Lithium fluoride-containing coatings for cathode active materials in Li-ion batteries

Patent metadata

Field	Value
Publication number	US-12218352-B2
Application number	US-202117226511-A
Country	US
Kind code	B2
Filing date	Apr 9, 2021
Priority date	Apr 9, 2020
Publication date	Feb 4, 2025
Grant date	Feb 4, 2025

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.

First claim

What is claimed is:

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.

Assignees

• Apple Inc

Inventors

• Dai Hongli
• Wu Huiming
• Lin Chi-Kai
• Erickson Michael J
• Bettge Martin
• Wang Xiaoping
• Li Yan
• Cui Yanjie
• Gilbert James A
• Yang Zhenzhen
• Vu Anh D
• Kropf Arthur Jeremy
• Iddir Hakim H
• Johnson Christopher S
• Carter John David

Classifications

• H01M4/525

  of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy · CPC title

• H01M10/0525

  Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries · CPC title

• H01M4/0471

  involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis · CPC title

• H01M4/505

  of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy · CPC title

• Y02E60/10

  Energy storage using batteries · CPC title