Classifications

• • H—ELECTRICITY
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  • 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
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  • C01G53/80—Compounds containing nickel, with or without oxygen or hydrogen, and containing one or more other elements
  • C01G53/82—Compounds containing nickel, with or without oxygen or hydrogen, and containing two or more other elements
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  • H01M4/362—Composites
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  • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
  • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
• • H—ELECTRICITY
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  • 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
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  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
  • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
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  • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
  • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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  • C01P2004/32—Spheres
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  • C01P2004/60—Particles characterised by their size
  • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/11—Powder tap density
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  • C01P2006/16—Pore diameter
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  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/40—Electric properties
• • H—ELECTRICITY
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  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
• • H—ELECTRICITY
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  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M2004/021—Physical characteristics, e.g. porosity, surface area
• • H—ELECTRICITY
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  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
  • H01M2004/028—Positive electrodes
• • 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 is a method for producing a nickel composite hydroxide particle, a positive electrode active material using the nickel composite hydroxide particle as a precursor, and a positive electrode active material, and in particular, a non-aqueous electrolyte having excellent discharge capacity and charge / discharge efficiency.
• the present invention relates to a method for producing a nickel composite hydroxide particle, a positive electrode active material using the nickel composite hydroxide particle as a precursor, and a positive electrode active material from which a secondary battery can be obtained.
• secondary batteries have been used in a wide range of fields such as portable devices and vehicles that use or use electricity as a power source from the viewpoint of reducing the environmental load.
• the secondary battery include a secondary battery using a non-aqueous electrolyte such as a lithium ion secondary battery.
• a secondary battery using a non-aqueous electrolyte such as a lithium ion secondary battery is suitable for miniaturization and weight reduction, and has excellent characteristics such as high cycle characteristics and high rate characteristics.
• Patent Document 1 a composite compound containing nickel and manganese having a tap density of 1.9 g / cm 3 or more and an average circularity of 0.960 or more has been proposed.
• a positive electrode active material having excellent cycle characteristics and rate characteristics can be obtained by improving the tap density and circularity, but other characteristics required as a positive electrode active material. There was room for improvement in terms of discharge capacity and charge / discharge efficiency.
• the present invention is a precursor of a positive electrode active material capable of obtaining a positive electrode active material capable of exhibiting high discharge capacity and high charge / discharge efficiency by being mounted on a secondary battery using a non-aqueous electrolyte.
• a positive electrode active material obtained from the precursor, and a method for producing the positive electrode active material is a precursor of a positive electrode active material capable of obtaining a positive electrode active material capable of exhibiting high discharge capacity and high charge / discharge efficiency by being mounted on a secondary battery using a non-aqueous electrolyte.
• the gist of the structure of the present invention is as follows. [1] Nickel composite hydroxide particles that are precursors of the positive electrode active material of a non-aqueous electrolyte secondary battery. Nickel composite hydroxide particles having a porosity of 45.0% or more and 55.0% or less. [2] Nickel composite hydroxide particles that are precursors of the positive electrode active material of the non-aqueous electrolyte secondary battery. Nickel composite hydroxide particles having an average circularity of 0.85 or more and 0.94 or less. [3] The nickel composite hydroxide particles according to [1], which have an average circularity of 0.85 or more and 0.94 or less.
• Nickel composite hydroxide particles Described in any one of [1] to [3], wherein the particle diameter (D50) of the nickel composite hydroxide particles having a cumulative volume percentage of 50% by volume is 5.0 ⁇ m or more and 25.0 ⁇ m or less.
• Nickel composite hydroxide particles One or more additive metals selected from the group in which the nickel composite hydroxide particles consist of Ni, Co, Mn, Al, Ca, Ti, V, Cr, Zr, Nb, Mo and W. It contains the element M and has a molar ratio of Ni: Co: M of 1-xy: x: y.
• the nickel composite hydroxide particle according to any one of [1] to [4], which is (meaning 0 ⁇ x ⁇ 0.2, 0 ⁇ y ⁇ 0.1).
• a positive electrode active material for a non-aqueous electrolyte secondary battery in which the nickel composite hydroxide particles according to any one of [1] to [5] are fired with a lithium compound.
• [7] In the step of adding a lithium compound to the nickel composite hydroxide particles according to any one of [1] to [5] to obtain a mixture, or in any one of [1] to [5].
