WO2012029729A1 - Hydroxyde de cobalt, procédé de production de celui-ci, oxyde de cobalt et procédé de production dudit hydroxyde - Google Patents

Hydroxyde de cobalt, procédé de production de celui-ci, oxyde de cobalt et procédé de production dudit hydroxyde Download PDF

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WO2012029729A1
WO2012029729A1 PCT/JP2011/069507 JP2011069507W WO2012029729A1 WO 2012029729 A1 WO2012029729 A1 WO 2012029729A1 JP 2011069507 W JP2011069507 W JP 2011069507W WO 2012029729 A1 WO2012029729 A1 WO 2012029729A1
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cobalt
liquid
cobalt hydroxide
particle
hydroxide
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Japanese (ja)
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大石　義英
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日本化学工業株式会社
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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
    • C01G51/04—Oxides; Hydroxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/45—Aggregated particles or particles with an intergrown morphology
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • C01P2004/52—Particles with a specific particle size distribution highly monodisperse size distribution
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/11—Powder tap density
    • 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 cobalt hydroxide or cobalt oxide, in particular, cobalt hydroxide or cobalt oxide suitably used as a raw material for producing a lithium cobalt composite oxide for a lithium secondary battery, and a method for producing the same.
  • lithium ion secondary batteries have been put to practical use as power sources for small electronic devices such as laptop computers, mobile phones, and video cameras.
  • lithium cobalt oxide LiCoO 2
  • research and development on lithium transition metal composite oxides has been active. Many proposals have been made.
  • lithium transition metal composite oxide lithium cobaltate (LiCoO 2 ), lithium nickelate (LiNiO 2 ), lithium manganate (LiMn 2 O 4 ) and the like are preferably used, and LiCoO 2 is particularly safe. Widely used in terms of charge / discharge capacity.
  • lithium cobaltate based complex oxides for lithium secondary batteries capable of higher capacity are required.
  • Patent Document 1 As a method for increasing the capacity of a lithium secondary battery, (1) by mixing large particles of lithium cobaltate and small particles of lithium cobaltate to increase the filling rate of the positive electrode active material, Methods of increasing capacity and increasing capacity (for example, Patent Document 1), (2) Changing the composition of LiCoO 2 to increase the capacity per weight, such as LiNi 0.85 Co 0.15 O 2 Conventionally, a method for increasing the capacity by the above (for example, Patent Document 2) has been performed.
  • the method (1) has a problem in that small particles generate a large amount of gas due to the reaction with the non-aqueous electrolyte that occurs when the battery is repeatedly charged and discharged repeatedly.
  • the method (2) since the lithium compound used in the production of LiNi 0.85 Co 0.15 O 2 remains as a residual alkali, battery safety, in particular, charge / discharge is repeated. There is a problem in that gas generation accompanying the reaction with the non-aqueous electrolyte that occurs at the time increases.
  • a method that replaces the conventional method is required.
  • a method of increasing the capacity of the lithium secondary battery a method of increasing the battery density per volume by increasing the particle size of LiCoO 2 to about 15 to 35 ⁇ m to increase the tap density can be considered.
  • cobalt hydroxide or cobalt oxide used as a raw material for producing LiCoO 2 is produced as particles having a particle size of 0.1 to 15 ⁇ m.
  • LiCoO 2 having a particle size of about 15 to 35 ⁇ m by reacting a lithium compound using cobalt hydroxide or cobalt oxide having a particle size of about 0.1 to 15 ⁇ m as a manufacturing raw material, It is necessary to increase the amount of lithium oxide to be reacted with cobalt oxide or cobalt oxide and to grow grains during the reaction.
  • LiCoO 2 of Li / Co ratio to be obtained the about is about 1.060, not use the lithium compound can not be obtained LiCoO 2 above 15 [mu] m.
  • the amount of lithium becomes excessive, a new problem arises that the capacity retention rate decreases.
  • LiCoO 2 having a particle size of about 15 to 35 ⁇ m can be obtained without excessively increasing the amount of lithium compound to be reacted with cobalt hydroxide or cobalt oxide. It is considered possible.
  • cobalt hydroxide or cobalt oxide having a large particle size of about 15 to 40 ⁇ m which has been manufactured by a conventional manufacturing method, has a weak secondary particle strength (hereinafter referred to as “secondary particle cohesiveness”). Therefore, when mixed with the lithium compound before the reaction with the lithium compound, the secondary particles are broken, and when reacted with the lithium compound, the particle size becomes small. End up.
  • the object of the present invention is to provide cobalt hydroxide and cobalt oxide having a high secondary particle strength even if the secondary particle size is large (hereinafter also referred to as “high secondary particle cohesion”). There is to get.
  • a solution cobalt aqueous solution
  • a solution cobalt aqueous solution
  • B solution alkaline aqueous solution
  • the aqueous solution of cobalt containing glycine is used, the molar ratio of cobalt to glycine in the aqueous solution of cobalt (liquid A) is in a specific range, and liquid A and liquid B are added to the aqueous solution of glycine (liquid C).
  • the primary particles are aggregated secondary particles, and the primary particles constituting the secondary particles are plate-like or columnar with a major axis length of 1.5 ⁇ m or more in image analysis of the SEM image.
  • cobalt hydroxide having needle-like primary particles and a tap density of 0.80 g / mL or more is obtained, and the cobalt hydroxide is highly cohesive even if the secondary particles have a large particle size.
