# US 11,909,032 B2 · Composite cathode active material, cathode and lithium battery each containing composite cathode active material, and preparation method of cathode active material

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- Number: US 11,909,032 B2
- Document ID: US11909032B2
- Status: Granted
- Kind: B2
- Application number: 16/504,620
- Filed: 2019-07-08
- Published: 2020-04-30
- Granted: 2024-02-20
- Earliest claimed: 2018-10-24
- Assignees: Samsung Electronics Co., Ltd.; Samsung SDI Co., Ltd.
- Applicants: Samsung Electronics Co., Ltd.; Samsung SDI Co., Ltd.
- Inventors: Sukgi Hong; Byongyong Yu; Donghee Yeon; Byungjin Choi
- Web page: https://patentgrep.com/patent/US11909032B2

## CPC

- C01G 53/42: containing alkali metals, e.g. LiNiO2
- H01M 4/366: {as layered products}
- C01G 53/506: with the molar ratio of nickel with respect to all the metals other than alkali metals higher than or equal to 0.8, e.g. Li(MzNixCoyMn1-x-y-z)O2 with x ≥ 0.8
- H01M 4/0471: {involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis}
- 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 4/525: of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
- H01M 4/626: {Metals}
- H01M 4/628: {Inhibitors, e.g. gassing inhibitors, corrosion inhibitors}
- C01P 2002/20: Two-dimensional structures
- C01P 2002/32: spinel-type (AB2O4)
- C01P 2002/52: containing elements as dopants
- C01P 2002/54: one element only
- 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 2002/85: by XPS, EDX or EDAX data
- C01P 2002/88: by thermal analysis data, e.g. TGA, DTA, DSC
- C01P 2004/04: obtained by TEM, STEM, STM or AFM
- C01P 2004/61: Micrometer sized, i.e. from 1-100 micrometer
- C01P 2004/62: Submicrometer sized, i.e. from 0.1-1 micrometer
- C01P 2004/64: Nanometer sized, i.e. from 1-100 nanometer
- C01P 2006/40: Electric properties
- H01M 4/5825: {Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines}
- H01M 2004/028: {Positive electrodes}
- Y02E 60/10: Energy storage using batteries
- Y02P 70/50: Manufacturing or production processes characterised by the final manufactured product
- 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)
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

A composite cathode active material includes: a core including a plurality of primary particles; and a shell on the core, wherein the primary particles include a first lithium transition metal oxide comprising nickel, the shell includes a first layer and a second layer on the first layer, the first layer includes a first composition containing a first metal, the second layer includes a second composition containing phosphorus, and the first metal includes at least one or more metal, other than nickel, belonging to any of Groups 2 to 5 and Groups 7 to 15 of the Periodic Table of the Elements. Also a cathode, and a lithium battery each including the composite cathode active material, and a method of preparing the composite cathode active material.

## Claims

### Claim 1

A composite cathode active material comprising:
a core comprising a plurality of primary particles; and
a shell on the core,
wherein the primary particles comprise a first lithium transition metal oxide comprising nickel,
wherein the shell comprises a first layer and a second layer on the first layer,
wherein the first layer comprises a first composition represented by Formula 1A:
M1bOc
wherein, in Formula 1A,
M1 comprises cobalt,
0.9≤b≤3.1, and 1.9≤c≤4.1,
the second layer comprises a second composition comprising cobalt and phosphorus, and an amount of the second composition included in the second layer is about 2 parts by weight or less based on 100 parts by weight of the first lithium transition metal oxide, and
wherein the core comprises a grain boundary located between primary particles of the plurality of primary particles, and the grain boundary comprises a third composition comprising Li2ZrO3.

### Claim 2 (depends on 1)

The composite cathode active material of claim 1, wherein the first composition has a different structure than the second composition.

### Claim 3 (depends on 1)

The composite cathode active material of claim 1, wherein the first composition has a layered crystal structure or a spinel crystal structure.

### Claim 4 (depends on 3)

The composite cathode active material of claim 3, wherein the layered crystal structure belongs to an R-3m space group, and the spinel crystal structure belongs to an Fd-3m space group.

### Claim 5 (depends on 1)

The composite cathode active material of claim 1, wherein the first layer is on a surface of a primary particle of the plurality of primary particles, and a concentration of M1 in Formula 1A comprised in the first layer is greater than a concentration of M1 comprised in the plurality of primary particles.

### Claim 6 (depends on 1)

The composite cathode active material of claim 1, wherein a thickness of the second layer is greater than a thickness of the first layer, the thickness of the first layer is 50 nanometers or less, and the thickness of the second layer is 500 nanometers or less.

