WO2017150506A1 - 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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Publication number
WO2017150506A1
WO2017150506A1 PCT/JP2017/007701 JP2017007701W WO2017150506A1 WO 2017150506 A1 WO2017150506 A1 WO 2017150506A1 JP 2017007701 W JP2017007701 W JP 2017007701W WO 2017150506 A1 WO2017150506 A1 WO 2017150506A1
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Prior art keywords
lithium
positive electrode
electrode active
composite oxide
active material
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PCT/JP2017/007701
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English (en)
Japanese (ja)
Inventor
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 JP2018503318A priority Critical patent/JP6516919B2/ja
Publication of WO2017150506A1 publication Critical patent/WO2017150506A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • 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 metal composite oxide having a layered crystal structure such as LiCoO 2 as a positive electrode active material.
  • 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 (WO2012 / 057289) includes Li element and at least one transition metal element selected from the group consisting of Ni, Co, and Mn (provided that the molar amount of Li element is the transition metal). More than 1.2 times the total molar amount of the elements.) Particles in which oxide (I) of at least one metal element selected from Zr, Ti, and Al is unevenly distributed on the surface of the lithium-containing composite oxide A positive electrode active material for a lithium ion secondary battery comprising (II) is disclosed.
  • Non-Patent Document 1 LiMO 2 (M: transition metal) having a layered crystal structure and Li 2 MnO 3
  • Patent Document 8 Japanese Patent Laid-Open No. 2008-270201
  • a positive electrode material for a lithium ion battery characterized in that an oxidation treatment is applied to the positive electrode material for a lithium ion battery, is disclosed.
  • Patent Document 9 Japanese Patent Laid-Open No. 2010-108873
  • the main active material is represented by the general formula: xLi 2 MO 3.
  • X is a number satisfying 0.4 ⁇ x ⁇ 1.0
  • M is one or more elements selected from the group consisting of Mn, Ti and Zr
  • A is B, Al, Ga and 1 or more elements selected from the group consisting of In, and 0 ⁇ y ⁇ 0.3 and 0 ⁇ z ⁇ 0.1.
  • the lithium manganese metal composite oxide having a layered crystal structure is particularly promising in that it has a high operating potential and can be expected to have a high energy density, and since it is based on Mn, the raw material cost can be reduced. Has been. However, since it operates at a high potential, it has a problem that gas is generated during high temperature storage. In order to solve such a problem, in order to suppress the reaction between the electrolytic solution and the lithium metal composite oxide, a method of coating the particle surface of the lithium manganese metal composite oxide with a metal or metal oxide can be considered. However, when the particle surface of the lithium manganese metal composite oxide is coated with a metal or metal oxide, a new problem arises that the rate characteristics of the battery deteriorate. In addition, the lithium manganese metal composite oxide having a layered crystal structure has a problem that the capacity retention rate during the cycle is low.
  • the present invention relates to a positive electrode active material containing a lithium manganese metal composite oxide having a layered crystal structure, and when used as a positive electrode active material of a lithium secondary battery, the reaction with the electrolyte is suppressed and the battery is stored at high temperature.
  • a new cathode active material for lithium secondary batteries that can reduce the amount of gas generated at the time, yet achieve the same or better rate characteristics, and further improve cycle characteristics It is something to be done.
  • the present invention has the general formula Li 1 + x Mn y M 1-xy O 2 (wherein x> 0.10, y ⁇ 0.40, 1-xy> 0.10, M is Co, 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
  • constitutituent element M a lithium manganese metal composite oxide having a layered crystal structure represented by any one or a combination of two or more thereof
  • a positive electrode active material for a lithium secondary battery comprising particles having a surface portion in which any one or a combination of two or more of the group consisting of Zr (referred to as “surface element A”) is present.
  • the atomic ratio of Mn and the atomic ratio of M (constituent element M is 2) measured by X-ray photoelectron spectroscopy (XPS) (hereinafter also referred to as “XPS”).
  • XPS X-ray photoelectron spectroscopy
  • the ratio (A / (Mn + M)) of the atomic ratio (A / (Mn + M)) of the surface element A to the total of the total of the atomic ratio in the case of two or more types is greater than 0.
  • the amount of surface lithium impurities is less than 0.80 wt%, and
  • XRD powder X-ray diffractometer
  • XRD X-Ray Diffractometer
  • a (003) plane with respect to an integrated intensity of a peak derived from the (104) plane Proposed is a positive electrode active material for a lithium secondary battery, wherein the ratio (003) / (104) of the integrated intensity of the peak derived from is greater than 0.90.
  • the positive electrode active material proposed by the present invention when used as a positive electrode active material for a lithium secondary battery, when used as a positive electrode active material for a lithium secondary battery, the reaction with the electrolyte is suppressed.
  • the amount of gas generated during high-temperature storage can be reduced, yet the rate characteristics can be made equal to or higher than that of the conventional positive electrode active material subjected to the surface treatment. Can be improved. Therefore, the positive electrode active material proposed by the present invention is particularly excellent as a positive electrode active material for batteries mounted on a vehicle, in particular, an electric vehicle (EV: Electric Vehicle) or a hybrid electric vehicle (HEV: Hybrid Electric Vehicle). It will be a thing.
