Composite cathode active material, cathode and lithium battery each containing composite cathode active material, and method of preparing composite cathode active material

Patent metadata

Field	Value
Publication number	US-11955631-B2
Application number	US-201916358795-A
Country	US
Kind code	B2
Filing date	Mar 20, 2019
Priority date	Oct 4, 2018
Publication date	Apr 9, 2024
Grant date	Apr 9, 2024

Abstract

A composite cathode active material, a cathode and a lithium battery each including the composite cathode active material, and a method of manufacturing the composite cathode active material. The composite cathode active material includes a core including a plurality of primary particles, and a shell disposed on the core, wherein a primary particle of the plurality of primary particles includes a lithium nickel transition metal oxide, the shell includes a first composition and a second composition, wherein the first composition contains a first metal and the second composition contains a second metal, wherein the first metal includes a metal of Groups 2, 4, 5, and 7 to 15, the second metal includes a metal of Group 3, and the first composition includes a first phase and the second composition includes a second phase that is distinguishable from the first phase.

First claim

What is claimed is:

1. A composite cathode active material for an organic electrolyte or solid electrolyte lithium battery comprising:
a core comprising a plurality of primary particles; and
a shell disposed on the core,
wherein
a primary particle of the plurality of primary particles includes a lithium nickel transition metal oxide, and

the shell includes a first composition and a second composition, wherein the first composition contains a first metal and the second composition contains a second metal, wherein
the first metal comprises nickel and cobalt,
the second metal comprises cerium, and

the first composition comprises a first phase and the second composition comprises a second phase that is distinguishable from the first phase,
wherein the first composition comprises a phase having a layered crystal structure and a phase having a spinel crystal structure,
wherein the core comprises a grain boundary between primary particles of the plurality of primary particles, and the grain boundary comprises Zr,
wherein the grain boundary comprises a third composition comprising a third phase having a monoclinic crystal structure, and the structure of the third composition belongs to a C2/m, C12/c1, or C2/c space group, wherein the lithium nickel transition metal oxide is represented by Formula 4:
Li a M4O 2-α X α   Formula 4

wherein in Formula 4,
0.9≤a≤1.2 and 0≤α<2,
M4 comprises nickel, a fourth metal, and a fifth metal, wherein the fourth metal is an element of Groups 2 to 13 of the Periodic Table and is different from nickel and the fifth metal,
X is F, S, or P, and
the amount of nickel in M4 is about 70 mole percent to less than about 100 mole percent, based on a total content of the lithium nickel transition metal oxide.

2. The composite cathode active material of claim 1 ,
wherein the layered crystal structure belongs to a space group R-3m, and
wherein the spinel crystal structure belongs to a space group Fd-3m.

3. The composite cathode active material of claim 1 , wherein the second composition comprises a phase having a fluorite crystal structure.

4. The composite cathode active material of claim 3 , wherein the fluorite crystal structure belongs to a space group Fm-3m.

5. The composite cathode active material of claim 1 , wherein the shell comprises:
a multi-layered structure comprising a first layer and a second layer, wherein the first layer includes a first composition, the second layer includes a second composition, and the second layer is located on the first layer.

6. The composite cathode active material of claim 5 ,
wherein a primary particle comprises the first layer on a surface of the primary particle, and
wherein a concentration of the first metal in the first layer is greater than a concentration of the first metal in the primary particle.

7. The composite cathode active material of claim 1 , wherein the first composition comprises the first metal and oxygen, or a composition comprising lithium, the first metal, and oxygen,
wherein
an amount of the lithium is 0 moles to about 3.3 moles of lithium, based on 1 mole of the first composition,
an amount of the first metal is about 0.7 moles to about 3.3 moles of the first metal, based on 1 mole of the first composition, and
an amount of the oxygen is about 1.7 moles to about 4.3 moles of oxygen, based on 1 mole of the first composition.

8. The composite cathode active material of claim 1 , wherein the shell comprises Co 3 O 4 .

9. The composite cathode active material of claim 1 , wherein an amount of the first composition or the first metal included in the shell is 10 parts by weight or less, based on 100 parts by weight of the lithium nickel transition metal oxide.

10. The composite cathode active material of claim 1 , wherein the second composition is a composition comprising the second metal and oxygen, wherein
an amount of the second metal is about 0.7 moles to about 1.3 moles, based on 1 mole of the second composition, and
an amount of the oxygen is about 1.7 moles to about 2.3 moles, based on 1 mole of the second composition.

