Cathode active material, cathode and lithium battery including the same, and method of preparing the cathode active material

Patent metadata

Field	Value
Publication number	US-10243210-B2
Application number	US-201615152861-A
Country	US
Kind code	B2
Filing date	May 12, 2016
Priority date	Dec 16, 2015
Publication date	Mar 26, 2019
Grant date	Mar 26, 2019

Abstract

A cathode active material includes a core capable of intercalating and deintercalating lithium ions; and a coating layer on at least a portion of the core, wherein the coating layer includes a composite including a metal oxide compound and a phosphate compound, the metal oxide compound is at least one compound selected from a lithium metal oxide and a metal oxide, the phosphate compound is at least one compound selected from a lithium phosphate, a lithium metal phosphate, and a metal phosphate, and a weight ratio of the metal oxide compound to the phosphate compound is from greater than 0 to about 1.

First claim

What is claimed is:

1. A cathode active material comprising:
a core capable of intercalating and deintercalating lithium ions; and
a coating layer on at least a portion of the core,
wherein the coating layer comprises a composite comprising a metal oxide compound and a phosphate compound,
wherein the metal oxide compound is at least one compound selected from a lithium metal oxide and a metal oxide,
wherein the phosphate compound is at least one compound selected from a lithium phosphate, a lithium metal phosphate, and a metal phosphate, and
wherein a weight ratio of the phosphate compound to the metal oxide compound is in a range of greater than 0 to about 1.

2. The cathode active material of claim 1 , wherein the metal oxide compound is the lithium metal oxide, and
the phosphate compound comprises lithium phosphate and the lithium metal phosphate.

3. The cathode active material of claim 2 , wherein the phosphate compound further comprises the metal phosphate.

4. The cathode active material of claim 1 , wherein the lithium metal oxide and the metal oxide are a compound represented by Formula 1:
Li 1−x MO 2   Formula 1

wherein, in Formula 1, 0≤x≤1, and
M is at least one metal element selected from Fe, Co, Mn, Al, Ni, Zr, Zn, and V.

5. The cathode active material of claim 4 , wherein M is at least one metal selected from Fe and Co.

6. The cathode active material of claim 1 , wherein the lithium phosphate comprises at least one compound selected from Li 3 PO 4 , LiPO 3 , Li 4 P 2 O 7 , and Li 2 O-P 2 O 5 .

7. The cathode active material of claim 1 , wherein the lithium metal phosphate and the metal phosphate are independently at least one compound selected from a compound represented by Formula 2 and a compound represented by Formula 3:
Li 1−y (M1)PO 4   Formula 2

wherein, in Formula 2, 0 ≤y≤1, and M1 is at least one metal element selected from Fe, Co, V, Mn, Ni, Zr, and Zn,
Li 1−z (M2)P 2 O 7   Formula 3

wherein, in Formula 3, 0 ≤z≤1, and M2 is at least one metal element selected from Fe, Co, V, Mn, Ni, Zr, and Zn.

8. The cathode active material of claim 7 , wherein M1 and M2 are Fe.

9. The cathode active material of claim 7 , wherein element M1 or M2 has a molar ratio in a range of about 0.0001 to about 0.1 based on 1 mole of the compound, except for lithium.

10. The cathode active material of claim 7 , wherein the element P has a molar ratio in a range of about 0.0001 to about 0.1 based on 1 mole of the compound, except lithium.

11. The cathode active material of claim 1 , wherein the phosphate compound comprises a compound represented by Formula 4:
Li a (M3)(PO 4 ) 3   Formula 4

wherein, in Formula 4, 0 ≤a≤1, and M3 is a metal element selected from Fe, V, and Ti.

12. The cathode active material of claim 1 , wherein the coating layer comprises at least one compound selected from LiFeO 2 and Li 3 PO 4 .