  • EV Electric Vehicle
  • HEV Hybrid Electric Vehicle
  • Cathode active material for a lithium secondary battery have the general formula (1): Li 1 + x Mn y M 1-x-y O 2 (wherein, x> 0.10, y ⁇ 0 .40, 1-xy> 0.10, M is Co, 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 type or a combination of two or more types (referred to as “constituent element M”))
  • On the surface of particles made of lithium manganese metal composite oxide having a crystal structure referred to as “present lithium manganese metal composite oxide particles”
  • one or more of the group consisting of Al, Ti and Zr (Hereinafter referred to as “surface element A”) having a surface portion (“
  • a positive electrode active material for a lithium secondary battery referred to as “present positive electrode active material”.
  • 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 manganese metal composite oxide particle. As long as this particle
  • the present lithium manganese metal composite oxide particles have the general formula (1): Li 1 + x Mn y M 1-xy O 2 (wherein x> 0.10, y ⁇ 0.40, 1-xy> 0.10, M is Co, Ni, Na, Mg, Al, Si, P, K, Ca, Ti, V, Cr, Fe, Cu, Zn, Ga, Y, Zr, Nb, Mo, In, Ta Lithium manganese metal composite oxidation having a layered crystal structure represented by any one or a combination of two or more of the group consisting of W, Re, and Ce (referred to as “constituent element M”) It is a particle consisting of things.
  • Li 1 + x Mn y M 1-xy O 2 “1 + x” is greater than 1.10 and not greater than 1.40, particularly not less than 1.14 or not greater than 1.30, and among these, 1 .15 or more or 1.25 or less is preferable.
  • M in the above formula (1) is Co, 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 of Mo, In, Ta, W, Re, and Ce may be used.
  • “y” indicating the molar ratio of Mn may be y ⁇ 0.40, especially y ⁇ 0.41 or 0.70> y, and especially y ⁇ 0.42 or 0. .65> y, more preferably y ⁇ 0.43 or 0.60 ⁇ y.
  • “1-xy” indicating the molar ratio of M may be 1-xy> 0.10, and in particular, 1-xy> 0.15 or 0.50> 1-x- y, more preferably 1-xy ⁇ 0.20 or 0.45> 1-xy.
  • the atomic ratio of the oxygen amount is described as “2” for convenience, but may have some non-stoichiometry.
  • the present lithium manganese 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 an amount of this level is considered to hardly affect the characteristics of the present lithium manganese 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 manganese 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 this surface portion is 0.1 nm to 300 nm from the viewpoint of suppressing the reaction with the electrolytic solution to reduce the amount of gas generated during high temperature storage, improving the cycle characteristics, and maintaining or improving the rate characteristics. It is preferably 0.2 nm or more or 220 nm or less, more preferably 0.3 nm or more or 150 nm or less, particularly 100 nm or less, especially 50 nm or less, and more preferably 25 nm or less.
  • the present lithium manganese metal composite oxide is suitable for use as a positive electrode active material of a lithium secondary battery, and in particular, an in-vehicle battery, particularly an electric vehicle (EV) or a hybrid electric vehicle (HEV: HEV). It is particularly excellent as a positive electrode active material for batteries mounted on Hybrid Electric Vehicle.
  • Whether or not the surface portion where the surface element A exists is present on the surface of the lithium manganese 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 atomic ratio of Mn which is a constituent element of the general formula (1)
  • the atomic ratio of M measured by X-ray photoelectron spectroscopy (XPS)
  • the ratio (A / (Mn + M)) of the atomic ratio of the surface element A to the sum of the sum (A / (Mn + M)) when the surface element A is two or more is smaller than 0.8. If the surface element A is present to such an extent that the ratio (A / (Mn + M)) is smaller than 0.8, it is possible to suppress the reaction with the electrolytic solution and improve the life characteristics.
  • 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 / (Mn + M)) is preferably larger than 0 and smaller than 0.8, particularly larger than 0.01 or 0.6 or less, more preferably 0.03 or more or 0.4 or less. Of these, 0.04 or more or 0.3 or less, among them, less than 0.2, and more preferably less than 0.15.
  • the ratio (A / (Mn + M)) may be adjusted and the subsequent heat treatment temperature may be adjusted.
  • the ratio (A / (Mn + M)) may be adjusted and the subsequent heat treatment temperature may be adjusted.
  • the intensity ratio (003) / (104) is preferably greater than 0.90. It means that the smaller the ratio (003) / (104), the larger the proportion occupied by the rock salt structure. It was found that if the ratio (003) / (104) is greater than 0.90, the proportion occupied by the rock salt structure is reduced, and the rate characteristics can be improved.
  • the ratio (003) / (104) is preferably larger than 0.90, and more preferably larger than 1.00.
  • this positive electrode active material in order to make the said ratio (003) / (104) larger than 0.90, what is necessary is just to adjust baking conditions or the quantity of the solvent or water in surface treatment. However, it is not limited to such a method.
  • the positive electrode active material preferably has a surface lithium impurity amount of less than 0.80 wt%. If the amount of surface lithium impurities is 0.80 wt% or less, it is preferable because unreacted residual lithium reacts with the electrolytic solution to suppress a reaction that causes deterioration of life characteristics. From this point of view, the amount of surface lithium impurities of the present positive electrode active material is preferably less than 0.80 wt%, more preferably greater than 0 wt% or less than 0.70 wt%, particularly less than 0.60 wt%, and particularly preferably less than 0.8 wt%. More preferably, it is less than 30 wt%.
