# US 12,009,517 B2 · Nickel-manganese composite hydroxide, method for producing the same, positive electrode active material for nonaqueous electrolyte secondary battery, method for producing the same, and nonaqueous electrolyte secondary battery

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- Number: US 12,009,517 B2
- Document ID: US12009517B2
- Status: Granted
- Kind: B2
- Application number: 18/134,130
- Filed: 2023-04-13
- Published: 2023-08-10
- Granted: 2024-06-11
- Earliest claimed: 2016-07-29
- Assignees: Sumitomo Metal Mining Co., Ltd.
- Applicants: Sumitomo Metal Mining Co., Ltd.
- Inventors: Haruki Kaneda; Yuki Koshika; Takaaki Ando
- Web page: https://patentgrep.com/patent/US12009517B2

## CPC

- H01M 4/505: of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
- C01G 53/504: with the molar ratio of nickel with respect to all the metals other than alkali metals higher than or equal to 0.5, e.g. Li(MzNixCoyMn1-x-y-z)O2 with x ≥ 0.5
- C01G 53/82: Compounds containing nickel, with or without oxygen or hydrogen, and containing two or more other elements
- H01M 4/525: of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
- C01P 2002/72: by d-values or two theta-values, e.g. as X-ray diagram
- C01P 2002/74: by peak-intensities or a ratio thereof only
- C01P 2004/51: Particles with a specific particle size distribution
- C01P 2004/61: Micrometer sized, i.e. from 1-100 micrometer
- C01P 2006/11: Powder tap density
- C01P 2006/12: Surface area
- C01P 2006/14: Pore volume
- C01P 2006/19: Oil-absorption capacity, e.g. DBP values
- C01P 2006/40: Electric properties
- H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- H01M 2004/8689: {Positive electrodes}
- Y02E 60/10: Energy storage using batteries
- Y02E 60/50: Fuel cells
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- C01G: COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F (metal hydrides {monoborane, diborane or addition complexes thereof} C01B6/00; salts of oxyacids of halogens C01B11/00; peroxides, salts or peroxyacids C01B15/00; thiosulfates, dithionites, polythionates C01B17/64; compounds containing selenium, or tellurium C01B19/00; binary compounds of nitrogen with metals C01B21/06; azides C01B21/08; {compounds containing nitrogen, other non-metals and metal C01B21/082}; metal amides C01B21/092; nitrites C01B21/50; {compounds of noble gases C01B23/0005}; phosphides C01B25/08; salts of oxyacids of phosphorus C01B25/16; carbides C01B32/90; compounds containing silicon C01B33/00; compounds containing boron C01B35/00; compounds having molecular sieve properties but not having base-exchange properties C01B37/00; compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites, C01B39/00; cyanides C01C3/08; salts of cyanamide C01C3/16; thiocyanates C01C3/20)
- C01P: INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

Provided are a positive electrode active material with which a nonaqueous electrolyte secondary battery having a high energy density can be obtained, a nickel-manganese composite hydroxide suitable as a precursor of the positive electrode active material, and production methods capable of easily producing these in an industrial scale. Provided is a nickel-manganese composite hydroxide represented by General Formula (1): NixMnyMz(OH)2+α and containing a secondary particle formed of a plurality of flocculated primary particles. The nickel-manganese composite hydroxide has a half width of a diffraction peak of a (001) plane obtained by X-ray diffraction measurement of at least 0.10° and up to 0.40° and has a degree of sparsity/density represented by [(void area within secondary particle/cross section of secondary particle)×100](%) of at least 0.5% and up to 10%. Also provided is a production method of the nickel-manganese composite hydroxide.

