JP2004149409A - Lithium-cobalt multiple oxide, method for producing the same, and nonaqueous electrolyte secondary battery - Google Patents
Lithium-cobalt multiple oxide, method for producing the same, and nonaqueous electrolyte secondary battery Download PDFInfo
- Publication number
- JP2004149409A JP2004149409A JP2003349599A JP2003349599A JP2004149409A JP 2004149409 A JP2004149409 A JP 2004149409A JP 2003349599 A JP2003349599 A JP 2003349599A JP 2003349599 A JP2003349599 A JP 2003349599A JP 2004149409 A JP2004149409 A JP 2004149409A
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- Prior art keywords
- lithium
- composite oxide
- cobalt
- cobalt composite
- secondary battery
- Prior art date
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- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims description 24
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 11
- 125000005843 halogen group Chemical group 0.000 claims abstract description 5
- 230000000737 periodic effect Effects 0.000 claims abstract description 4
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 4
- 239000002131 composite material Substances 0.000 claims description 62
- -1 cobalt oxyhydroxide Chemical compound 0.000 claims description 40
- 239000000203 mixture Substances 0.000 claims description 31
- 239000007774 positive electrode material Substances 0.000 claims description 16
- 150000002642 lithium compounds Chemical class 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 14
- 150000002366 halogen compounds Chemical class 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 claims description 2
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 abstract description 36
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 31
- 239000013543 active substance Substances 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 53
- 239000002245 particle Substances 0.000 description 20
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 229910017052 cobalt Inorganic materials 0.000 description 10
- 239000010941 cobalt Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 229910052736 halogen Inorganic materials 0.000 description 7
- 150000002367 halogens Chemical class 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 238000010304 firing Methods 0.000 description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 229910003002 lithium salt Inorganic materials 0.000 description 5
- 159000000002 lithium salts Chemical class 0.000 description 5
- 239000007800 oxidant agent Substances 0.000 description 5
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
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- 229910000361 cobalt sulfate Inorganic materials 0.000 description 4
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- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
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- 150000003839 salts Chemical class 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000007784 solid electrolyte Substances 0.000 description 4
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- 229910018871 CoO 2 Inorganic materials 0.000 description 3
- 229910018916 CoOOH Inorganic materials 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
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- 229910052742 iron Inorganic materials 0.000 description 3
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
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- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- KQHXBDOEECKORE-UHFFFAOYSA-L beryllium sulfate Chemical compound [Be+2].[O-]S([O-])(=O)=O KQHXBDOEECKORE-UHFFFAOYSA-L 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
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- 239000011575 calcium Substances 0.000 description 2
- 238000007600 charging Methods 0.000 description 2
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- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
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- SHFJWMWCIHQNCP-UHFFFAOYSA-M hydron;tetrabutylazanium;sulfate Chemical compound OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC SHFJWMWCIHQNCP-UHFFFAOYSA-M 0.000 description 2
- 238000004255 ion exchange chromatography Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
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- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010281 constant-current constant-voltage charging Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229920005994 diacetyl cellulose Polymers 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 150000004862 dioxolanes Chemical class 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- BLBBMBKUUHYSMI-UHFFFAOYSA-N furan-2,3,4,5-tetrol Chemical compound OC=1OC(O)=C(O)C=1O BLBBMBKUUHYSMI-UHFFFAOYSA-N 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910001853 inorganic hydroxide Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 230000010220 ion permeability Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 229910021470 non-graphitizable carbon Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 229920005608 sulfonated EPDM Polymers 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
- H01M4/1315—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx containing halogen atoms, e.g. 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
- H01M4/48—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
- 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
- H01M10/052—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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
-
- 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
-
- 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
Abstract
Description
本発明は、リチウムコバルト複合酸化物及びその製造方法、非水電解質二次電池、並びに、携帯用電子機器に関する。 The present invention relates to a lithium cobalt composite oxide and a method for producing the same, a nonaqueous electrolyte secondary battery, and a portable electronic device.
六方晶系の層状結晶構造を持つ遷移金属酸化物は、適当なサイズの金属イオンを結晶の格子サイト及び/又は格子間に導入できることが知られている。特に、リチウム層間化合物は、特定の電位差の下でリチウムイオンを結晶格子サイト及び/又は格子間に導入し、再びこれを取り出すことができる。そして、リチウムコバルト複合酸化物、LiCoO2を正極活物質としたリチウム二次電池は、高い体積エネルギー密度を有しているところ、携帯用電子機器を小型化、軽量化できるので、リチウム二次電池は携帯用パソコン、携帯電話の電源として急速に普及してきている。 It is known that transition metal oxides having a hexagonal layered crystal structure can introduce metal ions of a suitable size into lattice sites and / or interstitials of the crystal. In particular, the lithium intercalation compound can introduce lithium ions under a specific potential difference and introduce them again into crystal lattice sites and / or interlattices. A lithium secondary battery using a lithium-cobalt composite oxide and LiCoO 2 as a positive electrode active material has a high volume energy density and can reduce the size and weight of a portable electronic device. Is rapidly spreading as a power source for portable personal computers and mobile phones.
一方、高価なコバルトを安価な他の遷移金属、例えば、ニッケル、マンガン等に代替しようとする検討も行われている(例えば、特許文献1、特許文献2参照)。特許文献2には、LiCoxNi(1−x)O2(0.05≦x<1)の組成式で示される原料から得られるリチウム複合酸化物が記載されており、このリチウム複合酸化物は、リチウムコバルト複合酸化物(LiCoO2)のCo成分を部分的にNiに置き換えた後にも安定な結晶構造を保持し得るものである。このように従来の技術では、高価なコバルトをニッケル等に代替しようとしていた。
しかし、本発明者らが鋭意研究した結果、正極活物質として作用するリチウムコバルト複合酸化物(LiCoO2)のCo成分を部分的にNiに代替すると、却って、リチウム二次電池の放電特性が悪化することが分かった。そこで、本発明では、放電特性が向上したリチウム二次電池を提供することを目的とする。 However, as a result of intensive studies made by the present inventors, when the Co component of the lithium-cobalt composite oxide (LiCoO 2 ) acting as the positive electrode active material is partially replaced with Ni, the discharge characteristics of the lithium secondary battery deteriorate rather. I found out. Therefore, an object of the present invention is to provide a lithium secondary battery having improved discharge characteristics.
本発明は、より具体的には以下のようなものを提供する。 The present invention more specifically provides the following.
(1) Ni含有量が100ppm以下であり、かつ下記化学式1で表されることを特徴とするリチウムコバルト複合酸化物。
(2) 前記リチウムコバルト複合酸化物は、硫酸根を含有してなることを特徴とする(1)に記載のリチウムコバルト複合酸化物。 (2) The lithium-cobalt composite oxide according to (1), wherein the lithium-cobalt composite oxide contains a sulfate group.
(3) 前記Ni含有量が60ppm以下であることを特徴とする(1)または(2)に記載のリチウムコバルト複合酸化物。 (3) The lithium-cobalt composite oxide according to (1) or (2), wherein the Ni content is 60 ppm or less.
(4) 非水電解質二次電池用リチウムコバルト酸化物であることを特徴とする(1)から(3)いずれかに記載のリチウムコバルト複合酸化物。 (4) The lithium-cobalt composite oxide according to any one of (1) to (3), which is a lithium-cobalt oxide for a non-aqueous electrolyte secondary battery.
(5) Ni含有量が100ppm以下のオキシ水酸化コバルトとリチウム化合物との混合体を700〜1100℃に加熱することを特徴とするリチウムコバルト複合酸化物の製造方法。 (5) A method for producing a lithium-cobalt composite oxide, comprising heating a mixture of cobalt oxyhydroxide having a Ni content of 100 ppm or less and a lithium compound to 700 to 1100 ° C.
