Composite cathode active material, and cathode and lithium battery comprising composite cathode active material

Patent metadata

Field	Value
Publication number	US-11239456-B2
Application number	US-201916663105-A
Country	US
Kind code	B2
Filing date	Oct 24, 2019
Priority date	Nov 30, 2016
Publication date	Feb 1, 2022
Grant date	Feb 1, 2022

Abstract

A composite cathode active material, a cathode including the composite cathode active material, and a lithium battery including the cathode are provided. The composite cathode active material includes a core including a lithium metal oxide and a coating layer on the core, wherein the lithium metal oxide includes two or more transition metals including nickel (Ni), an amount of Ni within one mole of the two or more transition metals included in the lithium metal oxide is about 0.65 mol or greater, the coating layer includes LiF, and a resistance of the composite cathode active material is lower than that of the core.

First claim

What is claimed is:

1. A method for preparing a composite cathode active material, the method comprising:
preparing an electrolyte solution comprising a fluorine-containing lithium salt and a non-aqueous solvent;
preparing a coating mixture by mixing a lithium metal oxide, an alcohol, and the electrolyte solution;
separating the lithium metal oxide from the coating mixture to obtain a pre-coated lithium metal oxide; and
drying the pre-coated lithium metal oxide.

2. The method for preparing the composite cathode active material of claim 1 , wherein the alcohol is a linear or branched C 1 -C 10 alcohol.

3. The method for preparing the composite cathode active material of claim 1 , wherein the mixing the lithium metal oxide, the alcohol, and the electrolyte solution is performed at a temperature of 10° C. to 70° C.

4. The method for preparing the composite cathode active material of claim 1 , wherein the fluorine-containing lithium salt is at least one selected from LiPF 6 , LiBF 4 , LiSbF 6 , and LiAsF 6 .

5. The method for preparing the composite cathode active material of claim 1 , wherein the non-aqueous solvent is at least one selected from propylene carbonate, ethylene carbonate, fluoroethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, methylethyl carbonate, methylpropyl carbonate, ethylpropyl carbonate, methylisopropyl carbonate, dipropyl carbonate, dibutyl carbonate, benzonitrile, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, γ-butyrolactone, dioxolane, 4-methyldioxolane, N,N-dimethylformamide, dimethylacetamide, dimethylsulfoxide, dioxane, 1,2-dimethoxyethane, sulfolane, dichloroethane, chlorobenzene, nitrobenzene, diethylene glycol, and dimethyl ether.

6. The method for preparing the composite cathode active material of claim 1 , further comprising heat-treating the pre-coated lithium metal oxide.

7. The method for preparing the composite cathode active material of claim 6 , wherein the heat-treating is performed at a temperature of 400° C. to about 800° C. for 1 to 15 hours.

8. The method for preparing the composite cathode active material of claim 1 , wherein the composite cathode active material comprises:
a core comprising the lithium metal oxide; and
a coating layer on the core,
the lithium metal oxide including two or more transition metals including nickel (Ni),
an amount of Ni in one mole of the two or more transition metals being about 0.65 mol or greater, and
the coating layer comprising LiF.

9. The method for preparing the composite cathode active material of claim 8 , wherein a resistance of the composite cathode active material is lower than that of the core.

10. The method for preparing the composite cathode active material of claim 8 , wherein the coating layer further comprises a carbonaceous material.

11. The method for preparing the composite cathode active material of claim 8 , wherein the coating layer further comprises amorphous carbon.

12. The method for preparing the composite cathode active material of claim 8 , wherein the coating layer comprises LiF and a carbonaceous material in a single layer.

13. The method for preparing the composite cathode active material of claim 8 , wherein the coating layer has a multi-layer structure comprising a first coating layer and a second coating layer, the first coating layer comprising the LiF and the second coating layer comprising a carbonaceous material.

14. The method for preparing the composite cathode active material of claim 8 , wherein the coating layer is discontinuously disposed on the core.