• a method for producing a positive electrode active material for a non-aqueous electrolyte secondary battery in which the nickel composite hydroxide particles according to any one of [1] to [5] are fired with a lithium compound.
• the "void ratio" means that a predetermined amount of nickel composite hydroxide particles are contained in a cell having a constant volume and compressed at a pressure of 21.2 MPa to obtain nickel composite hydroxide.
• the compressed volume (V) of the physical particles is measured, and from the true density (d) of the nickel composite hydroxide particles, [mass of V-composite hydroxide particles x (1 / d)] / V x 100 (%). Means the value calculated in.
• a powder compressor which is an accessory of the high-precision surface tension meter DY-700 (manufactured by Kyowa Interface Science Co., Ltd.), is used to put a nickel composite hydroxylation into a cell having a diameter of 10 mm and a height of 100 mm (volume 7.85 ml).
• the compressed volume (V) can be measured by accommodating 6.5 g of physical particles and compressing them at a pressure of 21.2 MPa.
• the true density (d) is a value measured by a gas replacement type dry automatic density meter.
• the circularity is a spherical index when nickel composite hydroxide particles are projected two-dimensionally.
• the term "circularity" as used herein means that the nickel composite hydroxide particles to be measured are photographed one by one with a CCD camera or the like, and the circumference of a circle having the same area as the particle image / the circumference of the particle image. It means the calculated value.
• a wet flow type particle size / shape analyzer "FPIA-3000S” manufactured by Sysmex Corporation
• the “average circularity” in the present specification means a value obtained by analyzing the circularity based on the number of pieces and calculating the average value.
• the positive electrode active material using this nickel composite hydroxide as a precursor is mounted on the secondary battery. High discharge capacity and high charge / discharge efficiency can be exhibited.
• the positive electrode active material using the nickel composite hydroxide particles as a precursor is secondary. By mounting it on a battery, it can exhibit high discharge capacity and high charge / discharge efficiency.
• the void ratio is 45.0% or more and 55.0% or less, and the average circularity of the nickel composite hydroxide particles is 0.85 or more and 0.94 or less.
• nickel composite hydroxide particles which are the precursors of the positive electrode active material of the non-aqueous electrolyte secondary battery of the present invention.
• the nickel composite hydroxide particles (hereinafter, may be simply referred to as "nickel composite hydroxide particles of the present invention") which are precursors of the positive electrode active material of the non-aqueous electrolyte secondary battery of the present invention have a void ratio. However, it is 45.0% or more and 55.0% or less.
• the shape of the nickel composite hydroxide particles is adjusted so that a predetermined amount of voids are formed between the nickel composite hydroxide particles.
• the nickel composite hydroxide particles of the present invention impart high discharge capacity and high charge / discharge efficiency to the non-aqueous electrolyte secondary battery by having the void ratio of 45.0% or more and 55.0% or less. Can be done.
• the model of the device for compressing the powder used for calculating the porosity is a device capable of compressing the nickel composite hydroxide particles of the present invention contained in a cell having a constant volume at a pressure of 21.2 MPa. If there is, for example, a powder compressor (manufactured by Kyowa Interface Science Co., Ltd.), which is an accessory device of the high-precision surface tension meter DY-700, can be mentioned without particular limitation.
• the porosity is not particularly limited as long as it is in the range of 45.0% or more and 55.0% or less, but the lower limit thereof is 46.0% or more from the viewpoint of further improving the discharge capacity and charge / discharge efficiency. Is preferable.
• the upper limit of the porosity is to maintain the loading density of the positive electrode active material on the positive electrode, thereby increasing the discharge capacity and charge / discharge efficiency without impairing other characteristics of the positive electrode active material such as cycle characteristics. From the viewpoint of further improvement, 53.0% or less is preferable, and 52.0% or less is particularly preferable.
• the above upper limit value and lower limit value can be arbitrarily combined.
• the shape of the nickel composite hydroxide particles of the present invention is adjusted so as to have the above porosity.
• the shape of the nickel composite hydroxide particles of the present invention has, for example, an average circularity of 0.85 or more and 0.94 or less. Therefore, the nickel composite hydroxide particles of the present invention have a shape having a low circularity as compared with the conventional precursor.
• the nickel composite hydroxide particles of the present invention have an average circularity of 0.85 or more and 0.94 or less, it is possible to impart high discharge capacity and high charge / discharge efficiency to the non-aqueous electrolyte secondary battery. ..
