JP4493513B2 - 有機電解液及びそれを採用したリチウム電池 - Google Patents
有機電解液及びそれを採用したリチウム電池 Download PDFInfo
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- JP4493513B2 JP4493513B2 JP2005028054A JP2005028054A JP4493513B2 JP 4493513 B2 JP4493513 B2 JP 4493513B2 JP 2005028054 A JP2005028054 A JP 2005028054A JP 2005028054 A JP2005028054 A JP 2005028054A JP 4493513 B2 JP4493513 B2 JP 4493513B2
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- carbonate
- electrolyte
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- 229910052744 lithium Inorganic materials 0.000 title claims description 29
- 239000005486 organic electrolyte Substances 0.000 title claims description 29
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 27
- -1 cyclic organic compound Chemical class 0.000 claims description 32
- 239000008151 electrolyte solution Substances 0.000 claims description 32
- 239000002904 solvent Substances 0.000 claims description 20
- 239000003960 organic solvent Substances 0.000 claims description 19
- 229910003002 lithium salt Inorganic materials 0.000 claims description 11
- 159000000002 lithium salts Chemical class 0.000 claims description 11
- 238000009835 boiling Methods 0.000 claims description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 5
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical class CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 5
- 125000005740 oxycarbonyl group Chemical group [*:1]OC([*:2])=O 0.000 claims description 5
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 5
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical class CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 4
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical class CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical class COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical class COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical class CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 description 16
- 239000000203 mixture Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 10
- 229910001416 lithium ion Inorganic materials 0.000 description 10
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000006183 anode active material Substances 0.000 description 7
- 239000006182 cathode active material Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 239000006258 conductive agent Substances 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 150000002894 organic compounds Chemical class 0.000 description 5
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 description 4
- PIYNUZCGMLCXKJ-UHFFFAOYSA-N 1,4-dioxane-2,6-dione Chemical compound O=C1COCC(=O)O1 PIYNUZCGMLCXKJ-UHFFFAOYSA-N 0.000 description 4
