# US 12,119,492 B2 · Positive electrode active material for all-solid-state lithium ion secondary battery and method for manufacturing the same

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- Number: US 12,119,492 B2
- Document ID: US12119492B2
- Status: Granted
- Kind: B2
- Application number: 18/018,166
- Filed: 2021-07-29
- Published: 2023-08-24
- Granted: 2024-10-15
- Earliest claimed: 2020-07-30
- Assignees: Sumitomo Metal Mining Co., Ltd.
- Applicants: Sumitomo Metal Mining Co., Ltd.
- Inventors: Hitomi Nakamura; Ryosuke Okamoto; Kazuhide Hayashi; Mikako Toma
- Web page: https://patentgrep.com/patent/US12119492B2

## CPC

- 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
- C01G 53/42: containing alkali metals, e.g. LiNiO2
- H01B 1/08: oxides
- H01M 4/131: Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
- H01M 4/1391: of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
- H01M 4/36: Selection of substances as active materials, active masses, active liquids
- H01M 4/366: {as layered products}
- H01M 4/505: of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
- H01M 4/62: Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M 10/052: Li-accumulators
- H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- H01M 10/0562: Solid materials
- C01P 2002/52: containing elements as dopants
- C01P 2002/60: Compounds characterised by their crystallite size
- C01P 2002/72: by d-values or two theta-values, e.g. as X-ray diagram
- C01P 2002/76: by a space-group or by other symmetry indications
- C01P 2004/32: Spheres
- C01P 2004/45: Aggregated particles or particles with an intergrown morphology
- C01P 2004/51: Particles with a specific particle size distribution
- C01P 2004/61: Micrometer sized, i.e. from 1-100 micrometer
- C01P 2004/80: Particles consisting of a mixture of two or more inorganic phases
- C01P 2006/12: Surface area
- C01P 2006/40: Electric properties
- H01M 2004/021: {Physical characteristics, e.g. porosity, surface area}
- H01M 2004/028: {Positive electrodes}
- Y02E 60/10: Energy storage using batteries
- 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)
- H01B: CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES (selection for magnetic properties H01F1/00; waveguides H01P {; printed circuits H05K})
- 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

A positive electrode active material for an all-solid-state lithium ion secondary battery includes a lithium-nickel composite oxide particle and a coating layer coating a surface of the particle. The lithium-nickel composite oxide particle has a crystal structure belonging to a space group R-3m, contains at least Li, Ni, an element M, and Nb, a molar ratio among the elements being represented by Li:Ni:M:Nb=a:(1-x-y):x:y (0.98≤a≤1.15, 0<x≤0.5, 0<y≤0.03, 0<x+y≤0.5, and the element M, has a crystallite diameter of 140 nm or less, and has an eluted lithium ion amount of 0.30% by mass or more and 1.00% by mass or less. The coating layer is a composite oxide containing Li and at least one element.

## Claims

### Claim 1

A positive electrode active material for an all-solid-state lithium ion secondary battery, comprising a lithium-nickel composite oxide particle and a coating layer coating a surface of the particle, wherein
the lithium-nickel composite oxide particle
has a crystal structure belonging to a space group R-3m,
contains at least Li, Ni, an element M, and Nb,
a molar ratio among the elements being represented by Li:Ni:M:Nb=a:(1-x-y):x:y
(0.98≤ a≤1.15,
0<x≤0.5,
0<y≤0.03,
0<x+y≤0.5, and
the element M is at least one selected from the group consisting of Co, Al, Mn, Zr, Si, Zn, and Ti),
has a crystallite diameter of 140 nm or less as calculated by a Scherrer method from a diffraction peak attributed to a (003) plane measured by XRD, and
has an eluted lithium ion amount of 0.30% by mass or more and 1.00% by mass or less with respect to a total amount of the lithium-nickel composite oxide particles as determined by neutralization titration, and
the coating layer is a composite oxide containing Li and at least one element selected from the group consisting of Al, Si, Ti, V, Ga, Ge, Zr, Nb, Mo, Ta, and W.

### Claim 2 (depends on 1)

The positive electrode active material for an all-solid-state lithium ion secondary battery according to claim 1, wherein
the lithium-nickel composite oxide particles
include a secondary particle formed by aggregation of a plurality of primary particles,
have a porous structure having a plurality of voids in which no primary particle is present in the secondary particle, and
have a specific surface area of 0.3 m2/g or more and 2.0 m2/g or less as measured by a nitrogen adsorption BET method.

### Claim 3 (depends on 2)

The positive electrode active material for an all-solid-state lithium ion secondary battery according to claim 2, wherein at least a part of niobium contained in the lithium-nickel composite oxide particles is segregated at an interface between the primary particles.

### Claim 4 (depends on 1)

The positive electrode active material for an all-solid-state lithium ion secondary battery according to claim 1, wherein
the lithium-nickel composite oxide particles have a particle size (D50) corresponding to an integrated volume ratio of 50% in an integrated volume distribution curve of particle size distribution of 7 μm or less.

### Claim 5 (depends on 1)

The positive electrode active material for an all-solid-state lithium ion secondary battery according to claim 1, wherein
the coating layer has an average thickness of 2 nm or more and 15 nm or less.

### Claim 6 (depends on 1)

A method for manufacturing the positive electrode active material for an all-solid-state lithium ion secondary battery according to claim 1, the method comprising:
mixing a nickel composite compound, a niobium compound, and a lithium compound to obtain a mixture;
firing the mixture to obtain the lithium-nickel composite oxide particles; and
forming the coating layer by attaching a coating liquid containing at least one element selected from the group consisting of Al, Si, Ti, V, Ga, Ge, Zr, Nb, Mo, Ta, and W to surfaces of the lithium-nickel composite oxide particles.

### Claim 7 (depends on 6)

The method for manufacturing a positive electrode active material for an all-solid-state lithium ion secondary battery according to claim 6, wherein
the nickel composite compound contains a nickel composite oxide, and
the method further includes oxidation-roasting a nickel composite hydroxide adjusted by a crystallization reaction to obtain the nickel composite oxide.

### Claim 8 (depends on 6)

The method for manufacturing a positive electrode active material for an all-solid-state lithium ion secondary battery according to claim 6, the method further comprising heat-treating the lithium-nickel composite oxide particles having the coating layer formed on surfaces of the particles at 300° C. or higher after the coating.