# US 10,483,539 B2 · Positive electrode active material for non-aqueous electrolyte secondary batteries, production process therefor, and non-aqueous electrolyte secondary battery

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- Number: US 10,483,539 B2
- Document ID: US10483539B2
- Status: Granted
- Kind: B2
- Application number: 15/500,135
- Filed: 2015-07-01
- Published: 2017-09-14
- Granted: 2019-11-19
- Earliest claimed: 2014-07-31
- Assignees: Sumitomo Metal Mining Co., Ltd.
- Applicants: Sumitomo Metal Mining Co., Ltd.
- Inventors: Katsuya Inoue; Hiroyuki Toya
- Web page: https://patentgrep.com/patent/US10483539B2

## CPC

- H01M 4/505: of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
- C01G 53/502: containing lithium and cobalt
- 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 53/84: Hydroxides
- H01M 4/0471: {involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis}
- 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
- H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- C01P 2004/03: obtained by SEM
- C01P 2004/04: obtained by TEM, STEM, STM or AFM
- C01P 2004/61: Micrometer sized, i.e. from 1-100 micrometer
- C01P 2004/84: one phase coated with the other
- H01M 2004/028: {Positive electrodes}
- Y02E 60/10: Energy storage using batteries
- Y02T 10/70: Energy storage systems for electromobility, e.g. 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)
- 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
- Y02T: CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION

## Abstract

A positive electrode active material for a non-aqueous electrolyte secondary battery, which enables a non-aqueous electrolyte secondary battery to achieve great battery characteristics, and a process for producing the material, as well as a non-aqueous electrolyte secondary batter. Provided is a positive electrode active material for a non-aqueous electrolyte secondary battery, where secondary particles of lithium-nickel-cobalt-manganese composite oxide particles are composed of outer-shell parts with a high manganese concentration and central parts with a low manganese concentration, which are lower in manganese concentration than the outer-shell parts, primary particles constituting the outer-shell parts of the secondary particles with the high manganese concentration are composed of outer peripheral parts with a low manganese concentration and inner parts with a high manganese concentration, and the ratio of the manganese concentration in the inner part to the manganese concentration in the outer peripheral part is 1.5 to 2.5 in the primary particles.

## Claims

### Claim 1

A positive electrode active material for a non-aqueous electrolyte secondary battery, the positive electrode active material comprising hexagonal lithium-nickel-cobalt-manganese composite oxide particles represented by the general formula: Li1+sNixCoyMnzMtO2
wherein:
s, x, y, z, and t in the formula fall within the ranges of: −0.05≤s≤0.20; 0.1≤x≤0.7; 0.1≤y≤0.5; 0.1≤z≤0.5; and 0≤t≤0.05, and x, y, z, and t meet x+y+z+t=1,
M in the formula represents one or more additive elements selected from the group consisting of Ca, Mg, Al, Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, and W,
the lithium-nickel-cobalt-manganese composite oxide particles have a layered structure comprising secondary particles with aggregated primary particles,
the secondary particles each comprises an outer-shell part that has a high manganese concentration and a central part that has a low manganese concentration that is lower than the high manganese concentration in the outer-shell part of the secondary particle,
the primary particles constitute the outer-shell parts of the secondary particles,
each of the primary particles comprises an outer peripheral part that has a low manganese concentration and an inner part that has a high manganese concentration, and
a ratio of the high manganese concentration in the inner part of the primary particle to the low manganese concentration in the outer peripheral part of the primary particle is in a range of from 1.5 to 2.5.

### Claim 2 (depends on 1)

The positive electrode active material for a non-aqueous electrolyte secondary battery according to claim 1, wherein a ratio of the low manganese concentration in the central part of the secondary particle to the high manganese concentration in the outer-shell part of the secondary particle is 0.3 to 0.7.

### Claim 3 (depends on 1)

The positive electrode active material for a non-aqueous electrolyte secondary battery according to claim 1, wherein the positive electrode active material is 3 μm to 20 μm in average particle size.

### Claim 4 (depends on 1)

The positive electrode active material for a non-aqueous electrolyte secondary battery according to claim 1, wherein the primary particles are 0.2 μm to 0.5 μm in average particle size.

### Claim 5 (depends on 1)

The positive electrode active material for a non-aqueous electrolyte secondary battery according to claim 1, wherein the positive electrode active material has a breadth of a particle size distribution, [(d90−d10)/average particle size], that is 0.60 or less.

### Claim 6 (depends on 1)

The positive electrode active material for a non-aqueous electrolyte secondary battery according to claim 1, wherein the secondary particles have voids in the central parts of the secondary particles.

### Claim 7 (depends on 1)

A process for producing the positive electrode active material for a non-aqueous electrolyte secondary battery according to claim 1
the process comprises:
a crystallization step of obtaining nickel-cobalt-manganese composite hydroxide particles represented by the general formula: NixMnzMt(OH)2+α, wherein x, y, z, and t in the formula fall within the ranges of: 0.1≤x≤0.7; 0.1≤y≤0.5; 0.1≤z≤0.5; and 0≤t≤0.05, x, y, z, and t meet x+y+z+t=1, and M in the formula represents one or more additive elements selected from the group consisting of Ca, Mg, Al, Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, and W;
a mixing step of mixing the nickel-cobalt-manganese composite hydroxide particles with a lithium compound such that a ratio of the atom number of lithium will be in a range of from 0.95 to 1.20 with respect to a total of the atom numbers of metal elements other than lithium, thereby providing a lithium mixture; and
a calcining step in an oxidizing atmosphere including: (i) elevating a temperature of the lithium mixture from room temperature to a temperature in a range of from 400° C. to 550° C. over 0.5 hours to 1.5 hours and keeping the elevated temperature for 1 hour to 5 hours, and (ii) further elevating the temperature of the lithium mixture to a temperature in a range of from 850° C. to 950° C. over 0.5 hours to 1.0 hour and keeping the elevated temperature for 1 hour to 5 hours, thereby forming the lithium-nickel-cobalt-manganese composite oxide particles.

### Claim 8 (depends on 7)

The process for producing the positive electrode active material for a non-aqueous electrolyte secondary battery according to claim 7, the process further comprising, before the mixing step, a heat treatment step of applying a heat treatment at a temperature in a range of from 105° C. to 150° C. to the nickel-cobalt-manganese composite hydroxide particles.

### Claim 9 (depends on 7)

The process for producing a positive electrode active material for a non-aqueous electrolyte secondary battery according to claim 7, the process further comprising a grinding step of grinding the lithium-nickel-cobalt-manganese composite oxide particles obtained in the calcining step.

### Claim 10 (depends on 1)

A non-aqueous electrolyte secondary battery comprising a positive electrode, a negative electrode, a separator, and a non-aqueous electrolyte, wherein the positive electrode is the positive electrode active material for a non-aqueous electrolyte secondary battery according to claim 1.