alloy with lithium, etc.) and a carbonaceous material are used.
In particular, as a carbonaceous material, for example, a non-aqueous electrolyte secondary battery using a carbonaceous material capable of inserting and extracting lithium such as coke, artificial graphite, and natural graphite has been proposed. In such a non-aqueous electrolyte secondary battery, since lithium does not exist in a metal state, formation of dendrites is suppressed, and battery life and safety can be improved. In particular, non-aqueous electrolyte secondary batteries using graphite-based carbonaceous materials such as artificial graphite and natural graphite are attracting attention as meeting the demand for higher capacity.
また、非水系電解液二次電池の負荷特性、サイクル特性、保存特性、低温特性等の特性向上のために、電解質と主たる溶媒に加えて種々の化合物を含有させた電解液が提案されている。例えば、サイクル特性や保存特性向上のために、分子量が５００未満であり、窒素と硫黄が結合したＮＳ構造を有する化合物を含むことを特徴とする電解質が特許文献１に開示されている。
また、電池を停電時のバックアップ電源や、ポータブル機器の電源として用いる場合に、電池の自己放電を補うために常に微弱電流を流し、充電状態に保持する連続充電が行われる。こうした連続充電状態では電極の活性が常に高い状態であるので、電池の容量劣化が促進されたり、電解液の分解によりガスが発生する。このガス発生量が多い場合には、過充電等の異常時に内圧を感知して安全弁を作動させる円筒電池においては、安全弁が作動してしまうことがある。また、安全弁のない角形電池等では、電池がフクレたり、更には破裂することもある。 In addition, when the battery is used as a backup power source in the event of a power failure or a power source for a portable device, continuous charging is performed in which a weak current is always applied to maintain the charged state in order to compensate for the self-discharge of the battery. In such a continuously charged state, the activity of the electrode is always high, so that capacity deterioration of the battery is promoted or gas is generated due to decomposition of the electrolytic solution. When the amount of gas generated is large, the safety valve may be activated in a cylindrical battery that activates the safety valve by sensing the internal pressure when abnormality such as overcharge occurs. In addition, in a rectangular battery or the like without a safety valve, the battery may be blistered or even ruptured.
したがって、高容量、高温保存特性、負荷特性、サイクル特性だけでなく、連続充電特性についても改良することが求められる。連続充電特性としては、容量劣化が少ないことだけでなく、ガス発生を抑制することが強く求められる。
しかしながら特許文献１で開示されている１，１’−スルホニルジイミダゾール、Ｎ−ビスメチルチオメチレン−p−トルエンスルホンアミド、１−p−トリルスルホニルピロールは、８０℃以上の比較的高温での保存特性と、連続充電特性を共に向上させることはできない。
Therefore, it is required to improve not only high capacity, high temperature storage characteristics, load characteristics, cycle characteristics but also continuous charge characteristics. As continuous charging characteristics, not only is there little capacity deterioration, but it is also strongly required to suppress gas generation.
However, 1,1′-sulfonyldiimidazole, N-bismethylthiomethylene-p-toluenesulfonamide and 1-p-tolylsulfonylpyrrole disclosed in Patent Document 1 have storage characteristics at a relatively high temperature of 80 ° C. or higher. And, continuous charging characteristics cannot be improved together.
本発明者らは、上記目的を達成するために種々の検討を重ねた結果、特定の化合物を電解液中に含有させることによって、上記課題を解決できることを見出し、本発明を完成させるに至った。
すなわち、本発明の要旨は、負極および正極、並びに非水溶媒およびリチウム塩からなる電解液を含む非水系電解液電池において、非水電解液が更に一般式（１）で表される化合物を非水系電解液中に０．０１〜５質量％の割合で含有することを特徴とする非水系電解液電池に存する。
As a result of various studies to achieve the above object, the present inventors have found that the above problems can be solved by including a specific compound in the electrolytic solution, and have completed the present invention. .
That is, the gist of the present invention, the negative electrode and the positive electrode, as well as in the non-aqueous electrolyte battery comprising a nonaqueous solvent and an electrolyte consisting of a lithium salt, a nonaqueous electrolyte represented further by the general formula (1) compound non It exists in the aqueous electrolyte solution in the ratio of 0.01-5 mass%, and exists in the non-aqueous electrolyte battery characterized by the above-mentioned.
（式中、Ｒ1〜Ｒ3は、それぞれ独立して、フッ素原子で置換されていてもよい炭素数１〜１２のアルキル基、又はフッ素原子で置換されていてもよい炭素数６〜１２のアリール基を表す。なお、Ｒ1とＲ2は結合して環状構造を形成してもよい。） (In the formula, R 1 to R 3 are each independently an alkyl group having 1 to 12 carbon atoms which may be substituted with a fluorine atom , or 6 to 12 carbon atoms which may be substituted with a fluorine atom. Represents an aryl group , and R 1 and R 2 may combine to form a cyclic structure.)
負極および正極、並びに非水溶媒およびリチウム塩からなる電解液を含む非水系電解液電池において、電解液が一般式（１）で表される化合物を１種以上含有することにより、高容量で、保存特性、負荷特性および二次電池の場合にはサイクル特性に優れ、また、ガス発生量の少ない電池を作製することができ、非水系電解液電池の小型化、高性能化を達成することができる。 In a non-aqueous electrolyte battery including a negative electrode and a positive electrode, and an electrolyte solution composed of a non-aqueous solvent and a lithium salt, the electrolyte solution contains one or more compounds represented by the general formula (1). In the case of storage characteristics, load characteristics, and secondary batteries, it is excellent in cycle characteristics, and can produce a battery with a small amount of gas generation, and can achieve downsizing and high performance of a non-aqueous electrolyte battery. it can.
以下、本発明の実施の形態について詳細に説明するが、以下に記載する構成要件の説明は、本発明の実施態様の一例（代表例）であり、これらの内容に特定はされない。
本発明において、非水系電解液の主成分は、常用の非水系電解液と同じく、リチウム塩およびこれを溶解する非水溶媒である。
リチウム塩としては、この用途に用いることが知られているものであれば特に制限がなく、任意のものを用いることができ、具体的には以下のものが挙げられる。
DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail. However, the description of constituent elements described below is an example (representative example) of an embodiment of the present invention, and is not specified by these contents.
In the present invention, the main component of the non-aqueous electrolyte is a lithium salt and a non-aqueous solvent that dissolves the lithium salt, as in the case of a conventional non-aqueous electrolyte.
The lithium salt is not particularly limited as long as it is known to be used for this purpose, and any lithium salt can be used. Specific examples include the following.
無機リチウム塩：ＬｉＣｌＯ4等の過ハロゲン酸塩、ＬｉＰＦ6、ＬｉＢＦ4等のフッ化
物塩などが挙げられる。なかでも好ましいのは、ＬｉＰＦ6、ＬｉＢＦ4である。
含フッ素有機酸リチウム塩：ＬｉＣＦ3ＳＯ3等のパーフルオロアルカンスルホン酸塩、ＬｉＮ（ＣＦ3ＳＯ2）2、ＬｉＮ（Ｃ2Ｆ5ＳＯ2）2、ＬｉＮ（ＣＦ3ＳＯ2）（Ｃ4Ｆ9ＳＯ2）等のパーフルオロアルカンスルホン酸イミド、ＬｉＣ（ＣＦ3ＳＯ2）3等のパーフルオロアルカンスルホン酸メチド、ＬｉＰＦ4（ＣＦ3）2、ＬｉＰＦ4（Ｃ2Ｆ5）2、ＬｉＰＦ4（ＣＦ3ＳＯ2）2、ＬｉＰＦ4（Ｃ2Ｆ5ＳＯ2）2、等のパーフルオロアルカン基を有する有機リン酸塩、ＬｉＢＦ2（ＣＦ3）2、ＬｉＢＦ2（Ｃ2Ｆ5）2、ＬｉＢＦ2（ＣＦ3ＳＯ2）2、ＬｉＢＦ2（Ｃ2Ｆ5ＳＯ2）2等パーフルオロアルカン基を有する有機ホウ酸塩などが挙げられる。なかでも好ましいのは、ＬｉＣＦ3ＳＯ3、ＬｉＮ（ＣＦ3ＳＯ2）2およびＬｉＮ（Ｃ2Ｆ5ＳＯ2）2である。
Inorganic lithium salts: perhalogenates such as LiClO 4 and fluoride salts such as LiPF 6 and LiBF 4 . Of these, LiPF 6 and LiBF 4 are preferable.
Fluorine-containing organic acid lithium salt: perfluoroalkane sulfonate such as LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 2 ) 2 , LiN (CF 3 SO 2 ) (C 4 Perfluoroalkanesulfonic imides such as F 9 SO 2 ), perfluoroalkanesulfonic acid methides such as LiC (CF 3 SO 2 ) 3 , LiPF 4 (CF 3 ) 2 , LiPF 4 (C 2 F 5 ) 2 , LiPF 4 (CF 3 SO 2 ) 2 , LiPF 4 (C 2 F 5 SO 2 ) 2 , etc., organic phosphates having a perfluoroalkane group, LiBF 2 (CF 3 ) 2 , LiBF 2 (C 2 F 5 ) 2 , LiBF 2 (CF 3 SO 2 ) 2 , LiBF 2 (C 2 F 5 SO 2 ) 2 and the like, and organic borate having a perfluoroalkane group. Among these, LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 and LiN (C 2 F 5 SO 2 ) 2 are preferable.
これらのリチウム塩は単独で用いても、２種以上を併用してもよい。無機リチウム塩と含フッ素有機リチウム塩とを併用すると、高温保存した後の劣化が少なくなるので好ましい。この場合、リチウム塩に占める無機リチウム塩の割合は、７０〜９８質量％であることが望ましい。
また、非水溶媒がγ−ブチロラクトンを５５容量％以上含むものである場合には、リチウム塩に占めるＬｉＢＦ4の割合が５０質量％以上であることが好ましい。特に好ましくは、リチウム塩に占めるＬｉＢＦ4の割合が５０〜９５質量％であり、残りがＬｉＰＦ6、ＬｉＣＦ3ＳＯ3、ＬｉＮ（ＣＦ3ＳＯ2）2およびＬｉＮ（Ｃ2Ｆ5ＳＯ2）2よりなる群から選ばれるものからなる組合せである。
These lithium salts may be used alone or in combination of two or more. Use of an inorganic lithium salt and a fluorine-containing organic lithium salt in combination is preferable because deterioration after storage at high temperature is reduced. In this case, the proportion of the inorganic lithium salt in the lithium salt is desirably 70 to 98% by mass .