  • the present invention (1) is a secondary particle in which primary particles are aggregated, and as a primary particle constituting the secondary particle, a plate shape having a major axis length of 1.5 ⁇ m or more in image analysis of an SEM image, Cobalt hydroxide having columnar or needle-shaped primary particles and having a tap density of 0.80 g / mL or more is provided.
  • the present invention (2) is a cobalt aqueous solution containing glycine, and the cobalt aqueous solution (solution A) having a glycine content of 0.010 to 0.300 mol with respect to 1 mol of cobalt in terms of atoms.
  • solution A cobalt aqueous solution
  • solution B aqueous alkaline solution
  • Liquid C a neutralization reaction is performed at 55 to 75 ° C. to obtain a neutralization step to obtain cobalt hydroxide.
  • Cobalt hydroxide is provided.
  • the present invention (3) is a cobalt aqueous solution containing glycine, and the cobalt aqueous solution (solution A) having a glycine content of 0.010 to 0.300 mol per mol of cobalt in terms of atoms.
  • an aqueous alkaline solution (liquid B) are added to the aqueous glycine solution (liquid C) and neutralized at 55 to 75 ° C. to have a neutralization step for obtaining cobalt hydroxide.
  • a method for producing cobalt oxide is provided.
  • the present invention (4) is a secondary particle in which plate-like, columnar or needle-like primary particles are aggregated, and in the image analysis of the SEM image, the average value of the major axis of the primary particles constituting the secondary particle is Cobalt oxide characterized by being 1.5 ⁇ m or more is provided.
  • the present invention (5) is an oxidation firing step for obtaining cobalt oxide by firing the cobalt hydroxide obtained by performing the production method of cobalt hydroxide of the present invention (3) at 200 to 1000 ° C. to oxidize it.
  • the present invention provides a method for producing cobalt oxide characterized by comprising:
  • the cobalt hydroxide of the present invention is a secondary particle in which primary particles are aggregated, and as a primary particle constituting the secondary particle, a plate-like or columnar shape having a major axis length of 1.5 ⁇ m or more in image analysis of an SEM image Or it is a cobalt hydroxide characterized by having acicular primary particles and a tap density of 0.80 g / mL or more.
  • FIG. 21 is a schematic perspective view of primary particles constituting secondary particles
  • A) is a schematic perspective view of plate-like primary particles constituting secondary particles
  • B) is FIG. 2 is a schematic perspective view of prismatic primary particles constituting secondary particles
  • C) is a schematic perspective view of acicular primary particles constituting secondary particles.
  • the 21A includes a surface 1a on the surface side of the secondary particles and a surface 2a that intersects the surface 1a on the surface side.
  • the surface 1a on the surface side of the secondary particles appears entirely in the SEM image of the secondary particles, while the surface 2a that intersects the surface 1a on the surface side is mostly inside the secondary particles. Therefore, only a part of the surface appears in the SEM image of the secondary particles.
  • the length of the major axis of the primary particle is the longer diameter x of the surface 1a on the surface side of the secondary particle among the surfaces of the primary particle appearing in the SEM image.
  • the length of the minor axis of the primary particle is the shorter diameter y of the surface 1a on the surface side of the secondary particle among the surfaces of the primary particle appearing in the SEM image.
  • the framed portion is the contour of the surface 1a on the surface side of the secondary particle, and (B) Only the framed portion is shown.
  • symbol x of (B) of FIG. 22 is the length of the major axis of a primary particle, and the length shown by the code
  • symbol y is the length of the minor axis of a primary particle.
  • the framed portion is the contour of the surface 1a on the surface side of the secondary particle, (B) Shows only the framed portion.
  • symbol x of (B) of FIG. 23 is the length of the major axis of a primary particle, and the length shown by the code
  • symbol y is the length of the minor axis of a primary particle.
  • the shape of the plate-like primary particles shown in FIG. 21A is not limited to this, and the shape in the planar direction is not limited as long as it has a shape spreading in the planar direction. It may be a curved shape.
  • the columnar primary particles shown in FIG. 21B include a surface 1b on the surface side of secondary particles and a surface 2b that intersects the surface 1b on the surface side.
  • the surface 1b on the surface side of the secondary particles appears entirely in the SEM image of the secondary particles, while the surface 2b that intersects the surface 1b on the surface side is mostly inside the secondary particles. Therefore, only a part of the surface appears in the SEM image of the secondary particles.
  • the length of the major axis of the primary particle is the longer diameter x of the surface 1b on the surface side of the secondary particle among the surfaces of the primary particle appearing in the SEM image.
  • the length of the minor axis of the primary particle is the shorter diameter y of the surface 1b on the surface side of the secondary particle among the surfaces of the primary particle appearing in the SEM image.
  • the shape of the columnar primary particles shown in FIG. 21B is a quadrangular columnar shape, but is not limited to this, and may be a columnar shape or a prismatic shape other than the rectangular columnar shape, or a curved shape. The shape may be sufficient.
  • the length of the major axis of the primary particle is the longer diameter x of the surface 1c on the surface side of the secondary particle appearing in the SEM image.
  • the length of the minor axis of the primary particle is the shorter diameter y of the surface 1c on the surface side of the secondary particle appearing in the SEM image.
  • the major axis and the short diameter of a primary particle are when the surface of a secondary particle is planarly viewed.
  • the major axis and the minor axis are measured based on the shape of the primary particles in the plan view.
  • the cobalt hydroxide of the present invention is a secondary particle in which primary particles are aggregated.
