US20190013519A1 - Positive-electrode active material precursor for nonaqueous electrolyte secondary battery, positive-electrode active material for nonaqueous electrolyte secondary battery, method for manufacturing positive-electrode active material precursor for nonaqueous electrolyte secondary battery, and method for manufacturing positive-electrode active material for nonaqueous electrolyte secondary battery - Google Patents

Positive-electrode active material precursor for nonaqueous electrolyte secondary battery, positive-electrode active material for nonaqueous electrolyte secondary battery, method for manufacturing positive-electrode active material precursor for nonaqueous electrolyte secondary battery, and method for manufacturing positive-electrode active material for nonaqueous electrolyte secondary battery Download PDF

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US20190013519A1
US20190013519A1 US16/067,218 US201716067218A US2019013519A1 US 20190013519 A1 US20190013519 A1 US 20190013519A1 US 201716067218 A US201716067218 A US 201716067218A US 2019013519 A1 US2019013519 A1 US 2019013519A1
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aqueous solution
positive
active material
electrode active
equal
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Satoshi Matsumoto
Shuuzou OZAWA
Kikoo Uekusa
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Sumitomo Metal Mining Co Ltd
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Sumitomo Metal Mining Co Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525Selection 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
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00Compounds of nickel
    • C01G53/006Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00Compounds of nickel
    • C01G53/06Carbonates
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00Compounds of nickel
    • C01G53/40Nickelates
    • C01G53/42Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505Selection 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
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00Crystal-structural characteristics
    • C01P2002/50Solid solutions
    • C01P2002/52Solid solutions containing elements as dopants
    • C01P2002/54Solid solutions containing elements as dopants one element only
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/01Particle morphology depicted by an image
    • C01P2004/03Particle morphology depicted by an image obtained by SEM
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/30Particle morphology extending in three dimensions
    • C01P2004/32Spheres
    • C01P2004/34Spheres hollow
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/60Particles characterised by their size
    • C01P2004/61Micrometer sized, i.e. from 1-100 micrometer
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/40Electric properties
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M2004/025Electrodes composed of, or comprising, active material with shapes other than plane or cylindrical
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M2004/026Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028Positive electrodes
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Definitions

  • the present invention relates to a positive-electrode active material precursor for a nonaqueous electrolyte secondary battery, a positive-electrode active material for a nonaqueous electrolyte secondary battery, a method for manufacturing a positive-electrode active material precursor for a nonaqueous electrolyte secondary battery, and a method for manufacturing a positive-electrode active material for a nonaqueous electrolyte secondary battery.
  • a lithium-ion secondary battery is constituted with a negative electrode, a positive electrode, an electrolyte solution, and the like; as an active material in the negative electrode and the positive electrode, materials capable of sustaining lithium insertion and disinsertion are used.
  • lithium-ion secondary batteries that use lithium metal composite oxide having a layered or spinel structure as the positive electrode material have been advanced for practical use because a voltage as high as 4 V can be obtained, and hence, a high energy density can be realized.
  • lithium-cobalt composite oxide LiCoO 2
  • LiNiO 2 lithium-nickel composite oxide
  • nickel cheaper than cobalt lithium-nickel-cobalt-manganese composite oxide
  • LiMn 2 O 4 lithium-manganese composite oxide
  • manganese lithium-nickel-cobalt-manganese composite oxide
  • LiNi 0.5 Mn 0.5 O 2 lithium-nickel-cobalt-manganese composite oxide
  • lithium-rich nickel-cobalt-manganese composite oxide Li 2 MnO 3 —LiNi x Mn y Co z O 2 ).
  • lithium-rich nickel-cobalt-manganese composite oxide Li 2 MnO 3 —LiNi x Mn y Co z O 2
  • This lithium-rich nickel-cobalt-manganese composite oxide is a layered compound as is lithium-cobalt composite oxide or lithium-nickel composite oxide (see Non-Patent Document 1).
  • Patent Document 1 methods for manufacturing a precursor for obtaining lithium-rich nickel-cobalt-manganese composite oxide are disclosed in, for example, Patent Document 1 and Patent Document 2.
  • a positive-electrode active material used as the positive electrode material needs to have a large reaction surface area. Therefore, one may consider forming a particle to be contained in the positive-electrode active material, for example, as a particle having a hollow structure.
  • Patent Documents 1 and 2 disclose methods for manufacturing precursors, and compositions of positive-electrode active materials to be manufactured by using the precursors, the documents do not mention the structure of the particle of the positive-electrode active material, and in particular, do not examine the internal structure of a secondary particle.
  • the positive-electrode active material precursor includes secondary particles having an average particle diameter greater than or equal to 4 ⁇ m and less than or equal to 9 ⁇ m.
  • the secondary particle includes a sparse central portion and a dense outer shell portion outside of the central portion, formed of primary particles.
  • a positive-electrode active material precursor for a nonaqueous electrolyte secondary battery which enables to form a positive-electrode active material for the nonaqueous electrolyte secondary battery containing particles having a hollow structure.
  • FIG. 1 is an SEM image of a positive-electrode active material precursor for a nonaqueous electrolyte secondary battery according to an embodiment of the present invention
  • FIG. 2A is an SEM image of a positive-electrode active material for a nonaqueous electrolyte secondary battery obtained in Example 1 according to the present invention
  • FIG. 2B is a cross-sectional SEM image of a positive-electrode active material for a nonaqueous electrolyte secondary battery obtained in Example 1 according to the present invention.
  • FIG. 3 is a cross-sectional configuration diagram of a secondary battery produced in Examples and Comparative examples.
  • additive elements M in the general formula of the above nickel-cobalt-manganese carbonate compound contained in the positive-electrode active material precursor for the nonaqueous electrolyte secondary battery in the embodiment include Mo.
  • the additive elements M of the nickel-cobalt-manganese carbonate compound including Mo enable to raise the initial discharge capacity of the nonaqueous electrolyte secondary battery that uses the positive-electrode active material for the nonaqueous electrolyte secondary battery obtained from the positive-electrode active material precursor for the nonaqueous electrolyte secondary battery including the nickel-cobalt-manganese carbonate compound.
  • the content ratio of Mo is greater than or equal to 0.5 at % and less than or equal to 5 at % among the metal components in the above nickel-cobalt-manganese carbonate compound, namely, among Ni, Co, Mn, and the additive elements M.
  • having the content ratio of Mo greater than or equal to 0.5 at % among the metal components in the nickel-cobalt-manganese carbonate compound especially enables to raise the initial discharge capacity of the nonaqueous electrolyte secondary battery that uses the positive-electrode active material for the nonaqueous electrolyte secondary battery obtained from the positive-electrode active material precursor for the nonaqueous electrolyte secondary battery including the nickel-cobalt-manganese carbonate compound.
  • the positive-electrode active material precursor for the nonaqueous electrolyte secondary battery in the embodiment may contain a nickel-cobalt-manganese carbonate compound, or may be formed of a nickel-cobalt-manganese carbonate compound.
  • the precursor in the embodiment can have virtually spherical secondary particles formed by aggregated fine primary particles having a high isotropy.
  • the precursor in the embodiment may contain secondary particles having the average particle diameter greater than or equal to 4 ⁇ m and less than or equal to 9 ⁇ m. Note that the precursor in the embodiment may be formed of the above secondary particles.
  • the average particle diameter means a particle diameter calculated from a particle size distribution obtained with a laser diffraction and scattering method, with which the numbers of particles in respective particle diameter segments are accumulated to identify a particle diameter corresponding to the accumulated volume reaching 50% of the sum total volume of all the particles.
  • the average particle diameter in this specification means the same.
  • a secondary particle contained in the precursor in the embodiment may have a sparse central portion constituted with fine primary particles, and a dense outer shell portion outside of the central portion.
