WO2017150522A1 - Matière active d'électrode positive pour batterie secondaire au lithium - Google Patents

Matière active d'électrode positive pour batterie secondaire au lithium Download PDF

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WO2017150522A1
WO2017150522A1 PCT/JP2017/007756 JP2017007756W WO2017150522A1 WO 2017150522 A1 WO2017150522 A1 WO 2017150522A1 JP 2017007756 W JP2017007756 W JP 2017007756W WO 2017150522 A1 WO2017150522 A1 WO 2017150522A1
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positive electrode
lithium
electrode active
active material
composite oxide
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PCT/JP2017/007756
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English (en)
Japanese (ja)
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徹也 光本
大輔 鷲田
松嶋　英明
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三井金属鉱業株式会社
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Priority to JP2018503326A priority Critical patent/JP6343411B2/ja
Publication of WO2017150522A1 publication Critical patent/WO2017150522A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a positive electrode active material for a lithium secondary battery that can be used as a positive electrode active material for a lithium secondary battery.
  • Lithium batteries especially lithium secondary batteries, have features such as high energy density and long life, so they can be used for home appliances such as video cameras, portable electronic devices such as notebook computers and mobile phones. Used as a power source. Recently, the lithium secondary battery is also applied to a large battery mounted on an electric vehicle (EV), a hybrid electric vehicle (HEV), or the like.
  • EV electric vehicle
  • HEV hybrid electric vehicle
  • a lithium secondary battery is a secondary battery with a structure in which lithium is melted as ions from the positive electrode during charging, moves to the negative electrode and is stored, and reversely, lithium ions return from the negative electrode to the positive electrode during discharging. It is known to be caused by the potential of the positive electrode material.
  • lithium manganese oxide (LiMn 2 O 4 ) having a spinel structure and lithium metal composite oxides such as LiCoO 2 , LiNiO 2 and LiMnO 2 having a layered crystal structure are known. It has been.
  • LiCoO 2 has a layered crystal structure in which lithium atom layers and cobalt atom layers are alternately stacked via oxygen atom layers, has a large charge / discharge capacity, and is excellent in diffusibility of lithium ion storage / desorption. Therefore, many of the commercially available lithium secondary batteries employ a lithium cobalt metal composite oxide having a layered crystal structure such as LiCoO 2 as a positive electrode active material.
  • a lithium metal composite oxide having a layered crystal structure such as LiCoO 2 or LiNiO 2 is represented by a general formula LiMO 2 (M: transition metal).
  • the crystal structure of these lithium metal composite oxides having a layered crystal structure belongs to the space group R-3m ("-" is usually attached to the upper part of "3" and indicates reversal. The same applies hereinafter).
  • the Li ion, Me ion, and oxide ion occupy the 3a site, 3b site, and 6c site, respectively. It is known that a layer composed of Li ions (Li layer) and a layer composed of Me ions (Me layer) exhibit a layered crystal structure in which they are alternately stacked via O layers composed of oxide ions.
  • lithium metal composite oxide having such a layered crystal structure When a lithium metal composite oxide having such a layered crystal structure is used as a positive electrode active material for a lithium secondary battery, the lithium metal composite oxide and the electrolyte solution chemically react, particularly when charged and discharged at high temperatures. However, since the reactants change on the surface of the positive electrode active material, the battery capacity and life characteristics are deteriorated.
  • Patent Document 1 Japanese Patent Laid-Open No. 2001-291518
  • the surface of a lithium metal composite oxide having a layered crystal structure is composed of Mg, Al, Co, K, Na, Ca, Si, Ti, and V.
  • a positive electrode active material for a lithium secondary battery comprising a metal oxide or composite metal oxide layer selected from the group is disclosed.
  • Patent Document 2 Japanese Patent Laid-Open No. 2005-310744
  • a lithium metal composite oxide particle powder having a layered crystal structure is dispersed in an isopropyl alcohol solution and stirred, followed by heat treatment at 600 ° C.
  • a positive electrode active material having a particle surface coated with aluminum is disclosed.
  • Patent Document 3 Japanese Patent Laid-Open No. 2005-322616
  • a lithium metal composite oxide having a layered crystal structure and powdered metal aluminum are added to water to form a slurry, and further stirred to dissolve the metal aluminum.
  • a lithium-containing composite oxide in which the surface of the composite oxide obtained by drying at 80 ° C. is covered with a layer containing aluminum hydroxide, aluminum oxide and lithium carbonate is disclosed.
  • Patent Document 4 Japanese Patent Application Laid-Open No. 2005-346955 is obtained by adding aluminum stearate to a lithium metal composite oxide having a layered crystal structure, mixing and crushing with a ball mill, and heat-treating at 600 ° C. A lithium-containing composite oxide in which an aluminum compound is modified on the particle surface is disclosed.
  • Patent Document 5 discloses a positive electrode active in which lithium metal composite oxide particles having a layered crystal structure are subjected to surface modification in which a specific surface region contains a relatively high specific concentration of aluminum. Lithium metal composite oxide particles having a layered crystal structure as a substance, the surface layer containing aluminum, and the aluminum content within 5 nm of the surface layer is atomic ratio relative to the total of Ni and element M A positive electrode active material for a non-aqueous electrolyte secondary battery, characterized by comprising surface-modified lithium-containing composite oxide particles of 0.8 or more is disclosed.
  • Patent Document 6 Japanese Patent Application Laid-Open No. 2008-153017 discloses a layered crystal from the viewpoint of using as a positive electrode active material coated with a lithium composite oxide surface having a specific composition and a specific particle size and particle size distribution.
  • a lithium metal composite oxide having a structure having an average particle size D50 of 3 to 15 ⁇ m, a minimum particle size of 0.5 ⁇ m or more, a maximum particle size of 50 ⁇ m or less, and D10 / D50 of 0
  • a substance (A is Ti, Sn, Mg, A) on the surface of the lithium composite oxide for a non-aqueous electrolyte secondary battery composed of particles having a particle diameter of .60 to 0.90 and D10 / D90 of 0.30 to 0.70.
  • a positive electrode active material for a non-aqueous electrolyte secondary battery characterized by having a structure coated with a compound comprising at least one element selected from the group consisting of Zr, Al, Nb and Zn) That.
  • Patent Document 7 Japanese Patent Laid-Open No. 4-329267
  • a LiCoO 2 metal oxide is immersed in a 20% NaOH aqueous solution at a temperature of about 80 ° C. to perform an alkali treatment, whereby the surface of the metal oxide is treated.