  • primary particles constituting the secondary particles of cobalt hydroxide of the present invention plate-like, columnar, or needle-like primary particles having a major axis length of 1.5 ⁇ m or more in SEM image analysis, and other primary particles, That is, there are spherical or irregular primary particles, plate-like, columnar, or needle-like primary particles having a major axis length of less than 1.5 ⁇ m in SEM image analysis.
  • the cobalt hydroxide of the present invention necessarily has plate-like, columnar, or needle-like primary particles having a major axis length of 1.5 ⁇ m or more in SEM image analysis as primary particles constituting secondary particles.
  • the cobalt hydroxide of the present invention comprises (I) secondary particles in which primary particles having a major axis length of 1.5 ⁇ m or more in SEM image analysis are aggregated, or (II) SEM images.
  • the proportion of primary particles in the form of plates, columns and needles having a major axis length of 1.5 ⁇ m or more in the SEM image in the secondary particles is preferably 40% or more and 80% or more with respect to the entire secondary particles. Particularly preferably, 100% is more preferable.
  • the compressive strength and tap density of cobalt hydroxide are increased when the ratio of the primary particles having a major axis length of 1.5 ⁇ m or more in the SEM image is within the above range.
  • the abundance ratio of plate-like, columnar, and needle-like primary particles having a major axis length of 1.5 ⁇ m or more in the SEM image in the secondary particles means that the surface of the secondary particles is flat in the SEM image.
  • the ratio of the area of primary particles having a long diameter of 1.5 ⁇ m or more to the area of secondary particles of plate-like, columnar and needle-like particles is indicated.
  • image analysis is performed on the SEM image of the secondary particles, the secondary particles are projected in two dimensions, and 100 secondary particles are arbitrarily extracted.
  • the area of the extracted secondary particles and the area of primary particles having a major axis length of 1.5 ⁇ m or more in the secondary particles are measured.
  • the ratio of the total area of primary particles having a major axis length of 1.5 ⁇ m or more to the total area of 100 extracted secondary particles is obtained as a percentage.
  • the average value of the major axis of the plate-like, columnar or needle-like primary particles constituting the cobalt hydroxide secondary particles of the present invention is 1.5 ⁇ m or more, preferably 2.0 to 5.0 ⁇ m, particularly preferably 2. 5 to 4.5 ⁇ m.
  • the compressive strength and tap density of cobalt hydroxide are increased.
  • the average value of the major axis of the primary particles is obtained.
  • image analysis is performed on the SEM image of the secondary particles, the secondary particles are projected two-dimensionally, and 100 primary particles are arbitrarily extracted.
  • the length of the major axis is measured for each of the extracted primary particles.
  • the lengths of the major diameters of the 100 extracted primary particles are averaged, and the average value is taken as the average value of the major diameters of the primary particles constituting the secondary particles.
  • the hydroxide containing cobalt primary particles having a plate-like or columnar particle shape of a composite hydroxide containing cobalt and nickel were aggregated to form secondary particles.
  • the maximum value of the major axis of the primary particle of the composite oxide is less than 0.5 ⁇ m.
  • the cobalt hydroxide of the present invention is a secondary particle in which primary particles are aggregated, and the primary particle constituting the secondary particle has a major axis of 1.5 ⁇ m or more in the plate-like, columnar or needle-like primary particles.
  • the average value of the major axis of the plate-like, columnar or needle-like primary particles in the secondary particles is preferably 1.5 ⁇ m or more, particularly preferably 2.0 to 5.0 ⁇ mm, more preferably 2.5 to 4.5 ⁇ m.
  • the average value of the short diameter of the primary particles relating to the cobalt hydroxide of the present invention is preferably 0.1 ⁇ m or more, particularly preferably 0.2 to 1.5 ⁇ m, and more preferably 0.3 to 1.2 ⁇ m.
  • the compressive strength and tap density of cobalt hydroxide are increased.
  • the method for obtaining the average value of the minor axis of the primary particles is the average value of the major axis of the primary particles, except that the measurement target is the length of the minor axis of the primary particles instead of the length of the major axis of the primary particles. It is the same as how to find
  • the average particle size of the secondary particles of cobalt hydroxide of the present invention is preferably 10 to 40 ⁇ m, particularly preferably 15 to 40 ⁇ m.
  • the average particle size of lithium cobaltate obtained by reacting cobalt hydroxide with a lithium compound is 15 to 35 ⁇ m. Therefore, lithium cobalt oxide having a high capacity per volume can be obtained.
  • the average particle diameter of the secondary particles of cobalt hydroxide and the average particle diameter of the secondary particles of cobalt oxide are values measured by a laser diffraction / scattering method using Microtrack MT3300EXII manufactured by Nikkiso Co., Ltd. .
  • the tap density of the cobalt hydroxide of the present invention is 0.80 g / mL or more, preferably 1.00 to 2.50 g / mL, particularly preferably 1.50 to 2.50 g / mL.
  • a high tap density indicates that the secondary particles have a large number of primary particles having a plate-like, columnar, or needle-like shape having a major axis of 1.5 ⁇ m or more.
  • the compressive strength of the secondary particles of cobalt hydroxide of the present invention is 5 to 50 MPa, preferably 8 to 30 MPa.
  • the compressive strength of the cobalt hydroxide secondary particles is within the above range, the cobalt hydroxide secondary particles are unraveled when the both are mixed before the cobalt hydroxide and the lithium compound are reacted, and the particle size is reduced.
