Positive electrode material, preparation method and uses thereof

Patent metadata

Field	Value
Publication number	US-12176537-B2
Application number	US-202418435387-A
Country	US
Kind code	B2
Filing date	Feb 7, 2024
Priority date	Dec 29, 2018
Publication date	Dec 24, 2024
Grant date	Dec 24, 2024

Abstract

The present application relates to the electrochemical field, and in particular, to a positive electrode material, and an electrochemical energy storage apparatus having thereof. The present application provides a positive electrode material, including a substrate. The substrate includes secondary particles containing primary particles. A surface of the substrate is coated with an oxide coating layer. The oxide coating layer comprises a coating element, and the coating element is selected from one or more of Al, Ba, Zn, Ti, Zr, Mg, W, Y, Si, Sn, B, Co, or P. The electrochemical energy storage apparatus comprises the foregoing positive electrode material.

First claim

What is claimed is:

1. A positive electrode material comprising:
a substrate comprising secondary particles, wherein each secondary particle comprises a plurality of primary particles packed together, a molecular formula of the substrate is Li x Ni y CO z Mn k Al p O r A m , 0.95≤ x≤1.05, 0.70≤ y≤0.98, 0<z≤0.2, 0<k≤0.2, 0≤ p≤0.05, 1<r≤2, 0≤m≤2, m+r≤2, A is selected from F, Cl, Br, and any combinations thereof;
a coating layer disposed on a surface of the substrate, wherein the coating layer comprises an oxide of a coating element selected from Al, Ba, Zn, Ti, Zr, Mg, Y, Si, B, Co, P, and any combinations thereof,
wherein a powder resistivity ρ of the positive electrode material under a 12 MPa pressure is 500 Ω*cm-2,000 Ω*cm.

2. The positive electrode material of claim 1 , wherein the powder resistivity ρ of the positive electrode material under a 12 MPa pressure is 543 Ω*cm-1,653 Ω*cm.

3. The positive electrode material of claim 1 , wherein a content Mv of the coating element per unit volume of the positive electrode material is 400 μg/cm 3 to 15,000 μg/cm 3 .

4. The positive electrode material of claim 3 , wherein the content Mv of the coating element per unit volume of the positive electrode material is 800 μg/cm 3 to 10,000 μg/cm 3 .

5. The positive electrode material of claim 3 , wherein the powder resistivity ρ and the content Mv of the coating element satisfy: ρ/Mv≤1 Ω*cm 4 /μg.

6. The positive electrode material of claim 5 , wherein the powder resistivity ρ and the content Mv of the coating element satisfy: ρ/Mv≤0.5 Ω*cm 4 /μg.

7. The positive electrode material of claim 1 , wherein the coating element is selected from at least two of the group consisting of Al, Ba, Zn, Ti, Zr, Mg, Y, Si, B, Co, and P.

8. The positive electrode material of claim 1 , wherein the coating element is distributed on a surface of at least a part of the primary particles inside the secondary particles and distributed at grain boundaries between adjacent primary particles.

9. The positive electrode material of claim 1 , wherein a content of the coating element in the oxide coating layer is 60 wt % or more, based on a total content of the coating element in the positive electrode material.

10. The positive electrode material of claim 1 , wherein in the molecular formula of the substrate, 0.80≤y≤0.98, 0<z≤0.1, 0<k≤0.1, and 0≤p≤0.03.

11. The positive electrode material of claim 1 , wherein Dv50 of the secondary particles is 5 μm-18 μm, the primary particles have an average particle diameter of 0.1 μm-1 μm.

12. The positive electrode material of claim 1 , wherein a specific surface area of the positive electrode material is 0.1 m 2 /g-0.8 m 2 /g.

13. The positive electrode material of claim 1 , wherein a content of Li 2 CO 3 in residual lithium on a surface of the positive electrode material is less than 3,000 ppm, and a content of LiOH in the residual lithium on the surface of the positive electrode material is less than 5,000 ppm.

14. The positive electrode material of claim 13 , wherein in the residual lithium on the surface of the positive electrode material, the content of Li 2 CO 3 is less than the content of LiOH.

15. A method for preparing a positive electrode material, the method comprising:
forming a substrate, wherein the substrate comprises secondary particles, the secondary particle comprises a plurality of primary particles packed together, a molecular formula of the substrate is 0.70≤ y≤0.98, 0<z≤0.2, 0<k≤0.2, 0≤p≤0.05, 1≤r≤2, 0≤m≤2, m+r≤2, A is selected from F, Cl, Br, and any combinations thereof; and
forming a coating layer on a surface of the substrate, wherein the coating layer comprises an oxide of a coating element selected from Al, Ba, Zn, Ti, Zr, Mg, Y, Si, B, Co, P, and any combinations thereof,
wherein a powder resistivity ρ of the positive electrode material under a 12 MPa pressure is 500 Ω*cm-2,000 Ω*cm.

16. The method of claim 15 , wherein forming the substrate further comprises:
forming a mixture of a lithium source and a metal source, wherein the metal source comprises a metal element selected from the group consisting of Ni, Co, Mn, Al, and any combinations thereof; and
sintering the mixture.

17. The method of claim 16 , wherein the metal source is selected from the group consisting of Ni 0.5 Co 0.2 Mn 0.3 (OH) 2 , Ni 0.5 Co 0.25 Mn 0.25 (OH) 2 , Ni 0.55 Co 0.15 Mn 0.3 (OH) 2 , Ni 0.55 Co 0.1 Mn 0.35 (OH) 2 , Ni 0.55 Co 0.05 Mn 0.4 (OH) 2 , Ni 0.6 Co 0.2 Mn 0.2 (OH) 2 , Ni 0.75 Co 0.1 Mn 0.15 (OH) 2 , Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 , Ni 0.88 Co 0.05 Mn 0.07 (OH) 2 , 0.9Ni 0.8 Co 0.2 (OH) 2 ·0.1Al 2 (OH) 3 , 0.9Ni 0.9 Co 0.05 Mn 0.05 (OH) 2 ·0.1Al 2 (OH) 3 , and any combinations thereof,
wherein the lithium source is selected from the group consisting of LiOH·H 2 O, LiOH, Li 2 CO 3 , Li 2 O, and any combinations thereof.

18. The method of claim 16 , wherein the sintering is performed at a temperature of 800° C. with an oxygen concentration greater than or equal to 20%.

19. The method of claim 15 , wherein forming the coating layer further comprises:
mixing the substrate with a compound containing the coating element, wherein the compound is selected from the group consisting of Al 2 O 3 , ZnO, ZrO 2 , TiO 2 , MgO, WO 3 , Y 2 O 3 , Co 2 O 3 , Ba(NO 3 ) 2 , Co 2 O 3 , P 2 O 5 , H 3 BO 3 , and any combinations thereof; and
sintering the mixed substrate and compound.

20. The method of claim 15 , wherein the coating element has a dosage from 0.01 wt % to 0.5 wt %, based on a mass of the substrate, and sintering the mixed substrate and compound is performed at a temperature from 200° C.-700° C.

Assignees

• Contemporary Amperex Technology Hong Kong Ltd

Inventors

• Du Rui
• Liu Yongchao
• Wang Sihui
• Zhao Deyu
• Liu Na

Classifications

• H01M2004/028

  Positive electrodes · CPC title

• H01M2004/021

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

• H01M10/0525

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

• H01M4/505

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

• H01M4/485

  of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy (H01M4/505, H01M4/525 take precedence) · CPC title