### Claim 7 (depends on 1)

The composite cathode active material of claim 1,
wherein the first layer further comprises a first compound comprising
0 moles to about 3.3 moles of lithium per 1 mole of the first compound,
about 0.7 moles to about 3.3 moles of M1 in Formula 1A per 1 mole of the first compound, and
about 1.7 moles to about 4.3 moles of oxygen per 1 mole of the first compound.

### Claim 8 (depends on 1)

The composite cathode active material of claim 1, wherein
the first layer further comprises a second compound represented by Formula 1B:
LiaM1bOc Formula 1B
wherein, in Formula 1B, M1 is at least one of cobalt, magnesium, zirconium, aluminum, manganese, silicon, palladium, titanium, tin, iridium, platinum, ruthenium, cerium, boron, niobium, vanadium, iron, or zinc,
0<a≤3.1, 0.9≤b≤3.1, and 1.9≤c≤4.1.

### Claim 9 (depends on 1)

The composite cathode active material of claim 1, wherein the first composition comprises Co3O4.

### Claim 10 (depends on 1)

The composite cathode active material of claim 1, wherein an amount of the first composition contained in the first layer is 10 parts by weight or less, based on 100 parts by weight of the first lithium transition metal oxide, or wherein an amount of M1 of Formula 1A contained in the first layer is 10 parts by weight or less, based on 100 parts by weight of the first lithium transition metal oxide.

### Claim 11 (depends on 1)

The composite cathode active material of claim 1,
wherein the second composition is a composition comprising M1 of Formula 1A, phosphorus, and oxygen, or a composition comprising lithium, M1 of Formula 1A, phosphorus, and oxygen,
wherein the second composition comprises
0 moles to about 3.3 moles of lithium, per 1 mole of the second composition,
about 0.7 moles to about 3.3 moles of the first metal, per 1 mole of the second composition,
about 0.7 moles to about 2.3 moles of phosphorus, per 1 mole of the second composition, and
about 3.7 moles to about 8.3 moles of the oxygen, per 1 mole of the second composition.

### Claim 12 (depends on 1)

The composite cathode active material of claim 1,
wherein the second composition is represented by Formula 2 below:
LiaM2b(PO4)c Formula 2
wherein, in Formula 2, M2 is at least one of cobalt, magnesium, zirconium, aluminum, manganese, silicon, palladium, nickel, titanium, tin, molybdenum, iridium, platinum, ruthenium, cerium, boron, niobium, vanadium, iron, or zinc, and
0≤a≤3.1, 0.9≤b≤3.1, and 0.9≤c≤2.1.

### Claim 13 (depends on 1)

The composite cathode active material of claim 1, wherein the second composition comprises at least one of LiCoPO4 or Co3(PO4)2.

### Claim 14 (depends on 1)

The composite cathode active material of claim 1, wherein the third composition has a monoclinic crystal structure, and the monoclinic crystal structure belongs to a C2/m, C12/c1, or C2/c space group.

### Claim 15 (depends on 1)

The composite cathode active material of claim 1, wherein the shell further comprises the third composition.

### Claim 16 (depends on 1)

The composite cathode active material of claim 1, wherein the first lithium transition metal oxide comprises a second metal, wherein the second metal is zirconium, aluminum, cobalt, magnesium, manganese, silicon, molybdenum, palladium, titanium, tin, iridium, platinum, ruthenium, cerium, boron, niobium, vanadium, iron, or zinc.

### Claim 17 (depends on 1)

The composite cathode active material of claim 1,
wherein the first lithium transition metal oxide comprises lithium, nickel, a second metal, a third metal, and oxygen,
wherein the first lithium transition metal oxide comprises
about 0.1 moles to about 1.3 moles of lithium, per 1 mole of the first lithium transition metal oxide,
about 0.7 moles to about 0.99 moles of nickel, per 1 mole of the first lithium transition metal oxide,
about 0.001 moles to about 0.01 moles of the second metal, per 1 mole of the first lithium transition metal oxide,
about 0.01 moles to about 0.3 moles of the third metal, per 1 mole of the first lithium transition metal oxide, and
about 1.7 moles to about 2.3 moles of oxygen, per 1 mole of the first lithium transition metal oxide, and
wherein the third metal is a metal other than lithium, nickel, and the second metal.

### Claim 18 (depends on 1)

The composite cathode active material of claim 1, wherein the first lithium transition metal oxide is represented by Formula 4:
LiaM4O2-αXα Formula 4
wherein, in Formula 4, 0.9≤a≤1.1 and 0≤α<2,
M4 is nickel, a second metal, and a third metal, wherein the third metal comprises at least one element of Groups 2 to 13 of the Periodic Table, other than nickel and the second metal, and an amount of nickel contained in M4 is about 70 mole percent to about 100 mole percent, and
X is at least one of oxygen, fluorine, sulfur, or phosphorus.