  • an average particle size of 15 to 40 ⁇ m can be appropriately used by appropriately using particles having a large average particle size of 15 to 40 ⁇ m. 35 ⁇ m lithium cobaltate is obtained.
  • the compressive strength of the secondary particles is a value measured by Shimadzu Micro Compression Tester MTC-W.
  • lithium cobalt oxide having an average particle size of 15 to 35 ⁇ m can be appropriately used by appropriately using a cobalt hydroxide having a compressive strength in the above range and an average particle size of 15 to 40 ⁇ m. Therefore, the capacity per volume of the positive electrode active material for a lithium secondary battery can be increased.
  • the cobalt hydroxide of the present invention has little change in the particle size distribution of the secondary particles before and after the pulverization treatment even when pulverized with a shearing force similar to that of a household coffee mill, preferably the average of the secondary particles by the pulverization treatment
  • the decrease in particle size is 7.0 ⁇ m or less. Therefore, in the production of lithium cobaltate, when the cobalt hydroxide of the present invention and the lithium compound are mixed, the secondary particles of cobalt hydroxide are difficult to break, so that lithium cobaltate having a large average particle diameter can be obtained.
  • the cobalt hydroxide of the present invention is suitably produced by the following method for producing cobalt hydroxide of the present invention.
  • the method for producing cobalt hydroxide of the present invention is a cobalt aqueous solution containing glycine, and the cobalt aqueous solution (A) has a glycine content of 0.010 to 0.300 mol with respect to 1 mol of cobalt in terms of atoms.
  • Liquid) and an aqueous alkaline solution (liquid B) are added to an aqueous glycine solution (liquid C), and a neutralization reaction is performed at 55 to 75 ° C., thereby having a neutralization step of obtaining cobalt hydroxide.
  • This is a method for producing cobalt hydroxide.
  • the liquid A and the liquid B are added to the liquid C to react the cobalt salt in the liquid A and the alkali in the liquid B in the liquid C. It is a process to make.
  • Liquid A is an aqueous cobalt solution containing glycine (NH 2 CH 2 COOH). And A liquid is prepared by dissolving glycine and a cobalt salt in water.
  • the cobalt salt related to the liquid A is not particularly limited, and examples thereof include cobalt chloride, nitrate, sulfate, and the like. Among these, sulfate free from impurities due to chlorine is preferable. Moreover, you may coexist a small amount of other metal salts as needed. Examples of the metal salt that can coexist include metal salts such as nickel, manganese, magnesium, aluminum, and titanium.
  • the concentration of cobalt ions in the liquid A is not particularly limited, but is preferably 1.0 to 2.2 mol / L, particularly preferably 1.5 to 2.0 mol / L in terms of atoms.
  • the productivity is good and the precipitation of the cobalt salt from the liquid A is difficult to occur.
  • the cobalt ion concentration in the liquid A is less than the above range, the productivity tends to be low, and if it exceeds the above range, the cobalt salt tends to precipitate from the liquid A.
  • the content of glycine with respect to cobalt in the liquid A is 0.010 to 0.300 mol, preferably 0.050 to 0.200 mol with respect to 1 mol of cobalt in terms of atoms. Since the content of glycine with respect to cobalt in the liquid A is in the above range, even if the secondary particle diameter of cobalt hydroxide is large, the cohesiveness of the secondary particles can be increased. In the lithium acid production process, when mixed with a lithium compound, secondary particles are not released and the particle size can be maintained, so that lithium cobaltate having a large average particle size of 15 to 35 ⁇ m and a large particle size can also be obtained. On the other hand, if the content of glycine with respect to cobalt in the liquid A is less than the above range, the cohesiveness of the secondary particles of cobalt hydroxide is weakened. Productivity deteriorates because it remains in the reaction solution.
  • B liquid is an alkaline aqueous solution. And B liquid is prepared by dissolving an alkali in water.
  • the alkali related to the liquid B is not particularly limited, and examples thereof include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. Among these, sodium hydroxide is industrially inexpensive. preferable.
  • the concentration of the B solution and the total amount of alkali added to the C solution are appropriately selected depending on the concentration and total amount of cobalt ions in the A solution.
  • the concentration of solution B is preferably 5 to 15 mol / L, particularly preferably 5 to 10 mol / L.
  • C liquid is a glycine aqueous solution. And C liquid is prepared by dissolving glycine in water.
  • the glycine concentration in the reaction solution (solution C) during addition of solution A and solution B to solution C is preferably 0.010 to 0.250 mol / L, particularly preferably 0. 0.030 to 0.170 mol / L. That is, in the neutralization step, the glycine concentration in the liquid C before the reaction and the glycine concentration in the reaction liquid (the liquid C) during the neutralization reaction are preferably 0.010 to 0.250 mol / L, particularly preferably 0. The glycine concentration in solution C and the glycine concentration in solution A before the reaction are adjusted so as to be 0.030 to 0.170 mol / L.
  • the amount of liquid A and liquid B added to liquid C is the ratio of the total number of moles of hydroxide ions in liquid B to the total number of moles of cobalt ions converted into atoms in liquid A (total OH ions in liquid B Of the total Co ions in the liquid A) is preferably 1.8 to 2.1, particularly preferably 1.9 to 2.0.
  • the ratio of the total number of moles of hydroxide ions in liquid B to the total number of moles of cobalt ions converted into atoms in liquid A is within the above range, unreacted cobalt ions are present in the reaction liquid (liquid C). It becomes easy to obtain the target cobalt hydroxide without remaining.