  • a LiCoO 2 metal oxide that has been subjected to a coupling treatment using a titanate coupling agent with an increased OH group concentration is disclosed.
  • the present invention relates to a positive electrode active material containing a lithium metal composite oxide having a layered crystal structure, and when used as a positive electrode active material of a lithium secondary battery, suppresses the reaction with the electrolytic solution and improves the battery life characteristics.
  • a new positive electrode active material for a lithium secondary battery that can be improved and has a rate characteristic equivalent to or higher than that of a positive electrode active material that has been surface-treated as previously proposed. To do.
  • the present invention has the general formula Li 1 ⁇ x Co y M 1-xy O 2 (where 0.95 ⁇ 1 ⁇ x ⁇ 1.05, y ⁇ 0.8, 1-xy> 0, M is Mn, Ni, Na, Mg, Al, Si, P, K, Ca, Ti, V, Cr, Fe, Cu, Zn, Ga, Y, Zr, Nb, Mo, In, Ta, W, Re And a surface of a particle comprising a lithium cobalt metal composite oxide having a layered crystal structure represented by any one or a combination of two or more of the group consisting of Ce and Ce (referred to as “constituent element M”)
  • surface element A For a lithium secondary battery including particles having a surface portion in which any one or a combination of two or more of the group consisting of Al, Ti and Zr (referred to as “surface element A”) is present
  • a positive electrode active material The atomic ratio of Co and the atomic ratio of M (constituent element M is 2) measured by X-ray
  • the ratio (A / (Co + M)) of the atomic ratio of the surface element A (the total of the atomic ratio when the surface element A is two or more) to the total of the total of the atomic ratio in the case of more than one type is 0.07 Greater than 0.8 and The amount of surface lithium impurities is less than 0.15 wt%, and
  • XRD powder X-ray diffractometer
  • XRD X-Ray Diffractometer
  • the positive electrode active material proposed by the present invention when used as a positive electrode active material of a lithium secondary battery, it is possible to suppress the reaction with the electrolytic solution and improve the life characteristics in high temperature use under a high temperature environment. At the same time, the rate characteristics can be made equal to or higher than those of the conventional positive electrode active material subjected to the surface treatment. Therefore, the positive electrode active material proposed by the present invention is a battery for consumer use such as a mobile phone, a battery for vehicle use, particularly a battery mounted on an electric vehicle (EV) or a hybrid electric vehicle (HEV). It is particularly excellent as a positive electrode active material.
  • EV electric vehicle
  • HEV hybrid electric vehicle
  • the positive electrode active material for a lithium secondary battery has a general formula (1): Li 1 ⁇ x Co y M 1-xy O 2 (where 0.95 ⁇ 1 ⁇ x ⁇ 1.05, y ⁇ 0.8, 1-xy> 0, M is Mn, Ni, Na, Mg, Al, Si, P, K, Ca, Ti, V, Cr, Fe, Cu, Zn, Ga, Y, Zr, Nb, Mo, In, Ta, W, Re and Ce, any one kind or a combination of two or more kinds (this is referred to as “constituent element M”).
  • any one of the group consisting of Al, Ti and Zr on the surface of the particles composed of lithium cobalt metal composite oxide having a layered crystal structure referred to as “the present lithium cobalt metal composite oxide particles”
  • Grain having a surface portion on which one type or a combination of two or more types referred to as “surface element A”
  • surface element A the cathode active material for a lithium secondary battery containing
  • the present positive electrode active material may contain other components in addition to the present particles.
  • the present particles preferably occupy 80 wt% or more, particularly 90 wt% or more, and more preferably 95 wt% or more (including 100 wt%).
  • the present particle is a particle having a surface portion containing the surface element A on the surface of the present lithium cobalt metal composite oxide particle. As long as this particle
  • the lithium cobalt metal composite oxide particles have a general formula (1): Li 1 ⁇ x Co y M 1-xy O 2 (where 0.95 ⁇ 1 ⁇ x ⁇ 1.05, y ⁇ 0. 8, 1-xy> 0, M is Mn, Ni, Na, Mg, Al, Si, P, K, Ca, Ti, V, Cr, Fe, Cu, Zn, Ga, Y, Zr, Nb
  • a layered crystal structure represented by any one or a combination of two or more of the group consisting of Mo, In, Ta, W, Re, and Ce (referred to as “constituent element M”). It is a particle made of a lithium cobalt metal composite oxide.
  • Li 1 ⁇ x Co y M 1-xy O 2 “1 ⁇ x” is 0.95 to 1.05, particularly 0.97 or more or 1.03 or less, It is preferably 0.98 or more and 1.02 or less.
  • M in the above formula (1) is Mn, Ni, Na, Mg, Al, Si, P, K, Ca, Ti, V, Cr, Fe, Cu, Zn, Ga, Y, Zr, Nb, Any one or a combination of two or more selected from the group consisting of Mo, In, Ta, W, Re, and Ce may be used.
  • y ⁇ 0.8 may be satisfied, especially y ⁇ 0.9, particularly y ⁇ 0.95, and more preferably y ⁇ 0.97.
  • 1-xy is 0.25 or less, preferably less than 0.15, more preferably less than 0.10, and even more preferably less than 0.05.
  • the atomic ratio of the oxygen amount is described as “2” for convenience, but may have some non-stoichiometry.
  • the present lithium cobalt metal composite oxide particles may contain inevitable impurities.
  • each element of inevitable impurities may be contained if it is 0.17 wt% or less. This is because it is considered that the amount of this amount hardly affects the characteristics of the present lithium cobalt metal composite oxide particles.
  • any one or a combination of two or more of the group consisting of Al, Ti, and Zr exists on the surface of the lithium cobalt metal composite oxide particles. It is preferable to do this.
  • the surface portion described here is characterized in that a portion having a higher concentration of the surface element A than the inside of the particle is provided on the particle surface.
  • the thickness of the surface portion is preferably 1 nm to 300 nm from the viewpoints of suppressing the reaction with the electrolytic solution to improve the life characteristics and maintaining or improving the rate characteristics, and more preferably 4 nm or more or 220 nm or less. Among these, it is preferable that it is 8 nm or more or 150 nm or less.