  • the precursor in the embodiment can be especially suitably used as a material of a positive-electrode active material for a nonaqueous electrolyte secondary battery in the embodiment (also simply referred as the “positive-electrode active material”, below) that has a hollow structure as will be described later.
  • FIG. 1 shows an example of a scanning electron microscope photograph (also simply referred as an “SEM”, below) of the precursor in the embodiment.
  • the precursor in the embodiment contains virtually spherical secondary particles; specifically, the precursor contains virtually spherical secondary particles formed by aggregated multiple fine granular primary particles.
  • the particle has a structure that includes a sparse central portion formed of fine primary particles on the inside, and includes a dense outer shell portion on the outside.
  • the above central portion has a structure that has many voids between aggregated fine primary particles, and has the outer shell portion formed of dense primary particles outside of the central portion. Therefore, in the case of sintering the precursor in the embodiment, in the central portion, contraction caused by sintering starts occurring at a lower temperature compared with the outer shell portion. Then, during the sintering, the sintering proceeds from the center of a secondary particle where the sintering has started at the lower temperature, toward the outer shell portion where the sintering lags behind, and thereby, contraction occurs outward, to generate a space in the central portion. Also, considering the central portion has a lower density and a greater contraction rate, the central portion becomes to have a sufficient large space. In this way, the positive-electrode active material obtained after the sintering can have a hollow structure.
  • Secondary particles contained in the positive-electrode active material obtained by sintering the precursor in the embodiment may have a form of aggregated fine granular primary particle.
  • fine primary particles forming secondary particles contained in the positive-electrode active material have the average particle diameter less than or equal to 300 nm. This is because if the average particle diameter of primary particles exceeds 300 nm, sintering tends to proceed easily, and it may become difficult to have an electrolytic solution permeate into the hollow portion. If it is difficult to have an electrolytic solution permeate into the hollow portion, it may become difficult to sufficiently exhibit improvement in the rate characteristic, which is an advantage of the positive-electrode active material including hollow secondary particles.
  • the thickness of the outer shell portion is greater than or equal to 5% and less than or equal to 30% in terms of the ratio to the particle diameter of the secondary particle. Having the thickness of the outer shell portion greater than or equal to 5% in terms of the ratio to the particle diameter of the secondary particle enables to securely prevent the particle from being crushed in a pressing process when forming an electrode sheet that uses the positive-electrode active material. Therefore, the skeleton can be maintained after the pressing process, which enables to sufficiently improve the battery performance. However, if exceeding 30%, the central portion may not be formed to have a sufficient size, and an electrolytic solution may be poorly permeated; in such a case, improvement in the rate characteristic cannot be expected.
  • the particle diameter of a fine granular primary particle of the positive-electrode active material, and the ratio of the thickness of the outer shell portion to the particle diameter of a secondary particle in terms of the particle diameter of the secondary particle, which have been described as above, can be measured by observing the cross-section of the positive-electrode active material by using an SEM.
  • multiple secondary particles as particles of the positive-electrode active material are embedded in resin or the like, to which cross-sectional polisher processing or the like is applied so as to put it into a state in which cross-sectional observation of the particles can be performed. Then, the diameter or the maximum length of observable secondary particles is measured on a SEM image, from which calculation can be made for an average value of the ratio to the thickness of the outer shell portion.
  • the number of secondary particles to be evaluated is not limited in particular; it is favorable to evaluate multiple secondary particles, for example, 50 or more secondary particles.
  • a distance is measured for two points with which the shortest distance is obtained between the circumference of the outer shell portion and the inner circumference on the central portion side, to calculate the average thickness of the outer shell portion for each particle. Then, the average thickness is divided by a distance between any two points with which a maximum distance is obtained on the circumference of the secondary particle, as the secondary particle diameter; this enables to calculate the above ratio of the thickness of the outer shell portion for each particle.
  • secondary particles contained in the precursor in the embodiment has the average particle diameter greater than or equal to 4 ⁇ m and less than or equal to 9 ⁇ m, and it is more favorable to have the average particle diameter greater than or equal to 5 ⁇ m and less than or equal to 7 ⁇ m.
  • Having the average particle diameter greater than or equal to 4 ⁇ m and less than or equal to 9 ⁇ m enables to easily adjust secondary particles contained in the positive-electrode active material to be obtained from the precursor in the embodiment as the raw material, to have a predetermined average particle diameter, for example, greater than or equal to 4 ⁇ m and less than or equal to 8 ⁇ m.
  • the particle diameter of secondary particles contained in the precursor particles correlates with the particle diameter of secondary particles contained in the positive-electrode active material to be obtained, and hence, has an influence on characteristics of a battery that uses the positive-electrode active material as the positive electrode material.
  • the average particle diameter of secondary particles contained in the precursor in the embodiment is less than 4 ⁇ m, the average particle diameter of secondary particles contained in the positive-electrode active material to be obtained may become smaller; the packing density of the positive electrode may decline; and the battery capacity per volume may decline.
  • the average particle diameter of secondary particles contained in the precursor exceeds 9 ⁇ m, the specific surface area of the positive-electrode active material may decline; the interface with the electrolytic solution decreases; and the resistance of the positive electrode rises.
  • the void volume becomes greater, and it may become difficult to realize the electric discharge capacity per weight.
  • the method for manufacturing the precursor in the embodiment can produce the precursor as described already, the contents already described may be omitted in part.
  • the method for manufacturing the precursor in the embodiment is a method for manufacturing the precursor by crystallization reaction, which includes an initial aqueous solution preparation process, a nucleation process, and a nucleus growth process as will be described later, and may be performed, for example, by batch reactive crystallization. Note that the obtained precursor may be washed and dried as necessary.
  • the method may include the following processes.
  • the pH value of the mixed aqueous solution may be controlled to become greater than or equal to 8.0 at the reference reaction temperature of 25° C. by adding an alkaline aqueous solution; and in the nucleus growth process, the pH value of the mixed aqueous solution may be controlled to become greater than or equal to 6.0 and less than or equal to 7.5 at the reference reaction temperature of 25° C. by adding an alkaline aqueous solution.
  • the nucleation process may take a time greater than or equal to 1/20 and less than or equal to 3/10 of the combined time for adding the aqueous solution that contains nickel as a metal component, the aqueous solution that contains cobalt as a metal component, the aqueous solution that contains manganese as a metal component, and the ammonium ion supplier, to the initial aqueous solution.
  • the initial aqueous solution preparation process it is possible to prepare an initial aqueous solution that contains an ammonium ion supplier and water, in which the pH value is controlled to be greater than or equal to 9.0 and less than or equal to 12.0 by an alkaline aqueous solution at the reference reaction temperature of 25° C., and the liquid temperature is set to be greater than or equal to 25° C. and less than or equal to 50° C.
  • ammonium ion supplier is not limited in particular, it is favorable that the ammonium ion supplier is either of, for example, an ammonium carbonate aqueous solution, ammonia water, an ammonium chloride aqueous solution, or an ammonium sulfate aqueous solution.
  • the alkaline aqueous solution is an aqueous solution of one or more substances selected from among sodium carbonate, sodium bicarbonate, potassium carbonate, sodium hydroxide, and potassium hydroxide.
  • the initial aqueous solution is formed to have the pH greater than or equal to 9.0 because crystallites to become a nucleus can be aggregated to have an appropriate size, and the average particle diameter of secondary particles contained in the obtained precursor can be controlled within a suitable range.