When the non-aqueous solvent contains 55% by volume or more of γ-butyrolactone, the proportion of LiBF 4 in the lithium salt is preferably 50% by weight or more. Particularly preferably, the proportion of LiBF 4 in the lithium salt is 50 to 95% by mass , with the remainder being LiPF 6 , LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 and LiN (C 2 F 5 SO 2 ) 2. A combination consisting of those selected from the group consisting of:
非水系電解液中のリチウム塩の濃度は、通常０．５〜３モル／リットルである。濃度が低すぎると電解液の電気伝導率が不十分であり、濃度が高すぎると粘度上昇のため電気伝導率が低下し、電池性能が低下することがある。非水系電解液中のリチウム塩の濃度は、０．６モル／リットル以上であるのが好ましく、また、１．８モル／リットル以下、特に１．５モル／リットル以下であるのが好ましい。 The concentration of the lithium salt in the nonaqueous electrolytic solution is usually 0.5 to 3 mol / liter. If the concentration is too low, the electric conductivity of the electrolytic solution is insufficient. If the concentration is too high, the viscosity increases and the electric conductivity is lowered, and the battery performance may be lowered. The concentration of the lithium salt in the non-aqueous electrolyte is preferably 0.6 mol / liter or more, and is preferably 1.8 mol / liter or less, particularly preferably 1.5 mol / liter or less.
非水溶媒としても、従来から非水系電解液の溶媒として公知のものの中から適宜選択して用いることができる。例えば、アルキレンカーボネート類、ジアルキルカーボネート類、環状エーテル類、環状カルボン酸エステル類、鎖状カルボン酸エステル類、含燐有機溶媒等が挙げられる。
アルキレン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炭素数２〜４のアルキレン基を有するアルキレンカーボネートが挙げられ、これらの中では、エチレンカーボネート、プロピレンカーボネートが好ましい。
As the non-aqueous solvent, it can be appropriately selected from conventionally known solvents for non-aqueous electrolyte solutions. Examples thereof include alkylene carbonates, dialkyl carbonates, cyclic ethers, cyclic carboxylic acid esters, chain carboxylic acid esters, and phosphorus-containing organic solvents.
Examples of the alkylene carbonates include alkylene carbonates having an alkylene group having 2 to 4 carbon atoms such as ethylene carbonate, propylene carbonate, and butylene carbonate. Among these, ethylene carbonate and propylene carbonate are preferable.
ジアルキルカーボネート類としては、ジメチルカーボネート、ジエチルカーボネート、ジ−ｎ−プロピルカーボネート、エチルメチルカーボネート、メチル−ｎ−プロピルカーボネート、エチル−ｎ−プロピルカーボネート等の炭素数１〜４のアルキル基を有するジアルキルカーボネートが挙げられる。これらの中では、ジメチルカーボネート、ジエチルカーボネート、エチルメチルカーボネートが好ましい。 Examples of dialkyl carbonates include dimethyl carbonate, diethyl carbonate, di-n-propyl carbonate, ethyl methyl carbonate, methyl n-propyl carbonate, ethyl n-propyl carbonate, and the like, which are alkyl groups having 1 to 4 carbon atoms. Is mentioned. Among these, dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate are preferable.
環状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等が挙げられる。
鎖状エーテル類としては、ジメトキシエタン、ジメトキシメタン等が挙げられる。
環状カルボン酸エステル化合物としては、γ−ブチロラクトン、γ−バレロラクトン等が挙げられる。
Examples of cyclic ethers include tetrahydrofuran and 2-methyltetrahydrofuran.
Examples of chain ethers include dimethoxyethane and dimethoxymethane.
Examples of cyclic carboxylic acid ester compounds include γ-butyrolactone and γ-valerolactone.
鎖状カルボン酸エステルとしては、酢酸メチル、プロピオン酸メチル、プロピオン酸エチル、酪酸メチル等が挙げられる。
含燐有機溶媒としては、リン酸トリメチル、リン酸トリエチル、リン酸ジメチルエチル、リン酸メチルジエチル、リン酸エチレンメチル、リン酸エチレンエチル等が挙げられる。
Examples of chain carboxylic acid esters include methyl acetate, methyl propionate, ethyl propionate, and methyl butyrate.
Examples of the phosphorus-containing organic solvent include trimethyl phosphate, triethyl phosphate, dimethyl ethyl phosphate, methyl diethyl phosphate, ethylene methyl phosphate, ethylene ethyl phosphate, and the like.
これらは単独で用いても、２種類以上を併用してもよいが、２種以上の化合物を併用するのが好ましい。例えば、アルキレンカーボネートや環状カルボン酸エステル等の高誘電率溶媒と、ジアルキルカーボネートや鎖状カルボン酸エステル等の低粘度溶媒とを併用するのが好ましい。
非水溶媒の好ましい組合せの一つは、アルキレンカーボネートとジアルキルカーボネートを主体とする組合せである。なかでも、非水溶媒に占めるアルキレンカーボネートとジアルキルカーボネートとの合計が、８５容量％以上、好ましくは９０容量％以上、より好ましくは９５容量％以上であり、かつアルキレンカーボネートとジアルキルカーボネートとの容量比が１０：９０〜４５：５５、好ましくは２０：８０〜４５：５５のものである。この混合溶媒にリチウム塩と一般式（１）で表される化合物を含有させた非水系電解液は、サイクル特性と大電流放電特性およびガス発生抑制のバランスがよくなるので好ましい。
These may be used alone or in combination of two or more, but it is preferable to use in combination of two or more. For example, it is preferable to use a high dielectric constant solvent such as alkylene carbonate or cyclic carboxylic acid ester in combination with a low viscosity solvent such as dialkyl carbonate or chain carboxylic acid ester.
One preferable combination of the non-aqueous solvents is a combination mainly composed of alkylene carbonate and dialkyl carbonate. Among them, the total of alkylene carbonate and dialkyl carbonate in the non-aqueous solvent is 85% by volume or more, preferably 90% by volume or more, more preferably 95% by volume or more, and the volume ratio of alkylene carbonate to dialkyl carbonate. Of 10:90 to 45:55, preferably 20:80 to 45:55. A non-aqueous electrolyte solution containing a lithium salt and a compound represented by the general formula (1) in this mixed solvent is preferable because the balance between cycle characteristics, large current discharge characteristics, and gas generation suppression is improved.
アルキレンカーボネートとジアルキルカーボネートの好ましい組み合わせの具体例としては、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ジエチルカーボネート、エチレンカーボネートとエチルメチルカーボネート、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ジメチルカーボネートとエチルメチルカーボネート、エチレンカーボネートとジエチルカーボネートとエチルメチルカーボネート、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とエチルメチルカーボネート等が挙げられる。 Specific examples of preferred combinations of alkylene carbonate and dialkyl carbonate include ethylene carbonate and dimethyl carbonate, ethylene carbonate and diethyl carbonate, ethylene carbonate and ethyl methyl carbonate, ethylene carbonate and dimethyl carbonate and diethyl carbonate, ethylene carbonate and dimethyl carbonate and ethyl methyl. Examples thereof include carbonate, ethylene carbonate, diethyl carbonate and ethyl methyl carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate.
これらのエチレンカーボネートとジアルキルカーボネートとの組み合わせに、更にプロピレンカーボネートを加えた組み合わせも、好ましい組み合わせとして挙げられる。
プロピレンカーボネートを含有する場合には、エチレンカーボネートとプロピレンカーボネートの容量比は、通常９９：１〜４０：６０、好ましくは９５：５〜５０：５０である。
A combination in which propylene carbonate is further added to the combination of these ethylene carbonate and dialkyl carbonate is also mentioned as a preferable combination.
When propylene carbonate is contained, the volume ratio of ethylene carbonate to propylene carbonate is usually 99: 1 to 40:60, preferably 95: 5 to 50:50.
これらの中で、非対称ジアルキルカーボネートであるエチルメチルカーボネートを含有するものが更に好ましく、特に、エチレンカーボネートとジメチルカーボネートとエチルメチルカーボネート、エチレンカーボネートとジエチルカーボネートとエチルメチルカーボネート、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とエチルメチルカーボネートのエチレンカーボネートと対称ジアルキルカーボネートと非対称ジアルキルカーボネートを含有するものが、サイクル特性と大電流放電特性のバランスが良いので好ましい。 Among these, those containing ethyl methyl carbonate, which is an asymmetric dialkyl carbonate, are more preferable, and in particular, ethylene carbonate and dimethyl carbonate and ethyl methyl carbonate, ethylene carbonate and diethyl carbonate and ethyl methyl carbonate, ethylene carbonate and dimethyl carbonate and diethyl. Carbonate and ethyl methyl carbonate, ethylene carbonate, symmetric dialkyl carbonate and asymmetric dialkyl carbonate are preferred because they provide a good balance between cycle characteristics and large current discharge characteristics.
非水溶媒のなかで、好ましいものの他の一つとしては、エチレンカーボネート、プロピレンカーボネート、γ−ブチロラクトンおよびγ−バレロラクトンよりなる群から選ばれた有機溶媒を６０容量％以上含有するものである。この混合溶媒にリチウム塩と一般式（１）で表される化合物を含有させた非水系電解液は、高温で使用しても溶媒の蒸発や液漏れが少なくなる。なかでも、非水溶媒に占めるエチレンカーボネートとγ−ブチロラクトンとの合計が、８０容量％以上、好ましくは９０容量％以上であり、かつエチレンカーボネートとγ−ブチロラクトンとの容量比が５：９５〜４５：５５であるもの、または非水溶媒に占めるエチレンカーボネートとプロピレンカーボネートとの合計が、８０容量％以上、好ましくは９０容量％以上であり、かつエチレンカーボネートとプロピレンカーボネートの容量比が３０：７０〜６０：４０であるものである。この混合溶媒にリチウム塩と一般式（１）で表される化合物を含有させた非水系電解液は、サイクル特性と大電流放電特性等のバランスがよくなるので好ましい。 Among the non-aqueous solvents, another preferable one is one containing 60% by volume or more of an organic solvent selected from the group consisting of ethylene carbonate, propylene carbonate, γ-butyrolactone and γ-valerolactone. A non-aqueous electrolytic solution in which a lithium salt and a compound represented by the general formula (1) are contained in this mixed solvent reduces evaporation of the solvent and leakage even when used at a high temperature. Among these, the total of ethylene carbonate and γ-butyrolactone in the nonaqueous solvent is 80% by volume or more, preferably 90% by volume or more, and the volume ratio of ethylene carbonate and γ-butyrolactone is 5:95 to 45%. : 55, or the total of ethylene carbonate and propylene carbonate in the non-aqueous solvent is 80% by volume or more, preferably 90% by volume or more, and the volume ratio of ethylene carbonate to propylene carbonate is 30:70 to 60:40. A non-aqueous electrolyte solution containing a lithium salt and a compound represented by the general formula (1) in this mixed solvent is preferable because the balance between cycle characteristics and large current discharge characteristics is improved.
