Method for preparing a positive active material for a lithium secondary battery

• US 10,446,836 B2
• Filed: 11/09/2015
• Issued: 10/15/2019
• Est. Priority Date: 05/26/2015
• Status: Active Grant

• Current Assignee: Ningde Amperex Technology Limited
• Original Assignee: Ningde Amperex Technology Limited
• Inventors: Fang, Xiangpeng, Wu, Chengren, Liu, Na, Gao, Xuguang
• Primary Examiner(s): Pyon, Harold Y
• Assistant Examiner(s): Kang, Danny N
• Application Number:
  US14/935,451
• Publication Number:
  US 20160351898A1
• Time in Patent Office: 1,436 Days
• Field of Search: 252500
• 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 2220/20 Batteries in motive systems, e.g. vehicle, ship, plane
• CPC Class Codes: H01M 4/366 as layered products
• 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

Abstract

The present invention provides a method for preparing a positive active material for a secondary lithium battery. The method includes the steps of: synthesizing an intermediate product of a core represented by formula Li_xM_yN_1-yO_2-αA_β; adding P source into the intermediate product to obtain a phosphate which does not contain lithium; and adding lithium source into the mixture of the phosphate and Li_xM_yN_1-yO_2-αA_β and sintering to obtain the positive active material for secondary lithium battery. The method for preparing a positive active material for a secondary lithium battery of the present invention has the following advantages: 1) the P source can be dispersed on the surface of the core more uniformly; 2) the coating layer can be bonded to the core more tightly; and 3) the positive active material has higher rate discharge performance.

Claims

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

1) synthesizing a first intermediate product of a core represented by formula Li_xM_yN_1-yO_2-α

A_β

, wherein the first intermediate product is a compound containing an element represented by M or is a compound containing elements represented by M and N;

2) adding phosphorous (P) containing source into the first intermediate product of step

     1) and sintering a mixture of the phosphorous (P) containing source and the first intermediate product at 200˜

1200°

C., and obtaining a second intermediate product coated with a coating layer which does not contain lithium;

3) adding degradable lithium salt into the second intermediate product of step

     2) and sintering a mixture of the second intermediate product coated with the coating layer which does not contain lithium and the degradable lithium salt at 400˜

1200°

C., and obtaining a positive active material including a core and a coating layer coating the core;

wherein the core of the positive active material is a lithium transition metal oxide represented by formula Li_xM_yN_1-yO_2-α

A_β

, the coating layer is a lithium transition metal phosphate represented by formula Li_aM_bN′

_1-bPO_4-λ

B_ζ

in situ formed on a surface of the core, and the element represented by M is at least one of Ni, Co and Mn;

the element represented by N and N′

each is at least one of Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Ra, Al, Ga, In, Ge, Sn, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu;

element represented by A and B each is at least one of N, F, P, S, Cl, Se; and

0.9≤

x≤

1.2, 0.6≤

y≤

1.0, 0.9≤

a≤

1.1, 0.6≤

b≤

1.0, 0≤

α

≤

0.2, 0≤

β

≤

0.4, 0≤

λ

≤

0.5, 0≤

ζ

≤

0.5.

2. The method of claim 1, wherein the first intermediate product synthesized in step 1) is obtained via one of solid milling method, liquid coprecipitation method, sol-gel method, combustion method, solvothermal method and Pechini method.

3. The method of claim 1, wherein the first intermediate product in step 1) is a hydroxide;

a nitrate;

a carbonate;

an acetate;

an oxalate;

an organic salt containing C, N, O and H;

or is oxide particle obtained via sintering a mixture comprising two or more of a hydroxide, a nitrate, a carbonate, an acetate, an oxalate and an organic salt containing C, N, O and H.

4. The method of claim 1, wherein the first intermediate product in step 1) comprises loose secondary particles, secondary aggregates of loose nano particles, compact primary single crystal particles, compact secondary particles or any mixture thereof.

5. The method of claim 1, wherein the phosphorous (P) containing source in step 2) comprise at least one of elementary substance P, P₂O₃, P₂O₅, H₃PO₄, H₃PO₃, H₃PO₂, (NH₄)₃PO₄, (NH₄)₂HPO₄, (NH₄)H₂PO₄, (NH₄)₃PO₃, (NH₄)₃PO₂, phosphate ester, phosphite ester, and a compound containing element P and at least two elements of C, H, O, N.

6. The method of claim 1, wherein the phosphorous (P) containing source in step 2) uniformly disperses on the surface of the particles of the first intermediate product via one of solid milling method, solvothermal method, sol-gel method, liquid phase mixing method and vapor deposition method.

7. The method of claim 6, wherein the phosphorous (P) containing source in step 2) is elementary substance P, P₂O₃, P₂O₅, phosphate ester, phosphite ester which can be added via solid milling method;

or the phosphorous (P) containing source in step

     2) is H₃PO₄, H₃PO₃, H₃PO₂, (NH₄)₃PO₄, (NH₄)₂HPO₄, (NH₄)H₂PO₄, (NH₄)₃PO₃, (NH₄)₃PO₂ which can be added via one of solvothermal method, sol-gel method, liquid phase mixing method and vapor deposition method.

8. The method of claim 1, wherein in step 2) the element represented by N′

and the phosphorous (P) containing source are added at the same time, N′ and

N are same or different, the phosphate on the surface of the core in step

     2) is a phosphate containing element represented by M or a phosphate containing elements represented M and N′

.

9. The method of claim 1, wherein the sintering temperature in step 2) is 500˜

900°

C.

10. The method of claim 1, wherein the degradable lithium salt in step 3) is at least one of lithium carbonate, lithium hydroxide monohydrate, lithium hydroxide, lithium nitrate, lithium fluoride, lithium acetate and lithium oxalate.

11. The method of claim 1, wherein the sintering temperature in step 3) is 500˜

900°

C.