### Claim 19 (depends on 1)

The composite cathode active material of claim 1, wherein the first lithium transition metal oxide is represented by Formula 5:
LiaNibM5cM6dM7cO2-αXα Formula 5
wherein, in Formula 5, 0.9≤a≤1.1, 0.7<b<1.0, 0<c<0.3, 0<d<0.3, 0≤e<0.1, b+c+d+e=1, and 0≤α<2,
M5, M6, and M7 are different from each other and are each independently cobalt, manganese, zirconium, aluminum, rhenium, vanadium, chromium, iron, boron, ruthenium, titanium, niobium, molybdenum, magnesium, or platinum, and
X is at least one of oxygen, fluorine, sulfur, or phosphorus.

### Claim 20 (depends on 1)

The composite cathode active material of claim 1, wherein the first lithium transition metal oxide is represented by at least one of Formula 6, and Formula 7:
LiaNibCocMndM8cO2-αXα, and Formula 6
LiaNibCocAldM8eO2-αXα Formula 7
wherein, in Formulae 6 and 7, a, b, c, d, e, and α are each independently 0.9≤a≤1.1, 0.7<b<1.0, 0<c<0.1, 0<d<0.1, 0≤e<0.01, b+c+d+e=1, and 0≤α≤2,
M8 is at least one of zirconium, aluminum, vanadium, chromium, iron, rhenium, boron, ruthenium, titanium, niobium, molybdenum, magnesium, or platinum, and
X is at least one of oxygen, fluorine, sulfur, or phosphorus.

### Claim 21 (depends on 1)

The composite cathode active material of claim 1, wherein the first lithium transition metal oxide is represented by Formula 8:
aLi2MnO3·(1−a)LiMO2-αXα Formula 8
wherein, in Formula 8, 0<a<1 and 0≤α≤2,
M is at least two elements of nickel, cobalt, manganese, zirconium, aluminum, rhenium, vanadium, chromium, iron, boron, ruthenium, titanium, niobium, molybdenum, magnesium, or platinum, and
X is at least one of oxygen, fluorine, sulfur, or phosphorus.

### Claim 22 (depends on 1)

A cathode comprising the composite cathode active material according to claim 1.

### Claim 23 (depends on 22)

The cathode of claim 22, wherein the cathode further comprises a cathode active material having an olivine structure.

### Claim 24 (depends on 23)

The cathode of claim 23, wherein an amount of the cathode active material having the olivine structure is 10 weight percent or less, based on a total weight of the cathode active material.

### Claim 25 (depends on 22)

A lithium battery comprising:
the cathode according to claim 22;
an anode; and
an electrolyte between the cathode and the anode.

### Claim 26 (depends on 1)

A method of preparing a composite cathode active material, the method comprising:
providing a first lithium transition metal oxide;
mixing the first lithium transition metal oxide with a first metal precursor to prepare a first composition;
mixing the first composition with a phosphorus precursor to preparing a second composition;
drying the second composition; and
heat-treating the dried second composition at a temperature of about 400° C. to about 1000° C. under an oxidizing atmosphere to prepare the composite cathode active material of claim 1.

### Claim 27 (depends on 26)

The method of claim 26, wherein the providing the first lithium transition metal oxide comprises:
mixing a precursor of the first lithium transition metal oxide and a second metal precursor to prepare a mixture; and
heat-treating the mixture at a temperature of about 400° C. to about 1000° C. under an oxidizing atmosphere to prepare the first lithium transition metal oxide.

### Claim 28 (depends on 1)

The composite cathode active material of claim 1, wherein the first lithium transition metal oxide further comprises a second metal, wherein the second metal is zirconium.

### Claim 29

A composite cathode active material comprising:
a core comprising a plurality of primary particles; and
a shell on the core,
wherein the primary particles comprise a first lithium transition metal oxide comprising nickel,
wherein the first lithium transition metal oxide comprises a second metal, wherein the second metal comprises zirconium,
wherein the shell comprises a first layer and a second layer on the first layer,
wherein the first layer comprises a first composition represented by Formula 1A:
M1bOc
wherein, in Formula 1A,
M1 is at least one of cobalt, magnesium, zirconium, aluminum, manganese, silicon, palladium, titanium, tin, iridium, platinum, ruthenium, cerium, boron, niobium, vanadium, iron, and zinc,
0.9≤b≤3.1, and 1.9≤c≤4.1,
the second layer comprises a second composition comprising cobalt and phosphorus, and an amount of the second composition included in the second layer is about 2 parts by weight or less based on 100 parts by weight of the first lithium transition metal oxide, and
wherein the core comprises a grain boundary located between primary particles of the plurality of primary particles, and the grain boundary comprises a third composition comprising Li2ZrO3.