(6) Ni含有量が100ppm以下のオキシ水酸化コバルトとリチウム化合物との混合体に、ハロゲン化合物または硫酸塩化合物から選ばれる少なくとも1種以上をさらに混合して700〜1100℃に加熱することを特徴とするリチウムコバルト複合酸化物の製造方法。 (6) A mixture of cobalt oxyhydroxide having a Ni content of 100 ppm or less and a lithium compound is further mixed with at least one selected from a halogen compound and a sulfate compound, and heated to 700 to 1100 ° C. A method for producing a lithium cobalt composite oxide.
(7) (1)から(3)いずれかに記載のリチウムコバルト複合酸化物が正極活物質として、正極に含まれていることを特徴とする非水電解質二次電池。 (7) A non-aqueous electrolyte secondary battery, wherein the lithium-cobalt composite oxide according to any one of (1) to (3) is contained in a positive electrode as a positive electrode active material.
(8) (7)に記載の非水電解質二次電池を備えることを特徴とする携帯用電子機器。 (8) A portable electronic device comprising the nonaqueous electrolyte secondary battery according to (7).
本発明では、Ni含有量が100ppm以下であるリチウムコバルト複合酸化物を正極活物質として用いることにより、放電特性が向上したリチウム二次電池を提供することができる。このようなリチウム二次電池を用いることにより、携帯用電子機器を小型化、軽量化できる。 In the present invention, a lithium secondary battery having improved discharge characteristics can be provided by using a lithium-cobalt composite oxide having a Ni content of 100 ppm or less as a positive electrode active material. By using such a lithium secondary battery, a portable electronic device can be reduced in size and weight.
以下、本発明の正極活物質及び非水電解質二次電池を更に説明する。 Hereinafter, the positive electrode active material and the nonaqueous electrolyte secondary battery of the present invention will be further described.
<リチウムコバルト複合酸化物>
本発明に係るリチウムコバルト複合酸化物は、化学式1で表されることを特徴とするリチウムコバルト複合酸化物である。すなわち、本発明に係るリチウムコバルト複合酸化物としては、例えばNiが100ppm以下であるLixCoO2、LiCoO2Nz、LiCo1-yMyO2、またはLiCo1-yMyO2Nzが挙げられ、特にNiが極めて少ないLixCoO2およびハロゲン元素が含まれるLixCoO2Nzが好ましい(xは0.10≦x≦1.25、yは0≦y≦0.05、zは0≦z≦0.05を表す。)。このようなリチウムコバルト複合酸化物は、リチウムイオン非水電解質二次電池用正極活物質に好適に用いることができる。
<Lithium cobalt composite oxide>
The lithium-cobalt composite oxide according to the present invention is a lithium-cobalt composite oxide represented by Chemical Formula 1. That is, the lithium-cobalt composite oxide according to the present invention, for example, Ni is 100ppm or less Li x CoO 2, LiCoO 2 N z, LiCo 1-y
本発明に係るリチウムコバルト複合酸化物には、他の元素Mとして、例えばLi、Na、B、Ca、Mg、Si、Cu、Ce、Y、Ti、V、Mn、Fe、Sn、Zr、Sb、Nb、Ru、Pb、Hf、Ta、La、Pr及びNdからなる群より選択される少なくとも1種の元素が含まれていてもよい。また、ハロゲン原子Nとしては、フッ素、塩素、臭素及び沃素等のハロゲン原子が挙げられ、フッ素が特に好ましい。 In the lithium-cobalt composite oxide according to the present invention, as other elements M, for example, Li, Na, B, Ca, Mg, Si, Cu, Ce, Y, Ti, V, Mn, Fe, Sn, Zr, Sb , Nb, Ru, Pb, Hf, Ta, La, Pr, and Nd. Examples of the halogen atom N include halogen atoms such as fluorine, chlorine, bromine and iodine, and fluorine is particularly preferable.
本発明に係るリチウムコバルト複合酸化物では、Ni含有量が100ppm以下である。より好ましくはNi含有量が70ppm以下であり、Ni含有量が60ppm以下であることが更に好ましい。特に好ましくはNi含有量が30ppm以下である。 In the lithium cobalt composite oxide according to the present invention, the Ni content is 100 ppm or less. More preferably, the Ni content is 70 ppm or less, and further preferably, the Ni content is 60 ppm or less. Particularly preferably, the Ni content is 30 ppm or less.
リチウムコバルト複合酸化物中の硫酸根の含有量は、(分析で定量された硫酸根重量)/(合成により得られた正極活物質重量)で表され、0.01重量%以上5重量%以下が好ましい。更には0.05重量%以上2重量%以下がより好ましく、0.1重量%以上1重量%以下が特に好ましい。硫酸根の定量は種々の方法を用いることができる。例えば、試料を硝酸・過酸化水素などで完全に溶解後、イオンクロマトグラフにて硫酸根を定量することができる。また、ICP発光分析法又は滴定法により、硫酸根を定量することもできる。ICP発光分析法は、試料を硝酸及び過塩素酸により溶解し、ICP発光分析により硫黄を定量して硫酸根に換算する方法である。滴定法は、試料にクロム酸バリウムと希塩酸溶液を加え、アンモニアにて中和後濾過し、硫酸根と置換して生じる濾液中のCrO4 2−をヨウ素法で滴定して間接的に硫酸根を定量する方法(日本化学会編「実験化学講座15分析化学(下)」丸善株式会社出版、に記載の方法に準拠)である。 The content of sulfate in the lithium-cobalt composite oxide is represented by (weight of sulfate determined by analysis) / (weight of positive electrode active material obtained by synthesis), and is 0.01% by weight or more and 5% by weight or less. Is preferred. Further, the content is more preferably from 0.05% by weight to 2% by weight, and particularly preferably from 0.1% by weight to 1% by weight. Various methods can be used for the determination of sulfate groups. For example, after completely dissolving a sample with nitric acid, hydrogen peroxide, or the like, sulfate groups can be quantified by ion chromatography. Further, sulfate groups can be quantified by ICP emission spectrometry or titration. ICP emission spectrometry is a method in which a sample is dissolved with nitric acid and perchloric acid, sulfur is quantified by ICP emission spectrometry, and converted into sulfate. In the titration method, barium chromate and a dilute hydrochloric acid solution are added to a sample, and the mixture is neutralized with ammonia, filtered, and replaced with sulfate to titrate CrO 4 2- in the filtrate generated by the iodine method to indirectly determine sulfate. (Based on the method described in Maruzen Co., Ltd., “Experimental Chemistry Lecture 15 Analytical Chemistry (2)” edited by The Chemical Society of Japan).
また、リチウムコバルト複合酸化物中に含まれるハロゲン元素は、含有量が0.005〜2.5重量%であり、好ましくは0.05〜1.5重量%である。 The content of the halogen element contained in the lithium-cobalt composite oxide is 0.005 to 2.5% by weight, preferably 0.05 to 1.5% by weight.
リチウム二次電池の正極に含まれるリチウムコバルト複合酸化物では、リチウムコバルト複合酸化物中のNi含有量が少なくなるのに従って、リチウム二次電池の放電容量が増加し、電圧を維持し易くなる。従って、リチウム二次電池の体積エネルギー密度が増加して、携帯用電子機器を小型化、軽量化できる。また、前記リチウムコバルト複合酸化物中にフッ素化合物や硫酸根が更に存在することによって、負荷特性、サイクル特性、高温保存特性、低温特性及び安全性を向上させることができる。 In the lithium cobalt composite oxide contained in the positive electrode of the lithium secondary battery, as the Ni content in the lithium cobalt composite oxide decreases, the discharge capacity of the lithium secondary battery increases, and the voltage is easily maintained. Therefore, the volume energy density of the lithium secondary battery increases, and the size and weight of the portable electronic device can be reduced. In addition, load characteristics, cycle characteristics, high-temperature storage characteristics, low-temperature characteristics, and safety can be improved by further containing a fluorine compound and a sulfate group in the lithium-cobalt composite oxide.