  • C liquid glycine aqueous solution
  • the reaction temperature of the neutralization reaction is 55 to 75 ° C., preferably 60 to 75 ° C., particularly preferably 65 to 75 ° C. That is, in the neutralization step, the temperature of the reaction liquid (C liquid) when adding the A liquid and the B liquid to the C liquid, that is, the temperature of the C liquid before the reaction and the reaction liquid during the neutralization reaction (C liquid) ) Is 55 to 75 ° C., preferably 60 to 75 ° C., particularly preferably 65 to 75 ° C. When the temperature of the reaction liquid (C liquid) at the time of adding A liquid and B liquid to C liquid is in the said range, the average particle diameter of the secondary particle of cobalt hydroxide becomes large.
  • the pH of the reaction liquid (C liquid) when adding the A liquid and the B liquid to the C liquid that is, the pH of the C liquid before the reaction and the reaction liquid (C liquid) during the neutralization reaction
  • the pH is 9.0 to 11.0, preferably 9.5 to 10.5, particularly preferably 9.8 to 10.2.
  • the pH of the reaction liquid (liquid C) when adding liquid A and liquid B to liquid C is in the above range, cobalt hydroxide having a large average particle diameter of secondary particles and strong cohesion can be obtained.
  • the pH of the reaction liquid (C liquid) when adding the A liquid and the B liquid to the C liquid is lower than the above range, unreacted cobalt ions remain in the reaction liquid.
  • the resulting cobalt hydroxide tends to contain salts such as sulfate radicals as impurities.
  • the pH of the reaction liquid (C liquid) at the time of adding A liquid and B liquid to C liquid is higher than the said range, the average particle diameter of the cobalt hydroxide secondary particle will become small easily.
  • the pH of the reaction liquid (C liquid) when adding A liquid and B liquid to C liquid is, for example, the hydroxide ion concentration in B liquid, the cobalt ion in A liquid It is adjusted by selecting conditions such as the ratio of the concentration of hydroxide ions in the B liquid to the concentration and the ratio of the addition rate of the B liquid to the C liquid to the A liquid.
  • the ratio of the addition rate of hydroxide ions in solution B to the addition rate of cobalt ions in solution A when adding solution A and solution B to solution C is , Preferably 1.8 to 2.1, particularly preferably 1.9 to 2.0.
  • the ratio of the addition rate of hydroxide ions in solution B to the addition rate of cobalt ions in solution A is the reaction vessel relative to the addition rate (mol / min) of cobalt ions in solution A added to the reaction vessel. This refers to the ratio of the addition rate (mol / min) of hydroxide ions in the B liquid added to the B.
  • the addition time from the start of adding the liquid A and the liquid B to the liquid C to the end of the addition is not particularly limited, From the viewpoint of industrial advantage, it is preferably 0.5 to 10 hours, particularly preferably 1 to 5 hours.
  • the stirring speed of the reaction liquid (liquid C) when mixing liquid A and liquid B that is, the stirring speed of liquid C immediately before the reaction and the stirring of the reaction liquid (liquid C) during the neutralization reaction
  • the speed is appropriately selected depending on the size of the reaction vessel, the diameter of the stirring blade, the amount of the reaction solution, and the like, but the peripheral speed of the stirring blade is preferably 0.5 to 4.0 m / sec. Particularly preferred is 5 to 2.0 m / sec.
  • the stirring speed in the first time zone preferably the time zone immediately after the start of addition until 1 hour later, is moderated.
  • cobalt hydroxide (secondary particles) is obtained by performing the neutralization step in this manner.
  • the cobalt hydroxide particles (secondary particles) produced in the reaction solution are separated from the reaction solution by vacuum filtration, centrifugation, etc., and washed as necessary. ,dry.
  • Cobalt hydroxide obtained by carrying out the method for producing cobalt hydroxide of the present invention is a secondary particle in which primary particles are aggregated, and as a primary particle constituting the secondary particle, It has plate-like, columnar, or needle-like primary particles with a major axis length of 1.5 ⁇ m or more, has a unique particle shape with a tap density of 0.80 g / mL or more, and has secondary particles. Even if the average particle size of the particles is 15 to 40 ⁇ m, which is larger than the conventional one, the cohesion is strong.
  • the cobalt hydroxide obtained by carrying out the method for producing cobalt hydroxide of the present invention is a secondary particle when mixed with a lithium compound in the production process of lithium cobaltate. Even if the average particle size of the particles is as large as 15 to 40 ⁇ m, the secondary particles are difficult to break, and thus the average particle size of 15 to 40 ⁇ m is maintained even after mixing with the lithium compound.
  • the cobalt hydroxide obtained by carrying out the method for producing cobalt hydroxide of the present invention is pulverized with a shearing force similar to a household coffee mill, the average of secondary particles
  • the decrease in the particle size is small, preferably the decrease in the average particle size of the secondary particles due to the pulverization treatment is 7.0 ⁇ m or less, and the change in the particle size distribution before and after pulverization and mixing is small.
  • the average particle diameter of secondary particles of the cobalt hydroxide of the present invention is 15
  • a material having a particle size of ⁇ 40 ⁇ m it is not necessary to use a large amount of a lithium compound for particle growth when reacting with a lithium compound.
  • Lithium cobaltate having a small excess lithium amount as compared with the conventional lithium cobaltate having a large particle diameter of 0.900 to 1.040 in terms of the molar ratio of lithium to lithium (Li / Co) can be obtained.
  • a lithium secondary having a high capacity per volume and a high capacity retention rate.
  • a positive electrode active material for a battery can be provided.
