# US 12,763,328 B2 · Ternary precursor and preparation method therefor, ternary positive electrode material, and electric apparatus

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- Number: US 12,763,328 B2
- Document ID: US12763328B2
- Status: Granted
- Kind: B2
- Application number: 18/322,010
- Filed: 2023-05-23
- Published: 2024-06-20
- Granted: 2026-10-13
- Earliest claimed: 2021-09-18
- Assignees: Contemporary Amperex Technology (Hong Kong) Limited
- Applicants: Contemporary Amperex Technology (Hong Kong) Limited
- Inventors: Qi Wu; Chongheng Shen; Qiang Chen; Jingpeng Fan; Yuxiang Zhao; Qisen Huang
- Web page: https://patentgrep.com/patent/US12763328B2

## CPC

- 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
- C01G 53/05: Hydroxides; Oxyhydroxides
- C01G 53/84: Hydroxides
- H01M 4/505: of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
- C01P 2002/72: by d-values or two theta-values, e.g. as X-ray diagram
- C01P 2004/03: obtained by SEM
- C01P 2004/50: Agglomerated particles
- C01P 2004/51: Particles with a specific particle 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 2006/12: Surface area
- C01P 2006/40: Electric properties
- H01M 2004/021: {Physical characteristics, e.g. porosity, surface area}
- H01M 2004/028: {Positive electrodes}
- H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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)
- C01P: INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS

## Abstract

This application relates to a ternary precursor for making a material for positive electrodes in lithium batteries. In the ternary precursor, primary particles or whiskers of the ternary precursor are distributed in a radial direction. A deformation stacking fault probability fD of the ternary precursor is ≤2.5%. This application further relates to a preparation method of the ternary precursor, a ternary positive electrode material, a secondary battery, a battery module, a battery pack, and an electric apparatus.

## Claims

### Claim 1

A ternary precursor, wherein primary particles or whiskers of the ternary precursor are distributed in a radial direction; and
a deformation stacking fault probability fD of the ternary precursor is ≤2.5%, and the deformation stacking fault probability fD is calculated as follows:
fD=0.1552×B(101)−0.03233×B (102)−0.4399/D (001),
where B (101) is a full width at half maximum in an X-ray diffraction pattern of a (101) crystal plane of the ternary precursor, B (102) is a full width at half maximum in an X-ray diffraction pattern of a (102) crystal plane of the ternary precursor, and D (001) is a full width at half maximum in an X-ray diffraction pattern of a (001) crystal plane of the ternary precursor, where the full widths at half maximum are measured in degrees;
wherein the ternary precursor comprises an inner core and a shell enclosing the inner core, a radius R of the inner core is 0.1-6.0 μm, and a thickness h of the shell is 2-10 μm;
wherein a molecular formula of the inner core is [NixCoyMn(1-x-y)] (OH)2, wherein 0.8≤x<1.0,0<y<0.2, and x+y<1;
a molecular formula of the shell is [NiaCobMn(1-a-b)](OH)2, wherein 0.8≤a<1.0, 0<b<0.2, and a+b<1; and
Ni contents in the inner core and the shell make the following relationship hold: a≤x.

### Claim 2 (depends on 1)

The ternary precursor according to claim 1, wherein a volume distribution span of particles of the ternary precursor is (Dv90-Dv10)/Dv50≥1.3.

### Claim 3 (depends on 1)

The ternary precursor according to according to claim 1, wherein a volume-based median particle size Dv50 of particles of the ternary precursor is 5-15 μm.

### Claim 4 (depends on 1)

The ternary precursor according to according to claim 1, wherein a specific surface area BET of particles of the ternary precursor is ≥5-20 m2/g.

### Claim 5 (depends on 1)

The ternary precursor according to claim 1, wherein a tap density (TD) of particles of the ternary precursor is ≥1.9 g/cm3.

### Claim 6 (depends on 1)

The ternary precursor according to claim 1, wherein a cracking rate of particles of the ternary precursor is ≤20% at a pressure of 5 tons, wherein an expression of the cracking rate is a α=[Dv1 (before compression)-Dv1 (after compression)]/Dv1 (before compression),
wherein Dv1 (before compression) is a particle size at which cumulative distribution by volume of the ternary precursor before compression reaches 1% as counted from the small particle size side, measured in μm, and
Dv1 (after compression) is a particle size at which cumulative distribution by volume of the ternary precursor after compression reaches 1% as counted from the small particle size side, measured in μm.