  • the above surface lithium impurities are derived from Li that remains without reacting when fired. Therefore, in order to adjust the surface lithium impurity amount to the above range, 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 0.2 to 6.0 m 2 / g. If the specific surface area (SSA) of the positive electrode active material is 0.2 to 6.0 m 2 / g, a reaction field for inserting and desorbing Li can be sufficiently secured, so that the rate characteristics can be maintained. It is preferable because it is possible. From such a viewpoint, the specific surface area (SSA) of the present positive electrode active material is preferably 0.2 to 6.0 m 2 / g, more preferably 5.5 m 2 / g or less, and most preferably 5.0 m 2 / g or less. Of these, 4.7 m 2 / g or less is even more preferable. In order to set the specific surface area of the present lithium manganese metal composite oxide powder in the above range, it is preferable to adjust the firing conditions and the pulverization conditions. However, it is not limited to these adjustment methods.
  • the amount of LiOH measured by the following measuring method is preferably less than 0.40 wt% from the viewpoint of improving the rate characteristics, and more preferably less than 0.35 wt%, particularly 0.20 wt%. More preferably, it is less than.
  • this positive electrode active material in order to make the surface LiOH amount less than 0.40 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 amount of Li 2 CO 3 measured by the following measurement method is preferably less than 0.40 wt% from the viewpoint of improving the rate characteristics, and less than 0.38 wt%. More preferably, it is less than 30 wt%.
  • the present positive electrode active material in order to make the amount of Li 2 CO 3 less than 0.40 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 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, and are particularly suitable for electric vehicles (EV: Electric Vehicle). ) And a hybrid electric vehicle (HEV: Hybrid Electric Vehicle), it is particularly excellent for use as a positive electrode active material of a lithium battery used as a power source for driving a motor.
  • 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 lithium manganese metal composite oxide having a layered crystal structure (“ After the surface treatment (referred to as “the surface treatment step”) of the present lithium manganese metal composite oxide particle powder ”, the lithium manganese metal composite oxide particle powder after the surface treatment is subjected to a heat treatment (“ heat treatment step ”).
  • heat treatment step a heat treatment
  • the surface treatment step and the heat treatment step only have to be provided, other steps may be further provided.
  • 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.
  • the present lithium manganese 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 manganese metal composite oxide powder obtained by purchasing or the like can be used as the present lithium manganese metal composite oxide particle powder after being subjected to a predetermined treatment.
  • lithium compound used as a raw material for the lithium manganese 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 manganese compound used as a raw material for the lithium manganese metal composite oxide particle powder is not particularly limited.
  • manganese carbonate, manganese nitrate, manganese chloride, manganese dioxide, manganese oxide (iii), trimanganese tetraoxide, and the like can be used, and among these, manganese carbonate and manganese dioxide are preferable.
  • electrolytic manganese dioxide obtained by an electrolytic method is particularly preferable.
  • the type of nickel compound used as a raw material for the lithium manganese metal composite oxide particle powder is not particularly limited.
  • nickel carbonate, nickel nitrate, nickel chloride, nickel oxyhydroxide, nickel hydroxide, nickel oxide can be used. Of these, nickel carbonate, nickel hydroxide, and nickel oxide are preferred.
  • cobalt compound used as the raw material for the lithium manganese metal composite oxide particle powder 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.
  • the type of aluminum compound used for the raw material of the lithium manganese metal composite oxide particle powder is not particularly limited, and for example, aluminum carbonate, aluminum nitrate, aluminum chloride, aluminum oxyhydroxide, aluminum hydroxide, aluminum oxide can be used. Of these, aluminum carbonate, aluminum hydroxide, and aluminum oxide are preferable.
  • the type of magnesium compound used as a raw material for the lithium manganese metal composite oxide particle powder is not particularly limited, and for example, magnesium carbonate, magnesium nitrate, magnesium chloride, magnesium hydroxide, magnesium oxide, and the like can be used. Magnesium hydroxide and magnesium oxide are preferred.
  • hydroxides, carbonates, nitrates, and the like of other M elements in the above formula (1) can be used as raw materials for the present lithium manganese metal composite oxide particles.
  • the maximum particle size (Dmax) of the raw material is 10 ⁇ m or less, especially 5 ⁇ m or less, In particular, it is preferable to adjust to 4 ⁇ 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 manganese metal composite oxide particle powder it is preferable to perform preliminary firing at 500 to 870 ° C. and then to 700 to 1000 ° C. if necessary. It is also possible to perform the main baking at 700 to 1000 ° C. without performing the preliminary baking.
  • a gas for example, CO 2
  • a carbonate such as lithium carbonate (Li 2 CO 3 ), manganese carbonate, nickel carbonate, basic cobalt carbonate or the like is used as a raw material, it is preferably calcined.
  • grains can be raised or it can adjust to the desired particle size by baking at high temperature rather than temporary baking.
  • 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 firing is performed in a firing furnace in an air atmosphere, an oxygen gas atmosphere, an atmosphere in which an oxygen partial pressure is adjusted, a nitrogen gas-containing atmosphere, an argon gas-containing atmosphere, or a carbon dioxide gas-containing atmosphere.
