JP4717847B2 - 正極活物質及びこれを含むリチウム二次電池 - Google Patents
正極活物質及びこれを含むリチウム二次電池 Download PDFInfo
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- JP4717847B2 JP4717847B2 JP2007053643A JP2007053643A JP4717847B2 JP 4717847 B2 JP4717847 B2 JP 4717847B2 JP 2007053643 A JP2007053643 A JP 2007053643A JP 2007053643 A JP2007053643 A JP 2007053643A JP 4717847 B2 JP4717847 B2 JP 4717847B2
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- Prior art keywords
- lithium
- positive electrode
- active material
- electrode active
- secondary battery
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- 239000007774 positive electrode material Substances 0.000 title claims description 54
- 229910052744 lithium Inorganic materials 0.000 title claims description 45
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 40
- 239000011572 manganese Substances 0.000 claims description 47
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 claims description 43
- 229910052596 spinel Inorganic materials 0.000 claims description 43
- 239000011029 spinel Substances 0.000 claims description 43
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 15
- 229910015222 Ni1/3Mn1/3Co1/3O2 Inorganic materials 0.000 claims description 13
- 150000001450 anions Chemical class 0.000 claims description 10
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 claims description 9
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 229910016486 Ni0.4Mn0.4Co0.2 Inorganic materials 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 4
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- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
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- 238000000034 method Methods 0.000 description 12
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
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- 239000011651 chromium Substances 0.000 description 2
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 description 2
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- 150000002641 lithium Chemical class 0.000 description 1
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- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
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- 159000000002 lithium salts Chemical class 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910001000 nickel titanium Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 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
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000737 periodic effect Effects 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
