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WO2004082046A1 - Positive electrode active material powder for lithium secondary battery - Google Patents

Positive electrode active material powder for lithium secondary battery Download PDF

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Publication number
WO2004082046A1
WO2004082046A1 PCT/JP2004/003295 JP2004003295W WO2004082046A1 WO 2004082046 A1 WO2004082046 A1 WO 2004082046A1 JP 2004003295 W JP2004003295 W JP 2004003295W WO 2004082046 A1 WO2004082046 A1 WO 2004082046A1
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WO
WIPO (PCT)
Prior art keywords
lithium
composite oxide
powder
manganese composite
positive electrode
Prior art date
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Ceased
Application number
PCT/JP2004/003295
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French (fr)
Japanese (ja)
Inventor
Manabu Suhara
Takuya Mihara
Koichiro Ueda
Yukimitsu Wakasugi
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Seimi Chemical Co Ltd
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Seimi Chemical Co Ltd
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Publication date
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Priority to JP2005503600A priority Critical patent/JPWO2004082046A1/en
Publication of WO2004082046A1 publication Critical patent/WO2004082046A1/en
Priority to US11/133,322 priority patent/US20050220700A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/12—Complex oxides containing manganese and at least one other metal element
    • C01G45/1221—Manganates or manganites with trivalent manganese, tetravalent manganese or mixtures thereof
    • C01G45/1228—Manganates or manganites with trivalent manganese, tetravalent manganese or mixtures thereof of the type (MnO2)-, e.g. LiMnO2 or Li(MxMn1-x)O2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/40—Complex oxides containing cobalt and at least one other metal element
    • C01G51/42—Complex oxides containing cobalt and at least one other metal element containing alkali metals, e.g. LiCoO2
    • C01G51/44—Complex oxides containing cobalt and at least one other metal element containing alkali metals, e.g. LiCoO2 containing manganese
    • C01G51/50—Complex oxides containing cobalt and at least one other metal element containing alkali metals, e.g. LiCoO2 containing manganese of the type (MnO2)n-, e.g. Li(CoxMn1-x)O2 or Li(MyCoxMn1-x-y)O2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Complex oxides containing nickel and at least one other metal element
    • C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
    • C01G53/44—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2
    • 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
    • H01M4/52—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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/45—Aggregated particles or particles with an intergrown morphology
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • C01P2004/52—Particles with a specific particle size distribution highly monodisperse size distribution
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • 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
    • C01P2006/12—Surface area
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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 provides a lithium nickel cobalt manganese composite oxide powder for a lithium secondary battery positive electrode, which has a large volume capacity density, high safety, and excellent charge / discharge cycle durability.
  • the present invention relates to a positive electrode for a lithium secondary battery containing a powder, and a lithium secondary battery. Background art
  • non-aqueous electrolyte secondary batteries such as lithium secondary batteries
  • the positive electrode active material for non-aqueous electrolyte solution for a secondary battery L i Co 0 2, L i N i 0 2, L i N i a8 C o. 2 0 2, L iMn 2 0 4, L iMn0 composite oxide of lithium and transition metals such as 2 are known.
  • lithium cobalt composite oxide (L i Co0 2) as a positive electrode active material, a lithium alloy, graphite, lithium secondary batteries using carbon such as carbon fiber as a negative electrode, a high 4 V-class Since a voltage can be obtained, it is widely used as a battery with high energy density.
  • the active material be excellent in coating characteristics, self-discharge characteristics, and cycle characteristics.
  • the publication proposes a preferred embodiment in which Li CoO 2 has substantially no particle size distribution of 1 m or less or 25 / xm or more.
  • the coating characteristics and the cycle characteristics are improved, a material which sufficiently satisfies safety, volume capacity density, and weight capacity density has not been obtained.
  • Japanese Patent Application Laid-Open No. 2000-82466 discloses that the average particle diameter of lithium composite oxide particles is 0.1 to 50 m, A positive electrode active material that has two or more peaks in the distribution has been proposed. It has also been proposed to mix two types of positive electrode active materials having different average particle diameters to obtain a positive electrode active material having two or more peaks in the particle size distribution.
  • the weight capacity density and charge / discharge cycleability of the positive electrode may be improved, but the production of the positive electrode raw material powder having two types of particle size distribution is complicated, and the volume capacity density of the positive electrode, low No product that satisfies all of the requirements for completeness, coating uniformity, weight capacity density, and cycleability has been obtained.
  • Japanese Patent Application Laid-Open No. 3-201368 discloses that replacing 5 to 35% of Co atoms with W, Mn, Ta, Ti or Nb for improving cycle characteristics. Proposed.
  • Japanese Patent Application Laid-Open No. Hei 10-312805 discloses a hexagonal system in which the c-axis length of the lattice constant is 14.051 A or less, and the crystallite diameter of the crystallite in the (110) direction is 45 to 100 nm.
  • L i C O_ ⁇ 2 is possible to further improve the cycle characteristics to the cathode active material has been proposed.
  • JP 2001- the 80920 discloses, wherein L i X N i H, _ Z C o y Me 7 0 2 ( wherein, 0 ⁇ ⁇ 1. 1 , 0 ⁇ y ⁇ 0.6, O ⁇ z ⁇ 0.6), and an agglomerated granular lithium composite oxide in which fine powder is agglomerated, and a granular lithium composite oxide having a compressive strength per particle of 0.1-1.0 g g has been proposed.
  • the composite oxide has a problem of poor safety and poor high-current discharge characteristics, and at the compressive strength in the above-described small range, the volume capacity density, safety, cycle characteristics, and high-current discharge characteristics are low.
  • the present invention provides a lithium-nickel-cobalt-manganese composite oxide powder for a positive electrode of a lithium secondary battery, which satisfies these characteristics which have been difficult to achieve with the conventional techniques, and a lithium-nickel-cobalt-manganese composite oxide powder.
  • the purpose of the present invention is to provide a positive electrode for a lithium secondary battery and a lithium secondary battery. Disclosure of the invention
  • the present inventors have conducted intensive studies and found that a large number of fine particles of lithium nickel cobalt manganese composite oxide having a specific composition for a lithium secondary battery positive electrode are formed by agglomeration, and the aggregated particulate composite having a specific average particle diameter is formed. Focusing on the relationship between the compressive crushing strength of the oxide powder and the volume capacity density of the positive electrode for a lithium secondary battery using the powder, it was found that both were in a positive correlation. That is, it was found that the larger the compressive breaking strength of the powder, the higher the volume capacity density of the obtained positive electrode. In addition, it has been confirmed that such a large volume capacity density of the positive electrode can be achieved without impairing other properties required for the positive electrode, such as volume capacity density, safety, cycle characteristics, and high-current discharge characteristics.
  • the volume capacity density is large, and the characteristics such as safety, cycle characteristics, and high current discharge characteristics are sufficiently improved.
  • a satisfactory lithium nickel cobalt manganese composite oxide for a lithium secondary battery positive electrode can be obtained.
  • the relationship between the compressive crushing strength and the volume capacity density of the positive electrode found in the present invention is, as described in Patent Document 5, to obtain a high initial discharge capacity per weight and a high capacity retention rate.
  • the new technology is contradictory to the conventional technology that controls the compressive strength of the lithium cobalt composite oxide powder for the lithium secondary battery positive electrode within a specified range and must not be larger than a predetermined value. It is an idea.
  • the present invention has the following features.
  • a lithium nickel cobalt manganese composite oxide powder for lithium secondary batteries which is a composite oxide powder and has a compressive crushing strength of 50 MPa or more.
  • a positive electrode for a lithium secondary battery comprising the lithium nickel cobalt manganese composite oxide according to any one of (1) to (7).
  • Lithium nickel cobalt 1 for lithium secondary battery positive electrode of the present invention manganese composite oxide powder is represented by the general formula Li p N i x Co y Mn z M a 0 2 _ a F a.
  • M, p, x, y, z, Q, and a are defined above.
  • the lithium nickel cobalt manganese composite oxide powder of the present invention contains Ni and Mn as essential components.
  • Ni in the numerical range of X in the above general formula, the discharge capacity is improved. If X is less than 0.2, the discharge capacity will be low, and if it exceeds 0.5, the safety will be reduced, which is not preferable.
  • Mn within the numerical range of z in the above general formula, safety is improved. If z is less than 0.2, the safety will be insufficient. On the other hand, if it exceeds 0.5, the discharge capacity is reduced and the large current discharge characteristics are undesirably reduced.
  • M is a transition metal element or an alkaline earth metal excluding Ni, Co, and Mn, and the transition metal element is a group 4, 5, 6, 7, 8, 9, or 9 of the periodic table. Represents transition metals of Groups 10 and 11. Among them, M is at least one element selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Mg, Ca, Sr, Ba, and A1. Among them, Ti, Zr, Hf, Mg or A1 is preferred from the viewpoint of capacity development, safety, cycle durability and the like.
  • both M and F exist on the surface of the lithium nickel cobalt manganese composite oxide particles. It is not preferable that the particles exist inside the particles because not only the effect of improving the battery characteristics is small, but also the battery characteristics may deteriorate. Due to its presence on the surface, small amounts of addition do not cause deterioration in battery performance.> Important battery characteristics such as safety and charge / discharge cycle characteristics can be improved. Whether M and F are present on the surface can be determined by performing spectroscopic analysis, for example, XPS analysis, on the positive electrode particles.
  • the lithium nickel cobalt manganese composite oxide of the present invention needs to be a granular powder formed by agglomeration of a large number of fine particles represented by the above general formula.
  • the fine particles are not particularly limited, but preferably have an average particle diameter D 50 (hereinafter, also referred to as a volume average particle diameter) of 0.5 to 7 m.
  • the average particle diameter D50 of the composite oxide powder formed by agglomeration of a large number of the fine particles is preferably 3 to 15 m, more preferably 5 to 12 mm. If the average particle size of the composite oxide powder is smaller than 3, it is difficult to form a dense electrode layer, and if it is larger than 15 m, large current discharge characteristics are undesirably reduced.
  • the powder of the aggregated granular composite oxide of the present invention needs to have a compression breaking strength (hereinafter, also simply referred to as compression strength) of 5 OMPa or more.
  • the compressive strength (St) is a value determined by the formula of Hiramatsu et al. Shown in the following formula 1 ("Journal of the Mining Industry", Vol. 81, No. 932, December 1965, pp. 1024-1030).
  • the above-mentioned aggregated granular composite oxide powder has a compressive strength of less than 50 MPa, it is difficult to form a dense electrode layer, and the electrode density decreases. As a result, the above object of the present invention cannot be achieved.
  • the compressive strength is particularly preferably from 80 to 300 MPa.
  • the lithium nickel cobalt manganese composite oxide of the present invention has a specific surface area of preferably 0.3 to 2.0 m 2 / g, particularly preferably 0.4 to 1.0 Om 2 / g, and the particle shape is It is preferably a substantially spherical shape such as a spherical shape or an elliptical shape.
  • the lithium nickel cobalt manganese composite oxide satisfies such properties, effects such as high capacity, high cycle durability and high safety are achieved.
  • 0.94 ⁇ x / z ⁇ l.06 and the amount of residual alkali contained is preferably 0.25% by weight or less. It is preferably at most 15% by weight.
  • 0.94 ⁇ x / z ⁇ 1.06 high capacity and high cycle durability can be obtained, and when the amount of residual alkali is 0.25% by weight or less, deterioration of the battery during high-temperature storage is small. it can.
  • the present invention further provides the above-described general formula Li p N i s C o y Mn z M Q 0 2 - microparticles of a F lithium nickel Copal Bok manganese composite oxide represented by a is formed by a number agglomerated
  • a large particle size lithium secondary battery which is an agglomerated granular composite oxide powder having an average particle diameter D50 of 3 to 15 m, preferably 8 to 15 m, and having a compressive fracture strength of 50 MPa or more.
  • the lithium nickel cobalt manganese composite oxide powder having a large particle size and the lithium nickel cobalt manganese composite oxide powder having a small particle size are The density of the electrodes is further improved by mixing at a weight ratio of the box, particularly preferably at a weight ratio of 8.5: 1.5 to 7: 3.
  • the lithium-nickel-cobalt-manganese composite oxide of the present invention is obtained by mixing a lithium source, a nickel source, a cobalt source, a manganese source, and a mixture of an M element source and a fluorine source, if necessary, in an oxygen-containing atmosphere. It is formed by firing at about 150 ° C.
  • the lithium source lithium carbonate, lithium hydroxide, and the like can be used, and particularly, lithium carbonate is preferably used.
  • lithium carbonate is used as the lithium source, the cost is lower than when lithium hydroxide is used, for example, and the inexpensive and high-performance lithium nickel cobalt manganese composite oxide desired by the present invention can be easily obtained. It is preferable because it can be obtained.
  • nickel, cobalt, and manganese sources nickel-cobalt-manganese composite oxyhydroxide and the like are used.
  • a hydroxide, an oxide, a carbonate, and a fluoride are preferably selected.
  • metal fluoride, L i F, M g F 2 and the like are selected.
  • the firing temperature is lower than 700, lithiation is incomplete, and if it exceeds 150 ° C, the charge / discharge cycle durability and the initial capacity decrease.
  • the firing temperature is preferably from 900 to 100 ° C.
  • the firing is preferably performed in multiple stages. Preferred examples include firing at 700 ° C. for several hours and firing at 900 to 100 O: for several hours.