また、非水溶媒として含燐有機溶媒を用いるのも好ましい。含燐有機溶媒を非水溶媒中に、通常１０容量％以上、好ましくは１０〜８０容量％となるように含有させると、電解液の燃焼性を低下させることができる。特に、含燐有機溶媒と、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、γ−バレロラクトンおよびジアルキルカーボネートよりなる群から選ばれた非水溶媒を組み合わせて用いると、サイクル特性と大電流放電特性とのバランスがよくなるので好ましい。 It is also preferable to use a phosphorus-containing organic solvent as the non-aqueous solvent. When the phosphorus-containing organic solvent is contained in the non-aqueous solvent so as to be usually 10% by volume or more, preferably 10 to 80% by volume, the flammability of the electrolytic solution can be lowered. In particular, when a phosphorus-containing organic solvent and a nonaqueous solvent selected from the group consisting of ethylene carbonate, propylene carbonate, γ-butyrolactone, γ-valerolactone and dialkyl carbonate are used in combination, cycle characteristics and large current discharge characteristics This is preferable because the balance is improved.
なお、本明細書において、非水溶媒の容量は２５℃での測定値であるが、エチレンカーボネートのように２５℃で固体のものは融点での測定値を用いる。
一般式（１）で表される化合物において、Ｒ1〜Ｒ3はそれぞれ独立して、フッ素原子で置換されていてもよい炭素数１〜１２のアルキル基、フッ素原子で置換されていてもよい炭素数２〜１２のアルケニル基、フッ素原子で置換されていてもよい炭素数６〜１２のアリール基、フッ素原子で置換されていてもよい炭素数７〜１２のアラルキル基を表す。
In the present specification, the capacity of the non-aqueous solvent is a measured value at 25 ° C., but a measured value at the melting point is used for a solid at 25 ° C. such as ethylene carbonate.
In the compound represented by the general formula (1), R 1 to R 3 are each independently an alkyl group having 1 to 12 carbon atoms which may be substituted with a fluorine atom, or may be substituted with a fluorine atom. An alkenyl group having 2 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms which may be substituted with a fluorine atom, and an aralkyl group having 7 to 12 carbon atoms which may be substituted with a fluorine atom are represented.
なお、Ｒ2とＲ3は結合して含窒素脂肪族環を形成してもよく、含窒素脂肪族環としては、ピロリジン、ピペリジンなどが挙げられる。
また、Ｒ1とＲ2は結合して、環状構造を形成してもよく、環状構造としては、スルタム類が挙げられる。
炭素数１〜１２のアルキル基としてはメチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、ｎ−ブチル基、ｉ−ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ペンチル基等が挙げられる。なかでも好ましいのは炭素数１〜８、特に炭素数１〜４のアルキル基である。
R 2 and R 3 may combine to form a nitrogen-containing aliphatic ring, and examples of the nitrogen-containing aliphatic ring include pyrrolidine and piperidine.
R 1 and R 2 may combine to form a cyclic structure, and examples of the cyclic structure include sultams.
Examples of the alkyl group having 1 to 12 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, and pentyl group. Can be mentioned. Among these, an alkyl group having 1 to 8 carbon atoms, particularly 1 to 4 carbon atoms is preferable.
炭素数２〜１２のアルケニル基としてはビニル基、プロペニル基等が挙げられるが、炭素数２〜８、特に炭素数２〜４のものが好ましい。
炭素数６〜１２のアリール基としては、フェニル基、トリル基、キシリル基等が挙げられ、なかでもフェニル基が好ましい。
炭素数７〜１２のアラルキル基としては、ベンジル基、フェネチル基等が挙げられる。
Examples of the alkenyl group having 2 to 12 carbon atoms include a vinyl group and a propenyl group, and those having 2 to 8 carbon atoms, particularly those having 2 to 4 carbon atoms are preferable.
Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a tolyl group, and a xylyl group, and among them, a phenyl group is preferable.
Examples of the aralkyl group having 7 to 12 carbon atoms include benzyl group and phenethyl group.
これらのアルキル基、アルケニル基、アリール基、アラルキル基は、水素原子の一部または全部がフッ素原子で置換されていてもよいが、フッ素原子で置換されていないものが好ましい。
一般式（１）で表される化合物の具体例としては、Ｎ，Ｎ−ジメチルメタンスルホンアミド、Ｎ，Ｎ−ジエチルメタンスルホンアミド、Ｎ，Ｎ−ジプロピルメタンスルホンアミド、Ｎ−メチル−Ｎ−エチルメタンスルホンアミド、Ｎ−メチル−Ｎ−ベンジルメタンスルホンアミド、１−メタンスルホニルピロリジン、１−メタンスルホニルピペリジン、Ｎ，Ｎ−ビストリフルオロメチルメタンスルホンアミド等のメタンスルホンアミド類、Ｎ，Ｎ−ジエチルエタンスルホンアミド、Ｎ，Ｎ−ジメチルエタンスルホンアミド、Ｎ−メチル−Ｎ−エチルエタンスルホンアミド等のエタンスルホンアミド類、Ｎ，Ｎ−ジメチルビニルスルホンアミド等のビニルスルホンアミド類、Ｎ，Ｎ−ジメチルベンゼンスルホンアミド、Ｎ，Ｎ−ジエチルベンゼンスルホンアミド、Ｎ，Ｎ−ジプロピルベンゼンスルホンアミド、Ｎ，Ｎ−ジブチルベンゼンスルホンアミド等のベンゼンスルホンアミド類、Ｎ，Ｎ−ジメチルトリフルオロメタンスルホンアミド、Ｎ，Ｎ−ビストリフルオロメチルトリフルオロメタンスルホンアミド等のトリフルオロメタンスルホンアミド類、Ｎ，Ｎ−ジメチルペンタフルオロエタンスルホンアミド等のペンタフルオロエタンスルホンアミド類、Ｎ−メチルプロパンスルタム、Ｎ−エチルプロパンスルタム、Ｎ−ブチルプロパンスルタム、Ｎ−メチルブタンスルタム、Ｎ−エチルブタンスルタム、Ｎ−プロピルブタンスルタム等のスルタム類等が挙げられる。
In these alkyl groups, alkenyl groups, aryl groups and aralkyl groups, some or all of the hydrogen atoms may be substituted with fluorine atoms, but those not substituted with fluorine atoms are preferred.
Specific examples of the compound represented by the general formula (1) include N, N-dimethylmethanesulfonamide, N, N-diethylmethanesulfonamide, N, N-dipropylmethanesulfonamide, N-methyl-N- Methanesulfonamides such as ethylmethanesulfonamide, N-methyl-N-benzylmethanesulfonamide, 1-methanesulfonylpyrrolidine, 1-methanesulfonylpiperidine, N, N-bistrifluoromethylmethanesulfonamide, N, N-diethyl Ethanesulfonamides such as ethanesulfonamide, N, N-dimethylethanesulfonamide, N-methyl-N-ethylethanesulfonamide, vinylsulfonamides such as N, N-dimethylvinylsulfonamide, N, N-dimethyl Benzenesulfonamide, N, N-diethylbenze Benzenesulfonamides such as sulfonamide, N, N-dipropylbenzenesulfonamide, N, N-dibutylbenzenesulfonamide, N, N-dimethyltrifluoromethanesulfonamide, N, N-bistrifluoromethyltrifluoromethanesulfonamide, etc. Trifluoromethanesulfonamides, pentafluoroethanesulfonamides such as N, N-dimethylpentafluoroethanesulfonamide, N-methylpropane sultam, N-ethylpropane sultam, N-butylpropane sultam, N-methyl Examples include sultams such as butane sultam, N-ethylbutane sultam, N-propylbutane sultam, and the like.
これらの中でも、メタンスルホンアミド類、エタンスルホンアミド類が好ましく、発生ガス量が少なく、かつ、高温保存後の残存容量が高いので、Ｎ，Ｎ−ジメチルメタンスルホンアミド、Ｎ，Ｎ−ジエチルメタンスルホンアミド、Ｎ，Ｎ−ジエチルエタンスルホンアミド、Ｎ，Ｎ−ジメチルエタンスルホンアミドが特に好ましい。これらは単独で用いても、２種類以上を併用してもよい。 Among these, methanesulfonamides and ethanesulfonamides are preferable, and the amount of generated gas is small, and the remaining capacity after high-temperature storage is high. Therefore, N, N-dimethylmethanesulfonamide, N, N-diethylmethanesulfone Amides, N, N-diethylethanesulfonamide, and N, N-dimethylethanesulfonamide are particularly preferred. These may be used alone or in combination of two or more.
非水系電解液中における一般式（１）で表される化合物の割合は、通常０．０１質量％以上、好ましくは０．０５質量％以上、特に好ましくは０．１質量％以上であり、通常５質量％以下、好ましくは４質量％以下、特に好ましくは３質量％以下である。一般式（１）の化合物の割合が小さすぎると連続充電時のガス発生を十分に抑えられない。一方、大きすぎると電池の保存特性が低下する傾向にある。 The proportion of the compound represented by the general formula (1) in the non-aqueous electrolyte is usually 0.01% by mass or more, preferably 0.05% by mass or more, particularly preferably 0.1% by mass or more. 5% by mass or less, preferably 4% by mass or less, particularly preferably 3% by mass or less. If the ratio of the compound of the general formula (1) is too small, gas generation during continuous charging cannot be sufficiently suppressed. On the other hand, if it is too large, the storage characteristics of the battery tend to deteriorate.