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 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
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000001008 quinone-imine dye Substances 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 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
- 239000011593 sulfur Substances 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide 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
- 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
- H01M4/485—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
- 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
- H01M4/36—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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
- H01M4/581—Chalcogenides or intercalation compounds thereof
-
- 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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- 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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
Li1+xMn2−yMyO4−zAz (1)
(式中、Mは、酸化数2価または3価の金属を表し(M=B、Mg、Al、Ca、Sr、Co、Ni、Cr、Cu、Fe、Ti、Y及びZn);
Aは、−1価または−2価の陰イオンを表し;
0≦x≦0.2;
0≦y≦0.2;及び
0<z≦0.5である。)
Li1+aNibMncCo1−(b+c)O2 (2)
(式中、0≦a≦0.1;
0.2≦b≦0.7;
0.2≦c≦0.7;及び
b+c<1である。)
本明細書において、「活物質」とは、「活性物質」をも包含する意味である。
Li1+xMn2O3.95F0.05のリチウムマンガンスピネル酸化物と、Li1+aNi1/3Mn1/3Co1/3O2のリチウムニッケルコバルトマンガン複合酸化物を、重量比で1:1混合して正極活物質を製造した。該正極活物質に、カーボンブラックと決着剤のPVdFをそれぞれ5重量%ずつ混合し、溶媒のNMPと一緒に撹はんした後、金属集電体であるアルミニウムホイルにコーティングした。これを、120℃の真空オーブンで2時間以上乾燥し、正極を製造した。
Li1+xMn2O3.95F0.05の代りに、Li1+xMn2O3.8F0.2の置換されたリチウムマンガンスピネル酸化物を使用して正極活物質を製造した以外は、実施例1と同様にしてリチウム二次電池を組み立て、3.0〜4.2V電圧領域で充放電を進行しながら寿命特性を測定した。その結果を、下記表1に示す。
Li1+xMn2O3.95F0.05の代りに、Li1+xMn2O3.5F0.5の置換されたリチウムマンガンスピネル酸化物を使用して正極活物質を製造した以外は、実施例1と同様にしてリチウム二次電池を組み立て、3.0〜4.2V電圧領域で充放電を進行しながら寿命特性を測定した。その結果を、下記表1に示す。
Li1+xMn2O3.95F0.05の代りに、Li1+xMn2O3.95S0.05の置換されたリチウムマンガンスピネル酸化物を使用して正極活物質を製造した以外は、実施例1と同様にしてリチウム二次電池を組み立て、3.0〜4.2V電圧領域で充放電を進行しながら寿命特性を測定した。その結果を下記表1に示す。
Li1+xMn2O3.95F0.05の代りに、Li1+xMn2O3.8S0.2の置換されたリチウムマンガンスピネル酸化物を使用して正極活物質を製造した以外は、実施例1と同様にしてリチウム二次電池を組み立て、3.0〜4.2V電圧領域で充放電を進行しながら寿命特性を測定した。その結果を、下記表1に示す。
Li1+xMn2O3.95F0.05の代りに、Li1+xMn2O3.5S0.5の置換されたリチウムマンガンスピネル酸化物を使用して正極活物質を製造した以外は、実施例1と同様にしてリチウム二次電池を組み立て、3.0〜4.2V電圧領域で充放電を進行しながら寿命特性を測定した。その結果を、下記表1に示す。
Li1+xMn2O3.95F0.05の代りに、Li1+xMn2O4の非置換されたリチウムマンガンスピネル酸化物を使用して正極活物質を製造した以外は、実施例1と同様にしてリチウム二次電池を組み立て、3.0〜4.2V電圧領域で充放電を進行しながら寿命特性を測定した。その結果を、下記表1に示す。
Li1+xMn2O3.95F0.05の代りに、Li1+xMn2O3.3F0.7の置換されたリチウムマンガンスピネル酸化物を使用して正極活物質を製造した以外は、実施例1と同様にしてリチウム二次電池を組み立て、3.0〜4.2V電圧領域で充放電を進行しながら寿命特性を測定した。その結果を、下記表1に示す。