  • a temperature of 700 to 1100 ° C. means a temperature when a thermocouple is brought into contact with a fired product in a firing furnace
  • preferably 750 ° C. or higher or 1050 ° C. or lower, more preferably 800 Calcination is preferably carried out at a temperature of from °C to 1000 ° C., more preferably from 860 ° C. to 970 ° C. for 0.5 to 30 hours.
  • a fired product containing a plurality of metal elements can be regarded as a single phase of a lithium manganese 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 1100 ° C., particularly 750 ° C. or higher or 1050 ° C. or lower, particularly 800 ° C. or higher or 1000 ° C. or lower, more preferably 860 ° C. or higher or 970 ° 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 manganese 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 manganese 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 manganese 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 inside of the lithium manganese metal composite oxide particle powder.
  • the present lithium manganese 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.
  • the surface treatment of the present lithium manganese metal composite oxide particle powder produced as described above includes a surface treatment agent containing at least one of aluminum, titanium and zirconium, and is obtained as described above.
  • the lithium manganese 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 present lithium manganese 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 manganese metal composite oxide powder, and more preferably 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 manganese 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 manganese metal composite oxide powder ⁇ (M / lithium manganese 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 manganese 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 manganese 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 manganese metal composite oxide powder.
  • the amount of the organic solvent or water to be contacted 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 manganese metal composite oxide powder. Can be brought into contact with the lithium manganese 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 manganese 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 As a surface treatment agent, it is also possible to dry-process using inorganic compound powder as a surface treatment agent.
  • the atomic ratio of Mn which is a constituent element
  • the atomic ratio of M measured by X-ray photoelectron spectroscopy (XPS) (when the constituent element M has two or more types)
  • the lithium manganese metal composite oxide powder after the surface treatment is higher than 650 ° 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.
  • 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.
  • the reaction with the electrolyte can be suppressed, the amount of gas generated during high-temperature storage can be reduced, and the cycle characteristics can be improved.
  • the characteristics can be equal or better.
  • 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 650 ° C. and lower than 900 ° C. (: means a temperature when a thermocouple is brought into contact with the fired product in the firing furnace). Higher 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.
  • 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.
  • An aqueous polycarboxylic acid ammonium salt solution (SN Dispersant 5468 manufactured by San Nopco Co., Ltd.) was added as a dispersant to ion-exchanged water.
  • the amount of dispersant added was 6 wt% with respect to the total amount of raw materials.
  • Lithium carbonate, nickel hydroxide, electrolytic manganese dioxide, and lithium tetraborate were added to the above ion-exchanged water, and mixed and stirred to prepare a slurry having a solid content concentration of 40 wt%.
  • This slurry was wet pulverized for 45 minutes at 1300 rpm using a wet pulverizer (SC220 / 70A-VB-ZZ manufactured by Nippon Coke), the average particle diameter (D50) was 0.60 ⁇ m, and the maximum particle diameter (Dmax) was 2.
  • a mixed ground slurry of 3 ⁇ m was obtained.
  • the obtained mixed and pulverized slurry was granulated and dried using a thermal spray dryer (spray dryer, RL-10 manufactured by Okawara Chemical Co., Ltd.).
  • a twin jet nozzle was used for spraying, and granulation drying was performed by adjusting the temperature so that the spray pressure was 0.5 MPa, the slurry supply amount was 322 ml / min, and the outlet temperature of the drying tower was 100 to 110 ° C. .
  • the obtained granulated powder was calcined at 700 ° C. for 10 hours in an air atmosphere using a stationary electric furnace, and then main-fired at 950 ° C. for 22 hours in the air.
  • the fired mass obtained by firing was placed in a mortar and crushed with a pestle. Thereafter, the mixture was classified with a sieve having an opening of 53 ⁇ m, and the lithium transition metal oxide powder under the sieve was recovered.
  • the obtained lithium manganese metal composite oxide powder had a water content of 288 ppm measured at 110 to 300 ° C. by the Karl Fischer method.
  • the results were Li: 9.8%, Ni: 13.4%, and Mn: 38.8%.
  • Example 2 A lithium manganese metal composite oxide powder (sample) was obtained in the same manner as in Example 1 except that lithium carbonate was mixed with aluminum hydroxide as the surface treatment agent. In addition, lithium carbonate was added so that it might become the amount of Li of the same mole number as the amount of Al in aluminum hydroxide.
  • aqueous polycarboxylic acid ammonium salt solution (SN Dispersant 5468 manufactured by San Nopco Co., Ltd.) was added as a dispersant to ion-exchanged water. It added so that the amount of dispersing agents might be 6 wt% with respect to the total amount of the Li raw material, Ni raw material, Mn raw material, etc. which are mentioned later. The dispersant was sufficiently dissolved and mixed in ion exchange water.
  • lithium tetraborate was weighed so as to be 0.15 wt% with respect to the lithium manganese metal composite oxide obtained from the above.
  • the weighed raw materials were mixed and stirred in the above-described ion-exchanged water in which the dispersant was dissolved in advance to prepare a slurry having a solid content concentration of 40 wt%.
  • D50 was 0.62 ⁇ m by pulverization with a wet pulverizer at 1300 rpm for 45 minutes.