  • the present lithium cobalt metal composite oxide is suitable for use as a positive electrode active material of a lithium secondary battery, and is used for consumer use batteries such as mobile phones and in-vehicle batteries, in particular, electric vehicles (EV: Electric Vehicle). ) And hybrid electric vehicles (HEV: Hybrid Electric Vehicle) are particularly excellent as positive electrode active materials for batteries.
  • EV Electric Vehicle
  • HEV Hybrid Electric Vehicle
  • Whether or not the surface portion where the surface element A exists is present on the surface of the lithium cobalt metal composite oxide particle is determined by whether or not the concentration of the surface element A is higher on the particle surface than inside the particle. can do. Specifically, for example, when the particle is observed with a scanning transmission electron microscope (STEM), the determination can be made based on whether or not the peak of the surface element A is observed on the surface of the particle.
  • STEM scanning transmission electron microscope
  • the ratio (A / (Co + M)) of the sum of atomic ratios is preferably larger than 0.07 and smaller than 0.8. If the surface element A is present to such an extent that the ratio (A / (Co + M)) is smaller than 0.8, it is possible to suppress the reaction with the electrolytic solution and improve the life characteristics. Further, the rate characteristics can be made equal to or higher than those of conventionally proposed positive electrode active materials subjected to surface treatment.
  • the ratio (A / (Co + M)) is preferably larger than 0.07 and smaller than 0.8, more preferably larger than 0.10 and smaller than or equal to 0.6, more preferably larger than 0.12 and larger than 0.4. Hereinafter, among them, it is more preferably greater than 0.15 and not greater than 0.3.
  • the surface treatment is performed.
  • the amount of the surface element A in the agent may be adjusted, and the subsequent heat treatment temperature may be adjusted. However, it is not limited to these methods.
  • the integration of the (003) plane-derived peak with respect to the integrated intensity of the (104) plane-derived peak is preferably greater than 1.15.
  • the ratio (003) / (104) is preferably greater than 1.15, more preferably greater than 1.20, and more preferably greater than 1.30. preferable.
  • the ratio (003) / (104) is greater than 3.00, the anisotropy of expansion / contraction due to the insertion / desorption of lithium increases, so that the cycle characteristics deteriorate.
  • the ratio (003) / (104) is less than 3.00, particularly 2.50 or less, more preferably less than 2.00. Preferably it is less than 1.70.
  • the firing conditions are adjusted or the amount of the solvent or water in the surface treatment is adjusted. Just do it. However, it is not limited to such a method.
  • the positive electrode active material preferably has a surface lithium impurity amount of 0.15 wt% or less. If the amount of surface lithium impurities is 0.15 wt% or less, it is preferable because the unreacted residual lithium reacts with the electrolytic solution to suppress a reaction that causes deterioration of life characteristics. From this point of view, the surface lithium impurity amount of the present positive electrode active material is preferably 0.15 wt% or less, more preferably greater than 0 wt% or even more preferably 0.10 wt% or less. Here, it is considered that the above surface lithium impurities are derived from Li that remains without reacting when fired.
  • the raw material mixing conditions and the firing conditions are adjusted and reacted sufficiently, and the unreacted components are further reacted by adjusting the surface treatment conditions and the heat treatment conditions. You may adjust to.
  • the present invention is not limited to this.
  • the positive electrode active material preferably has a specific surface area (SSA) of 0.1 to 2 m 2 / g. If the specific surface area (SSA) of the present positive electrode active material is 0.1 to 2 m 2 / g, a sufficient reaction field for Li insertion / desorption can be secured, and the rate characteristics can be maintained. preferable. From this viewpoint, the specific surface area (SSA) of the present positive electrode active material is preferably 0.1 to 2 m 2 / g, more preferably 1.5 m 2 / g or less, particularly 1.3 m 2 / g or less. Of these, 1.0 m 2 / g or less is more preferable. In order to set the specific surface area of the present lithium cobalt metal composite oxide powder within the above range, it is preferable to adjust the firing conditions and the crushing conditions. However, it is not limited to these adjustment methods.
  • the LiOH amount measured by the following measurement method is preferably less than 0.07 wt%, and more preferably less than 0.05 wt%, from the viewpoint of improving the rate characteristics.
  • the surface LiOH amount less than 0.07 wt%
  • the amount of Li 2 CO 3 measured by the following measurement method is less than 0.15 wt%, particularly less than 0.13 wt%, and particularly less than 0.10 wt% from the viewpoint of improving the rate characteristics. Is preferred.
  • this positive electrode active material in order to make the amount of Li 2 CO 3 less than 0.15 wt%, it is preferable to react the unreacted components sufficiently by adjusting the surface treatment conditions and heat treatment conditions. However, it is not limited to these adjustment methods.
  • the positive electrode active material preferably has a tap density of 2.0 g / cm 3 or more, particularly 2.1 g / cm 3 or more or 3.2 g / cm 3 or less, and more preferably 2.2 g / cm 3 or more. It is particularly preferably 1 g / cm 3 or less, more preferably 2.2 g / cm 3 or more, or 3.0 g / cm 3 or less.
  • the tap density of the present positive electrode active material is 2.0 g / cm 3 or more, the electrode density can be increased, and thus the volume energy density can be increased.
  • the material is baked at a high temperature of 700 ° C. or higher, or a substance that increases the reactivity at the time of baking, such as a boron compound or a fluorine compound
  • the positive electrode active material is preferably produced by firing and using dense raw materials. However, it is not limited to these adjustment methods.
  • the positive electrode active material can be produced, for example, by mixing a conductive material made of carbon black or the like and a binder made of Teflon (registered trademark) binder or the like. At this time, the present positive electrode active material and another positive electrode active material may be used in combination as necessary.
  • a positive electrode mixture is used for the positive electrode, for example, a material that can occlude / desorb lithium such as lithium or carbon is used for the negative electrode, and lithium hexafluorophosphate (LiPF 6 ) or the like is used for the non-aqueous electrolyte.
  • a lithium secondary battery can be constructed using a lithium salt dissolved in a mixed solvent such as ethylene carbonate-dimethyl carbonate.
  • the present invention is not limited to the battery having such a configuration.
  • Lithium batteries equipped with this positive electrode active material as at least one of the positive electrode active materials exhibit excellent life characteristics (cycle characteristics) when repeatedly used for charge and discharge. It is particularly excellent in the use of a positive electrode active material of a lithium battery used as a power source for driving a motor mounted on an electric vehicle (EV: Electric Vehicle) or a hybrid electric vehicle (HEV: Hybrid Electric Vehicle).
