COMPOSITE CATHODE ACTIVE MATERIAL, PREPARATION METHOD THEREOF, CATHODE INCLUDING THE MATERIAL, AND LITHIUM BATTERY INCLUDING THE CATHODE

• US 20160190585A1
• Filed: 12/28/2015
• Published: 06/30/2016
• Est. Priority Date: 12/26/2014
• Status: Abandoned Application

• Current Assignee: Industry Foundation Of Chonnam National University (Chonnam National University), Samsung Electronics Co. Ltd., Samsung SDI Company Limited
• Original Assignee: Industry Foundation Of Chonnam National University (Chonnam National University), Samsung Electronics Co. Ltd., Samsung SDI Company Limited
• Inventors: Kim, Donghan, Hong, Sukgi, Kim, Jaekook, Kim, Sungjin, Gim, Jihyeon, Song, Jinju, Yoon, Jaegu, Park, Kwangjin, Park, Jinhwan
• Application Number:
  US14/979,726
• Publication Number:
  US 20160190585A1
• Time in Patent Office: Days
• US Class Current: 1/1
• CPC Class Codes: H01M 10/052 Li-accumulators
• CPC Class Codes: H01M 2004/028 Positive electrodes
• CPC Class Codes: H01M 4/364 as mixtures
• CPC Class Codes: H01M 4/366 as layered products
• CPC Class Codes: H01M 4/485 of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy H01M4/505, H01M4/525 take precedence
• CPC Class Codes: H01M 4/505 of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
• CPC Class Codes: H01M 4/525 of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
• CPC Class Codes: H01M 4/5825 Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y02T 10/70 Energy storage systems for electromobility, e.g. batteries

Abstract

A composite cathode active material including: a lithium composite oxide; a metal phosphate represented by Formula 1, preparation methods thereof, a cathode and a lithium battery.

M_xP_yO_z   Formula 1

wherein, in Formula 1, M is vanadium, niobium, tantalum, or a combination thereof, 1≦y/x≦1.33, and 4≦z/y≦5.

Claims

1. A composite cathode active material comprising:

a lithium composite oxide; and

a metal phosphate represented by Formula 1,

M_xP_yO_z  

 

Formula 1

wherein, in Formula 1, M is vanadium, niobium, tantalum, or a combination thereof, 1≦

y/x≦

1.33, and 4≦

z/y≦

5.

2. The composite cathode active material of claim 1, wherein, in Formula 1, x is between 1 and 3, y is between 1 and 4, and z is between 4 and 20.

3. The composite cathode active material of claim 1, wherein the metal phosphate represented by Formula 1 is VPO₄, V₃(PO₄)₄, TaPO₄, Ta₃(PO₄)₄, NbPO₄, or Nb₃(PO₄)₄.

4. The composite cathode active material of claim 1, wherein the lithium composite oxide is a compound represented by Formulas 2 to 4, or a combination thereof:

LiM₂O₄  

 

Formula 2

wherein, in Formula 2, M is nickel, manganese, cobalt, or a combination thereof,

Li_1+xM<sub>1−

x</sub>O₂  

 

Formula 3

wherein, in Formula 3, M is Ni, Co, Mn, titanium, V, iron, Nb, molybdenum, or a combination thereof, and 0<

x≦

0.3, and

Li_aNi_bCo_cMn_dM_eO₂  

 

Formula 4

wherein, in Formula 4, 1.1≦

a<

1.5, 0<

b<

1, 0≦

c<

1, 0<

d<

1, 0≦

e<

1, and 0<

b+c+d+e<

1, and M is Ti, V, Fe, Nb, Mo, or a combination thereof.

5. The composite cathode active material of claim 1, wherein the lithium composite oxide is a compound represented by Formula 5:

Li_1+x1M<sub>1−

x1</sub>O₂  

 

Formula 5

wherein, in Formula 5, M is Ni, Co, Mn, Ti, V, Fe, Nb, Mo, or a combination thereof, and

0.1≦

x1≦

0.3

6. The composite cathode active material of claim 1, wherein the metal phosphate represented by Formula 1 is amorphous.

7. The composite cathode active material of claim 1, wherein an amount of the metal phosphate represented by Formula 1 is in a range of about 0.01 part by weight to about 40 parts by weight, based on 100 parts by weight of the composite cathode active material.

