Aluminum-doped lithium cobalt manganese oxide batteries

Patent metadata

Field	Value
Publication number	US-11757096-B2
Application number	US-202016999307-A
Country	US
Kind code	B2
Filing date	Aug 21, 2020
Priority date	Aug 21, 2019
Publication date	Sep 12, 2023
Grant date	Sep 12, 2023

Abstract

Compounds, particles, and cathode active materials that can be used in lithium ion batteries are described herein. Methods of making such compounds, powders, and cathode active materials are described.

First claim

We claim:

1. A plurality of particles comprising a compound represented by Formula (I):
Li α Co 1-x-y-z Mn x Me z Al y O δ ,  Formula (I)

wherein 0.95≤α<1.30, 0<x≤0.05, 300 ppm≤y≤10,000 ppm, 0≤z≤0.1,
wherein Me is at least one element selected from B, Na, Mg, P, Ti, Ca, V, Cr, Fe, Ni, Cu, Zn, Sc, Y, Ga, Zr, Ru, Mo, La, Si, Nb, Ge, In, Sn, Sb, Te, and Ce, and 1.98≤δ≤2.04, and
wherein at an average particle surface, a molar ratio of Al/Co is at least 0.2 and equal to or less than 0.75.

2. The plurality of particles of claim 1 ,
wherein Me is at least one element selected from Ni, B, Na, Mg, Ti, Ca, V, Cr, Fe, Cu, Zn, Sc, Y, Ga, Zr, La, Ru, and Mo.

3. The plurality of particles of claim 1 , wherein an molar ratio of Mn/Co is at least 0.02, wherein the compound is Li 0.98 Co 0.97 Mn 0.017 Al 0.013 O 2 .

4. The plurality of particles according to claim 1 , wherein at an average of 10 nm beneath the average particle surface:
the average atomic percent of Al is lower than the average atomic percent of Al at the average particle surface; and/or
the average atomic percent of Co is higher than the average atomic percent of Co at the average particle surface.

5. The plurality of particles according to claim 1 , wherein y is equal to a sum of y 1 and y 2 , wherein y 1 includes Al from an Al 2 O 3 coating, and wherein y 2 includes doped Al.

6. The plurality of particles according to claim 1 , wherein y 1 ranges from 300 ppm to 10,000 ppm; and/or wherein y 2 ranges from 0 to 10,000 ppm.

7. The plurality of particles according to claim 1 , wherein 0.02≤x≤0.04.

8. A plurality of particles comprising a compound represented by Formula (II):
( x )[Li 2 MnO 3 ]·(1- x )[Li β Co (1-u-w-v) Mn u Me v Al w O 2 ]  (II)

wherein 0.95≤β<1.0, 0<x≤0.05, 0≤u≤0.05, 0≤v≤0.1, 300 ppm≤w≤10,000 ppm,
wherein Me is at least one element selected from B, Na, Mg, P, Ti, Ca, V, Cr, Fe, Ni, Cu, Zn, Sc, Y, Ga, Zr, Ru, Mo, La, Si, Nb, Ge, In, Sn, Sb, Te, and Ce, and wherein at an average particle surface, a molar ratio of Al/Co is at least 0.2.

9. The plurality of particles of claim 8 ,
wherein Me is at least one element selected from Ni, B, Na, Mg, Ti, Ca, V, Cr, Fe, Cu, Zn, Sc, Y, Ga, Zr, La, Ru, and Mo.

10. The plurality of particles of claim 8 , wherein at the average particle surface the ratio of Mn/Co is at least 0.02.

11. The plurality of particles according to claim 7 , wherein at an average of 10 nm beneath the average particle surface:
the average atomic percent of Al is lower than the average atomic percent of Al at the average particle surface; and/or
the average atomic percent of Co is higher than the average atomic percent of Co at the average particle surface.

12. The plurality of particles according to claim 7 , wherein y is equal to a sum of y 1 and y 2 , and wherein y 1 includes Al from an Al 2 O 3 coating, and wherein y 2 includes doped Al.

13. The plurality of particles according to claim 7 , wherein y 1 ranges from 300 ppm to 10000 ppm; and/or wherein y 2 ranges from 0 to 10000 ppm.

14. The plurality of particles according to claim 7 , wherein 0.02≤x≤0.04.

15. The plurality of particles according to claim 1 , wherein a mean diameter of the particles is at least 5 μm.

16. The plurality of particles according to claim 1 , wherein a mean diameter of the particles is at least 20 μm.

17. The plurality of particles according to claim 1 , wherein the particles comprise secondary particles, each secondary particle comprising a plurality of primary particles sintered together.