  • a mixed powder of a lithium source, a nickel source, a cobalt source, a manganese source, and an optional M element source and a fluorine source is used at 700 to 150 ° C in an oxygen-containing atmosphere as described above. After baking for 5 to 20 hours, and cooling and pulverizing and classifying the obtained baking product, agglomerated particles in which fine particles of a lithium nickel cobalt manganese composite oxide of preferably 0.3 to 7 m are condensed are obtained. A composite oxide powder is formed.
  • the average particle size of the formed aggregated granular composite oxide powder divided by the compressive strength is controlled. Can be.
  • a positive electrode for a lithium secondary battery is manufactured from the lithium nickel cobalt manganese composite oxide, acetylene black, graphite, It is formed by mixing a carbon-based conductive material such as a rubber and a binder.
  • a binder polyvinylidene fluoride, polytetrafluoroethylene, polyamide, carboxymethylcellulose, an acrylic resin, or the like is preferably used.
  • the powder, conductive material and binder of the lithium nickel cobalt manganese composite oxide of the present invention are used as a slurry or a kneaded material using a solvent or a dispersion medium, and are applied to a positive electrode current collector such as an aluminum foil or a stainless steel foil.
  • a positive electrode for a lithium secondary battery is manufactured.
  • a porous polyethylene, a porous polypropylene film or the like is used as a separator.
  • various solvents can be used as a solvent for the electrolyte solution of the battery, and among them, a carbonate ester is preferable.
  • Carbonate can be used in any of a ring shape and a chain shape.
  • Examples of the cyclic carbonate include propylene carbonate and ethylene carbonate (EC).
  • Examples of the chain carbonate include dimethyl carbonate, dimethyl carbonate (DEC), ethyl methyl carbonate (EMC), methyl propyl carbonate, methyl isopropyl carbonate and the like.
  • the above carbonate esters can be used alone or in combination of two or more. Further, it may be used by mixing with another solvent.
  • the combined use of a chain carbonate and a cyclic carbonate may improve discharge characteristics, cycle durability, and charge / discharge efficiency.
  • a vinylidene fluoride-hexafluoro propylene copolymer for example, manufactured by Atochem Co., Ltd .: Inaichi Co., Ltd.
  • a gel polymer containing vinylidene fluoride-fluoropropyl vinyl ether copolymer As the solute added to the above-mentioned electrolyte solvent or polymer electrolyte, cio 4 —,
  • Any one or more of the salts are preferably used.
  • the electrolyte solvent or the polymer electrolyte comprising the lithium salt 0.2 to 2.2. It is preferred to add at a concentration of O mo 1/1 (liter). Outside this range, the ionic conductivity decreases and the electrical conductivity of the electrolyte decreases. Among them, 0.5 to 1.5 mo 1/1 is particularly preferred.
  • a material capable of occluding and releasing lithium ions is used as the negative electrode active material.
  • the material forming the negative electrode active material is not particularly limited, and examples thereof include lithium metal, lithium alloy, carbon material, oxides, carbon compounds, and silicon carbide compounds mainly composed of metals in Groups 14 or 15 of the periodic table. , A silicon oxide compound, titanium sulfide, a boron carbide compound, and the like.
  • As the carbon material those obtained by thermally decomposing organic substances under various pyrolysis conditions, artificial graphite, natural graphite, soil graphite, expanded graphite, flaky graphite and the like can be used.
  • the oxide a compound mainly composed of tin oxide can be used.
  • a copper foil, a nickel foil, or the like is used as the negative electrode current collector.
  • Such a negative electrode is preferably manufactured by kneading the active material with an organic solvent to form a slurry, and applying the slurry to a metal foil collector, drying and pressing to obtain the slurry.
  • the shape of the lithium battery using the lithium nickel cobalt manganese composite oxide of the present invention as a positive electrode active material is not particularly limited. Sheets, films, folds, rolled bottomed cylinders, buttons, etc. are selected according to the application.
  • the X-ray diffraction analysis was performed using a RINT-2000 type Rigaku Corporation, Cu- ⁇ tube, tube voltage 40 KV, tube current 40 mA, light receiving slit 15 mm, The measurement was performed under the condition of a sampling width of 0.02 °.
  • particle size analysis was performed using a RINT-2000 type Rigaku Corporation, Cu- ⁇ tube, tube voltage 40 KV, tube current 40 mA, light receiving slit 15 mm.
  • Microtrac HRA X-100 from Leed + Northrup was used.
  • a sulfate aqueous solution containing nickel sulfate, cobalt sulfate, and manganese sulfate, an ammonia aqueous solution, and a sodium hydroxide aqueous solution were continuously added to the reaction tank, and the pH of the slurry in the reaction tank was 11 and the temperature was 50 ° C.
  • the solution was supplied while stirring the inside of the reaction vessel.
  • the amount of liquid in the reaction system was adjusted by an over-the-mouth method, and the overflowed coprecipitated slurry was removed. Filtration, washing with water, and drying at 70 ° C. yielded a nickel-cobalt-manganese composite hydroxide powder.
  • the obtained hydroxide is dispersed in a 6% by weight aqueous sodium persulfate solution containing 3% by weight of sodium hydroxide, and the mixture is stirred at 20 ° C. for 12 hours to obtain a nickel-cobalt-manganese composite oxyhydroxide.
  • a nickel-cobalt-manganese composite oxyhydroxide was synthesized.
  • This composite oxyhydroxide powder is mixed with lithium carbonate powder having an average particle size of 20 / m, and calcined in air at 900 ° C for 16 hours, followed by mixing and pulverization to obtain LiNi 1/3 Co 1/3 Mn 1/3 to give 0. 2 powder.
  • the specific surface area of this positive electrode powder determined by the nitrogen adsorption method was 0.58 m 2 / g, and the volume average particle diameter D50 was 11.
  • the powder X-ray diffraction spectrum using Cu- ⁇ ; lines was similar to the rhombohedral system (R-3m).
  • the SEM observation of the positive electrode powder particles revealed that the primary particles were innumerably aggregated to form secondary particles, and the shape was spherical or round.
  • LiNi 1/3 Co 1/3 Mn 1/3 0 2 powder obtained was measured compressive strength using a micro compression testing machine MCT-W500 manufactured by Shimadzu. That is, the test load was 100 mN, the load speed was 3.874 mN / sec, and the measurement was performed on 10 arbitrary particles with a known particle size using a flat indenter with a diameter of 50 m, and the compressive strength was obtained. Met.
  • 10 g of this LiNi 1/3 Co 1/3 Mn 1/3 0 2 powder was dispersed in 100 g of pure water, filtered, and the potential difference was measured with 0.02N HC 1 to determine the amount of residual alkali. 0.12% by weight.
  • the positive electrode powder, acetylene black, graphite powder, and PVDF binder were mixed at a solid content weight ratio of 88Z3Z3 / 6, and an N-methylpyrrolidone solvent was added thereto, followed by ball mill mixing to prepare a coating slurry.
  • This slurry was applied to one side of a 20- ⁇ m-thick aluminum foil current collector by the doctor blade method, the solvent was removed by hot-air drying, and then roll-pressed four times to produce a positive electrode sheet.
  • the apparent density of the electrode layer was determined from the thickness of the electrode layer of the positive electrode body and the weight of the electrode layer per unit area, and was found to be 3.14 gZcc.
  • the positive electrode sheet is used for the positive electrode
  • a 25-m-thick porous polypropylene is used for the separator
  • a 500-m-thick metallic lithium foil is used for the negative electrode
  • a 20-m nickel-nickel foil is used for the negative electrode current collector.
  • a simple sealed lithium battery cell made of stainless steel was assembled in an argon glove box using 1M LiPF 6 / EC + DEC (1: 1) as an electrolyte.
  • 1M LiPF 6 / EC + DEC (1: 1) as an electrolyte.
  • the battery was charged with CC-CV up to 4.3 V with a load current of, and discharged to 2.5 V with a load current of 20 mA per 1 g of the positive electrode active material to determine the initial discharge capacity. Further, a charge / discharge cycle test was performed 30 times.
  • the initial weight discharge capacity density at 2.5 to 4.3 V at 25 ° C was 161 mAh / g, and the initial volume discharge capacity density was 444 mA hZC C--electrode layer.
  • the charge / discharge efficiency was 89%, and the capacity retention after 30 charge / discharge cycles was 97.0%.
  • a nickel-cobalt-manganese composite oxyhydroxide (Ni / Co / Mn atomic ratio 1/1/1) was obtained in the same manner as in Example 1 except that the stirring speed in the coprecipitation slurry and the slurry concentration were increased.
  • the particle size distribution of the composite oxide was measured by a laser scattering method. As a result, the volume average particle size D 50 was 8.7 / 2 m.
  • the composite Okishi hydroxide powder was mixed with lithium carbonate powder, form baked in the same manner as in Example 1 to obtain a LiN 3 Co 1/3 Mn 1/3 0 2 powder were mixed and ground.
  • the specific surface area of this positive electrode powder measured by a nitrogen adsorption method was 0.70 m 2 / g, and the volume average particle diameter D50 was 9.4 im.
  • the powder X-ray diffraction spectrum using Cu-Ko! Line was similar to the rhombohedral system (R-3m).
  • the breaking strength of the particles determined in the same manner as in Example 1 was 114 Mpa.
  • the amount of residual alkali in the positive electrode powder was determined in the same manner as in Example 1, and found to be 0.13% by weight.
  • a positive electrode body sheet was prepared in the same manner as in Example 1.
  • the electrode layer density of the obtained positive electrode body sheet was 3.13 g / cc.
  • a simple closed cell made of stainless steel was assembled and the charge / discharge performance was evaluated in the same manner as in Example 1.
  • the initial weight discharge capacity density at 25 was 160 mA h / g
  • the initial volume discharge capacity density was 44 I mA h / CC one electrode layer
  • the initial charge / discharge efficiency was 91.0%.
  • the capacity retention rate after 30 charge / discharge cycles was 97.3%.
  • a nickel cobalt manganese composite oxyhydroxide was prepared in the same manner as in Example 1 except that the composition ratio of the aqueous sulfate solution containing nickel sulfate, cobalt sulfate and manganese sulfate was changed. (Ni / Co / Mn atomic ratio: 0.38 / 0.24 / 0.38) was obtained.
  • the composite oxide powder particles were formed by innumerable primary particles forming secondary particles, and were spherical or elliptical in shape. Lithium carbonate powder was mixed with this composite oxide powder, and UNi was used in the same manner as in Example 1. 38 Co. . To obtain a 24 M3 ⁇ 4 38 0 2 powder.
  • the specific surface area of the positive electrode powder determined by the nitrogen adsorption method was 0.63 m 2 / g, and the volume average particle diameter D50 was 12.1 m.
  • the powder X-ray diffraction spectrum of this positive electrode powder using Cu-rays was similar to that of rhombohedral (R-3m).
  • the rupture strength of the particles determined in the same manner as in Example 1 was 135 Mpa. Further, the amount of residual alkali in the positive electrode powder was determined in the same manner as in Example 1, and found to be 0.16% by weight.
  • a positive electrode body sheet was prepared in the same manner as in Example 1.
  • the electrode layer density of the obtained positive electrode body sheet was 3.08 g / cc.
  • a simple closed cell made of stainless steel was assembled in the same manner as in Example 1, and the charge / discharge performance was evaluated.
  • the initial weight discharge capacity density at 25 ° C was 158 mAh / 'g
  • the initial volume discharge capacity density was 428 mAh ZCC--electrode layer
  • the capacity retention rate after 30 charge / discharge cycles was 96.1%.
  • Ni / Co / Mn atomic ratio 1/1/1 nickel cobalt manganese composite oxyhydroxide synthesized in Example 1
  • lithium carbonate powder and zirconium oxide powder were added to the composite oxyhydroxide powder.
  • Lithium fluoride powder was mixed, fired in the same manner as in Example 1, and mixed and ground to obtain Li (Ni 1/3 Co 1/3 Mn 1/3 ) a 995 Zr ⁇ OuF ⁇ powder.
  • the specific surface area of this positive electrode powder measured by a nitrogen adsorption method was 0.55 m 2 / g, and the volume average particle diameter D50 was 11.4 H1.
  • the powder X-ray diffraction spectrum of the positive electrode powder using Cu-Ka line was similar to a rhombohedral system (R-3 ⁇ ).
  • the breaking strength of the particles determined in the same manner as in Example 1 was 150 MPa.
  • the amount of residual alkali in the positive electrode powder was determined in the same manner as in Example 1 and found to be 0.12% by weight.
  • a positive electrode body sheet was prepared in the same manner as in Example 1.
  • the electrode layer density of the obtained positive electrode body sheet was 3.11 g / cc.
  • a simple closed cell made of stainless steel was assembled in the same manner as in Example 1 and the charge / discharge performance was evaluated.
  • the initial weight discharge capacity density at 25 ° C was 162 mAh / g.
  • the initial volume discharge capacity density was 435 mAh ZCC-electrode layer, and the capacity retention rate after 30 charge / discharge cycles was 98.0%.
  • the nickel-cobalt-manganese composite oxyhydroxide (Ni / Co / Mn atomic ratio 1 / 1/1) was obtained.
  • the particle size distribution of the composite oxide was measured by a laser scattering method. As a result, the volume average particle size D50 was 2.6 m.
  • Nickel-cobalt-manganese composite Okishi hydroxide and lithium carbonate powder obtained was combined mixed, and calcined in the same manner as in Example 1, to obtain a LiNi 1/3 Co 1/3 Mn 1/3 0 2 powder and mixed powder ⁇ Was.
  • the specific surface area of this positive electrode powder determined by a nitrogen adsorption method was 0.83 m 2 / g, and the volume average particle diameter D50 was 3.1.
  • the powder X-ray diffraction spectrum using Cu- ⁇ rays was similar to the rhombohedral system (R-3 ⁇ ).
  • the breaking strength of the particles determined in the same manner as in Example 1 was 135 Mpa.
  • the amount of residual alkali in the positive electrode powder was determined in the same manner as in Example 1 and found to be 0.15% by weight.
  • Example 2 Same as Example 1 except that 20 parts by weight of the small particle size positive electrode powder and 80 parts by weight of the large particle size positive electrode powder synthesized in Example 1 having a mean particle size of 11.5 microns were mixed. Thus, a positive electrode sheet was prepared. The ratio of the average particle size D 50 of the small particle size to the average particle size D 50 of the large particle size was 1 Z3.7. The electrode layer density of the obtained positive electrode body sheet was 3.24 g / cc.
  • a nickel-cobalt-manganese composite oxyhydroxide was prepared in the same manner as in Example 1 except that the oxygen concentration in the slurry was increased and the stirring density was lowered, while the slurry concentration was lowered.
  • a positive electrode sheet was produced in the same manner as in Example 1.
  • the electrode layer density of the obtained positive electrode body sheet was 2.91 g / cc.
  • a simple closed cell made of stainless steel was assembled in the same manner as in Example 1 and the charge / discharge performance was evaluated.
  • the initial weight discharge capacity density at 25 ° C was 156 mAh / g
  • the initial volume discharge capacity density was 399 mAliZCC-electrode layer
  • the initial charge / discharge efficiency was 87%.
  • the capacity retention after 30 charge / discharge cycles was 93.2%.
  • the initial volume discharge capacity density and the initial weight discharge capacity density are large, the initial charge / discharge efficiency, the charge / discharge cycle stability, and the safety are high.
  • the present invention provides a positive electrode for a lithium secondary battery, and a lithium secondary battery, comprising a powder of the same, the lithium nickel cobalt manganese composite oxide powder.