Li1+xMn2O3.95F0.05の代りに、Li1+xMn2O3.3S0.7の置換されたリチウムマンガンスピネル酸化物を使用して正極活物質を製造した以外は、実施例1と同様にしてリチウム二次電池を組み立て、3.0〜4.2V電圧領域で充放電を進行しながら寿命特性を測定した。その結果を、下記表1に示す。
Li1+xMn2O3.95S0.05の置換されたリチウムマンガンスピネル酸化物とLi1+aNi1/3Mn1/3Co1/3O2のリチウムニッケルコバルトマンガン複合酸化物を、90:10の重量比として正極活物質を製造した以外は、実施例1と同様にしてリチウム二次電池を組み立て、3.0〜4.2V電圧領域で充放電を進行しながら寿命特性を測定した。その結果を、下記表2に示す。
Li1+xMn2O3.95S0.05の置換されたリチウムマンガンスピネル酸化物とLi1+aNi1/3Mn1/3Co1/3O2のリチウムニッケルコバルトマンガン複合酸化物を70:30の重量比として正極活物質を製造した以外は、実施例1と同様にしてリチウム二次電池を組み立て、3.0〜4.2V電圧領域で充放電を進行しながら寿命特性を測定した。その結果を、下記表2に示す。
Li1+xMn2O3.95S0.05の置換されたリチウムマンガンスピネル酸化物とLi1+aNi1/3Mn1/3Co1/3O2のリチウムニッケルコバルトマンガン複合酸化物を30:70の重量比として正極活物質を製造した以外は、実施例1と同様にしてリチウム二次電池を組み立て、3.0〜4.2V電圧領域で充放電を進行しながら寿命特性を測定した。その結果を、下記表2に示す。
Li1+xMn2O3.95S0.05の置換されたリチウムマンガンスピネル酸化物とLi1+aNi1/3Mn1/3Co1/3O2のリチウムニッケルコバルトマンガン複合酸化物を10:90の重量比として正極活物質を製造した以外は、実施例1と同様にしてリチウム二次電池を組み立て、3.0〜4.2V電圧領域で充放電を進行しながら寿命特性を測定した。その結果を、下記表2に示す。
Li1+xMn2O3.95S0.05の置換されたリチウムマンガンスピネル酸化物のみを使用して正極活物質を製造した以外は、実施例1と同様にしてリチウム二次電池を組み立て、3.0〜4.2V電圧領域で充放電を進行しながら寿命特性を測定した。その結果を、下記表2に示す。
Li1+aNi1/3Mn1/3Co1/3O2のリチウムニッケルコバルトマンガン複合酸化物のみを使用して正極活物質を製造した以外は、実施例1と同様にしてリチウム二次電池を組み立て、3.0〜4.2V電圧領域で充放電を進行しながら寿命特性を測定した。その結果を、下記表2に示す。
Li1+xMn2O3.95S0.05の置換されたリチウムマンガンスピネル酸化物とLi1+aNi0.4Mn0.4Co0.2O2のリチウムニッケルコバルトマンガン複合酸化物を90:10の重量比として正極活物質を製造した以外は、実施例1と同様にしてリチウム二次電池を組み立て、3.0〜4.2V電圧領域で充放電を進行しながら寿命特性を測定した。その結果を、下記表3に示す。
Li1+xMn2O3.95S0.05の置換されたリチウムマンガンスピネル酸化物とLi1+aNi0.4Mn0.4Co0.2O2のリチウムニッケルコバルトマンガン複合酸化物を70:30の重量比として正極活物質を製造した以外は、実施例1と同様にしてリチウム二次電池を組み立て、3.0〜4.2V電圧領域で充放電を進行しながら寿命特性を測定した。その結果を、下記表3に示す。
Li1+xMn2O3.95S0.05の置換されたリチウムマンガンスピネル酸化物とLi1+aNi0.4Mn0.4Co0.2O2のリチウムニッケルコバルトマンガン複合酸化物を50:50の重量比として正極活物質を製造した以外は、実施例1と同様にしてリチウム二次電池を組み立て、3.0〜4.2V電圧領域で充放電を進行しながら寿命特性を測定した。その結果を、下記表3に示す。
Li1+xMn2O3.95S0.05の置換されたリチウムマンガンスピネル酸化物とLi1+aNi0.4Mn0.4Co0.2O2のリチウムニッケルコバルトマンガン複合酸化物を50:50の重量比として正極活物質を製造した以外は、実施例1と同様にしてリチウム二次電池を組み立て、3.0〜4.2V電圧領域で充放電を進行しながら寿命特性を測定した。その結果を、下記表3に示す。
Li1+xMn2O3.95S0.05の置換されたリチウムマンガンスピネル酸化物とLi1+aNi0.4Mn0.4Co0.2O2のリチウムニッケルコバルトマンガン複合酸化物を10:90の重量比として正極活物質を製造した以外は、実施例1と同様にしてリチウム二次電池を組み立て、3.0〜4.2V電圧領域で充放電を進行しながら寿命特性を測定した。その結果を、下記表3に示す。
Li1+aNi0.4Mn0.4Co0.2O2のリチウムニッケルコバルトマンガン複合酸化物のみを使用して正極活物質を製造した以外は、実施例1と同様にしてリチウム二次電池を組み立て、3.0〜4.2V電圧領域で充放電を進行しながら寿命特性を測定した。その結果を、下記表3に示す。
Li1+xMn1.9Al0.1O3.95S0.05の置換されたリチウムマンガンスピネル酸化物とLi1+aNi1/3Mn1/3Co1/3O2のリチウムニッケルコバルトマンガン複合酸化物を90:10の重量比として正極活物質を製造した以外は、実施例1と同様にしてリチウム二次電池を組み立て、3.0〜4.2V電圧領域で充放電を進行しながら寿命特性を測定した。その結果を、下記表4に示す。
Li1+xMn1.9Al0.1O3.95S0.05の置換されたリチウムマンガンスピネル酸化物とLi1+aNi1/3Mn1/3Co1/3O2のリチウムニッケルコバルトマンガン複合酸化物を70:30の重量比として正極活物質を製造した以外は、実施例1と同様にしてリチウム二次電池を組み立て、3.0〜4.2V電圧領域で充放電を進行しながら寿命特性を測定した。その結果を、下記表4に示す。