<オキシ水酸化コバルト>
本発明の製造方法では、Ni含有量が100ppm以下のオキシ水酸化コバルト(CoOOH)が用いられる。Ni含有量が70ppm以下のオキシ水酸化コバルト(CoOOH)を用いることがより好ましく、Ni含有量が60ppm以下のオキシ水酸化コバルトを用いることが更に好ましい。特に好ましくはNi含有量が30ppm以下のオキシ水酸化コバルトである。反応物中のニッケル含有量が低減するのに従って、本発明の製造方法で得られるリチウムコバルト複合酸化物中のNi含有量が低減するからである。オキシ水酸化コバルトは、CoOOHが主成分として考えられるが、その他として、Co3O4、CoCO3等が含まれていると考えられる。
<Cobalt oxyhydroxide>
In the production method of the present invention, cobalt oxyhydroxide (CoOOH) having a Ni content of 100 ppm or less is used. More preferably, cobalt oxyhydroxide (CoOOH) having a Ni content of 70 ppm or less is used, and even more preferably, cobalt oxyhydroxide having a Ni content of 60 ppm or less is used. Particularly preferred is cobalt oxyhydroxide having a Ni content of 30 ppm or less. This is because as the nickel content in the reactant decreases, the Ni content in the lithium-cobalt composite oxide obtained by the production method of the present invention decreases. CoOOH is considered to be the main component of the cobalt oxyhydroxide, but it is also considered that Co 3 O 4 , CoCO 3 and the like are contained as other components.
本発明の製造方法に用いられるオキシ水酸化コバルトがどのような製造方法で得られたかについては、特に、限定されない。例えば、硝酸コバルト、塩化コバルト、硫酸コバルト等の2価のコバルトを有する化合物を、酸化剤で酸化させた後、アルカリで中和したもの等を用いることができる。 There is no particular limitation on the production method of the cobalt oxyhydroxide used in the production method of the present invention. For example, a compound obtained by oxidizing a compound having divalent cobalt such as cobalt nitrate, cobalt chloride, and cobalt sulfate with an oxidizing agent and then neutralizing with an alkali can be used.
上記酸化剤としては特に限定されず、例えば、空気、酸素、オゾン;過マンガン酸(HMnO4)及びM3MnO4等で表されるその塩;クロム酸(CrO3)及びM3 2Cr2O7、M3 2CrO4、M3CrO3X、CrO2X2等で表されるその関連化合物;F2、Cl2、Br2、I2等のハロゲン;H2O2、Na2O2、BaO2等の過酸化物;ペルオキソ酸及びM3 2S2O8、M3 2SO5、H2CO3、CH3CO3H等で表される化合物又はその塩;酸素酸及びM3MClO、M3BrO、M3IO、M3ClO3、M3BrO3、M3IO3、M3ClO4、M3IO4、Na3H2IO6、KIO4等で表される化合物又はその塩等を挙げることができる。式中、M3は、アルカリ金属元素を表す。上記アルカリ金属元素としては特に限定されず、例えば、リチウム、ナトリウム、カリウム、ルビジウム等が挙げられる。また、Xはハロゲン元素を示す。
There are no particular restrictions regarding the oxidizing agent, for example, air, oxygen, ozone, permanganic acid (HMnO 4) and M 3 a salt thereof MnO 4 or the like; chromic acid (CrO 3) and M 3 2 Cr 2 O 7, M 3 2 CrO 4 ,
中和するアルカリとしては特に限定されず、水酸化リチウム、水酸化ナトリウム、水酸化カリウム、水酸化マグネシウム、水酸化カルシウム、水酸化バリウム、水酸化アンモニウム等の無機水酸化物の水溶液等を好適に用いることができる。 The alkali to be neutralized is not particularly limited, and is preferably an aqueous solution of an inorganic hydroxide such as lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, and ammonium hydroxide. Can be used.
上記オキシ水酸化コバルトは、例えば、硝酸コバルト、塩化コバルト、硫酸コバルト等の2価のコバルトを有する化合物を水に溶解させて水溶液とし、上記酸化剤及び上記アルカリを添加して、中和と酸化とを同時に行うことにより得ることができる。また、上記2価のコバルトを有する化合物を含む水溶液に上記アルカリを加えて、2価の水酸化コバルトを合成した後、酸化剤を添加して酸化することにより上記オキシ水酸化コバルトを得ることもできる。更に、上記2価のコバルトを有する化合物を含む水溶液に上記酸化剤を添加した後、上記アルカリを添加して中和することにより上記オキシ水酸化コバルトを得ることもできる。 The cobalt oxyhydroxide is prepared by dissolving a compound having divalent cobalt such as cobalt nitrate, cobalt chloride, and cobalt sulfate in water to form an aqueous solution, and adding the oxidizing agent and the alkali to neutralize and oxidize. And at the same time. Alternatively, the above-mentioned alkali may be added to the aqueous solution containing the compound having divalent cobalt to synthesize divalent cobalt hydroxide, and then the above-mentioned cobalt oxyhydroxide may be obtained by adding and oxidizing an oxidizing agent. it can. Furthermore, the cobalt oxyhydroxide can also be obtained by adding the oxidizing agent to an aqueous solution containing the compound having divalent cobalt and then neutralizing by adding the alkali.
<リチウム化合物>
本発明の製造方法には、リチウム化合物が使用される。リチウム化合物は特に限定されないが、例えば水酸化リチウム、炭酸リチウム、硝酸リチウム等の無機リチウム塩を好適に用いる事ができる。リチウム化合物としては、炭酸リチウムが工業的に入手し易く、安価であるため好ましい。リチウム化合物の濃度は純度が高いことが好ましい。
<Lithium compound>
In the production method of the present invention, a lithium compound is used. The lithium compound is not particularly limited. For example, inorganic lithium salts such as lithium hydroxide, lithium carbonate, and lithium nitrate can be suitably used. As the lithium compound, lithium carbonate is preferable because it is industrially easily available and inexpensive. The concentration of the lithium compound is preferably high in purity.
<硫酸塩化合物>
本発明に係る製造方法では、硫酸塩化合物を含有させることができる。無機あるいは有機の硫酸塩化合物を添加して用いることができ、無機塩としては、硫酸鉄、硫酸コバルト、硫酸ニッケル、硫酸亜鉛、硫酸銅、硫酸リチウム、硫酸カリウム、硫酸マグネシウム、硫酸ベリリウム、硫酸ストロンチウム、硫酸バリウム、及びこれらの水和物を用いることができる。また、有機塩としては、硫酸水素テトラブチルアンモニウム、トリフルオロメタンスルホン酸、1−ナフチルアミン−2−スルホン酸、1−ナフチルアミン−5−スルホン酸、1−ナフトール−3、6−ジスルホン酸、p−ブロモベンゼンスルホン酸、p−アニリンスルホン酸、o−キシレン−4−スルホン酸、ジメチルスルホン、o−スルホ安息香酸、及び5−スルホサリチル酸等を用いることができる。これらの中でも、硫酸コバルト、硫酸マグネシウムが好ましく用いられる。
<Sulfate compound>
In the production method according to the present invention, a sulfate compound can be contained. An inorganic or organic sulfate compound can be added and used. As the inorganic salt, iron sulfate, cobalt sulfate, nickel sulfate, zinc sulfate, copper sulfate, lithium sulfate, potassium sulfate, magnesium sulfate, beryllium sulfate, strontium sulfate , Barium sulfate, and their hydrates can be used. Examples of the organic salt include tetrabutylammonium hydrogen sulfate, trifluoromethanesulfonic acid, 1-naphthylamine-2-sulfonic acid, 1-naphthylamine-5-sulfonic acid, 1-naphthol-3, 6-disulfonic acid, and p-bromo acid. Benzenesulfonic acid, p-anilinesulfonic acid, o-xylene-4-sulfonic acid, dimethyl sulfone, o-sulfobenzoic acid, 5-sulfosalicylic acid, and the like can be used. Among these, cobalt sulfate and magnesium sulfate are preferably used.