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Abstract

A lithium-nickel-cobalt-manganese composite oxide powder for positive electrodes of lithium secondary batteries having a high volumetric capacity, high safety, and excellent charge/discharge cycle durability is disclosed. The lithium-nickel-cobalt-manganese composite oxide powder for lithium secondary batteries is represented by the general formula: LipNixCoyMnzMqO2-aFa (wherein M represents a transition metal element other than Ni, Co and Mn or an alkaline earth metal element, 0.9 ≤ p ≤ 1.1, 0.2 ≤ x ≤ 0.5, 0.1 ≤ y ≤0.4, 0.2 ≤ z ≤0.5, 0 ≤ q ≤0.05, 1.9 ≤ 2-a ≤ 2.1, x+y+z+q = 1, and 0 ≤ a ≤ 0.02). The lithium-nickel-cobalt-manganese composite oxide powder is composed of agglomerate of composite oxide particles having an average particle diameter D50 of 3-15 μm wherein many particles of lithium-nickel-cobalt-manganese composite oxide are gathered together, and has a compressive breaking strength of not less than 50 MPa.

Description

明 細 書 リチウムニ次電池用正極活物質粉末 技術分野  Description Positive active material powder for lithium secondary batteries Technical field

本発明は、 体積容量密度が大きく、 安全性が高く、 かつ充放電サイクル耐久性に 優れた、 リチウムニ次電池正極用リチウムニッケルコバルトマンガン複合酸化物粉 末、 該リチウムニッケルコバルトマンガン複合酸ィ匕物粉末を含むリチウム二次電池 用正極、 及びリチウム二次電池に関する。 背景技術  The present invention provides a lithium nickel cobalt manganese composite oxide powder for a lithium secondary battery positive electrode, which has a large volume capacity density, high safety, and excellent charge / discharge cycle durability. The present invention relates to a positive electrode for a lithium secondary battery containing a powder, and a lithium secondary battery. Background art

近年、 機器のポータブル化、 コ一ドレス化が進むにつれ、 小型、 軽量でかつ高工 ネルギー密度を有するリチウムニ次電池などの非水電解液二次電池に対する需要が ますます高まっている。 かかる非水電解液二次電池用の正極活物質には、 L i Co 02、 L i N i 02、 L i N i a8C o。 202、 L iMn204、 L iMn02などのリチウ ムと遷移金属の複合酸化物が知られている。 In recent years, as devices have become more portable and less dressed, the demand for non-aqueous electrolyte secondary batteries, such as lithium secondary batteries, which are small, lightweight, and have high energy density, has been increasing. According to the positive electrode active material for non-aqueous electrolyte solution for a secondary battery, L i Co 0 2, L i N i 0 2, L i N i a8 C o. 2 0 2, L iMn 2 0 4, L iMn0 composite oxide of lithium and transition metals such as 2 are known.

なかでも、 リチウムコバルト複合酸化物 (L i Co02) を正極活物質として用 い、 リチウム合金、 グラフアイト、 カーボンファイバーなどのカーボンを負極とし て用いたリチウム二次電池は、 4 V級の高い電圧が得られるため、 高エネルギー密 度を有する電池として広く使用されている。 Among them, have use lithium cobalt composite oxide (L i Co0 2) as a positive electrode active material, a lithium alloy, graphite, lithium secondary batteries using carbon such as carbon fiber as a negative electrode, a high 4 V-class Since a voltage can be obtained, it is widely used as a battery with high energy density.

しかしながら、 L i Co〇2を正極活物質として用いた非水系二次電池の場合、 正極電極層の単位体積当たりの容量密度及び安全性の更なる向上が望まれるととも に、 充放電サイクルを繰り返し行うことにより、 その電池放電容量が徐々に減少す るというサイクル特性の劣化、 重量容量密度の問題、 あるいは低温での放電容量低 下が大きいという問題などがあつた。 However, if the non-aqueous secondary battery using L i Co_〇 2 as a positive electrode active material, the together the further improvement of capacity density and safety of per unit volume of the positive electrode layer is desired, the charge-discharge cycle There were problems such as deterioration of cycle characteristics such that the battery discharge capacity was gradually reduced by repeated use, problems of weight capacity density, and problems of large decrease in discharge capacity at low temperatures.

これらの問題の一部を解決するために、 特開平 6 _ 243897号公報には、 正 極活物質である L i Co02の平均粒径を 3〜9 m、 及び粒径 3〜15 mの粒 子群の占める体積を全体積の 75%以上とし、 かつ CuKo!を線源とする X線回 折によって測定される 20=約 19° と 45° 回折ピーク強度比を特定値とするこ とにより、 塗布特性、 自己放電特性、 サイクル性に優れた活物質とすることが提案 されている。 更に、 該公報には、 L i Co02の粒径が 1 m以下又は 25 /xm以 上の粒径分布を実質的に有さないものが好ましい態様として提案されている。 しか し、 かかる正極活物質では、 塗布特性ならびにサイクル特性は向上するものの、 安 全性、 体積容量密度、 重量容量密度を充分に満足するものは得られていない。 To solve some of these problems, JP-A-6 _ 243897, positive electrode active material in which L i CO0 2 having an average particle size of the 3 to 9 m, and particle size 3 to 15 m of The volume occupied by the particle group should be 75% or more of the total volume, and the specific intensity should be 20 = about 19 ° and 45 ° diffraction peak intensity ratio measured by X-ray diffraction using CuKo! As the source. Thus, it has been proposed that the active material be excellent in coating characteristics, self-discharge characteristics, and cycle characteristics. Further, the publication proposes a preferred embodiment in which Li CoO 2 has substantially no particle size distribution of 1 m or less or 25 / xm or more. However, with such a positive electrode active material, although the coating characteristics and the cycle characteristics are improved, a material which sufficiently satisfies safety, volume capacity density, and weight capacity density has not been obtained.

また、 正極の重量容量密度と充放電サイクル性を改良するために、 特開 2000 -82466号公報には、 リチウム複合酸化物粒子の平均粒径が 0. 1〜 50 m であり、 かつ、 粒度分布にピークが 2個以上存在する正極活物質が提案されている。 また併せて平均粒径の異なる 2種の正極活物質を混合して粒度分布にピークが 2個 以上存在する正極活物質とすることも提案されている。 かかる提案においては正極 の重量容量密度と充放電サイクル性が改善される場合もあるが、 2種類の粒径分布 を有する正極原料粉末を製造する煩雑さがあるとともに、 正極の体積容量密度、 安 全性、 塗工均一性、 重量容量密度、 サイクル性のいずれをも満足するものは得られ ていない。  In order to improve the weight capacity density and charge / discharge cycleability of the positive electrode, Japanese Patent Application Laid-Open No. 2000-82466 discloses that the average particle diameter of lithium composite oxide particles is 0.1 to 50 m, A positive electrode active material that has two or more peaks in the distribution has been proposed. It has also been proposed to mix two types of positive electrode active materials having different average particle diameters to obtain a positive electrode active material having two or more peaks in the particle size distribution. In such a proposal, the weight capacity density and charge / discharge cycleability of the positive electrode may be improved, but the production of the positive electrode raw material powder having two types of particle size distribution is complicated, and the volume capacity density of the positive electrode, low No product that satisfies all of the requirements for completeness, coating uniformity, weight capacity density, and cycleability has been obtained.

また、 電池特性に関する課題を解決するために、 特開平 3— 201368号公報 に Co原子の 5〜35%を W、 Mn、 Ta、 T i又は Nbで置換することがサイク ル特性改良のために提案されている。 また、 特開平 10 - 312805号公報には、 格子定数の c軸長が 14. 051 A以下であり、 結晶子の （110) 方向の結晶子 径が 45〜100 nmである、 六方晶系の L i C o〇2を正極活物質とすることに よりサイクル特性を向上させることが提案されている。 Also, in order to solve the problem relating to battery characteristics, Japanese Patent Application Laid-Open No. 3-201368 discloses that replacing 5 to 35% of Co atoms with W, Mn, Ta, Ti or Nb for improving cycle characteristics. Proposed. Japanese Patent Application Laid-Open No. Hei 10-312805 discloses a hexagonal system in which the c-axis length of the lattice constant is 14.051 A or less, and the crystallite diameter of the crystallite in the (110) direction is 45 to 100 nm. L i C O_〇 2 is possible to further improve the cycle characteristics to the cathode active material has been proposed.

更に、 特開 2001— 80920号公報には、 式 L i XN i H,_ZC oyMe702 (式中、 0<χ<1. 1、 0<y≤0.6、 O≤z≤0.6である。 )を有し、 微粉末が 凝集した凝集粒状リチウム複合酸化物であって、 一粒当りの圧縮強度が 0.1-1.0 g ίである粒子状リチウム複合酸化物が提案されている。 しかし、 該複合酸化物に は安全性が乏しくかつ大電流放電特性が劣る問題があるともに、 上記のような小さ い範囲の圧縮強度では、 体積容量密度、 安全性、 サイクル特性、 大電流放電特性な どの点において充分に満足する特性を有するリチウム複合酸化物を得ることはでき ない。 上記のように、 従来の技術では、 リチウム複合酸化物を正極活物質に用いたリチ ゥム二次電池において、 体積容量密度、 安全性、 サイクル特性、 大電流放電特性な どを充分に満足するものは未だ得られていない。 本発明は、 これらの従来技術では 達成が困難であったこれらの特性を満足する、 リチウム二次電池正極用リチウム二 ッケルコバルトマンガン複合酸化物粉末、 該リチウムニッケルコバルトマンガン複 合酸化物粉末を含むリチウム二次電池用正極、 及びリチウム二次電池の提供を目的 とする。 発明の開示 Further, JP 2001- the 80920 discloses, wherein L i X N i H, _ Z C o y Me 7 0 2 ( wherein, 0 <χ <1. 1 , 0 <y≤0.6, O≤z ≤0.6), and an agglomerated granular lithium composite oxide in which fine powder is agglomerated, and a granular lithium composite oxide having a compressive strength per particle of 0.1-1.0 g g has been proposed. . However, the composite oxide has a problem of poor safety and poor high-current discharge characteristics, and at the compressive strength in the above-described small range, the volume capacity density, safety, cycle characteristics, and high-current discharge characteristics are low. It is not possible to obtain a lithium composite oxide having sufficiently satisfactory characteristics in some points. As described above, in the conventional technology, a lithium secondary battery using a lithium composite oxide as the positive electrode active material sufficiently satisfies the volume capacity density, safety, cycle characteristics, large current discharge characteristics, etc. Things have not yet been obtained. The present invention provides a lithium-nickel-cobalt-manganese composite oxide powder for a positive electrode of a lithium secondary battery, which satisfies these characteristics which have been difficult to achieve with the conventional techniques, and a lithium-nickel-cobalt-manganese composite oxide powder. The purpose of the present invention is to provide a positive electrode for a lithium secondary battery and a lithium secondary battery. Disclosure of the invention

本発明者は鋭意研究を進めたところ、 リチウムニ次電池正極用の特定組成を有す るリチウムニッケルコバルトマンガン複合酸化物の微粒子が多数凝集して形成され、 特定の平均粒子径を有する凝集粒状複合酸化物粉末の圧縮破壌強度と該粉末を使用 したリチウム二次電池用正極の体積容量密度との関係に注目し、 両者が正の相関関 係にあることを見出した。 即ち、 上記粉末の圧縮破壊強度が大きいほど、 得られる 正極が大きい体積容量密度が得られることを見出した。 しかもかかる正極の大きい 体積容量密度は、 体積容量密度、 安全性、 サイクル特性、 大電流放電特性などの正 極が必要とする他の特性を損なうことなく達成されることも確認された。  The present inventors have conducted intensive studies and found that a large number of fine particles of lithium nickel cobalt manganese composite oxide having a specific composition for a lithium secondary battery positive electrode are formed by agglomeration, and the aggregated particulate composite having a specific average particle diameter is formed. Focusing on the relationship between the compressive crushing strength of the oxide powder and the volume capacity density of the positive electrode for a lithium secondary battery using the powder, it was found that both were in a positive correlation. That is, it was found that the larger the compressive breaking strength of the powder, the higher the volume capacity density of the obtained positive electrode. In addition, it has been confirmed that such a large volume capacity density of the positive electrode can be achieved without impairing other properties required for the positive electrode, such as volume capacity density, safety, cycle characteristics, and high-current discharge characteristics.