  • EV Electric Vehicle
  • HEV Hybrid Electric Vehicle
  • a “hybrid vehicle” is a vehicle that uses two power sources, an electric motor and an internal combustion engine.
  • the term “lithium battery” is intended to encompass all batteries containing lithium or lithium ions in the battery, such as lithium primary batteries, lithium secondary batteries, lithium ion secondary batteries, and lithium polymer batteries.
  • a particle powder of the above lithium cobalt metal composite oxide having a layered crystal structure using a surface treatment agent containing at least one of aluminum, titanium, and zirconium (“ After the surface treatment (referred to as “the surface treatment step”) of the present lithium cobalt metal composite oxide particle powder ”, the lithium cobalt metal composite oxide particle powder after the surface treatment is subjected to a heat treatment (“ heat treatment step ”).
  • heat treatment step a heat treatment agent containing at least one of aluminum, titanium, and zirconium
  • a crushing step may be inserted after the heat treatment step, or a crushing step or a classification step may be inserted before the surface treatment step. Moreover, you may add another process. Moreover, it is not the intention which limits the manufacturing method of this positive electrode active material to this method.
  • the present lithium cobalt metal composite oxide particle powder can be obtained by mixing raw materials, granulating and drying as necessary, firing, heat treatment as necessary, and further pulverizing as necessary.
  • the lithium cobalt metal composite oxide powder obtained by purchasing or the like can be used as the present lithium cobalt metal composite oxide particle powder after being subjected to a predetermined treatment.
  • lithium compound used as a raw material of the present lithium cobalt metal composite oxide particle powder examples include lithium hydroxide (including LiOH and LiOH.H 2 O), lithium carbonate (Li 2 CO 3 ), lithium nitrate (LiNO 3 ), Examples thereof include lithium oxide (Li 2 O), other fatty acid lithium, lithium halide, and the like.
  • the type of cobalt compound used as a raw material for the lithium cobalt metal composite oxide particle powder is not particularly limited, and for example, basic cobalt carbonate, cobalt nitrate, cobalt chloride, cobalt oxyhydroxide, cobalt hydroxide, cobalt oxide, etc. should be used. Among these, basic cobalt carbonate, cobalt hydroxide, cobalt oxide, and cobalt oxyhydroxide are preferable.
  • hydroxide salts, carbonates, nitrates, etc. of the M element in the above formula (1) can be used as raw materials for the present lithium cobalt metal composite oxide particle powder.
  • a raw material mixing method dry mixing or wet mixing can be performed.
  • dry mixing it can be mixed using a ball mill or a precision mixer.
  • wet mixing it is preferable to add a liquid medium such as water or a dispersant to make a slurry.
  • dry pulverization may be performed.
  • the maximum particle size (Dmax) of the raw material is 20 ⁇ m or less, in particular, 10 ⁇ m or less before mixing the raw materials in order to improve the homogeneity at the time of mixing the raw materials except for the raw material coarse powder. In particular, it is preferable to adjust so as to be 5 ⁇ m or less.
  • the granulation method may be either wet or dry as long as various raw materials are dispersed in the granulated particles without being separated. Extrusion granulation method, rolling granulation method, fluidized granulation method, mixed granulation method, spraying method A dry granulation method, a pressure molding granulation method, or a flake granulation method using a roll or the like may be used. At this time, when wet granulation is performed, it is necessary to sufficiently dry before firing.
  • a drying method at this time it may be dried by a known drying method such as a spray heat drying method, a hot air drying method, a vacuum drying method, a freeze drying method, etc., among which the spray heat drying method is preferable.
  • the spray heat drying method is preferably carried out using a heat spray dryer (spray dryer) (referred to herein as “spray drying method”).
  • a coprecipitated powder to be fired by, for example, a so-called coprecipitation method (referred to herein as “coprecipitation method”).
  • coprecipitation method after the raw material is dissolved in a solution, the coprecipitation powder can be obtained by adjusting the conditions such as pH and causing precipitation.
  • the powder strength is relatively low, and voids tend to occur between the particles. Therefore, when the spray drying method is adopted, the crushing strength after the crushing step after the firing step, which will be described later, is higher than that of a conventional crushing method, for example, a crushing method using a coarse crusher having a rotation speed of about 1000 rpm. It is preferable to employ a high grinding method.
  • the firing step for obtaining the present lithium cobalt metal composite oxide particle powder it is preferable to calcine at 500 to 870 ° C. as necessary, followed by firing at 700 to 1000 ° C. It is also possible to perform the main baking at 700 to 1000 ° C. without performing the preliminary baking. By calcining, a gas (for example, CO 2 ) generated from a component contained in the raw material can be extracted. And in this baking, the crystallinity of particle
  • a gas for example, CO 2
  • the pre-baking is performed at a temperature of 500 to 870 ° C. in a baking furnace in an air atmosphere, an oxygen gas atmosphere, an atmosphere in which an oxygen partial pressure is adjusted, a carbon dioxide gas-containing atmosphere, or other atmosphere ( : Means the temperature when a thermocouple is brought into contact with the fired product in the firing furnace.)
  • Baking is preferably performed so as to hold.
  • the kind of baking furnace is not specifically limited. For example, it can be fired using a rotary kiln, a stationary furnace, or other firing furnace.
  • the main baking is performed at a temperature of 700 to 1000 ° C. in a baking furnace in an air atmosphere, an oxygen gas atmosphere, an atmosphere in which an oxygen partial pressure is adjusted, a carbon dioxide gas-containing atmosphere, or other atmosphere (: It means the temperature when a thermocouple is brought into contact with the fired product in the firing furnace.), Preferably 750 ° C. or higher or 950 ° C. or lower, more preferably 800 ° C. or higher or 950 ° C. or lower, and even more preferably 830 ° C.
  • the baking is preferably performed at 910 ° C. or lower for 0.5 to 30 hours.
  • a firing condition in which a fired product including a plurality of metal elements can be regarded as a single phase of a lithium cobalt metal composite oxide having a target composition is preferable to select a firing condition in which a fired product including a plurality of metal elements can be regarded as a single phase of a lithium cobalt metal composite oxide having a target composition.
  • the kind of baking furnace is not specifically limited. For example, it can be fired using a rotary kiln, a stationary furnace, or other firing furnace.
  • the temperature is 700 to 1000 ° C., particularly 750 ° C. or higher or 950 ° C. or lower, particularly 800 ° C. or higher or 950 ° C. or lower, and more preferably 830 ° C. or higher or 910 ° C. or lower.