8. The composite cathode active material of claim 1, wherein the composite cathode active material comprises a lithium composite oxide and a coating layer including the metal phosphate represented by Formula 1 on at least a portion of a surface of the lithium composite oxide.

9. A method of preparing the composite cathode active material of claim 1, the method comprising:

mixing a metal phosphate represented by Formula 1 and a lithium composite oxide to prepare the composite cathode active material;

M_xP_yO_z  

 

Formula 1

wherein, in Formula 1, M is vanadium, niobium, tantalum, or a combination thereof, 1≦

y/x≦

1.33, and 4≦

z/y≦

5.

10. The method of claim 9, wherein the metal phosphate represented by Formula 1 is prepared by:

preparing a salt solution comprising vanadium, niobium, tantalum, or a combination thereof by mixing a salt comprising vanadium, niobium, tantalum, or a combination thereof and a solvent;

adding a phosphoric acid material to the salt solution comprising M to form a reaction product; and

drying the reaction product to prepare the metal phosphate represented by Formula 1.

11. The method of claim 10, wherein the reaction product of the salt solution comprising vanadium, niobium, tantalum, or a combination thereof and the phosphoric acid material is formed in a temperature range of about 25°

C. to about 80°

C.

12. The method of claim 10, wherein the phosphoric acid material comprises phosphoric acid, polyphosphoric acid, phosphonic acid, orthophosphoric acid, pyrophosphoric acid, triphosphoric acid, metaphosphoric acid, ammonium hydrogen phosphate, a derivative thereof, or a combination thereof.

13. The method of claim 10, wherein an amount of the metal phosphate represented by Formula 1 is in a range of about 0.01 part by weight to about 40 parts by weight, based on 100 parts by weight of a total weight of the metal phosphate represented by Formula 1 and the lithium composite oxide.

14. A method of preparing the composite cathode active material of claim 1, the method comprising:

providing a salt solution comprising vanadium, niobium, tantalum, or a combination thereof by mixing a salt comprising vanadium, niobium, tantalum, or a combination thereof and a solvent;

adding a phosphoric acid-based material and a lithium composite oxide to the salt solution to form a reaction product; and

drying the reaction product to prepare the composite cathode active material.

15. The method of claim 14, wherein the salt solution and the phosphoric acid material are contacted in a temperature range of about 25°

C. to about 80°

C.

16. The method of claim 14, wherein the phosphoric acid material comprises phosphoric acid, polyphosphoric acid, phosphonic acid, orthophosphoric acid, pyrophosphoric acid, triphosphoric acid, metaphosphoric acid, ammonium hydrogen phosphate, a derivative thereof, or a combination thereof.

17. The method of claim 14, wherein an amount of the metal phosphate represented by Formula 1 is in a range of about 0.01 part by weight to about 40 parts by weight, based on 100 parts by weight of a total weight of the metal phosphate represented by Formula 1 and the lithium composite oxide.

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

19. A lithium battery comprising the cathode of claim 18, an anode, and an electrolyte.

20. The lithium battery of claim 19, wherein the lithium battery has an average discharge voltage of 3.40V (vs. Li) or higher in state where the battery is charged at a 0.1 C constant current rate to a voltage of about 4.8 V and then discharged at a 0.1 C constant current rate until the voltage reached about 2 V.

21. A composite cathode active material comprising:

a lithium composite oxide represented by Formula 5;

Li_1+x1M<sub>1−

x1</sub>O₂  

 

Formula 5

wherein, in Formula 5, M is Ni, Co, and Mn, and 0.1≦

x1≦

0.3; and

a metal phosphate represented by Formula 1,

M_xP_yO_z  

 

Formula 1

wherein, in Formula 1, M is vanadium, 1≦

y/x≦

1.33, and 4≦

z/y≦

5.