• the average circularity of the nickel composite hydroxide particles of the present invention is not particularly limited as long as it is in the range of 0.85 or more and 0.94 or less, but the lower limit thereof maintains the loading density of the positive electrode active material on the positive electrode. By doing so, 0.87 or more is preferable, and 0.89 or more is particularly preferable, from the viewpoint of further improving the discharge capacity and charge / discharge efficiency without impairing other characteristics of the positive electrode active material such as cycle characteristics.
• the upper limit of the average circularity is preferably 0.92 or less, and particularly preferably 0.91 or less, from the viewpoint of further improving the discharge capacity and charge / discharge efficiency. The above upper limit value and lower limit value can be arbitrarily combined.
• the components of the nickel composite hydroxide particles of the present invention include, for example, nickel (Ni), cobalt (Co), manganese (Mn), aluminum (Al), calcium (Ca), titanium (Ti), vanadium ( A composite hydroxide containing one or more additive metal elements M selected from the group consisting of V), chromium (Cr), zirconium (Zr), niobium (Nb), molybdenum (Mo) and tungsten (W). Can be mentioned. That is, the nickel composite hydroxide particles contain Ni and Co as essential metal components, and further contain Mn, Al, Ca, Ti, V, Cr, Zr, Nb, Mo and W as additive metal elements (M). Contains one or more of these metallic elements.
• the molar ratio of Ni: Co: M is not particularly limited and can be appropriately selected depending on the conditions of use of the positive electrode active material obtained from the nickel composite hydroxide particles and the like.
• Examples of the molar ratio of Ni: Co: M include 1-xy: x: y (meaning 0 ⁇ x ⁇ 0.2, 0 ⁇ y ⁇ 0.1).
• the additive metal element preferably contains Al and Mn, and is particularly preferably Al, from the viewpoint of further improving the discharge capacity and charge / discharge efficiency.
• the nickel composite hydroxide particles of the present invention are secondary particles formed by aggregating a plurality of primary particles.
• the particle size of the nickel composite hydroxide particles of the present invention is not particularly limited, but for example, the lower limit of the particle size having a cumulative volume percentage of 50% by volume (hereinafter, may be simply referred to as "D50") is the density. From the viewpoint of improvement, 5.0 ⁇ m or more is preferable, and 8.0 ⁇ m or more is particularly preferable.
• the upper limit of D50 of the nickel composite hydroxide particles of the present invention is preferably 25.0 ⁇ m or less, and particularly preferably 20.0 ⁇ m or less, from the viewpoint of improving the contact property with the non-aqueous electrolyte. The above upper limit value and lower limit value can be arbitrarily combined.
• the lower limit of the particle diameter (hereinafter, may be simply referred to as “D90”) in which the cumulative volume percentage of the nickel composite hydroxide particles of the present invention is 90% by volume is 10.0 ⁇ m or more from the viewpoint of improving the density. Is preferable, and 15.0 ⁇ m or more is particularly preferable.
• the upper limit of D90 of the nickel composite hydroxide particles of the present invention is preferably 40.0 ⁇ m or less, and particularly preferably 35.0 ⁇ m or less, from the viewpoint of improving the contact with the non-aqueous electrolyte. The above upper limit value and lower limit value can be arbitrarily combined.
• the lower limit of the particle diameter (hereinafter, may be simply referred to as “D10”) in which the cumulative volume percentage of the nickel composite hydroxide particles of the present invention is 10% by volume is 1.0 ⁇ m or more from the viewpoint of improving the density. Is preferable, and 5.0 ⁇ m or more is particularly preferable.
• the upper limit of D10 of the nickel composite hydroxide particles of the present invention is preferably 15.0 ⁇ m or less, and particularly preferably 10.0 ⁇ m or less, from the viewpoint of improving the contact with the non-aqueous electrolyte. The above upper limit value and lower limit value can be arbitrarily combined.
• D10, D50, and D90 mean particle diameters measured by a particle size distribution measuring device using a laser diffraction / scattering method.
• the particle size distribution width of the nickel composite hydroxide particles of the present invention is not particularly limited and can be appropriately selected depending on the conditions of use of the positive electrode active material, for example, the lower limit of (D90-D10) / D50. Is preferably 0.40 or more, more preferably 0.50 or more, and particularly preferably 0.70 or more, from the viewpoint of improving the loading density of the positive electrode active material.