  • the main calcination is preferably performed so as to hold for 5 to 30 hours.
  • the heat treatment after firing for obtaining the present lithium cobalt metal composite oxide particle powder is preferably performed when the crystal structure needs to be adjusted.
  • As the heat treatment atmosphere at that time it is preferable to perform the heat treatment under the conditions of an oxidizing atmosphere such as an air atmosphere, an oxygen gas atmosphere, or an atmosphere with an adjusted oxygen partial pressure.
  • the pulverization after the firing or the heat treatment is preferably performed using a high-speed rotary pulverizer or the like. If pulverization is performed by a high-speed rotary pulverizer, it is possible to pulverize a portion where the particles are aggregated or weakly sintered, and to suppress distortion of the particles. However, the present invention is not limited to a high-speed rotary pulverizer.
  • the pin mill is known as a rotary disk crusher, and is a type of crusher that draws in powder from a raw material supply port by rotating a rotating disk with pins to make the inside negative pressure. Therefore, since the fine particles have a light mass, they easily get on the air current and pass through the clearance in the pin mill, while the coarse particles are reliably crushed. Therefore, when pulverizing with a pin mill, aggregation between particles and weakly sintered portions can be surely solved, and distortion can be suppressed from entering into the particles.
  • the rotational speed of the high-speed rotary pulverizer is preferably 4000 rpm or more, more preferably 5000 rpm or more or 12000 rpm or less, and particularly preferably 7000 rpm or more or 10000 rpm or less.
  • the classification after firing has the technical significance of adjusting the particle size distribution of the agglomerated powder and removing foreign matter, it is preferable to classify by selecting a sieve having a preferred size.
  • the lithium cobalt metal composite oxide particles thus produced preferably have a moisture content of 50 to 1000 ppm measured at 110 to 300 ° C. by the Karl Fischer method. If the moisture content is 50 ppm or more, the reaction with the coupling agent among the surface treatment agents can be enhanced, and the surface treatment effect can be enhanced. On the other hand, if the water content is 1000 ppm or less, it is preferable in that the battery characteristics can be made equal or more. From this point of view, the water content of the present lithium cobalt metal composite oxide particle powder is preferably 50 to 1000 ppm, more preferably 50 ppm or more and 700 ppm or less, especially 50 ppm or more and 500 ppm or less, and more preferably 400 ppm or less. Is more preferable.
  • the water content measured at 110 to 300 ° C. by the Karl Fischer method is measured in a device at 110 ° C. in a nitrogen atmosphere using a Karl Fischer moisture meter (for example, CA-100 manufactured by Mitsubishi Chemical Corporation). This is the amount of water released when a sample is heated for 45 minutes, then heated to 300 ° C. and heated at 300 ° C. for 45 minutes.
  • the water measured at 110 to 300 ° C. by the Karl Fischer method is considered to be mainly water chemically bonded to the lithium cobalt metal composite oxide particle powder.
  • the present lithium cobalt metal composite oxide particle powder produced as described above is mainly dried or dehumidified. And a method for controlling the humidity in storage. However, it is not limited to such a method.
  • a surface treatment agent containing at least one of aluminum, titanium and zirconium is obtained as described above.
  • the lithium cobalt metal composite oxide powder may be contacted.
  • an organometallic compound containing at least one of aluminum, titanium, and zirconium such as a titanium coupling agent, an aluminum coupling agent, a zirconium coupling agent, a titanium-aluminum coupling agent, a titanium-zirconium coupling agent, or an aluminum.
  • a surface treatment agent such as zirconium coupling agent or titanium / aluminum / zirconium coupling agent is dispersed in an organic solvent to form a dispersion, and the dispersion and the lithium cobalt metal composite oxide obtained as described above.
  • a method of performing surface treatment by bringing particle powder into contact with each other can be mentioned.
  • Examples of the surface treatment agent include compounds having an organic functional group and a hydrolyzable group in the molecule. Among these, those having phosphorus (P) in the side chain are preferable.
  • the coupling agent having phosphorus (P) in the side chain is particularly excellent in binding property with the binder because of better compatibility with the binder.
  • a surface treatment agent equivalent to 0.1 to 20 wt% is brought into contact with 100 wt% of the lithium cobalt metal composite oxide powder, particularly 0.5 wt% or more or 10 wt% or less, of which 1 wt%. % Or more, or 5 wt% or less, more preferably 1 wt% or more or 3 wt% or less of the surface treatment agent is more preferably brought into contact with the lithium cobalt metal composite oxide powder.
  • the ratio of the total number of moles of aluminum, titanium and zirconium in the surface treatment agent to the number of moles of the present lithium cobalt metal composite oxide powder ⁇ (M / lithium cobalt metal composite oxide powder) ⁇ 100 (M: Al, Ti, Zr) ⁇ is 0.005 to 4%, especially 0.04% or more or 2% or less, and more preferably 0.08% or more or 1% or less.
  • the lithium cobalt metal composite oxide powder and the surface treatment agent are brought into contact with each other so that the content is 0.08% or more or 0.6% or less.
  • the amount of the dispersion in which the surface treatment agent is dispersed in an organic solvent or water is 0.2 to 20 wt%, particularly 1 wt% or more or 15 wt% or less with respect to 100 wt% of the present lithium cobalt metal composite oxide powder. It is preferable that the amount is adjusted to 2 wt% or more or 10 wt% or less, more preferably 2 wt% or more or 7 wt% or less, and this amount of dispersion is brought into contact with the lithium cobalt metal composite oxide powder.
  • the amount of the organic solvent or water to be brought into contact is large, lithium in the layered crystal structure will be eluted.
  • the amount of dispersion dispersed in a solvent or water is preferably limited as described above.
  • the surface treatment agent is mixed with the atmosphere or oxygen by bringing a small amount of the surface treatment agent or a dispersion in which the surface treatment agent is dispersed in an organic solvent or water into contact with the lithium cobalt metal composite oxide powder. Can be brought into contact with the lithium cobalt metal composite oxide powder.
  • the dispersion in which the above amount of the surface treatment agent or the surface treatment agent is dispersed in an organic solvent is not brought into contact with the lithium cobalt metal composite oxide powder at one time and mixed, but divided into several times. It is preferable to repeat the process of contacting and mixing.