  • the cobalt hydroxide of the present invention is cobalt hydroxide obtained by performing a neutralization step according to the method for producing cobalt hydroxide of the present invention. That is, the cobalt hydroxide of the present invention is a cobalt aqueous solution containing glycine, and the aqueous solution of cobalt (solution A) has a glycine content of 0.010 to 0.300 mol per mol of cobalt in terms of atoms.
  • the method for producing cobalt oxide of the present invention comprises an oxidation and firing step of obtaining cobalt oxide by firing and oxidizing cobalt hydroxide obtained by performing the method of producing cobalt hydroxide of the present invention at 200 to 1000 ° C. It is a manufacturing method of the cobalt oxide characterized by having.
  • the firing temperature when firing the cobalt hydroxide is 200 to 1000 ° C., preferably 300 to 900 ° C.
  • the firing time is 2 to 20 hours, preferably 2 to 10 hours.
  • the firing atmosphere is an oxidizing atmosphere such as in air or oxygen gas.
  • the cobalt oxide obtained by carrying out the method for producing cobalt oxide of the present invention may be appropriately pulverized, crushed and classified.
  • the cobalt oxide of the present invention is a secondary particle in which primary particles are aggregated, and as a primary particle constituting the secondary particle, a plate shape, columnar shape, or needle having a major axis length of 1.5 ⁇ m or more in image analysis of an SEM image And has a unique particle shape having a tap density of 0.80 g / mL or more.
  • the average value of the major axis of the plate-like, columnar or needle-like primary particles is preferably 1.5 ⁇ m or more, particularly preferably 2.0 to 5.0 ⁇ m, and more preferably 2.5 to 4. .5 ⁇ m.
  • the average particle diameter of the secondary particles of cobalt oxide of the present invention is 10 to 40 ⁇ m, preferably 15 to 40 ⁇ m, and the compressive strength of the secondary particles is 5 to 50 MPa, preferably 8 to 30 MPa.
  • the cobalt oxide of the present invention has little change in the particle size distribution of the secondary particles before and after the pulverization treatment even if the pulverization treatment is performed with a shearing force similar to a household coffee mill.
  • the decrease in diameter is 7.0 ⁇ m or less.
  • the cobalt oxide of the present invention is used as a raw material for the production of lithium cobaltate
  • the positive electrode active material for a lithium secondary battery having a high capacity per volume and a high capacity retention rate, like the cobalt hydroxide of the present invention. Can be provided.
  • the cobalt oxide of the present invention can be obtained, for example, by calcining and oxidizing cobalt hydroxide obtained by the method for producing cobalt hydroxide of the present invention at 200 to 700 ° C., preferably 300 to 500 ° C.
  • the method for producing lithium cobaltate using the cobalt hydroxide of the present invention or the cobalt oxide of the present invention comprises a particle mixing step of mixing the cobalt hydroxide of the present invention or the cobalt oxide of the present invention and a lithium compound, and particle mixing. And a firing reaction step of obtaining lithium cobaltate by firing the particle mixture obtained in the step at 800 to 1150 ° C.
  • the particle mixing step is a step of mixing the cobalt hydroxide of the present invention or the cobalt oxide of the present invention with a lithium compound.
  • lithium compound which concerns on a particle
  • lithium compound which concerns on a particle
  • the average particle size of the lithium compound is preferably 0.1 to 200 ⁇ m, preferably 2 to 50 ⁇ m because of good reactivity.
  • the ratio of the number of moles of lithium in terms of atoms to the number of moles of cobalt in terms of atoms is 0.900 to 1.040, preferably 0.950 to 1.030, particularly preferably 0.980 to 1.020.
  • the ratio of the number of moles of lithium in terms of atoms to the number of moles of cobalt in terms of atoms is in the above range, the capacity retention rate of lithium cobaltate is increased.
  • examples of the method of mixing the cobalt hydroxide of the present invention or the cobalt oxide of the present invention with the lithium compound include a ribbon mixer, a Henschel mixer, a super mixer, and a nauter mixer.
  • the cobalt hydroxide of the present invention or the particle mixture of the cobalt oxide of the present invention and the lithium compound obtained in the particle mixing step is heated to thereby oxidize the cobalt hydroxide of the present invention or the oxidation of the present invention.
  • cobalt and a lithium compound are reacted to obtain lithium cobaltate.
  • the calcination reaction temperature is 800 to 1150 ° C, preferably 900 to 1100 ° C.
  • the firing reaction time is 1 to 30 hours, preferably 5 to 20 hours.
  • the firing reaction atmosphere is an oxidizing atmosphere such as in air or oxygen gas.
  • the produced lithium cobaltate is crushed or classified as necessary to obtain lithium cobaltate.
  • the average particle size of the lithium cobalt oxide obtained by using the cobalt hydroxide of the present invention or the cobalt oxide of the present invention is preferably 15 to 35 ⁇ m, particularly preferably 18 to 30 ⁇ m, so that high filling is possible. Therefore, according to the lithium cobalt oxide obtained by using the cobalt hydroxide of the present invention or the cobalt oxide of the present invention, the capacity per volume of the lithium secondary battery can be increased.
  • the average particle diameter of lithium cobaltate is a value measured by a laser diffraction / scattering method using Microtrack MT3300EXII manufactured by Nikkiso Co., Ltd.
  • the molar ratio of lithium in terms of atoms to the cobalt in terms of atoms is 0.900 to 1.040. Since the amount of excess lithium is small compared with the conventional large particle size lithium cobalt oxide, the capacity retention rate of the lithium secondary battery is increased.
