# US 12,006,230 B2 · Process for making a nickel composite hydroxide

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- Number: US 12,006,230 B2
- Document ID: US12006230B2
- Status: Granted
- Kind: B2
- Application number: 17/290,876
- Filed: 2019-10-30
- Published: 2021-12-02
- Granted: 2024-06-11
- Earliest claimed: 2018-11-09
- Assignees: BASF SE
- Applicants: BASF SE
- Inventors: Thorsten Beierling; Daniela Pfister
- Web page: https://patentgrep.com/patent/US12006230B2

## CPC

- C01G 53/84: Hydroxides
- C01G 53/66: containing alkaline earth metals, e.g. SrNiO3 or SrNiO2
- C01P 2002/50: Solid solutions
- C01P 2002/52: containing elements as dopants
- C01P 2004/51: Particles with a specific particle size distribution
- C01P 2004/61: Micrometer sized, i.e. from 1-100 micrometer
- C01P 2006/12: Surface area
- 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
- 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)
- C01P: INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- 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

Described herein is a process for making a nickel composite hydroxide with a mean particle diameter d50 in the range from 3 to 20 μm including combining (a) an aqueous solution of water-soluble salts of nickel and of at least one of cobalt and manganese, and, optionally, at least one of Al, Mg, B, or transition metals other than nickel, cobalt, and manganese, (b) an aqueous solution of an alkali metal hydroxide and (c) an aqueous solution of alkali metal (bi)carbonate or ammonium (bi)carbonate in the molar ratio of 0.001:1 to 0.04:1, and, optionally, (d) an aqueous solution of alkali metal aluminate, in a continuous stirred tank reactor or in a cascade of at least two continuous stirred tank reactors.

## Claims

### Claim 1

A nickel composite hydroxide in particulate form with a mean particle diameter d50 in the range from 3 to 20 μm and a width of particle diameter distribution, calculated as [(d90−d10)/(d50)], of at least 0.61, containing in the range of from 60 to 95 mole-% Ni and at least one transition metal selected from the group consisting of Co and Mn, and in the range of from 0.1 to 3.0% by weight of carbonate, with respect to said nickel composite hydroxide.

### Claim 2 (depends on 1)

The nickel composite hydroxide according to claim 1 having a composition according to general formula (II)
(NiaCobAlc)1-d-MdOx(OH)y(CO3)z (II)
wherein
a is in the range from 0.60 to 0.95,
b is in the range of from 0.025 to 0.2,
c is in the range of from 0.005 to 0.1,
d is in the range of from zero to 0.05, and
M is selected from the group consisting of Mg, B and transition metals other than Co and Ni, and combinations of at least two of the foregoing,
wherein a+b+c=1.0,
0≤x<1,
1<y≤2.1, and
0<z≤0.25.

### Claim 3 (depends on 1)

The nickel composite hydroxide according to claim 1 wherein the metal part has a composition according to general formula (III)
(NiaCobAlc)1-d-Md (III)
wherein:
a is in the range from 0.80 to 0.95,
b is in the range of from 0.025 to 0.195,
c is in the range of from 0.02 to 0.05,
d is in the range of from zero to 0.035, and
M is selected from the group consisting of one or more of Ti, Zr, Nb, W, and Mg, and combinations of Mg and at least one of Ti, Zr, Nb, and W,
wherein a+b+c=1.0 and
b+c<0.20.

### Claim 4 (depends on 1)

The nickel composite hydroxide according to claim 1 wherein said nickel composite hydroxide has a specific surface (BET) in the range of from 5 to 70 m2/g.

### Claim 5 (depends on 1)

A method of using the nickel composite hydroxide according to claim 1, the method comprising using the nickel composite hydroxide as a precursor for the manufacture of cathode active materials for lithium ion batteries.

### Claim 6 (depends on 1)

A process for making the nickel composite hydroxide of claim 1 comprising combining
(a) an aqueous solution of water-soluble salts of nickel and of at least one of cobalt and manganese, and, optionally, at least one of Al, Mg, B, or transition metals other than nickel, cobalt, and manganese,
(b) an aqueous solution of an alkali metal hydroxide,
(c) an aqueous solution of alkali metal (bi)carbonate or ammonium (bi)carbonate in the molar ratio of 0.001:1 to 0.04:1, referring to alkali metal hydroxide, and, optionally,
(d) an aqueous solution of alkali metal aluminate,
in a continuous stirred tank reactor or in a cascade of at least two continuous stirred tank reactors in one or more steps, wherein
solutions (b) and (c) are combined first followed by combination with solution (a) and optionally with solution (d),
or solutions (a) and (c) are combined first followed by combination with solution (b) and optionally with solution (d),
or solutions (a), (b), (c) and optionally (d) are combined simultaneously.

### Claim 7 (depends on 6)

The process according to claim 6 wherein said nickel composite hydroxide contains a combination of transition metals and further metals according to general formula (I)
(NiaCobAlc)1-dMd (I)
wherein
a is in the range from 0.70 to 0.95,
b is in the range of from 0.025 to 0.2,
c is in the range of from 0.005 to 0.1,
d is in the range of from zero to 0.05, and
M is selected from the group consisting of Mg, B and transition metals other than Co and Ni, and combinations of at least two of the foregoing,
wherein a+b+c=1.0.

### Claim 8 (depends on 6)

The process according to claim 6, wherein said process is carried out a pH value in the range of from 11.5 to 12.8.

### Claim 9 (depends on 6)

The process according to claim 6, wherein said process is carried out in a cascade of at least two continuous stirred tank reactors, and wherein (a) is combined with (b) and (c) in the first tank reactor at a pH value in the range of from 12.0 to 12.8 and in the second tank reactor at a pH value in the range of from 11.5 to 12.4.

### Claim 10 (depends on 7)

The process according to claim 7, wherein M includes Mg in the range of from 0.1 to 2.5 mole-% with respect to the metals in said nickel composite hydroxide.

### Claim 11 (depends on 6)

The process according to claim 6, wherein the water-soluble salts are selected from the group consisting of sulfates and nitrates.

### Claim 12 (depends on 6)

The process according to claim 6, wherein said process includes the addition of a solution (d) comprising alkali metal aluminate.