JP4291195B2 - 非水電解質二次電池 - Google Patents
非水電解質二次電池 Download PDFInfo
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- JP4291195B2 JP4291195B2 JP2004099430A JP2004099430A JP4291195B2 JP 4291195 B2 JP4291195 B2 JP 4291195B2 JP 2004099430 A JP2004099430 A JP 2004099430A JP 2004099430 A JP2004099430 A JP 2004099430A JP 4291195 B2 JP4291195 B2 JP 4291195B2
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- secondary battery
- positive electrode
- active material
- electrolyte secondary
- aqueous electrolyte
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- 239000011255 nonaqueous electrolyte Substances 0.000 title claims description 46
- 239000008151 electrolyte solution Substances 0.000 claims description 40
- 150000001875 compounds Chemical class 0.000 claims description 23
- 239000007774 positive electrode material Substances 0.000 claims description 23
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 17
- 229910052744 lithium Inorganic materials 0.000 claims description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 15
- 239000007773 negative electrode material Substances 0.000 claims description 13
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 12
- COVZYZSDYWQREU-UHFFFAOYSA-N Busulfan Chemical compound CS(=O)(=O)OCCCCOS(C)(=O)=O COVZYZSDYWQREU-UHFFFAOYSA-N 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical compound C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 claims description 10
- 239000007770 graphite material Substances 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 claims description 4
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 230000000737 periodic effect Effects 0.000 claims description 2
- 238000003860 storage Methods 0.000 description 29
- 230000000052 comparative effect Effects 0.000 description 14
- 230000000694 effects Effects 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 230000006866 deterioration Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- 239000011149 active material Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- -1 LiCF 3 SO 3 Inorganic materials 0.000 description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 150000005678 chain carbonates Chemical class 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical group [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical group OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 150000005676 cyclic carbonates Chemical class 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 239000002905 metal composite material Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- WDXYVJKNSMILOQ-UHFFFAOYSA-N 1,3,2-dioxathiolane 2-oxide Chemical compound O=S1OCCO1 WDXYVJKNSMILOQ-UHFFFAOYSA-N 0.000 description 1
- BJEWLOAZFAGNPE-UHFFFAOYSA-N 1-ethenylsulfonylethane Chemical compound CCS(=O)(=O)C=C BJEWLOAZFAGNPE-UHFFFAOYSA-N 0.000 description 1
- MBDUIEKYVPVZJH-UHFFFAOYSA-N 1-ethylsulfonylethane Chemical compound CCS(=O)(=O)CC MBDUIEKYVPVZJH-UHFFFAOYSA-N 0.000 description 1
- YBJCDTIWNDBNTM-UHFFFAOYSA-N 1-methylsulfonylethane Chemical compound CCS(C)(=O)=O YBJCDTIWNDBNTM-UHFFFAOYSA-N 0.000 description 1
- QSQFARNGNIZGAW-UHFFFAOYSA-N 2-methylsulfonyloxyethyl methanesulfonate Chemical compound CS(=O)(=O)OCCOS(C)(=O)=O QSQFARNGNIZGAW-UHFFFAOYSA-N 0.000 description 1