<ハロゲン化合物>
本発明の製造方法では、ハロゲン化合物を含有させることができる。添加するハロゲン化合物としては、Li、Mg、Al、Ca、Ti、V、Cr、Mn、Fe、Coから選ばれた少なくとも1種以上の金属元素と、前記フッ素、塩素、臭素などのハロゲン元素とのそれぞれの組み合わせが可能であるが、この中でも、LiF、MgF2が好ましく用いられる。
<Halogen compound>
In the production method of the present invention, a halogen compound can be contained. Examples of the halogen compound to be added include at least one metal element selected from Li, Mg, Al, Ca, Ti, V, Cr, Mn, Fe, and Co, and a halogen element such as the fluorine, chlorine, and bromine. Each combination is possible, and among them, LiF and MgF 2 are preferably used.
<製造方法>
本発明に係る製造方法では、例えば、まず、上記のオキシ水酸化コバルトとリチウム化合物、好ましくは炭酸リチウムを混合し、混合物を得る。混合は、乾式又は湿式のいずれの方法でもよいが、製造が容易であるため乾式が好ましい。乾式混合の場合は、原料を均一に混合するためのブレンダーを用いることが好ましい。混合工程における原料のリチウム化合物とオキシ水酸化コバルトの配合割合は、Co原子とLi原子のモル比(Li/Co)で0.99〜1.06であり、好ましくは0.99〜1.02である。
<Production method>
In the production method according to the present invention, for example, first, the above cobalt oxyhydroxide and a lithium compound, preferably lithium carbonate, are mixed to obtain a mixture. Mixing may be performed by either a dry method or a wet method, but a dry method is preferred because of easy production. In the case of dry mixing, it is preferable to use a blender for uniformly mixing the raw materials. The mixing ratio of the lithium compound as the raw material and the cobalt oxyhydroxide in the mixing step is 0.99 to 1.06, preferably 0.99 to 1.02 in molar ratio of Co atom to Li atom (Li / Co). It is.
本発明に係る製造方法では、オキシ水酸化コバルトとリチウム化合物との混合体に更に、硫酸塩化合物又はハロゲン化合物から選ばれる少なくとも1種以上の化合物を添加して上記と同様な方法で混合することが好ましい。 In the production method according to the present invention, at least one compound selected from a sulfate compound or a halogen compound is further added to a mixture of cobalt oxyhydroxide and a lithium compound, and the mixture is mixed in the same manner as described above. Is preferred.
なお、オキシ水酸化コバルトの平均粒子径は、特に限定されないが、例えば1〜20μm、好ましくは8〜15μmである。また、リチウム化合物の平均粒子径は、オキシ水酸化コバルトと同様に、特に制限されないが、例えば1〜100μm、好ましくは1〜20μmである。 The average particle size of the cobalt oxyhydroxide is not particularly limited, but is, for example, 1 to 20 μm, and preferably 8 to 15 μm. The average particle size of the lithium compound is not particularly limited, as in the case of cobalt oxyhydroxide, but is, for example, 1 to 100 μm, and preferably 1 to 20 μm.
次に混合物を焼成する。焼成温度は、700〜1100℃が好ましく、850〜1050℃が更に好ましい。焼成時間は、1〜24時間、好ましくは2〜10時間である。焼成温度が700℃より小さくなると、リチウムコバルト複合酸化物が十分に合成できず原料となるオキシ水酸化コバルトやリチウム化合物が残存し、好ましくない。一方、焼成温度が1100℃より高くなると目的とするリチウムコバルト複合酸化物の分解が始まり、リチウムコバルト複合酸化物を正極活物質として用いたリチウム二次電池の電池特性、特に放電末期の電圧による容量劣化やサイクル特性が劣化することから好ましくない。 Next, the mixture is fired. The firing temperature is preferably from 700 to 1100C, more preferably from 850 to 1050C. The firing time is 1 to 24 hours, preferably 2 to 10 hours. If the calcination temperature is lower than 700 ° C., the lithium-cobalt composite oxide cannot be sufficiently synthesized, and the cobalt oxyhydroxide or the lithium compound as a raw material remains, which is not preferable. On the other hand, when the firing temperature is higher than 1100 ° C., the decomposition of the target lithium-cobalt composite oxide starts, and the battery characteristics of the lithium secondary battery using the lithium-cobalt composite oxide as the positive electrode active material, particularly, the capacity at the end of discharge voltage It is not preferable because of deterioration and cycle characteristics.
焼成は、大気中又は酸素雰囲気中のいずれで行ってもよく、特に制限されるものではない。焼成後は、適宜冷却し、必要に応じ粉砕してリチウムコバルト複合酸化物を得る。なお、必要に応じて行われる粉砕は、焼成して得られるリチウムコバルト複合酸化物がもろく結合したブロック状のものである場合等に適宜行うが、リチウムコバルト複合酸化物の粒子自体は特定の平均粒子径、BET比表面積を有するものである。即ち、得られるリチウムコバルト複合酸化物は、レーザー法により求められる平均粒子径が1〜30μm、好ましくは3〜20μm、特に好ましくは5〜15μmであり、BET比表面積が0.1〜2.0m2/g、好ましくは0.2〜1.5m2/g、特に好ましくは0.2〜1.0m2/gである。 The firing may be performed in the air or in an oxygen atmosphere, and is not particularly limited. After the calcination, the mixture is appropriately cooled and pulverized as necessary to obtain a lithium-cobalt composite oxide. The pulverization performed as necessary is appropriately performed, for example, when the lithium-cobalt composite oxide obtained by firing is in the form of a brittlely bonded block, but the lithium-cobalt composite oxide particles themselves have a specific average It has a particle diameter and a BET specific surface area. That is, the obtained lithium-cobalt composite oxide has an average particle diameter determined by a laser method of 1 to 30 μm, preferably 3 to 20 μm, particularly preferably 5 to 15 μm, and a BET specific surface area of 0.1 to 2.0 m. 2 / g, preferably 0.2~1.5m 2 / g, particularly preferably 0.2~1.0m 2 / g.
上記したリチウムコバルト複合酸化物及びオキシ水酸化コバルトに対するニッケルの含有量は、重量%で0より大きく100ppm以下、格別に好ましくは0〜60ppmである。この理由として、リチウムコバルト複合酸化物中のニッケル原子はコバルト原子と同じサイトに置換されて、充放電容量に寄与するコバルトの原子数が少なくなるからである。またニッケル原子は異なる価数でコバルトに置換されるため電荷保証のために充放電に必要な3価のコバルトが更に少なくなってしまうことが考えられる。ニッケル含有量の下限値は特に限定されない。 The content of nickel with respect to the above-described lithium cobalt composite oxide and cobalt oxyhydroxide is greater than 0 and less than or equal to 100 ppm by weight, particularly preferably 0 to 60 ppm. The reason for this is that nickel atoms in the lithium-cobalt composite oxide are replaced at the same site as the cobalt atoms, and the number of cobalt atoms contributing to the charge / discharge capacity decreases. In addition, since nickel atoms are replaced by cobalt with different valences, it is conceivable that trivalent cobalt required for charging and discharging for charge assurance is further reduced. The lower limit of the nickel content is not particularly limited.