本発明に係る非水系電解液は、本発明の効果を損ねない範囲で、分子内に不飽和結合を有する環状炭酸エステルや従来公知の過充電防止剤、脱酸剤、脱水剤などの種々の助剤を含有していてもよい。
分子内に不飽和結合を有する環状炭酸エステルとしては、ビニレンカーボネート系化合物、ビニルエチレンカーボネート系化合物、メチレンエチレンカーボネート系化合物等が挙げられ、これらのうち、ビニレンカーボネート、ビニルエチレンカーボネート、特にビニレンカーボネートが好ましい。
The non-aqueous electrolyte solution according to the present invention is not limited to various effects such as a cyclic carbonate having an unsaturated bond in the molecule, a conventionally known overcharge inhibitor, a deoxidizer, and a dehydrator as long as the effects of the present invention are not impaired. An auxiliary agent may be contained.
Examples of the cyclic carbonate having an unsaturated bond in the molecule include vinylene carbonate compounds, vinyl ethylene carbonate compounds, methylene ethylene carbonate compounds, etc. Among these, vinylene carbonate, vinyl ethylene carbonate, particularly vinylene carbonate are included. preferable.
ビニレンカーボネート系化合物としては、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、４，５−ジメチルビニレンカーボネート、４，５−ジエチ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等が挙げられる。
ビニルエチレンカーボネート系化合物としては、ビニルエチレンカーボネート、４−メチル−４−ビニルエチレンカーボネート、４−エチル−４−ビニルエチレンカーボネート、４−ｎ−プロピル−４−ビニルエチレンカーボネート、５−メチル−４−ビニルエチレンカーボネート、４，４−ジビニルエチレンカーボネート、４，５−ジビニルエチレンカーボネート等が挙げられる。
Examples of the vinylene carbonate-based compound include vinylene carbonate, methyl vinylene carbonate, ethyl vinylene carbonate, 4,5-dimethyl vinylene carbonate, 4,5-diethyl vinylene carbonate, fluorovinylene carbonate, trifluoromethyl vinylene carbonate, and the like.
Examples of the vinyl ethylene carbonate compound include vinyl ethylene carbonate, 4-methyl-4-vinyl ethylene carbonate, 4-ethyl-4-vinyl ethylene carbonate, 4-n-propyl-4-vinyl ethylene carbonate, 5-methyl-4- Examples include vinyl ethylene carbonate, 4,4-divinyl ethylene carbonate, 4,5-divinyl ethylene carbonate, and the like.
メチレンエチレンカーボネート系化合物としては、４，４−ジメチル−５−メチレンエチレンカーボネート、４，４−ジエチル−５−メチレンエチレンカーボネート等が挙げられる。
これらは単独で用いても、２種類以上を併用してもよい。
非水系電解液が分子内に不飽和結合を有する環状炭酸エステル化合物を含有する場合、非水系電解液中におけるその割合は、通常０．０１質量％以上、好ましくは０．１質量％以上、特に好ましくは０．３質量％以上、最も好ましくは０．５質量％以上であり、通常８質量％以下、好ましくは４質量％以下、特に好ましくは３質量％以下である。
Examples of the methylene ethylene carbonate compound include 4,4-dimethyl-5-methylene ethylene carbonate and 4,4-diethyl-5-methylene ethylene carbonate.
These may be used alone or in combination of two or more.
When the non-aqueous electrolyte contains a cyclic carbonate compound having an unsaturated bond in the molecule, the proportion in the non-aqueous electrolyte is usually 0.01% by mass or more, preferably 0.1% by mass or more, particularly Preferably it is 0.3 mass % or more, Most preferably, it is 0.5 mass % or more, Usually 8 mass % or less, Preferably it is 4 mass % or less, Most preferably, it is 3 mass % or less.
分子内に不飽和結合を有する環状炭酸エステルを電解液に含有させることにより、電池のサイクル特性を向上させることができる。その理由は明かではないが、負極の表面に安定な保護被膜を形成することができるためと推測される。含有量が少ないとこの特性が十分に向上しない。なお、分子内に不飽和結合を有する環状炭酸エステルを電解液中に含有させると、一般に連続充電時においてガスの発生量が増加するという問題があるが、一般式（１）で表される化合物と併用するとガス発生量の増加を抑制することができる。しかし、含有量が多すぎると高温保存時にガスが発生し、電池の内圧が上昇することがあるので、含有量は上記の範囲にするのが好ましい。 By including in the electrolyte a cyclic carbonate having an unsaturated bond in the molecule, the cycle characteristics of the battery can be improved. Although the reason is not clear, it is presumed that a stable protective film can be formed on the surface of the negative electrode. If the content is small, this property is not sufficiently improved. In addition, when a cyclic carbonate having an unsaturated bond in the molecule is contained in the electrolyte, there is a problem that the amount of gas generated generally increases during continuous charging, but the compound represented by the general formula (1) When used together, an increase in the amount of gas generated can be suppressed. However, if the content is too high, gas is generated during high-temperature storage, and the internal pressure of the battery may increase. Therefore, the content is preferably in the above range.
特に、一般式（１）で表される化合物のうちでも、水素原子の一部または全部がフッ素原子で置換された化合物は、還元分解されやすいので、負極の表面に安定な保護被膜を形成できる分子内に不飽和結合を有する環状炭酸エステルを併用することにより、還元分解を抑制できると考えられる。
過充電防止剤としては、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；２，４−ジフルオロアニソール、２，５−ジフルオロアニソールおよび２，６−ジフルオロアニソ−ル等の含フッ素アニソール化合物などが挙げられる。これらは２種類以上併用して用いてもよい。非水系電解液中における過充電防止剤の割合は、通常０．１〜５質量％である。過充電防止剤を含有させることにより、過充電等のときに電池の破裂・発火を抑制することができる。
In particular, among the compounds represented by the general formula (1), compounds in which some or all of the hydrogen atoms are substituted with fluorine atoms are easily reductively decomposed, so that a stable protective film can be formed on the surface of the negative electrode. It is considered that reductive decomposition can be suppressed by using a cyclic carbonate having an unsaturated bond in the molecule.
As the overcharge inhibitor, aromatic compounds such as biphenyl, alkylbiphenyl, terphenyl, partially hydrogenated terphenyl, cyclohexylbenzene, t-butylbenzene, t-amylbenzene, diphenyl ether, dibenzofuran; 2-fluorobiphenyl, Partially fluorinated products of the above aromatic compounds such as o-cyclohexylfluorobenzene and p-cyclohexylfluorobenzene; fluorinated anisole compounds such as 2,4-difluoroanisole, 2,5-difluoroanisole and 2,6-difluoroanisole Etc. Two or more of these may be used in combination. The ratio of the overcharge inhibitor in the non-aqueous electrolyte is usually 0.1 to 5% by mass . By containing an overcharge preventing agent, rupture / ignition of the battery can be suppressed during overcharge or the like.
一般にこれらの過充電防止剤は、電解液の溶媒成分よりも正極および負極上で反応しやすいために、連続充電時や高温保存時においても電極の活性の高い部位で反応してしまい、これらの化合物が反応すると電池の内部抵抗が大きく上昇したり、ガス発生によって、連続充電後の放電特性や、高温保存後の放電特性を著しく低下させる原因となっていたが、本発明の電解液に添加した場合は、放電特性の低下を抑制することができる。 In general, these overcharge inhibitors react more easily on the positive electrode and the negative electrode than the solvent component of the electrolytic solution, and thus react at a highly active site of the electrode even during continuous charging or storage at high temperatures. When the compound reacts, the internal resistance of the battery is greatly increased, or the generation of gas causes the discharge characteristics after continuous charging and the discharge characteristics after high temperature storage to be significantly reduced. In this case, it is possible to suppress a decrease in discharge characteristics.
他の助剤としては、フルオロエチレンカーボネート、トリフルオロプロピレンカーボネート、フェニルエチレンカーボネート、エリスリタンカーボネートおよびスピロ−ビス−ジメチレンカーボネート等のカーボネート化合物；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、無水グルタコン酸、無水イタコン酸、無水ジグリコール酸、シクロヘキサンジカルボン酸無水物、シクロペンタンテトラカルボン酸二無水物およびフェニルコハク酸無水物等のカルボン酸無水物；エチレンサルファイト、１，３−プロパンスルトン、１，４−ブタンスルトン、メタンスルホン酸メチル、ブスルファン、スルホラン、スルホレン、ジメチルスルホンおよびテトラメチルチウラムモノスルフィド等の含硫黄化合物；１−メチル−２−ピロリジノン、１−メチル−２−ピペリドン、３−メチル−２−オキサゾリジノン、１，３−ジメチル−２−イミダゾリジノンおよびＮ−メチルスクシイミド等の含窒素化合物；ヘプタン、オクタン、シクロヘプタン等の炭化水素化合物、フルオロベンゼン、ジフルオロベンゼン、ヘキサフルオロベンゼン、ベンゾトリフルオライド等の含フッ素芳香族化合物などが挙げられる。これらは２種類以上併用して用いてもよい。 Other auxiliaries include carbonate compounds such as fluoroethylene carbonate, trifluoropropylene carbonate, phenylethylene carbonate, erythritan carbonate and spiro-bis-dimethylene carbonate; succinic anhydride, glutaric anhydride, maleic anhydride, citracone anhydride Carboxylic acid anhydrides such as acid, glutaconic anhydride, itaconic anhydride, diglycolic anhydride, cyclohexanedicarboxylic anhydride, cyclopentanetetracarboxylic dianhydride and phenylsuccinic anhydride; ethylene sulfite, 1,3- Sulfur-containing compounds such as propane sultone, 1,4-butane sultone, methyl methanesulfonate, busulfan, sulfolane, sulfolene, dimethyl sulfone and tetramethylthiuram monosulfide; 1-methyl-2 Nitrogen-containing compounds such as pyrrolidinone, 1-methyl-2-piperidone, 3-methyl-2-oxazolidinone, 1,3-dimethyl-2-imidazolidinone and N-methylsuccinimide; heptane, octane, cycloheptane, etc. Examples thereof include hydrocarbon compounds, fluorine-containing aromatic compounds such as fluorobenzene, difluorobenzene, hexafluorobenzene, and benzotrifluoride. Two or more of these may be used in combination.
