US20040191628A1 - Non-aqueous electrolyte secondary battery, positive electrode active material and method of manufacturing the same - Google Patents

Non-aqueous electrolyte secondary battery, positive electrode active material and method of manufacturing the same Download PDF

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US20040191628A1
US20040191628A1 US10/801,655 US80165504A US2004191628A1 US 20040191628 A1 US20040191628 A1 US 20040191628A1 US 80165504 A US80165504 A US 80165504A US 2004191628 A1 US2004191628 A1 US 2004191628A1
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lithium
oxide
magnesium
positive electrode
aqueous electrolyte
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Takao Inoue
Masahisa Fujimoto
Masaharu Itaya
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Sanyo Electric Co Ltd
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Sanyo Electric Co Ltd
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Assigned to SANYO ELECTRIC CO., LTD. reassignment SANYO ELECTRIC CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: FUJIMOTO, MASAHISA, INOUE, TAKAO, ITAYA, MASAHARU
Publication of US20040191628A1 publication Critical patent/US20040191628A1/en
Priority to US12/205,270 priority Critical patent/US7709151B2/en
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    • H—ELECTRICITY
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    • 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
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G17/00—Cultivation of hops, vines, fruit trees, or like trees
    • A01G17/04—Supports for hops, vines, or trees
    • A01G17/10—Holders for boughs or branches
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G17/00—Cultivation of hops, vines, fruit trees, or like trees
    • A01G17/04—Supports for hops, vines, or trees
    • A01G17/12—Tree-bands
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G7/00—Botany in general
    • A01G7/06—Treatment of growing trees or plants, e.g. for preventing decay of wood, for tingeing flowers or wood, for prolonging the life of plants
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/12—Manganates manganites or permanganates
    • C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
    • C01G45/1228—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [MnO2]n-, e.g. LiMnO2, Li[MxMn1-x]O2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/009—Compounds containing, besides iron, two or more other elements, with the exception of oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/40—Cobaltates
    • C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/40—Cobaltates
    • C01G51/66—Cobaltates containing alkaline earth metals, e.g. SrCoO3
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/66—Nickelates containing alkaline earth metals, e.g. SrNiO3, SrNiO2
    • 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
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of 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
    • H01M4/50—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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C01P2002/54—Solid solutions containing elements as dopants one element only
    • C—CHEMISTRY; METALLURGY
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    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/77—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by unit-cell parameters, atom positions or structure diagrams
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • 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