  • the pH value of the initial aqueous solution exceeds 12.0, nuclei may be generated excessively in the nucleation process, which may make the average particle diameter of secondary particles contained in the obtained precursor too small. Also, grape-shaped aggregated secondary particles having undetermined forms tend to be generated in a great quantity, which could be a factor to lower the repletion when formed as a positive-electrode active material. Therefore, it is favorable that the pH value of the initial aqueous solution is less than or equal to 12.0, and it is more favorable to be less than or equal to 11.0.
  • the initial aqueous solution may be prepared, for example, in a reaction vessel, and in this case, although the fluid volume of the initial aqueous solution to be prepared in the reaction vessel is not limited in particular, it is favorable to prepare a fluid volume such that the initial aqueous solution can be stirred when causing reaction in the vessel.
  • the ammonia concentration becomes greater than or equal to 3 g/L and less than or equal to 15 g/L.
  • ammonia concentration of the initial aqueous solution and the mixed aqueous solution it is favorable to control the ammonia concentration of the initial aqueous solution and the mixed aqueous solution, the latter of which will be described later, to become greater than or equal to 3 g/L and less than or equal to 15 g/L during the processes ranging from the initial aqueous solution preparation process to the nucleus growth process.
  • ammonia concentration in the initial aqueous solution and the mixed aqueous solution exceeds 15 g/L, amine complexes mainly of nickel are generated in a great quantity, the quantity not to be separated increases, and the nickel concentration in a precursor to be obtained may decline. In this case, to obtain a precursor having the target composition ratio, extra nickel needs to be added, which may lead to a cost increase. Therefore, it is favorable the ammonia concentration of the initial aqueous solution to be less than or equal to 15 g/L.
  • liquid temperature greater than or equal to 25° C. enables to maintain the saturation solubility within a proper range, for example, for the ammonium ion supplier and the alkaline aqueous solution, and enables to prevent a part of components from separating in the nucleus growth process and the like.
  • liquid temperature exceeds 50° C.
  • ammonia in the ammonium ion supplier evaporates at an accelerated rate, and hence, it may become difficult to control the ammonia concentration. Therefore, a temperature less than or equal to 50° C. is favorable as described above.
  • liquid temperature of the mixed aqueous solution is favorable to control the liquid temperature of the mixed aqueous solution to be greater than or equal to 25° C. less than or equal to 50° C. also in the nucleation process and the nucleus growth process, which will be described later.
  • the initial aqueous solution can be prepared in a reaction vessel, and it is possible to have an inactive gas atmosphere in the reaction vessel, specifically, in a space delimited with the reaction vessel, the surface of the liquid in the reaction vessel, and the lid of the reaction vessel. Specifically, it is possible to have a nitrogen gas atmosphere. In this case, it is favorable that the oxygen concentration is less than 1 vol % in the reaction vessel.
  • carbon dioxide gas may be supplied into the reaction vessel. Also in the case of supplying carbon dioxide gas, it is favorable that the oxygen concentration is less than 1 vol % in the reaction vessel. In the nucleation process and in the nucleus growth process, which will be described later, it is possible to use the same atmosphere in the reaction vessel as described here.
  • the metal-component-containing mixed aqueous solution may be prepared in this process.
  • a mixed aqueous solution so as to form nuclei, by adding and mixing, under the presence of carbonate ions, an aqueous solution that contains nickel as a metal component, an aqueous solution that contains cobalt as a metal component, an aqueous solution that contains manganese as a metal component, and an ammonium ion supplier, with the initial aqueous solution.
  • the pH value of the mixed aqueous solution described above it is possible to control the pH value of the mixed aqueous solution described above to be greater than or equal to 8.0 at the reference reaction temperature of 25° C., by adding an alkaline aqueous solution.
  • the alkaline aqueous solution can be supplied, for example, by dropping into the initial aqueous solution.
  • reactive crystallization can be performed in the nucleation process by taking a time greater than or equal to 1/20 and less than or equal to 3/10 of the total time of the crystallization, in other words, by taking a time greater than or equal to 1/20 and less than or equal to 3/10 of the combined time of the nucleation process and the nucleus growth process, by adding the metal-component-containing aqueous solutions including an aqueous solution that contains nickel as a metal component to the initial aqueous solution.
  • having the time of the nucleation process to be less than or equal to 3/10 of the crystallization time included in the entire manufacturing process enables to prevent sparse secondary particles from growing too large, and when made as a positive-electrode active material, enables to form an outer shell portion having a sufficient thickness.
  • Sufficiently securing the thickness of the outer shell portion enables to maintain the skeleton, for example, in press-forming of an electrode, and enables to especially improve the battery performance, which is favorable.
  • the same aqueous solutions can be used as in the case of the initial aqueous solution preparation process that has already been described. Also, the concentration and the like may be adjusted in a different way.
  • an aqueous solution that contains nickel as a metal component, an aqueous solution that contains cobalt as a metal component, and an aqueous solution that contains manganese as a metal component, which are to be added in the initial aqueous solution in the nucleation process will be described.
  • Each of an aqueous solution that contains nickel as a metal component, an aqueous solution that contains cobalt as a metal component, and an aqueous solution that contains manganese as a metal component may contain a metallic compound that contains the metal component.
  • an aqueous solution that contains cobalt as a metal component may contain a metallic compound that contains cobalt.
  • the metallic compound it is favorable to use a water-soluble metallic compound, and as such water-soluble metallic compounds, nitrate, sulfate, hydrochloride, and the like may be listed. Specifically, nickel sulfate, cobalt sulfate, manganese sulfate, and the like may be suitably used. Note that a compound that contains a hydrate may also be used.
  • solutions of an aqueous solution that contains nickel as a metal component, an aqueous solution that contains cobalt as a metal component, and an aqueous solution that contains manganese as a metal component may be partially or entirely mixed in advance, to be added to the initial aqueous solution as the metal-component-containing mixed aqueous solutions.
  • composition ratio of each metal in the precursor to be obtained becomes substantially the same as the composition ratio of the metal in each of the metal-component-containing mixed aqueous solutions. Therefore, it is favorable to prepare each of the metal-component-containing mixed aqueous solutions by adjusting the ratio of a metallic compound to be dissolved such that the composition ratio of each metal contained in the metal-component-containing mixed aqueous solution to be added in the initial aqueous solution in the nucleation process, becomes equivalent to the composition ratio of the metal in the precursor to be generated.
  • the metal-component-containing aqueous solutions including an aqueous solution that contains nickel as a metal component may be added simultaneously in the initial aqueous solution at predetermined ratios.
  • the metal-component-containing aqueous solutions including an aqueous solution that contains nickel as a metal component are not mixed, and individually added to the initial aqueous solution, it is favorable to prepare each of the metal-component-containing mixed aqueous solutions such that the composition ratio of each metal becomes equivalent to the composition ratio of the metal in the precursor to be generated, in the entirety of the metal-component-containing aqueous solutions to be added.
  • the adjusted individual metal-component-containing aqueous solutions can be supplied simultaneously into the reaction vessel at predetermined ratios.
  • an aqueous solution that contains one or more additive elements also simply referred as an “aqueous solution that contains the additive elements”, below
  • additive elements also simply referred as an “aqueous solution that contains the additive elements”, below
  • Mg, Ca, Al, Ti, V, Cr, Zr, Nb, Mo, and W also simply referred as the “additive element(s)”, below
  • metal-component-containing aqueous solutions including an aqueous solution that contains nickel as a metal component are mixed as a single metal-component-containing mixed aqueous solution, to be added in the initial aqueous solution, the metal-component-containing mixed aqueous solution may have been added and mixed with aqueous solutions that contain the respective additive elements.
  • metal-component-containing aqueous solutions including an aqueous solution that contains nickel as a metal component are not mixed, and individually added in the initial aqueous solution, accordingly, it is possible to add aqueous solutions that contain the respective additive elements individually to the initial aqueous solution.