  • the obtained pulverized slurry was granulated and dried using a thermal spray dryer (spray dryer, RL-10 manufactured by Okawara Kako Co., Ltd.). At this time, a twin jet nozzle was used for spraying, and granulation drying was performed by adjusting the temperature so that the spray pressure was 0.5 MPa, the slurry supply amount was 322 ml / min, and the outlet temperature of the drying tower was 100 to 110 ° C.
  • the obtained granulated powder was calcined at 700 ° C. in the atmosphere for 10 hours using a stationary electric furnace. Subsequently, the obtained calcined powder was fired at 940 ° C. for 20 hours 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 manganese metal composite oxide (sample) under the sieve was collected.
  • the lithium manganese metal composite oxide (sample) was Li: 9.9%, Ni: 13.5%, and Mn: 38.1%.
  • An aqueous polycarboxylic acid ammonium salt solution (SN Dispersant 5468 manufactured by San Nopco Co., Ltd.) was added as a dispersant to the ion-exchanged water.
  • the amount of dispersant added was 6 wt% with respect to the total amount of raw materials.
  • Lithium carbonate, nickel hydroxide, cobalt oxyhydroxide, and electrolytic manganese dioxide were added to the above ion-exchanged water, and mixed and stirred to prepare a slurry having a solid content concentration of 40 wt%.
  • This slurry was wet pulverized using a wet pulverizer (SC220 / 70A-VB-ZZ manufactured by Nippon Coke) for 45 minutes, and the average particle size (D50) was 0.56 ⁇ m and the maximum particle size (Dmax) was 2.
  • D50 wet pulverizer
  • Dmax maximum particle size
  • a mixed ground slurry of 3 ⁇ m was obtained.
  • the obtained mixed and pulverized slurry was granulated and dried using a thermal spray dryer (spray dryer, RL-10 manufactured by Okawara Chemical Co., Ltd.).
  • a twin jet nozzle was used for spraying, and granulation drying was performed by adjusting the temperature so that the spray pressure was 0.50 MPa, the slurry supply amount was 336 ml / min, and the outlet temperature of the drying tower was 100 to 110 ° C. .
  • the obtained granulated powder was temporarily fired at 700 ° C. for 10 hours in an air atmosphere using a stationary electric furnace, and then main-fired at 940 ° C. for 22 hours in the air.
  • the fired mass obtained by firing was placed in a mortar and crushed with a pestle. Thereafter, the mixture was classified with a sieve having an opening of 53 ⁇ m, and the lithium transition metal oxide powder under the sieve was recovered.
  • the obtained lithium manganese metal composite oxide powder had a water content of 463 ppm measured at 110 to 300 ° C. by the Karl Fischer method.
  • lithium carbonate was added so that it might become the amount of Li of the same mole number as the amount of Al in an aluminum coupling agent.
  • the lithium manganese metal composite oxide obtained by the heat treatment was classified with a sieve having an opening of 53 ⁇ m to obtain a lithium manganese metal composite oxide (sample) under the sieve.
  • An aqueous polycarboxylic acid ammonium salt solution (SN Dispersant 5468 manufactured by San Nopco Co., Ltd.) was added as a dispersant to the ion-exchanged water.
  • the amount of dispersant added was 6 wt% with respect to the total amount of raw materials.
  • Lithium carbonate, nickel hydroxide, cobalt oxyhydroxide, and electrolytic manganese dioxide were added to the above ion-exchanged water, and mixed and stirred to prepare a slurry having a solid content concentration of 40 wt%.
  • This slurry was wet pulverized using a wet pulverizer (SC220 / 70A-VB-ZZ, manufactured by Nippon Coke) for 45 minutes, and the average particle diameter (D50) was 0.58 ⁇ m and the maximum particle diameter (Dmax) was 2.
  • D50 wet pulverizer
  • Dmax maximum particle diameter
  • a mixed ground slurry of 3 ⁇ m was obtained.
  • the obtained mixed and pulverized slurry was granulated and dried using a thermal spray dryer (spray dryer, RL-10 manufactured by Okawara Chemical Co., Ltd.).
  • a twin jet nozzle was used for spraying, and granulation drying was performed by adjusting the temperature so that the spray pressure was 0.52 MPa, the slurry supply amount was 330 ml / min, and the outlet temperature of the drying tower was 100 to 110 ° C. .
  • the obtained granulated powder was temporarily fired at 700 ° C. for 10 hours in an air atmosphere using a stationary electric furnace, and then main-fired at 940 ° C. for 22 hours in the air.
  • the fired mass obtained by firing was placed in a mortar and crushed with a pestle. Thereafter, the mixture was classified with a sieve having an opening of 53 ⁇ m, and the lithium transition metal oxide powder under the sieve was recovered.
  • lithium manganese metal composite oxide 3 parts by mass of a titanium coupling agent (Ajinomoto Fine Techno Co., Ltd. Preneact (registered trademark) KR-46B) as a surface treatment agent and isopropyl alcohol as a solvent are used. 8 parts by mass were mixed using a cutter mill (Milcer 720G manufactured by Iwatani Corporation). Next, the mixed lithium manganese metal composite oxide powder was dried by placing it in a drier at 100 ° C. for 1 hour in the air. Further, lithium carbonate was mixed with the dried powder, and then placed in a mortar, placed in a stationary furnace, and heat-treated at 730 ° C. for 5 hours in an oxygen atmosphere.