かくして本発明では、 上記凝集粒状複合酸化物粉末の圧縮破壊強度を従来にない ような大きくすることにより、 体積容量密度が大きく、 かつ安全性、 サイクル特性、 大電流放電特性などの特性を充分に満足するリチウムニ次電池正極用リチウムニッ ケルコバルトマンガン複合酸化物を得ることができる。  Thus, in the present invention, by increasing the compressive rupture strength of the above-mentioned aggregated granular composite oxide powder to a level not seen in the past, the volume capacity density is large, and the characteristics such as safety, cycle characteristics, and high current discharge characteristics are sufficiently improved. A satisfactory lithium nickel cobalt manganese composite oxide for a lithium secondary battery positive electrode can be obtained.

本発明で見出された、 上記した圧縮破壌強度と正極の体積容量密度との関係は、 特許文献 5に記載されるように、 高い重量当りの初期放電容量や容量保持率を得る ためにリチウムニ次電池正極用のリチウムコバル卜複合酸化物粉末の圧縮強度は所 定範囲内に制御し、 所定以上に大きくしてはならないとする従来の技術とは相反す るものであり、 新規な技術思想である。  The relationship between the compressive crushing strength and the volume capacity density of the positive electrode found in the present invention is, as described in Patent Document 5, to obtain a high initial discharge capacity per weight and a high capacity retention rate. The new technology is contradictory to the conventional technology that controls the compressive strength of the lithium cobalt composite oxide powder for the lithium secondary battery positive electrode within a specified range and must not be larger than a predetermined value. It is an idea.

かくして、 本発明は、 下記の特徴を有する。  Thus, the present invention has the following features.

( 1 ) 一般式 L ipN i xC oyM nzMa02— aFa (但し、 Mは N i， C o , M n以外の 遷移金属元素またはアルカリ土類金属元素である。 0 . 9≤p≤l . 1、 0 . 2≤ W 200 (1) In formula L i p N i x C o y M n z M a 0 2 - a F a ( where, M is N i, C o, a transition metal element or an alkaline earth metal element other than M n 0.9 ≤p≤l .1, 0.2 ≤ W 200

4 x≤0. 5、 0. l≤y≤0. 4、 0. 2≤z≤0. 5、 0≤q≤0. 05、 1. 9≤2 - a≤2. 1、 x + y + z+d=l、 0≤a≤0. 02) で表されるリチウ ムニッケルコバルトマンガン複合酸化物の微粒子が多数凝集して形成された、 平均 粒子径 D 50が 3〜 15 の凝集粒状複合酸化物粉末であり、 かつ粉末の圧縮破 壊強度が 50 MP a以上であることを特徴とするリチウムニ次電池用リチウムニッ ケルコバル卜マンガン複合酸化物粉末。 4 x≤0.5, 0.l≤y≤0.4, 0.2.2≤z≤0.5, 0≤q≤0.0.05, 1.9≤2-a≤2.1.1, x + y + z + d = l, 0≤a≤0.02) Agglomerated particles with an average particle diameter D50 of 3 to 15 formed by the aggregation of a large number of fine particles of lithium nickel cobalt manganese composite oxide A lithium nickel cobalt manganese composite oxide powder for lithium secondary batteries, which is a composite oxide powder and has a compressive crushing strength of 50 MPa or more.

(2) 粉末の比表面積が 0. 3〜2. 0m2Zgであり、 粒子形状が略球状である 上記 1に記載のリチウムニッケルコバルトマンガン複合酸化物粉末。 (2) The lithium-nickel-cobalt-manganese composite oxide powder as described in (1) above, wherein the powder has a specific surface area of 0.3 to 2.0 m 2 Zg and a substantially spherical particle shape.

(3) 0. 94≤x/z≤l. 06であり、 含有される残存アルカリ量が 0. 25 重量％以下である上記 （1) または （2) に記載のリチウムニッケルコバルトマン ガン複合酸化物粉末。  (3) The lithium-nickel-cobalt manganese composite oxidation according to (1) or (2) above, wherein 0.94≤x / z≤l.06 and the amount of residual alkali contained is 0.25% by weight or less. Thing powder.

C4) 粉末の圧縮破壊強度が 80〜30 OMPaである上記 （1) 、 （2) または ( 3 ) に記載のリチウムニッケルコバル卜マンガン複合酸化物粉末。  C4) The lithium nickel cobalt manganese composite oxide powder according to the above (1), (2) or (3), wherein the powder has a compressive fracture strength of 80 to 30 OMPa.

(5) 一般式 LipN ixCoyMnzMQ02—aFa (但し、 Mは N i， Co, Mn以外の 遷移金属元素またはアルカリ土類金属元素である。 0. 9≤p≤l. 1、 0. 2≤ x≤0. 5、 0. l≤y≤0. 4、 0. 2≤z≤0. 5、 0≤Q≤0. 05、 1. 9≤2 - a≤2. 1、 x + y + z +q=l, 0≤a≤0. 02) で表されるリチウ ムニッケルコバルトマンガン複合酸化物の微粒子が多数凝集して形成された、 平均 粒子径 D 50が 3〜 15 imの凝集粒状複合酸化物粉末であり、 かつ粉末の圧縮破 壊強度が 50 M P a以上である大粒径のリチウムニ次電池用リチウムニッケルコバ ルトマンガン複合酸化物粉末と、 該大粒径の平均粒径 D 50の 1/2〜1/5の平均粒 径を有する小粒径のリチウムニ次電池用リチウムニッケルコバルトマンガン複合酸 化物粉末とを、 9 ： 1〜6： 4の重量比で混合されてなることを特徴とするリチウ ムニ次電池用リチウムニッケルコバルトマンガン複合酸化物粉末。 (5) the general formula Li p N i x Co y Mn z M Q 0 2 -. A F a ( where, M is N i, Co, is a transition metal element or an alkaline earth metal element other than Mn 0. 9 ≤p≤l. 1, 0.2 ≤ x≤0.5, 0.l≤y≤0.4, 0.2 ≤z≤0.5, 0≤Q≤0.05, 1.9≤2 -Average particle formed by agglomeration of a large number of fine particles of lithium nickel cobalt manganese composite oxide expressed by a≤2.1, x + y + z + q = l, 0≤a≤0.02) A lithium-nickel-cobalt-manganese composite oxide powder for a lithium secondary battery having a particle diameter D50 of 3 to 15 im and having a particle size of 50 MPa or more; A lithium nickel cobalt manganese composite oxide powder for a lithium secondary battery having a small particle diameter having an average particle diameter of 1/2 to 1/5 of the large particle diameter D50, 9: 1 to 6: 4. Characterized by being mixed in a weight ratio of Titanium nickel cobalt manganese composite oxide powder.

(6) 粉末の圧縮破壊強度が 5 OMPa以上である大粒径のリチウム二次電池用リ チウムニッケルコバルトマンガン複合酸化物粉末と、 該大粒径の平均'粒径 D 50の 1/2〜1/5の平均粒径を有する小粒径のリチウム二次電池用リチウムニッケルコバ  (6) a lithium nickel cobalt manganese composite oxide powder for a lithium secondary battery having a large particle diameter, which has a compressive fracture strength of 5 OMPa or more, Lithium nickel edge for lithium secondary battery with small particle size with average particle size of 1/5

'複合酸化物粉末とを、 8. 5 : 1. 5-7： 3の重量比で混合されて なる上記 （5) に記載のリチウム二次電池用リチウムニッケルコバルトマンガン複 合酸化物粉末。 'Mixed with composite oxide powder in a weight ratio of 8.5: 1.5-7: 3 The lithium nickel cobalt manganese composite oxide powder for a lithium secondary battery according to the above (5).

( 7 ) リチウムニッケルコバルトマンガン複合酸化物の微粒子が多数凝集して形成 された平均、粒子径 D 50が 8〜15 mである上記 (5) 又は （6) に記載のリチ ゥム二次電池用リチウムニッケルコバルトマンガン複合酸化物粉末。  (7) The lithium secondary battery according to the above (5) or (6), wherein a large number of fine particles of lithium nickel cobalt manganese composite oxide are formed by agglomeration, and the average particle diameter D50 is 8 to 15 m. For lithium nickel cobalt manganese composite oxide powder.

(8) 上記 （1) 〜 （7) のいずれかに記載のリチウムニッケルコバルトマンガン 複合酸化物を含むリチウムニ次電池用正極。  (8) A positive electrode for a lithium secondary battery, comprising the lithium nickel cobalt manganese composite oxide according to any one of (1) to (7).

(9) 上記 （8) に記載された正極を使用したリチウム二次電池。 本発明で何故にリチウムニッケルコバルトマンガン複合酸化物粉末の圧縮破壊強 度を大きくすることにより正極の体積容量密度を大きくできるかの理由については 必ずしも明らかではないが、 ほぼ次のように推察される。 リチウムニッケルコバル トマンガン複合酸化物凝集体粉末を圧密化して正極を形成する際、 該粉末の圧縮破 壊強度が高いと、 圧密化際の圧縮応力エネルギーが粉末の破壊に使用されないため、 圧縮応力が個々の粉末にそのまま作用する結果、 粉末を構成する粒子同士の滑りに よる高充填化が達成できる。 一方、 粉末の圧縮破壊強度が低いと圧縮応力エネルギ 一が粉末の破壊に使用される結果、 個々の粉末を形成する粒子にかかる圧力が低下 し、 粒子同士の滑りによる圧密化が起こりにくいため、 正極密度の向上が図れない と思われる。 発明を実施するための最良の形態  (9) A lithium secondary battery using the positive electrode described in (8) above. The reason why the volume capacity density of the positive electrode can be increased by increasing the compressive fracture strength of the lithium nickel cobalt manganese composite oxide powder in the present invention is not necessarily clear, but is presumed as follows. . When the lithium nickel cobalt manganese composite oxide aggregate powder is compacted to form a positive electrode, if the powder has a high compressive crushing strength, the compressive stress energy during the compaction is not used to break the powder, so that the compressive stress is reduced. As a result of acting on individual powders as they are, high packing can be achieved by the sliding of the particles constituting the powders. On the other hand, when the compressive fracture strength of the powder is low, the compressive stress energy is used to break the powder, so that the pressure applied to the particles forming the individual powders decreases, and consolidation due to slippage between the particles hardly occurs. It seems that the positive electrode density cannot be improved. BEST MODE FOR CARRYING OUT THE INVENTION

本発明のリチウムニ次電池正極用のリチウムニッケルコバル 1、マンガン複合酸化 物粉末は、 一般式 LipN ixCoyMnzMa02_aFaで表される。 かかる一般式におけ る、 M、 p、 x、 y、 z、 Q、 及び aは上記に定義される。 なかでも、 p、 Q、 X、 y、 z、 Q、 及び aは下記が好ましい。 0. 98≤p≤l. 05、 0. 25≤x≤ 0. 42、 0. 25≤y≤0. 35、 0. 25≤z≤0. 42、 0≤q≤0. 02、 1. 95≤2 - a≤2. 05、 x + y+z +q= 1, 0≤a≤0. 01。 ここで、 aが 0より大きいときには、 酸素原子の一部がフッ素原子に置換された複合酸化物 になるが、 この場合には、 得られた正極活物質の安全性が向上する。 本発明のリチウムニッケルコバルトマンガン複合酸化物粉末は、 N iおよび Mn を必須成分として含有する。 N iを上記一般式における Xの数値範囲内で含むこと により、 放電容量の向上する。 Xが 0. 2未満では放電容量が低くなり、 一方、 0. 5を超えると安全性が低下するので好ましくない。 また、 M nを上記一般式におけ る zの数値範囲内で含むことにより、 安全性が向上する。 zが 0. 2未満では安全 性が不充分となり、 一方、 0. 5を超えると放電容量低下ゃ大電流放電特性が低下 するので好ましくない。 Lithium nickel cobalt 1 for lithium secondary battery positive electrode of the present invention, manganese composite oxide powder is represented by the general formula Li p N i x Co y Mn z M a 0 2 _ a F a. In such general formulas, M, p, x, y, z, Q, and a are defined above. Among them, p, Q, X, y, z, Q, and a are preferably as follows. 0.98≤p≤l.05, 0.25≤x≤0.42, 0.25≤y≤0.35, 0.25≤z≤0.42, 0≤q≤0.02, 1. 95≤2-a≤2.05, x + y + z + q = 1, 0≤a≤0.01. Here, when a is larger than 0, a composite oxide is obtained in which a part of oxygen atoms is replaced by fluorine atoms. In this case, the safety of the obtained positive electrode active material is improved. The lithium nickel cobalt manganese composite oxide powder of the present invention contains Ni and Mn as essential components. By including Ni in the numerical range of X in the above general formula, the discharge capacity is improved. If X is less than 0.2, the discharge capacity will be low, and if it exceeds 0.5, the safety will be reduced, which is not preferable. Further, by including Mn within the numerical range of z in the above general formula, safety is improved. If z is less than 0.2, the safety will be insufficient. On the other hand, if it exceeds 0.5, the discharge capacity is reduced and the large current discharge characteristics are undesirably reduced.

