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

Patent metadata

Field	Value
Publication number	US-11101461-B2
Application number	US-202016751653-A
Country	US
Kind code	B2
Filing date	Jan 24, 2020
Priority date	Jun 24, 2013
Publication date	Aug 24, 2021
Grant date	Aug 24, 2021

Abstract

A composite cathode active material, a method of preparing the composite cathode active material, a cathode including the composite cathode active material, and a lithium battery including the cathode. The composite cathode active material includes a lithium intercalatable material; and a garnet oxide, wherein an amount of the garnet oxide is about 1.9 wt % or less, based on a total weight of the composite cathode active material.

First claim

What is claimed is:

1. A composite cathode active material comprising:
a core comprising a lithium compound represented by Formula 12
Li x Me y M z PO 4−α X α   Formula 12

wherein in Formula 12,
0.90≤x≤1.1, 0≤y≤0.9, 0≤z≤0.5, 1-y-z>0, 0≤α≤2,
Me comprises at least one of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Al, Mg, Zr, or B,
M comprises at least one of Mg, Ca, Sr, Ba, Ti, Zr, Nb, Mo, W, Zn, Al, Si, Ni, Mn, Cr, Fe, Mg, Sr, V, or a rare earth element, and
X comprises at least one of F, S, or P; and
a shell disposed on at least a portion of the core, the shell comprising a garnet oxide.

2. The composite cathode active material of claim 1 , wherein the lithium compound of the core is a compound represented by Formula 13
Li x M y M′ z PO 4-d X d   Formula 13

wherein in Formula 13
0.9≤x≤1.1, 0≤y≤1, 0≤z≤1, 1.9≤x+y+z≤2.1, 0≤d≤0.2,
M comprises at least one of Fe, Mn, Ni, or Co,
M′ comprises at least one of Mg, Ca, Sr, Ba, Ti, Zr, Nb, Mo, W, Zn, Al, or Si, and
X comprises at least one of S or F.

3. The composite cathode active material of claim 1 , wherein the shell and the core form a mechanochemical bond.

4. The composite cathode active material of claim 1 , wherein the garnet oxide is represented by Formula 1
L 5+x E 3 (Me z M 2−z )O d   Formula 1

wherein
L comprises at least one of a monovalent cation or a bivalent cation, wherein L comprises Li,
E comprises at least one of a monovalent cation or a trivalent cation,
Me and M are each independently a trivalent, a 4-valent, a 5-valent, or a 6-valent cation,
0≤x≤3, 0≤z≤2, and 0≤d≤12, and
O is optionally substituted with at least one of a 5-valent, a 6-valent, or a 7-valent anion.

5. The composite cathode active material of claim 1 , wherein the garnet oxide is represented by Formula 2
Li 5+x La 3 (Zr z A 2−z )O 12   Formula 2

wherein
A comprises at least one of Sc, Ti, V, Y, Nb, Hf, Ta, Al, Si, Ga, or Ge,
0≤x≤3, and 0≤z≤2.

6. The composite cathode active material of claim 1 , wherein the garnet oxide comprises at least one of Li 7 La 3 Zr 2 O 12 , Li 6.75 La 3 (Zr 1.75 Nb 0.25 )O 12 , Li 7.5 Rb 0.25 La 2.75 Zr 2 O 12 , Li 8 Rb 0.5 La 2.5 Zr 2 O 12 , Li 9 RbLa 2 Zr 2 O 12 , Li 7.125 Rb 0.0625 La 2.9375 Zr 2 O 12 , Li 6 SrLa 2 Ta 2 O 12 , or Li 7.125 K 0.0625 La 2.9375 Zr 2 O 12 .

7. The composite cathode active material of claim 1 , wherein an amount of the garnet oxide is about 1.9 weight percent or less, based on a total weight of the composite cathode active material.

8. The composite cathode active material of claim 1 , wherein the shell further comprises a carbonaceous material.

9. The composite cathode active material of claim 8 , wherein the carbonaceous material comprises at least one of a carbon nanotube, a carbon nanofiber, graphene, graphite, an expanded graphite, a carbon nanopowder, a hard carbon, or a soft carbon.

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

11. A lithium battery comprising the cathode of claim 10 .

12. The lithium battery of claim 11 , wherein the lithium battery comprises an electrolyte, and the electrolyte is a liquid or a solid.

13. The lithium battery of claim 11 , wherein the lithium battery comprises an anode, and the anode comprises an anode active material, wherein the anode active material comprises lithium metal, a lithium-alloyable metal, a transition metal oxide, a non-transition metal oxide, a carbonaceous material or combination thereof.

