# US 2018/0006302 A1 · Cathode material of lithium cobalt oxide for a lithium ion secondary battery and preparation methods and applications thereof

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- Number: US 2018/0006302 A1
- Document ID: US20180006302A1
- Status: Published application
- Kind: A1
- Application number: 15/498,527
- Filed: 2017-04-27
- Published: 2018-01-04
- Earliest claimed: 2016-07-01
- Assignees: Shenzhen Zhenhua E-CHEM Co., Ltd.; Guizhou Zhenhua E-CHEM Inc.; Guizhou Zhenhua E-CHEM Co., Ltd, Shenzhen branch
- Applicants: Shenzhen Zhenhua E-CHEM Co., Ltd.; Guizhou Zhenhua E-CHEM Co., Ltd.; Guizhou Zhenhua E-CHEM Co., Ltd, Shenzhen branch
- Inventors: Lu Li; Xingping Wu; Maogang Fu; Ansheng Hu; Ming Mei; Xin Huang; Qianxin Xiang
- Web page: https://patentgrep.com/patent/US20180006302A1

## CPC

- 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 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 4/366: {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 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- 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

The invention relates to a cathode material of lithium cobalt oxide for a lithium ion secondary battery and preparation methods and applications thereof. A cathode material comprises a core material and a coating layer, wherein the core material is LixCo(1−y)AyO(2+z), wherein 1.0≦x≦1.11, 0≦y≦0.02, −0.2<z<0.2, and A is one or two or more selected from the group consisting of Al, Mg, Y, Zr and Ti, wherein the coating layer is LiaMbBcOd, wherein M is a lithium ion active metal element and one or two or more selected from the group consisting of Co, Ni, Mn and Mo, and B is an inactive element, and one or two or more selected from the group consisting of Al, Mg, Ti, Zr and Y, and 0.95<b+c<2.5, and the molar ratio of Li to the active metal element M is 0<a/b<1. The battery prepared by the cathode material has advantages of high capacity, high compacted density and excellent cycling stability etc., under high voltage.

## Claims

### Claim 1

A cathode material of lithium cobalt oxide for a lithium ion secondary battery is characterized by comprising a core material and a coating layer,
wherein the core material is LixCo(1−y)AyO(2+z), wherein 1.0≦x≦1.11, 0≦y≦0.02, −0.2<z<0.2, and A is one or two or more selected from the group consisting of Al, Mg, Y, Zr and Ti,
wherein the coating layer is LiaMbBcOd, wherein M is a lithium ion active metal element, which is one or two or more selected from the group consisting of Co, Ni, Mn and Mo; and B is an inactive element, which is one or two or more selected from the group consisting of Al, Mg, Ti, Zr, and Y, and 0.95<b+c<2.5, and the molar ratio of Li to the active metal element M is 0<a/b<1.

### Claim 2 (depends on 1)

The cathode material according to claim 1, wherein the weight percentage of lithium ion active metal M accounts for 0.1 wt. % to 10 wt. % of the cathode material in the coating layer.

### Claim 3 (depends on 1)

The cathode material according to claim 1, wherein the weight percentage of lithium ion active metal M accounts for 0.8 wt. % to 8.5 wt. % of the cathode material in the coating layer.

### Claim 4 (depends on 1)

The cathode material according to claim 1, wherein the molar ratio of Li to the active metal element M is 0.1≦a/b≦0.9.

### Claim 5 (depends on 2)

The cathode material according to claim 2, wherein the molar ratio of Li to the active metal element M is 0.1≦a/b≦0.9.

### Claim 6 (depends on 1)

The cathode material according to claim 1, wherein the molar ratio of Li to the active metal element M is 0.4≦a/b≦0.9.

### Claim 7 (depends on 1)

The cathode material according to claim 1, wherein b/(b+c) is more than 0.3 and less than 1 in the coating layer.

### Claim 8 (depends on 2)

The cathode material according to claim 2, wherein b/(b+c) is more than 0.3 and less than 1 in the coating layer.

### Claim 9 (depends on 4)

The cathode material according to claim 4, wherein b/(b+c) is more than 0.3 and less than 1 in the coating layer.