• the upper limit of (D90-D10) / D50 of the nickel composite hydroxide particles of the present invention makes various characteristics of the positive electrode active material uniform regardless of the particle size of the nickel composite hydroxide particles. From this point of view, 1.10 or less is preferable, and 1.00 or less is particularly preferable.
• the above upper limit value and lower limit value can be arbitrarily combined.
• the BET specific surface area of the nickel composite hydroxide particles of the present invention is not particularly limited, but for example, the lower limit thereof is from the viewpoint of improving the filling degree of the positive electrode active material in the positive electrode and the contact area with the non-aqueous electrolyte. 30 m 2 / g or more is preferable, and 35 m 2 / g or more is particularly preferable.
• the upper limit of the BET specific surface area of the nickel composite hydroxide particles of the present invention, from the viewpoint of improving the crush strength of the positive electrode active material is preferably not more than 60 m 2 / g, and particularly preferably 50 m 2 / g.
• the above upper limit value and lower limit value can be arbitrarily combined.
• a solution containing a metal salt for example, a solution containing a nickel salt (for example, sulfate), a cobalt salt (for example, a sulfate) and a salt of an added metal element (for example, a sulfate) is mixed with the solution.
• a neutralization reaction is carried out in the reaction vessel to prepare crude nickel composite hydroxide particles, which are in the form of a slurry containing the crude nickel composite hydroxide particles.
• a suspension of As the solvent of the suspension, for example, water is used.
• the complexing agent is not particularly limited as long as it can form a complex with an ion of a metal element, for example, nickel, cobalt, or an ion of an additive metal element in an aqueous solution, and examples thereof include an ammonium ion feeder. Be done.
• the ammonium ion feeder include aqueous ammonia, ammonium sulfate, ammonium chloride, ammonium carbonate, ammonium fluoride and the like.
• an alkali metal hydroxide for example, sodium hydroxide or potassium hydroxide
• the metal of the metal salt solution for example, nickel, cobalt, added metal
• the metal of the metal salt solution for example, nickel, cobalt, added metal
• the element undergoes a co-precipitation reaction to prepare crude nickel composite hydroxide particles.
• the temperature of the reaction vessel is controlled in the range of, for example, 10 ° C to 80 ° C, preferably 20 to 70 ° C.
• the pH adjuster and the ammonium ion feeder are supplied to the reaction vessel to cause a co-precipitation reaction, the ammonia concentration of the mixture in the reaction vessel and the pH based on the liquid temperature of 40 ° C.
• the reaction vessel is charged.
• the stirring rotation speed and residence time of the installed agitator within a predetermined range, the void ratio between the nickel composite hydroxide particles can be adjusted to 45.0% or more and 55.0% or less, and the nickel composite hydroxylation can be adjusted.
• the average circularity of the particles can be adjusted to 0.85 or more and 0.94 or less.
• the preferable range of the ammonia concentration and the pH based on the liquid temperature of 40 ° C. may need to be adjusted depending on the composition of the crude nickel composite hydroxide particles.
• the ammonia concentration is 12.0 g / L. Less than is preferable, and 7.0 g / L or more and 11.0 g / L or less are particularly preferable.
• the pH based on the liquid temperature of 40 ° C. is preferably 11.0 or more and 12.5 or less, and particularly preferably 11.5 or more and 12.3 or less.
• the stirring rotation speed of the stirring device needs to be appropriately adjusted because the shearing force applied to the particles changes depending on the volume of the reaction tank, the type of the stirring blade, and the residence time. For example, when three propeller blades are used in a reaction vessel having a volume of 15 L and a coprecipitation reaction is carried out with a residence time of 5 to 10 hours, the stirring rotation speed is preferably 1000 rpm or more and 1500 rpm or less, and particularly preferably 1100 rpm or more and 1400 rpm or less. ..
• Examples of the stirring device used in the method for producing nickel composite hydroxide particles of the present invention include a stirring device having a stirring blade having a plurality of propeller blades at the tip of the stirring shaft.
• a batch type that does not discharge can be mentioned.
• the crude nickel composite hydroxide particles obtained in the neutralization reaction step are filtered from the suspension and then washed with an alkaline aqueous solution to remove impurities contained in the crude nickel composite hydroxide particles.
