Granted Patent B2

US 12,218,352 · App. 17/226,511 · Granted Feb 4, 2025

Inventors: Hongli Dai (Los Altos, CA); Huiming Wu (San Jose, CA); Chi-Kai Lin (Sunnyvale, CA); Michael J. Erickson (San Jose, CA); Martin Bettge (Santa Clara, CA); Xiaoping Wang (Naperville, IL); Yan Li (Westmont, IL); Yanjie Cui (Arlington Heights, IL); James A. Gilbert (Bolingbrook, IL); Zhenzhen Yang (Godfrey, IL); Anh D. Vu (Lemont, IL); Arthur Jeremy Kropf (Westmont, IL); Hakim H. Iddir (Hoffman Estates, IL); Christopher S. Johnson (Naperville, IL); John David Carter (Bolingbrook, IL)

Assignee: Apple Inc.

H01M4/582H01M4/0471H01M4/505H01M4/525H01M10/0525

Abstract

Claims (58)

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 AlF 3 , CaF 2 , MgF 2 , and LaF 2 ; and

a metal oxide comprising a material selected from the group consisting of TiO 2 , MgO, La 2 O 3 , CaO, and Al 2 O 3 , wherein an amount of the metal oxide is 1000-20000 ppm.

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

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

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

5. 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.

6. The plurality of particles of claim 1 , wherein the material comprises

Li a Co 1-x-y M y Mn x O d   (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.

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

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

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

10. The plurality of particles according to claim 1 , wherein the material comprises

Li α CO 1-x-y-z Mn x Al y Ni z O δ   (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.

11. The plurality of particles according to claim 10 , wherein the material comprises Li 0.992 Co 0.97 Mn 0.02 Al 0.01 O 2 or Li 0.99 Co 0.95 Mn 0.03 Ni 0.02 O 2 .

12. A plurality of particles, each particle comprising:

a bulk material represented by formula:

Li α CO (1-x-2y) Me x (M1M2) y O z   (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 AlF 3 , CaF 2 , MgF 2 , and LaF 2 ;

a metal oxide comprising a material selected from the group consisting of MgO, La 2 O 3 , CaO, and Al 2 O 3 , wherein an amount of the metal oxide is 1000-20000 ppm; and

an accompanying oxide comprising one or more of Al 2 O 3 and/or TiO 2 ; and

0.001 to 0.2 atomic fraction Co.

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

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

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

16. The plurality of particles according to claim 12 , wherein the metal oxide is MgO and the accompanying oxide comprises Al 2 O 3 .

17. The plurality of particles of according to claim 12 , wherein the metal oxide is MgO and the accompanying oxide comprises Al 2 O 3 and TiO 2 .

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

19. A battery comprising:

a cathode of claim 18 ;

a separator; and

an anode.

20. 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 MgF 2 , LaF 3 , CaF 2 , and AlF 3 and the accompanying oxide comprising one or more of Al 2 O 3 and/or TiO 2 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.

Assignments (1)

Continuity (2)

References Cited (9)