15. The method for preparing the composite cathode active material of claim 13 , wherein the coating layer completely covers the core.

16. The method for preparing the composite cathode active material of claim 8 , wherein a thickness of the coating layer is about 2 nm to about 500 nm.

17. The method for preparing the composite cathode active material of claim 13 , wherein a thickness of the second coating layer is about 1 nm to about 100 nm.

18. The method for preparing the composite cathode active material of claim 1 , wherein the lithium metal oxide is represented by Formula 1:
Li 1+a [Ni 1−x M x ]O 2−b X b   Formula 1

wherein, in Formula 1, 0≤a≤0.2, 0.01≤b≤0.1, 0.01≤x≤0.35;
M is at least one selected from Al, Co, Mn, Mg, Zn, Fe, Cr, Ga, Mo, W, Ti, Sc, V, Cr, Fe, B, Si, Ga, Ge, As, Zr, Ru, Rh, Pt, Ag, and Sn; and
X is F or S.

19. The method for preparing the composite cathode active material of claim 1 , wherein the lithium metal oxide is represented by Formula 2:
Li 1+a [Ni 1−x−y Co x M′ y ]O 2−b X b   Formula 2

wherein, in Formula 2, 0≤a≤0.2, 0.01≤b≤0.1, 0.01≤x≤0.35, 0.01≤y≤0.35, 0.65≤1−x−y≤0.95;
M is at least one selected from Al, Mn, Mg, Zn, Fe, Cr, Ga, Mo, W, Ti, Sc, V, Cr, Fe, B, Si, Ga, Ge, As, Zr, Ru, Rh, Pt, Ag, and Sn; and
X is F or S.

20. The method for preparing the composite cathode active material of claim 1 , wherein the lithium metal oxide is represented by one selected from Formulae 3 to 6:
Li 1+a [Ni 1−x−y Co x Mn y ]O 2−b X b   Formula 3

wherein, in Formula 3, 0≤a≤0.2, 0.01≤b≤0.1, 0.01≤x≤0.35, 0.01≤y≤0.35, 0.65≤1−x−y≤0.95; and
X is F or S;
Li 1+a [Ni 1−x−y Co x Al y ]O 2−b X b   Formula 4

wherein, in Formula 4, 0≤a≤0.2, 0.01≤b≤0.1, 0.01≤x≤0.35, 0.01≤y≤0.35, 0.65≤1−x−y≤0.95; and
X is F or S;
Li 1+a [Ni 1−x−y−z Co x Mn y Al z ]O 2−b X b   Formula 5

wherein, in Formula 5, 0≤a≤0.2, 0.01≤b≤0.1, 0.01≤x≤0.35, 0.01≤y≤0.35, 0.01≤z≤0.35, 0.65≤1−x−y−z≤0.95; and
X is F or S;
Li 1+a [Ni 1−x−y−z−v Co x Mn y Al z Mg v ]O 2−b X b   Formula 6

wherein, in Formula 6, 0≤a≤0.2, 0.01≤b≤0.1, 0.01≤x≤0.35, 0.01≤y≤0.35, 0.01≤y≤0.35, 0.01≤z≤0.35, 0.01≤v≤0.15, 0.65≤1−x−y−z−v≤0.95, and
X is F or S.

21. The method for preparing the composite cathode active material of claim 8 , wherein the core is a secondary particle comprising a plurality of aggregated primary particles.

22. A cathode comprising the composite cathode active material prepared by the method of claim 1 .

23. A lithium battery comprising the cathode of claim 22 .

Assignees

• Samsung Sdi Co Ltd

Inventors

• Song Yumi
• Kwon Seonyoung
• Kim Kihyun
• Kim Soohyeon
• Kim Jinhwa
• Moon Joongho
• Lee Jaeho
• Cho Kwanghwan
• Choi Soonbong
• Hong Mingzi

Classifications

• 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

• H01M4/131 Primary

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

• Y02T10/70

  Energy storage systems for electromobility, e.g. batteries · CPC title

• H01M10/0525

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