Cathode materials having oxide surface species

Patent metadata

Field	Value
Publication number	US-11962002-B2
Application number	US-202318463208-A
Country	US
Kind code	B2
Filing date	Sep 7, 2023
Priority date	Dec 17, 2021
Publication date	Apr 16, 2024
Grant date	Apr 16, 2024

Abstract

The present disclosure concerns lithium zirconium phosphate (LZP) chemical oxides for coated cathode active materials, which are useful in cathodes (i.e., positive electrodes) of rechargeable lithium-batteries for reversibly storing lithium ions (Li+).

First claim

What is claimed is:

1. A composition comprising:
a cathode active material; and
at least one oxide bonded to the cathode active material;
wherein the at least one oxide bonded to the cathode active material comprises lithium (Li), oxygen (O), and at least one of zirconium (Zr) and phosphorus (P);
wherein the molar ratios of Li, Zr, P, and O, are represented by the formula Li x Zr y P a O d , wherein 0.05≤x≤25.0, 0≤y≤5.0, 0≤a≤16.0; and 2.0≤d≤55.0; and
wherein subscripts x, y, a, and d, are selected so the at least one oxide is charge neutral and y and a are not both zero;
wherein the composition has a ratio of Zr:Ni, as measured by x-ray photoelectron spectroscopy (XPS) of 0.3 to 3.2; and
wherein the cathode active material is LiNi x Mn y Co z O 2 , x+y+z=1, 0≤x≤1, 0≤y≤1, and 0≤z≤1; and
wherein the composition comprises between about 5 weight % and 10 weight % of lithium as measured by inductively coupled plasma (ICP) analysis, less than about 1 weight % of zirconium as measured by inductively coupled plasma (ICP) analysis, less than about 0.5 weight % of phosphorus as measured by inductively coupled plasma (ICP) analysis, less than about 65 weight % of manganese, cobalt, and nickel as measured by inductively coupled plasma (ICP) analysis, or a combination thereof.

2. The composition of claim 1 , comprising:
a cathode active material having a surface and an oxide bonded to the surface;
wherein the oxide is selected from the group consisting of:
LiZr 2 (PO 4 ) 3 ;
Li 2 ZrO 3 ;
Li 3 ZrPO 6 ;
Li 5 PZrO 7 ;
Li 7 ZrPO 8 ;
Li 24 Zr 3 P 14 O 53 ; and
combinations thereof;
wherein the composition has a ratio of Zr:Ni, as measured by x-ray photoelectron spectroscopy (XPS) of 0.3 to 3.2.

3. The composition of claim 1 , wherein the oxide is amorphous or crystalline.

4. The composition of claim 1 , wherein the oxide comprises a compound of the formula:
Li x Zr y P a O d , wherein 0.05≤x≤7.0, 0≤y≤3.0, 0≤a≤6.0; and 2.0≤d≤20.0
Li x Zr y P a O d , wherein 0.05≤x≤1.5, 1≤y≤3, 1.0≤a≤6.0; and 2.0≤d≤20.0;
Li x Zr y P a O d , wherein 0.05≤x≤1.5, 1≤y≤3, 2.0≤a≤4.0; and 10.0≤d≤14.0;
Li x Zr y P a O d , wherein 20.0≤x≤25.0, 2.0≤y≤5.0, 10.0≤a≤16.0; and 50.0≤d ≤55.0; or
Li x Zr y O d , wherein 1.0≤x≤3, 0≤y≤2, and 2.0≤d≤5.0.

5. The composition of claim 1 , wherein the oxide comprises a compound selected from LiZr 2 (PO 4 ) 3 , Li 3 ZrPO 6 , Li 5 PZrO 7 , Li 7 ZrPO 8 , Li 2 ZrO 3 , and Li 24 Zr 3 P 14 O 53 .

6. The composition of claim 1 , wherein the oxide is lattice-matched with the cathode active material.

7. The composition of claim 1 , wherein the cathode active material is LiNi x Mn y Co z O 2 and either (a)-(h):
(a) x is 0.8, y is 0.1, and z is 0.1;
(b) x is 0.6, y is 0.2, and z is 0.2;
(c) x is 0.5, y is 0.3, and z is 0.2;
(d) x is ⅓, y is ⅓, and z is ⅓.
(e) 0.8≤x≤0.97, 0≤y≤0.2, and 0≤z≤0.2;
(f) 0.8≤x≤0.90, 0≤y≤0.2, and 0≤z≤0.2;
(g) 0.8≤x≤0.85, 0≤y≤0.2, and 0≤z≤0.2; or
(h) 0.8≤x≤0.83, 0≤y≤0.2, and 0≤z≤0.2.

8. The composition of claim 1 , characterized by an atomic percent ratio of Zr:Ni as determined by XPS between about 0.5 to 2.5.

9. The composition of claim 1 , characterized by an atomic percent ratio of Zr:Ni of about 0.38, about 0.55, about 1.1, about 1.3, about 3.0, or about 3.2.

10. The composition of claim 1 , wherein the ratio of phosphorus to manganese, cobalt, and nickel (P:Mn+Co+Ni) is at least about 0.001 by weight percent as measured by inductively coupled plasma (ICP) analysis; at least about 0.002 by weight percent as measured by inductively coupled plasma (ICP) analysis; or at least about 0.08 by weight percent as measured by inductively coupled plasma (ICP) analysis.

11. The composition of claim 1 , wherein the oxide bonded to the cathode active material is a coating on the cathode active material.

12. The composition of claim 11 , wherein the coating is continuous.

13. The composition of claim 11 , wherein the coating is discontinuous.

14. The composition of claim 11 , wherein the coating comprises crystalline domains as determined by TEM analysis.

15. The composition of claim 11 , wherein the coating comprises amorphous domains as determined by TEM analysis.

16. The composition of claim 11 , wherein the coating comprises crystalline domains and amorphous domains as determined by TEM analysis and wherein the crystalline domains are in contact with the cathode and the amorphous domains are in contact with the crystalline domains.

17. The composition of claim 11 , wherein the coating has a thickness, T, as determined by TEM analysis, that is between about 0.7 nm≤T≤20 nm.

18. An oxide having the following formula, Li x Zr y P a O d , wherein 0.05≤x≤25.0, 0≤y≤5.0, 0≤a≤16.0; and 2.0≤d≤55.0; wherein the formula is charge neutral and wherein the oxide is bonded to cathode active material selected from lithium cobalt oxide (LCO), lithium nickel cobalt aluminum oxide (NCA), lithium nickel manganese cobalt oxide (NMC), lithium iron phosphate (LFP), and combinations thereof.

19. A cathode comprising the composition of claim 1 .

Assignees

• Quantumscape Battery Inc

Inventors

• Chao Cheng-Chieh
• Chavez Sarah
• Chung Hyeseung
• Ito Seitaro
• Katoh Yuki
• Lokshin Konstantin
• Ohash Akinari
• Silver Jessa
• Tian Yaosen
• Xu Virgil
• Yu Zhenfeng

Classifications

• H01M2004/021

  Physical characteristics, e.g. porosity, surface area · CPC title

• H01M4/505

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

• H01M4/0471

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

• Y02E60/10

  Energy storage using batteries · CPC title

• C01P2006/40

  Electric properties · CPC title