POSITIVE ACTIVE MATERIAL FOR RECHARGEABLE LITHIUM BATTERY

• US 20140342229A1
• Filed: 12/12/2012
• Published: 11/20/2014
• Est. Priority Date: 12/12/2011
• Status: Abandoned Application

• Current Assignee: Applied Materials Incorporated, Industry-Academic Cooperation Foundation Yonsei University
• Original Assignee: Applied Materials Incorporated, Industry-Academic Cooperation Foundation Yonsei University
• Inventors: Kwak, Byung-Sung Leo, Gordon, Joseph G. II, Nalamasu, Omkaram, Sun, Yangkook, Kim, Wongi, Oh, Seugmin
• Application Number:
  US14/363,023
• Publication Number:
  US 20140342229A1
• Time in Patent Office: Days
• US Class Current: 429/219
• CPC Class Codes: C01B 25/45 containing plural metal, or metal and ammonium
• CPC Class Codes: C01B 25/455 containing halogen completely halogenated alkali metal phosphates C01D, e.g. lithium hexafluorophosphate C01D15/005
• CPC Class Codes: H01M 10/052 Li-accumulators
• CPC Class Codes: H01M 10/0525 Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• CPC Class Codes: H01M 2004/028 Positive electrodes
• CPC Class Codes: H01M 4/0471 involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
• CPC Class Codes: H01M 4/136 Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
• CPC Class Codes: H01M 4/366 as layered products
• CPC Class Codes: H01M 4/5815 Sulfides
• CPC Class Codes: H01M 4/582 Halogenides
• CPC Class Codes: H01M 4/5825 Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
• CPC Class Codes: H01M 4/587 for inserting or intercalating light metals
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

Disclosed are a cathode active material for a lithium secondary battery, and a lithium secondary battery including the same. The disclosed cathode active material includes a core including a compound represented by Formula 1; and a shell including a compound represented by Formula 2, in which the core and the shell have different material compositions.

Claims

1. A cathode active material for a lithium secondary battery, comprising:

a core comprising a compound represented by Formula 1; and

a shell comprising a compound represented by Formula 2,

wherein the core and the shell have different material compositions,

wherein

Li_x1M1_y1M2_z1PO_4-w1E_w1 

 

[Formula 1]

Li_x2M3_y2M4_z2PO_4-w2E_w2 

 

[Formula 2]

in the Formulas 1 and 2,

M1, M2, M3 and M4 are the same or different, and each is independently selected from the group consisting of Ni, Co, Mn, Fe, Na, Mg, Ca, Ti, V, Cr, Cu, Zn, Ge, Sr, Ag, Ba, Zr, Nb, Mo, Al, Ga, B and a combination thereof,

E is selected from the group consisting of F, S, and a combination thereof,

0<

x1≦

1, 0≦

y1≦

1, 0≦

z1≦

1, and 0<

x1+y1+z1≦

2,

0≦

w1≦

0.5,

0<

x2≦

1, 0≦

y2≦

1, 0≦

z2≦

1, and 0<

x2+y2+z2≦

2 and,

0≦

w2≦

0.5.

2. The cathode active material for the lithium secondary battery, as claimed in claim 1, wherein M1 and M3 are the same materials, and M2 and M4 are the same materials, in which x1=x2, y1<

y2, and z1>

z2.

3. The cathode active material for the lithium secondary battery, as claimed in claim 2, wherein M1 and M3 are selected from the group consisting of Fe, Co, Ni, Mn, and a combination thereof, and M2 and M4 are selected from the group consisting of Mn, Ni, Co, Fe, and a combination thereof.

4. The cathode active material for the lithium secondary battery, as claimed in claim 1, wherein M1 and M3 are different materials.

5. The cathode active material for the lithium secondary battery, as claimed in claim 1, wherein M2 and M4 are different materials.

6. The cathode active material for the lithium secondary battery, as claimed in claim 1, wherein M1 is different from M2,

the core has a structure in which in a direction away from a center of

the core, a concentration of M1 increases, and a concentration of M2 decreases,

M1 is selected from the group consisting of Fe, Co, Ni, Mn, and a combination thereof, and

M2 is selected from the group consisting of Mn, Ni, Co, Fe, and a combination thereof.