  • a titanium coupling agent Align (registered trademark) KR-46B)
  • KR-46B isopropyl alcohol as a solvent
  • An aqueous polycarboxylic acid ammonium salt solution (SN Dispersant 5468 manufactured by San Nopco Co., Ltd.) was added as a dispersant to the ion-exchanged water.
  • the amount of dispersant added was 6 wt% with respect to the total amount of raw materials.
  • Lithium carbonate, nickel hydroxide, and electrolytic manganese dioxide were added to the above-described ion-exchanged water, and mixed and stirred to prepare a slurry having a solid content concentration of 40 wt%.
  • This slurry was wet pulverized at 1300 rpm for 45 minutes using a wet pulverizer (Nippon Coke SC220 / 70A-VB-ZZ), the average particle diameter (D50) was 0.64 ⁇ m, and the maximum particle diameter (Dmax) was 2.
  • a mixed ground slurry of 3 ⁇ m was obtained.
  • the obtained mixed and pulverized slurry was granulated and dried using a thermal spray dryer (spray dryer, RL-10 manufactured by Okawara Chemical Co., Ltd.).
  • a twin jet nozzle was used for spraying, and granulation drying was performed by adjusting the temperature so that the spray pressure was 0.51 MPa, the slurry supply amount was 340 ml / min, and the drying tower outlet temperature was 100 to 110 ° C. .
  • the obtained granulated powder was temporarily fired at 700 ° C. for 10 hours in an air atmosphere using a stationary electric furnace, and then main-fired at 940 ° C. for 22 hours in the air.
  • the fired mass obtained by firing was placed in a mortar and crushed with a pestle. Thereafter, the mixture was classified with a sieve having an opening of 53 ⁇ m, and the lithium transition metal oxide powder under the sieve was recovered.
  • the obtained lithium manganese metal composite oxide powder had a water content of 458 ppm measured at 110 to 300 ° C. by the Karl Fischer method.
  • the results were Li: 9.4%, Ni: 16.6%, and Mn: 36.5%.
  • a zirconium coupling agent (Kenrich Petrochemicals Ken-React (registered trademark) NZ12) as a surface treatment agent and isopropyl as a solvent are obtained with respect to the obtained lithium manganese metal composite oxide.
  • 8 parts by mass of alcohol was mixed using a cutter mill (Milcer 720G manufactured by Iwatani Corporation).
  • the mixed lithium manganese metal composite oxide powder was dried by placing it in a drier at 100 ° C. for 1 hour in the air. Furthermore, after mixing lithium carbonate with the dried powder, it put into the mortar, set
  • lithium carbonate was added so that it might become the amount of Li of the same mole number as the amount of Zr in a zirconium coupling agent.
  • the lithium manganese metal composite oxide obtained by the heat treatment was classified with a sieve having an opening of 53 ⁇ m to obtain a lithium manganese metal composite oxide (sample) under the sieve.
  • An aqueous polycarboxylic acid ammonium salt solution (SN Dispersant 5468 manufactured by San Nopco Co., Ltd.) was added as a dispersant to the ion-exchanged water.
  • the amount of dispersant added was 6 wt% with respect to the total amount of raw materials.
  • Lithium carbonate, nickel hydroxide, electrolytic manganese dioxide, and aluminum hydroxide were added to the above ion-exchanged water, and mixed and stirred to prepare a slurry with a solid content concentration of 40 wt%.
  • This slurry was wet pulverized for 45 minutes at 1300 rpm using a wet pulverizer (SC220 / 70A-VB-ZZ manufactured by Nippon Coke), the average particle diameter (D50) was 0.60 ⁇ m, and the maximum particle diameter (Dmax) was 2.
  • a mixed ground slurry of 3 ⁇ m was obtained.
  • the obtained mixed and pulverized slurry was granulated and dried using a thermal spray dryer (spray dryer, RL-10 manufactured by Okawara Chemical Co., Ltd.).
  • the obtained lithium manganese metal composite oxide powder had a water content of 464 ppm measured at 110 to 300 ° C. by the Karl Fischer method.
  • Li 9.4%, Ni: 16.6%, Mn: 36.4%, Al: 0.03%. It was.
  • lithium manganese metal composite oxide 3 parts by mass of a titanium coupling agent (Ajinomoto Fine Techno Co., Ltd. Preneact (registered trademark) KR-46B) as a surface treatment agent and isopropyl alcohol as a solvent are used. 8 parts by mass were mixed using a cutter mill (Milcer 720G manufactured by Iwatani Corporation). Next, the mixed lithium manganese metal composite oxide powder was dried by placing it in a drier at 100 ° C. for 1 hour in the air. The dried powder was put in a mortar, placed in a static oven, and heat-treated at 720 ° C. for 5 hours in an oxygen atmosphere. The lithium manganese metal composite oxide obtained by the heat treatment was classified with a sieve having an opening of 53 ⁇ m to obtain a lithium manganese metal composite oxide (sample) under the sieve.