14. A composite cathode active material comprising:
a core comprising comprises a lithium compound represented by Formula 10
Li x Mn 2−y M y O 4−α X α   Formula 10

wherein in Formula 10,
0.90≤x≤1.1, 0≤y≤0.9, 0≤α≤2,
M comprises at least one of Mg, Ca, Sr, Ba, Ti, Zr, Nb, Mo, W, Zn, Al, Si, Ni, Mn, Cr, Fe, Mg, Sr, V, or a rare earth element, and
X comprises at least one of F, S, or P; and
a shell disposed on at least a portion of the core, the shell comprising a garnet oxide.

15. The composite cathode active material of claim 14 , wherein the shell and the core form a mechanochemical bond.

16. The composite cathode active material of claim 14 , wherein the garnet oxide is represented by Formula 1
L 5+x E 3 (Me z N 2−z )O d   Formula 1

wherein
L comprises at least one of a monovalent cation and a bivalent cation, wherein L comprises Li,
E comprises at least one of a monovalent cation or a trivalent cation,
Me and M are each independently comprise a trivalent, a 4-valent, a 5-valent, or a 6-valent cation,
0≤x≤3, 0≤z≤2, 0≤d≤12, and
O is optionally substituted with at least one of a 5-valent, a 6-valent, or a 7-valent anion.

17. The composite cathode active material of claim 14 , wherein the garnet oxide is represented by Formula 2
Li 5+x La 3 (Zr z A 2−z )O 12   Formula 2

wherein in Formula 2
A comprises at least one of Sc, Ti, V, Y, Nb, Hf, Ta, Al, Si, Ga, or Ge,
0≤x≤3, and 0≤z≤2.

18. The composite cathode active material of claim 14 , wherein the garnet oxide comprises at least one of Li 7 La 3 Zr 2 O 12 , Li 6.75 La 3 (Zr 1.75 Nb 0.25 )O 12 , Li 7.5 Rb 0.25 La 2.75 Zr 2 O 12 , Li 8 Rb 0.5 La 2.5 Zr 2 O 12 , Li 9 RbLa 2 Zr 2 O 12 , Li 7.125 Rb 0.0625 La 2.9375 Zr 2 O 12 , Li 6 SrLa 2 Ta 2 O 12 , or Li 7.125 K 0.0625 La 2.9375 Zr 2 O 12 .

19. The composite cathode active material of claim 14 , wherein an amount of the garnet oxide is about 1.9 weight percent or less, based on a total weight of the composite cathode active material.

20. The composite cathode active material of claim 14 , wherein the shell further comprises a carbonaceous material.

21. The composite cathode active material of claim 20 , wherein the carbonaceous material comprises at least one of a carbon nanotube, a carbon nanofiber, graphene, graphite, an expanded graphite, a carbon nanopowder, a hard carbon, or a soft carbon.

22. A cathode comprising the composite cathode active material of claim 14 .

23. A lithium battery comprising
the cathode of claim 22 ;
an anode; and
an electrolyte between the cathode and the anode.

24. The lithium battery of claim 23 , wherein the lithium battery comprises an electrolyte, and the electrolyte is a liquid or a solid.

25. The lithium battery of claim 23 , wherein the anode comprises an anode active material, wherein the anode active material comprises lithium metal, a lithium-alloyable metal, a transition metal oxide, a non-transition metal oxide, a carbonaceous material or combination thereof.

26. A method of preparing a composite cathode active material, the method comprising:
contacting a lithium compound and a garnet oxide to form a shell comprising the garnet oxide on a core comprising the lithium compound to prepare the composite cathode active material,
wherein the lithium compound is represented by Formula 12
Li x Me y M z PO 4−α X α   Formula 12

wherein in Formula 12,
0.90≤x≤1.1, 0≤y≤0.9, 0≤z≤0.5, 1-y-z>0, 0≤α≤2,
Me comprises at least one of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Al, Mg, Zr, or B,
M comprises at least one of Mg, Ca, Sr, Ba, Ti, Zr, Nb, Mo, W, Zn, Al, Si, Ni, Mn, Cr, Fe, Mg, Sr, V, or a rare earth element, and
X comprises at least one of O, F, S, or P.

27. A method of preparing a composite cathode active material, the method comprising:
contacting a lithium compound and a garnet oxide to form a shell comprising the garnet oxide disposed on a core

Assignees

• Samsung Electronics Co Ltd

Inventors

• Mun Jun-Young
• Lee Jae-Myung
• Kim Gue-Sung
• Kang Yoon-Sok
• Kim Myung-Hoon
• Park Jun-Ho
• Park Jin-Hwan
• Yoon Jae-Gu
• Choi Byung-Jin

Classifications

• H01M4/583

  Carbonaceous material, e.g. graphite-intercalation compounds or CFx · CPC title

• H01M4/48 Primary

  of inorganic oxides or hydroxides · CPC title

• H01M10/052

  Li-accumulators · CPC title

• H01M2004/028

  Positive electrodes · CPC title

• H01M4/625

  Carbon or graphite · CPC title