  • inorganic compound powder it is based on the total of the atomic ratio of Co, which is a constituent element, and the atomic ratio of M (total of atomic ratios when there are two or more constituent elements M) measured by XPS. Control the ratio (A / (Co + M)) of the atomic ratio of the surface element A (the total of the atomic ratios when there are two or more surface elements A), the thickness of the surface portion, etc. It is preferable to adjust the conditions.
  • the surface-treated lithium cobalt metal composite oxide powder is higher than 700 ° C. and lower than 900 ° C. (in a fired product in the furnace) in an atmosphere having an oxygen concentration of 20 to 100%. It is preferable to perform heat treatment so that the temperature when the thermocouple is brought into contact, that is, the product temperature, is maintained for a predetermined time. When the temperature is 900 ° C. or higher, the surface treatment element diffuses into the crystal structure, and the ratio (A / (Co + M)) of the atomic ratio of the surface element A (the total of the atomic ratios when the surface element A is two or more types). Is unfavorable because it becomes smaller.
  • the organic solvent or water can be volatilized or the side chain of the surface treatment agent can be decomposed, and aluminum, titanium, or zirconium in the surface treatment agent can be diffused deeper from the surface. It is possible to suppress the reaction with the electrolytic solution and improve the life characteristics, and the rate characteristics can be equal to or higher than that of the conventional positive electrode active material subjected to the surface treatment. . Furthermore, it is preferable to set the heat treatment temperature to be equal to or lower than the main firing temperature, since the crushing load after the heat treatment can be reduced.
  • the treatment atmosphere in the heat treatment step is preferably an oxygen-containing atmosphere.
  • an oxygen-containing atmosphere having an oxygen concentration of 20 to 100% is preferable, and 30% or more or 100% or less, especially 50% or more or 100% or less, more preferably 60% or more or 100% or less, Of these, an oxygen-containing atmosphere of 80% or more or 100% or less is more preferable.
  • the treatment temperature in the heat treatment step is preferably higher than 700 ° C. and lower than 900 ° C. (meaning the temperature when a thermocouple is brought into contact with the fired product in the firing furnace). Or 880 ° C. or lower, more preferably 850 ° C. or lower, more preferably 720 ° C. or higher, or lower than 800 ° C.
  • the treatment time in the heat treatment step is preferably 0.5 to 20 hours, depending on the treatment temperature, and is preferably 1 hour or more or 10 hours or less, more preferably 3 hours or more or 10 hours or less. Is more preferable.
  • the type of furnace is not particularly limited. For example, it can be fired using a rotary kiln, a stationary furnace, or other firing furnace.
  • the lithium cobalt metal composite oxide powder may be crushed. At this time, it is preferable to crush the lithium cobalt metal composite oxide powder at a crushing strength at which the change rate of the specific surface area (SSA) before and after crushing is 100 to 250%. Crushing after heat treatment is preferably performed so that the new surface under the surface treatment layer is not exposed so as to maintain the effect of the surface treatment, so that the change rate of the specific surface area (SSA) before and after crushing is It is preferably 100 to 200%, more preferably 175% or less, more preferably 150% or less, and even more preferably 125% or less.
  • a crushing device for example, a pin mill
  • a pin mill that crushes with a pin attached to a crushing plate that rotates at high speed in a relative direction
  • classification may be performed as necessary.
  • the classification at this time has the technical significance of adjusting the particle size distribution of the agglomerated powder and removing foreign matter, and therefore, it is preferable to classify by selecting a sieve having a preferred size.
  • a mixed raw material was obtained.
  • the obtained mixed raw material was baked at 850 ° C. for 22 hours in an air atmosphere using a stationary electric furnace.
  • the fired lump obtained by firing was put in a mortar and crushed with a pestle and classified with a sieve having an opening of 53 ⁇ m, and the lithium cobalt metal composite oxide powder under the sieve was recovered.
  • the obtained lithium cobalt metal composite oxide powder had a water content of 241 ppm measured at 110 to 300 ° C. by the Karl Fischer method.
  • Li 7.0%, Co: 60.9%, and Mg: 0.1%.
  • a titanium coupling agent (Ajinomoto Fine Techno Co., Ltd. Preneact (registered trademark) KR-46B) (3.0 wt%) as a surface treatment agent and isopropyl alcohol (7.6 wt%) as a solvent are mixed and mixed in a solvent.
  • a dispersion in which an aluminum coupling agent was dispersed was prepared. Thereafter, 10.6 wt% of the dispersion was added to 100 wt% of the lithium cobalt metal composite oxide powder obtained by firing, and mixed using a cutter mill (Milcer 720G manufactured by Iwatani Corporation). Next, it vacuum-dried at 100 degreeC for 1 hour.
  • lithium carbonate was added so that it might become 3.9 wt% with respect to an aluminum coupling agent, and it mixed using the cutter mill.
  • heat treatment was performed in an atmosphere having an oxygen concentration of 98% so as to maintain the product temperature at 730 ° C. for 5 hours to obtain a lithium cobalt metal composite oxide powder.
  • the lithium cobalt metal composite oxide obtained by the heat treatment was classified with a sieve having an opening of 53 ⁇ m to obtain a lithium cobalt metal composite oxide powder (sample) under the sieve.
  • Example 2 Zirconium coupling agent (KENRICH PETROCHMICALS, INC. Ken-React (registered trademark) NZ12) was used as the surface treatment agent, and the amount of lithium carbonate added after vacuum drying was 3.0% with respect to the zirconium coupling agent.
  • a lithium cobalt metal composite oxide powder (sample) was obtained in the same manner as in Example 1 except that the content was changed to%.
  • Example 3 A lithium cobalt metal composite oxide powder (sample) was obtained in the same manner as in Example 2 except that the surface treatment and vacuum drying were followed by heat treatment without adding lithium carbonate and the heat treatment temperature was changed to 770 ° C. It was.
  • the weighed raw material was put into a PP container, Zr balls were added and ball mill mixing was performed to obtain a mixed raw material.
  • the obtained mixed raw material was baked at 850 ° C. for 22 hours in an air atmosphere using a stationary electric furnace.
  • the fired lump obtained by firing was put in a mortar and crushed with a pestle and classified with a sieve having an opening of 53 ⁇ m, and the lithium cobalt metal composite oxide powder under the sieve was recovered.
  • they were Li: 7.0 and Co: 59.4%.
  • the weighed raw material was put into a PP container, Zr balls were added and ball mill mixing was performed to obtain a mixed raw material.