### Claim 10 (depends on 1)

The cathode material according to claim 1, wherein the active metal element M is one or two or more selected from the group consisting of Ni, Mn and Co.

### Claim 11 (depends on 2)

The cathode material according to claim 2, wherein the active metal element M is one or two or more selected from the group consisting of Ni, Mn and Co.

### Claim 12 (depends on 4)

The cathode material according to claim 4, wherein the active metal element M is one or two or more selected from the group consisting of Ni, Mn and Co.

### Claim 13 (depends on 10)

The cathode material according to claim 10, wherein the active metal element includes Ni and Mn.

### Claim 14 (depends on 11)

The cathode material according to claim 11, wherein the active metal element includes Ni and Mn.

### Claim 15 (depends on 12)

The cathode material according to claim 12, wherein the active metal element includes Ni and Mn.

### Claim 16 (depends on 13)

The cathode material according to claim 13, wherein the active metal elements are Co, Ni and Mn.

### Claim 17 (depends on 14)

The cathode material according to claim 14, wherein the active metal elements are Co, Ni and Mn.

### Claim 18 (depends on 15)

The cathode material according to claim 15, wherein the active metal elements are Co, Ni and Mn.

### Claim 19 (depends on 1)

The cathode material according to claim 1, wherein y is more than or equal to 0 and less than or equal to 0.01 in the core material.

### Claim 20 (depends on 2)

The cathode material according to claim 2, wherein y is more than or equal to 0 and less than or equal to 0.01 in the core material.

### Claim 21 (depends on 4)

The cathode material according to claim 4, wherein y is more than or equal to 0 and less than or equal to 0.01 in the core material.

### Claim 22 (depends on 19)

The cathode material according to claim 19, wherein y is more than or equal to 0.005 and less than or equal to 0.01 in the core material.

### Claim 23 (depends on 1)

The cathode material according to claim 1, wherein z is more than or equal to −0.1 and less than or equal to 0.1 in the core material.

### Claim 24 (depends on 2)

The cathode material according to claim 2, wherein z is more than or equal to −0.1 and less than or equal to 0.1 in the core material.

### Claim 25 (depends on 4)

The cathode material according to claim 4, wherein z is more than or equal to −0.1 and less than or equal to 0.1 in the core material.

### Claim 26 (depends on 10)

The cathode material according to claim 10, wherein z is more than or equal to −0.1 and less than or equal to 0.1 in the core material.

### Claim 27 (depends on 19)

The cathode material according to claim 19, wherein z is more than or equal to −0.1 and less than or equal to 0.1 in the core material.

### Claim 28 (depends on 1)

The cathode material according to claim 1, wherein the structure of the cathode material is selected from the group consisting of α-NaFeO2 layer, spinel or olivine structure.

### Claim 29 (depends on 28)

The cathode material according to claim 28, wherein a X-ray diffraction spectrum of the cathode material is shown as an α-NaFeO2 layer structure containing (003), (104), (110), (018), (012) and (006) characteristic peaks, wherein, the ratio of the (003) characteristic peak intensity to the (104) characteristic peak intensity is greater than 1.0.

### Claim 30 (depends on 29)

The cathode material according to claim 29, wherein a ratio of the (110) characteristic peak intensity to the (018) characteristic peak intensity is between 0.5 and 1.4.

### Claim 31 (depends on 29)

The cathode material according to claim 29, wherein a ratio of the (012) characteristic peak intensity to the (006) characteristic peak intensity is between 0.2 and 2.5.

### Claim 32 (depends on 1)

The cathode material according to claim 1, wherein the particle diameter of the core material is 5 μm to 25 μm.

### Claim 33 (depends on 32)

The cathode material according to claim 32, wherein the particle diameter of the core material is 14 μm to 17 μm.

### Claim 34 (depends on 1)

A preparation method for preparing the cathode material of claim 1, which is characterized by comprising the following steps:
mixing a compound containing constituent elements of the coating layer as raw materials according to the stoichiometric ratio, adding the core material and sintering the obtained mixture to obtain the cathode material.