<Ni含有量の測定法>
過塩素酸で煮沸しながらリチウムコバルト複合酸化物(0.5g)を完全に溶解後、100mlになるように蒸留水を添加してその溶液中のNi量をICP発光分析装置(理学電機社製)により定量を行った。
<Method for measuring Ni content>
After completely dissolving the lithium-cobalt composite oxide (0.5 g) while boiling with perchloric acid, distilled water was added to make 100 ml and the amount of Ni in the solution was measured by an ICP emission spectrometer (manufactured by Rigaku Corporation). ).
<硫酸根の測定方法>
硫酸根の定量は、以下の方法により行った。試料0.5gを30mlビーカーに秤量し、硝酸1部に対して水1部を加えた希硝酸6ml及び過酸化水素水1部に対して水1部を加えた過酸化水素水4mlを加え、ホットプレート上で加熱し、完全に溶解させる。次いで、放冷した後、100mlメスフラスコに移し、定容する。さらに、10倍に希釈し、イオンクロマトグラフ(米国DIONEX社製、2000i/s型)にて硫酸根を定量した。
<Method for measuring sulfate>
Sulfate groups were quantified by the following method. 0.5 g of a sample was weighed in a 30 ml beaker, 6 ml of diluted nitric acid obtained by adding 1 part of water to 1 part of nitric acid, and 4 ml of hydrogen peroxide solution obtained by adding 1 part of water to 1 part of hydrogen peroxide solution, Heat on a hot plate to dissolve completely. Then, after allowing to cool, it is transferred to a 100 ml volumetric flask and the volume is fixed. Further, the mixture was diluted 10-fold, and sulfate groups were quantified by ion chromatography (manufactured by Dionex, USA, 2000i / s type).
<ハロゲン元素の測定方法>
[フッ化物イオンの定量]
得られたLiCoO2について水蒸気蒸留を行ない、ランタン−アリザリンコンプレキソン吸光光度法またはイオン電極法を適用してフッ化物イオンを定量した(JIS K 0102 34に準拠)。
<Halogen element measurement method>
[Quantitative determination of fluoride ion]
The obtained LiCoO 2 was subjected to steam distillation, and a fluoride ion was quantified by applying a lanthanum-alizarin complexone spectrophotometric method or an ion electrode method (based on JIS K 0102234).
<電池作成方法>
リチウム二次電池正極活物質には、上記リチウムコバルト複合酸化物が用いられる。正極活物質は、後述するリチウム二次電池の正極合剤、すなわち、正極活物質、導電剤、結着剤、及び必要に応じてフィラー等とからなる混合物の一原料である。本発明に係るリチウム二次電池正極活物質は、上記リチウムコバルト複合酸化物からなるため、他の原料と共に混合して正極合剤を調製する際に混練が容易であり、また、得られた正極合剤を正極集電体に塗布する際の塗工性が容易になる。
<How to make batteries>
The lithium-cobalt composite oxide is used as a positive electrode active material for a lithium secondary battery. The positive electrode active material is one raw material of a positive electrode mixture of a lithium secondary battery described later, that is, a mixture of a positive electrode active material, a conductive agent, a binder, and if necessary, a filler and the like. Since the lithium secondary battery positive electrode active material according to the present invention is composed of the above-described lithium-cobalt composite oxide, it is easy to knead when preparing a positive electrode mixture by mixing with other raw materials, and the obtained positive electrode The coatability when applying the mixture to the positive electrode current collector is facilitated.
本発明に係るリチウム二次電池は、上記リチウムコバルト複合酸化物を正極活物質に用いるものである。正極、負極、セパレーター、及びリチウム塩を含有する非水電解質からなる。正極は、例えば、正極集電体上に正極合剤を塗布乾燥等して形成されるものであり、正極合剤は正極活物質、導電剤、結着剤、及び必要により添加されるフィラー等からなる。 The lithium secondary battery according to the present invention uses the above lithium cobalt composite oxide as a positive electrode active material. It comprises a positive electrode, a negative electrode, a separator, and a non-aqueous electrolyte containing a lithium salt. The positive electrode is formed, for example, by applying a positive electrode mixture onto a positive electrode current collector and drying the positive electrode mixture. The positive electrode mixture includes a positive electrode active material, a conductive agent, a binder, and a filler that is added as necessary. Consists of
正極集電体としては、構成された電池において化学変化を起こさない電子伝導体であれば特に制限されるものでないが、例えば、ステンレス鋼、ニッケル、アルミニウム、チタン、焼成炭素、アルミニウムやステンレス鋼の表面にカーボン、ニッケル、チタン、銀を表面処理させたもの等が挙げられる。 The positive electrode current collector is not particularly limited as long as it is an electronic conductor that does not cause a chemical change in the configured battery.For example, stainless steel, nickel, aluminum, titanium, calcined carbon, aluminum and stainless steel Examples thereof include those whose surfaces are surface-treated with carbon, nickel, titanium, and silver.
導電剤としては、例えば、天然黒鉛及び人工黒鉛等の黒鉛、カーボンブラック、アセチレンブラック、炭素繊維、カーボンナノチューブや金属、ニッケル粉等の導電性材料が挙げられ、天然黒鉛としては、例えば、鱗状黒鉛、鱗片状黒鉛及び土状黒鉛等が挙げられる。これらは、1種又は2種以上組み合わせて用いることができる。導電剤の配合比率は、正極合剤中、1〜50重量%、好ましくは2〜30重量%である。 Examples of the conductive agent include conductive materials such as graphite such as natural graphite and artificial graphite, carbon black, acetylene black, carbon fiber, carbon nanotube and metal, and nickel powder.Examples of natural graphite include scale-like graphite. , Flaky graphite and earthy graphite. These can be used alone or in combination of two or more. The mixing ratio of the conductive agent is 1 to 50% by weight, preferably 2 to 30% by weight in the positive electrode mixture.
結着剤としては、例えば、ポリフッ化ビニリデン、ポリビニルアルコール、カルボキシメチルセルロース、ヒドロキシプロピルセルロース、再生セルロース、ジアセチルセルロース、ポリビニルピロリドン、エチレン−プロピレン−ジエンターポリマー(EPDM)、スルホン化EPDM、スチレンブタジエンゴム、フッ素ゴム、ポリエチレンオキシドなどの多糖類、熱可塑性樹脂、ゴム弾性を有するポリマー等が挙げられ、これらは1種または2種以上組み合わせて用いることができる。結着剤の配合比率は、正極合剤中、2〜30重量%、好ましくは5〜15重量%である。 Examples of the binder include polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, regenerated cellulose, diacetyl cellulose, polyvinyl pyrrolidone, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene butadiene rubber, Examples thereof include polysaccharides such as fluororubber and polyethylene oxide, thermoplastic resins, and polymers having rubber elasticity. These can be used alone or in combination of two or more. The mixing ratio of the binder is 2 to 30% by weight, preferably 5 to 15% by weight in the positive electrode mixture.
