# US 12,215,040 B2 · Lithium nickel manganese oxide composite material, preparation method thereof and lithium ion battery

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- Number: US 12,215,040 B2
- Document ID: US12215040B2
- Status: Granted
- Kind: B2
- Application number: 17/641,820
- Filed: 2020-10-28
- Published: 2023-03-16
- Granted: 2025-02-04
- Earliest claimed: 2020-05-25
- Assignees: Svolt Energy Technology Co., Ltd.
- Applicants: Svolt Energy Technology Co., Ltd.
- Inventors: Jiali Ma; Hongxin Yang; Weijun Jiang; Qiqi Qiao; Mingzhu Sun; Xinpei Xu; Zetao Shi; Pengfei Wang; Sixian Chen
- Web page: https://patentgrep.com/patent/US12215040B2

## CPC

- C01G 53/44: containing manganese
- C01G 53/50: of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2
- H01M 4/366: {as layered products}
- 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 4/62: Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M 4/628: {Inhibitors, e.g. gassing inhibitors, corrosion inhibitors}
- C01P 2004/03: obtained by SEM
- C01P 2004/84: one phase coated with the other
- C01P 2006/40: Electric properties
- H01M 2004/028: {Positive electrodes}
- Y02E 60/10: Energy storage using batteries
- 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

## Abstract

Provided are a lithium nickel manganese oxide composite material, a preparation method thereof and a lithium ion battery. The preparation method includes: a first calcining process is performed on a nano-oxide and a nickel-manganese precursor, to obtain an oxide-coated nickel-manganese precursor; and a second calcining process is performed on the precursor and a lithium source material, to obtain the lithium nickel manganese oxide, and a temperature of the first calcining process is lower than the second calcining process. A a lower temperature, the nano-oxide may be melted, a denser nano-oxide coating layer is formed on the surface of the precursor, so the oxide-coated nickel-manganese precursor is obtained. At a higher temperature, the nano-oxide, a nickel-manganese material and a lithium element may be more deeply combined. A problem that the nano-oxide layer is easy to fall off is solved, and cycle performance of the lithium nickel manganese oxide is greatly improved.

## Claims

### Claim 1

A preparation method for a lithium nickel manganese oxide composite material, the preparation method comprises:
performing a first calcining process on a nano-oxide and a nickel-manganese precursor, to obtain an oxide-coated nickel-manganese precursor; wherein the nickel-manganese precursor is represented by NixMny(OH)2, 0.50≤x≤0.92, 0.50≤y≤0.8; the nano-oxide is selected from two or more in a group consisting of an aluminum oxide, a zirconium oxide, a titanium oxide, a niobium oxide, a tungsten oxide, a lanthanum oxide and a molybdenum oxide; and
performing a second calcining process on the oxide-coated nickel-manganese precursor and a lithium source material, to obtain the lithium nickel manganese oxide composite material, and a temperature of the first calcining process is lower than a temperature of the second calcining process.

### Claim 2 (depends on 1)

The preparation method according to claim 1, wherein before performing the first calcining process, the preparation method further comprises:
performing a first mixing step on the nano-oxide and the nickel-manganese precursor, to obtain a first mixture;
wherein the first mixing step process is mixed for 10-20 min at a rotation speed of 2000-3000 rpm.

### Claim 3 (depends on 2)

The preparation method according to claim 2, wherein the first calcining process is a temperature programmed process;
the first calcining process comprises:
in an oxygen atmosphere, increasing a temperature of a first calcining reaction to a first target temperature at a rate of 3-5° C./min, and a holding time is 4-6 h, wherein the first target temperature is 300-600° C.; and
decreasing the temperature of the first calcining reaction to a room temperature, to obtain the oxide-coated nickel-manganese precursor.

### Claim 4 (depends on 3)

The preparation method according to claim 3, wherein the nano-oxide is a mixture of zirconium oxide and aluminum oxide, a weight ratio of the zirconium oxide, the aluminum oxide and the nickel-manganese precursor is (0.001-0.003):(0.001-0.003):1.

### Claim 5 (depends on 4)

The preparation method according to claim 4, wherein before performing the second calcining process, the preparation method further comprises:
performing a second mixing step on the oxide-coated nickel-manganese precursor and the lithium source material, to obtain a second mixture;
wherein the second mixing step process is mixed for 10-20 min at a rotation speed of 2000-3000 rpm.

