# US 12,002,947 B2 · Electrode active composition, preparation method thereof, electrode, battery, and apparatus

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- Number: US 12,002,947 B2
- Document ID: US12002947B2
- Status: Granted
- Kind: B2
- Application number: 18/109,812
- Filed: 2023-02-14
- Published: 2023-06-29
- Granted: 2024-06-04
- Earliest claimed: 2020-09-10
- Assignees: Contemporary Amperex Technology Co., Limited
- Applicants: Contemporary Amperex Technology Co., Limited
- Inventors: Yingjie Guan; Yongchao Liu; Qisen Huang; Na Liu; Chengdu Liang
- Web page: https://patentgrep.com/patent/US12002947B2

## CPC

- H01M 4/364: {as mixtures}
- 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 4/485: of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy (H01M4/505, H01M4/525 take precedence)
- H01M 4/505: of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
- 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 4/621: {Binders}
- H01M 2004/021: {Physical characteristics, e.g. porosity, surface area}
- Y02E 60/10: Energy storage using batteries
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

This application relates to an electrode active composition, a preparation method thereof, an electrode, a battery, and an apparatus. The electrode active composition includes: a first component, the first component being lithium cobalt oxide particles; and a second component, the second component being ternary material particles. The first component includes lithium cobalt oxide particles with a particle size greater than 11 μm and lithium cobalt oxide particles with a particle size less than 6 μm, and a ratio in number of the lithium cobalt oxide particles with a particle size greater than 11 μm to the lithium cobalt oxide particles with a particle size less than 6 μm is 0.2-4.8, and in some embodiments, 0.2-2.8. A summed number of the lithium cobalt oxide particles with a particle size greater than 11 μm and the lithium cobalt oxide particles with a particle size less than 6 μm accounts for above 90% of a total number of particles in the first component.

## Claims

### Claim 1

An electrode active composition, comprising:
a plurality of first particles of lithium cobalt oxide having a formula of LixCoyM1(1-y)O2, wherein x satisfies 0.95≤x≤1.05, y satisfies 0.8≤y≤1, and M1 is selected from the group consisting of Zr, Mg, Ti, Sr, W, Nb, Al, P, F, S, and any combination thereof; and
a plurality of second particles, each one of the second particles having a core-coating layer structure, the core-coating layer structure comprising a core and a coating layer, wherein
the core of the second particles is a ternary material selected from the group consisting of lithium nickel cobalt aluminum oxide, lithium nickel manganese cobalt oxide, and a combination thereof; and
the coating layer is disposed on at least a partial surface of the core and comprises a reaction product of a sulfur-containing compound and a lithium-containing compound, the reaction product comprises Li, S, and O, S in the coating layer accounts for 400 ppm-5000 ppm in the second particles by weight, the reaction product further comprises an element selected from the group consisting of P, F, or a combination thereof, when the reaction product comprises P, P accounts for 500 ppm-3000 ppm in the second particles by weight, and when the reaction product comprises F, F accounts for 200 ppm-1500 ppm in the second particles by weight;
wherein the plurality of first particles comprise lithium cobalt oxide particles with a particle size greater than 11 μm and lithium cobalt oxide particles with a particle size less than 6 and a ratio in number of the lithium cobalt oxide particles with a particle size greater than 11 μm to the lithium cobalt oxide particles with a particle size less than 6 μm is 0.2-4.8; and
a summed number of the lithium cobalt oxide particles with a particle size greater than 11 and the lithium cobalt oxide particles with a particle size less than 6 μm accounts for above 90% of a total number of particles in the first particles.

### Claim 2 (depends on 1)

The electrode active composition according to claim 1, wherein a weight ratio of the first particles to the second particles is 1:1 to 9:1.

### Claim 3 (depends on 1)

The electrode active composition according to claim 1, wherein a particle size of the second particles is 2 μm-6 μm.

### Claim 4 (depends on 1)

The electrode active composition according to claim 1, wherein:
the second particles have at least a single crystal structure.

### Claim 5 (depends on 1)

The electrode active composition according to claim 1, wherein
a chemical formula of the lithium nickel manganese cobalt oxide is LiaNibCocMndM2(1-b-c-d)O2, wherein 0.5≤a≤1.2, 0.65≤b≤1, 0<c≤0.35, 0<d≤0.35, and M2 is selected from the group consisting of Zr, Zn, Ti, Sr, Sb, Y, W, Al, B, P, F, S, and any combination thereof; and
a chemical formula of the lithium nickel cobalt aluminum oxide is LixNieCofAlgM3(1-e-f-g)O2, 0.5≤x≤1.2, 0.5≤e≤1, 0<f≤0.5, 0<g≤0.5, and M3 is selected from the group consisting of Zr, Mg, Ba, Ti, Sr, Sb, Y, W, B, or any combination thereof.

### Claim 6 (depends on 1)

The electrode active composition according to claim 1, wherein a compacted density of the electrode active composition is ≥4.05 g/cm3, and the compacted density is a density of a briquette formed by pressing the electrode active composition for 30 seconds under a pressure of 5 tons.

### Claim 7 (depends on 1)

The electrode active composition according to claim 1, wherein the coating layer further contains B and B accounts for 500 ppm-3000 ppm in the second particles by weight.

### Claim 8 (depends on 1)

The electrode active composition according to claim 1, wherein
the lithium-containing compound is selected from the group consisting of: Li2O, LiOH, Li2CO3, LiNO3, LiPF6, lithium oxalate, lithium acetate, and any combinations thereof.