## Claims

### Claim 1

A method for producing a nickel-manganese composite hydroxide represented by General Formula (1): NixMnyMz(OH)2+α in Formula (1), M is at least one element selected from Co, Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, Fe, and W; and x, y, z, and a satisfy 0.1≤x≤0.9, 0.05≤y≤0.8, 0≤z≤0.8, x+y+z=1.0, and 0≤α≤0.4 and containing a secondary particle formed of a plurality of flocculated primary particles;
the method comprising a crystallization process of forming the nickel-manganese composite hydroxide by neutralizing a salt containing at least nickel and a salt containing at least manganese in a reaction aqueous solution; and
in the reaction aqueous solution in the crystallization process, a dissolved oxygen concentration is adjusted to fall within a range of at least 0.2 mg/L and up to 4.6 mg/L, and a dissolved nickel concentration is adjusted to fall within a range of at least 700 mg/L and up to 1,500 mg/L.

### Claim 2 (depends on 1)

The method for producing a nickel-manganese composite hydroxide according to claim 1, wherein a stirring power loaded to the reaction aqueous solution in the crystallization process is adjusted to fall within a range of at least 3 kW/m3 and up to 15 kW/m3.

### Claim 3 (depends on 1)

The method for producing a nickel-manganese composite hydroxide according to claim 1, wherein a temperature of the reaction aqueous solution in the crystallization process is adjusted to fall within a range of at least 35° C. and up to 60° C.

### Claim 4 (depends on 1)

The method for producing a nickel-manganese composite hydroxide according to claim 1, wherein a pH value in the crystallization process measured based on a temperature of the reaction aqueous solution at 25° C. is adjusted to fall within a range of at least 10.0 and up to 13.0.

### Claim 5 (depends on 1)

The method for producing a nickel-manganese composite hydroxide according to claim 1, wherein the crystallization process includes continuously adding a mixed aqueous solution including nickel and manganese into a reaction vessel and overflowing slurry including nickel-manganese composite hydroxide particles formed by neutralization to recover the secondary particle.

### Claim 6

A method for producing a positive electrode active material for a nonaqueous electrolyte secondary battery, the positive electrode active material comprising: a lithium-nickel-manganese composite oxide represented by General Formula (2): Li1+tNixMnyMzO2+β in Formula (2), M is at least one additional element selected from Co, Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, Fe, and W; and t, x, y, z, and β satisfy −0.05≤t≤0.5, 0.1≤x≤0.9, 0.05≤y≤0.8, 0≤z≤0.8, x+y+z=1.0, and 0≤β≤0.5 and contains a secondary particle formed of a plurality of flocculated primary particles,
the method comprising:
a process of providing a nickel-manganese composite hydroxide represented by General Formula (1): NixMnyMz(OH)2+α in Formula (1), M is at least one element selected from Co, Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, Fe, and W; and x, y, z, and a satisfy 0.1≤x≤0.9, 0.05≤y≤0.8, 0≤z≤0.8, x+y+z=1.0, and 0≤α≤0.4 and containing a secondary particle formed of a plurality of flocculated primary particles, wherein the nickel-manganese composite hydroxide has a half width of a diffraction peak of a (001) plane obtained by X-ray diffraction measurement of at least 0.10° and up to 0.40° and has a degree of sparsity/density represented by [(void area within secondary particle/cross section of secondary particle)×100](%) of at least 0.5% and up to 10%;
a process of mixing the nickel-manganese composite hydroxide with a lithium compound to obtain a mixture; and
a process of firing the mixture to obtain the lithium-nickel-manganese composite oxide.

### Claim 7 (depends on 6)

The method for producing a positive electrode active material for a nonaqueous electrolyte secondary battery according to claim 6, wherein the nickel-manganese composite hydroxide is obtained by the method comprising a crystallization process of forming the nickel-manganese composite hydroxide by neutralizing a salt containing at least nickel and a salt containing at least manganese in a reaction aqueous solution; and
in the reaction aqueous solution in the crystallization process, a dissolved oxygen concentration is adjusted to fall within a range of at least 0.2 mg/L and up to 4.6 mg/L, and a dissolved nickel concentration is adjusted to fall within a range of at least 700 mg/L and up to 1,500 mg/L.