非水系電解液中におけるこれらの助剤の割合は、通常０．１〜５質量％である。これらの助剤を含有することにより、高温保存後の容量維持特性やサイクル特性を向上させることができる。
本発明に係る非水系電解液は、非水系有機溶媒に、リチウム塩、一般式（１）で表される化合物、および必要に応じて他の化合物を溶解することにより調製することができる。非水系電解液の調製に際しては、各原料は、予め脱水しておくのが好ましい。通常５０ｐｐｍ以下、好ましくは３０ｐｐｍ以下まで脱水するのがよい。
The ratio of these auxiliaries in the nonaqueous electrolytic solution is usually 0.1 to 5% by mass . By containing these auxiliaries, capacity maintenance characteristics and cycle characteristics after high-temperature storage can be improved.
The non-aqueous electrolyte solution according to the present invention can be prepared by dissolving a lithium salt, a compound represented by the general formula (1), and, if necessary, other compounds in a non-aqueous organic solvent. In preparing the non-aqueous electrolyte solution, each raw material is preferably dehydrated in advance. Usually, it is good to dehydrate to 50 ppm or less, preferably 30 ppm or less.
本発明に係る非水系電解液は、二次電池用、特にリチウム二次電池用の電解液として用いるのに好適である。以下、この電解液を用いた本発明に係るリチウム二次電池について説明する。
本発明に係るリチウム二次電池は、電解液以外は従来公知のリチウム二次電池と同様であり、通常、正極と負極とが本発明に係る非水系電解液が含浸されている多孔膜を介してケースに収納されている。従って、本発明に係る二次電池の形状は特に制限されるものではなく、円筒型、角型、ラミネート型、コイン型、大型等のいずれであってもよい。本発明に係るリチウム二次電池は、前述のように連続充電状態におけるガス発生量が少ないので、過充電等の異常時に電池内圧の上昇により作動する電流遮断装置を備えた電池の連続充電状態での電流遮断装置の異常作動を防止することができる。また、外装体の厚みが０．４ｍｍ以下で、外装体の材質が金属アルミニウムまたはアルミニウム合金を主体とした電池においては、電池内圧の上昇による電池のフクレという問題が生じやすいが、本発明に係るリチウム二次電池では、ガス発生が少ないので、このような問題が生ずるのを防止することができる。
The nonaqueous electrolytic solution according to the present invention is suitable for use as an electrolytic solution for a secondary battery, particularly for a lithium secondary battery. Hereinafter, a lithium secondary battery according to the present invention using this electrolytic solution will be described.
The lithium secondary battery according to the present invention is the same as a conventionally known lithium secondary battery except for the electrolytic solution, and usually the positive electrode and the negative electrode are interposed through a porous film impregnated with the nonaqueous electrolytic solution according to the present invention. In the case. Therefore, the shape of the secondary battery according to the present invention is not particularly limited, and may be any of a cylindrical shape, a square shape, a laminate shape, a coin shape, a large size, and the like. The lithium secondary battery according to the present invention has a small amount of gas generation in the continuous charge state as described above. The abnormal operation of the current interrupting device can be prevented. In addition, in a battery whose outer casing has a thickness of 0.4 mm or less and whose outer casing is mainly made of metal aluminum or aluminum alloy, there is a tendency for the battery to bulge due to an increase in battery internal pressure. Since lithium secondary batteries generate less gas, it is possible to prevent such problems from occurring.
負極活物質としては、リチウムを吸蔵・放出可能な炭素質材料や金属化合物、リチウム金属およびリチウム合金を用いることができる。これらの負極活物質は、単独で用いても、２種類以上を混合して用いてもよい。
リチウムを吸蔵・放出可能な炭素質材料としては、黒鉛や黒鉛の表面を黒鉛に比べて非晶質の炭素で被覆したものが好ましい。
As the negative electrode active material, a carbonaceous material or metal compound capable of inserting and extracting lithium, lithium metal and lithium alloy can be used. These negative electrode active materials may be used alone or in combination of two or more.
The carbonaceous material capable of inserting and extracting lithium is preferably graphite or a surface of graphite coated with amorphous carbon as compared with graphite.
黒鉛は、学振法によるＸ線回折で求めた格子面（００２面）のｄ値（層間距離）が０．３３５〜０．３３８ｎｍ、特に０．３３５〜０．３３７ｎｍであるものが好ましい。また、学振法によるＸ線回折で求めた結晶子サイズ（Ｌｃ）は、通常３０ｎｍ以上、好ましくは５０ｎｍ以上、特に好ましくは１００ｎｍ以上である。灰分は、通常１質量％以下、好ましくは０．５質量％以下、特に好ましくは０．１質量％以下である。 Graphite preferably has a lattice plane (002 plane) d value (interlayer distance) of 0.335 to 0.338 nm, particularly 0.335 to 0.337 nm, as determined by X-ray diffraction using the Gakushin method. The crystallite size (Lc) determined by X-ray diffraction by the Gakushin method is usually 30 nm or more, preferably 50 nm or more, particularly preferably 100 nm or more. The ash content is usually 1% by mass or less, preferably 0.5% by mass or less, and particularly preferably 0.1% by mass or less.
黒鉛の表面を非晶質の炭素で被覆したものとして好ましいのは、Ｘ線回折における格子面（００２面）のｄ値が０．３３５〜０．３３８ｎｍである黒鉛を核材とし、その表面に該核材よりもＸ線回折における格子面（００２面）のｄ値が大きい炭素質材料が付着しており、かつ核材と核材よりもＸ線回折における格子面（００２面）のｄ値が大きい炭素質材料との割合が質量比で９９／１〜８０／２０であるものである。これを用いると、高い容量で、かつ電解液と反応しにくい負極を製造することができる。 The graphite surface coated with amorphous carbon is preferably graphite having a d-value of 0.335 to 0.338 nm on the lattice plane (002 plane) in X-ray diffraction as a core material. A carbonaceous material having a larger d-value on the lattice plane (002 plane) in X-ray diffraction than the core material is attached, and the d-value on the lattice plane (002 plane) in X-ray diffraction is greater than that of the core material and the core material. The ratio with respect to the carbonaceous material having a large is 99/1 to 80/20 in mass ratio. When this is used, a negative electrode having a high capacity and hardly reacting with the electrolytic solution can be produced.
炭素質材料の粒径は、レーザー回折・散乱法によるメジアン径で、通常１μｍ以上、好ましくは３μｍ以上、より好ましくは５μｍ以上、最も好ましくは７μｍ以上であり、通常１００μｍ以下、好ましくは５０μｍ以下、より好ましくは４０μｍ以下、最も好ましくは３０μｍ以下である。
炭素質材料のＢＥＴ法による比表面積は、通常０．３ｍ2／ｇ以上、好ましくは０．５ｍ2／ｇ以上、より好ましくは０．７ｍ2／ｇ以上、最も好ましくは０．８ｍ2／ｇ以上であり、通常２５．０ｍ2／ｇ以下、好ましくは２０．０ｍ2／ｇ以下、より好ましくは１５．０ｍ2／ｇ以下、最も好ましくは１０．０ｍ2／ｇ以下である。
The particle size of the carbonaceous material is a median diameter measured by a laser diffraction / scattering method and is usually 1 μm or more, preferably 3 μm or more, more preferably 5 μm or more, most preferably 7 μm or more, and usually 100 μm or less, preferably 50 μm or less, More preferably, it is 40 micrometers or less, Most preferably, it is 30 micrometers or less.
The specific surface area of the carbonaceous material by the BET method is usually 0.3 m 2 / g or more, preferably 0.5 m 2 / g or more, more preferably 0.7 m 2 / g or more, and most preferably 0.8 m 2 / g. or more, usually 25.0 m 2 / g or less, preferably 20.0 m 2 / g, more preferably 15.0 m 2 / g or less, and most preferably 10.0 m 2 / g or less.
また、炭素質材料は、アルゴンイオンレーザー光を用いたラマンスペクトルで分析し、１５７０〜１６２０ｃｍ-1の範囲にあるピークＰAのピーク強度をＩA、１３００〜１４００ｃｍ-1の範囲にあるピークＰBのピーク強度をＩBとした場合、ＩBとＩAの比で表されるＲ値（＝ＩB／ＩA）が、０．０１〜０．７の範囲であるものが好ましい。また、１５７０〜１６２０ｃｍ-1の範囲にあるピークの半値幅が、２６ｃｍ-1以下、特に２５ｃｍ-1以下であるものが好ましい。
リチウムを吸蔵・放出可能な金属化合物としては、Ａｇ、Ｚｎ、Ａｌ、Ｇａ、Ｉｎ、Ｓｉ、Ｇｅ、Ｓｎ、Ｐｂ、Ｐ、Ｓｂ、Ｂｉ、Ｃｕ、Ｎｉ、Ｓｒ、Ｂａ等の金属を含有する化合物が挙げられ、これらの金属は単体、酸化物、リチウムとの合金などとして用いられる。本発明においては、Ｓｉ、Ｓｎ、Ｇｅ及びＡｌから選ばれる元素を含有するものが好ましく、Ｓｉ、Ｓｎ及びＡｌから選ばれる金属の酸化物又はリチウム合金がより好ましい。
リチウムを吸蔵・放出可能な金属化合物あるいはこの酸化物やリチウムとの合金は、一般に黒鉛に代表される炭素材料に比較し、単位質量あたりの容量が大きいので、より高エネルギー密度が求められるリチウムイオン二次電池において好適である。
Further, the carbonaceous material is analyzed by Raman spectrum using argon ion laser light, the peak is the peak intensity of the peak P A in the range of 1570~1620cm -1 I A, in the range of 1300~1400cm -1 P If the peak intensity of the B was I B, R value represented by the ratio of I B and I a (= I B / I a) is what is preferably in the range of 0.01 to 0.7. Further, the half width of the peak in the range of 1570～1620Cm -1 is, 26cm -1 or less, are preferred in particular 25 cm -1 or less.
Examples of metal compounds capable of inserting and extracting lithium include compounds containing metals such as Ag, Zn, Al, Ga, In, Si, Ge, Sn, Pb, P, Sb, Bi, Cu, Ni, Sr, and Ba. These metals are used as simple substances, oxides, alloys with lithium, and the like. In the present invention, those containing an element selected from Si, Sn, Ge and Al are preferred, and oxides or lithium alloys of metals selected from Si, Sn and Al are more preferred.