• Purified nickel composite hydroxide particles nickel composite hydroxide particles of the present invention
• solid-liquid separation is performed, and if necessary, the solid phase containing the nickel composite hydroxide particles is washed with water, and the nickel composite hydroxide particles are heat-treated and dried to obtain powdery nickel composite water. Oxide particles can be obtained.
• the positive electrode active material of the non-aqueous electrolyte secondary battery using the nickel composite hydroxide particles of the present invention as a precursor (hereinafter, may be simply referred to as “the positive electrode active material of the present invention”) will be described.
• the positive electrode active material of the present invention is in an embodiment in which the nickel composite hydroxide particles of the present invention, which are precursors, are fired with, for example, a lithium compound.
• the crystal structure of the positive electrode active material of the present invention is a layered structure, and is more preferably a hexagonal crystal structure or a monoclinic crystal structure from the viewpoint of obtaining a secondary battery having a high discharge capacity.
• the positive electrode active material of the present invention can be used, for example, as the positive electrode active material of a lithium ion secondary battery.
• a step of preparing nickel composite hydroxide particles into nickel composite oxide particles may be carried out in advance.
• oxidation by firing at a temperature of 300 ° C. or higher and 800 ° C. or lower for 1 hour or more and 10 hours or less in an atmosphere in which oxygen gas is present. Processing can be mentioned.
• a method for producing a positive electrode active material using the nickel composite hydroxide particles of the present invention as a precursor will be described.
• a lithium compound is added to nickel composite hydroxide particles or nickel composite oxide particles to prepare nickel composite hydroxide particles or nickel composite oxide particles and a lithium compound.
• the lithium compound is not particularly limited as long as it is a compound having lithium, and examples thereof include lithium carbonate and lithium hydroxide.
• the positive electrode active material of the present invention can be produced by calcining the mixture obtained as described above.
• the firing conditions include a firing temperature of 700 ° C. or higher and 1000 ° C. or lower, a heating rate of 50 ° C./h or higher and 300 ° C./h or lower, and a firing time of 5 hours or more and 20 hours or less.
• the firing atmosphere is not particularly limited, and examples thereof include the atmosphere and oxygen.
• the firing furnace used for firing is not particularly limited, and examples thereof include a stationary box furnace and a roller Haworth continuous furnace.
• the fired product obtained as described above may be washed.
• Pure water or an alkaline cleaning solution can be used for cleaning.
• the alkaline cleaning solution include LiOH (lithium hydroxide), NaOH (sodium hydroxide), KOH (potassium hydroxide), Li 2 CO 3 (lithium carbonate), Na 2 CO 3 (sodium carbonate), and K 2 CO 3.
• Examples thereof include an aqueous solution of one or more hydroxides selected from the group consisting of (potassium carbonate) and (NH 4 ) 2 CO 3 (ammonium carbonate) and hydrates thereof. Ammonia can also be used as the alkaline cleaning solution.
• the cleaning step as a method of bringing the cleaning liquid into contact with the fired product, for example, a method of putting the fired product into the aqueous solution of each cleaning liquid and stirring it, or a method of applying the aqueous solution of each cleaning liquid as shower water to the fired product.
• a method in which the fired product is put into the aqueous solution of the cleaning liquid and stirred, the fired product is separated from the aqueous solution of each cleaning liquid, and then the aqueous solution of each cleaning liquid is used as shower water and applied to the fired product after separation. can be mentioned.
• the cleaning material When performing the above cleaning, after cleaning, the cleaning material is separated from the cleaning liquid by filtration or the like, and heat treatment is performed.
• the heat treatment conditions include a heat treatment temperature of 100 ° C. or higher and 600 ° C. or lower, and a heat treatment time of 1 hour or longer and 20 hours or lower.
• the atmosphere of the heat treatment is not particularly limited, and examples thereof include an atmosphere, oxygen, and a vacuum atmosphere.
• the positive electrode includes a positive electrode current collector and a positive electrode active material layer using the positive electrode active material of the present invention formed on the surface of the positive electrode current collector.
• the positive electrode active material layer has the positive electrode active material of the present invention, a binder (binding agent), and, if necessary, a conductive auxiliary agent.
• the conductive auxiliary agent is not particularly limited as long as it can be used for a non-aqueous electrolyte secondary battery, and for example, a carbon material can be used. Examples of the carbon material include graphite powder, carbon black (for example, acetylene black), and fibrous carbon material.
