# US 12,218,352 B2 · Lithium fluoride-containing coatings for cathode active materials in Li-ion batteries

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- Number: US 12,218,352 B2
- Document ID: US12218352B2
- Status: Granted
- Kind: B2
- Application number: 17/226,511
- Filed: 2021-04-09
- Published: 2021-10-14
- Granted: 2025-02-04
- Earliest claimed: 2020-04-09
- Assignees: Apple Inc.
- Applicants: Apple Inc.
- Inventors: Hongli Dai; Huiming Wu; Chi-Kai Lin; Michael J. Erickson; Martin Bettge; Xiaoping Wang; Yan Li; Yanjie Cui; James A. Gilbert; Zhenzhen Yang; Anh D. Vu; Arthur Jeremy Kropf; Hakim H. Iddir; Christopher S. Johnson; John David Carter
- Web page: https://patentgrep.com/patent/US12218352B2

## CPC

- H01M 4/366: {as layered products}
- H01M 4/582: {Halogenides}
- H01M 4/0471: {involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis}
- 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
- Y02E 60/10: Energy storage using batteries
- 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

The disclosure provides a plurality of particles. Each particle may include a material comprising 0.95 to 1.30 mole fraction Li, at least 0.60 and less than 1.00 mole fraction Co, up to 10,000 ppm Al, 1.90 to 2.10 mole fraction O, and up to 0.30 mole fraction M, where M is at least one element selected from B, Na, Mg, P, Ti, Ca, V, Cr, Fe, Mn, Ni, Cu, Zn, Al, Sc, Y, Ga, Zr, Ru, Mo, La, Si, Nb, Ge, In, Sn, Sb, Te, and Ce. Each particle may also include a surface composition comprising a mixture of LiF and a metal fluoride. An amount of fluorine (F) is greater than 0 and less than or equal to 5000 ppm. The metal fluoride comprises a material selected from the group consisting of AlF3, CaF2, MgF2, and LaF2. The surface composition may also include a metal oxide comprising a material selected from the group consisting of TiO2, MgO, La2O3, CaO, and Al2O3. An amount of the metal oxide is greater than 0 and less than or equal to 20000 ppm.

## Claims

### Claim 1

A plurality of particles, each particle comprising:
a material comprising:
0.95 to 1.30 mole fraction Li;
at least 0.60 and less than 1.00 mole fraction Co;
up to 10,000 ppm Al;
1.90 to 2.10 mole fraction O; and
up to 0.30 mole fraction M;
wherein M is at least one element selected from B, Na, Mg, P, Ti, Ca, V, Cr, Fe, Mn, Ni, Cu, Zn, Al, Sc, Y, Ga, Zr, Ru, Mo, La, Si, Nb, Ge, In, Sn, Sb, Te, and Ce; and
a surface composition comprising:
a mixture of LiF and a metal fluoride, wherein an amount of fluorine (F) is 500-5000 ppm; wherein the metal fluoride comprises a material selected from the group consisting of AlF3, CaF2, MgF2, and LaF2; and
a metal oxide comprising a material selected from the group consisting of TiO2, MgO, La2O3, CaO, and Al2O3, wherein an amount of the metal oxide is 1000-20000 ppm.

### Claim 2 (depends on 1)

The plurality of particles of claim 1, wherein M comprises Mn.

### Claim 3 (depends on 1)

The plurality of particles of claim 1, wherein the surface composition comprises 0 to 0.2 atomic fraction Co.

### Claim 4 (depends on 1)

The plurality of particles of claim 1, wherein the surface composition comprises up to 0.05 atomic fraction Mn.

### Claim 5 (depends on 1)

The plurality of particles of claim 1, wherein an amount of Al and/or Ti in an accompanying oxide ranges from 100 ppm to 10,000 ppm.

### Claim 6 (depends on 1)

The plurality of particles of claim 1, wherein the material comprises
LiaCo1-x-yMyMnxOd (I)
wherein M is at least one element selected from B, Na, Mg, P, Ti, Ca, V, Cr, Fe, Ni, Cu, Zn, Al, Sc, Y, Ga, Zr, Ru, Mo, La, Si, Nb, Ge, In, Sn, Sb, Te, and Ce,
wherein 0.95≤a≤1.30 per mole fraction, 0<x≤0.30 per mole fraction, 0<y≤0.10 per mole fraction, and 1.98≤d≤2.04 per mole fraction.

### Claim 7 (depends on 6)

The plurality of particles according to claim 6, wherein 0.95≤a≤0.99.