Lithium ions that require higher energy density because metal compounds that can occlude and release lithium, or their oxides and alloys with lithium, generally have a larger capacity per unit mass than carbon materials typified by graphite. It is suitable for a secondary battery.
正極活物質としては、リチウムコバルト酸化物、リチウムニッケル酸化物、リチウムマンガン酸化物等のリチウム遷移金属複合酸化物材料などのリチウムを吸蔵・放出可能な材料が挙げられる。これらの化合物は、ＬｉXＣｏＯ2、ＬｉXＮｉＯ2、ＬｉXＭｎＯ2、ＬｉXＣｏ1-yＭyＯ2、ＬｉXＮｉ1-yＭyＯ2、ＬｉXＭｎ1-yＭyＯ2等であり、ここでＭはＦｅ、Ｃｏ、Ｎｉ、Ｍｎ、Ｍｇ、Ｃｕ、Ｚｎ、Ａｌ、Ｓｎ、Ｂ、Ｇａ、Ｃｒ、Ｖ、Ｓｒ、Ｔｉから選ばれる少なくとも１種であり、０．４≦ｘ≦１．２、０≦ｙ≦０．６である。 Examples of the positive electrode active material include materials capable of inserting and extracting lithium, such as lithium transition metal composite oxide materials such as lithium cobalt oxide, lithium nickel oxide, and lithium manganese oxide. These compounds are Li x CoO 2 , Li x NiO 2 , Li x MnO 2 , Li x Co 1 -y My O 2 , Li x Ni 1 -y My O 2 , Li x Mn 1 -y My O 2 or the like, where M is at least one selected from Fe, Co, Ni, Mn, Mg, Cu, Zn, Al, Sn, B, Ga, Cr, V, Sr, Ti; 4 ≦ x ≦ 1.2 and 0 ≦ y ≦ 0.6.
特にＬｉXＣｏ1-yＭyＯ2、ＬｉXＮｉ1-yＭyＯ2、ＬｉXＭｎ1-yＭyＯ2等で表される、コバルト、ニッケル、マンガンの一部を他の金属で置き換えたものは、その構造を安定化させることができるので好ましい。正極活物質は単独で用いても、複数を併用しても良い。
活物質を結着する結着剤としては、電極製造時に使用する溶媒や電解液に対して安定な材料であれば、任意のものを使用することができる。例えば、ポリフッ化ビニリデン、ポリテトラフルオロエチレン等のフッ素系樹脂、ポリエチレン、ポリプロピレン等のポリオレフィン、スチレン・ブタジエンゴム、イソプレンゴム、ブタジエンゴム等の不飽和結合を有するポリマー及びその共重合体、エチレン−アクリル酸共重合体、エチレン−メタクリル酸共重合体等のアクリル酸系ポリマー及びその共重合体などが挙げられる。
Especially represented by Li X Co 1-y M y O 2, Li X Ni 1-y M y O 2, Li X Mn 1-y M y O 2 , etc., cobalt, nickel, and other part of manganese A metal replacement is preferable because the structure can be stabilized. The positive electrode active materials may be used alone or in combination.
As the binder for binding the active material, any material can be used as long as it is a material that is stable with respect to the solvent and the electrolyte used in manufacturing the electrode. For example, fluororesins such as polyvinylidene fluoride and polytetrafluoroethylene, polyolefins such as polyethylene and polypropylene, polymers having unsaturated bonds such as styrene / butadiene rubber, isoprene rubber and butadiene rubber, and copolymers thereof, ethylene-acrylic Examples thereof include acrylic acid polymers such as acid copolymers and ethylene-methacrylic acid copolymers, and copolymers thereof.
電極中には、機械的強度や電気伝導度を高めるために増粘剤、導電材、充填剤などを含有させてもよい。
増粘剤としては、カルボキシルメチルセルロース、メチルセルロース、ヒドロキシメチルセルロース、エチルセルロース、ポリビニルアルコ−ル、酸化スターチ、リン酸化スターチ、ガゼイン等が挙げられる。
The electrode may contain a thickener, a conductive material, a filler and the like in order to increase mechanical strength and electrical conductivity.
Examples of the thickener include carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, ethyl cellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch, and casein.
導電材としては、銅またはニッケル等の金属材料、グラファイトまたはカーボンブラック等の炭素材料などが挙げられる。
電極の製造は、常法によればよい。例えば、負極または正極活物質に、結着剤、増粘剤、導電材、溶媒等を加えてスラリー化し、これを集電体に塗布、乾燥した後に、プレスすることによって形成することができる。
また、活物質に結着剤や導電材などを加えたものをそのままロール成形してシート電極としたり、圧縮成形によりペレット電極としたり、蒸着・スパッタ・メッキ等の手法で集電体上に電極材料の薄膜形成をすることもできる。
Examples of the conductive material include metal materials such as copper and nickel, and carbon materials such as graphite and carbon black.
The electrode may be manufactured by a conventional method. For example, it can be formed by adding a binder, a thickener, a conductive material, a solvent or the like to a negative electrode or a positive electrode active material to form a slurry, applying the slurry to a current collector, drying it, and then pressing it.
In addition, a material obtained by adding a binder or a conductive material to an active material is roll-formed as it is to form a sheet electrode, a pellet electrode is formed by compression molding, and an electrode is formed on the current collector by a technique such as vapor deposition, sputtering, or plating. A thin film of material can also be formed.
負極活物質層の乾燥、プレス後の密度は、通常１．４５ｇ／ｃｍ3以上であり、好まし
くは１．５５ｇ／ｃｍ3以上、特に好ましくは１．６０ｇ／ｃｍ3以上である。負極活物質層の密度が高いほど電池の容量が増加するので好ましい。また、正極活性層の乾燥、プレス後の密度は、通常３．０ｇ／ｃｍ3以上である。正極活性層の密度が低すぎると電池の
容量が不十分となる。
Drying of the negative electrode active material layer, the density after pressing is usually 1.45 g / cm 3 or more, preferably 1.55 g / cm 3 or more, particularly preferably 1.60 g / cm 3 or more. A higher density of the negative electrode active material layer is preferable because the battery capacity increases. The density of the positive electrode active layer after drying and pressing is usually 3.0 g / cm 3 or more. If the density of the positive electrode active layer is too low, the battery capacity becomes insufficient.
集電体としては各種のものが用いることができるが、通常は金属や合金が用いられる。負極の集電体としては、銅、ニッケル、ステンレス等が挙げられ、好ましいのは銅である。また、正極の集電体としては、アルミニウム、チタン、タンタル等の金属またはその合金が挙げられ、好ましいのはアルミニウムまたはその合金である。
正極と負極の間には、短絡を防止するために多孔膜を介在させる。この場合、電解液は多孔膜に含浸させて用いる。多孔膜の材質や形状は、電解液に安定であり、かつ保液性に優れていれば、特に制限はなく、ポリエチレン、ポリプロピレン等のポリオレフィンを原料とする多孔性シ−トまたは不織布等が好ましい。
Various types of current collectors can be used, but metals and alloys are usually used. Examples of the current collector for the negative electrode include copper, nickel, and stainless steel, and copper is preferred. Examples of the current collector for the positive electrode include metals such as aluminum, titanium, and tantalum, and alloys thereof, and aluminum or an alloy thereof is preferable.
A porous film is interposed between the positive electrode and the negative electrode to prevent a short circuit. In this case, the electrolytic solution is used by impregnating the porous membrane. The material and shape of the porous membrane is not particularly limited as long as it is stable to the electrolytic solution and has excellent liquid retention, and a porous sheet or nonwoven fabric made of polyolefin such as polyethylene and polypropylene is preferable. .
本発明に係る電池に使用する電池の外装体の材質も任意であり、ニッケルメッキを施した鉄、ステンレス、アルミニウムまたはその合金、ニッケル、チタン等が用いられる。 The material of the battery casing used in the battery according to the present invention is also arbitrary, and nickel-plated iron, stainless steel, aluminum or an alloy thereof, nickel, titanium, or the like is used.
以下に、実施例および比較例を挙げて本発明をさらに具体的に説明するが、本発明は、その要旨を超えない限りこれらの実施例に限定されるものではない。
［負極の製造］
Ｘ線回折における格子面（００２面）のｄ値が０．３３６ｎｍ、結晶子サイズ（Ｌｃ）が６５２ｎｍ、灰分が０．０７質量％、レーザー回折・散乱法によるメジアン径が１２μｍ、ＢＥＴ法による比表面積が７．５ｍ2／ｇ、アルゴンイオンレーザー光を用いたラマ
ンスペクトル分析から求めたＲ値（＝ＩB／ＩAが）０．１２、１５７０〜１６２０ｃｍ-1の範囲にあるピークの半値幅が１９．９ｃｍ-1である天然黒鉛粉末９４質量部とポリフッ化ビニリデン６質量部とを混合し、Ｎ−メチル−２−ピロリドンを加えスラリー状にした。このスラリーを厚さ１８μｍの銅箔の片面に均一に塗布、乾燥した後、負極活性層の密度が１．５ｇ／ｃｍ3になるようにプレスして負極とした。
［正極の製造］
ＬｉＣｏＯ2８５質量部、カーボンブラック６質量部とポリフッ化ビニリデン（呉羽化
学社製、商品名「ＫＦ−１０００」）９質量部を混合し、Ｎ−メチル−２−ピロリドンを
加えスラリー化し、これを厚さ２０μｍのアルミニウム箔の両面に均一に塗布、乾燥した後、正極活性層の密度が３．０ｇ／ｃｍ3になるようにプレスして正極とした。
［リチウム二次電池の製造］
上記の正極、負極、およびポリエチレン製のセパレーターを、負極、セパレーター、正極、セパレーター、負極の順に積層して電池要素を作製した。この電池要素をアルミニウム（厚さ４０μｍ）の両面を樹脂層で被覆したラミネートフィルムからなる袋内に正極負極の端子を突設させながら挿入した後、後述する電解液を袋内に注入し、真空封止を行い、シート状電池を作製した。
［容量評価］
リチウム二次電池を、電極間の密着性を高めるためにガラス板で挟んだ状態で、２５℃において、０．２Ｃに相当する定電流で４．２Ｖまで充電した後、０．２Ｃの定電流で３Ｖまで放電した。これを３サイクル行って電池を安定させ、４サイクル目は、０．５Ｃの定電流で４．２Ｖまで充電後、４．２Ｖの定電圧で電流値が０．０５Ｃになるまで充電を実施し、０．２Ｃの定電流で３Ｖまで放電して、初期放電容量を求めた。
［連続充電特性の評価］
容量評価試験の終了した電池を、エタノール浴中に浸して体積を測定した後、６０℃において、０．５Ｃの定電流で定電流充電を行い、４．２５Ｖに到達した後、定電圧充電に切り替え、１週間連続充電を行った。
EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to these examples unless it exceeds the gist.