### Claim 6 (depends on 5)

The preparation method according to claim 5, wherein the second calcining process is a temperature programmed process;
the second calcining process comprises:
in an oxygen atmosphere, increasing a temperature of a second calcining reaction to a second target temperature at a rate of 3-5° C./min, and holding time is 8-12 h, wherein the second target temperature is 910-950° C.; and
decreasing the temperature of the second calcining reaction to a room temperature, to obtain the lithium nickel manganese oxide composite material.

### Claim 7 (depends on 3)

The preparation method according to claim 3, wherein before performing the second calcining process, the preparation method further comprises:
performing a second mixing step on the oxide-coated nickel-manganese precursor and the lithium source material, to obtain a second mixture;
wherein the second mixing step process is mixed for 10-20 min at a rotation speed of 2000-3000 rpm.

### Claim 8 (depends on 2)

The preparation method according to claim 2, wherein the nano-oxide is a mixture of zirconium oxide and aluminum oxide, a weight ratio of the zirconium oxide, the aluminum oxide and the nickel-manganese precursor is (0.001-0.003):(0.001-0.003):1.

### Claim 9 (depends on 2)

The preparation method according to claim 2, wherein before performing the second calcining process, the preparation method further comprises:
performing a second mixing step on the oxide-coated nickel-manganese precursor and the lithium source material, to obtain a second mixture;
wherein the second mixing step process is mixed for 10-20 min at a rotation speed of 2000-3000 rpm.

### Claim 10 (depends on 1)

The preparation method according to claim 1, wherein before performing the second calcining process, the preparation method further comprises:
performing a second mixing step on the oxide-coated nickel-manganese precursor and the lithium source material, to obtain a second mixture;
wherein the second mixing step process is mixed for 10-20 min at a rotation speed of 2000-3000 rpm.

### Claim 11 (depends on 10)

The preparation method according to claim 10, wherein the second calcining process is a temperature programmed process;
the second calcining process comprises:
in an oxygen atmosphere, increasing a temperature of a second calcining reaction to a second target temperature at a rate of 3-5° C./min, and holding time is 8-12 h, wherein the second target temperature is 910-950° C.; and
decreasing the temperature of the second calcining reaction to a room temperature, to obtain the lithium nickel manganese oxide composite material.

### Claim 12 (depends on 10)

The preparation method according to claim 10, wherein a ratio of a mole number of a Li element in the lithium source material to a sum of mole numbers of a Ni element and a Mn element in the oxide-coated nickel-manganese precursor is (1.00˜1.05):1.

### Claim 13 (depends on 10)

The preparation method according to claim 10, wherein the second calcining process further comprises: decreasing the temperature of the second calcining reaction to the room temperature, to obtain a second calcined product; and performing ultracentrifugal grinding and sieving on the product of the second calcining process, wherein a sieving aperture of the sieving process is 300-400 meshes, to obtain the lithium nickel manganese oxide composite material in the form of a single crystal.

### Claim 14 (depends on 1)

A lithium nickel manganese oxide composite material, wherein the lithium nickel manganese oxide composite material is prepared by the preparation method according to claim 1.

### Claim 15 (depends on 14)

The lithium nickel manganese oxide composite material according to claim 14, wherein in the lithium nickel manganese oxide composite material, a coating amount of the nano-oxide is 0.1-0.3%.

### Claim 16 (depends on 14)

A lithium ion battery, comprising a positive electrode material, wherein the positive electrode material comprises the lithium nickel manganese oxide composite material according to claim 14.

### Claim 17 (depends on 14)

The lithium nickel manganese oxide composite material according to claim 14, wherein before performing the first calcining process, the preparation method further comprises:
performing a first mixing step on the nano-oxide and the nickel-manganese precursor, to obtain a first mixture;
wherein the first mixing step process is mixed for 10-20 min at a rotation speed of 2000-3000 rpm.

### Claim 18 (depends on 17)

The lithium nickel manganese oxide composite material according to claim 17, wherein the nano-oxide is a mixture of zirconium oxide and aluminum oxide, a weight ratio of the zirconium oxide, the aluminum oxide and the nickel-manganese precursor is (0.001-0.003):(0.001-0.003):1.

### Claim 19 (depends on 1)

The preparation method according to claim 1, wherein a particle size of the nano-oxide is 300-700 nm.

### Claim 20 (depends on 1)

The preparation method according to claim 1, the preparation method further comprises: sieving a product of the first calcining process, to obtain the oxide-coated nickel-manganese precursor, and a sieving aperture of the sieving process is 300-400 meshes.