フィラーは正極合剤において正極の体積膨張等を抑制するものであり、必要により添加される。フィラーとしては、構成された電池において化学変化を起こさない繊維状材料であれば何でも用いることができるが、例えば、ポリプロピレン、ポリエチレン等のオレフィン系ポリマー、ガラス、炭素等の繊維が用いられる。フィラーの添加量は特に限定されないが、正極合剤中、0〜30重量%が好ましい。 The filler suppresses volume expansion and the like of the positive electrode in the positive electrode mixture, and is added as necessary. As the filler, any fibrous material that does not cause a chemical change in the configured battery can be used. For example, olefin polymers such as polypropylene and polyethylene, fibers such as glass and carbon are used. The addition amount of the filler is not particularly limited, but is preferably 0 to 30% by weight in the positive electrode mixture.
負極は、負極集電体上に負極材料を塗布乾燥等して形成される。負極集電体としては、構成された電池において化学変化を起こさない電子伝導体であれは特に制限されるものでないが、例えば、ステンレス鋼、ニッケル、銅、チタン、アルミニウム、焼成炭素、銅やステンレス鋼の表面にカーボン、ニッケル、チタン、銀を表面処理させたもの、及びアルミニウム−カドミウム合金等が挙げられる。 The negative electrode is formed by applying and drying a negative electrode material on a negative electrode current collector. The negative electrode current collector is not particularly limited as long as it is an electronic conductor that does not cause a chemical change in the configured battery.For example, stainless steel, nickel, copper, titanium, aluminum, calcined carbon, copper or stainless steel Examples thereof include a steel surface treated with carbon, nickel, titanium, and silver, and an aluminum-cadmium alloy.
負極材料としては、特に制限されるものではないが、例えば、炭素質材料や金属複合酸化物、リチウム金属、リチウム合金等が挙げられる。炭素質材料としては、例えば、難黒鉛化炭素材料、黒鉛系炭素材料等が挙げられる。金属複合酸化物としては、例えば、SnpM1-pM2 qOr(式中、M1はMn、Fe、Pb及びGeから選ばれる1種以上の元素を示し、M2はAl、B、P、Si、周期律表第1族、第2族、第3族及びハロゲン元素から選ばれる1種以上の元素を示し、0<p≦1、1≦q≦3、1≦r≦8を示す。)等の化合物が挙げられる。 The negative electrode material is not particularly limited, and examples thereof include a carbonaceous material, a metal composite oxide, lithium metal, and a lithium alloy. Examples of the carbonaceous material include a non-graphitizable carbon material and a graphite-based carbon material. As the metal composite oxide, for example, Sn p M 1 -pm in 2 q O r (wherein, M 1 is represents one or more elements selected Mn, Fe, Pb, and Ge, M 2 is Al, B , P, Si, at least one element selected from the first, second, and third groups of the periodic table and a halogen element, and 0 <p ≦ 1, 1 ≦ q ≦ 3, 1 ≦ r ≦ 8 Are shown.) And the like.
セパレーターとしては、大きなイオン透過度を持ち、所定の機械的強度を持った絶縁性の薄膜が用いられる。耐有機溶剤性と疎水性からポリプロピレンなどのオレフィン系ポリマーあるいはガラス繊維あるいはポリエチレンなどからつくられたシートや不織布が用いられる。セパレーターの孔径としては、一般的に電池用として有用な範囲であればよく、例えば、0.01〜10μmである。セパレーターの厚みとしては、一般的な電池用の範囲であればよく、例えば5〜300μmである。なお、後述する電解質としてポリマーなどの固体電解質が用いられる場合には、固体電解質がセパレーターを兼ねるようであってもよい。また、放電や充放電特性を改良する目的で、ピリジン、トリエチルフォスファイト、トリエタノールアミン等の化合物を電解質に添加してもよい。 As the separator, an insulating thin film having a high ion permeability and a predetermined mechanical strength is used. Sheets and nonwoven fabrics made of olefin polymers such as polypropylene, glass fiber, polyethylene, or the like are used because of their organic solvent resistance and hydrophobicity. The pore size of the separator may be generally in a range useful for batteries, and is, for example, 0.01 to 10 μm. The thickness of the separator may be in a range for a general battery, and is, for example, 5 to 300 μm. When a solid electrolyte such as a polymer is used as an electrolyte to be described later, the solid electrolyte may also serve as a separator. Further, a compound such as pyridine, triethyl phosphite, and triethanolamine may be added to the electrolyte for the purpose of improving the discharge and charge / discharge characteristics.
リチウム塩を含有する非水電解質は、非水電解質とリチウム塩とからなるものである。非水電解質としては、非水電解液又は有機固体電解質が用いられる。非水電解液としては、例えば、N−メチル−2−ピロリジノン、プロピレンカーボネート、エチレンカーボネート、ブチレンカーボネート、ジメチルカーボネート、ジエチルカーボネート、γ−ブチロラクトン、1,2−ジメトキシエタン、テトラヒドロキシフラン、2−メチルテトラヒドロフラン、ジメチルスルフォキシド、1,3−ジオキソラン、ホルムアミド、ジメチルホルムアミド、ジオキソラン、アセトニトリル、ニトロメタン、蟻酸メチル、酢酸メチル、リン酸トリエステル、トリメトキシメタン、ジオキソラン誘導体、スルホラン、3−メチル−2−オキサゾジノン、プロピレンカーボネート誘導体、テトラヒドロフラン誘導体、ジエチルエーテル、1,3−プロパンサルトン等の非プロトン性有機溶媒の1種または2種以上を混合した溶媒が挙げられる。 The non-aqueous electrolyte containing a lithium salt is composed of a non-aqueous electrolyte and a lithium salt. As the non-aqueous electrolyte, a non-aqueous electrolyte or an organic solid electrolyte is used. Examples of the non-aqueous electrolyte include N-methyl-2-pyrrolidinone, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, γ-butyrolactone, 1,2-dimethoxyethane, tetrahydroxyfuran, and 2-methyl Tetrahydrofuran, dimethyl sulfoxide, 1,3-dioxolan, formamide, dimethylformamide, dioxolan, acetonitrile, nitromethane, methyl formate, methyl acetate, phosphoric acid triester, trimethoxymethane, dioxolane derivative, sulfolane, 3-methyl-2- One or more aprotic organic solvents such as oxazodinone, propylene carbonate derivatives, tetrahydrofuran derivatives, diethyl ether, 1,3-propanesultone, etc. Mixed solvents thereof.
有機固体電解質としては、例えば、ポリエチレン誘導体又はこれを含むポリマー、ポリプロピレンオキサイド誘導体又はこれを含むポリマー、リン酸エステルポリマー等が挙げられる。リチウム塩としては、上記非水電解質に溶解するものが用いられ、例えば、LiClO4、LiBF4、LiPF6、LiCF3SO3、LiCF3CO2、LiAsF6、LiSbF6、LiB10Cl10、LiAlCl4、クロロボランリチウム、低級脂肪族カルボン酸リチウム、四フェニルホウ酸リチウム等の1種または2種以上を混合した塩が挙げられる。
Examples of the organic solid electrolyte include a polyethylene derivative or a polymer containing the same, a polypropylene oxide derivative or a polymer containing the same, and a phosphate ester polymer. The lithium salt, which is soluble in the non-aqueous electrolyte is used, for example, LiClO 4, LiBF 4, LiPF 6,
本発明に係るリチウム二次電池の形状はボタン、シート、シリンダー、角等いずれにも適用できる。本発明に係るリチウム二次電池の用途は、特に限定されないが、例えば、ノートパソコン、ラップトップパソコン、ポケットワープロ、携帯電話、コードレス電話子機、ポータブルCDプレーヤー、ラジオ等の電子機器、自動車、電動車両、ゲーム機器等の民生用電子機器が挙げられる。なお、リチウム二次電池は、非水電解質二次電池に含まれる。 The shape of the lithium secondary battery according to the present invention can be applied to any of buttons, sheets, cylinders, corners and the like. The use of the lithium secondary battery according to the present invention is not particularly limited. For example, notebook computers, laptop computers, pocket word processors, mobile phones, cordless telephones, portable CD players, radios and other electronic devices, automobiles, electric Examples include consumer electronic devices such as vehicles and game devices. Note that the lithium secondary battery is included in the nonaqueous electrolyte secondary battery.