[Manufacture of negative electrode]
The d value of the lattice plane (002 plane) in X-ray diffraction is 0.336 nm, the crystallite size (Lc) is 652 nm, the ash content is 0.07% by mass , the median diameter by laser diffraction / scattering method is 12 μm, and the ratio by BET method Surface area is 7.5 m 2 / g, R value (= I B / I A ) determined from Raman spectrum analysis using argon ion laser light is 0.12, and half width of peak in the range of 1570 to 1620 cm −1 There was mixed with natural graphite powder 94 parts by weight of polyvinylidene fluoride 6 parts by a 19.9cm -1, slurried added N- methyl-2-pyrrolidone. This slurry was uniformly applied to one side of a 18 μm thick copper foil, dried, and then pressed to obtain a negative electrode active layer having a density of 1.5 g / cm 3 to form a negative electrode.
[Production of positive electrode]
LiCoO 2 85 parts by weight of carbon black 6 parts by weight of polyvinylidene fluoride (Kureha Chemical Co., Ltd., trade name "KF-1000") 9 parts by weight were mixed and slurried added N- methyl-2-pyrrolidone, it After uniformly applying and drying on both surfaces of an aluminum foil having a thickness of 20 μm, the positive electrode active layer was pressed to a density of 3.0 g / cm 3 to obtain a positive electrode.
[Manufacture of lithium secondary batteries]
The positive electrode, the negative electrode, and the polyethylene separator were laminated in the order of the negative electrode, the separator, the positive electrode, the separator, and the negative electrode to prepare a battery element. This battery element was inserted into a bag made of a laminate film in which both surfaces of aluminum (thickness: 40 μm) were coated with a resin layer while projecting positive and negative terminals, and then an electrolyte solution described later was injected into the bag to create a vacuum. Sealing was performed to produce a sheet-like battery.
[Capacity evaluation]
A lithium secondary battery is charged to 4.2 V at a constant current corresponding to 0.2 C at 25 ° C. in a state of being sandwiched between glass plates in order to enhance adhesion between electrodes, and then a constant current of 0.2 C Was discharged to 3V. This is done for 3 cycles to stabilize the battery. In the 4th cycle, after charging to 4.2V with a constant current of 0.5C, charging is performed until the current value reaches 0.05C with a constant voltage of 4.2V. The initial discharge capacity was determined by discharging to 3 V at a constant current of 0.2C.
[Evaluation of continuous charge characteristics]
After the capacity evaluation test was completed, the volume was measured by immersing the battery in an ethanol bath. Then, constant current charging was performed at a constant current of 0.5 C at 60 ° C., and after reaching 4.25 V, constant voltage charging was performed. Switching was performed continuously for one week.
電池を冷却させた後、エタノール浴中に浸して体積を測定し、連続充電の前後の体積変化から発生したガス量を求めた。
発生ガス量の測定後、２５℃において０．２Ｃの定電流で３Ｖまで放電させ、連続充電試験後の残存容量を測定し、連続充電試験前の放電容量を１００とした場合の連続充電後の残存容量を求めた。
［高温保存特性の評価］
容量評価試験の終了した電池を、０．５Ｃの定電流で４．２Ｖまで充電後、４．２Ｖの定電圧で電流値が０．０５Ｃになるまで充電し、その後、８５℃で３日間保存した。電池を十分に冷却させた後、２５℃において０．２Ｃの定電流で３Ｖまで放電させて保存試験後の残存容量を測定し、保存試験前の放電容量を１００とした場合の保存後の残存容量を求めた。
［サイクル特性の評価］
容量評価試験の終了した電池を、２５℃において、０．５Ｃの定電流で４．２Ｖまで充電後、４．２Ｖの定電圧で電流値が０．０５Ｃになるまで充電し、１Ｃの定電流で３Ｖまで放電をするサイクル試験を実施した。サイクル試験前の放電容量を１００とした場合の２００サイクル後の放電容量を求めた。
（実施例１）
乾燥アルゴン雰囲気下、エチレンカーボネートとエチルメチルカーボネートとの混合物（容量比３：７）９９質量部にＮ，Ｎ−ジメチルメタンスルホンアミド１質量部を加え、次いで十分に乾燥したＬｉＰＦ6を１．０モル／リットルの割合となるように溶解して電
解液とした。
After the battery was cooled, it was immersed in an ethanol bath to measure the volume, and the amount of gas generated from the volume change before and after continuous charging was determined.
After measuring the amount of generated gas, discharge to 3 V at a constant current of 0.2 C at 25 ° C., measure the remaining capacity after the continuous charge test, and after the continuous charge when the discharge capacity before the continuous charge test is 100 The remaining capacity was determined.
[Evaluation of high-temperature storage characteristics]
After the capacity evaluation test is completed, the battery is charged to 4.2 V with a constant current of 0.5 C, charged to a current value of 0.05 C with a constant voltage of 4.2 V, and then stored at 85 ° C. for 3 days. did. After sufficiently cooling the battery, discharge to 3 V at a constant current of 0.2 C at 25 ° C., measure the remaining capacity after the storage test, and the remaining after storage when the discharge capacity before the storage test is 100 The capacity was determined.
[Evaluation of cycle characteristics]
After the capacity evaluation test was completed, the battery was charged at a constant current of 0.5 C to 4.2 V at 25 ° C., and then charged at a constant voltage of 4.2 V until the current value reached 0.05 C. A constant current of 1 C A cycle test was conducted to discharge to 3V. The discharge capacity after 200 cycles when the discharge capacity before the cycle test was taken as 100 was determined.
Example 1
Under a dry argon atmosphere, 1 part by mass of N, N-dimethylmethanesulfonamide was added to 99 parts by mass of a mixture of ethylene carbonate and ethyl methyl carbonate (volume ratio 3: 7), and then sufficiently dried LiPF 6 was added to 1.0 parts. It melt | dissolved so that it might become a ratio of mol / liter, and it was set as the electrolyte solution.
得られた電解液を用いて、リチウム二次電池を作成し、連続充電特性、高温保存特性、サイクル特性の評価を行った。連続充電特性、高温保存特性の評価結果を表−１に示す。サイクル特性の評価結果を表−２に示す。
（比較例１）
エチレンカーボネートとエチルメチルカーボネートとの混合物（容量比３：７）に十分に乾燥したＬｉＰＦ6を１．０モル／リットルの割合となるように溶解した電解液を用い
て、リチウム二次電池を作成し、連続充電特性、高温保存特性、サイクル特性の評価を行った。連続充電特性、高温保存特性の評価結果を表−１に示す。サイクル特性の評価結果を表−２に示す。
（比較例２）
エチレンカーボネートとエチルメチルカーボネートとの混合物（容量比３：７）９９質量部に1,1'-スルホニルジイミダゾール１質量部を加え、次いで十分に乾燥したＬｉＰＦ6を１．０モル／リットルの割合となるように溶解して電解液とした。この電解液を用いて、リチウム二次電池を作成し、連続充電特性、高温保存特性の評価を行った。結果を表−１に示す。
（実施例２）
エチレンカーボネートとエチルメチルカーボネートとの混合物（容量比３：７）９７質量部に、ビニレンカーボネート２質量部、Ｎ，Ｎ−ジメチルメタンスルホンアミド１質量部を加え、次いで十分に乾燥したＬｉＰＦ6を１．０モル／リットルの割合となるように
溶解して電解液とした。
Using the obtained electrolytic solution, a lithium secondary battery was prepared, and continuous charge characteristics, high-temperature storage characteristics, and cycle characteristics were evaluated. Table 1 shows the evaluation results of the continuous charge characteristics and the high temperature storage characteristics. The evaluation results of cycle characteristics are shown in Table-2.
(Comparative Example 1)
A lithium secondary battery was prepared using an electrolytic solution in which LiPF 6 sufficiently dried in a mixture of ethylene carbonate and ethyl methyl carbonate (capacity ratio 3: 7) was dissolved at a ratio of 1.0 mol / liter. Then, continuous charge characteristics, high-temperature storage characteristics, and cycle characteristics were evaluated. Table 1 shows the evaluation results of the continuous charge characteristics and the high temperature storage characteristics. The evaluation results of cycle characteristics are shown in Table-2.
(Comparative Example 2)
1 part by weight of 1,1′-sulfonyldiimidazole is added to 99 parts by weight of a mixture of ethylene carbonate and ethyl methyl carbonate (volume ratio 3: 7), and then fully dried LiPF 6 is added at a ratio of 1.0 mol / liter. It was dissolved so as to obtain an electrolyte solution. Using this electrolytic solution, a lithium secondary battery was prepared, and continuous charge characteristics and high-temperature storage characteristics were evaluated. The results are shown in Table-1.
(Example 2)
To 97 parts by mass of a mixture of ethylene carbonate and ethyl methyl carbonate (volume ratio 3: 7), 2 parts by mass of vinylene carbonate and 1 part by mass of N, N-dimethylmethanesulfonamide were added, and then LiPF 6 which was sufficiently dried was added to 1 part. An electrolytic solution was prepared by dissolving at a rate of 0.0 mol / liter.
この電解液を用いて、リチウム二次電池を作成し、連続充電特性、高温保存特性、サイクル特性の評価を行った。連続充電特性、高温保存特性の評価結果を表−１に示す。サイクル特性の評価結果を表−２に示す。
（比較例３）
エチレンカーボネートとエチルメチルカーボネートとの混合物（容量比３：７）９８質量部に、ビニレンカーボネート２質量部を加え、次いで十分に乾燥したＬｉＰＦ6を１．０モル／リットルの割合となるように溶解して電解液とした。
Using this electrolytic solution, a lithium secondary battery was prepared, and continuous charge characteristics, high-temperature storage characteristics, and cycle characteristics were evaluated. Table 1 shows the evaluation results of the continuous charge characteristics and the high temperature storage characteristics. The evaluation results of cycle characteristics are shown in Table-2.