  • an aqueous solution including an additive element by using, for example, a compound that contains the additive element.
  • the compounds containing the additive elements it is favorable to use water-soluble compounds that include, for example, titanium sulfate, ammonium peroxotitanate, potassium titanium oxalate, vanadium sulfate, ammonium vanadate, chromous sulfate, potassium chromate, zirconium sulfate, zirconium nitrate, niobium oxalate, ammonium molybdate, sodium tungstate, and ammonium tungstate, which can be selected in accordance with the element to be added.
  • the above additive elements of the above nickel-cobalt-manganese carbonate compound include molybdenum. Therefore, as an aqueous solution containing the additive elements, it is possible to favorably use, for example, an aqueous solution containing a compound that contains molybdenum.
  • the additive elements includes molybdenum, as described already, as described already, it is favorable that the content ratio of Mo is greater than or equal to 0.5 at % and less than or equal to 5 at % among the metal components in the above nickel-cobalt-manganese carbonate compound, namely, among Ni, Co, Mn, and the additive elements M. Therefore, it is favorable to adjust the amount of an aqueous solution to be added that contains the additive elements so that the content ratio of Mo among the metal components in the nickel-cobalt-manganese carbonate compound contained in the precursor to be obtained is within the above range.
  • the additive elements are uniformly dispersed in a secondary particle contained in the precursor (also simply referred as a “precursor particle”, below) and/or are uniformly coated on the surface of the secondary particle.
  • a mixed aqueous solution so as to form nuclei, by adding and mixing, under the presence of carbonate ions, an aqueous solution that contains nickel as a metal component, an aqueous solution that contains cobalt as a metal component, an aqueous solution that contains manganese as a metal component, and an ammonium ion supplier, with the initial aqueous solution.
  • the method of supplying carbonate ions is not limited in particular; for example, it is possible to supply carbonate ions into the mixed aqueous solution by supplying carbon dioxide gas into the reaction vessel.
  • nucleation process it is possible to form a mixed aqueous solution so as to form nuclei, by adding and mixing, under the presence of carbonate ions, an aqueous solution that contains nickel as a metal component and the like with the initial aqueous solution.
  • the concentration of the metallic compound in the mixed aqueous solution is greater than or equal to 1 mol/L and less than or equal to 2.6 mol/L, and it is more favorable to be greater than or equal to 1.5 mol/L and less than or equal to 2.2 mol/L.
  • the concentration of the metallic compound in the mixed aqueous solution exceeds 2.6 mol/L, it may exceed the saturated concentration at normal temperature, and hence, crystals may be separated again, and may clog laying pipes in a facility.
  • the concentration of a metallic compound means the concentration of the metallic compound that originates from an aqueous solution that contains nickel as a metal component; an aqueous solution that contains cobalt as a metal component; an aqueous solution that contains manganese as a metal component; and an aqueous solution that contains additive elements that have been further added depending on cases, which have been added to the mixed aqueous solution.
  • nucleus growth process it is possible to grow nuclei by adding and mixing, under the presence of carbonate ions, an aqueous solution that contains nickel as a metal component, an aqueous solution that contains cobalt as a metal component, an aqueous solution that contains manganese as a metal component, and an ammonium ion supplier, with the mixed aqueous solution formed in the nucleation process.
  • the metal-component-containing aqueous solutions including the aqueous solution that contains nickel as a metal component, the ammonium ion supplier, and the alkaline aqueous solution, and instead, to add an acid aqueous solution to the mixed aqueous solution formed in the nucleation process, so as to lower the pH value of the mixed aqueous solution.
  • it is favorable to add the acid so that the pH value of the mixed aqueous solution at the reference reaction temperature of 25° C. becomes greater than or equal to 6.0 and less than or equal to 7.5, and it is more favorable to add the acid to make the pH greater than or equal to 6.5 and less than or equal to 7.5.
  • anions in the acid of the acid aqueous solution to be used are not limited in particular, an inorganic acid may be used preferably because an organic acid having a high molecular weight has a low dissociation constant, and may provoke a buffer action of reactive crystallization.
  • Any inorganic acid has a high dissociation constant, and can be suitably used; in the case of using an inorganic acid as the acid of the acid aqueous solution, it is favorable to use an acid aqueous solution of either sulfuric acid, nitric acid, or hydrochloric acid.
  • the metal-component-containing aqueous solutions including the aqueous solution that contains nickel as a metal component, and the ammonium ion supplier with the mixed aqueous solution.
  • the nucleus growth process enables to deposit dense crystals on the surface of each sparse secondary particle formed in the nucleation process, so as to form the secondary particle having sparse and dense portions.
  • the metal-component-containing mixed aqueous solutions including the aqueous solution that contains nickel as a metal component may be partially or entirely mixed as a single metal-component-containing mixed aqueous solution to be added to the mixed aqueous solution. Also, in the case where mixing multiple metallic compounds makes specific metallic compounds react with each other to generate an unnecessary compound, each of the metal-component-containing aqueous solutions may be added individually in the initial aqueous solution.
  • aqueous solutions as in the nucleation process can be used as the metal-component-containing aqueous solutions including the aqueous solution containing nickel as a metal component, the ammonium ion supplier, and the alkaline aqueous solution. Also, the concentration and the like may be adjusted in a different way.
  • an alkaline aqueous solution in the mixed aqueous solution so as to control the pH value of the mixed aqueous solution at the reference reaction temperature of 25° C. to be greater than or equal to 6.0 and less than or equal to 7.5.
  • having the pH value of the mixed aqueous solution less than or equal to 7.5 enables to securely prevent generation of nuclei more than required for crystal growth. Therefore, it is possible to prevent spread of particle size distribution, and to obtain spherical and uniform secondary particles. Especially, it is possible to prevent generation of grape-shaped aggregated secondary particles having undetermined forms.
  • an inactive gas for example, nitrogen gas
  • it is favorable to have an inactive gas atmosphere in the reaction vessel for example, it is favorable to have a nitrogen gas atmosphere.
  • carbon dioxide gas as the source of carbonate ions
  • the nucleus growth process can be performed for a period of time in the entire time of the crystallization process in the manufacturing process, excluding the time during which the nucleation process has been performed.
  • the method for manufacturing the precursor in the embodiment may further include a coating process of coating secondary particles contained in the precursor obtained in the nucleus growth process, with the additive elements.
  • the coating process may be, for example, either one of the following processes.
  • the coating process may be a process in which a slurry having precursor particles suspended is first added with an aqueous solution that contains the additive elements, and thereby, crystallization reaction deposits the additive elements on the surface of precursor particles.
  • the coating process may be a process of spraying and drying slurry or an aqueous solution that contains the additive elements, on precursor particles.
  • the coating process may be a process of spraying and drying slurry in which precursor particles and compounds containing the additive elements are suspended.
  • the coating process may be a process of mixing precursor particles and compounds that contain the additive elements by solid-phase synthesis.
  • aqueous solutions as in the nucleation process can be used as the aqueous solutions that contains the additive elements described here.
  • an alkoxide solution that contains the additive elements may be used instead of the aqueous solutions that contain the additive elements.
  • the initial aqueous solution and the mixed aqueous solution are added with aqueous solutions that contain the additive elements, to perform the coating process so as to coat the surface of precursor particles with the additive elements, it is favorable to reduce the quantity of ions of the additive elements to be added in the initial aqueous solution and the mixed aqueous solution in the nucleation process and the nucleus growth process, by the quantity used for coating.
  • coating process that coats the surface of precursor particles with the additive elements as described above may be applied to precursor particles after completion of the nucleus growth process and after having heated.