### Claim 9 (depends on 1)

The electrode active composition according to claim 1, wherein the sulfur-containing compound is selected from the group consisting of: mercaptan, thiophenol, thioether, thioaldehyde, thioketone, thionocarboxylic acid, sulphoxide, sulfone, sulfur oxoacid, R1-S(═O)2—R2, R1-C(═S)—R2,
R1-C—S—C—R2, R1-S(═O)2—LiN—S(═O)2—R2, sulfamide, sulfamic acid, lithium bisfluorosulfonimide, thiopropionamide, thioisobutyramide, propylene sulfide, methyl ethyl sulfide, or and any combination thereof, wherein R1 and R2 are each independently selected from the group consisting of hydroxyl, amino, C1-6 alkyl, aryl, a halogen atom selected from the group consisting of F, Cl, Br, and I, and a hydrogen atom.

### Claim 10

A method of making an electrode active composition, the method comprising:
providing a plurality of first particles of lithium cobalt oxide having a formula of LixCoyM1(1-y)O2, wherein x satisfies 0.95≤x≤1.05, y satisfies 0.8≤y≤1, and M1 is selected from the group consisting of Zr, Mg, Ti, Sr, W, Nb, Al, P, F, S, and any combination thereof;
providing a plurality of second particles having a core-coating layer structure, wherein providing the plurality of second particles further comprises:
providing a core comprising a ternary material selected from the group consisting of lithium nickel cobalt aluminum oxide, lithium nickel manganese cobalt oxide, or a combination thereof;
providing a coating layer precursor comprising a sulfur-containing compound, wherein the sulfur-containing compound is selected from the group consisting of mercaptan, thiophenol, thioether, thioaldehyde, thioketone, thionocarboxylic acid, sulphoxide, sulfone, sulfur oxoacid, sulfamide, sulfamic acid, lithium bisfluorosulfonimide, thiopropionamide, thioisobutyramide, propylene sulfide, methyl ethyl sulfide, R1-S(═O)2—R2, R1-C(═S)—R2,
R1-C—S—C—R2, or R1-S(═O)2—LiN—S(═O)2—R2, and any combination thereof, wherein R1 and R2 are each independently selected from hydroxyl, amino, Ci-6 alkyl, aryl, a halogen atom selected from the group consisting of F, Cl, Br, and I, and a hydrogen atom; and
treating the core with the coating layer precursor to form a reaction product as the coating layer on at least a part of a surface of the core, wherein the reaction product comprises Li, S, and O, and S in the coating layer accounts for 400 ppm-5000 ppm in the second particles by weight; and
mixing the plurality of first particles and the plurality of second particles;
wherein the plurality of first particles comprise first lithium cobalt oxide particles with a particle size greater than 11 μm and second lithium cobalt oxide particles with a particle size less than 6 μm, and a ratio in number of the lithium cobalt oxide particles with a particle size greater than 11 μm to the lithium cobalt oxide particles with a particle size less than 6 μm is 0.2-4.8; and
a summed number of the first lithium cobalt oxide particles with a particle size greater than 11 μm and the second lithium cobalt oxide particles with a particle size less than 6 μm accounts for above 90% of a total number of particles in the plurality of first particles.

### Claim 11 (depends on 10)

The method according to claim 10, further comprising: mixing the first lithium cobalt oxide particles and the second lithium cobalt oxide particles to obtain the plurality of first particles,
wherein a particle size Dv50 of the first lithium cobalt oxide particles is 17 μm-21 μm;
a particle size Dv50 of the second lithium cobalt oxide particles is 4 μm-8 μm; and
a weight ratio of the first lithium cobalt oxide particles to the second lithium cobalt oxide particles is 3:1 to 15:1.

### Claim 12 (depends on 10)

The method according to claim 10, wherein the core further comprises an alkaline lithium-containing compound on the surface of the core, and the reaction product is formed by a reaction of the alkaline lithium-containing compound and the sulfur-containing compound of the coating layer precursor.

### Claim 13 (depends on 10)

The method according to claim 10, wherein the coating layer precursor further comprises a neutral or acidic lithium-containing compound.

### Claim 14 (depends on 10)

The method according to claim 10, wherein treating the core with the coating layer precursor further comprises:
applying, on the surface of the core, a solution in which the coating layer precursor is dissolved; and
treating the core with the coating layer precursor at a temperature of 80° C.-300° C. for 3 h-20 h.

### Claim 15 (depends on 1)

An electrode, wherein the electrode comprises the electrode active composition according to claim 1.

### Claim 16 (depends on 1)

A battery, wherein the battery comprises the electrode active composition according to claim 1.

### Claim 17 (depends on 16)

An apparatus, wherein the apparatus comprises the battery according to claim 16, and the battery serves as a power supply unit or an energy storage unit of the apparatus; and
the apparatus is an electric apparatus, and the battery is configured to supply power to the electric apparatus.

### Claim 18 (depends on 10)

The method according to claim 10, wherein the coating layer precursor further comprises a fluorine-containing compound, the reaction product further comprises F, and F accounts for 200 ppm-1500 ppm in the second particles by weight.

### Claim 19 (depends on 10)

The method according to claim 10, wherein the coating layer precursor further comprises a phosphor-containing compound, the reaction product further comprises P, and P accounts for 500 ppm-3000 ppm in the second particles by weight.