(Comparative Example 3)
To 98 parts by mass of a mixture of ethylene carbonate and ethyl methyl carbonate (volume ratio 3: 7), 2 parts by mass of vinylene carbonate is added, and then sufficiently dried LiPF 6 is dissolved at a rate of 1.0 mol / liter. Thus, an electrolytic solution was obtained.
この電解液を用いて、リチウム二次電池を作成し、連続充電特性、高温保存特性、サイクル特性の評価を行った。連続充電特性、高温保存特性の評価結果を表−１に示す。サイクル特性の評価結果を表−２に示す。
（比較例４）
エチレンカーボネートとエチルメチルカーボネートとの混合物（容量比３：７）９７質量部に、ビニレンカーボネート２質量部、1,1'-スルホニルジイミダゾール１質量部を加
え、次いで十分に乾燥したＬｉＰＦ6を１．０モル／リットルの割合となるように溶解し
て電解液とした。
Using this electrolytic solution, a lithium secondary battery was prepared, and continuous charge characteristics, high-temperature storage characteristics, and cycle characteristics were evaluated. Table 1 shows the evaluation results of the continuous charge characteristics and the high temperature storage characteristics. The evaluation results of cycle characteristics are shown in Table-2.
(Comparative Example 4)
To 97 parts by mass of a mixture of ethylene carbonate and ethyl methyl carbonate (volume ratio 3: 7), 2 parts by mass of vinylene carbonate and 1 part by mass of 1,1′-sulfonyldiimidazole are added, and then 1 part of fully dried LiPF 6 is added. An electrolytic solution was prepared by dissolving at a rate of 0.0 mol / liter.
この電解液を用いて、リチウム二次電池を作成し、連続充電特性、高温保存特性の評価を行った。結果を表−１に示す。
（比較例５）
エチレンカーボネートとエチルメチルカーボネートとの混合物（容量比３：７）９７重量部に、ビニレンカーボネート２重量部と１−ｐ−トリルスルホニルピロール１重量部を添加し、次いで十分に乾燥したＬｉＰＦ6を１．０モル／リットルの割合となるように溶解して電解液とした。
Using this electrolytic solution, a lithium secondary battery was prepared, and continuous charge characteristics and high-temperature storage characteristics were evaluated. The results are shown in Table-1.
(Comparative Example 5)
Mixture of ethylene carbonate and ethyl methyl carbonate (volume ratio 3: 7) to 97 parts by weight, the addition of vinylene carbonate 2 parts by weight of 1-p-tri Angeles Ruhonirupiroru 1 part by weight, then LiPF 6 was thoroughly dried 1 An electrolytic solution was prepared by dissolving at a rate of 0.0 mol / liter.
この電解液を用いて、リチウム二次電池を作成し、連続充電特性、高温保存特性の評価を行った。結果を表−１に示す。
（実施例３）
エチレンカーボネートとエチルメチルカーボネートとの混合物（容量比３：７）９７．５質量部に、ビニレンカーボネート２質量部、Ｎ，Ｎ−ジメチルメタンスルホンアミド０．５質量部を加え、次いで十分に乾燥したＬｉＰＦ6を１．０モル／リットルの割合となるように溶解して電解液とした。
Using this electrolytic solution, a lithium secondary battery was prepared, and continuous charge characteristics and high-temperature storage characteristics were evaluated. The results are shown in Table-1.
(Example 3)
To 97.5 parts by mass of a mixture of ethylene carbonate and ethyl methyl carbonate (volume ratio 3: 7), 2 parts by mass of vinylene carbonate and 0.5 parts by mass of N, N-dimethylmethanesulfonamide were added and then sufficiently dried. LiPF 6 was dissolved at a rate of 1.0 mol / liter to obtain an electrolytic solution.
この電解液を用いて、リチウム二次電池を作成し、連続充電特性、高温保存特性の評価を行った。結果を表−１に示す。
（実施例４）
エチレンカーボネートとエチルメチルカーボネートとの混合物（容量比３：７）９７．５質量部に、ビニレンカーボネート２質量部、Ｎ，Ｎ−ジメチルエタンスルホンアミド０．５質量部を加え、次いで十分に乾燥したＬｉＰＦ6を１．０モル／リットルの割合となるように溶解して電解液とした。
Using this electrolytic solution, a lithium secondary battery was prepared, and continuous charge characteristics and high-temperature storage characteristics were evaluated. The results are shown in Table-1.
Example 4
To 97.5 parts by mass of a mixture of ethylene carbonate and ethyl methyl carbonate (volume ratio 3: 7), 2 parts by mass of vinylene carbonate and 0.5 parts by mass of N, N-dimethylethanesulfonamide were added and then sufficiently dried. LiPF 6 was dissolved at a rate of 1.0 mol / liter to obtain an electrolytic solution.
この電解液を用いて、リチウム二次電池を作成し、連続充電特性、高温保存特性の評価を行った。結果を表−１に示す。
（実施例５）
エチレンカーボネートとエチルメチルカーボネートとの混合物（容量比３：７）９７．５質量部に、ビニレンカーボネート２質量部、Ｎ，Ｎ−ジブチルベンゼンスルホンアミド０．５質量部を加え、次いで十分に乾燥したＬｉＰＦ6を１．０モル／リットルの割合となるように溶解して電解液とした。
Using this electrolytic solution, a lithium secondary battery was prepared, and continuous charge characteristics and high-temperature storage characteristics were evaluated. The results are shown in Table-1.
(Example 5)
To 97.5 parts by mass of a mixture of ethylene carbonate and ethyl methyl carbonate (volume ratio 3: 7), 2 parts by mass of vinylene carbonate and 0.5 parts by mass of N, N-dibutylbenzenesulfonamide were added and then sufficiently dried. LiPF 6 was dissolved at a rate of 1.0 mol / liter to obtain an electrolytic solution.
この電解液を用いて、リチウム二次電池を作成し、連続充電特性、高温保存特性の評価を行った。結果を表−１に示す。
（実施例６）
エチレンカーボネートとエチルメチルカーボネートとの混合物（容量比３：７）９７．５質量部に、ビニレンカーボネート２質量部、Ｎ，Ｎ−ジエチルメタンスルホンアミド０．５質量部を加え、次いで十分に乾燥したＬｉＰＦ6を１．０モル／リットルの割合となるように溶解して電解液とした。
Using this electrolytic solution, a lithium secondary battery was prepared, and continuous charge characteristics and high-temperature storage characteristics were evaluated. The results are shown in Table-1.
(Example 6)
To 97.5 parts by mass of a mixture of ethylene carbonate and ethyl methyl carbonate (volume ratio 3: 7), 2 parts by mass of vinylene carbonate and 0.5 parts by mass of N, N-diethylmethanesulfonamide were added and then thoroughly dried. LiPF 6 was dissolved at a rate of 1.0 mol / liter to obtain an electrolytic solution.
この電解液を用いて、リチウム二次電池を作成し、連続充電特性、高温保存特性の評価を行った。結果を表−１に示す。
Using this electrolytic solution, a lithium secondary battery was prepared, and continuous charge characteristics and high-temperature storage characteristics were evaluated. The results are shown in Table-1.
表−１、２から明らかなように、本発明に係る電池は、連続充電した場合にもガスの発生量が少なく、連続充電後および高温保存後の電池特性やサイクル特性に優れていることがわかる。 As is clear from Tables 1 and 2, the battery according to the present invention has a small amount of gas generation even when continuously charged, and is excellent in battery characteristics and cycle characteristics after continuous charging and after high-temperature storage. Recognize.
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| JP5066807B2 (en) * | 2005-12-21 | 2012-11-07 | ソニー株式会社 | Lithium secondary battery electrolyte and lithium secondary battery |
| JP5407666B2 (en) * | 2009-08-28 | 2014-02-05 | 日産自動車株式会社 | Secondary battery electrolyte and nonaqueous electrolyte secondary battery using the same |
| US8802301B2 (en) * | 2009-11-06 | 2014-08-12 | GM Global Technology Operations LLC | Lithium ion battery electrolyte including a vitreous eutectic mixture |
| WO2012115119A1 (en) * | 2011-02-22 | 2012-08-30 | 三菱化学株式会社 | Non-aqueous electrolyte solution and battery using same |
| US20130052509A1 (en) * | 2011-08-25 | 2013-02-28 | GM Global Technology Operations LLC | Lithium ion battery with electrolyte-embedded separator particles |
| JP5834771B2 (en) * | 2011-10-26 | 2015-12-24 | 三菱化学株式会社 | Non-aqueous electrolyte and battery using the same |
| JP6081262B2 (en) * | 2013-03-28 | 2017-02-15 | 住友精化株式会社 | Non-aqueous electrolyte additive, non-aqueous electrolyte, and electricity storage device |
| JP7172015B2 (en) | 2017-09-12 | 2022-11-16 | セントラル硝子株式会社 | Additive for non-aqueous electrolyte, electrolyte for non-aqueous electrolyte battery, and non-aqueous electrolyte battery |
| KR102130029B1 (en) * | 2018-03-16 | 2020-07-03 | 삼성에스디아이 주식회사 | Electrolyte for rechargeable lithium battery and rechargeable lithium battery |
| KR20210126569A (en) | 2019-02-19 | 2021-10-20 | 가부시키가이샤 아데카 | Composition for electrolyte, non-aqueous electrolyte and non-aqueous electrolyte secondary battery |
| KR102411934B1 (en) | 2019-05-31 | 2022-06-22 | 삼성에스디아이 주식회사 | Electrolyte for lithium secondary battery and lithium secondary battery including the same |
| KR102449845B1 (en) * | 2019-07-15 | 2022-09-29 | 삼성에스디아이 주식회사 | Electrolyte for rechargeable lithium battery and rechargeable lithium battery |
| CN113764728B (en) * | 2020-06-01 | 2023-11-14 | 比亚迪股份有限公司 | Electrolyte and lithium metal battery |
| CN114497737B (en) * | 2022-01-13 | 2023-08-25 | 珠海冠宇电池股份有限公司 | Nonaqueous electrolyte and lithium ion battery containing same |
| CN116154108B (en) * | 2023-03-30 | 2024-01-23 | 宁德新能源科技有限公司 | Secondary battery and electricity utilization device comprising same |
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