Li1+xMn1.9Al0.1O3.95S0.05の置換されたリチウムマンガンスピネル酸化物とLi1+aNi1/3Mn1/3Co1/3O2のリチウムニッケルコバルトマンガン複合酸化物を50:50の重量比として正極活物質を製造した以外は、実施例1と同様にしてリチウム二次電池を組み立て、3.0〜4.2V電圧領域で充放電を進行しながら寿命特性を測定した。その結果を、下記表4に示す。
Li1+xMn1.9Al0.1O3.95S0.05の置換されたリチウムマンガンスピネル酸化物とLi1+aNi1/3Mn1/3Co1/3O2のリチウムニッケルコバルトマンガン複合酸化物を30:70の重量比として正極活物質を製造した以外は、実施例1と同様にしてリチウム二次電池を組み立て、3.0〜4.2V電圧領域で充放電を進行しながら寿命特性を測定した。その結果を、下記表4に示す。
Li1+xMn1.9Al0.1O3.95S0.05の置換されたリチウムマンガンスピネル酸化物とLi1+aNi1/3Mn1/3Co1/3O2のリチウムニッケルコバルトマンガン複合酸化物を10:90の重量比として正極活物質を製造した以外は、実施例1と同様にしてリチウム二次電池を組み立て、3.0〜4.2V電圧領域で充放電を進行しながら寿命特性を測定した。その結果を、下記表4に示す。
Li1+xMn1.9Al0.1O3.95S0.05の置換されたリチウムマンガンスピネル酸化物のみを使用して正極活物質を製造した以外は、実施例1と同様にしてリチウム二次電池を組み立て、3.0〜4.2V電圧領域で充放電を進行しながら寿命特性を測定した。その結果を、下記表4に示す。
Claims (8)
- 下記式(1)で表されるリチウムマンガンスピネル酸化物と、及び
下記式(2)で表されるリチウムニッケルコバルトマンガン酸化物との混合物を含んでなり、
前記リチウムマンガンスピネル酸化物と、リチウムニッケルコバルトマンガン酸化物の混合比が、重量基準で10:90〜90:10である、二次電池用正極活物質。
Li1+xMn2−yMyO4−zAz (1)
Li1+aNibMncCo1−(b+c)O2 (2)
(上記式(1)及び式(2)において、
Mは、酸化数2価又は3価の金属を表し、
Aは、−1価又は2価の陰イオンを表し、かつ、Aは、F、Cl、Br、S及びこれらの組み合わせからなる群より選択されるものであり、
0≦x≦0.2、
0≦y≦0.2、
0<z≦0.5、
0≦a≦0.1、
0.2≦b≦0.7、
0.2≦c≦0.7、
b+c<1である。) - 前記Mが、B、Mg、Al、Ca、Sr、Co、Ni、Cr、Cu、Fe、Ti、Y及びZnからなる群より選択される一種又は二種以上のものである、請求項1に記載の二次電池用正極活物質。
- 前記zが、0.01〜0.2である、請求項1に記載の二次電池用正極活物質。
- 前記式(2)で表されるリチウムニッケルコバルトマンガン酸化物が、Li1+aNi1/3Mn1/3Co1/3O2である、請求項1に記載の二次電池用正極活物質。
- 前記式(2)で表されるリチウムニッケルコバルトマンガン酸化物が、Li1+aNi0.4Mn0.4Co0.2O2であることを特徴とする、請求項1に記載の二次電池用正極活物質。
- 前記リチウムマンガンスピネル酸化物と、リチウムニッケルコバルトマンガン酸化物の混合比が、重量基準で30:70〜90:10である、請求項1に記載の二次電池用正極活物質。
- 請求項1〜6の何れか一項に記載の二次電池用正極活物質を備えてなる、リチウム二次電池。
- 請求項7に記載のリチウム二次電池を単位電池として備えてなる、電池モジュール。
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KR100801637B1 (ko) | 2006-05-29 | 2008-02-11 | 주식회사 엘지화학 | 양극 활물질 및 그것을 포함하고 있는 리튬 이차전지 |
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- 2007-03-05 JP JP2007053643A patent/JP4717847B2/ja active Active
- 2007-05-29 WO PCT/KR2007/002589 patent/WO2007139333A1/en active Application Filing
- 2007-05-29 EP EP07746736.3A patent/EP2036149B1/en active Active
- 2007-05-29 US US12/227,837 patent/US7816033B2/en active Active
- 2007-05-29 CN CN2007800277582A patent/CN101496200B/zh active Active
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Also Published As
Publication number | Publication date |
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CN101496200A (zh) | 2009-07-29 |
CN101496200B (zh) | 2011-11-09 |
US7816033B2 (en) | 2010-10-19 |
US20100012886A1 (en) | 2010-01-21 |
JP2007317639A (ja) | 2007-12-06 |
EP2036149A1 (en) | 2009-03-18 |
KR20070114411A (ko) | 2007-12-04 |
EP2036149A4 (en) | 2011-07-06 |
EP2036149B1 (en) | 2013-08-28 |
KR100801637B1 (ko) | 2008-02-11 |
WO2007139333A1 (en) | 2007-12-06 |
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