また、 Mは、 N i, Co, Mnを除く遷移金属元素又はアルカリ土類金属であり、 該遷移金属元素は周期表の 4族、 5族、 6族、 7族、 8族、 9族、 10族及び 11 族の遷移金属を表す。 なかでも、 Mは、 T i、 Z r、 Hf、 V、 Nb、 Ta、 Mg、 C a、 S r、 B a、 及び A 1からなる群から選ばれる少なくとも 1つの元素が選択 される。 なかでも、 容量発現性、 安全性、 サイクル耐久性などの見地より、 T i、 Z r、 Hf、 Mg又は A1が好ましい。  M is a transition metal element or an alkaline earth metal excluding Ni, Co, and Mn, and the transition metal element is a group 4, 5, 6, 7, 8, 9, or 9 of the periodic table. Represents transition metals of Groups 10 and 11. Among them, M is at least one element selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Mg, Ca, Sr, Ba, and A1. Among them, Ti, Zr, Hf, Mg or A1 is preferred from the viewpoint of capacity development, safety, cycle durability and the like.

本発明において、 上記 Mおよび/または Fを含有せしめる場合は、 M及び Fのい ずれもリチウムニッケルコバルトマンガン複合酸化物粒子の表面に存在しているこ とが好ましい。 粒子の内部に存在していると、 電池特性の改良効果が小さいのみな らず、 電池特性が低下する場合があるので好ましくない。 表面に存在することによ り、 少量の添加で電池性能の低下を招来することなく > 安全性、 充放電サイクル特 性等の重要な電池特性を改良できる。 M及び Fが表面に存在するか否かは正極粒子 について、 分光分析例えば、 XPS分析を行うことにより判断できる。  In the present invention, when M and / or F is contained, it is preferable that both M and F exist on the surface of the lithium nickel cobalt manganese composite oxide particles. It is not preferable that the particles exist inside the particles because not only the effect of improving the battery characteristics is small, but also the battery characteristics may deteriorate. Due to its presence on the surface, small amounts of addition do not cause deterioration in battery performance.> Important battery characteristics such as safety and charge / discharge cycle characteristics can be improved. Whether M and F are present on the surface can be determined by performing spectroscopic analysis, for example, XPS analysis, on the positive electrode particles.

本発明のリチウムニッケルコバルトマンガン複合酸化物は、 上記一般式で表わさ れる微粒子が多数凝集して形成された粒状粉末であることが必要である。 上記微粒 子は、 特には限定されないが、 その平均粒子径 D 50 (以下、 体積平均粒径ともい う） が 0. 5〜7 mが好ましい。 そして、 該微粒子が多数凝集して形成された複 合酸化物粉末の平均粒子径 D 50は 3〜 15 mが好ましく、 さらに 5〜12 ΠΙ が好ましい。 複合酸化物粉末の平均粒子径が 3 よりも小さいと緻密な電極層を 形成しにくくなり、 逆に 15 mよりも大きいと大電流放電特性が低下し好ましく ない。 また、 本発明の凝集粒状複合酸化物の粉末は、 圧縮破壊強度 （以下では、 単に圧 縮強度ともいう。 ） として、 5 OMPa以上有することが必要である。 かかる圧縮 強度 （S t) は、 下記数式 1に示す平松らの式 （ 「日本鉱業会誌」 81巻、 932号 1965年 12月号、 1024〜1030ページ） により求めた値である。 The lithium nickel cobalt manganese composite oxide of the present invention needs to be a granular powder formed by agglomeration of a large number of fine particles represented by the above general formula. The fine particles are not particularly limited, but preferably have an average particle diameter D 50 (hereinafter, also referred to as a volume average particle diameter) of 0.5 to 7 m. The average particle diameter D50 of the composite oxide powder formed by agglomeration of a large number of the fine particles is preferably 3 to 15 m, more preferably 5 to 12 mm. If the average particle size of the composite oxide powder is smaller than 3, it is difficult to form a dense electrode layer, and if it is larger than 15 m, large current discharge characteristics are undesirably reduced. Further, the powder of the aggregated granular composite oxide of the present invention needs to have a compression breaking strength (hereinafter, also simply referred to as compression strength) of 5 OMPa or more. The compressive strength (St) is a value determined by the formula of Hiramatsu et al. Shown in the following formula 1 ("Journal of the Mining Industry", Vol. 81, No. 932, December 1965, pp. 1024-1030).

(数式 1) S

Figure imgf000008_0001
(d :粒子径、 P ··粒子にかかった荷重） 上記の凝集粒状複合酸化物粉末の圧縮強度が 50 M P aよりも小さい場合には、 緻密な電極層を形成しにくく、 電極密度が低下してしまい、 本発明の上記した目的 が達成することはできない。 なかでも、 該圧縮強度は、 80〜300MPaが特に 好適である。 (Formula 1) S
Figure imgf000008_0001
(d: particle size, load applied to the particles) If the above-mentioned aggregated granular composite oxide powder has a compressive strength of less than 50 MPa, it is difficult to form a dense electrode layer, and the electrode density decreases. As a result, the above object of the present invention cannot be achieved. Among them, the compressive strength is particularly preferably from 80 to 300 MPa.

さらに、 本発明のリチウムニッケルコバルトマンガン複合酸化物は、 比表面積が 好ましくは 0. 3〜2. 0m2/g、 特に好ましくは 0. 4〜1. Om2/gであり、 粒子形状が、 球状、 楕円状などの略球状であるのが好適である。 リチウムニッケル コバルトマンガン複合酸化物がかかる特性を満たすことにより、 特に、 高容量、 高 サイクル耐久性、 高安全性などの効果が達成される。 Furthermore, the lithium nickel cobalt manganese composite oxide of the present invention has a specific surface area of preferably 0.3 to 2.0 m 2 / g, particularly preferably 0.4 to 1.0 Om 2 / g, and the particle shape is It is preferably a substantially spherical shape such as a spherical shape or an elliptical shape. When the lithium nickel cobalt manganese composite oxide satisfies such properties, effects such as high capacity, high cycle durability and high safety are achieved.

また、 本発明のリチウムニッケルコバル卜マンガン複合酸化物においては、 0. 94≤x/z≤l. 06であり、 含有される残存アルカリ量が 0. 25重量％以下 が好ましく、 特に、 0. 15重量％以下であるのが好適である。 0. 94≤x/z ≤1. 06であると、 高容量や高サイクル耐久性が得られ、 また、 残存アルカリ量 が 0. 25重量％以下であると高温保存時の電池の劣化が少なくできる。  Further, in the lithium nickel cobalt manganese composite oxide of the present invention, 0.94≤x / z≤l.06, and the amount of residual alkali contained is preferably 0.25% by weight or less. It is preferably at most 15% by weight. When 0.94≤x / z≤1.06, high capacity and high cycle durability can be obtained, and when the amount of residual alkali is 0.25% by weight or less, deterioration of the battery during high-temperature storage is small. it can.

本発明はさらに、 上述の一般式 LipN isC oyMnzMQ02-aFaで表されるリチウ ムニッケルコパル卜マンガン複合酸化物の微粒子が多数凝集して形成された、 平均 粒子径 D 50が 3〜 15 m、 好ましくは 8〜 15 mの凝集粒状複合酸化物粉末 であり、 かつ粉末の圧縮破壊強度が 50 M P a以上である大粒径のリチウムニ次電 池用リチウムニッケルコバルトマンガン複合酸化物粉末と、 該大粒径の平均粒径 D 50の 1/2〜1/5の平均粒径を有する小粒径のリチウム二次電池用リチウムニッケ ルコバルトマンガン複合酸化物粉末とを、 9 ： 1〜6 ： 4の重量比で混合して、 リ チウムニ次電池用リチウムニッケルコバルトマンガン複合酸化物粉末を形成するこ ともできる。 このように、 大粒径のリチウムニッケルコバルトマンガン複合酸化物 粉末と、 小粒径のリチウムニッケルコバルトマンガン複合酸ィヒ物粉末とを、 上記範 囲の重量比、 なかでも好ましくは 8 . 5 : 1 . 5〜7 ： 3の重量比で混合すること により、 電極の密度が更に向上する。 The present invention further provides the above-described general formula Li p N i s C o y Mn z M Q 0 2 - microparticles of a F lithium nickel Copal Bok manganese composite oxide represented by a is formed by a number agglomerated A large particle size lithium secondary battery which is an agglomerated granular composite oxide powder having an average particle diameter D50 of 3 to 15 m, preferably 8 to 15 m, and having a compressive fracture strength of 50 MPa or more. A lithium-nickel-cobalt-manganese composite oxide powder; and a lithium-nickel-cobalt-manganese composite oxide for a lithium secondary battery having a small particle diameter having an average particle diameter of 1/2 to 1/5 of the large particle diameter D50 And a mixed powder with a weight ratio of 9: 1 to 6: 4 to form lithium nickel cobalt manganese composite oxide powder for lithium secondary batteries. Thus, the lithium nickel cobalt manganese composite oxide powder having a large particle size and the lithium nickel cobalt manganese composite oxide powder having a small particle size are The density of the electrodes is further improved by mixing at a weight ratio of the box, particularly preferably at a weight ratio of 8.5: 1.5 to 7: 3.

本発明のリチウムニッケルコバルトマンガン複合酸化物は、 リチウム源、 ニッケ ル源、 コバルト源、 マンガン源、 及び必要に応じて使用される M元素源及びフッ素 源の混合物を酸素含有雰囲気下において 7 0 0〜1 0 5 0 °Cで焼成して形成される。 上記リチウム源としては、 炭酸リチウム、 水酸化リチウムなどが使用できるが、 特に、 炭酸リチウムが使用されることが好ましい。 リチウム源として炭酸リチウム を使用した場合には、 例えば水酸化リチウムを使用した場合に比べて低コストにな り、 本発明の所望とする安価で高性能のリチウムニッケルコバルトマンガン複合酸 化物が容易に得られるので好ましい。 また、 ニッケル、 コバルト、 マンガン源とし ては、 ニッケルコバルトマンガン複合ォキシ水酸ィヒ物などが用いられる。 一方、 必 要に応じて使用される元素 Mの原料としては、 好ましくは、 水酸化物、 酸化物、 炭 酸塩、 フッ化物が選択される。 フッ素源としては、 金属フッ化物、 L i F、 M g F 2などが選択される。 The lithium-nickel-cobalt-manganese composite oxide of the present invention is obtained by mixing a lithium source, a nickel source, a cobalt source, a manganese source, and a mixture of an M element source and a fluorine source, if necessary, in an oxygen-containing atmosphere. It is formed by firing at about 150 ° C. As the lithium source, lithium carbonate, lithium hydroxide, and the like can be used, and particularly, lithium carbonate is preferably used. When lithium carbonate is used as the lithium source, the cost is lower than when lithium hydroxide is used, for example, and the inexpensive and high-performance lithium nickel cobalt manganese composite oxide desired by the present invention can be easily obtained. It is preferable because it can be obtained. As the nickel, cobalt, and manganese sources, nickel-cobalt-manganese composite oxyhydroxide and the like are used. On the other hand, as a raw material of the element M used as necessary, a hydroxide, an oxide, a carbonate, and a fluoride are preferably selected. As the fluorine source, metal fluoride, L i F, M g F 2 and the like are selected.

上記焼成温度が、 7 0 0 より小さい場合にはリチウム化が不完全となり、 逆に 1 0 5 0 °Cを超える場合には充放電サイクル耐久性や初期容量が低下してしまう。 特に、 焼成温度は 9 0 0〜1 0 0 0 °Cが好適である。 焼成は多段で行うことが好ま しい。 好ましい例として、 7 0 0 °Cで数時間焼成し、 9 0 0〜1 0 0 O :で数時間 焼成する例が挙げられる。  If the firing temperature is lower than 700, lithiation is incomplete, and if it exceeds 150 ° C, the charge / discharge cycle durability and the initial capacity decrease. In particular, the firing temperature is preferably from 900 to 100 ° C. The firing is preferably performed in multiple stages. Preferred examples include firing at 700 ° C. for several hours and firing at 900 to 100 O: for several hours.

リチウム源、 ニッケル源、 コバルト源、 マンガン源、 及び必要に応じて使用され る M元素源及びフッ素源の混合粉体を上記のように 7 0 0〜1 0 5 0 °Cで酸素含有 雰囲気において 5〜2 0時間焼成処理し、 得られた焼成物を冷却後、 粉砕、 分級す ることにより、 好ましくは 0 . 3〜 7 mのリチウムニッケルコバルトマンガン複 合酸化物の微粒子が凝縮した凝集粒状複合酸化物粉末が形成される。 この場合、 コ バルト源等の原料の性状、 リチウム化の焼成温度、 焼成時間などの条件を選択する ことにより、 形成される凝集粒状複合酸化物粉末の平均粒子径ゃ圧縮強度を制御す ることができる。  A mixed powder of a lithium source, a nickel source, a cobalt source, a manganese source, and an optional M element source and a fluorine source is used at 700 to 150 ° C in an oxygen-containing atmosphere as described above. After baking for 5 to 20 hours, and cooling and pulverizing and classifying the obtained baking product, agglomerated particles in which fine particles of a lithium nickel cobalt manganese composite oxide of preferably 0.3 to 7 m are condensed are obtained. A composite oxide powder is formed. In this case, by controlling the properties of the raw material such as the cobalt source, the sintering temperature for lithiation, the sintering time, and the like, the average particle size of the formed aggregated granular composite oxide powder divided by the compressive strength is controlled. Can be.