  • the obtained mixed raw material was baked for 22 hours at 1000 ° C. in an air atmosphere using a stationary electric furnace.
  • the fired lump obtained by firing was put in a mortar and crushed with a pestle and classified with a sieve having an opening of 53 ⁇ m, and the lithium cobalt metal composite oxide powder under the sieve was recovered.
  • they were Li: 7.1 and Co: 59.5%.
  • Titanium coupling agent (Ajinomoto Fine Techno Co., Ltd. Preneact (registered trademark) KR-44) 0.1 wt% as a surface treatment agent and isopropyl alcohol as a solvent with respect to the lithium cobalt metal oxide powder produced in Comparative Example 3 0.25 wt% was mixed to prepare a dispersion in which an aluminum coupling agent was dispersed in a solvent. Thereafter, 0.35 wt% of the dispersion was added to 100 wt% of the lithium cobalt metal composite oxide powder obtained by firing, and mixed using a cutter mill (Milcer 720G manufactured by Iwatani Corporation).
  • lithium cobalt metal complex oxide powder obtained by the heat treatment was classified with a sieve having an opening of 53 ⁇ m to obtain a lithium cobalt metal composite oxide powder (sample) under the sieve.
  • XPS Quantam 2000 manufactured by ULVAC-PHI.
  • the equipment specifications and conditions used for the measurement are as follows.
  • X-ray source AlK ⁇ 1 (1486.8 eV)
  • Tube voltage 15 kV
  • Tube current 3mA
  • X-ray irradiation area 200 ⁇ m ⁇
  • Measurement conditions Narrow measurement for state / semi-quantitative path energy: 23.5 eV
  • Measurement interval 0.1 eV Sputtering rate: 1-10nm / min (SiO2 conversion)
  • the XPS data was analyzed using data analysis software ("Multipack Ver6.1A" manufactured by ULVAC-PHI). The trajectory used for the calculation was determined for each element, and the analysis was performed considering the sensitivity coefficient.
  • the ratio of the atomic ratio of the surface element A to the total of the atomic ratio of Co, which is a constituent element, and the atomic ratio of M (A / (Co + M)) was confirmed to be larger than 0.07 and smaller than 0.8.
  • the surface lithium impurity amount was obtained by adding the amount of lithium hydroxide and the amount of lithium carbonate calculated from the above titration.
  • the water-soluble solvent used in the measurement was passed through a 60 ⁇ m filter, the solvent refractive index was 1.33, the particle permeability was transmissive, the particle refractive index was 2.46, the shape was non-spherical, and the measurement range was 0.133. ⁇ 704.0 ⁇ m, the measurement time was 30 seconds, and the average value measured twice was D50.
  • the specific surface areas of the lithium cobalt metal composite oxide powders (samples) obtained in the examples and comparative examples were measured as follows. First, 2.0 g of a sample (powder) was weighed into a glass cell (standard cell) for a fully automatic specific surface area measuring device Macsorb (manufactured by Mountec Co., Ltd.), and set in an autosampler. After replacing the inside of the glass cell with nitrogen gas, heat treatment was performed at 250 ° C. for 15 minutes in the nitrogen gas atmosphere. Thereafter, cooling was performed for 4 minutes while flowing a mixed gas of nitrogen and helium. After cooling, the sample (powder) was measured by the BET single point method. Note that a mixed gas of 30% nitrogen and 70% helium was used as the adsorption gas during cooling and measurement.
  • X-ray diffraction measurement was performed on the lithium cobalt metal composite oxides obtained in Examples and Comparative Examples, and peak search was performed on the obtained X-ray diffraction patterns using the integrated powder X-ray analysis software PDXL2 manufactured by Rigaku Corporation. .
  • Data processing is performed automatically for background removal and K ⁇ 2 removal, and the ratio of the integrated intensity of the peak derived from the (003) plane to the integrated intensity of the peak derived from the (104) plane belonging to the crystal structure of the space group R-3m (003) / (104) was calculated.
  • XRD measurement conditions Radiation source: CuK ⁇ (line focal point), wavelength: 1.541836 ⁇ Operation axis: 2 ⁇ / ⁇ , Measurement method: Continuous, Count unit: cps Start angle: 15.0 °, end angle: 120.0 °, integration count: 1 sampling width: 0.01 °, scan speed: 1.0 ° / min Voltage: 40 kV, current: 40 mA Divergence slit: 0.2 mm, Divergence length restriction slit: 2 mm Scattering slit: 2 °, light receiving slit: 0.15 mm Offset angle: 0 ° Goniometer radius: 285 mm, optical system: concentrated method attachment: ASC-48 Slit: D / teX Ultra slit detector: D / teX
  • PVDF was dissolved in NMP in advance, and the positive electrode active material and acetylene black were added and kneaded to prepare a positive electrode mixture slurry (solid content concentration 50 mass%).
  • the coating machine After coating this positive electrode mixture slurry on an aluminum foil as a current collector at a conveying speed of 20 cm / min using a coating machine, the coating machine is used to hold 70 ° C. for 2 minutes. After heating as described above, drying was performed so as to hold 120 ° C. for 2 minutes to form a positive electrode mixture layer to obtain an aluminum foil with a positive electrode mixture layer.
  • the aluminum foil with the positive electrode mixture layer was punched out to 13 mm ⁇ after punching the electrode into a size of 50 mm ⁇ 100 mm and using a roll press machine to press and dense with a press linear pressure of 3 t / cm.
  • the mixture was heated from room temperature to 200 ° C. and dried by heating so as to be held at 200 ° C. for 6 hours to obtain a positive electrode.
  • the negative electrode was made of metallic Li of ⁇ 14 mm ⁇ thickness 0.6 mm, and a separator in which an electrolytic solution in which LiPF 6 was dissolved to 1 mol / L was placed in a carbonate-based mixed solvent was placed to prepare a 2032 type coin battery. .
  • Rate characteristics evaluation test As described above, a rate characteristic evaluation test was performed using a coin battery after evaluating the discharge capacity. After constant current and constant potential charging to 4.3 V at 25 ° C. and 0.1 C, constant current discharging was performed to 3.0 V at 5 C. In the above evaluation, a discharge capacity of 5C up to 4.3-3.0V was obtained. The 5 C discharge capacity / 0.1 C discharge capacity ⁇ 100 was calculated as an index of rate characteristics. The larger the value, the better the rate characteristics.