<携帯用電子機器>
本発明では、上記の非水電解質二次電池を含有する携帯用電子機器が提供される。携帯用電子機器としては、例えば、ノートパソコン、ポケットワープロ、携帯電話、コードレス電話子機、ポータブルCDプレーヤー、ラジオ、ゲーム機器等が挙げられる。
<Portable electronic devices>
According to the present invention, there is provided a portable electronic device including the above non-aqueous electrolyte secondary battery. Examples of the portable electronic device include a notebook computer, a pocket word processor, a mobile phone, a cordless telephone handset, a portable CD player, a radio, a game device, and the like.
以下、本発明のリチウムコバルト複合酸化物及び非水電解質二次電池を更に説明する。 Hereinafter, the lithium-cobalt composite oxide and the nonaqueous electrolyte secondary battery of the present invention will be further described.
下記の実施例及び比較例では、炭酸リチウム(平均粒子径は10〜15μmが好ましく、ここでは、例えば11.0μmである)と、Ni含有量が25、49、98、205又は502ppmのオキシ水酸化コバルト(QNI社Chem Grade)(平均粒子径10〜15μmが好ましく、ここでは、例えば12.0μmである。)をLi/Co原子比が0.99〜1.060となるように秤量し、乳鉢で十分混合して均一な混合物を調製した。次いで、該混合物をアルミナ坩堝に充填し、電気加熱炉に入れて大気雰囲気下で昇温し、700〜1100℃の温度で10時間保持して焼成処理し、得られた焼成物を大気中で冷却した後、粉砕、分級することによって合成した。 In the following Examples and Comparative Examples, lithium carbonate (average particle diameter is preferably 10 to 15 μm, here, for example, 11.0 μm) and oxywater having a Ni content of 25, 49, 98, 205 or 502 ppm Cobalt oxide (Chem Grade, QNI) (average particle diameter is preferably 10 to 15 μm, here, for example, 12.0 μm) is weighed so that the Li / Co atomic ratio becomes 0.99 to 1.060, The mixture was thoroughly mixed in a mortar to prepare a uniform mixture. Next, the mixture is charged into an alumina crucible, placed in an electric heating furnace, heated in an air atmosphere, and held at a temperature of 700 to 1100 ° C. for 10 hours to perform a firing treatment. After cooling, it was synthesized by pulverization and classification.
[実施例1]
950℃で10時間焼成して、Ni含有量28ppmのリチウムコバルト複合酸化物(LiCoO2)を得た。平均粒子径は10.2μmであった。
[Example 1]
The mixture was calcined at 950 ° C. for 10 hours to obtain a lithium cobalt composite oxide (LiCoO 2 ) having a Ni content of 28 ppm. The average particle size was 10.2 μm.
[実施例2]
800℃で10時間焼成して、Ni含有量45ppmのリチウムコバルト複合酸化物(LiCoO2)を得た。平均粒子径は12.0μmであった。
[Example 2]
Calcination was performed at 800 ° C. for 10 hours to obtain a lithium-cobalt composite oxide (LiCoO 2 ) having a Ni content of 45 ppm. The average particle size was 12.0 μm.
[実施例3]
1000℃で10時間焼成して、Ni含有量58ppmのリチウムコバルト複合酸化物(LiCoO2)を得た。平均粒子径は11.2μmであった。
[Example 3]
By calcining at 1000 ° C. for 10 hours, a lithium cobalt composite oxide (LiCoO 2 ) having a Ni content of 58 ppm was obtained. The average particle size was 11.2 μm.
[実施例4]
1050℃で10時間焼成して、Ni含有量96ppmのリチウムコバルト複合酸化物(LiCoO2)を得た。平均粒子径は10.5μmであった。
[Example 4]
The mixture was calcined at 1050 ° C. for 10 hours to obtain a lithium cobalt composite oxide (LiCoO 2 ) having a Ni content of 96 ppm. The average particle size was 10.5 μm.
[実施例5]
Li/Coモル比1.04に相当する炭酸リチウム、オキシ水酸化コバルトとLiCoO2当たりSO4が2000ppmに相当する硫酸カルシウムを混合し、1060℃で5時間焼成して、Ni、SO4含有量がそれぞれ40ppm、1905ppmのリチウムコバルト複合酸化物(LiCoO2)を得た。平均粒子径は12.5μmであった。
[Example 5]
A lithium / cobalt oxyhydroxide equivalent to a Li / Co molar ratio of 1.04 and calcium sulfate equivalent to 2,000 ppm of SO 4 per LiCoO 2 are mixed and calcined at 1060 ° C. for 5 hours to obtain a Ni and SO 4 content. Obtained lithium cobalt composite oxide (LiCoO 2 ) of 40 ppm and 1905 ppm, respectively. The average particle size was 12.5 μm.
[実施例6]
Li/Coモル比1.04に相当する炭酸リチウム、オキシ水酸化コバルトにLiCoO2当たりFが3000ppmに相当するMgF2を混合し、1060℃で5時間焼成して、Ni、F含有量がそれぞれ40ppm、820ppmのリチウムコバルト複合酸化物(LiCoO2)を得た。平均粒子径は12.2μmであった。
[Example 6]
The lithium carbonate and the cobalt oxyhydroxide corresponding to a Li / Co molar ratio of 1.04 were mixed with MgF 2 corresponding to 3000 ppm of F per LiCoO 2 and baked at 1060 ° C. for 5 hours. 40 ppm and 820 ppm of lithium cobalt composite oxide (LiCoO 2 ) were obtained. The average particle size was 12.2 μm.
[実施例7]
Li/Coモル比1.04に相当する炭酸リチウム、オキシ水酸化コバルトにLiCoO2当たりSO4が1500ppmに相当する硫酸カルシウムとFが2000ppmに相当するMgF2を混合し、1060℃で5時間焼成して、Ni、F、SO4がそれぞれ40ppm、540ppm、1950ppmのリチウムコバルト複合酸化物(LiCoO2)を得た。平均粒子径は12.9μmであった。
[Example 7]
Lithium carbonate and cobalt oxyhydroxide corresponding to a Li / Co molar ratio of 1.04 are mixed with calcium sulfate corresponding to 1500 ppm of SO 4 and MgF 2 corresponding to 2000 ppm of F per LiCoO 2 and baked at 1060 ° C. for 5 hours. Thus, lithium-cobalt composite oxides (LiCoO 2 ) containing 40 ppm, 540 ppm, and 1950 ppm of Ni, F, and SO 4 respectively were obtained. The average particle size was 12.9 μm.
[比較例1]
1060℃で10時間焼成して、Ni含有量201ppmのリチウムコバルト複合酸化物(LiCoO2)を得た。平均粒子径は10.7μmであった。
[Comparative Example 1]
The mixture was calcined at 1060 ° C. for 10 hours to obtain a lithium cobalt composite oxide (LiCoO 2 ) having a Ni content of 201 ppm. The average particle size was 10.7 μm.
[比較例2]
820℃で10時間焼成して、Ni含有量490ppmのリチウムコバルト複合酸化物(LiCoO2)を得た。平均粒子径は11.2μmであった。
[Comparative Example 2]
The mixture was calcined at 820 ° C. for 10 hours to obtain a lithium cobalt composite oxide (LiCoO 2 ) having a Ni content of 490 ppm. The average particle size was 11.2 μm.