18. The plurality of particles according to claim 1 , wherein the compound comprises varied Co coordination to Al.

19. The plurality of particles according to claim 1 , wherein the compound comprises a plurality of peaks including at least one of Al5Co, Al4Co, Al3Co, Al2Co, and Al1Co detected in nuclear magnetic resonance (NMR).

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

21. A cathode comprising the cathode active material of claim 18 .

22. A battery comprising
a cathode of claim 21 ,
a separator, and
an anode.

23. A method of making the plurality particles according to claim 1 comprising:
coating a first plurality of particles comprising the compound of Formula (I) with a Al 2 O 3 coating,
Li α Co 1-x-y-z Mn x Me z Al y O δ ,  Formula (I)

wherein 0.95≤α≤1.30, 0<x≤0.05, 300 ppm≤y≤10,000 ppm, 0≤z<0.1, and 1.98≤δ≤2.04, wherein Me is at least one element selected from B,
Na, Mg, P, Ti, Ca, V, Cr, Fe, Ni, Cu, Zn, Sc, Y, Ga, Zr, Ru, Mo, La, Si, Nb, Ge, In, Sn, Sb, Te, and Ce, wherein y is equal to a sum of y 1 and y 2 , wherein y 1 includes Al from the Al 2 O 3 coating, and y 2 includes doped Al; and
annealing the first plurality of particles at a temperature of at least 700° C. to form a second plurality of particles according to claim 1 .

24. A method of making the plurality particles according to claim 7 , comprising:
coating a first plurality of particles comprising the compound of Formula (I) with a Al 2 O 3 coating,
( x )[Li 2 MnO 3 ]·(1- x )[Li β Co (1-u-w-v) Mn u Me v Al w O 2 ]  (II)

wherein 0.95≤β<1.30, 0<x≤0.05, 0≤u≤0.05, 0≤v≤01, 300 ppm≤w≤10,000 ppm, and 1.98≤δ≤2.04, wherein Me is at least one element selected from
B, Na, Mg, P, Ti, Ca, V, Cr, Fe, Ni, Cu, Zn, Sc, Y, Ga, Zr, Ru, Mo, La, Si, Nb, Ge, In, Sn, Sb, Te, and Ce; and
annealing the first plurality of particles at a temperature of at least 700° C. to form a second plurality of particles according to claim 7 .

25. A plurality of particles comprising a compound represented by Formula (I):
Li α Co 1-x-y-z Mn x Me z Al y O δ ,  Formula (I)

wherein 0.95≤α<1.30, 0<x≤0.05, 0 ppm≤y≤10,000 ppm, 300 ppm≤z≤5000 ppm,
wherein Me is La, and 1.98≤δ≤2.04, and
wherein at an average particle surface, an molar ratio of La/Co is at least 0.06.

26. A plurality of particles comprising a compound represented by Formula (I):
Li α Co 1-x-y-z Mn x Me z Al y O δ ,  Formula (I)

wherein 0.95≤α<1.30, 0<x≤0.05, 0 ppm≤y≤10,000 ppm, 300 ppm≤z≤5000 ppm,
wherein Me is Mg, and 1.98≤δ≤2.04, and wherein at an average particle surface, an molar ratio of Mg/Co is at least 0.20.

27. A plurality of particles comprising a compound represented by Formula (I):
Li α Co 1-x-y-z Mn x Me z Al y O δ ,  Formula (I)

wherein 0.95≤α<1.30, 0<x≤0.05, 0 ppm≤y≤10,000 ppm, 300 ppm≤z≤5000 ppm,
wherein Me is Ti, and 1.98≤δ≤2.04, and
wherein at an average particle surface, an molar ratio of Ti/Co is at least 0.08.

28. A plurality of particles comprising a compound represented by Formula (I):
Li α Co 1-x-y-z Mn x Me z Al y O δ ,  Formula (I)

wherein 0.95≤a<1.30, 0<x≤0.05, 0 ppm≤y≤10,000 ppm, 300 ppm≤z≤5000 ppm,
wherein Me is Zr, and 1.98≤δ≤2.04, and
wherein at an average particle surface, an molar ratio of Zr/Co is at least 0.02.

Assignees

• Apple Inc

Inventors

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

Classifications

• H01M4/525 Primary

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

• H01M4/366

  as layered products · CPC title

• H01M4/62

  Selection of inactive substances as ingredients for active masses, e.g. binders, fillers · CPC title

• H01M4/505

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

• H01M4/1391

  of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx · CPC title