  • the amount of the initial aqueous solution, the metal-component-containing mixed aqueous solutions, and the like supplied into the reaction vessel is not limited in particular; it is favorable to adjust the amount so that at the moment when the reactive crystallization completes, the concentration of crystallized materials is greater than or equal to 30 g/L and less than or equal to 200 g/L, and more favorably to be greater than or equal to 80 g/L and less than or equal to 150 g/L.
  • the load of a stirrer of the reaction vessel may become too heavy, and especially in the case of performing operations by a large-sized reaction vessel, a special motor having an excessive torque may be required. Therefore, it is favorable to adjust the amount of supply to the reaction vessel so that the concentration of crystallized materials may become less than or equal to 200 g/L.
  • a device adopting a scheme of not collecting generated materials until reaction in the nucleus growth process is completed for example, a normally used batch reaction vessel or the like having a stirrer installed may be considered.
  • a problem that growing particles are collected simultaneously with an overflowing liquid does not arise. Therefore, particle size distribution becomes narrow, and particles having nearly the same particle diameter can be obtained, which is favorable.
  • a device that is capable of controlling the atmosphere such as a device of a direct vent type.
  • Using a device that is capable of controlling the atmosphere in the reaction vessel enables to form precursor particles having the structure as described above, and enables to securely advance reaction of each process.
  • an aqueous solution of precursor particles which is a slurry containing the precursor particles, can be obtained. Furthermore, after having completed the nucleus growth process, a cleaning process and a drying process may be performed.
  • the slurry containing precursor particles may be filtered, and then, washed with water and filtered again.
  • Filtering may be performed by a method that is used normally, for example, by using a centrifuge and a suction filter.
  • washing with water may be performed by a method that is used normally, which simply needs to be capable of removing residual materials contained in precursor particles.
  • the drying temperature may be set, for example, greater than or equal to 100° C. and less than or equal to 230° C., to dry cleaned precursor particles.
  • the precursor can be obtained.
  • additive elements M in the general formula of the above lithium-metal compound oxide contained in the positive-electrode active material for the nonaqueous electrolyte secondary battery in the embodiment include Mo.
  • the additive elements M of the lithium-metal compound oxide including Mo enable to raise the initial discharge capacity of the nonaqueous electrolyte secondary battery that uses the positive-electrode active material containing the lithium-metal compound oxide.
  • the content ratio of Mo is greater than or equal to 0.5 at % and less than or equal to 5 at % among the metal components other than Li in the lithium-metal compound oxide, namely, among Ni, Co, Mn, and the additive elements M.
  • having the content ratio of Mo greater than or equal to 0.5 at % among the metal components in the lithium-metal compound oxide especially enables to raise the initial discharge capacity of the nonaqueous electrolyte secondary battery that uses the positive-electrode active material for the nonaqueous electrolyte secondary battery containing the lithium-metal compound oxide.
  • having the content ratio of Mo less than or equal to 5 at % among the metal components in the lithium-metal compound oxide enables to more securely prevent the sphericity of the lithium-metal compound oxide from declining.
  • the lithium-metal compound oxide may contain secondary particles having the average particle diameter greater than or equal to 4 ⁇ m and less than or equal to 8 ⁇ m, and the secondary particles may have a particle shape that includes an outer shell portion and a hollow portion surrounded by the outer shell portion.
  • secondary particles contained in the positive-electrode active material in the embodiment that have the structure including the outer shell portion and the hollow portion, and have the predetermined average particle diameter, enable the positive-electrode active material to have a high density and a high initial discharge capacity, and to be used as a positive-electrode active material for a nonaqueous electrolyte secondary battery.
  • the positive-electrode active material in the embodiment may be formed of the secondary particles described above.
  • the positive-electrode active material in the embodiment may contain a lithium-metal compound oxide, which is a lithium-rich nickel-cobalt-manganese composite oxide being a solid solution of two types of layered compounds represented by Li 2 M1O 3 and LiM2O 2 .
  • a lithium-metal compound oxide which is a lithium-rich nickel-cobalt-manganese composite oxide being a solid solution of two types of layered compounds represented by Li 2 M1O 3 and LiM2O 2 .
  • M1 represents metallic elements at least including Mn that are adjusted to be tetravalent on average
  • M2 represents metallic elements at least including Ni, Co, and Mn that are adjusted to be trivalent on average.
  • Li 2 M1O 3 is not 0% in terms of the abundance ratio of Li 2 M1O 3 and LiM2O 2 as it is lithium-rich.
  • secondary particles contained in the positive-electrode active material in the embodiment has the average particle diameter greater than or equal to 4 ⁇ m and less than or equal to 8 ⁇ m, and it is favorable to be greater than or equal to 5 ⁇ m and less than or equal to 7 ⁇ m.
  • Having the average particle diameter greater than or equal to 4 ⁇ m enables to increase the packing density of the particles when formed in a positive electrode, and to improve the battery capacity per volume of the positive electrode.
  • having the average particle diameter less than or equal to 8 ⁇ m enables to enlarge the specific surface area of the positive-electrode active material; enables to sufficiently secure the interface between the positive electrode and the electrolytic solution of the battery; enables to control the resistance of the positive electrode; and enables to improve the output characteristic of the battery.
  • adjusting the average particle diameter of the positive-electrode active material in the embodiment to be contained in a predetermined range enables to increase the battery capacity per volume in a battery that uses the positive-electrode active material in the embodiment for the positive electrode, and enables to obtain a high-output battery characteristic.
  • the secondary particle contained in the positive-electrode active material in the embodiment may have a hollow structure that includes a hollow portion on the inside of the secondary particle and an outer shell portion on the outside of the hollow portion.
  • Having such a hollow structure enables to enlarge the surface area for reaction, and allows an electrolytic solution to permeate from the interfaces or voids between primary particles in the outer shell portion, which then enables to absorb and discharge lithium through the reaction interface on the primary particle surfaces on the side of the hollow portion in the particle, by which movement of Li ions and electrons is not hindered, and thus, enables to raise the output characteristic of the battery.
  • the thickness of the outer shell portion is greater than or equal to 5% and less than or equal to 30%, and it is more favorable to be greater than or equal to 10% and less than or equal to 25% in terms of the ratio to the particle diameter of the secondary particle.
  • Having the thickness of the outer shell portion greater than or equal to 5% in terms of the ratio to the particle diameter of the secondary particle enables to raise the strength of the secondary particle; prevents the particle from fracturing when handled as a granular material and when formed in a positive electrode of a battery; and enables to raise the battery characteristic.
  • the thickness of the outer shell portion less than or equal to 30% in terms of the ratio to the particle diameter of the secondary particle enables to sufficiently secure interfaces or voids between particles through which an electrolytic solution can enter the hollow portion inside of the secondary particle. Therefore, the surface of the hollow portion, which is the inner surface of the particle, can sufficiently contribute to cell reaction, which enables to lower the positive electrode resistance, and enables to raise the output characteristic.
  • the thickness of the outer shell portion in the absolute value is within a range greater than or equal to 0.5 ⁇ m and less than or equal to 2.0 ⁇ m, and it is more favorable to be within a range greater than or equal to 0.8 ⁇ m and less than or equal to 1.5 ⁇ m.
  • the positive-electrode active material in the embodiment as the positive electrode of, for example, a 2032-type coin battery
  • a high initial discharge capacity greater than or equal to 200 mAh/g and a high rate characteristic can be obtained with the battery, which exemplifies superior characteristics as a positive-electrode active material for a nonaqueous electrolyte secondary battery.
  • the initial discharge capacity is greater than or equal to 250 mAh/g.
  • the method for manufacturing the positive-electrode active material in the embodiment is not limited in particular as long as the method can manufacture the positive-electrode active material in which particles have the structure of the positive-electrode active material as described already; it is favorable to adopt the following method because the positive electrode active can be manufactured more securely.