  • a titanium coupling agent Align (registered trademark) KR-46B)
  • KR-46B isopropyl alcohol as a solvent
  • An aqueous polycarboxylic acid ammonium salt solution (SN Dispersant 5468 manufactured by San Nopco Co., Ltd.) was added as a dispersant to the ion-exchanged water.
  • the amount of dispersant added was 6 wt% with respect to the total amount of raw materials.
  • Lithium carbonate, nickel hydroxide, cobalt oxyhydroxide, electrolytic manganese dioxide, and titanium oxide were added to the ion-exchanged water described above, mixed and stirred to prepare a slurry having a solid content concentration of 40 wt%.
  • This slurry was wet pulverized using a wet pulverizer (SC220 / 70A-VB-ZZ, manufactured by Nippon Coke) for 45 minutes, and the average particle diameter (D50) was 0.58 ⁇ m and the maximum particle diameter (Dmax) was 2.
  • D50 wet pulverizer
  • Dmax maximum particle diameter
  • a mixed ground slurry of 3 ⁇ m was obtained.
  • the obtained mixed and pulverized slurry was granulated and dried using a thermal spray dryer (spray dryer, RL-10 manufactured by Okawara Chemical Co., Ltd.).
  • a twin jet nozzle was used for spraying, and granulation drying was performed by adjusting the temperature so that the spray pressure was 0.50 MPa, the slurry supply amount was 330 ml / min, and the outlet temperature of the drying tower was 100 to 110 ° C. .
  • the obtained granulated powder was temporarily fired at 700 ° C. for 10 hours in an air atmosphere using a stationary electric furnace, and then main-fired at 940 ° C. for 22 hours in the air.
  • the fired mass obtained by firing was placed in a mortar and crushed with a pestle. Thereafter, the mixture was classified with a sieve having an opening of 53 ⁇ m, and the lithium transition metal oxide powder under the sieve was recovered.
  • the obtained lithium manganese metal composite oxide powder had a water content of 484 ppm measured at 110 to 300 ° C. by the Karl Fischer method.
  • An aqueous polycarboxylic acid ammonium salt solution (SN Dispersant 5468 manufactured by San Nopco Co., Ltd.) was added as a dispersant to the ion-exchanged water.
  • the amount of dispersant added was 6 wt% with respect to the total amount of raw materials.
  • Lithium carbonate, nickel hydroxide, and electrolytic manganese dioxide were added to the above-described ion-exchanged water, and mixed and stirred to prepare a slurry having a solid content concentration of 40 wt%.
  • This slurry was wet pulverized at 1300 rpm for 45 minutes using a wet pulverizer (SC220 / 70A-VB-ZZ manufactured by Nippon Coke), the average particle diameter (D50) was 0.66 ⁇ m, and the maximum particle diameter (Dmax) was 2.
  • a mixed ground slurry of 3 ⁇ m was obtained.
  • the obtained mixed and pulverized slurry was granulated and dried using a thermal spray dryer (spray dryer, RL-10 manufactured by Okawara Chemical Co., Ltd.).
  • a twin jet nozzle was used for spraying, and granulation drying was performed by adjusting the temperature so that the spray pressure was 0.51 MPa, the slurry supply amount was 340 ml / min, and the drying tower outlet temperature was 100 to 110 ° C. .
  • the obtained granulated powder was temporarily fired at 700 ° C. for 10 hours in an air atmosphere using a stationary electric furnace, and then main-fired at 940 ° C. for 22 hours in the air.
  • the fired mass obtained by firing was placed in a mortar and crushed with a pestle. Thereafter, the mixture was classified with a sieve having an opening of 53 ⁇ m, and the lithium transition metal oxide powder under the sieve was recovered.
  • Li 9.2%, Ni: 17.0%, and Mn: 37.2%.
  • 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 Sputter rate: 1-10 nm / min (SiO2 equivalent)
  • 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 atomic ratio calculated above was confirmed by considering the interference of the NiLMM peak and comparing with the composition ratio of the chemical analysis result described above.
  • the atomic ratio of Mn and the atomic ratio of M are measured by X-ray photoelectron spectroscopy (XPS). It was confirmed that the ratio of the atomic ratio of the surface element A to the total of (A / (Mn + M)) was larger than 0 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 manganese 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 manganese metal composite oxides (samples) obtained in Examples and Comparative Examples, and peak search was performed using the integrated powder X-ray analysis software PDXL2 manufactured by Rigaku Corporation in the obtained X-ray diffraction patterns. Went. 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. .
  • 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 is punched into a size of 50 mm ⁇ 100 mm, and then pressed and dense at a press line pressure of 3 t / cm using a roll press machine, and then punched into a 40 mm ⁇ 29 mm square. It was.
  • 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 positive electrode sheet obtained above and the negative electrode sheet coated with graphite were cut into a size of 3.1 cm ⁇ 4.2 cm to form a negative electrode. Between the positive electrode and the negative electrode, 1 mol of LiPF 6 was added to a carbonate-based mixed solvent. A separator (porous polyethylene film) impregnated with an electrolytic solution dissolved so as to be / L was placed, and a laminate type battery was produced.
  • a laminate type battery was prepared by the above-described method, and allowed to stand for 12 hours, and then charged at a constant current and a constant potential at 0.05C to 4.55 V at 25 ° C., and then discharged at a constant current to 2.5 V. Thereafter, the measurement environment temperature was set at 45 ° C. and left for 4 hours, and the battery was charged at 0.1 C until it reached 4.55 V. After maintaining the voltage for 7 days, the battery was discharged to 2.5 V. The gas generation amount (mL) generated so far was measured by the immersion volume method (solvent replacement method based on Archimedes' principle).