Definitions

  • the present invention relates to a non-aqueous electrolyte secondary battery, positive electrode active material, and method of manufacturing the same.
  • Metal oxides having a layered rock-salt structure such as lithium cobaltate, are currently used as high-voltage positive electrode active materials for lithium-ion batteries.
  • metal oxides have a capacity as low as 124 to 150 mAh/g, techniques for higher-capacity are under development, and intensive research on substitution materials is being carried out (refer to, for example, JP-2001-243951-A and JP-2001-155729-A).
  • Lithium cobaltate has a theoretical capacity approximately as high as 274 mAh/g. However, 55% of the theoretical capacity, which is approximately 150 mAh/g, is said to be the limitation of its use as positive electrode active material at present. For this reason, it is desired that the capacity of lithium cobaltate be increased.
  • An object of the present invention is to provide a non-aqueous electrolyte secondary battery having improved capacity, a positive electrode active material capable of improving the capacity, and method of manufacturing the same.
  • a non-aqueous electrolyte secondary battery comprises a negative electrode; a positive electrode including a positive electrode active material capable of storage and release of lithium; and a non-aqueous electrolyte, wherein the positive electrode active material has a rock-salt structure containing lithium and is composed of an oxide containing magnesium substituted for part of lithium.
  • the ion When magnesium is positioned in an octahedral 3b site in the layered rock-salt structure, the ion has a radius of 0.86 ⁇ , which is similar to the radius of an ion of 0.90 ⁇ when lithium is positioned in an octahedral 3b site. Therefore, the layered rock-salt structure is stabilized by substitution of magnesium in an octahedral 3b site. In this manner, an oxide in which a phase change hardly occurs on insertion and release of excessive lithium can be realized. As a result, the capacity of an oxide can be increased, leading to improved capacity of a non-aqueous secondary battery.
  • M1 is a metal of at least one type selected from the group consisting of cobalt, manganese, iron and nickel.
  • 0.5 ⁇ a ⁇ 1 and 0 ⁇ b ⁇ 0.25 are preferable. This allows sufficiently increased capacity of a lithium transition metal complex oxide.
  • the magnesium may be electrochemically substituted for the part of lithium in the oxide.
  • the magnesium may be chemically substituted for the part of lithium in the oxide.
  • a positive electrode active material capable of storage and release of lithium has a layered rock-salt structure containing lithium and is composed of an oxide containing magnesium substituted for part of lithium.
  • the magnesium is substituted for part of an octahedral 3b site in the layered rock-salt structure, so that the layered rock-salt structure is stabilized. In this manner, an oxide in which a phase change hardly occurs on insertion and release of excessive lithium can be realized. As a result, the capacity of a positive electrode active material can be increased.
  • M1 is a metal of at least one type selected from the group consisting of cobalt, manganese, iron and nickel.
  • 0.5 ⁇ a ⁇ 1 and 0 ⁇ b ⁇ 0.25 are preferable. This allows sufficiently increased capacity of a lithium transition metal complex oxide.
  • the magnesium may be electrochemically substituted for the part of lithium in the oxide.
  • the magnesium may be chemically substituted for the part of lithium in the oxide.
  • the magnesium may be electrochemically substituted for the part of lithium in the oxide using a non-aqueous electrolyte including an imide salt or a sulfonate in which a cation is magnesium.
  • the magnesium may be electrochemically substituted for the part of lithium in the oxide using a non-aqueous electrolyte including a sulfonyl imide salt in which a cation is magnesium.
  • a method of manufacturing a positive electrode active material according to still another aspect of the present invention comprises the step of electrochemically substituting magnesium for part of lithium in an oxide having a layered rock-salt structure containing lithium.
  • magnesium is substituted for the part of lithium in an octahedral 3b site in the layered rock-salt structure, so that the layered rock-salt structure is stabilized.
  • an oxide in which a phase change hardly occurs on insertion and release of excessive lithium can be realized.
  • the step of substituting may include the steps of preparing a cell in which a negative electrode and a positive electrode including the oxide are disposed in a non-aqueous electrolyte including a lithium salt (electrolyte salt); extracting the part of lithium in the oxide by charging the cell; after extracting the part of lithium in the oxide, replacing the non-aqueous electrolyte including a lithium salt (electrolyte salt) with a non-aqueous electrolyte including a lithium salt (electrolyte salt); and after the replacement of non-aqueous electrolyte, inserting magnesium into the oxide by discharging the cell.
  • a lithium salt electrolyte salt
  • the replacement of non-aqueous electrolyte can facilitate the substitution of magnesium for the part of lithium in the oxide.
  • the oxide may include a lithium transition metal complex oxide, and the transition metal may include at least one type of metal selected from the group consisting of cobalt, manganese, iron, and nickel.
  • the oxide may include lithium cobaltate.
  • the step of substituting may comprise the step of electrochemically substituting magnesium for the part of lithium in the oxide using a non-aqueous electrolyte including an imide salt or a sulfonate in which a cation is magnesium.
  • the step of substituting may comprise the step of electrochemically substituting magnesium for the part of lithium in the oxide using a non-aqueous electrolyte including a sulfonyl imide salt in which a cation is magnesium.
  • the substitution of magnesium for the part of lithium in the oxide can be facilitated.
  • FIG. 1 is a diagram showing the layered rock-salt structure of LiCoO 2 ;
  • FIG. 2 is a diagram showing a test cell using lithium cobaltate containing magnesium atoms substituted for part of lithium atoms as a positive electrode active material;
  • FIG. 3 is a diagram showing the measurement results of discharge curves of lithium cobaltate before and after substitution of magnesium atoms for lithium atoms;
  • FIG. 4 is a diagram showing the measurement results of XRD patterns of a positive electrode before and after substitution of magnesium atoms for lithium atoms.
  • the non-aqueous electrolyte secondary battery according to the present embodiment comprises a negative electrode, a positive electrode, and a non-aqueous electrolyte.
  • carbon materials such as graphite, lithium metal, lithium alloy, or the like capable of storage and release of lithium atoms (Li) may be used.
  • a lithium transition metal complex oxide having a layered rock-salt structure containing lithium and in which magnesium atoms (Mg) are substituted for part of lithium atoms is used.
  • the lithium transition metal complex oxide Li a Mg b CoO 2 , Li a Mg b MnO 2 , Li a Mg b FeO 2 , Li a Mg b NiO 2 , and or like may be used.
  • a+2b 1, 0 ⁇ a ⁇ 1, and 0 ⁇ b ⁇ 0.5.
  • the above-mentioned lithium transition metal complex oxide is formed by chemical or electrochemical substitution of magnesium atoms (Mg) for part of lithium atoms (Li) in LiCoO 2 , LiMnO 2 , LiFeO 2 , LiNiO 2 , or the like, as described later.
  • non-aqueous solvent for the non-aqueous electrolyte