7. The cathode active material for the lithium secondary battery, as claimed in claim 1, wherein the core has a diameter of about 5 to 20 μ

m.

8. The cathode active material for the lithium secondary battery, as claimed in claim 1, wherein M3 is different from M4,

the shell has a structure in which in a direction away from an interface between the core and the shell, a concentration of M3 increases, and a concentration of M4 decreases,

M3 is selected from the group consisting of Fe, Co, Ni, Mn, and a combination thereof, and

M4 is selected from the group consisting of Mn, Ni, Co, Fe, and a combination thereof.

9. The cathode active material for the lithium secondary battery, as claimed in claim 1, wherein the shell has a thickness of about 100 nm to 5 μ

m.

10. The cathode active material for the lithium secondary battery, as claimed in claim 1, further comprising a carbon coating layer on a surface of the shell.

11. The cathode active material for the lithium secondary battery, as claimed in claim 10, wherein the carbon coating layer has a thickness of about 10 nm to 200 nm.

12. The cathode active material for the lithium secondary battery, as claimed in claim 1, further comprising an interlayer between the core and the shell,

wherein the interlayer comprises a compound represented by Formula 3, and

a material composition of the interlayer is different from the material compositions of the core and the shell,

wherein

Li_x3M5_y3M6_z3PO_4-w3E_w3 

 

[Formula 3]

in Formula 3,

M5 and M6 are the same or different, and each is independently selected from the group consisting of Ni, Co, Mn, Fe, Na, Mg, Ca, Ti, V, Cr, Cu, Zn, Ge, Sr, Ag, Ba, Zr, Nb, Mo, Al, Ga, B, and a combination thereof,

E is selected from the group consisting of F, S, and a combination thereof,

0≦

x3≦

1, 0≦

y3≦

1, 0≦

z3≦

1, and 0<

x3+y3+z32, and

0≦

w3≦

0.5.

13. The cathode active material for the lithium secondary battery, as claimed in claim 12, wherein M1, M3, and M5 are the same materials, and M2, M4, and M6 are the same materials, in which x1=x2=x3, y1<

y3<

y2, and z1>

z3>

z2.

14. The cathode active material for the lithium secondary battery, as claimed in claim 13, wherein M1, M3, and M5 are selected from the group consisting of Fe, Co, Ni, Mn, and a combination thereof, and M2, M4, and M6 are selected from the group consisting of Mn, Ni, Co, Fe, and a combination thereof.

15. The cathode active material for the lithium secondary battery, as claimed in claim 12, wherein M1, M3, and M5 are different materials.

16. The cathode active material for the lithium secondary battery, as claimed in claim 12, wherein M2, M4, and M6 are different materials.

17. The cathode active material for the lithium secondary battery, as claimed in claim 12, wherein M5 is different from M6,

the interlayer has a structure in which in a direction away from the core, a concentration of M5 increases, and a concentration of M6 decreases,

M5 is selected from the group consisting of Fe, Co, Ni, Mn, and a combination thereof, and

M6 is selected from the group consisting of Mn, Ni, Co, Fe, and a combination thereof.

18. The cathode active material for the lithium secondary battery, as claimed in claim 12, wherein the interlayer has a thickness of about 100 nm to 24 μ

m.

19. The cathode active material for the lithium secondary battery, as claimed in claim 1, which has a diameter of about 5 μ

m to 25 μ

m.

20. The cathode active material for the lithium secondary battery, as claimed in claim 1, which has a tap density of about 1 g/cm³ to 2 g/cm³.

33. A lithium secondary battery comprising:

a cathode comprising a cathode active material;

an anode comprising an anode active material; and

an electrolyte,

wherein the cathode active material is the cathode active material for the lithium secondary battery as claimed in any one of claims 1 to 18.

21. A method for preparing a cathode active material for a lithium secondary battery, the method comprising the steps of:

forming a core precursor by mixing an M1 source, an M2 source, and a phosphoric acid source;

forming a core-shell precursor by mixing the core precursor with an M3 source, an M4 source, and a phosphoric acid source, the core-shell precursor comprising a shell precursor formed on a surface of the core precursor;

forming a core-shell composite by performing a heat treatment on the core-shell precursor; and

mixing the core-shell composite with a lithium source, followed by calcination,

wherein M1, M2, M3, and M4 are the same or different, and each is independently selected from the group consisting of Ni, Co, Mn, Fe, Na, Mg, Ca, Ti, V, Cr, Cu, Zn, Ge, Sr, Ag, Ba, Zr, Nb, Mo, Al, Ga, B and a combination thereof.