かかるリチウムニッケルコバルトマンガン複合酸化物からリチウムニ次電池用の 正極を製造する場合には、 かかる複合酸化物の粉末に、 アセチレンブラック、 黒鉛、 ックなどのカーボン系導電材と結合材を混合することにより形成さ れる。 上記結合材には、 好ましくは、 ポリフッ化ビニリデン、 ポリテトラフルォロ エチレン、 ポリアミド、 カルポキシメチルセルロース、 アクリル樹脂などが用いら れる。 When a positive electrode for a lithium secondary battery is manufactured from the lithium nickel cobalt manganese composite oxide, acetylene black, graphite, It is formed by mixing a carbon-based conductive material such as a rubber and a binder. As the binder, polyvinylidene fluoride, polytetrafluoroethylene, polyamide, carboxymethylcellulose, an acrylic resin, or the like is preferably used.

本発明のリチウムニッケルコバルトマンガン複合酸化物の粉末、 導電材及ぴ結合 材を溶媒又は分散媒を使用し、 スラリー又は混練物とし、 これをアルミニウム箔、 ステンレス箔などの正極集電体に塗布などにより担持せしめてリチウムニ次電池用 の正極が製造される。  The powder, conductive material and binder of the lithium nickel cobalt manganese composite oxide of the present invention are used as a slurry or a kneaded material using a solvent or a dispersion medium, and are applied to a positive electrode current collector such as an aluminum foil or a stainless steel foil. Thus, a positive electrode for a lithium secondary battery is manufactured.

本発明のリチウムニッケルコバルトマンガン複合酸化物を正極活物質に用いるリ チウムニ次電池において、 セパレー夕としては、 多孔質ポリエチレン、 多孔質ポリ プロピレンのフィルムなどが使用される。 また、 電池の電解質溶液の溶媒としては、 種々の溶媒が使用できるが、 なかでも炭酸エステルが好ましい。 炭酸エステルは環 状、 鎖状いずれも使用できる。 環状炭酸エステルとしては、 プロピレンカーボネー ト、 エチレンカーボネート (E C) などが例示される。 鎖状炭酸エステルとしては、 ジメチルカ一ポネート、 ジェチルカーボネート (D E C) 、 ェチルメチルカーポネ 一卜 (EM C) 、 メチルプロピル力一ポネート、 メチルイソプロピルカーボネート などが例示される。  In the lithium secondary battery using the lithium-nickel-cobalt-manganese composite oxide of the present invention as a positive electrode active material, a porous polyethylene, a porous polypropylene film or the like is used as a separator. Further, various solvents can be used as a solvent for the electrolyte solution of the battery, and among them, a carbonate ester is preferable. Carbonate can be used in any of a ring shape and a chain shape. Examples of the cyclic carbonate include propylene carbonate and ethylene carbonate (EC). Examples of the chain carbonate include dimethyl carbonate, dimethyl carbonate (DEC), ethyl methyl carbonate (EMC), methyl propyl carbonate, methyl isopropyl carbonate and the like.

本発明では、 上記炭酸エステルを単独で又は 2種以上を混合して使用できる。 ま た、 他の溶媒と混合して使用してもよい。 また、 負極活物質の材料によっては、 鎖 状炭酸エステルと環状炭酸エステルを併用すると、 放電特性、 サイクル耐久性、 充 放電効率が改良できる場合がある。  In the present invention, the above carbonate esters can be used alone or in combination of two or more. Further, it may be used by mixing with another solvent. In addition, depending on the material of the negative electrode active material, the combined use of a chain carbonate and a cyclic carbonate may improve discharge characteristics, cycle durability, and charge / discharge efficiency.

また、 本発明のリチウムニッケルコバルトマンガン複合酸化物を正極活物質に用 いるリチウム二次電池においては、 フッ化ビニリデン一へキサフルォ口プロピレン 共重合体 （例えばアトケム社製：商品名力イナ一） あるいはフッ化ビニリデンーパ 一フルォロプロピルビニルエーテル共重合体を含むゲルポリマ一電解質としても良 い。 上記の電解質溶媒又はポリマー電解質に添加される溶質としては、 c i o4—、Further, in a lithium secondary battery using the lithium nickel cobalt manganese composite oxide of the present invention as a positive electrode active material, a vinylidene fluoride-hexafluoro propylene copolymer (for example, manufactured by Atochem Co., Ltd .: Inaichi Co., Ltd.) or It is also good as a gel polymer containing vinylidene fluoride-fluoropropyl vinyl ether copolymer. As the solute added to the above-mentioned electrolyte solvent or polymer electrolyte, cio 4 —,

C F3S〇3 -、 B F4—、 P F6—、 A s F6 -、 S b F6—、 C F3C 02—、 (C F3S 〇2) 2N—などをァニオンとするリチウム塩のいずれか 1種以上が好ましく使用さ れる。 上記リチウム塩からなる電解質溶媒又はポリマー電解質対して、 0 . 2〜2 . O m o 1 / 1 (リットル） の濃度で添加するのが好ましい。 この範囲を逸脱すると、 イオン伝導度が低下し、 電解質の電気伝導度が低下する。 なかでも、 0. 5〜1 . 5 m o 1 / 1が特に好ましい。 Lithium with CF 3 S〇 3- , BF 4 —, PF 6 —, As F 6 —, S b F 6 —, CF 3 C 0 2 —, (CF 3 S〇 2 ) 2 N—, etc. as anions Any one or more of the salts are preferably used. With respect to the electrolyte solvent or the polymer electrolyte comprising the lithium salt, 0.2 to 2.2. It is preferred to add at a concentration of O mo 1/1 (liter). Outside this range, the ionic conductivity decreases and the electrical conductivity of the electrolyte decreases. Among them, 0.5 to 1.5 mo 1/1 is particularly preferred.

本発明のリチウムニッケルコバルトマンガン複合酸化物を正極活物質に用いるリ チウム電池において、 負極活物質には、 リチウムイオンを吸蔵、 放出可能な材料が 用いられる。 この負極活物質を形成する材料は特に限定されないが、 例えばリチウ ム金属、 リチウム合金、 炭素材料、 周期表 1 4、 または 1 5族の金属を主体とした 酸化物、 炭素化合物、 炭化ケィ素化合物、 酸化ケィ素化合物、 硫化チタン、 炭化ホ ゥ素化合物などが挙げられる。 炭素材料としては、 種々の熱分解条件で有機物を熱 分解したものや人造黒鉛、 天然黒鉛、 土壌黒鉛、 膨張黒鉛、 鱗片状黒鉛などを使用 できる。 また、 酸化物としては、 酸化スズを主体とする化合物が使用できる。 負極 集電体としては、 銅箔、 ニッケル箔などが用いられる。 かかる負極は、 上記活物質 を有機溶媒と混練してスラリーとし、 該スラリーを金属箔集電体に塗布、 乾燥、 プ レスして得ることにより好ましくは製造される。  In the lithium battery using the lithium nickel cobalt manganese composite oxide of the present invention as a positive electrode active material, a material capable of occluding and releasing lithium ions is used as the negative electrode active material. The material forming the negative electrode active material is not particularly limited, and examples thereof include lithium metal, lithium alloy, carbon material, oxides, carbon compounds, and silicon carbide compounds mainly composed of metals in Groups 14 or 15 of the periodic table. , A silicon oxide compound, titanium sulfide, a boron carbide compound, and the like. As the carbon material, those obtained by thermally decomposing organic substances under various pyrolysis conditions, artificial graphite, natural graphite, soil graphite, expanded graphite, flaky graphite and the like can be used. As the oxide, a compound mainly composed of tin oxide can be used. A copper foil, a nickel foil, or the like is used as the negative electrode current collector. Such a negative electrode is preferably manufactured by kneading the active material with an organic solvent to form a slurry, and applying the slurry to a metal foil collector, drying and pressing to obtain the slurry.

本発明のリチウムニッケルコバルトマンガン複合酸化物を正極活物質に用いるリ チウム電池の形状には特に制約はない。 シート状、 フィルム状、 折り畳み状、 巻回 型有底円筒形、 ボタン形などが用途に応じて選択される。  The shape of the lithium battery using the lithium nickel cobalt manganese composite oxide of the present invention as a positive electrode active material is not particularly limited. Sheets, films, folds, rolled bottomed cylinders, buttons, etc. are selected according to the application.

実施例 Example

以下に実施例により本発明を具体的に説明するが、 本発明はこれらの実施例に限 定されないことはもちろんである。  Hereinafter, the present invention will be described specifically with reference to Examples, but it is needless to say that the present invention is not limited to these Examples.

なお、 実施例において、 X線回析分析は、 株式会社リガクの RINT- 2000型を用い、 Cu-Κ α管球、 管電圧 4 0 KV、 管電流 4 0 mA、 受光スリット 1 5 mm、 サ ンプリング幅 0 . 0 2 ° の条件で行った。 本発明において、 粒度分析には  In the examples, the X-ray diffraction analysis was performed using a RINT-2000 type Rigaku Corporation, Cu-Κα tube, tube voltage 40 KV, tube current 40 mA, light receiving slit 15 mm, The measurement was performed under the condition of a sampling width of 0.02 °. In the present invention, particle size analysis

Leed+Northrup社の Microtrac HRA X - 100型を用いた。 Microtrac HRA X-100 from Leed + Northrup was used.

[実施例 1 ]  [Example 1]

反応槽に硫酸ニッケルと硫酸コバルトと硫酸マンガンを含有する硫酸塩水溶液と、 アンモニア水溶液と、 水酸化ナトリウム水溶液とをそれぞれ連続的に、 反応槽のス ラリーの P Hが 11、 温度が 50°Cになるように反応槽内を攪拌しつつ供給した。 ォ ーバ一フ口一方式で反応系内の液量を調節し、 オーバーフローした共沈スラリーを 濾過、 水洗し、 次いで 70°Cで乾燥することにより、 ニッケルコバルトマンガン複 合水酸化物粉体を得た。 得られた水酸化物を、 水酸化ナトリウムを 3重量％含有す る 6重量％過硫酸ナトリウム水溶液に分散させ、 20°Cで 12時間攪拌することによ り、 ニッケルコバルトマンガン複合ォキシ水酸化物を合成した。 A sulfate aqueous solution containing nickel sulfate, cobalt sulfate, and manganese sulfate, an ammonia aqueous solution, and a sodium hydroxide aqueous solution were continuously added to the reaction tank, and the pH of the slurry in the reaction tank was 11 and the temperature was 50 ° C. The solution was supplied while stirring the inside of the reaction vessel. The amount of liquid in the reaction system was adjusted by an over-the-mouth method, and the overflowed coprecipitated slurry was removed. Filtration, washing with water, and drying at 70 ° C. yielded a nickel-cobalt-manganese composite hydroxide powder. The obtained hydroxide is dispersed in a 6% by weight aqueous sodium persulfate solution containing 3% by weight of sodium hydroxide, and the mixture is stirred at 20 ° C. for 12 hours to obtain a nickel-cobalt-manganese composite oxyhydroxide. Was synthesized.

この複合ォキシ水酸化物粉末に平均粒径 20/ mの炭酸リチウム粉末を混合し、 大 気中で 900°Cで 16時間焼成し、 混合粉碎することにより、 LiNi1/3Co1/3Mn1/302粉末 を得た。 また、 この正極粉末の窒素吸着法による比表面積は 0.58m2/g、 体積平均 粒径 D50は 11. であった。 Cu- Κο;線を使用した粉末 X線回折スぺクトルは菱 面体系 （R- 3m) 類似であった。 この正極粉末粒子は SEM観察において、 1次粒子 が無数に凝集して二次粒子を形成したものであり、 かつその形状が球状もしくは精 円状であった。 得られた LiNi1/3Co1/3Mn1/302粉末について、 島津製作所の微小圧縮試 験機 MCT- W500を用いて圧縮強度を測定した。 即ち、 試験荷重を 100mN、 負 荷速度 3.874mN/secとし、 直径 50^ mの平面タイプの圧子を用いて、 粒径既知 の任意の粒子 10個について測定を行い、 圧縮強度を求めた結果 142MPaであった。 また、 この LiNi1/3Co1/3Mn1/302粉末 10 gを純水 100 g中に分散し、 ろ過後 0.02N の HC 1で電位差測定して残存アルカリ量を求めたところ、 0. 12重量％でぁっ た。 This composite oxyhydroxide powder is mixed with lithium carbonate powder having an average particle size of 20 / m, and calcined in air at 900 ° C for 16 hours, followed by mixing and pulverization to obtain LiNi 1/3 Co 1/3 Mn 1/3 to give 0. 2 powder. The specific surface area of this positive electrode powder determined by the nitrogen adsorption method was 0.58 m 2 / g, and the volume average particle diameter D50 was 11. The powder X-ray diffraction spectrum using Cu-Κ; lines was similar to the rhombohedral system (R-3m). The SEM observation of the positive electrode powder particles revealed that the primary particles were innumerably aggregated to form secondary particles, and the shape was spherical or round. For LiNi 1/3 Co 1/3 Mn 1/3 0 2 powder obtained was measured compressive strength using a micro compression testing machine MCT-W500 manufactured by Shimadzu. That is, the test load was 100 mN, the load speed was 3.874 mN / sec, and the measurement was performed on 10 arbitrary particles with a known particle size using a flat indenter with a diameter of 50 m, and the compressive strength was obtained. Met. In addition, 10 g of this LiNi 1/3 Co 1/3 Mn 1/3 0 2 powder was dispersed in 100 g of pure water, filtered, and the potential difference was measured with 0.02N HC 1 to determine the amount of residual alkali. 0.12% by weight.