  • non-aqueous solvents generally used in non-aqueous electrolyte secondary batteries
  • At least one type selected from, for example, ethylene carbonate, diethyl carbonate, dimethyl carbonate, propylene carbonate, cyclic ether, chain ether, or carbonate fluoride may be used.
  • lithium salts (electrolyte salts) generally used for non-aqueous electrolyte secondary batteries may-be used, and at least one selected from, for example, LiBF 4 , LiPF 6 , LiCF 3 SO 3 , LiC 4 FgSO 3 , LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 2 ) 2 , LiN (CF 3 SO 2 ) (COCF 3 ), and LiAsF 6 may be used.
  • LiBF 4 LiPF 6
  • LiN (C 2 F 5 SO 2 ) 2 LiN (CF 3 SO 2 ) (COCF 3 )
  • LiAsF 6 LiAsF 6
  • FIG. 1 is a diagram showing the layered rock-salt structure of LiCoO 2 : (a) in a cubic representation, and (b) in a hexagonal representation.
  • the layered rock-salt structure of LiCoO 2 has a basic skeleton in which oxygen atoms form a cubic closest packed arrangement having -A-B-C-stacked layers, where the numbers of anions and cations are equal, and where all spaces in octahedral oxygen are occupied with cations. Moreover, cobalt and lithium atoms individually form single layers in octahedral 3a sites and octahedral 3b sites between (111) oxygen layers, respectively, forming alternate stacked layers.
  • magnesium atoms are substituted for part of lithium atoms in octahedral 3b sites, so that the layered rock-salt structure is stabilized. In this manner, a lithium transition metal complex oxide in which a phase change hardly occurs on insertion and release of excessive lithium atoms can be realized.
  • (CF 3 SO 3 ) 2 Mg, (CH 3 SO 3 ) 2 Mg, (C 4 F 9 SO 3 ) 2 Mg, (C 6 F 5 SO 3 ) 2 Mg, (C 6 H 5 SO 3 ) 2 Mg, (C 8 F 17 SO 3 ) 2 Mg, or the like may be used.
  • the electrolyte salt is dissolved for use in a non-aqueous solvent (organic solvent) at a concentration of 0.1 to 1.5 M, preferably at a concentration of 0.5 to 1.5 M.
  • non-aqueous electrolyte solvent used at the time of electrochemical substitution of magnesium atoms (Mg) for lithium atoms (Li)
  • non-aqueous solvents generally used for batteries may be used.
  • organic solvent for example, cyclic ester carbonate, chain ester carbonate, esters, cyclic ethers, chain ethers, nitriles, amides, or the like may be used.
  • Cyclic ester carbonates may be illustrated by ethylene carbonate, propylene carbonate, butylene carbonate, and the like. Substances obtained by fluorinating part of or all of hydrogen atoms in the above-mentioned substances can also be used, such as trifluoropropylene carbonate and fluoroethyl carbonate.
  • Esters may be illustrated by methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, ⁇ -butyrolactone, and the like.
  • Chain ethers may be illustrated by 1,2-dimethoxyethane, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dihexyl ether, ethyl vinyl ether, butyl vinyl ether, methyl phenyl ether, ethyl phenyl ether, butyl phenyl ether, pentylphenyl ether, methoxytoluene, benzyl ethyl ether, diphenyl ether, dibenzyl ether, o-dimethoxybenzene, 1,2-diethoxyethane, 1,2-dibutoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, 1,1-dimethoxymethane, 1,1-diethoxyethane, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl, and the
  • Nitriles may be illustrated by acetonitrile and the like, and amides may be illustrated by dimethylformamide and the like.
  • the positive electrode active material formed by the method in the present embodiment has a stable rock-salt structure. Accordingly, a phase change hardly occurs on insertion and release of excessive lithium atoms. As a result, the capacity of a positive electrode active material can be increased, leading to improved capacity of a non-aqueous secondary battery.
  • Example 1 the test cell shown in FIG. 2 was prepared to measure the discharge capacity of lithium cobaltate in which magnesium atoms are substituted for part of lithium atoms.
  • a positive electrode 1 , a negative electrode 2 , and a reference electrode 3 are disposed in a cell vessel 10 .
  • a separator 4 is inserted between the positive electrode 1 and negative electrode 2 .
  • a non-aqueous electrolyte 5 is poured into the cell vessel 10 .
  • Example 1 lithium cobaltate (LiCoO2), a conducting agent made of carbon, and a binder made of polyvinilidene di fluoride (PVdF) were mixed at a weight ratio of 90:5:5, respectively, and N-methyl-2-pyrrolidone was added to the mixture to prepare a slurry. This slurry was applied to a current collector made of aluminum foil, forming the positive electrode 1 . Metallic lithium was used for the negative electrode 2 and reference electrode 3 .
  • LiCoO2 lithium cobaltate
  • PVdF polyvinilidene di fluoride
  • a non-aqueous electrolyte including a lithium salt
  • lithium hexafluorophosphate LiPF 6
  • DEC diethyl carbonate
  • a non-aqueous electrolyte including a magnesium salt
  • magnesium bis (trifluoromethyl sulfonyl) imide (((CF 3 SO 2 ) 2 N) 2 Mg) dissolved as a solute at a ratio of 1 mol/l in a solvent of ⁇ -butyrolactone ((CH 2 ) 3 OCO)
  • test cell thus prepared was discharged at a constant current by the following manner to evaluate the positive electrode active material.
  • Table 1 shows non-aqueous electrolyte and charge and discharge conditions.
  • FIG. 3 shows the measurement results of discharge curves of lithium cobaltate before and after substitution of magnesium atoms for lithium atoms.
  • ⁇ -BL denotes ⁇ -butyrolactone
  • Mg (TFSI) 2 denotes magnesium bis (trifluoromethyl sulfonyl) imide.
  • the above-mentioned non-aqueous electrolyte including a lithium salt is poured into the cell vessel 10 .
  • the test cell was charged, and then discharged.
  • the current density during charge and discharge was set to 1 mA/cm 2 .
  • the charge capacity was 120 mAh/g
  • the discharge capacity was 110 mAh/g.
  • the test cell was charged while the above-mentioned non-aqueous electrolyte including a lithium salt is held in the cell vessel 10 .
  • the current density during charge was 1 mA/cm 2.
  • the non-aqueous electrolyte in the cell vessel 10 was replaced with the above-mentioned non-aqueous electrolyte including a magnesium salt, and the test cell was discharged.
  • the current density during discharge was 0.025 mA/cm 2 .
  • the electrolyte in the cell vessel 10 was replaced with the above-mentioned non-aqueous electrolyte including a lithium salt, and the test cell was discharged.
  • the current density during discharge was 0.025 mA/cm 2 .
  • the discharge capacity was 124 mAh/g.
  • the test cell was charged while the above-mentioned non-aqueous electrolyte including a lithium salt is held in the cell vessel 10 .
  • the current density during discharge was 0.05 mA/cm 2 .
  • the charge capacity was 135 mAh/g.
  • the test cell was subsequently discharged.
  • the current density during discharge was 0.05 mA/cm 2 .
  • the discharge capacity was 136 mAh/g.
  • Example 2 a structural change in lithium cobaltate before and after substitution of magnesium atoms (Mg) for part of lithium atoms (Li) was confirmed by XRD (X-ray diffraction) measurement.
  • FIG. 4 shows the measurement results of XRD patterns of the positive electrode before and after substitution of magnesium atoms for lithium atoms.
  • thin solid line below represents an XRD pattern before substitution of magnesium atoms for lithium atoms
  • thick solid line above represents an XRD pattern after substitution of magnesium atoms for lithium atoms.
  • Black rhombuses represent reflection peaks from lithium cobaltate (LiCoO 2 ), and white circles represent reflection peaks from Al 2 O 3 .
  • the reflection peaks from Al 2 O 3 were derived from an aluminum oxide on the surface of the current collector.