- 229910013870 LiPF 6 Inorganic materials 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000005755 formation reaction Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000004743 Polypropylene Substances 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
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000011244 liquid electrolyte Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 229920005609 vinylidenefluoride/hexafluoropropylene copolymer Polymers 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 239000002952 polymeric resin Substances 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910013705 LiNi 1-x Mn Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical class CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 150000005678 chain carbonates Chemical class 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- GXHFUVWIGNLZSC-UHFFFAOYSA-N meldrum's acid Chemical compound CC1(C)OC(=O)CC(=O)O1 GXHFUVWIGNLZSC-UHFFFAOYSA-N 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
- H01M6/168—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
- H01M2300/0037—Mixture of solvents
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
- H01M2300/0037—Mixture of solvents
- H01M2300/004—Three solvents
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Primary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
(参考例1)
エチレンカーボネート30体積%、プロピレンカーボネート10体積%、及びエチルメチルカーボネ−ト60体積%よりなる混合有機溶媒に、環状有機化合物としてラクチドを0.1質量%添加し、リチウム塩としては1M LiPF6を使用して、有機電解液を製造した。
前記ラクチドの添加量を1質量%としたことを除いては、参考例1と同じ方法で有機電解液を製造した。
前記ラクチドの添加量を2質量%としたことを除いては、参考例1と同じ方法で有機電解液を製造した。
環状有機化合物として、ラクチドの代りにエプシロン−カプロラクトン0.1質量%を添加したことを除いては、参考例1と同じ方法で有機電解液を製造した。
前記エプシロン−カプロラクトンの添加量を1質量%としたことを除いては、参考例4と同じ方法で有機電解液を製造した。
前記エプシロン−カプロラクトンの添加量を2質量%としたことを除いては、参考例4と同じ方法で有機電解液を製造した。
環状有機化合物として、ラクチドの代りにジグリコール酸無水物0.1質量%を添加したことを除いては、参考例1と同じ方法で有機電解液を製造した。
前記ジグリコール酸無水物の添加量を1質量%としたことを除いては、参考例7と同じ方法で有機電解液を製造した。
前記ジグリコール酸無水物の添加量を2質量%としたことを除いては、参考例7と同じ方法で有機電解液を製造した。
環状有機化合物として、ラクチドの代りに[1,4]ジオキサン−2,5−ジオン 0.1質量%を添加したことを除いては、参考例1と同じ方法で有機電解液を製造した。
前記[1,4]ジオキサン−2,5−ジオンの添加量を1質量%としたことを除いては、参考例10と同じ方法で有機電解液を製造した。
前記[1,4]ジオキサン−2,5−ジオンの添加量を2質量%としたことを除いては、参考例10と同じ方法で有機電解液を製造した。
環状有機化合物として、ラクチドの代りに[1,3,5,7]テトロオキソナン−8,9−ジオン0.1質量%を添加したことを除いては、参考例1と同じ方法で有機電解液を製造した。
前記[1,3,5,7]テトロオキソナン−8,9−ジオンの添加量を1質量%としたことを除いては、実施例13と同じ方法で有機電解液を製造した。
前記[1,3,5,7]テトロオキソナン−8,9−ジオンの添加量を2質量%としたことを除いては、実施例13と同じ方法で有機電解液を製造した。
環状有機化合物として、ラクチドの代りに[2,2]−ジメチル−1,3−ジオキサン−4,6−ジオン 0.1質量%を添加したことを除いては、参考例1と同じ方法で有機電解液を製造した。
前記[2,2]−ジメチル−1,3−ジオキサン−4,6−ジオンの添加量を1質量%としたことを除いては、実施例16と同じ方法で有機電解液を製造した。
前記[2,2]−ジメチル−1,3−ジオキサン−4,6−ジオンの添加量を2質量%としたことを除いては、実施例16と同じ方法で有機電解液を製造した。
エチレンカーボネート30体積%、プロピレンカーボネート10体積%、及びエチルメチルカーボネート60体積%よりなる混合有機溶媒に、リチウム塩としては1M LiPF6を使用して、有機電解液を製造した。
