# US 11,909,044 B2 · Precursor of a positive electrode material for a rechargeable lithium-ion battery

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- Number: US 11,909,044 B2
- Document ID: US11909044B2
- Status: Granted
- Kind: B2
- Application number: 17/287,148
- Filed: 2019-10-23
- Published: 2021-12-16
- Granted: 2024-02-20
- Earliest claimed: 2018-10-24
- Assignees: Umicore AG & Co. KG; Umicore Korea Ltd.
- Applicants: Umicore; Umicore Korea Ltd.
- Inventors: Maxime Blangero; Liang Zhu; YuRi Lee; Kris Driesen
- Web page: https://patentgrep.com/patent/US11909044B2

## CPC

- C01G 53/82: Compounds containing nickel, with or without oxygen or hydrogen, and containing two or more other elements
- 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 53/504: with the molar ratio of nickel with respect to all the metals other than alkali metals higher than or equal to 0.5, e.g. Li(MzNixCoyMn1-x-y-z)O2 with x ≥ 0.5
- H01M 4/505: of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
- C01P 2002/52: containing elements as dopants
- C01P 2004/61: Micrometer sized, i.e. from 1-100 micrometer
- C01P 2004/84: one phase coated with the other
- C01P 2006/40: Electric properties
- H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- 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

A precursor compound for manufacturing a lithium transition metal based oxide powder usable as an active positive electrode material in lithium-ion batteries, the precursor being either one of a metal-bearing M′-hydroxide, -oxyhydroxide or -carbonate, with M′=Ni1-x-y-zMnxCOyAz with x>0, y>0, 0.70≤1-x-y-z≤0.95 and 0≤z<0.1, the precursor comprising having a core comprising a metal-bearing compound M′c and a shell comprising a metal-bearing compound M′s, wherein M′c=Ni1-xc-yc-zcMnxcCOycAzc with 0<xc≤0.2, 0<yc≤0.2, 0≤zc<0.1 and 0.75≤1-x-y-z≤0.95, and M′s=Ni1-xs-ys-zsMnxsCOysAzs with 0<xs≤0.25, 0.75<ys≤0.95, 0≤zs<0.1 and 0≤1-xs-ys-zs≤0.10.

## Claims

### Claim 1

A precursor compound for manufacturing a lithium transition metal-based oxide powder usable as an active positive electrode material in lithium-ion batteries, the precursor being one of a metal-bearing M′-hydroxide, -oxyhydroxide or -carbonate, with M′=Ni1-x-y-zMnxCoyAz with x>0, y>0, 0.70≤1x-y-z≤0.95, 0≤z<0.1, and A comprising one or more of Ti, Mg, W, Zr, Cr, V or Al, and the precursor comprising
a core comprising a metal-bearing compound M′c and
a shell comprising a metal-bearing compound M′s,
wherein M′c=Ni1-xc-yc-zcMnxcCoycAzc with 0<xc≤0.2 , 0<yc≤0.2, 0≤zc≤0.1 and 0.75≤1-xc-yc-zc≤0.95, and M′s=Ni1-xs-ys-zsMnxsCoysAzs with 0<xs≤0.25, 0.75<ys≤0.95, 0≤zs<0.1 and 0≤1-xs-ys-zs≤0.10.

### Claim 2 (depends on 1)

The precursor compound of claim 1, wherein 0.05≤xs≤0.25.

### Claim 3 (depends on 1)

The precursor compound of claim 1, wherein 1-xs-ys-zs=0.

### Claim 4 (depends on 1)

The precursor compound of claim 1, wherein the precursor compound has an average radius R, and the shell has an average thickness Ts, with Ts being between 0.5 and 5% of R.

### Claim 5 (depends on 1)

The precursor compound of claim 1, wherein the precursor is a M′-hydroxide or -oxyhydroxide, wherein 0.05<xc<0.15, 0.05<yc<0.15, zc=0 and 0.75<1-x-y-z<0.85, and wherein 0.05<xs<0.15, 0.85<ys<0.95 and zs=0.

### Claim 6 (depends on 1)

A method for manufacturing a lithium transition metal-based oxide powder usable as an active positive electrode material in lithium-ion batteries comprising:
providing a precursor compound according to claim 1,
mixing the precursor compound with LiOH, and
sintering the mixture at a temperature superior or equal to 680° C. and inferior or equal to 800° C.

### Claim 7 (depends on 6)

The method according to claim 6, wherein the step of providing the precursor compound comprises:
providing a first aqueous solution comprising M′cSO4, NaOH and NH3, wherein the content of OH−ions is at least twice the content of M′c ions,
precipitating M′c(OH)2 as a core material,
providing a second aqueous solution comprising the precipitated M′c(OH)2, M′sSO4, NaOH and NH3, thereby precipitating the precursor compound comprising the M′c(OH)2 core material and a shell material comprising M′s.