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050260495A1 (en) * 2004-05-21 2005-11-24 Tiax Llc Lithium metal oxide materials and methods of synthesis and use
US20060194119A1 (en) * 2005-02-25 2006-08-31 Son Mi Y Lithium secondary battery with high performance
US20060204846A1 (en) * 2005-03-11 2006-09-14 Takuya Sunagawa Lithium secondary battery
WO2007006584A2 (de) * 2005-07-14 2007-01-18 Elsper Ruediger Anorganische feststoffkationenleiter und herstellungsverfahren
US20100009254A1 (en) * 2005-09-08 2010-01-14 Masaharu Itaya Non-Aqueous Electrolyte Secondary Battery
US9917302B2 (en) 2011-10-11 2018-03-13 Samsung Sdi Co., Ltd. Electrode active material for lithium secondary battery, method of preparing the electrode active material, electrode for lithium secondary battery including the same, and lithium secondary battery using the same
US9923244B2 (en) 2014-03-11 2018-03-20 Sanyo Electric Co., Ltd. Nonaqueous electrolyte secondary battery
US11183691B2 (en) 2016-12-21 2021-11-23 Lg Chem, Ltd. Metal-doped positive electrode active material for high voltage
US11670770B2 (en) 2017-06-26 2023-06-06 Semiconductor Energy Laboratory Co., Ltd. Method for manufacturing positive electrode active material, and secondary battery
US11799080B2 (en) 2017-05-19 2023-10-24 Semiconductor Energy Laboratory Co., Ltd. Positive electrode active material, method for manufacturing positive electrode active material, and secondary battery