  • the method for manufacturing the positive-electrode active material in the embodiment may include the following processes.
  • the heat treatment temperature is set greater than or equal to 105° C. because if the heating temperature is less than 105° C., surplus moisture in precursor particles may not be removed, and the above variation cannot be controlled.
  • the heat treatment temperature is set less than or equal to 600° C. because if the heating temperature exceeds 600° C., particles may sinter by the heat treatment, and compound oxide particles having a uniform particle diameter may not be obtained. It is possible to control the above variation by obtaining, in advance by analysis, metal components contained in particles of the precursor corresponding to the heat treatment condition, and determining the ratio to the lithium compound.
  • the heat treatment atmosphere is not limited in particular, it is favorable to be a non-reducible atmosphere, and it is favorable to execute the heat treatment in an air current in which the treatment can be simply applied.
  • the heat treatment time is not limited in particular, if the time is less than 1 hour, removal of surplus moisture of the precursor may not be sufficiently performed. Therefore, it is favorable to be at least 1 hour or longer, and it is more favorable to be 2 hours or longer and 15 hours or shorter.
  • the facility used for heat treatment is not limited in particular, which simply needs to be capable of heating precursor particles in a non-reducible atmosphere, or preferably in an air current; an electric furnace or the like that does not generate gas may be used suitably.
  • the mixing process is a process of adding and mixing a lithium compound to heat-treated particles that have been obtained by heating in the above heat treatment process, to forma lithium mixture.
  • the heat-treated particles that have been obtained by heating in the heat treatment process contain nickel-cobalt-manganese carbonate compound particles and/or nickel-cobalt-manganese compound oxide particles.
  • Li/Me does not change before and after the sintering process
  • Li/Me obtained in this mixing process turns out to Li/Me in the positive-electrode active material. Therefore, mixing is performed in which Li/Me in the lithium mixture is the same as Li/Me in the positive-electrode active material to be obtained.
  • the lithium compound used for forming the lithium mixture is not limited in particular, one or more selected from among, for example, lithium hydroxide, lithium nitrate, and lithium carbonate may be preferably used as the lithium compound because these are readily available.
  • lithium hydroxide and lithium carbonate are selected from among lithium hydroxide and lithium carbonate as the lithium compound used when forming the lithium mixture.
  • a common mixer for mixing; for example, a shaker mixer, a Lödige Mixer, a Julia Mixer, a V blender, or the like may be used.
  • the sintering process is a process of sintering the lithium mixture obtained in the above mixing process, to form the positive-electrode active material.
  • the lithium mixture is sintered in the sintering process, lithium in the lithium compound diffuses in heat-treated particles, and thereby, a lithium-nickel-cobalt-manganese compound oxide is formed.
  • the sintering temperature of the lithium mixture in this process is not limited in particular; for example, it is favorable to be greater than or equal to 600° C. less than or equal to 1000° C., and it is more favorable to be greater than or equal to 800° C. less than or equal to 900° C.
  • the sintering temperature exceeds 1000° C.
  • sintering may occur violently among compound oxide particles, and abnormal particle growth may occur, which may make the sintered particles bulky to an extent that the form of spherical secondary particles having the hollow structure cannot be maintained.
  • a positive-electrode active material has a reduced specific surface area, in the case of using it for a battery, the resistance of the positive electrode may rise, and the battery capacity may decline.
  • reaction it is possible to make the reaction further uniform by holding it at a temperature near the melting point of the lithium compound for 1 hour or longer and 5 hours or shorter. In the case of holding the temperature near the melting point of the lithium compound, after that, it is possible to raise the temperature to the predetermined sintering temperature.
  • the holding time at the sintering temperature is 2 hours or longer, and it is more favorable to be 4 hours or longer and 24 hours or shorter.
  • the atmosphere for the sintering it is more favorable to be an atmosphere having the oxygen concentration greater than or equal to 18 vol % and less than or equal to 100 vol %, and it is especially favorable to be a mixed atmosphere of oxygen of such an oxygen concentration and an inactive gas. In other words, it is favorable to perform the sintering in the air or in an oxygen-containing gas.
  • the atmosphere having the oxygen concentration greater than or equal to 18 vol % is favorable because setting the oxygen concentration to be greater than or equal to 18 vol % enables to sufficiently improve crystallinity of the lithium-nickel-cobalt-manganese compound oxide.
  • the furnace used for the sintering is not limited in particular and simply needs to be capable of heating the lithium mixture in the air or in an oxygen-containing gas, an electric furnace that does not generate gas is favorable from the viewpoint of keeping the atmosphere in the furnace uniform. Also, it is possible to use either of a batch furnace or a continuous furnace.
  • the calcinating temperature is lower than the sintering temperature, and is greater than or equal to 350° C. and less than or equal to 800° C., and it is more favorable to be greater than or equal to 450° C. less than or equal to 780° C.
  • the calcinating time is 1 hour or longer and 10 hours or shorter, and it is more favorable to be 3 hours or longer and 6 hours or shorter.
  • lithium has diffused into the heat-treated particles sufficiently, which enables to obtain a uniform lithium-nickel-cobalt-manganese compound oxide, and is favorable.
  • Particles of the lithium-nickel-cobalt-manganese compound oxide obtained by the sintering process may have been aggregated or slightly sintered.
  • the particles may be cracked. This enables to obtain the positive-electrode active material in the embodiment including the lithium-nickel-cobalt-manganese compound oxide.
  • rack is used here to mean an operation to loosen an aggregate of multiple secondary particles generated by sintering or necking between the secondary particles during the sintering, by giving mechanical energy to the aggregate so as to separate the secondary particles from each other without hardly destroying the secondary particle themselves.
  • the nonaqueous electrolyte secondary battery in the embodiment can have a positive electrode that uses the positive-electrode active material as described already.
  • the nonaqueous electrolyte secondary battery in the embodiment may have substantially the same structure as a common nonaqueous electrolyte secondary battery except that the positive electrode material described already is used as the positive-electrode active material.
  • the secondary battery in the embodiment may have a structure that includes a case, a positive electrode and a negative electrode accommodated in this case, a nonaqueous electrolyte, and a separator.
  • the secondary battery in the embodiment may include an electrode body that has the positive electrode and the negative electrode stacked via the separator. Furthermore, it is possible to have a structure sealed in the case by having the nonaqueous electrolyte permeate the electrode body, and making connections, by using leads for current collection, between the positive electrode current collector of the positive electrode and a positive electrode terminal extending to the outside, and between the negative electrode current collector of the negative electrode and a negative electrode terminal extending to the outside.
  • the structure of the secondary battery in the embodiment is not limited to the above example, and the external shape to be adopted may be any of various shapes including a cylindrical shape and a stacked shape.
  • the positive electrode is a sheet-shaped member that can be formed by applying a paste of a positive-electrode composite material containing the positive-electrode active material described already, to the surface of a current collector made of, for example, aluminum foil, and drying the paste.
  • the positive electrode is properly processed in accordance with a battery to be used.
  • Such processes may include, for example, a cutting process for forming a suitable size in accordance with a target battery, a process of compression by pressure using a roll press in order to raise the electrode density, and the like.
  • the positive electrode composite material paste may be formed by adding, kneading, and mixing a solvent with the positive electrode composite material.
  • the positive electrode composite material may be formed by mixing a powdered positive-electrode active material described already with a conductive material and a binding agent.
  • the conductive material is added in order to give a suitable conductivity to the electrode.
  • This conductive material is not limited in particular; for example, carbon black materials, such as graphite (natural graphite, artificial graphite, expanded graphite, etc.), acetylene black, and Ketjenblack, may be used.
  • the binding agent plays a role of binding positive-electrode active material particles.