  • the amount of gas generated per positive electrode active material amount (mL / g) was calculated.
  • the numerical value of Comparative Example 1 is set to 100, and an index is used.
  • the numerical value of Comparative Example 2 is set as 100, and the values are described as indexes.
  • any of the group consisting of Al, Ti and Zr is formed on the surface of the particles made of lithium manganese metal composite oxide having a layered crystal structure.
  • Mn which is a constituent element measured by X-ray photoelectron spectroscopy (XPS) with respect to a positive electrode active material for a lithium secondary battery including active particles having a surface portion in which one kind or a combination of two or more kinds is present
  • XPS X-ray photoelectron spectroscopy
  • 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 greater than 0.90, it has been found that rate characteristics can be improved.
  • Example is an Example about lithium manganese metal complex oxide which has a layered crystal structure of a specific composition
  • general formula Li 1 + x Mn y M 1-xy O 2 (wherein x> 0.10, y ⁇ 0.40, 1-xy> 0.10, M represents Co, Ni, Na, Mg, Al, Any one of the group consisting of Si, P, K, Ca, Ti, V, Cr, Fe, Cu, Zn, Ga, Y, Zr, Nb, Mo, In, Ta, W, Re, and Ce or Particles made of a lithium manganese metal composite oxide having a layered crystal structure represented by a combination of two or more kinds (referred to as “constituent element M”) are used as a core material, and Al, Ti and Zr are formed on the surface thereof.
  • the ratio of the atomic ratio of the surface element A to the sum of the ratio and the atomic ratio of M (A / (Mn + M)) is greater than 0 and less than 0.8, and the surface lithium impurity amount is less than 0.80 wt%;
  • the ratio (003) / (104) of the integrated intensity of the peak derived from the (003) plane to the integrated intensity of the peak derived from the (104) plane is greater than 0.90, any of the constituent elements M listed above Elements also have common problems and properties, for example, since all the constituent elements M have the common property of contributing to the stabilization of the crystal structure, similar effects can be obtained.
  • Co, Ni, Al, and Ti are used as the constituent element M.
  • the number of moles of constituent elements to be used is designed so that Na, Mg, Si, P, K, Ca, V, Cr, Fe When Cu, Zn, Ga, Y, Zr, Nb, Mo, In, Ta, W, Re, and Ce are used in place of or in combination with Co, Ni, Al, and Ti, the same as in the above embodiment It can be considered that the effect of can be obtained.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

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+xMnyM1-x-yO2 (dans la formule, x > 0,10, y ≥ 0,40, 1 - x - y > 0,10, et M est n'importe quel élément ou une combinaison de deux éléments ou plus du groupe constitué par Co, 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/(Mn + M)) du rapport atomique de l'élément de surface A à la somme des rapports atomiques de Mn et M tel que mesuré par XPS est supérieur à 0 mais inférieur à 0,8, la quantité d'impuretés de lithium de surface est inférieure à 0,80 % en poids, et le rapport d'intensité intégrée de pic (003)/(104) tel que mesuré par XRD est supérieur à 0,90.
PCT/JP2017/007701 2016-02-29 2017-02-28 Matière active d'électrode positive pour batterie secondaire au lithium WO2017150506A1 (fr)

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WO2020208872A1 (fr) * 2019-04-12 2020-10-15 住友化学株式会社 Poudre d'oxyde complexe de lithium-métal et matériau actif d'électrode positive de batterie secondaire au lithium
CN113169333A (zh) * 2018-11-30 2021-07-23 株式会社Posco 锂二次电池正极活性物质及包括该物质的锂二次电池
EP3846260A4 (fr) * 2018-08-31 2021-11-10 Panasonic Intellectual Property Management Co., Ltd. Matériau actif d'électrode positive et batterie comprenant ce dernier
CN114709413A (zh) * 2022-04-14 2022-07-05 远景动力技术(江苏)有限公司 三元材料及其应用

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JP2015536558A (ja) * 2013-10-29 2015-12-21 エルジー・ケム・リミテッド 正極活物質の製造方法、及びこれによって製造されたリチウム二次電池用正極活物質

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JP2014049309A (ja) * 2012-08-31 2014-03-17 Toyota Motor Corp 活物質材料、全固体電池、および活物質材料の製造方法
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Publication number Priority date Publication date Assignee Title
EP3846260A4 (fr) * 2018-08-31 2021-11-10 Panasonic Intellectual Property Management Co., Ltd. Matériau actif d'électrode positive et batterie comprenant ce dernier
CN113169333A (zh) * 2018-11-30 2021-07-23 株式会社Posco 锂二次电池正极活性物质及包括该物质的锂二次电池
WO2020208872A1 (fr) * 2019-04-12 2020-10-15 住友化学株式会社 Poudre d'oxyde complexe de lithium-métal et matériau actif d'électrode positive de batterie secondaire au lithium
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CN114709413A (zh) * 2022-04-14 2022-07-05 远景动力技术(江苏)有限公司 三元材料及其应用

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