• the binder is not particularly limited, but is limited to polymer resins such as polyvinylidene fluoride (PVdF), butadiene rubber (BR), polyvinyl alcohol (PVA), carboxymethyl cellulose (CMC), polytetrafluoroethylene (PTFE), and the like. A combination of these can be mentioned.
• the positive electrode current collector is not particularly limited, but a band-shaped member made of a metal material such as Al, Ni, or stainless steel can be used. Among them, from the viewpoint of being easy to process and inexpensive, examples thereof include those made of Al as a forming material and processed into a thin film.
• a positive electrode active material slurry is prepared by mixing the positive electrode active material of the present invention, a binder, and a conductive auxiliary agent if necessary.
• the positive electrode active material slurry is applied to a positive electrode current collector by a known filling method, dried, pressed and fixed to obtain a positive electrode.
• a positive electrode obtained as described above a negative electrode including a negative electrode current collector and a negative electrode active material layer containing a negative electrode active material formed on the surface of the negative electrode current collector, an electrolytic solution containing a predetermined electrolyte, and a separator.
• LiClO 4 LiPF 6, LiAsF 6, LiSbF 6, LiBF 4, LiCF 3 SO 3, LiN (SO 2 CF 3) 2, LiN (SO 2 C 2 F 5) 2 , LiN (SO 2 CF 3 ) (COCF 3 ), Li (C 4 F 9 SO 3 ), LiC (SO 2 CF 3 ) 3 , Li 2 B 10 Cl 10 , LiBOB (where BOB is bis (oxalato) ) Borate), LiFSI (here, FSI stands for bis (fluorosulfonyl) image), lower aliphatic carboxylic acid lithium salt, lithium salt such as LiAlCl 4 and the like. These may be used alone or in combination of two or more.
• Examples of the solvent of the electrolyte contained in the electrolytic solution include propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, 4-trifluoromethyl-1,3-dioxolan-2-one, 1,2.
• Carbonates such as -di (methoxycarbonyloxy) ethane; 1,2-dimethoxyethane, 1,3-dimethoxypropane, pentafluoropropylmethyl ether, 2,2,3,3-tetrafluoropropyldifluoromethyl ether, tetrahydrofuran, Ethers such as 2-methyl tetrahydrofuran; esters such as methyl formate, methyl acetate, ⁇ -butyrolactone; nitriles such as acetonitrile and butyronitrile; amides such as N, N-dimethylformamide, N, N-dimethylacetamide; 3 Carbamates such as -methyl-2-oxazolidone; sulfur-containing compounds such as sulfolane, dimethylsulfoxide, and 1,3-propanesartone, or those in which a fluoro group is further introduced into these organic solvents (hydrogen atoms of the dispersion medium).
• a solid electrolyte may be used instead of the electrolytic solution containing the electrolyte.
• the solid electrolyte include organic polymer electrolytes such as polyethylene oxide-based polymer compounds and polymer compounds containing at least one of a polyorganosiloxane chain or a polyoxyalkylene chain.
• a gel type compound in which a non-aqueous electrolytic solution is retained in a polymer compound can also be used.
• the solid electrolytes include Li 2 S-SiS 2 , Li 2 S-GeS 2 , Li 2 S-P 2 S 5 , Li 2 S-B 2 S 3 , Li 2 S-SiS 2 -Li 3 PO 4 an inorganic solid electrolyte containing sulfides such as Li 2 S-SiS 2 -Li 2 SO 4, Li 2 S-GeS 2 -P 2 S 5 can be mentioned. These may be used alone or in combination of two or more.
• the separator examples include materials having a form such as a porous film, a non-woven fabric, and a woven fabric using a material such as a polyolefin resin such as polyethylene and polypropylene, a fluororesin, and a nitrogen-containing aromatic polymer.
• stirrer one having a stirrer blade having three propeller blades at the tip of the stirring shaft was used.
• the temperature of the mixed solution in the reaction vessel was maintained at 40.0 ° C.
• the crude nickel composite hydroxide particles produced by the neutralization reaction were allowed to stay in the reaction vessel for 10 hours, then overflowed from the overflow pipe of the reaction vessel and taken out as a suspension.
• the suspension of the crude nickel composite hydroxide particles taken out was filtered, washed with an alkaline aqueous solution, and solid-liquid separated. Then, the separated solid phase was washed with water, and further subjected to each treatment of dehydration and drying to obtain purified nickel composite hydroxide particles.
