# US 2021/0280863 A1 · Cathode materials for secondary batteries

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- Number: US 2021/0280863 A1
- Document ID: US20210280863A1
- Status: Published application
- Kind: A1
- Application number: 16/809,332
- Filed: 2020-03-04
- Published: 2021-09-09
- Earliest claimed: 2020-03-04
- Assignees: Uchicago Argonne, LLC
- Applicants: Uchicago Argonne, LLC
- Inventors: Tongchao Liu; Khalil Amine
- Web page: https://patentgrep.com/patent/US20210280863A1

## CPC

- H01M 4/131: Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
- H01M 4/505: of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
- C01G 53/502: containing lithium and cobalt
- 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
- C01G 53/506: with the molar ratio of nickel with respect to all the metals other than alkali metals higher than or equal to 0.8, e.g. Li(MzNixCoyMn1-x-y-z)O2 with x ≥ 0.8
- C01G 53/51: containing sodium
- H01M 4/1391: of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
- 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 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- H01M 10/054: Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
- C01P 2002/20: Two-dimensional structures
- C01P 2002/32: spinel-type (AB2O4)
- C01P 2002/52: containing elements as dopants
- C01P 2004/03: obtained by SEM
- C01P 2004/04: obtained by TEM, STEM, STM or AFM
- C01P 2004/32: Spheres
- C01P 2004/84: one phase coated with the other
- C01P 2006/40: Electric properties
- H01M 2004/021: {Physical characteristics, e.g. porosity, surface area}
- H01M 2004/028: {Positive electrodes}
- Y02E 60/10: Energy storage using 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
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

A cathode active material includes a composition expressed as: Li1+β(NixMnyCoz)M1α(Nix′Mny′Coz′)M21−αO2; or Na1+β(NixMnyCoz)M1α(Nix′Mny′Coz′)M21−αO2; where: M1 represents a core composition comprising of Ni, Mn, and/or Co or a combination of at two of thereof; M2 represents a surface composition having at least 50% Co, and, optionally Ni and/or Mn; the structure of M2 may be a composite structure and includes a rock-salt or disordered rock-salt phase; 0.5≤α<1, 0≤x≤1, 0≤y≤0.5, 0≤z≤1, 0≤x′≤0.5, 0≤y′≤0.5, 0.5≤z′≤1, and −0.1≤β≤0.1; the sum of x, y and z is 0.9-1.1, and the sum of x′, y′ and z′ is 0.9-1.1.

## Claims

### Claim 1

A cathode active material comprising:
a composition expressed as:
Li1+β(NixMnyCoz)M1α(Nix′Mny′Coz′)M21−αO2; or
Na1+β(NixMnyCoz)M1α(Nix′Mny′Coz′)M21−αO2;
wherein:
M1 represents a core composition comprising of Ni, Mn, and/or Co or a combination of at two of thereof;
M2 represents a surface composition comprising at least 50% Co, and, optionally Ni and/or Mn;
the structure of M2 may be a composite structure and comprises a rock-salt or disordered rock-salt phase;
0.5≤α<1, 0≤x≤1, 0≤y≤0.5, 0≤z≤1, 0≤x′≤0.5, 0≤y′≤0.5, 0.5≤z′≤1, and −0.1≤β≤0.1;
the sum of x, y and z is 0.9-1.1, and the sum of x′, y′ and z′ is 0.9-1.1.

### Claim 2 (depends on 1)

The cathode active material of claim 1, wherein 0.8≤α<1, 0.6≤x≤1, 0≤y≤0.4, 0≤z≤0.4, 0≤x′≤0.5, 0≤y′≤0.5, and 0.5≤z′≤1.

### Claim 3 (depends on 0, 1)

The cathode active material of claim 1, 0.9≤α<1, 0≤x≤0.2, 0≤y≤0.2, 0.8≤z≤1, 0≤x′≤0.5, 0≤y′≤0.5, and 0.5≤z′≤1.

### Claim 4 (depends on 1)

The cathode active material of claim 1, wherein M2 comprises from about 60 mol % to about 90 mol % Co.

### Claim 5 (depends on 1)

The cathode material of claim 1, wherein the cathode active material comprises a particle having a generally spherical morphology and a vector radius defined thereby.

### Claim 6 (depends on 5)

The cathode material of claim 5, wherein the composite structure of M2 comprises the rock-salt or disordered rock-salt phase near a surface of the particle, and, optionally, a layered structure and/or a spinel structure nearer a central portion of the particle.

### Claim 7 (depends on 2)

The cathode material of claim 2, wherein the Ni concentration is constant or partly/continuously decreased along the vector radius, the Mn concentration is constant or partly/continuously decreases or increases nearer the surface of the particle, and the Co concentration partly/continuously increases along the vector radius.