- MAIFZJHANFOZHK-UHFFFAOYSA-N 3-methylsulfonyloxypropyl methanesulfonate Chemical compound CS(=O)(=O)OCCCOS(C)(=O)=O MAIFZJHANFOZHK-UHFFFAOYSA-N 0.000 description 1
- QTNVULGCBFTXBM-UHFFFAOYSA-N 5-methylsulfonyloxypentyl methanesulfonate Chemical compound CS(=O)(=O)OCCCCCOS(C)(=O)=O QTNVULGCBFTXBM-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910015118 LiMO Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 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
- 239000003125 aqueous solvent Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910021437 lithium-transition metal oxide Inorganic materials 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
- 238000005259 measurement Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229910052705 radium Inorganic materials 0.000 description 1
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
-
- 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
- H01M10/0567—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
- H01M10/056—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
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M2010/4292—Aspects relating to capacity ratio of electrodes/electrolyte or anode/cathode
-
- 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
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- 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
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
〔正極活物質の作製〕
Li2CO3とCo3O4とZrO2とMgOを、Li:Co:Zr:Mgのモル比が1:0.99:0.005:0.005となるように石川式らいかい乳鉢にて混合した後、空気雰囲気中にて850℃で20時間熱処理した。その後、粉砕することにより、平均粒子径が約14μmのリチウム含有遷移金属複合酸化物を得た。BET比表面積は0.4m2/gであった。
このようにして得た正極活物質に、導電剤としての炭素と、結着剤としてのポリフッ化ビニリデンと、分散媒としてのN−メチル−2−ピロリドンを、活物質と導電剤と結着剤の重量比が90:5:5の比率になるようにして加えた後に混練して、正極スラリーを作製した。作製したスラリーを集電体としてのアルミニウム箔上に塗布した後、乾燥し、その後圧延ローラーを用いて圧延し、集電タブを取り付けることにより、正極を作製した。
増粘剤であるカルボキシメチルセルロースを水に溶かした水溶液中に、負極活物質としての人造黒鉛と、結着剤としてのスチレン−ブタジエンゴムとを、活物質と結着剤と増粘剤の重量比が95:3:2の比率になるようにして加えた後に混練して、負極スラリーを作製した。作製したスラリーを集電体としての銅箔上に塗布した後、乾燥し、その後圧延ローラーを用いて圧延し、集電タブを取り付けることにより、負極を作製した。
エチレンカーボネート(EC)とジエチルカーボネート(DEC)とを体積比2:8で混合した溶媒に対し、ヘキサフルオロリン酸リチウム(LiPF6)を、濃度が1mol/リットルとなるように溶解し、さらにビニレンカーボネート(VC)を溶媒と溶質の合計に対し、1.0重量%、1,4−ブタンジオールジメタンスルホネート(BDDMS)を1.0重量%添加して、電解液を作製した。
このようにして得た正極及び負極を、セパレーターを介して対向するように巻取って巻取り体を作製し、Ar雰囲気下のグローブボックス中にて、巻取り体を電解液とともにアルミニウムラミネートに封入することにより、電池規格サイズとして、厚み3.6mm×幅3.5cm×長さ6.2cmの非水電解質二次電池A1を得た。
作製した非水電解質二次電池を、650mAの定電流で、電圧が4.4Vに達するまで充電し、さらに、4.4Vの定電圧で電流値が32mAになるまで充電した後、650mAの定電流で、電圧が2.75Vに達するまで放電することにより、電池の保存前放電容量(mAh)を測定した。
電解液の作製において、1,4−ブタンジオールジメタンスルホネート(BDDMS)を0.5重量%添加したこと以外は実施例1と同様にして、電解液を作製した。
電解液の作製において、1,4−ブタンジオールジメタンスルホネート(BDDMS)を1.5重量%添加したこと以外は実施例1と同様にして、電解液を作製した。
電解液の作製において、1,4−ブタンジオールジメタンスルホネート(BDDMS)1.0重量%に代えて、ジビニルスルホン(VS)0.5重量%とする以外は実施例1と同様にして、電解液を作製した。
電解液の作製において、ジビニルスルホン(VS)の添加量を0.2重量%としたこと以外は実施例4と同様にして、電解液を作製した。
電解液の作製において、1,4−ブタンジオールジメタンスルホネート(BDDMS)を添加せずにビニレンカーボネート(VC)のみを添加したこと以外は実施例1と同様にして、電解液を作製した。
電解液の作製において、1,4−ブタンジオールジメタンスルホネート(BDDMS)1.0重量%に代えて、エチレンサルファイト(ES)2.0重量%とする以外は実施例1と同様にして、電解液を作製した。
正極活物質の作製において、ZrO2及びMgOを添加せず、Li2CO3とCo3O4を、LiとCoのモル比が1:1となるようにして正極活物質を作製したこと以外は比較例1と同様にして、正極活物質を作製した。
電解液の作製において、ビニレンカーボネート(VC)1.0重量%と1,4−ブタンジオールジメタンスルホネート(BDDMS)1.0重量%を添加したこと以外は比較例3と同様にして、電解液を作製した。