• Example 2 Production of Nickel Composite Hydroxide Particles of Example 2 Same as Example 1 except that the pH of the mixed solution in the reaction vessel was maintained at 11.9 based on the liquid temperature of 40 ° C. and the ammonia concentration was maintained at 7.5 g / L. To obtain purified nickel composite hydroxide particles.
• Example 3 Production of Nickel Composite Hydroxide Particles of Example 3 The ratio of nickel sulfate, cobalt sulfate and aluminum sulfate was changed, the pH of the mixture in the reaction vessel was 12.0 based on the liquid temperature of 40 ° C, and the ammonia concentration was 9. Purified nickel composite hydroxide particles were obtained in the same manner as in Example 1 except that the concentration was maintained at 0 g / L.
• Example 4 Production of Nickel Composite Hydroxide Particles of Example 4 The ratio of nickel sulfate, cobalt sulfate and aluminum sulfate was changed to the same ratio as in Example 3, and the temperature of the mixed solution in the reaction vessel was changed to 45.0 ° C. for the reaction. Purified nickel composite hydroxide particles were obtained in the same manner as in Example 1 except that the residence time in the tank was 6 hours.
• Nickel Composite Hydroxide Particles of Comparative Example The pH of the mixed solution in the reaction tank was maintained at 12.7 based on the liquid temperature of 40 ° C., the ammonia concentration was maintained at 12.0 g / L, the stirring speed was 1500 rpm, and the reaction tank was used. Purified nickel composite hydroxide particles were obtained in the same manner as in Example 1 except that the particles were allowed to stay in the mixture for 14 hours.
• the evaluation items of the physical properties of the nickel composite hydroxide particles of Examples 1 to 4 and Comparative Examples are as follows.
• composition analysis After dissolving the obtained nickel composite hydroxide particles in hydrochloric acid, an inductively coupled plasma emission spectrometer (Optima 7300DV, manufactured by PerkinElmer Japan Co., Ltd.) is used. It was done using.
• Table 1 below shows the evaluation results of the physical properties of the nickel composite hydroxide particles of Examples 1 to 4 and Comparative Examples.
• Porosity (%) Nickel composite hydroxide particles were placed in a cell with a diameter of 10 mm and a height of 100 mm (volume 7.85 ml) using a powder compressor, which is an accessory of the high-precision surface tension meter DY-700 (manufactured by Kyowa Interface Science Co., Ltd.).
• the compressed volume (V) of the nickel composite hydroxide particles per 6.5 g of mass was measured by accommodating 6.5 g of the mass and compressing at a pressure of 21.2 MPa. From the true density (d) of the nickel composite hydroxide particles, the porosity was calculated by [mass of V-composite hydroxide particles ⁇ (1 / d)] / V ⁇ 100.
• the true density (d) was measured using a gas replacement type dry automatic density meter "Accupic II 1340" (manufactured by Shimadzu Corporation).
• the measurement conditions for the true density were a filling pressure of 19.500 psig, an equilibrium rate of 0.005 psig / min, a sample weight of 3.0000 g, and a helium gas as the gas.
• Nickel composite hydroxide particles Nickel composite hydroxide using a wet flow type particle size / shape analyzer "FPIA-3000S" (manufactured by Sysmex Co., Ltd.) and an objective lens standard (10x). After measuring the particles under the HRP measurement mode condition, the circularity was analyzed based on the number of particles, and the average value was calculated to obtain the average circularity.
• FPIA-3000S wet flow type particle size / shape analyzer
• Table 2 below shows the average circularity, true density, and porosity of the nickel composite hydroxide particles of Examples 1 to 4 and Comparative Examples.
• the nickel composites of Examples 1 and Comparative Examples A positive electrode active material was produced using hydroxide particles.
• a step of oxidizing the nickel composite hydroxide particles to prepare the nickel composite oxide particles was carried out in advance.
• nickel composite oxide particles of Example 1 and Comparative Example were prepared by firing at a temperature of 690 ° C. for 5 hours in an atmospheric atmosphere.
• lithium hydroxide powder was added and mixed with the nickel composite oxide particles of Example 1 and Comparative Example so that the molar ratio of Li / (Ni + Co + Al) was 1.07, respectively, and nickel composite oxidation was performed.