この正極粉末、 アセチレンブラック、 黒鉛粉末、 PVDFパインダ一を固形分重 量比として 88Z3Z3/6で混合し、 N—メチルピロリドン溶媒を添加してボー ルミル混合により、 塗工スラリーを調製した。 このスラリーをドクタープレード方 式により厚さ 20ミクロンのアルミニウム箔集電体の片面に塗工し、 熱風乾燥によ り溶媒を除去したのち、 ロールプレス圧延を 4回おこない正極体シートを作製した。 正極体の電極層の厚みと単位面積あたりの電極層の重量から電極層の見かけ密度を 求めたところ、 3. 14 gZc cであった。  The positive electrode powder, acetylene black, graphite powder, and PVDF binder were mixed at a solid content weight ratio of 88Z3Z3 / 6, and an N-methylpyrrolidone solvent was added thereto, followed by ball mill mixing to prepare a coating slurry. This slurry was applied to one side of a 20-μm-thick aluminum foil current collector by the doctor blade method, the solvent was removed by hot-air drying, and then roll-pressed four times to produce a positive electrode sheet. The apparent density of the electrode layer was determined from the thickness of the electrode layer of the positive electrode body and the weight of the electrode layer per unit area, and was found to be 3.14 gZcc.

この正極体シートを正極に用い、 セパレー夕には厚さ 25 mの多孔質ポリプロ ピレンを用い、 厚さ 500 mの金属リチウム箔を負極に用い、 負極集電体にニッ ケル箔 20 mを使用し、 電解液には 1M L i PF6/EC+DEC (1 : 1) を用いてステンレス製簡易密閉型リチウム電池セルをアルゴングローブボックス内 で組立てた。 この電池について、 まず、 25 にて正極活物質 1 gにっき 20mA の負荷電流で 4. 3 Vまで CC- CVで充電し、 正極活物質 1 gにっき 20mAの負荷 電流にて 2 . 5 Vまで放電して初期放電容量を求めた。 更に充放電サイクル試験を 30回行った。 The positive electrode sheet is used for the positive electrode, a 25-m-thick porous polypropylene is used for the separator, a 500-m-thick metallic lithium foil is used for the negative electrode, and a 20-m nickel-nickel foil is used for the negative electrode current collector. Then, a simple sealed lithium battery cell made of stainless steel was assembled in an argon glove box using 1M LiPF 6 / EC + DEC (1: 1) as an electrolyte. For this battery, first, at 25 The battery was charged with CC-CV up to 4.3 V with a load current of, and discharged to 2.5 V with a load current of 20 mA per 1 g of the positive electrode active material to determine the initial discharge capacity. Further, a charge / discharge cycle test was performed 30 times.

その結果、 2 5 °Cにおける 2 . 5〜 4. 3 Vにおける初期重量放電容量密度は 161mA h / gであり、 初期体積放電容量密度は 4 4 4 mA hZC C—電極層であ り、 初期充放電効率は 89%であり、 30回充放電サイクル後の容量維持率は 97. 0% であった。  As a result, the initial weight discharge capacity density at 2.5 to 4.3 V at 25 ° C was 161 mAh / g, and the initial volume discharge capacity density was 444 mA hZC C--electrode layer. The charge / discharge efficiency was 89%, and the capacity retention after 30 charge / discharge cycles was 97.0%.

[実施例 2 ]  [Example 2]

共沈スラリー中の攪拌速度、 及びスラリー濃度を高めた他は実施例 1と同様にし てニッケルコバルトマンガン複合ォキシ水酸化物 (Ni/Co/Mn原子比 1/1/1) を得た。 この複合酸化物の粒度分布をレーザー散乱方式で測定した。 その結果体積平均粒径 D 50は 8. 7/2 mであった。  A nickel-cobalt-manganese composite oxyhydroxide (Ni / Co / Mn atomic ratio 1/1/1) was obtained in the same manner as in Example 1 except that the stirring speed in the coprecipitation slurry and the slurry concentration were increased. The particle size distribution of the composite oxide was measured by a laser scattering method. As a result, the volume average particle size D 50 was 8.7 / 2 m.

この複合ォキシ水酸化物粉末に炭酸リチウム粉末を混合し、 実施例 1と同様に焼 成し、 混合粉砕して LiN 3Co1/3Mn1/302粉末を得た。 この正極粉末の窒素吸着法によ る比表面積は 0. 70m2/ gであり、 体積平均粒径 D50は 9. 4 imであった。 また、 Cu-Ko!線を使用した粉末 X線回折スペクトルは菱面体系 （R- 3m) 類似であった。 例 1と同様にして粒子の破壊強度を求めた結果、 114M p aであった。 また、 この 正極粉末の残存アルカリ量を実施例 1と同様にして求めたところ 0. 13重量％であ つた。 The composite Okishi hydroxide powder was mixed with lithium carbonate powder, form baked in the same manner as in Example 1 to obtain a LiN 3 Co 1/3 Mn 1/3 0 2 powder were mixed and ground. The specific surface area of this positive electrode powder measured by a nitrogen adsorption method was 0.70 m 2 / g, and the volume average particle diameter D50 was 9.4 im. The powder X-ray diffraction spectrum using Cu-Ko! Line was similar to the rhombohedral system (R-3m). The breaking strength of the particles determined in the same manner as in Example 1 was 114 Mpa. The amount of residual alkali in the positive electrode powder was determined in the same manner as in Example 1, and found to be 0.13% by weight.

この正極粉末を用いて実施例 1と同様にして正極体シートを作製した。 得られ得 た正極体シートの電極層密度は 3 . 1 3 g/ c cであった。 この正極体シ一トを正 極に用い、 実施例 1と同様にして、 ステンレス製簡易密閉セルを組立て充放電性能 を評価した。 その結果、 2 5 における初期重量放電容量密度は 160mA h/ gで あり、 初期体積放電容量密度は 4 4 I mA h/C C一電極層であり、 初期充放電効 率は 91. 0%であった。 また、 30回充放電サイクル後の容量維持率は 97. 3%であつ た。  Using this positive electrode powder, a positive electrode body sheet was prepared in the same manner as in Example 1. The electrode layer density of the obtained positive electrode body sheet was 3.13 g / cc. Using this positive electrode sheet as the positive electrode, a simple closed cell made of stainless steel was assembled and the charge / discharge performance was evaluated in the same manner as in Example 1. As a result, the initial weight discharge capacity density at 25 was 160 mA h / g, the initial volume discharge capacity density was 44 I mA h / CC one electrode layer, and the initial charge / discharge efficiency was 91.0%. Was. The capacity retention rate after 30 charge / discharge cycles was 97.3%.

[実施例 3 ]  [Example 3]

硫酸ニッケルと硫酸コバルトと硫酸マンガンを含有する硫酸塩水溶液の組成比変 えた他は実施例 1と同様にしてニッケルコバル卜マンガン複合ォキシ水酸化物 (Ni/Co/Mn原子比 0.38/0.24/0.38) を得た。 この複合酸化物粉末粒子は S EM観 察において、 1次粒子が無数に凝集して二次粒子を形成したものであり、 かつその 形状が球状もしくは楕円状であった。 この複合酸化物粉末に炭酸リチウム粉末を混 合し、 実施例 1と同様にして UNi。.38Co。.24M¾ 3802粉末を得た。 この正極粉末の窒素 吸着法による比表面積は 0.63m2/gであり、 体積平均粒径 D50は 12.1 mであつ た。 また、 この正極粉末の Cu- 線を使用した粉末 X線回折スぺクトルは菱面体 系 （R- 3m) 類似であった。 例 1と同様にして粒子の破壌強度を求めた結果、 135M p aであった。 また、 この正極粉末の残存アルカリ量を実施例 1と同様にして求め たところ 0. 16重量％であった。 A nickel cobalt manganese composite oxyhydroxide was prepared in the same manner as in Example 1 except that the composition ratio of the aqueous sulfate solution containing nickel sulfate, cobalt sulfate and manganese sulfate was changed. (Ni / Co / Mn atomic ratio: 0.38 / 0.24 / 0.38) was obtained. In the SEM observation, the composite oxide powder particles were formed by innumerable primary particles forming secondary particles, and were spherical or elliptical in shape. Lithium carbonate powder was mixed with this composite oxide powder, and UNi was used in the same manner as in Example 1. 38 Co. . To obtain a 24 M¾ 38 0 2 powder. The specific surface area of the positive electrode powder determined by the nitrogen adsorption method was 0.63 m 2 / g, and the volume average particle diameter D50 was 12.1 m. The powder X-ray diffraction spectrum of this positive electrode powder using Cu-rays was similar to that of rhombohedral (R-3m). The rupture strength of the particles determined in the same manner as in Example 1 was 135 Mpa. Further, the amount of residual alkali in the positive electrode powder was determined in the same manner as in Example 1, and found to be 0.16% by weight.

この正極粉末を用いて実施例 1と同様にして正極体シートを作製した。 得られ得 た正極体シートの電極層密度は 3. 08 g/c cであった。 この正極体シートを正 極に用い、 実施例 1と同様にして、 ステンレス製簡易密閉セルを組立て、 充放電性 能を評価した。 その結果、 25 °Cにおける初期重量放電容量密度は 158mA h/'g であり、 初期体積放電容量密度は 428mAhZCC—電極層であり、 30回充放 電サイクル後の容量維持率は 96.1%であった。  Using this positive electrode powder, a positive electrode body sheet was prepared in the same manner as in Example 1. The electrode layer density of the obtained positive electrode body sheet was 3.08 g / cc. Using this positive electrode sheet as the positive electrode, a simple closed cell made of stainless steel was assembled in the same manner as in Example 1, and the charge / discharge performance was evaluated. As a result, the initial weight discharge capacity density at 25 ° C was 158 mAh / 'g, the initial volume discharge capacity density was 428 mAh ZCC--electrode layer, and the capacity retention rate after 30 charge / discharge cycles was 96.1%. Was.

[実施例 4]  [Example 4]

実施例 1で合成した二ッケルコバルトマンガン複合ォキシ水酸化物 (Ni/Co/Mn 原子比 1/1/1) を用い、 該複合ォキシ水酸化物粉末に炭酸リチウム粉末と酸化ジル コニゥム粉末とフッ化リチウム粉末を混合し、 実施例 1と同様に焼成し、 混合粉碎 して、 Li(Ni1/3Co1/3Mn1/3)a 995 Zr ^OuF^粉末を得た。 この正極粉末の窒素吸着法 による比表面積は 0.55m2/gであり、 体積平均粒径 D50は 11.4 H1であった。 ま た、 この正極粉末の Cu-Ka線を使用した粉末 X線回折スペクトルは菱面体系 （R - 3ι) 類似であった。 例 1と同様にして粒子の破壊強度を求めた結果、 150Mp aで あった。 また、 この正極粉末の残存アルカリ量を実施例 1と同様にして求めたとこ ろ 0. 12重量％であった。 Using nickel cobalt manganese composite oxyhydroxide (Ni / Co / Mn atomic ratio 1/1/1) synthesized in Example 1, lithium carbonate powder and zirconium oxide powder were added to the composite oxyhydroxide powder. Lithium fluoride powder was mixed, fired in the same manner as in Example 1, and mixed and ground to obtain Li (Ni 1/3 Co 1/3 Mn 1/3 ) a 995 Zr ^ OuF ^ powder. The specific surface area of this positive electrode powder measured by a nitrogen adsorption method was 0.55 m 2 / g, and the volume average particle diameter D50 was 11.4 H1. Further, the powder X-ray diffraction spectrum of the positive electrode powder using Cu-Ka line was similar to a rhombohedral system (R-3ι). The breaking strength of the particles determined in the same manner as in Example 1 was 150 MPa. The amount of residual alkali in the positive electrode powder was determined in the same manner as in Example 1 and found to be 0.12% by weight.

この正極粉末を用いて実施例 1と同様にして正極体シートを作製した。 得られた 正極体シートの電極層密度は 3. 11 g/c cであった。 この正極体シートを正極 に用い、 実施例 1と同様にしてステンレス製簡易密閉セルを組立て充放電性能を評 価した。 その結果、 25°Cにおける初期重量放電容量密度は 162mAh/gであ り、 初期体積放電容量密度は 435mAhZCC—電極層であり、 30回充放電サ ィクル後の容量維持率は 98.0%であった。 Using this positive electrode powder, a positive electrode body sheet was prepared in the same manner as in Example 1. The electrode layer density of the obtained positive electrode body sheet was 3.11 g / cc. Using this positive electrode body sheet as the positive electrode, a simple closed cell made of stainless steel was assembled in the same manner as in Example 1 and the charge / discharge performance was evaluated. As a result, the initial weight discharge capacity density at 25 ° C was 162 mAh / g. The initial volume discharge capacity density was 435 mAh ZCC-electrode layer, and the capacity retention rate after 30 charge / discharge cycles was 98.0%.

[実施例 5]  [Example 5]

共沈の溶液中の酸素濃度を低め、 攪拌速度を高め、 スラリー濃度を高めた他は実 施例 1と同様にしてニッケルコバルトマンガン複合ォキシ水酸化物 （Ni/Co/Mn原 子比 1/1/1) を得た。 この複合酸化物の粒度分布をレーザー散乱方式で測定した。 その結果体積平均粒径 D50は 2. 6 mであった。  Except that the oxygen concentration in the coprecipitation solution was reduced, the stirring speed was increased, and the slurry concentration was increased, the nickel-cobalt-manganese composite oxyhydroxide (Ni / Co / Mn atomic ratio 1 / 1/1) was obtained. The particle size distribution of the composite oxide was measured by a laser scattering method. As a result, the volume average particle size D50 was 2.6 m.