エチレンカーボネート30体積%、プロピレンカーボネート10体積%、及びエチルメチルカーボネート60体積%よりなる混合有機溶媒に重合性有機化合物としてメタクリル酸メチルを0.1質量%添加し、リチウム塩としては1M LiPF6を使用して、有機電解液を製造した。
前記メタクリル酸メチルの添加量を1質量%としたことを除いては、比較例2と同じ方法で有機電解液を製造した。
前記メタクリル酸メチルの添加量を2質量%としたことを除いては、比較例2と同じ方法で有機電解液を製造した。
(参考例19〜30および実施例31〜36)
LiCoO2 95wt%、結着剤としてPVdF 2wt%及びカーボン導電剤3wt%を混合し、ここにNメチルピロリドン(NMP)(100ml)及びセラミックボールを加えた後、この混合物を200mlプラスチック瓶に入れて10時間の間よく混練させた。次いで、15μmの厚さのアルミ箔上に250μm間隔のドクターブレイドでキャスティングしてカソード電極を得た後、これを約110℃のオーブンに入れて約12時間乾燥させてNMPを完全に気化させた。前記カソード電極をロールプレスして95μmの厚さのカソードを得た。
比較例1〜4によって製造された有機電解液を使用したことを除いては、参考例19と同じ方法で角形電池を製造した。
(充電後、電池の厚さ変化テスト)
参考例19〜30、実施例31〜36、及び比較例5〜8で製造した電池を4.2Vまで充電した後、充電前後による電池厚さの膨脹分についてマイクロメータを使用して測定し、その結果を表1に示す。
(電池のサイクル特性テスト)
参考例19〜30、実施例31〜36、及び比較例5〜8で製造した電池に対して1Cレートで充放電を実施し、初期容量対比100回サイクルでの容量維持率をサイクル特性対応値と定めて、その結果を表1に示す。
Claims (7)
- リチウム塩、及び誘電率が30ないし100の溶媒と沸点が77℃ないし150℃の溶媒とよりなる混合有機溶媒を含む有機電解液において、
少なくとも一つのオキシカルボニル基を有する六員環ないし九員環の環状有機化合物をさらに含み、
前記環状有機化合物は、[1,3,5,7]テトロオキソナン−8,9−ジオンまたは[2,2]−ジメチル−1,3−ジオキサン−4,6−ジオンであることを特徴とする有機電解液。 - 前記環状有機化合物が、前記混合有機溶媒の全質量を基準として0.1ないし2質量%であることを特徴とする請求項1に記載の有機電解液。
- 前記環状有機化合物が、前記混合有機溶媒の全質量を基準として0.25ないし1質量%であることを特徴とする請求項2に記載の有機電解液。
- 前記リチウム塩の濃度は、0.5ないし2.0Mであることを特徴とする請求項1〜3のいずれか1項に記載の有機電解液。
- 前記誘電率が30ないし100の溶媒は、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及びγブチロラクトンよりなる群から選ばれた少なくとも1種であることを特徴とする請求項1〜4のいずれか1項に記載の有機電解液。
- 前記沸点が77℃ないし150℃の溶媒は、ジメチルカーボネート、エチルメチルカーボネート、ジエチルカーボネート、ジプロピルカーボネート、ジメトキシエタン、ジエトキシエタン及び脂肪酸エステル誘導体よりなる群から選ばれた少なくとも1種であることを特徴とする請求項1〜5のいずれか1項に記載の有機電解液。
- カソードと、
アノードと、
請求項1ないし6のいずれか1項による有機電解液と、を含むことを特徴とするリチウム電池。
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KR100709207B1 (ko) | 2004-06-30 | 2007-04-18 | 삼성에스디아이 주식회사 | 리튬 이차 전지 |
KR100709208B1 (ko) | 2004-06-30 | 2007-04-19 | 삼성에스디아이 주식회사 | 리튬 이차 전지 |
FI121311B (fi) * | 2005-05-03 | 2010-09-30 | M Real Oyj | Menetelmä paperin- ja kartonginvalmistukseen soveltuvan mekaanisen massan valmistamiseksi |
JP5017800B2 (ja) * | 2005-05-12 | 2012-09-05 | ソニー株式会社 | 二次電池用電解質および二次電池 |
WO2006134653A1 (ja) * | 2005-06-15 | 2006-12-21 | Mitsubishi Chemical Corporation | リチウム二次電池 |
CN101213702B (zh) * | 2005-07-01 | 2010-05-26 | 株式会社Lg化学 | 用于非水性电解质的添加剂及使用其的二次电池 |
JP6079264B2 (ja) * | 2012-01-25 | 2017-02-15 | 三菱化学株式会社 | 非水系電解液及びそれを用いた非水系電解液二次電池 |
JP6575519B2 (ja) | 2014-06-16 | 2019-09-18 | 日本電気株式会社 | 電解液及び二次電池 |
JP6648694B2 (ja) | 2014-06-16 | 2020-02-14 | 日本電気株式会社 | 電解液及び二次電池 |
CN104157908A (zh) * | 2014-08-20 | 2014-11-19 | 厦门大学 | 一种锂盐电解液及其制备方法与应用 |
CN105826606B (zh) * | 2016-05-16 | 2020-02-18 | 宁德时代新能源科技股份有限公司 | 一种电解液以及包含该电解液的锂离子电池 |
CN105914403B (zh) * | 2016-06-28 | 2018-08-21 | 宁德时代新能源科技股份有限公司 | 一种电解液及使用该电解液的锂离子电池 |
CN111971844A (zh) * | 2018-04-16 | 2020-11-20 | 松下知识产权经营株式会社 | 非水电解质二次电池 |
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