  • the tap density of the lithium cobalt oxide obtained by using the cobalt hydroxide of the present invention or the cobalt oxide of the present invention is preferably 2.4 g / mL or more, particularly preferably 2.6 to 3.2 g / mL. .
  • Cobalt aqueous solution 1 Cobalt aqueous solution 1 was prepared by dissolving 425.5 g of industrial cobalt sulfate heptahydrate and 5.7 g of glycine in water and further adding water to make the total volume 1 L. At this time, the cobalt ion concentration in the cobalt aqueous solution 1 is 1.5 mol / L in terms of atoms, the glycine concentration is 0.075 mol / L, and the glycine is 0.1 mol per 1 mol of cobalt in terms of atoms. It was 050 mol.
  • Cobalt aqueous solution 2 Cobalt sulfate aqueous solution 2 was prepared by dissolving 425.5 g of industrial cobalt sulfate heptahydrate and 1.1 g of glycine in water and further adding water to make the total volume 1 L. At this time, the cobalt ion concentration in the cobalt aqueous solution 2 is 1.5 mol / L in terms of atoms, the glycine concentration is 0.015 mol / L, and glycine is 0.1 mol per mol of cobalt in terms of atoms. It was 010 mol.
  • Cobalt aqueous solution 3 425.5 g of industrial cobalt sulfate heptahydrate was dissolved in water, and water was further added to make the total volume 1 L, whereby an aqueous cobalt solution 3 was prepared. At this time, the cobalt ion concentration in the cobalt aqueous solution 3 was 1.5 mol / L in terms of atoms.
  • Cobalt aqueous solution 4 Cobalt sulfate aqueous solution 4 was prepared by dissolving 425.5 g of industrial cobalt sulfate heptahydrate and 0.9 g of glycine in water and further adding water to make the total volume 1 L.
  • the cobalt ion concentration in the cobalt aqueous solution 4 is 1.5 mol / L in terms of atoms
  • the glycine concentration is 0.012 mol / L
  • glycine is 0.1 mol per mol of cobalt in terms of atoms. It was 008 mol.
  • Alkaline aqueous solution 1 Sodium hydroxide was dissolved in water so as to obtain a 25% by mass aqueous sodium hydroxide solution to prepare 0.5 L of an aqueous alkaline solution 1. At this time, the concentration of the alkaline aqueous solution 1 was 7.9 mol / L.
  • Example 6 Manufacture of cobalt hydroxide> Except for the reaction conditions shown in Table 1, the reaction was carried out under the same conditions as in Examples 1 to 5 to obtain cobalt hydroxide.
  • Table 2 shows the average particle diameter, compressive strength, pulverization characteristics, and tap density of the obtained secondary particles of cobalt hydroxide.
  • Example 7 ⁇ Manufacture of cobalt oxide>
  • the cobalt hydroxide obtained in Example 3 was calcined in the atmosphere at 500 ° C. for 5 hours to obtain cobalt oxide (Co 3 O 4 ).
  • Table 2 shows the secondary average average particle size, compressive strength, grinding characteristics, and tap density of the obtained cobalt oxide.
  • the battery performance test was conducted as follows. ⁇ Production of lithium secondary battery> 91% by weight of the lithium cobaltate obtained in Examples 8 to 11 and Comparative Examples 5 to 8, 6% by weight of graphite powder, and 3% by weight of polyvinylidene fluoride were mixed to obtain a positive electrode agent, which was used as N-methyl-2- A kneaded paste was prepared by dispersing in pyrrolidinone. The kneaded paste was applied to an aluminum foil, dried, pressed and punched into a disk with a diameter of 15 mm to obtain a positive electrode plate.
  • a coin-type lithium secondary battery was manufactured using each member such as a separator, a negative electrode, a positive electrode, a current collector plate, a mounting bracket, an external terminal, and an electrolytic solution.
  • a metal lithium foil is used for the negative electrode
  • 1 of ethylene carbonate and methyl ethyl carbonate is used for the electrolyte.
  • a stirring agitation speed of “1.0 to 2.0” means that stirring was performed at 1.0 m / sec for 1 hour after the start of mixing and then at 2.0 m / sec.
  • the average particle size of secondary particles (a) indicates the average particle size before pulverization with a home mixer, and the average particle size of secondary particles (b) is pulverized with a home mixer. The average particle diameter of the subsequent secondary particles is shown. ** In Table 2, the abundance ratio is the ratio of the total area of primary particles having a major axis of 1.5 ⁇ m or more to the total area of secondary particles.
  • lithium cobaltate having a small excess lithium amount can be obtained even if the average particle size is large, and thus a lithium secondary battery having a high capacity per volume and a high capacity retention rate can be produced. .

Abstract

Le but de l'invention est d'obtenir de l'hydroxyde de cobalt et de l'oxyde de cobalt, chacun ayant une agrégabilité élevée même si une taille de particule secondaire est grande. L'invention concerne l'hydroxyde de cobalt caractérisé en ce qu'il est sous la forme de particules secondaires obtenues par agrégation de particules primaires, comprenant, comme particules primaires constituant les particules secondaires, des particules primaires sous la forme d'une plaque, d'un pilier, ou d'une aiguille ayant une longueur d'axe majeur déterminée par analyse d'image SEM de 1,5 µm ou plus, et ayant une masse volumique après tassement de 0,80 g/ml ou plus.
