Recycling method of olivine-based cathode material for lithium secondary battery, cathode material fabricated therefrom, and cathode and lithium secondary battery including the same

Patent metadata

Field	Value
Publication number	US-9643846-B2
Application number	US-201313944457-A
Country	US
Kind code	B2
Filing date	Jul 17, 2013
Priority date	Mar 14, 2013
Publication date	May 9, 2017
Grant date	May 9, 2017

Abstract

The present invention relates to a method for recycling LiFePO 4 , which is an olivine-based cathode material for a lithium secondary battery. The present invention is characterized in that a cathode material including LiFePO 4 is synthesized using, as precursors, amorphous FePO 4 .XH 2 O and crystalline FePO 4 .2H 2 O (metastrengite) obtained by chemically treating LiFePO 4 as an olivine-based cathode material for a lithium secondary battery, which is produced from a waste battery. Since a cathode fabricated from the LiFePO 4 cathode material synthesized according to the present invention does not deteriorate the capacity, output characteristics, cycle efficiency and performance of the secondary battery and the cathode material of the lithium secondary battery may be recycled, the secondary battery is economically efficient.

First claim

What is claimed is:

1. A method for recycling an olivine-based cathode material for a lithium secondary battery, the method including:
a first step of recovering a cathode material comprising LiFePO 4 from lithium secondary battery cathode scraps;
a second step of synthesizing amorphous FePO 4 .XH 2 O using the recovered cathode material; and
a third step of synthesizing crystalline FePO 4 .2H 2 O using the amorphous FePO 4 .XH 2 O.

2. The method of claim 1 , further comprising a fourth step of synthesizing a cathode material comprising LiFePO 4 using the crystalline FePO 4 .2H 2 O after the third step.

3. The method of claim 2 , wherein, in the fourth step, the cathode material comprising LiFePO4 is synthesized by mixing a lithium source material and a carbon source material with the crystalline FePO 4 .2H 2 O and subjecting the mixture to heat treatment.

4. The method of claim 3 , wherein the crystalline FePO4.2H2O and the lithium source material are mixed such that a molar ratio of Fe to Li is 1:1, and the heat treatment is performed in a reducing atmosphere or inert atmosphere.

5. The method of claim 3 , wherein the lithium source material comprises one or more selected from the group consisting of LiOH.H 2 O, Li 2 CO 3 , LiCl, Li 3 PO 4 , and a combination thereof.

6. The method of claim 3 , wherein the carbon source material comprises one or more selected from the group consisting of carbon black, acetylene black, sucrose, and a combination thereof.

7. The method of claim 3 , wherein the carbon source material is added in an amount of 1 to 10% by weight based on a weight of the finally produced LiFePO 4 cathode active material.

8. The method of claim 3 , wherein the heat treatment is performed at 500° C. to 800° C. for 6 to 24 hours.

9. The method of claim 1 , wherein, in the first step, the cathode material is recovered from the cathode scraps by subjecting the cathode scraps to heat treatment in an oxidizing atmosphere and then removing a current collector.

10. The method of claim 9 , wherein the heat treatment is performed at a temperature of 300° C. to 500° C.

11. The method of claim 1 , wherein, in the second step, amorphous FePO 4 .XH 2 O is synthesized by dissolving the recovered cathode material in an acid and then injecting ammonia water into the solution to precipitate amorphous FePO 4 .XH 2 O, and the amorphous FePO 4 .XH 2 O is separated through a filtration process.

12. The method of claim 11 , further comprising oxidizing Fe present in the cathode material by subjecting the recovered cathode material to heat treatment before the recovered cathode material is dissolved in the acid.

13. The method of claim 12 , wherein the heat treatment is performed at 700° C. to 900° C.

14. The method of claim 11 , wherein the acid comprises one or more selected from the group consisting of nitric acid, hydrochloric acid, sulfuric acid, and a combination thereof.

15. The method of claim 11 , wherein the second step is performed by adding ammonia water to the solution to adjust the pH to 5 to 6 and maintaining the solution at 20° C. to 70° C. for 1 to 12 hours.

16. The method of claim 1 , wherein the third step is performed by synthesizing crystalline FePO 4 .2H 2 O by treating amorphous FePO 4 .XH 2 O with an acid solution having a pH of 1 to 2.

17. The method of claim 16 , wherein the acid solution comprises a phosphoric acid solution.

18. The method of claim 17 , wherein a concentration of the phosphoric acid solution is 5 mol/l.

Assignees

• Korea Inst Sci & Tech

Inventors

• Kim Hyung Sun
• Cho Byung Won
• Lee Hwa Young
• Shin Eun Jung
• Kim Soo
• Chung Kyung Yoon

Classifications

• Y02W30/84

  Recycling of batteries or fuel cells · CPC title

• H01M10/54

  Reclaiming serviceable parts of waste accumulators · CPC title

• C01B25/45 Primary

  containing plural metal, or metal and ammonium · CPC title

• C01B25/375

  of iron · CPC title

• H01M4/5825

  Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines · CPC title