得られたニッケルコバルトマンガン複合ォキシ水酸化物と炭酸リチウム粉末を混 合し、 実施例 1と同様に焼成し、 混合粉碎して LiNi1/3Co1/3Mn1/302粉末を得た。 また、 この正極粉末の窒素吸着法による比表面積は 0. 83m2/ gであり、 体積平均粒径 D50は 3. 1 であった。 また、 Cu- Κα線を使用した粉末 X線回折スぺクトル は菱面体系 （R- 3πι) 類似であった。 例 1と同様にして粒子の破壊強度を求めた結果、 135Mp aであった。 また、 この正極粉末の残存アルカリ量を実施例 1と同様に して求めたところ 0. 15重量％であった。 Nickel-cobalt-manganese composite Okishi hydroxide and lithium carbonate powder obtained was combined mixed, and calcined in the same manner as in Example 1, to obtain a LiNi 1/3 Co 1/3 Mn 1/3 0 2 powder and mixed powder碎Was. The specific surface area of this positive electrode powder determined by a nitrogen adsorption method was 0.83 m 2 / g, and the volume average particle diameter D50 was 3.1. The powder X-ray diffraction spectrum using Cu-α rays was similar to the rhombohedral system (R-3πι). The breaking strength of the particles determined in the same manner as in Example 1 was 135 Mpa. In addition, the amount of residual alkali in the positive electrode powder was determined in the same manner as in Example 1 and found to be 0.15% by weight.

この小粒径の正極粉末 20重量部と実施例 1で合成した平均粒径 1 1. 5ミクロ ンの大粒径の正極粉末 80重量部を混合した正極混合粉末を用いて実施例 1と同様 にして正極体シー卜を作製した。 小粒径の平均粒径 D 50の、 大粒径の平均粒径 D 50に対する比率は 1 Z3. 7であった。 得られた正極体シートの電極層密度は 3. 24 g/c cであった。  Same as Example 1 except that 20 parts by weight of the small particle size positive electrode powder and 80 parts by weight of the large particle size positive electrode powder synthesized in Example 1 having a mean particle size of 11.5 microns were mixed. Thus, a positive electrode sheet was prepared. The ratio of the average particle size D 50 of the small particle size to the average particle size D 50 of the large particle size was 1 Z3.7. The electrode layer density of the obtained positive electrode body sheet was 3.24 g / cc.

この正極体シートを正極に用い、 実施例 1と同様にして、 ステンレス製簡易密閉 セルを組立て充放電性能を評価した。 その結果、 25 °Cにおける初期重量放電容量 密度は 16 ImAh/gであり、 初期体積放電容量密度は 458mAh/CC—電 極層であり、 初期充放電効率は 91.0%であった。 また、 30回充放電サイクル後の 容量維持率は 97.3%であった。  Using this positive electrode body sheet as the positive electrode, a simple closed cell made of stainless steel was assembled and the charge / discharge performance was evaluated in the same manner as in Example 1. As a result, the initial mass discharge capacity density at 25 ° C was 16 ImAh / g, the initial volume discharge capacity density was 458 mAh / CC—electrode layer, and the initial charge / discharge efficiency was 91.0%. The capacity retention rate after 30 charge / discharge cycles was 97.3%.

[比較例 1 ]  [Comparative Example 1]

スラリー中の酸素濃度を高め、 攪拌溥度を低め、 一方、 スラリー濃度を低めた他 は実施例 1と同様にして、 ニッケルコバルトマンガン複合ォキシ水酸化物  A nickel-cobalt-manganese composite oxyhydroxide was prepared in the same manner as in Example 1 except that the oxygen concentration in the slurry was increased and the stirring density was lowered, while the slurry concentration was lowered.

(Ni/Co/Mn原子比 1/1/1) を得た。 この複合ォキシ水酸化物粉末に水酸ィ匕リチウム 1水和物を混合し、 実施例 1と同様に焼成し、 混合粉砕して LiNi1/3Co1/3Mn1/302粉末 を得た。 該粉末の平均粒径は 13. 5/im、 比表面積は 0.96m2Zgであった。 Cu- Κο;線を使用した粉末 X線回折スペクトルは菱面体系 （R- 3m) 類似であった。 実施 例 1と同様にして粒子の破壊強度を求めた結果、 27.2 Mp aであった。 (Ni / Co / Mn atomic ratio 1/1/1) was obtained. The composite Okishi hydroxide powder was mixed with Mizusani匕lithium monohydrate, and fired in the same manner as in Example 1, LiNi 1/3 Co 1/3 Mn 1/3 0 2 powder were mixed together and ground Got. The average particle size of the powder was 13.5 / im, and the specific surface area was 0.96 m 2 Zg. The powder X-ray diffraction spectrum using Cu-Κ; lines was similar to the rhombohedral system (R-3m). The breaking strength of the particles determined in the same manner as in Example 1 was 27.2 MPa.

この正極粉末を用いて実施例 1と同様にして正極体シ一トを作製した。 得られた 正極体シートの電極層密度は 2. 91 g/c cであった。 この正極体シートを正極 に用い、 実施例 1と同様にしてステンレス製簡易密閉セルを組立て充放電性能を評 価した。 その結果、 25 °Cにおける初期重量放電容量密度は 156mAh/gであ り、 初期体積放電容量密度は 399mAliZCC—電極層であり、 初期充放電効率 は 87%であった。 また、 30回充放電サイクル後の容量維持率は 93.2%であった。 産業上の利用可能性  Using this positive electrode powder, a positive electrode sheet was produced in the same manner as in Example 1. The electrode layer density of the obtained positive electrode body sheet was 2.91 g / cc. Using this positive electrode body sheet as the positive electrode, a simple closed cell made of stainless steel was assembled in the same manner as in Example 1 and the charge / discharge performance was evaluated. As a result, the initial weight discharge capacity density at 25 ° C was 156 mAh / g, the initial volume discharge capacity density was 399 mAliZCC-electrode layer, and the initial charge / discharge efficiency was 87%. The capacity retention after 30 charge / discharge cycles was 93.2%. Industrial applicability

本発明によれば、 初期体積放電容量密度および初期重量放電容量密度が大きく、 初期充放電効率、 充放電サイクル安定性、 及び安全性が高い、 リチウム二次電池正 極用リチウムニッケルコバルトマンガン複合酸化物粉末、 該リチウムニッケルコバ ルトマンガン複合酸化物粉末を含む、 リチウム二次電池用正極、 及びリチウム二次 電池が提供される。  According to the present invention, the initial volume discharge capacity density and the initial weight discharge capacity density are large, the initial charge / discharge efficiency, the charge / discharge cycle stability, and the safety are high. The present invention provides a positive electrode for a lithium secondary battery, and a lithium secondary battery, comprising a powder of the same, the lithium nickel cobalt manganese composite oxide powder.

Claims

請求の 範 囲 The scope of the claims 1. 一般式 LipN
Figure imgf000017_0001
a (但し、 Mは N i , Co, Mn以外の遷 移金属元素またはアルカリ土類金属元素である。 0. 9≤p≤l. 1， 0. 2≤ x≤0. 5、 0. l≤y≤0. 4、 0. 2≤z≤0. 5、 0≤q≤0. 05、 1. 9≤2-a≤2. 1、 x + y + z +q= 1, 0≤ a≤ 0 v 02) で表されるリチ ゥムニッケルコバル卜マンガン複合酸化物の微粒子が多数凝集して形成された、 平均粒子径 D 50が 3〜 15 の凝集粒状複合酸化物粉末であり、 かつ粉 の 圧縮破壞強度が 50 M P a以上であることを特徴とするリチウムニ次電池用リチ ゥムニッケルコバルトマンガン複合酸化物粉末。 1. General formula Li p N
Figure imgf000017_0001
a (where M is a transition metal element or an alkaline earth metal element other than Ni, Co, and Mn. 0.9≤p≤l.1, 0.2≤x≤0.5, 0.l ≤y≤0.4, 0.2≤z≤0.5, 0≤q≤0.0.05, 1.9≤2-a≤2.1, x + y + z + q = 1, 0≤a ≤ 0 v 02) fine particles of lithium © arm nickel cobalt Bok manganese composite oxide represented by is formed by a number aggregated, the mean particle diameter D 50 is agglomerated particulate composite oxide powder 3-15, and A lithium nickel cobalt manganese composite oxide powder for lithium secondary batteries, wherein the powder has a compressive fracture strength of 50 MPa or more. 2. 粉末の比表面積が 0. 3〜2. 0m2/gであり、 粒子形状が略球状である請 求項 1に記載のリチウムニッケルコバル卜マンガン複合酸化物粉末。 2. The lithium nickel cobalt manganese composite oxide powder according to claim 1, wherein the powder has a specific surface area of 0.3 to 2.0 m 2 / g and the particle shape is substantially spherical. 3. 0. 94≤x/z≤ 1. 06であり、 含有される残存アルカリ量が 0. 25重 量％以下である請求項 1または 2に記載のリチウムニッケルコバルトマンガン複 合酸化物粉末。  3. The lithium-nickel-cobalt-manganese composite oxide powder according to claim 1, wherein 0.04 ≦ x / z ≦ 1.06, and the amount of residual alkali contained is 0.25% by weight or less. 4. 粉末の圧縮破壊強度が 80〜300MPaである請求項 1、 2または 3に記載 のリチウムニッケルコバルトマンガン複合酸化物粉末。  4. The lithium nickel cobalt manganese composite oxide powder according to claim 1, 2 or 3, wherein the powder has a compressive fracture strength of 80 to 300 MPa. 5. —般式 LipN ixCoyMnzMa02—aFa (伹し、 Mは N i , Co, Mn以外の遷 移金属元素またはアル力リ土類金属元素である。 0. 9≤p≤ 1. 1、 0. 2≤ x≤0. 5、 0. l≤y≤0. 4、 0. 2≤z≤0. 5、 0≤q≤0. 05、 1. 9≤2 - a≤2. 1、 + ^+z + q= l, 0≤a≤0. 02) で表されるリチ ゥムニッケルコバルトマンガン複合酸化物の微粒子が多数凝集して形成された、 平均粒子径 D 50が 3〜 15 mの凝集粒状複合酸化物粉末であり、 かつ粉末の 圧縮破壊強度が 50 M P a以上である大粒径のリチウムニ次電池用リチウムニッ ゲルコバルトマンガン複合酸化物粉末と、 該大粒径の平均粒径 D 50の \1〜 1/5の平均粒径を有する小粒径のリチウムニ次電池用リチウムニッケルコバルト マンガン複合酸化物粉末とを、 9 ： 1〜6 ： 4の重量比で混合されてなることを 特徴とするリチウム二次電池用リチウムニッケルコバルトマンガン複合酸ィヒ物粉 末。 5. —General formula Li p N x Co y Mn z M a 0 2 — a F a (where M is a transition metal element other than N i, Co, Mn or an alkaline earth metal element) 0.9 ≤ p ≤ 1.1, 0.2 ≤ x ≤ 0.5, 0.1 ≤ y ≤ 0.4, 0.2 ≤ z ≤ 0.5, 0 ≤ q ≤ 0.05, 1 9≤2-a≤2.1, + ^ + z + q = l, 0≤a≤0.02) In addition, it is an agglomerated granular composite oxide powder having an average particle diameter D50 of 3 to 15 m, and has a compressive fracture strength of 50 MPa or more. Product powder, and a lithium nickel cobalt manganese composite oxide powder for a lithium secondary battery having a small particle diameter having an average particle diameter of 1 to 1/5 of the large particle diameter D 50 9: 1 to 1 Lithium for lithium secondary batteries characterized by being mixed in a weight ratio of 6: 4 Arm nickel-cobalt-manganese composite acid I dry matter Powder. 6. 粉末の圧縮破壊強度が 5 OMPa以上である大粒径のリチウム二次電池用リチ ゥムニッケルコバルトマンガン複合酸ィヒ物粉末と、 該大粒径の平均粒径 D 50の 1/2〜1/5の平均粒径を有する小粒径のリチウム二次電池用リチウムニッケルコ バルトマンガン複合酸化物粉末とを、 8. 5 : 1. 5〜7 ： 3の重量比で混合さ れてなる請求項 5に記載のリチウム二次電池用リチウムニッケルコバルトマンガ ン複合酸化物粉末。 6. A lithium nickel cobalt manganese composite acid powder for a lithium secondary battery having a large particle size having a compressive fracture strength of 5 OMPa or more, and 1/2 of the average particle size D50 of the large particle size A lithium nickel cobalt manganese composite oxide powder having an average particle diameter of about 1/5 and having a small particle diameter for lithium secondary batteries is mixed in a weight ratio of 8.5: 1.5 to 7: 3. The lithium nickel cobalt manganese composite oxide powder for a lithium secondary battery according to claim 5. 7. リチウムニッケルコバルトマンガン複合酸化物の微粒子が多数凝集して形成さ れた平均粒子径 D 50力 S8〜15 IIIである請求項 5又は 6に記載のリチウムニ次 電池用リチウムニッケルコバルトマンガン複合酸化物粉末。  7. The lithium-nickel-cobalt-manganese composite oxide for lithium secondary batteries according to claim 5 or 6, wherein the average particle diameter formed by agglomeration of a large number of fine particles of the lithium-nickel-cobalt-manganese composite oxide is D50 force S8 to 15III. Thing powder. 8 · 請求項 1〜 7のいずれかに記載のリチウムニッケルコバルトマンガン複合酸化 物を含むリチウムニ次電池用正極。  8 · A positive electrode for a lithium secondary battery, comprising the lithium nickel cobalt manganese composite oxide according to any one of claims 1 to 7. 9. 請求項 8に記載された正極を使用したリチウム二次電池。 9. A lithium secondary battery using the positive electrode according to claim 8.
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CN1701451A (en) 2005-11-23
JPWO2004082046A1 (en) 2006-06-15
KR20050044771A (en) 2005-05-12
KR100629129B1 (en) 2006-09-27
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