  • PVDF was dissolved in NMP in advance, and the positive electrode active material and acetylene black were added and kneaded to prepare a positive electrode mixture slurry (solid content concentration 50 mass%).
  • the coating machine After coating this positive electrode mixture slurry on an aluminum foil as a current collector at a conveying speed of 20 cm / min using a coating machine, the coating machine is used to hold 70 ° C. for 2 minutes. After heating as described above, drying was performed so as to hold 120 ° C. for 2 minutes to form a positive electrode mixture layer to obtain an aluminum foil with a positive electrode mixture layer.
  • the aluminum foil with the positive electrode mixture layer was punched into a size of 50 mm ⁇ 100 mm, press-thickened at a press linear pressure of 3 t / cm using a roll press machine, and then punched out to 16 mm ⁇ .
  • the substrate was heated from room temperature to 200 ° C. and dried by heating so as to be held at 200 ° C. for 6 hours.
  • metal Li of ⁇ 19 mm ⁇ thickness 0.6 mm was used.
  • the separator 4 a separator made of a microporous polypropylene resin in which an electrolytic solution in which LiPF 6 was dissolved at 1 mol / L in a carbonate-based mixed solvent was impregnated was used.
  • the positive electrode 3 which consists of the said positive electrode compound material was arrange
  • a separator 4 was disposed on the upper surface of the positive electrode 3, and the separator was fixed by a spacer 5. Further, on the upper surface of the separator, a negative electrode 6 in which metal Li is fixed to the lower surface side is arranged, a spacer 7 that also serves as a negative electrode terminal is arranged, and the upper body 2 is put on the top and tightened with a screw to seal the battery.
  • an electrochemical evaluation cell TOMCEL registered trademark
  • the percentage (%) of the numerical value obtained by dividing the discharge capacity at the 61st cycle by the discharge capacity at the 2nd cycle was determined as the high temperature cycle life characteristic value.
  • the life characteristic values (4.5 V capacity retention rate @ 45 ° C.) of each Example and Comparative Example are shown as relative values when the high temperature cycle life characteristic value of Comparative Example 4 is 100.
  • any one of the group consisting of Al, Ti and Zr is formed on the surface of the particles made of lithium cobalt metal composite oxide having a layered crystal structure.
  • the ratio of the integrated intensity of the peak derived from the (003) plane to the integrated intensity of the peak derived from the (104) plane (003 ) / (104) is larger than 1.15 and smaller than 3.00, it was found that rate characteristics can be improved.
  • the above examples are an example of a lithium cobalt metal complex oxide having a layered crystal structure having a specific composition, as a result of addition the inventors of the above embodiment has performed a number of tests, the general formula Li 1 ⁇ x Co y M 1-xy O 2 (where 0.95 ⁇ 1 ⁇ x ⁇ 1.05, y ⁇ 0.8, 1-xy> 0, M is Mn, Ni, Na , Mg, Al, Si, P, K, Ca, Ti, V, Cr, Fe, Cu, Zn, Ga, Y, Zr, Nb, Mo, In, Ta, W, Re, and Ce Particles made of a lithium cobalt metal composite oxide having a layered crystal structure represented by any one kind or a combination of two or more kinds (referred to as “constituent element M”) are used as a core material, Any one or a combination of two or more of the group consisting of Al, Ti and Zr (this In the positive electrode active material for a lithium secondary battery including particles having a surface portion
  • the above example uses Mg as the constituent element M. Considering the difference from Co and the ion radius.
  • Mn, Ni, Na, Al, Si, P, K, Ca, Ti, V, Cr, Fe, Cu, Zn, Ga, Y, Zr, Nb By designing the number of moles of constituent elements used, Mn, Ni, Na, Al, Si, P, K, Ca, Ti, V, Cr, Fe, Cu, Zn, Ga, Y, Zr, Nb, It is considered that the same effect as in the above embodiment can be obtained even when any one or a combination of two or more of the group consisting of Mo, In, Ta, W, Re, and Ce is used. it can.

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Abstract

L'invention concerne une matière active d'électrode positive pour une batterie secondaire au lithium, ladite matière comprenant des particules actives qui sont représentées par la formule générale Li1±xCoyM1-x-yO2 (dans la formule, 0,95 ≤ 1 ± x ≤ 1,05, y ≥ 0,8, 1 - x - y > 0, et M est n'importe quel élément ou une combinaison de deux éléments ou plus du groupe constitué par Mn, Ni, Na, Mg, Al, Si, P, K, Ca, Ti, V, Cr, Fe, Cu, Zn, Ga, Y, Zr, Nb, Mo, In, Ta, W, Re, et Ce), présentent une structure cristalline en couches, et sont dotées, sur leur surface, d'une partie de surface dans laquelle est présent n'importe quel élément ou une combinaison de deux éléments ou plus (appelés « élément de surface A ») du groupe constitué par Al, Ti et Zr, et étant caractérisée en ce que le rapport (A/(Co + M)) du rapport atomique de l'élément de surface A à la somme des rapports atomiques de Co et M tel que mesuré par XPS est de 0,07 à 0,8, la quantité d'impuretés de lithium de surface est inférieure à 0,15 % en poids, et le rapport d'intensité intégrée de pic (003)/(104) tel que mesuré par XRD est de 1,15 à 3,00.
PCT/JP2017/007756 2016-02-29 2017-02-28 Matière active d'électrode positive pour batterie secondaire au lithium WO2017150522A1 (fr)

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KR20220089243A (ko) * 2020-12-21 2022-06-28 주식회사 포스코 양극 활물질 및 이를 포함하는 리튬 이차 전지
KR20220089244A (ko) * 2020-12-21 2022-06-28 주식회사 포스코 양극 활물질 및 이를 포함하는 리튬 이차 전지
KR102580745B1 (ko) 2020-12-21 2023-09-19 포스코홀딩스 주식회사 양극 활물질 및 이를 포함하는 리튬 이차 전지
KR102580744B1 (ko) 2020-12-21 2023-09-19 포스코홀딩스 주식회사 양극 활물질 및 이를 포함하는 리튬 이차 전지
KR102580743B1 (ko) 2020-12-21 2023-09-19 포스코홀딩스 주식회사 양극 활물질 및 이를 포함하는 리튬 이차 전지
WO2024184744A1 (fr) * 2023-03-07 2024-09-12 株式会社半導体エネルギー研究所 Matériau actif d'électrode positive et batterie

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