• a mixed powder of physical particles and lithium hydroxide was obtained.
• the obtained mixed powder was calcined to obtain lithium metal composite oxide particles.
• the firing conditions were an oxygen atmosphere, a firing temperature of 700 ° C., a heating rate of 200 ° C./h, and a firing time of 6 hours.
• a box furnace was used for firing.
• the lithium metal composite oxide particles obtained as described above were washed with water.
• the washing was carried out by adding a lithium metal composite oxide to pure water, stirring the slurry-like liquid obtained for 10 minutes, and dehydrating the liquid.
• the wet cake obtained by the above washing was heat-treated at 150 ° C. for 12 hours in a vacuum atmosphere to obtain a positive electrode active material.
• a positive electrode plate was produced using the positive electrode active material obtained as described above, and an evaluation battery was assembled using the produced positive electrode plate. Specifically, the obtained positive electrode active material, the conductive agent (acetylene black), and the binder (polyvinylidene fluoride) were mixed at a weight ratio of 92: 5: 3, respectively, and N-methyl-2- Pyrrolidone was added and kneaded and dispersed to prepare a slurry of the positive electrode active material. The obtained slurry was applied to an aluminum foil using a baker-type applicator and dried at 60 ° C. for 3 hours and at 150 ° C. for 12 hours. A roll-pressed electrode after drying was punched out to an area of 1.65 cm 2 and used as a positive electrode plate.
• the conductive agent acetylene black
• the binder polyvinylidene fluoride
• the positive electrode plate obtained as described above is placed on the lower lid of a part for coin-type battery R2032 (manufactured by Hosen Co., Ltd.) with the aluminum foil side facing down, and a laminated film separator (porous polyethylene) is placed on the lower lid. A heat-resistant porous layer (thickness 16 ⁇ m) was placed on the quality film. 300 ⁇ l of the electrolytic solution was injected therein.
• the electrolytic solution used was a mixture of ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate in a 30:35:35 (volume ratio) mixture in which LiPF 6 was dissolved at a concentration of 1 mol / l.
• the negative electrode was placed above the laminated film separator, covered with a gasket, and crimped with a caulking machine to produce a lithium secondary battery (coin-type battery R2032).
• Discharge capacity Charge / discharge was performed under the following conditions, and the discharge capacity of the initial charge / discharge was defined as the discharge capacity. The discharge capacity was evaluated at a ratio of 100 in Examples. Test temperature: 25 ° C Maximum charge voltage 4.3V, charge current 0.2C, constant current constant voltage charge Minimum discharge voltage 2.5V, discharge current 0.2C, constant current discharge (2) Charge / discharge efficiency The charge / discharge efficiency is the charge / discharge efficiency in the above charge / discharge test. The ratio of the initial discharge capacity to the initial charge capacity was defined as the charge / discharge efficiency. The charge / discharge efficiency was evaluated at a ratio of 100 in Examples.
• Example 1 in which the positive electrode active material was prepared using the precursor (nickel composite hydroxide particles) having a porosity of 46.1%, excellent discharge capacity and charge / discharge efficiency were obtained.
• the average circularity of the precursor was 0.90.
• the average circularity was 0.87, and the average circularity was 0.85 or more and 0.94 or less as in Example 1.
• Example 3 in which the porosity is 49.5% and the porosity is 45.0% or more and 55.0% or less as in Example 1, excellent discharge capacity and charge / discharge are performed as in Example 1. It turns out that efficiency can be obtained.
• Example 3 in which the porosity is 49.5% and the porosity is 45.0% or more and 55.0% or less as in Example 1, excellent discharge capacity and charge / discharge are performed as in Example 1. It turns out that efficiency can be obtained.
• Example 4 in which the porosity is 51.3% and the porosity is 45.0% or more and 55.0% or less as in Example 1, excellent discharge capacity and charge / discharge are performed as in Example 1. It turns out that efficiency can be obtained.
• Example 4 in Example 4, the average circularity was 0.88, and the average circularity was 0.85 or more and 0.94 or less as in Example 1.
• the nickel composite hydroxide particles of the present invention can be mounted on a secondary battery using a non-aqueous electrolyte to obtain a positive electrode active material capable of exhibiting high discharge capacity and high charge / discharge efficiency. Since it can be used as a precursor, it can be used in a wide range of fields such as portable devices and vehicles.

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