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4524881B2 (ja) * 2000-08-14 2010-08-18 ソニー株式会社 非水電解質二次電池
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WO2021053448A1 (ja) * 2019-09-20 2021-03-25 株式会社半導体エネルギー研究所 二次電池用正極、二次電池および電子機器
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5591543A (en) * 1993-09-16 1997-01-07 Ramot University Authority For Applied Research And Industrial Development Ltd. Secondary electrochemical cell
US6171723B1 (en) * 1997-10-10 2001-01-09 3M Innovative Properties Company Batteries with porous components
US20030013017A1 (en) * 2000-12-27 2003-01-16 Masatoshi Nagayama Positive electrode active material for non-aqueous electrolyte secondary cell and cell using the same

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06168722A (ja) * 1992-11-26 1994-06-14 Japan Storage Battery Co Ltd 非水電解質電池
JP3624663B2 (ja) * 1996-12-24 2005-03-02 株式会社日立製作所 電池
JP2000200607A (ja) * 1998-07-13 2000-07-18 Ngk Insulators Ltd リチウム二次電池
JP2000123834A (ja) * 1998-10-09 2000-04-28 Gs Melcotec Kk 非水電解液二次電池
JP2000149942A (ja) * 1998-11-02 2000-05-30 Toyota Central Res & Dev Lab Inc リチウムマンガン複合酸化物およびこれを正極活物質に用いたリチウム二次電池
JP4650774B2 (ja) * 1999-06-07 2011-03-16 株式会社豊田中央研究所 リチウム二次電池正極活物質用リチウムニッケル複合酸化物およびそれを用いたリチウム二次電池
JP2001110413A (ja) * 1999-10-01 2001-04-20 Mitsui Mining & Smelting Co Ltd リチウム二次電池用正極材料及びこれを用いたリチウム二次電池
JP2001155729A (ja) 1999-11-24 2001-06-08 Sumitomo Metal Mining Co Ltd 非水系電解質二次電池用正極活物質および該正極活物質を用いた非水系電解質二次電池
JP2001243951A (ja) 2000-02-28 2001-09-07 Sumitomo Metal Mining Co Ltd 非水系電解質二次電池用正極活物質および該正極活物質を用いた非水系電解質二次電池
JP2001256975A (ja) * 2000-03-14 2001-09-21 Toyota Central Res & Dev Lab Inc リチウム二次電池正極活物質用リチウムニッケル複合酸化物、その製造方法およびそれを用いたリチウム二次電池
JP3858699B2 (ja) * 2002-01-11 2006-12-20 株式会社豊田中央研究所 リチウム二次電池正極活物質用リチウムニッケル複合酸化物およびそれを用いたリチウム二次電池
JP2003346797A (ja) * 2002-05-24 2003-12-05 Japan Storage Battery Co Ltd ニッケルリチウム複合酸化物を用いた非水電解質二次電池