  • the binding agent used for this positive electrode composite material is not limited in particular; it is possible to use, for example, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), fluororubber, ethylene-propylene-diene rubber, styrene-butadiene, cellulose-based resin, and polyacrylic acid.
  • activated carbon or the like may be added to the positive electrode composite material, and by adding activated carbon or the like, it is possible to increase the capacity of electric double layers of the positive electrode.
  • the solvent is to dissolve the binding agent to disperse the positive-electrode active material, the conductive material, activated carbon, and the like in the binding agent.
  • This solvent is not limited in particular; for example, an organic solvent such as N-methyl-2-pyrrolidone may be used.
  • the mixing ratio of each substance in the positive electrode composite material paste is not limited in particular.
  • the content of the positive-electrode active material greater than or equal to 60 mass parts and less than or equal to 95 mass parts
  • the content of the conductive material greater than or equal to 1 mass part and less than or equal to 20 mass parts
  • the content of the binding agent greater than or equal to 1 mass part and less than or equal to 20 mass parts.
  • the negative electrode is a sheet-shaped member formed by applying a negative electrode composite material paste to the surface of a current collector of metallic foil such as copper, and drying the paste.
  • a negative electrode composite material paste to the surface of a current collector of metallic foil such as copper, and drying the paste.
  • components constituting the negative electrode composite material paste, its combination, and materials of the current collector are formed by substantially the same method as the positive electrode, and various processes may be performed when necessary as done with the positive electrode.
  • the negative electrode composite material paste is formed to be a paste by adding a suitable solvent to the negative electrode composite material in which a negative electrode active material and a binding agent are mixed.
  • the negative electrode active material for example, a substance containing lithium such as metallic lithium or lithium alloy, or an insertion material capable of sustaining insertion and deinsertion of lithium ions may be used.
  • the insertion material is not limited in particular; for example, a sintered object of an organic compound such as natural graphite, artificial graphite, and a phenol resin; and a powdery form of a carbon substance such as coke, may be used.
  • a sintered object of an organic compound such as natural graphite, artificial graphite, and a phenol resin
  • a powdery form of a carbon substance such as coke
  • resin containing fluoride such as PVDF
  • an organic solvent such as N-methyl-2-pyrrolidone
  • the separator is placed to be sandwiched between the positive electrode and the negative electrode, and has a function to separate the positive electrode and the negative electrode and to hold the electrolyte.
  • a separator may be a thin film of, for example, polyethylene or polypropylene having a large number of fine openings, and is not particularly limited as long as it has the above functions.
  • the nonaqueous electrolyte is obtained by dissolving a lithium salt as a supporting salt in an organic solvent.
  • organic solvent it is possible to use substances selected from among cyclic carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, and trifluoropropylene carbonate; chain carbonates such as diethyl carbonate, dimethyl carbonate, ethylmethyl carbonate, and dipropyl carbonate; ether compounds such as tetrahydrofuran, 2-methyltetrahydrofuran, and dimethoxyethane; sulfur compounds such as ethylmethylsulfone and butane sultone; and phosphorus compounds such as triethyl phosphate and trioctyl phosphate.
  • cyclic carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, and trifluoropropylene carbonate
  • chain carbonates such as diethyl carbonate, dimethyl carbonate, ethylmethyl carbonate, and dipropyl carbonate
  • ether compounds such as tetrahydrofuran, 2-methyltetrahydr
  • LiPF 6 LiBF 4 , LiClO 4 , LiAsF 6 , LiN(CF 3 SO 2 ) 2 , and a composite salt of these.
  • nonaqueous electrolyte may contain a radical scavenger, a surfactant, a flame retardant, and the like in order to improve battery characteristics.
  • the nonaqueous electrolyte secondary battery in the embodiment may have a configuration, for example, as described above that includes the positive electrode using the positive-electrode active material described already. Therefore, it is possible to obtain a high initial discharge capacity and a low positive electrode resistance, to realize a high-capacity and high-output battery.
  • the secondary battery of the embodiment is suitably used as a power source of a small mobile electronic device (a notebook personal computer, a mobile phone terminal, etc.) that demands a high capacity all the time.
  • a small mobile electronic device a notebook personal computer, a mobile phone terminal, etc.
  • the secondary battery of the embodiment is also suitable for a power source for driving a motor that demands a high output.
  • a battery is made greater in size, securing the safety may become difficult, and an expensive protection circuit may be indispensable.
  • the secondary battery of the embodiment has a superior safety, securing the safety becomes easier, the protection circuit becomes simplified, and the manufacturing cost can be reduced.
  • the reduced size and higher output enable the secondary battery of the embodiment to be suitably used as a power source for a transportation device that is installed in a limited space.
  • a precursor was prepared by the following procedure.
  • the initial aqueous solution was stirred, and the temperature in the vessel was set to 25° C. Note that the temperature had been maintained until completion of the nucleus growth process.
  • the reaction vessel was filled with a nitrogen atmosphere (oxygen concentration of 0.3 vol %).
  • a proper amount of a sodium carbonate aqueous solution of 2 mol/L was added to this reaction vessel, so as to adjust the pH value of the reaction liquid in the vessel to 10.0 at the reference liquid temperatures of 25° C.
  • Ni:Co:Mn 0.167:0.167:0.666.
  • This metal component-containing mixed aqueous solution was added to the initial aqueous solution in the reaction vessel at a rate of 10.9 ml/min to prepare a mixed aqueous solution.
  • an ammonium carbonate aqueous solution of 2.7 mol/L was simultaneously added to the initial aqueous solution at a constant rate, to maintain the same value of the ammonia concentration in the generated mixed aqueous solution as in the initial aqueous solution. Furthermore, a sodium carbonate aqueous solution of 2 mol/L as an alkaline aqueous solution was added so as to control the pH value to become 9 (at the reference liquid temperatures of 25° C.).
  • the nucleation process was performed for 1/10 of the combined time, which turned out to be 24 minutes. In other words, crystallization was performed for 1/10 of the entire crystallization time.
  • the obtained generated material was filtered, washed and dried to obtain a precursor.
  • pH was controlled by a pH controller by adjusting the supplying flow rate of the sodium carbonate aqueous solution of 2 mol/L, and the range of fluctuation was within a range of the setting value (7.0) plus/minus 0.2.
  • the average particle diameter D 50 was measured for the precursor by using a laser diffraction-scattering particle size distribution measuring device (“Microtrack HRA” manufactured by Nikkiso Co., Ltd.), and as a result, D 50 turned out to be 5.8 ⁇ m.
  • the obtained precursor particles were observed by using an SEM (Scanning Electron Microscope S-4700 manufactured by Hitachi High-Technologies Corporation) with a magnification factor of 5000. It was confirmed that the obtained precursor particles were constituted with virtually spherical secondary particles, and the particle diameters were virtually uniform. In this way, in the case where it was confirmed by SEM observation that a precursor was constituted with virtually spherical secondary particles, the sphericity was evaluated as excellent (designated with a circle mark, below); or in the case where it was confirmed that a precursor was constituted with non-spherical secondary particles, the sphericity was evaluated as poor (designated with a cross mark, below). A result of SEM observation is shown in FIG. 1 .
  • a sample of the obtained precursor was embedded in resin, and then, was processed with a cross-sectional polisher, to perform SEM observation. It was confirmed that this precursor was constituted with secondary particles, and the secondary particle was constituted with a sparse central portion and a dense outer shell portion formed of granular fine primary particles.
  • the secondary particle of either of the obtained precursors was constituted with a dense outer shell portion.
  • Heat treatment was applied to the precursor at 500° C. for 2 hours in an airflow (oxygen: 21 vol %) to obtain composite oxide particles as heat-treated particles.
