# US 11,440,811 B2 · Ternary precursor particles and method for manufacturing the same

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- Number: US 11,440,811 B2
- Document ID: US11440811B2
- Status: Granted
- Kind: B2
- Application number: 16/504,537
- Filed: 2019-07-08
- Published: 2019-11-28
- Granted: 2022-09-13
- Earliest claimed: 2017-11-28
- Assignees: XTC New Energy Materials (Xiamen) Co., Ltd.
- Applicants: XTC New Energy Materials(Xiamen) LTD.
- Inventors: Yue-Fei Ma; Jun Zheng
- Web page: https://patentgrep.com/patent/US11440811B2

## CPC

- C01G 53/84: Hydroxides
- C01G 53/40: Complex oxides containing nickel and at least one other metal element
- 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 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 2002/50: Solid solutions
- C01P 2004/32: Spheres
- C01P 2004/52: highly monodisperse size distribution
- C01P 2004/61: Micrometer sized, i.e. from 1-100 micrometer
- C01P 2004/84: one phase coated with the other
- C01P 2006/11: Powder tap density
- C01P 2006/40: Electric properties
- 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 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

Ternary precursor particles used for a lithium-ion battery, the ternary precursor particles having a NixCoyMnz(OH)2, wherein, x+y+z=1, 0<x<1, 0<y<1, 0<z<1; each ternary precursor particle is a spheroidal structure, and comprises a shell, a transition layer and a particle core; the shell is a dense structure, the particle core is a porous structure, the transition layer surrounds the particle core and is sandwiched between the shell and the particle core; each ternary precursor particle is a mixture formed by mixing the nickel hydroxide, the cobalt hydroxide and the manganese hydroxide at the atomic level; a crystallinity of the shell is greater than a crystallinity of the transition layer, and the crystallinity of the transition layer is greater than a crystallinity of the particle core.

## Claims

### Claim 1

A method for manufacturing ternary precursor particles comprising:
dissolving a nickel source, a cobalt source and a manganese source in a deionized water to form a first mixed solution comprising nickel ions, cobalt ions and manganese ions;
adding the first mixed solution and a first alkaline solution into a first reactor, and adding a first complexing agent into the first reactor, the first mixed solution reacting with hydroxide ions in the first reactor to generate crystal seeds; wherein the first reactor comprises a base solution before adding the first mixed solution and a first alkaline solution into a first reactor, a liquid level of the base solution is higher than a feed inlet of the reactor;
adding the crystal seeds, a second complexing agent, a second mixed solution, and a second alkaline solution into a second reactor to chemically react and form a slurry comprising sediments, wherein the second mixed solution is formed by dissolving a nickel source, a cobalt source and a manganese source in a deionized water, a solid content of the slurry in the second reactor is adjusted by a filtration return process for 1 hour to 12 hours to be maintained from 700 g/L to 1600 g/L;
transferring the slurry into an aging tank for further chemical reactions, separating the sediments from the slurry by a solid-liquid separation process, and washing the separated sediments by deionized water; and
drying the sediments from the aging tank in an oxygen-rich atmosphere to obtain the ternary precursor particles, the precursor particles being a spheroidal structure and comprising a shell, a particle core of a porous structure, and a transition layer surrounding the particle core and sandwiched between the shell and the particle core, wherein a density of the shell is greater than a density of the particle core.

### Claim 2 (depends on 1)

The method for manufacturing ternary precursor particles of claim 1, wherein the first reactor and the second reactor are reaction kettles having a large liquid circulation throughput of 10 m3/h to 40 m3/h, each of the reaction kettles is an induction draft tube structure.

### Claim 3 (depends on 1)

The method for manufacturing ternary precursor particles of claim 1, wherein the first complexing agent is continuously added into the first reactor for 1 hour to 24 hours, a concentration of the first complexing agent gradually increasing from 0 g/L to 45 g/L.

### Claim 4 (depends on 1)

The method for manufacturing ternary precursor particles of claim 1, wherein the first mixed solution reacts with the hydroxide ions in the first reactor at a pH value of 10.5 to 12.8 and a temperature of 40 degrees Celsius to 80 degrees Celsius.

### Claim 5 (depends on 1)

The method for manufacturing ternary precursor particles of claim 1, wherein crystal seeds each has a diameter ranging from 1 μm to 9 μm.

### Claim 6 (depends on 1)

The method for manufacturing ternary precursor particles of claim 1, wherein the crystal seeds, the second complexing agent, the second mixed solution and the second alkaline solution chemically react at a pH value of 10.5 to 12.8.

### Claim 7 (depends on 1)

The method for manufacturing ternary precursor particles of claim 1, wherein the separated sediments are dried at a temperature of 270 degrees Celsius to 350 degrees Celsius for 1 hour to 4 hours.

### Claim 8 (depends on 1)

The method for manufacturing ternary precursor particles of claim 1, wherein each of the first alkaline solution and the second alkaline solution is selected from at least one of sodium hydroxide solution and potassium hydroxide solution; each of the first complexing agent and the second complexing agent is selected from a group consisting of ammonium hydroxide, ammonium sulfate, ethylenediaminetetraacetic acid, sodium bicarbonate, oxalic acid, and any combination thereof.

### Claim 9 (depends on 1)

The method for manufacturing ternary precursor particles of claim 1, wherein hydroxide ions of the first alkaline solution and metal cations of the first mixed solution are in a molar ratio of 0.5:1 to 2.8:1.

### Claim 10 (depends on 1)

The method for manufacturing ternary precursor particles of claim 1, wherein a ratio of a molar concentration of metal cations in the second mixed solution to a molar concentration of the metal cations in the first mixed solution is 0.4 to 1.5.

### Claim 11 (depends on 1)

The method for manufacturing ternary precursor particles of claim 1, wherein the further chemical reactions in the aging tank occurs at a pH value of 10 to 13.

### Claim 12 (depends on 1)

The method for manufacturing ternary precursor particles of claim 1, wherein the sediments from the aging tank are washed by the deionized water until a pH value of the sediments is less than 8.