### Claim 35 (depends on 34)

The preparation method according to claim 34, wherein the compound is selected from the group consisting of oxides, hydroxides, oxyhydroxides, carbonates, sulfates, nitrates and organometallic compounds of the constituent elements.

### Claim 36 (depends on 34)

The preparation method according to claim 34, the process of sintering includes the following steps:
a first sintering in the temperature range of 900 to 1100° C. for a period of 2 to 24 hours.

### Claim 37 (depends on 35)

The preparation method according to claim 35, the process of sintering includes the following steps:
a first sintering in the temperature range of 900 to 1100° C. for a period of 2 to 24 hours.

### Claim 38 (depends on 36)

The preparation method according to claim 36, the process of sintering further comprises the following steps:
a second sintering in the temperature range of 600-1100° C. for a period of 2 to 24 hours.

### Claim 39 (depends on 37)

The preparation method according to claim 37, the process of sintering further comprises the following steps:
a second sintering in the temperature range of 600-1100° C. for a period of 2 to 24 hours.

### Claim 40

A cathode material composition for a lithium ion secondary battery, which is characterized by comprising a cathode material of lithium cobalt oxide in a weight fraction of 40% to 100%,
wherein the cathode material comprises a core material and a coating layer,
wherein the core material is LixCo(1−y)AyO(2+z), wherein 1.0≦x≦1.11, 0≦y≦0.02, −0.2<z<0.2, and A is one or two or more selected from the group consisting of Al, Mg, Y, Zr and Ti,
wherein the coating layer is LiaMbBcOd, wherein M is a lithium ion active metal element, which is one or two or more selected from the group consisting of Co, Ni, Mn and Mo; and B is an inactive element, which is one or two or more selected from the group consisting of Al, Mg, Ti, Zr, and Y, and 0.95<b+c<2.5, and the molar ratio of Li to the active metal element M is 0<a/b<1.

### Claim 41 (depends on 40)

The cathode material composition for a lithium ion secondary battery according to claim 40, wherein the weight percentage of lithium ion active metal M accounts for 0.1 wt. % to 10 wt. % of the cathode material in the coating layer.

### Claim 42 (depends on 40)

The cathode material composition for a lithium ion secondary battery according to claim 40, wherein the molar ratio of Li to the active metal element M is 0.1≦a/b≦0.9.

### Claim 43

A positive electrode of a lithium ion battery prepared by a raw material containing a cathode material of lithium cobalt oxide as a cathode active material,
wherein the cathode material comprises a core material and a coating layer,
wherein the core material is LixCo(1−y)AyO(2+z), wherein 1.0≦x≦1.11, 0≦y≦0.02, −0.2<z<0.2, and A is one or two or more selected from the group consisting of Al, Mg, Y, Zr and Ti,
wherein the coating layer is LiaMbBcOd, wherein M is a lithium ion active metal element, which is one or two or more selected from the group consisting of Co, Ni, Mn and Mo; and B is an inactive element, which is one or two or more selected from the group consisting of Al, Mg, Ti, Zr, and Y, and 0.95<b+c<2.5, and the molar ratio of Li to the active metal element M is 0<a/b<1.

### Claim 44 (depends on 43)

The positive electrode of a lithium ion battery according to claim 43, wherein the weight percentage of lithium ion active metal M accounts for 0.1 wt. % to 10 wt. % of the cathode material in the coating layer.

### Claim 45 (depends on 43)

The positive electrode of a lithium ion battery according to claim 43, wherein the molar ratio of Li to the active metal element M is 0.1≦a/b≦0.9.

### Claim 46 (depends on 43)

The positive electrode of a lithium ion battery according to claim 43, wherein the active metal element M is one or two or more selected from the group consisting of Ni, Mn and Co.

### Claim 47 (depends on 43)

A lithium ion battery prepared by using the positive electrode of a lithium ion battery of claim 43.

### Claim 48 (depends on 1)

A use of the cathode material of claim 1 in the lithium electric energy field.

### Claim 49 (depends on 47)

A use of the lithium ion battery of claim 47 in the lithium electric energy field.