  • Lithium carbonate was weighed so that Li/Me, which is the ratio of the number (Li) of lithium atoms to the sum (Me) of the numbers of the other metal atoms, became 1.5, and the weighed lithium carbonate was mixed with the above composite oxide particles to prepare a lithium mixture.
  • the mixing was performed by using a shaker mixer device (“TURBULA Type T2C” manufactured by Willy A. Bachofen AG (WAB)).
  • the obtained lithium mixture was calcined at 500° C. for 4 hours in the atmosphere (oxygen: 21 vol %), sintered at 850° C. for 10 hours, cooled, and then, cracked to obtain a positive-electrode active material.
  • a positive-electrode active material represented by Li 1.47 Ni 0.166 Co 0.167 Mn 0.667 O 2 was obtained.
  • the particle size distribution of the obtained positive-electrode active material was measured by using substantially the same method as in the case of the precursor, and the average particle diameter turned out to be 5.7 ⁇ m.
  • FIG. 2A A result of SEM observation of this positive-electrode active material is shown in FIG. 2A .
  • particles contained in the obtained positive-electrode active material are virtually spherical, and the particle diameters were virtually uniform.
  • the sphericity was evaluated as excellent (designated with a circle mark, below); or in the case of being constituted with non-spherical secondary particles, the sphericity was evaluated as poor (designated with a cross mark, below).
  • FIG. 2B a cross-sectional image of a typical particle is illustrated in FIG. 2B as a result of cross-sectional SEM observation of a positive-electrode active material. From FIG. 2B , it was confirmed that this positive-electrode active material had a hollow structure including an outer shell portion constituted with sintered primary particles, and a hollow portion inside of the outer shell portion. The ratio of the thickness of the outer shell portion to the particle diameter of the positive-electrode active material obtained from this observation was approximately 22%.
  • the evaluation is designated as “hollow”, below.
  • solid in the case where it was confirmed by the cross-sectional SEM observation that a particle of a positive-electrode active material was formed as a particle whose inside is not hollow, but filled with the material, the evaluation is designated as “solid”, below.
  • the evaluation in the case where hollow particles and solid particles coexisted, the evaluation is designated as “hollow, solid”, below.
  • the specific surface area of the obtained positive-electrode active material was obtained by using a flow type gas adsorption specific surface area measuring device (Multisorb manufactured by Yuasa-Ionics Co., Ltd.), which turned out to be 5.2 m 2 /g.
  • a 2032-type coin battery was produced by using the obtained positive-electrode active material, and evaluated.
  • FIG. 3 schematically illustrates a cross-sectional view of the coin battery.
  • this coin battery 10 is configured to have a case 11 and an electrode 12 accommodated in the case 11 .
  • the case 11 includes a positive electrode can 111 that is hollow and has an opening at one end, and a negative electrode can 112 disposed in the opening of the positive electrode can 111 .
  • the negative electrode can 112 is disposed in the opening of the positive electrode can 111 such that a space for accommodating the electrode 12 is formed between the negative electrode can 112 and the positive electrode can 111 .
  • the electrode 12 is constituted with a positive electrode 121 , a separator 122 , and a negative electrode 123 that are staked in this order, and is accommodated in the case 11 such that the positive electrode 121 contacts the inner surface of the positive electrode can 111 , and the negative electrode 123 contacts the inner surface of the negative electrode can 112 .
  • the case 11 has a gasket 113 that is fixed so as to maintain an electrically insulated state between the positive electrode can 111 and the negative electrode can 112 .
  • the gasket 113 has a function to seal the gap between the positive electrode can 111 and the negative electrode can 112 so as to make the interior of the case 11 airtight and liquid-tight with respect to the outside.
  • the coin battery 10 was produced as follows. First, 52.5 mg of the obtained positive-electrode active material, 15 mg of acetylene black, and 7.5 mg of polytetrafluoroethylene resin (PTFE) were intermixed with a solvent (N-methyl-2-pyrrolidone), which was then press-molded to produce the positive electrode 121 having the diameter of 11 mm and the thickness of 100 ⁇ m. The produced positive electrode 121 was dried in a vacuum dryer at 120° C. for 12 hours. By using the positive electrode 121 , the negative electrode 123 , the separator 122 , and an electrolytic solution, the coin battery 10 was produced in a glove box filled with an Ar atmosphere where the dew point was controlled to be ⁇ 80° C.
  • a solvent N-methyl-2-pyrrolidone
  • the negative electrode 123 a negative electrode sheet was used, which had been punched out of copper foil to be shaped as a disk having the diameter of 14 mm, to which graphite powder having the average particle diameter of approximately 20 ⁇ m and polyvinylidene fluoride were applied. Also as the separator 122 , a porous polyethylene film having the thickness of 25 ⁇ m was used.
  • the electrolytic solution a mixed solution was used that contained equal amounts of ethylene carbonate (EC) and diethyl carbonate (DEC) with 1 M of LiClO 4 as the supporting electrolyte (manufactured by Toyama Pharmaceutical Industry Co., Ltd.).
  • the coin battery 10 was charged with a charging potential set to 4.4 V, to obtain a Nyquist plot by using a frequency response analyzer and a potentiogalvanostat (1255B manufactured by Solartron) to perform measurement with an alternating current impedance method.
  • This Nyquist plot represented the sum of characteristic curves of the solution resistance, the resistance and the capacity of the negative electrode, and the resistance and the capacity of the positive electrode. Therefore, based on this Nyquist plot, an equivalent circuit was used for fitting calculation and for calculating the resistance of the positive electrode.
  • the resistance of the positive electrode of Example 2 was set as a reference, and normalized to 1 so as to perform a relative evaluation.
  • an ammonium molybdate solution was added to the metal component-containing mixed aqueous solution.
  • ammonium molybdate was added and mixed with the metal component-containing mixed aqueous solution so as to have the Mo ratio of 1.0 at % in the metal component-containing mixed aqueous solution among the sum of Mo and the other transition metal elements Ni, Co, and Mn.
  • an ammonium molybdate solution was added to the metal component-containing mixed aqueous solution.
  • ammonium molybdate was added and mixed with the metal component-containing mixed aqueous solution so as to have the Mo ratio of 3.0 at % in the metal component-containing mixed aqueous solution among the sum of Mo and the other transition metal elements Ni, Co, and Mn.
  • an ammonium molybdate solution was added to the metal component-containing mixed aqueous solution.
  • ammonium molybdate was added and mixed with the metal component-containing mixed aqueous solution so as to have the Mo ratio of 5.0 at % in the metal component-containing mixed aqueous solution among the sum of Mo and the other transition metal elements Ni, Co, and Mn.
  • an ammonium molybdate solution was added to the metal component-containing mixed aqueous solution.
  • ammonium molybdate was added and mixed with the metal component-containing mixed aqueous solution so as to have the Mo ratio of 0.5 at % in the metal component-containing mixed aqueous solution among the sum of Mo and the other transition metal elements Ni, Co, and Mn.
  • an ammonium tungstate solution was added to the metal component-containing mixed aqueous solution.
  • ammonium tungstate was added and mixed with the metal component-containing mixed aqueous solution so as to have the W ratio of 0.5 at % in the metal component-containing mixed aqueous solution among the sum of W and the other transition metal elements Ni, Co, and Mn.
  • a positive-electrode active material precursor for a nonaqueous electrolyte secondary battery a positive-electrode active material for a nonaqueous electrolyte secondary battery, a method for manufacturing a positive-electrode active material precursor for a nonaqueous electrolyte secondary battery, and a method for manufacturing a positive-electrode active material for a nonaqueous electrolyte secondary battery have been described with the embodiments and examples. Note that the present invention is not limited to the embodiments and examples described above; various transformations and modifications can be made within the scope of the subject matters of the present invention described in the claims.

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