### Claim 8 (depends on 6)

The plurality of particles according to claim 6, wherein 0<x≤0.10.

### Claim 9 (depends on 6)

The plurality of particles according to claim 6, wherein 0<y≤0.05.

### Claim 10 (depends on 1)

The plurality of particles according to claim 1, wherein the material comprises
LiαCO1-x-y-zMnxAlyNizOδ (II)
wherein 0.95≤α≤1.30 per mole fraction, 0<x≤0.07, 0 ppm≤y≤10,000 ppm by weight, 0≤z≤0.07 per mole fraction, and 1.98≤8≤2.04 per mole fraction.

### Claim 11 (depends on 10)

The plurality of particles according to claim 10, wherein the material comprises Li0.992Co0.97Mn0.02Al0.01O2 or Li0.99Co0.95Mn0.03Ni0.02O2.

### Claim 12

A plurality of particles, each particle comprising:
a bulk material represented by formula:
LiαCO(1-x-2y)Mex(M1M2)yOz (III)
wherein Me is selected from one or more of Li, Mg, Al, P, Ca, Ti, Zr, V, Cr, Mn, Fe, Ni, Cu, Zn, Ru, Sn, B, Na, Sc, Y, Ga, Mo, La, Si, Nb, Ge, In, Sn, Sb, Te, and Ce;
wherein M1 is a metal having a +2 oxidation state selected from the group consisting of Ni, Mg, and Zn;
wherein M2 is a metal having a +4 oxidation state selected from the group consisting of Mn, Ti, Zr, and V;
wherein M1M2 represents pairs of M1 and M2; and
wherein 0<x≤0.30 per mole fraction, 0<y≤0.40 per mole fraction, 0.95≤α≤1.40 per mole fraction, and 1.90≤z≤2.10 per mole fraction; and
a surface composition comprising:
a mixture of LiF and a metal fluoride, wherein an amount of fluorine (F) is 500-5000 ppm, wherein the metal fluoride comprises a material selected from the group consisting of AlF3, CaF2, MgF2, and LaF2;
a metal oxide comprising a material selected from the group consisting of MgO, La2O3, CaO, and Al2O3, wherein an amount of the metal oxide is 1000-20000 ppm; and
an accompanying oxide comprising one or more of Al2O3 and/or TiO2; and
0.001 to 0.2 atomic fraction Co.

### Claim 13 (depends on 12)

The plurality of particles of claim 12, wherein the surface composition comprises up to 0.05 atomic fraction Mn.

### Claim 14 (depends on 12)

The plurality of particles according to claim 12, wherein 0<x≤0.10.

### Claim 15 (depends on 12)

The plurality of particles according to claim 12, wherein 0<y≤0.05.

### Claim 16 (depends on 12)

The plurality of particles according to claim 12, wherein the metal oxide is MgO and the accompanying oxide comprises Al2O3.

### Claim 17 (depends on 12)

The plurality of particles of according to claim 12, wherein the metal oxide is MgO and the accompanying oxide comprises Al2O3 and TiO2.

### Claim 18 (depends on 1)

A cathode comprising a cathode active material, the cathode active material comprising the plurality of particles of claim 1.

### Claim 19 (depends on 18)

A battery comprising:
a cathode of claim 18;
a separator; and
an anode.

### Claim 20 (depends on 1)

A method of forming the plurality of particles of claim 1, the method comprising:
coating a coating mixture comprising a metal fluoride comprising a material selected from the group consisting of MgF2, LaF3, CaF2, and AlF3 and the accompanying oxide comprising one or more of Al2O3 and/or TiO2 over a plurality of cores, each core comprising the material comprising:
0.95 to 1.30 mole fraction Li;
at least 0.60 and less than 1.00 mole fraction Co;
up to 10,000 ppm Al;
1.90 to 2.10 mole fraction O; and
up to 0.30 mole fraction M;
wherein M is at least one element selected from B, Na, Mg, P, Ti, Ca, V, Cr, Fe, Mn, Ni, Cu, Zn, Al, Sc, Y, Ga, Zr, Ru, Mo, La, Si, Nb, Ge, In, Sn, Sb, Te, and Ce to produce a plurality of coated cores; and
heating the plurality of coated cores to an elevated temperature of at least 700° C. for a period of time, wherein the metal fluoride of the coating mixture reacts with the lithium cobalt oxide-based bulk material to form the surface composition comprising the lithium fluoride (LiF) and the metal oxide.