### Claim 8 (depends on 3)

The cathode material of claim 3, wherein the Co concentration is constant or partly/continuously decreases along the vector radius of the particle, the Mn concentration is constant or partly/continuously decreases or increases nearer the surface of the particle, and the Ni concentration partly/continuously increases along the vector radius of the particle.

### Claim 9 (depends on 7)

The cathode active material of claim 7, wherein a concentration of any metals change by one or more slopes.

### Claim 10 (depends on 1)

The cathode active material of claim 1 further comprising a dopant cation.

### Claim 11 (depends on 10)

The cathode active material of claim 10, wherein the composition is expressed as:
Li1+β(NixMnyCozTδ)M1α(Nix′Mny′Coz′Tγ′)M21−αO2; or
Na1+β(NixMnyCozTδ)M1α(Nix′Mny′Coz′T65 ′)M21−αO2;
wherein:
T and T′ are dopant cations and are individually an alkaline earth metal, a transition metal other than Ni, Mn, and Co, or a combination of any two or more thereof;
0≤δ≤0.1, 0≤γ≤0.1, 0.5≤α<1, 0≤x≤1, 0≤y≤0.5, 0≤z≤1, 0≤x′≤0.5, 0≤y′≤0.5, 0.5≤z′≤1, and −0.1≤β≤0.1;
the sum of x, y and z is 0.9-1.1, and the sum of x′, y′ and z′ is 0.9-1.1.

### Claim 12 (depends on 5)

The cathode active material of claim 5 further comprising a surface coating on the particle.

### Claim 13 (depends on 12)

The cathode active material of claim 12, wherein the surface coating comprises a metal oxide, a metal fluoride, a metal phosphate, a conductive carbon coating, a conductive polymer (such as PEDOT), or a combination of any two or more thereof.

### Claim 14

A cathode active material expressed as δLi2M1′O3.(1-δ)LiM2′O2, wherein M1′ comprises one or more of Mn, Ni, and Co; M2′ comprises at least 50% Co mol % and a rock-salt or disordered rock-salt phase, and, optionally, Ni and/or Mn, and 0<δ<1.

### Claim 15 (depends on 14)

The cathode active material of claim 14, comprising a particle having a generally spherical morphology and a vector radius defined thereby, and which is characterized in that the composite structure of M2′ comprises a rock-salt or disordered rock-salt phase near a surface of the particle, and, optionally, a layered structure and/or a spinel structure nearer a central portion of the particle.

### Claim 16 (depends on 15)

The cathode active material of claim 15, wherein a concentration of the Ni, Mn, and Co in M1 are constant or partly/continuously decreased along the vector radius; and the Co, Ni, and Mn in M2 continuously increases along the vector radius.

### Claim 17

A process of preparing a cathode active material, the process comprising:
providing a first aqueous metal ion solution;
providing a second aqueous metal ion solution;
combining M1 and M2 and with a precipitating agent to form a precipitate;
isolating the precipitate;
mixing the precipitate with a lithium or sodium salt to form a mixture; and
heating-treating the mixture to form the cathode active material that is expressed as:
Li1+β(NixMnyCoz)M1α(Nix′Mny′Coz′)M21−αO2; or
Na1+β(NixMnyCoz)M1α(Nix′Mny′Coz′)M21−αO2;
wherein:
M1 represents a core composition comprising of Ni, Mn, and/or Co or a combination of at two of thereof;
M2 represents a surface composition comprising at least 50% Co, and, optionally Ni and/or Mn;
the structure of M2 may be a composite structure and comprises a rock-salt or disordered rock-salt phase;
0.5≤α<1, 0≤x≤1, 0≤y≤0.5, 0≤z≤1, 0≤x′≤0.5, 0≤y′≤0.5, 0.5≤z′≤1, and −0.1≤β≤0.1, the sum of x, y and z is 0.9-1.1, and the sum of x′, y′ and z′ is 0.9-1.1.

### Claim 18 (depends on 17)

The process of claim 17, wherein M1 and/or M2 are established in particles of the precipitate along a vector radius defined from the center of the particle to the surface; a concentration gradient of Ni, Mn, and Co of M1 and M2 is established in particles of the precipitate along a vector radius defined from the center of the particle to the surface.

### Claim 19 (depends on 18)

The process of claim 18, wherein:
the heat-treating comprises at least one calcination step at a heating rate to a temperature of about 680° C. to about 1200° C. the calcination step is conducted in an oxygen atmosphere, an air atmosphere, or in an oxygen-enriched air atmosphere.