<粒度分布測定法>
ここで、本明細書に記載する平均粒子径はレーザー散乱粒度分布測定装置により得られた値を示すものとする。測定装置は特に限定されるものではないが、本明細書では日機装社製レーザー式粒度分布測定装置(Microtrac)を用いた。
<Particle size distribution measurement method>
Here, the average particle size described in this specification indicates a value obtained by a laser scattering particle size distribution measuring device. The measuring device is not particularly limited, but a laser type particle size distribution measuring device (Microtrac) manufactured by Nikkiso Co., Ltd. is used in this specification.
<電池性能試験>
(I)リチウム2次電池の作製;
上記のように製造した実施例1〜7及び比較例1〜2のリチウムコバルト複合酸化物91重量%、黒鉛粉末6重量%、ポリフッ化ビニリデン3重量%を混合して正極剤とし、これをN−メチル−2−ピロリジノンに分散させて混練ペーストを調製した。該混練ペーストをアルミ箔に塗布した後に乾燥、プレスして直径15mmの円盤に打ち抜いて正極板を得た。
<Battery performance test>
(I) Preparation of lithium secondary battery;
91% by weight of the lithium-cobalt composite oxide, 6% by weight of graphite powder, and 3% by weight of polyvinylidene fluoride prepared in Examples 1 to 7 and Comparative Examples 1 and 2 prepared as described above were mixed to form a positive electrode. -Methyl-2-pyrrolidinone was dispersed to prepare a kneaded paste. The kneading paste was applied to an aluminum foil, dried, pressed, and punched into a disk having a diameter of 15 mm to obtain a positive electrode plate.
図1で、この正極板を用いて、セパレーター1、負極2、正極3、集電板4、取り付け金具5、外部端子6、電解液7等の各部材を使用してリチウム二次電池、即ち、非水電解質二次電池を製作した。このうち、負極は金属リチウム箔を用い、電解液にはエチレンカーボネートとジエチルカーボネートの1:1混練液1リットルにLiPF61モルを溶解したものを使用した。
In FIG. 1, using this positive electrode plate, a lithium secondary battery, that is, a separator 1, a
(II)電池の性能評価;
作製したリチウム二次電池を室温で作動させ、初期放電容量を測定して電池性能を評価した。
(II) battery performance evaluation;
The produced lithium secondary battery was operated at room temperature, the initial discharge capacity was measured, and the battery performance was evaluated.
(III)評価方法;
放電容量は正極に対してCCCV(1.0C)で4.3Vまで充電した後、2.7Vまで放電させ放電容量を測定した。また、実施例1〜7、並びに、比較例1及び2で調製したリチウムコバルト複合酸化物を正極活物質として作成したリチウム二次電池について、電圧と放電容量の関係を図2に示した。
(III) evaluation method;
The discharge capacity was measured by charging the positive electrode to 4.3 V at CCCV (1.0 C) and then discharging to 2.7 V to measure the discharge capacity. FIG. 2 shows the relationship between the voltage and the discharge capacity of the lithium secondary batteries prepared using the lithium cobalt composite oxide prepared in Examples 1 to 7 and Comparative Examples 1 and 2 as the positive electrode active material.
<実験結果>
実施例1〜7、並びに、比較例1及び2で得られた活物質を電極塗布して2.7V〜4.3V(vs.Li/Li+)で定電流充放電試験を行った。その充放電カーブを示す。充放電電流は0.2Cで行った。実施例1〜7で得られた活物質はいずれも初期放電容量が158mAH/g以上であり、比較例1及び2で得られた活物質に比べて大きな放電容量が得られることが分かった。これは、リチウムコバルト複合酸化物に含有されているNiがCoに置換されて固溶体を形成するために、容量として使われているCo量が減少して容量減少が生じているからであると考えられる。これらの結果から、実施例1〜7のリチウム複合酸化物は、非水電解質二次電池として優れているものであることが確認された。
<Experimental results>
The active materials obtained in Examples 1 to 7 and Comparative Examples 1 and 2 were coated with an electrode, and a constant current charge / discharge test was performed at 2.7 V to 4.3 V (vs. Li / Li + ). The charge / discharge curve is shown. The charge / discharge current was 0.2 C. Each of the active materials obtained in Examples 1 to 7 had an initial discharge capacity of 158 mAH / g or more, and it was found that a larger discharge capacity was obtained than the active materials obtained in Comparative Examples 1 and 2. This is thought to be because Ni contained in the lithium-cobalt composite oxide was replaced with Co to form a solid solution, and the amount of Co used as the capacity decreased, resulting in a decrease in capacity. Can be From these results, it was confirmed that the lithium composite oxides of Examples 1 to 7 were excellent as nonaqueous electrolyte secondary batteries.
1 セパレーター
2 負極
3 正極
4 集電板
5 取り付け金具
6 外部端子
7 電解液
DESCRIPTION OF SYMBOLS 1
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JP2003349599A JP4846195B2 (en) | 2002-10-10 | 2003-10-08 | Lithium cobalt composite oxide, method for producing the same, and nonaqueous electrolyte secondary battery |
KR1020030070539A KR20040032796A (en) | 2002-10-10 | 2003-10-10 | Lithium Cobalt Composite Oxide, Method for preparing the Same and Nonaqueous Electrolyte Secondary Battery |
CA002462062A CA2462062A1 (en) | 2003-10-08 | 2004-03-26 | Lithium cobalt compound oxide and manufacturing methods thereof, and non-aqeuous eletrolyte secondary cell |
TW093108828A TW200514291A (en) | 2003-10-08 | 2004-03-31 | Lithium-cobalt compound oxide, method for producing the same, and non-aqueous electrolyte secondary battery |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2006160571A (en) * | 2004-12-08 | 2006-06-22 | Tanaka Chemical Corp | Mg SOLID SOLUTION COBALT OXYHYDROXIDE PARTICLE AND ITS PRODUCING METHOD |
JP2009026640A (en) * | 2007-07-20 | 2009-02-05 | Nippon Chem Ind Co Ltd | Positive electrode active material for lithium secondary battery, manufacturing method thereof, and lithium secondary battery |
EP2352190A2 (en) * | 2008-11-10 | 2011-08-03 | LG Chem, Ltd. | Positive active material with improved high voltage characteristics |
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2006160571A (en) * | 2004-12-08 | 2006-06-22 | Tanaka Chemical Corp | Mg SOLID SOLUTION COBALT OXYHYDROXIDE PARTICLE AND ITS PRODUCING METHOD |
JP4652791B2 (en) * | 2004-12-08 | 2011-03-16 | 株式会社田中化学研究所 | Mg solid solution cobalt oxyhydroxide particles and production method thereof |
JP2009026640A (en) * | 2007-07-20 | 2009-02-05 | Nippon Chem Ind Co Ltd | Positive electrode active material for lithium secondary battery, manufacturing method thereof, and lithium secondary battery |
EP2352190A2 (en) * | 2008-11-10 | 2011-08-03 | LG Chem, Ltd. | Positive active material with improved high voltage characteristics |
JP2012508444A (en) * | 2008-11-10 | 2012-04-05 | エルジー・ケム・リミテッド | Cathode active material with improved properties at high voltages |
EP2352190A4 (en) * | 2008-11-10 | 2013-07-03 | Lg Chemical Ltd | Positive active material with improved high voltage characteristics |
US8945770B2 (en) | 2008-11-10 | 2015-02-03 | Lg Chem, Ltd. | Cathode active material exhibiting improved property in high voltage |
JP2016054151A (en) * | 2008-11-10 | 2016-04-14 | エルジー・ケム・リミテッド | Cathode active material showing improved characteristics at high voltage |
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JP4846195B2 (en) | 2011-12-28 |
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