22. The method as claimed in claim 21, wherein the M1 source, the M2 source, the M3 source, and the M4 source comprise sulfur oxide, nitrogen oxide, acetic oxide, hydroxide, chloride, oxalate, fluoride, carbonate, or a combination thereof of M1, M2, M3 and M4, respectively.

23. The method as claimed in claim 21, wherein the phosphoric acid source comprises phosphoric acid (H₃PO₄), ammonium phosphate dibasic ((NH₄)₂HPO₄), ammonium phosphate trihydrate ((NH₄)₃PO₄.3H₂O)), metaphosphoric acid, orthophosphoric acid, monoammonium phosphate (NH₄H₂PO₄), or a combination thereof.

24. The method as claimed in claim 21, wherein the lithium source comprises lithium phosphate (Li₃PO₄), lithium nitrate (LiNO₃), lithium acetate (LiCH₃COOH), lithium carbonate (Li₂CO₃), lithium hydroxide (LiOH), lithium dihydrogen phosphate (LiH₂PO₄), or a combination thereof.

25. The method as claimed in claim 21, wherein the heat treatment is performed at a temperature ranging from about 300°

C. to 700°

C.

26. The method as claimed in claim 21, wherein the calcination is carried out at a temperature ranging from about 600°

C. to 900°

C.

27. The method as claimed in claim 21, further comprising the step of forming a carbon coating layer on a surface of the core-shell composite, after the step of forming the core-shell composite.

28. The method as claimed in claim 21, further comprising the step of forming an interlayer precursor on the surface of the core precursor by mixing the core precursor with an M5 source, an M6 source, and a phosphoric acid source, after the step of forming the core precursor, wherein M5 and M6 are the same or different, and each is independently selected from the group consisting of Ni, Co, Mn, Fe, Na, Mg, Ca, Ti, V, Cr, Cu, Zn, Ge, Sr, Ag, Ba, Zr, Nb, Mo, Al, Ga, B, and a combination thereof.

29. The method as claimed in claim 28, wherein the M5 source and the M6 source comprises sulfur oxide, nitrogen oxide, acetic oxide, phosphorus oxide, chloride, oxalate, fluoride, carbonate, or a combination thereof of M5 and M6, respectively, and

the phosphoric acid source comprises phosphoric acid (H₃PO₄), ammonium phosphate dibasic ((NH₄)₂HPO₄), ammonium phosphate trihydrate ((NH₄)₃PO₄.3H₂O)), metaphosphoric acid, orthophosphoric acid, monoammonium phosphate (NH₄H₂PO₄), or a combination thereof.

30. A method for preparing a cathode active material for a lithium secondary battery, the method comprising the steps of:

forming a core precursor by mixing an M1 source and an M2 source;

forming a core-shell precursor by mixing the core precursor with an M3 source, and an M4 source, the core-shell precursor comprising a shell precursor formed on a surface of the core precursor; and

mixing the core-shell precursor with a lithium source and a phosphoric acid source, followed by calcination,

wherein M1, M2, M3, and M4 are the same or different, and each is independently selected from the group consisting of Ni, Co, Mn, Fe, Na, Mg, Ca, Ti, V, Cr, Cu, Zn, Ge, Sr, Ag, Ba, Zr, Nb, Mo, Al, Ga, B and a combination thereof.

31. The method as claimed in claim 30, further comprising the step of forming a carbon coating layer on a surface of the core-shell precursor, after the step of forming the core-shell precursor.

32. The method as claimed in claim 30, further comprising the step of forming an interlayer precursor on the surface of the core precursor by mixing the core precursor with an M5 source and an M6 source, after the step of forming the core precursor,

wherein M5, and M6 are the same or different, and each is independently selected from the group consisting of Ni, Co, Mn, Fe, Na, Mg, Ca, Ti, V, Cr, Cu, Zn, Ge, Sr, Ag, Ba, Zr, Nb, Mo, Al, Ga, B and a combination thereof.