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103964514A (zh) * 2013-01-29 2014-08-06 宁波科博特钴镍有限公司 一种正八面体四氧化三钴的制备方法
US10741828B2 (en) 2016-07-05 2020-08-11 Semiconductor Energy Laboratory Co., Ltd. Positive electrode active material including lithium cobaltate coated with lithium titanate and magnesium oxide
US11094927B2 (en) 2016-10-12 2021-08-17 Semiconductor Energy Laboratory Co., Ltd. Positive electrode active material particle and manufacturing method of positive electrode active material particle
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US11670770B2 (en) 2017-06-26 2023-06-06 Semiconductor Energy Laboratory Co., Ltd. Method for manufacturing positive electrode active material, and secondary battery
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03187922A (ja) * 1989-12-08 1991-08-15 Minnesota Mining & Mfg Co <3M> β水酸化コバルトの製造方法
JPH0922692A (ja) * 1995-07-04 1997-01-21 Matsushita Electric Ind Co Ltd 非水電解液電池活物質用コバルト水酸化物と四酸化三コバルトおよびその製造法
JPH10247497A (ja) * 1996-12-05 1998-09-14 Samsung Display Devices Co Ltd リチウム２次電池用陽極活物質の製造方法
JPH11505798A (ja) * 1995-05-26 1999-05-25 エイチ・シー・スタルク・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング・ウント・コンパニー・コマンジツトゲゼルシヤフト 長球的に集塊した塩基性炭酸コバルト（ｉｉ）及び長球的に集塊した水酸化コバルト（ｉｉ）、それらの製法及び使用法
JPH11292549A (ja) * 1998-04-13 1999-10-26 Ishihara Sangyo Kaisha Ltd 水酸化コバルトおよびその製造方法
JP2002060225A (ja) * 2000-08-18 2002-02-26 Ishihara Sangyo Kaisha Ltd コバルト酸リチウム凝集体、コバルト酸化物凝集体及びそれらの製造方法並びに該コバルト酸リチウム凝集体を用いてなるリチウム電池
JP2004182564A (ja) * 2002-12-05 2004-07-02 Nippon Chem Ind Co Ltd コバルト酸リチウム、その製造方法及び非水電解質二次電池
JP2004220897A (ja) * 2003-01-14 2004-08-05 Seimi Chem Co Ltd リチウム二次電池用正極活物質粉末

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101486494B (zh) * 2009-02-20 2010-09-08 武汉理工大学 一种碱式碳酸钴纳米材料的合成方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03187922A (ja) * 1989-12-08 1991-08-15 Minnesota Mining & Mfg Co <3M> β水酸化コバルトの製造方法
JPH11505798A (ja) * 1995-05-26 1999-05-25 エイチ・シー・スタルク・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング・ウント・コンパニー・コマンジツトゲゼルシヤフト 長球的に集塊した塩基性炭酸コバルト（ｉｉ）及び長球的に集塊した水酸化コバルト（ｉｉ）、それらの製法及び使用法
JPH0922692A (ja) * 1995-07-04 1997-01-21 Matsushita Electric Ind Co Ltd 非水電解液電池活物質用コバルト水酸化物と四酸化三コバルトおよびその製造法
JPH10247497A (ja) * 1996-12-05 1998-09-14 Samsung Display Devices Co Ltd リチウム２次電池用陽極活物質の製造方法
JPH11292549A (ja) * 1998-04-13 1999-10-26 Ishihara Sangyo Kaisha Ltd 水酸化コバルトおよびその製造方法
JP2002060225A (ja) * 2000-08-18 2002-02-26 Ishihara Sangyo Kaisha Ltd コバルト酸リチウム凝集体、コバルト酸化物凝集体及びそれらの製造方法並びに該コバルト酸リチウム凝集体を用いてなるリチウム電池
JP2004182564A (ja) * 2002-12-05 2004-07-02 Nippon Chem Ind Co Ltd コバルト酸リチウム、その製造方法及び非水電解質二次電池
JP2004220897A (ja) * 2003-01-14 2004-08-05 Seimi Chem Co Ltd リチウム二次電池用正極活物質粉末

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103964514A (zh) * 2013-01-29 2014-08-06 宁波科博特钴镍有限公司 一种正八面体四氧化三钴的制备方法
US10741828B2 (en) 2016-07-05 2020-08-11 Semiconductor Energy Laboratory Co., Ltd. Positive electrode active material including lithium cobaltate coated with lithium titanate and magnesium oxide
US11043660B2 (en) 2016-07-05 2021-06-22 Semiconductor Energy Laboratory Co., Ltd. Positive electrode active material including lithium cobaltate coated with lithium titanate and magnesium oxide
US11094927B2 (en) 2016-10-12 2021-08-17 Semiconductor Energy Laboratory Co., Ltd. Positive electrode active material particle and manufacturing method of positive electrode active material particle
US11444274B2 (en) 2017-05-12 2022-09-13 Semiconductor Energy Laboratory Co., Ltd. Positive electrode active material particle
US11489151B2 (en) 2017-05-12 2022-11-01 Semiconductor Energy Laboratory Co., Ltd. Positive electrode active material particle
US11799080B2 (en) 2017-05-19 2023-10-24 Semiconductor Energy Laboratory Co., Ltd. Positive electrode active material, method for manufacturing positive electrode active material, and secondary battery
US11670770B2 (en) 2017-06-26 2023-06-06 Semiconductor Energy Laboratory Co., Ltd. Method for manufacturing positive electrode active material, and secondary battery

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