13. The cathode active material of claim 12 , wherein the coating layer further comprises at least one compound selected from FePO 4 , Li 3 Fe 2 (PO 4 ) 3 , and LiFePO 4 .

14. The cathode active material of claim 1 , wherein an amount of the coating layer is about 0.1 weight percent to about 10 weight percent based on the total weight of the core.

15. The cathode active material of claim 1 , wherein, a peak intensity of a phosphorous 2p binding energy in a range of about 130 electron volts to about 135 electron volts is greater than a peak intensity of an iron 2p binding energy in a range of about 710 eV to about 715 eV, as measured by X-ray photoelectron spectroscopy.

16. The cathode active material of claim 15 , wherein a peak intensity ratio of the phosphorous 2p binding energy to the iron 2p binding energy is in a range of about 1:0.1 to about 1:0.9.

17. The cathode active material of claim 1 , wherein an amount of lithium present on a surface of the core is about 20 weight percent to about 60 weight percent of an amount of lithium present on a surface of a core of a cathode active material which does not comprise the coating layer and is capable of intercalating and deintercalating lithium ions.

18. The cathode active material of claim 1 , wherein the core has a layered structure.

19. The cathode active material of claim 1 , wherein the core comprises a compound represented by Formula 5:
Li a1 Ni b1 (M4) c1 O 2   Formula 5

wherein, in Formula 5, 0.8<a1<1.3, 0.5≤b1<1.0, and 0<c1≤0.5; and M4 is at least one metal element selected from Mn, V, Cr, Fe, Co, Zr, Re, Al, B, Mg, Ga, Ge, Nb, Zn, Cd, Ti, V, Ca, Si, Cu, Sn, Sr, Sc, W, and Y.

20. A lithium battery comprising:
a cathode comprising the cathode active material of claim 1 ;
an anode; and
an electrolyte between the cathode and the anode.

21. A method of preparing a cathode active material, the method comprising:
adding a metal oxide compound precursor and a phosphate compound precursor to a core material capable of intercalating and deintercalating lithium ions to obtain a mixture; and
drying the mixture; and
heat-treating the dried mixture to prepare a cathode active material, the cathode active material comprising:
a core capable of intercalating and deintercalating lithium ions; and
a coating layer on at least a portion of the core,
wherein the coating layer is a composite coating layer comprising a metal oxide compound and a phosphate compound,
the metal oxide compound is at least one compound selected from a lithium metal oxide and a metal oxide, and
the phosphate compound is at least one compound selected from lithium phosphate, a lithium metal phosphate, and a metal phosphate, and
wherein a weight ratio of the phosphate compound to the metal oxide compound is greater than 0 to about 1.

22. The method of claim 21 , wherein the metal oxide compound precursor is at least one selected from a metal nitrate, a metal hydroxide, a metal alkoxide, and a hydride thereof.

23. The method of claim 21 , wherein the phosphate compound precursor is at least one selected from (NH 4 ) 2 HPO 4 and NH 4 H 2 PO 4 .

24. The method of claim 21 , wherein the heat-treating of the mixture is performed in an air atmosphere or an oxide atmosphere at a temperature in a range of about 350° C. to about 900° C.

25. The method of claim 21 , wherein an amount of lithium on a surface of the core is about 20 weight percent to about 60 weight percent of an amount of lithium on a core of a cathode active material which does not comprise a coating layer and is capable of intercalating and deintercalating lithium ions.

Assignees

• Samsung Electronics Co Ltd
• Samsung Sdi Co Ltd

Inventors

• Park Junho
• Park Kwangjin
• Shin Dongwook
• Yoon Jaegu
• Hong Sukgi

Classifications

• H01M50/414

  Synthetic resins, e.g. thermoplastics or thermosetting resins · CPC title

• H01M50/417

  Polyolefins · CPC title

• H01M50/489

  Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties · CPC title

• H01M4/625

  Carbon or graphite · CPC title

• H01M4/525

  of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy · CPC title