電解液の作製において、ビニレンカーボネート(VC)1.0重量%とジビニルスルホン(VS)0.5重量%を添加したこと以外は比較例3と同様にして、電解液を作製した。
Claims (9)
- 黒鉛材料を負極活物質として含む負極と、コバルト酸リチウムを正極活物質の主成分として含む正極と、非水電解液とを備える非水電解質二次電池において、前記コバルト酸リチウムが0.05〜2.0mol%の周期律表IVA族元素及び0.1〜2.0mol%のIIA族元素を含み、かつ前記非水電解液がスルホニル基を有する化合物を0.2〜1.5重量%含んでいることを特徴とする非水電解質二次電池。
- 前記正極活物質中のIVA族元素がジルコニウムであり、IIA族元素がマグネシウムであることを特徴とする請求項1に記載の非水電解質二次電池。
- 前記非水電解液がさらにビニレンカーボネートを0.5〜4重量%含んでいることを特徴とする請求項1または2に記載の非水電解質二次電池。
- 前記スルホニル基を有する化合物が、1,4−ブタンジオールジメタンスルホネート、及びジビニルスルホンのうち少なくとも1種であることを特徴とする請求項1〜3のいずれか1項に記載の非水電解質二次電池。
- 前記非水電解液が、スルホニル基を有する化合物として、1,4−ブタンジオールジメタンスルホネートを0.5〜1.5重量%含んでいることを特徴とする請求項1〜4のいずれか1項に記載の非水電解質二次電池。
- 前記非水電解液が、スルホニル基を有する化合物として、ジビニルスルホンを0.2〜0.5重量%含んでいることを特徴とする請求項1〜5のいずれか1項に記載の非水電解質二次電池。
- 前記非水電解液が溶媒として、ジエチルカーボネートを含んでいることを特徴とする請求項1〜6のいずれか1項に記載の非水電解質二次電池。
- 充電終止電圧を4.3Vとした場合の、正極と負極の充電容量比が1.0〜1.2となるように前記正極活物質及び前記負極活物質が含まれていることを特徴とする請求項1〜7のいずれか1項に記載の非水電解質二次電池。
- 充電終止電圧を4.4Vとした場合の、正極と負極の充電容量比が1.0〜1.2となるように前記正極活物質及び前記負極活物質が含まれていることを特徴とする請求項1〜7のいずれか1項に記載の非水電解質二次電池。
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JP2004099430A JP4291195B2 (ja) | 2004-03-30 | 2004-03-30 | 非水電解質二次電池 |
US10/563,124 US7767343B2 (en) | 2004-03-30 | 2005-02-18 | Nonaqueous electrolyte secondary battery using lithium cobalt oxide as a positive active material and a nonaqueous electrolyte containing a sulfonyl-containing compound |
PCT/JP2005/002576 WO2005099021A1 (ja) | 2004-03-30 | 2005-02-18 | 非水電解質二次電池 |
EP05710409.3A EP1739783B1 (en) | 2004-03-30 | 2005-02-18 | Nonaqueous electrolyte secondary battery |
CA2525923A CA2525923C (en) | 2004-03-30 | 2005-02-18 | Nonaqueous electrolyte secondary battery |
KR1020067020316A KR101026287B1 (ko) | 2004-03-30 | 2005-02-18 | 비수성 전해질 이차 전지 |
CNB2005800004533A CN100544108C (zh) | 2004-03-30 | 2005-02-18 | 非水电解质二次电池 |
TW094106203A TWI359520B (en) | 2004-03-30 | 2005-03-02 | Nonaqueous electrolyte secondary battery |
US12/801,631 US8597834B2 (en) | 2004-03-30 | 2010-06-17 | Nonaqueous electrolyte secondary battery using lithium cobalt oxide as a positive active material and a nonaqueous electrolyte containing a sulfonyl-containing compound and vinylene carbonate |
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JP4841133B2 (ja) * | 2004-11-16 | 2011-12-21 | 三洋電機株式会社 | 非水電解質二次電池 |
JP4951913B2 (ja) * | 2005-09-27 | 2012-06-13 | ソニー株式会社 | リチウムイオン二次電池 |
JP2008071746A (ja) * | 2006-08-14 | 2008-03-27 | Sanyo Electric Co Ltd | 非水電解質二次電池 |
EP1978587B1 (en) * | 2007-03-27 | 2011-06-22 | Hitachi Vehicle Energy, Ltd. | Lithium secondary battery |
KR20090050951A (ko) | 2007-11-16 | 2009-05-20 | 산요덴키가부시키가이샤 | 비수전해질 이차전지 |
US20130029218A1 (en) * | 2010-02-08 | 2013-01-31 | Nec Energy Devices, Ltd. | Nonaqueous electrolyte secondary battery |
JP6457205B2 (ja) * | 2014-06-19 | 2019-01-23 | 三井化学株式会社 | リチウム二次電池 |
KR102209828B1 (ko) | 2014-07-16 | 2021-01-29 | 삼성에스디아이 주식회사 | 리튬 전지용 전해질 첨가제, 이를 포함하는 전해질 및 상기 전해질을 채용한 리튬 전지 |
CN107093765B (zh) | 2017-04-28 | 2020-03-31 | 张家港市国泰华荣化工新材料有限公司 | 一种非水电解液及二次电池 |
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US8597834B2 (en) | 2013-12-03 |
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US7767343B2 (en) | 2010-08-03 |
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