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5591543A (en) * 1993-09-16 1997-01-07 Ramot University Authority For Applied Research And Industrial Development Ltd. Secondary electrochemical cell
US6171723B1 (en) * 1997-10-10 2001-01-09 3M Innovative Properties Company Batteries with porous components
US20030013017A1 (en) * 2000-12-27 2003-01-16 Masatoshi Nagayama Positive electrode active material for non-aqueous electrolyte secondary cell and cell using the same

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7381496B2 (en) * 2004-05-21 2008-06-03 Tiax Llc Lithium metal oxide materials and methods of synthesis and use
US20050260495A1 (en) * 2004-05-21 2005-11-24 Tiax Llc Lithium metal oxide materials and methods of synthesis and use
US20080286460A1 (en) * 2004-05-21 2008-11-20 Tiax Llc Lithium metal oxide materials and methods of synthesis and use
US20060194119A1 (en) * 2005-02-25 2006-08-31 Son Mi Y Lithium secondary battery with high performance
WO2006091020A1 (en) * 2005-02-25 2006-08-31 Lg Chem, Ltd. Lithium secondary battery with high performance
US20060204846A1 (en) * 2005-03-11 2006-09-14 Takuya Sunagawa Lithium secondary battery
WO2007006584A3 (de) * 2005-07-14 2007-04-12 Ruediger Elsper Anorganische feststoffkationenleiter und herstellungsverfahren
WO2007006584A2 (de) * 2005-07-14 2007-01-18 Elsper Ruediger Anorganische feststoffkationenleiter und herstellungsverfahren
US20100009254A1 (en) * 2005-09-08 2010-01-14 Masaharu Itaya Non-Aqueous Electrolyte Secondary Battery
US8852799B2 (en) 2005-09-08 2014-10-07 C/O Intellectual Property H.Q., Sanyo Electric Co., Ltd. Non-aqueous electrolyte secondary battery
US9917302B2 (en) 2011-10-11 2018-03-13 Samsung Sdi Co., Ltd. Electrode active material for lithium secondary battery, method of preparing the electrode active material, electrode for lithium secondary battery including the same, and lithium secondary battery using the same
US9923244B2 (en) 2014-03-11 2018-03-20 Sanyo Electric Co., Ltd. Nonaqueous electrolyte secondary battery
US11183691B2 (en) 2016-12-21 2021-11-23 Lg Chem, Ltd. Metal-doped positive electrode active material for high voltage
US11799080B2 (en) 2017-05-19 2023-10-24 Semiconductor Energy Laboratory Co., Ltd. Positive electrode active material, method for manufacturing positive electrode active material, and secondary battery
US11670770B2 (en) 2017-06-26 2023-06-06 Semiconductor Energy Laboratory Co., Ltd. Method for manufacturing positive electrode active material, and secondary battery

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US7709151B2 (en) 2010-05-04
CN1532967A (zh) 2004-09-29
KR101076501B1 (ko) 2011-10-24
CN1297022C (zh) 2007-01-24
JP2004288579A (ja) 2004-10-14
JP4404564B2 (ja) 2010-01-27
US20090011336A1 (en) 2009-01-08

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