11. The composite cathode active material of claim 1 , wherein the second composition is represented by Formula 2:
M2 b O c   Formula 2

wherein in Formula 2,
M2 is Ce, and
0.9≤b≤1.1 and 1.9≤c≤2.1.

12. The composite cathode active material of claim 1 , wherein the second composition comprises CeO 2 .

13. The composite cathode active material of claim 1 , wherein an amount of the second composition or second metal included in the shell is 10 parts by weight or less, based on 100 parts by weight of the lithium nickel transition metal oxide.

14. The composite cathode active material of claim 1 , wherein the grain boundary comprises a third composition comprising lithium, Zr, and oxygen, and
an amount of the lithium is about 1.7 moles to about 2.3 moles, based on 1 mole of the third composition,
an amount of Zr is about 0.7 moles to about 1.3 moles, based on 1 mole of the third composition, and
an amount of the oxygen is about 2.7 moles to about 3.3 moles, based on 1 mole of the third composition.

15. The composite cathode active material of claim 1 , wherein the grain boundary comprises a third composition represented by Formula 3:
Li a M3 b O c   Formula 3

wherein in Formula 3,
M3 is Zr, and
1.9≤a≤2.1, 0.9≤b≤1.1, and 2.9≤c≤3.1.

16. The composite cathode active material of claim 1 , wherein the shell further includes a fifth composition including a fifth metal.

17. The composite cathode active material of claim 1 , wherein
an amount of the nickel is about 0.7 moles to about 0.99 moles, based on 1 mole of the lithium nickel transition metal oxide,
an amount of the fourth metal is about 0.01 moles to about 0.3 moles, based on 1 mole of the lithium nickel transition metal oxide, and
an amount of the fifth metal is about 0.0005 moles to about 0.01 moles, based on 1 mole of the lithium nickel transition metal oxide.

18. The composite cathode active material of claim 1 , wherein the lithium nickel transition metal oxide is represented by Formula 5:
Li a Ni b M5 c M6 d M7 e O 2-α X α   Formula 5

wherein in Formula 5,
0.9≤a≤1.2, 0.7≤b≤1, 0≤c≤0.3, 0≤d≤0.3, 0≤e≤0.1, b+c+d+e=1, and 0≤α<2,
M5, M6, and M7 are different from each other, and are each Co, Mn, Zr, Al, Re, V, Cr, Fe, B, Ru, Ti, Nb, Mo, Mg, or Pt, and
X is F, S, or P.

19. The composite cathode active material of claim 1 , wherein the lithium nickel transition metal oxide is represented by Formula 6 or Formula 7:
Li a Ni b Co c Mn d M8 e O 2-α X α   Formula 6

Li a Ni b Co c Al d M8 e O 2-α X α   Formula 7

wherein in Formulae 6 and 7,
0.9≤a≤1.2, 0.7<b<1, 0<c<0.1, 0<d<0.1, 0≤e<0.01, b+c+d+e=1, and 0≤α<2,
M8 is Zr, Al, V, Cr, Fe, Re, B, Ru, Ti, Nb, Mo, Mg, or Pt, and
X is F, S, or P.

20. The composite cathode active material of claim 1 , wherein the lithium nickel transition metal oxide is represented by Formula 8:
aLi 2 MnO 3 ·(1− a )LiMO 2−α X α   Formula 8

wherein in Formula 8,
0<a<1 and 0≤α<2,
M comprises
Ni and
Co, Mn, Zr, Al, Re, V, Cr, Fe, B, Ru, Ti, Nb, Mo, Mg, Pt, or a combination thereof, and

X is F, S, or P.

21. A cathode comprising the composite cathode active material of claim 1 .

22. The cathode of claim 21 , further comprising a cathode active material having an olivine structure.

23. The cathode of claim 21 , wherein an amount of the cathode active

Assignees

• Samsung Electronics Co Ltd
• Samsung Sdi Co Ltd

Inventors

• Shin Dongwook
• Hong Sukgi
• Park Jinhwan
• Choi Byungjin

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

• C01G53/44

  containing manganese · CPC title

• H01M4/0471

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

• H01M4/131

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

• H01M4/366 Primary

  as layered products · CPC title