### Claim 7 (depends on 1)

The ternary precursor according to claim 1, wherein the ternary precursor is doped with element M, the element M is one or more of Zr, W, Al, Sr, Ti, Ca, Sb, Mg, Zn, Te, and Fe.

### Claim 8

A preparation method of ternary precursor, comprising:
providing a first mixed nickel-cobalt-manganese metal salt solution and a second mixed nickel-cobalt-manganese metal salt solution;
adding a first base solution having a first pH value and a first ammonia concentration to a first reactor, and adding the first mixed nickel-cobalt-manganese metal salt solution, an alkali solution, and ammonia to the first reactor to maintain the pH value and the ammonia concentration unchanged, so as to form a seed crystal slurry of ternary precursor; and
adding water as a base solution to a second reactor, adding the seed crystal slurry of ternary precursor to adjust the base solution to a second pH value and a second ammonia concentration, and adding the second mixed nickel-cobalt-manganese metal salt solution, an alkali solution, ammonia, and the seed crystal slurry of ternary precursor to the second reactor to maintain the pH value and the ammonia concentration unchanged, so as to form a ternary precursor;
wherein primary particles or whiskers of the ternary precursor are distributed in a radial direction; and a deformation stacking fault probability fD of the ternary precursor is ≤2.5%, and the deformation stacking fault probability fD is calculated as follows:
fD=0.1552×B (101)−0.03233×B (102)−0.4399/D (001),
where B (101) is a full width at half maximum in an X-ray diffraction pattern of a (101) crystal plane of the ternary precursor, B (102) is a full width at half maximum in an X-ray diffraction pattern of a (102) crystal plane of the ternary precursor, and D (001) is a full width at half maximum in an X-ray diffraction pattern of a (001) crystal plane of the ternary precursor, where the full widths at half maximum are measured in degrees;
wherein the ternary precursor comprises an inner core and a shell enclosing the inner core, a radius R of the inner core is 0.1-6.0 μm, and a thickness h of the shell is 2-10 μm;
wherein a molar ratio of nickel, cobalt, and manganese in the first mixed nickel-cobalt-manganese metal salt solution is x: y: (1-x-y), wherein 0.8≤x<1.0, 0<y<0.2, and x+y<1; and a molar ratio of nickel, cobalt, and manganese in the second mixed nickel-cobalt-manganese metal salt solution is a: b: (1-a-b), wherein 0.8≤a<1.0, 0<b<0.2, a+b<1, and a≤x.

### Claim 9 (depends on 8)

The method according to claim 8, wherein the first pH value is 11.5-12.5; and the first ammonia concentration is 0.2-0.6 mol/L.

### Claim 10 (depends on 8)

The method according to claim 8, wherein the second pH value is 11.0-12.0; and the second ammonia concentration is 0.2-0.6 mol/L.

### Claim 11 (depends on 8)

The method according to claim 8, wherein a solid-liquid ratio of the seed crystal slurry of ternary precursor in the second reactor is 0.1-0.2.

### Claim 12 (depends on 8)

The method according to according to claim 8, wherein a volume-based median particle size Dv50 of the seed crystal slurry of ternary precursor is 1-5 μm; and a volume-based median particle size Dv50 of the ternary precursor is 5-15 μm.

### Claim 13 (depends on 1)

A ternary positive electrode material, made of the ternary precursor according to claim 1.

### Claim 14 (depends on 13)

The ternary positive electrode material according to claim 13, wherein the ternary positive electrode material comprises secondary particles formed by aggregation of a plurality of primary particles, wherein the plurality of primary particles are arranged in a radial direction of the secondary particles.

### Claim 15 (depends on 13)

The ternary positive electrode material according to claim 13, wherein a volume-based median particle size Dv50 of the ternary positive electrode material is 5-15 μm.

### Claim 16 (depends on 13)

A secondary battery, comprising the ternary positive electrode material according to claim 13.

### Claim 17 (depends on 16)

A battery module, comprising the secondary battery according to claim 16.

### Claim 18 (depends on 1)

The ternary precursor according to according to claim 1, wherein said X-ray diffraction patterns are measured with a Brucker D8DISCOER X-ray diffractometer performing a slow (1°/min) scan as a 2θ angle of 10-70°.