Method of producing cathode active material for lithium secondary battery

Patent metadata

Field	Value
Publication number	US-9745194-B2
Application number	US-201214113731-A
Country	US
Kind code	B2
Filing date	Apr 25, 2012
Priority date	Apr 28, 2011
Publication date	Aug 29, 2017
Grant date	Aug 29, 2017

Abstract

The invention provides a method of producing a cathode active material for a lithium secondary battery, whereby it is possible to configure a lithium secondary battery in which the discharge capacity is improved and elution of lithium ions from the lithium metal phosphate is suppressed when washing the lithium metal phosphate after the same was synthesized. The method of producing a cathode active material for a lithium secondary battery includes synthesizing a lithium metal phosphate represented by a composition formula LiMPO 4 , wherein the element M represents one or two or more of transition metals selected from among Fe, Mn, Co and Ni, and after the synthesis, washing the lithium metal phosphate with a washing liquid containing lithium ion.

First claim

The invention claimed is:

1. A method of producing a cathode active material for a lithium secondary battery, wherein the method comprises:
synthesizing a lithium metal phosphate represented by a composition formula LiMPO 4 , wherein the element M represents one or two or more of transition metals selected from Fe, Mn, Co and Ni, and then
washing the lithium metal phosphate with a washing liquid containing lithium ions,
wherein a solvent of the washing liquid consists of water.

2. The method of producing a cathode active material for a lithium secondary battery according to claim 1 , wherein a solute of the washing liquid comprises at least one of LiClO 4 , Li 2 CO 3 , LiOH, LiPF 6 , Li 3 PO 4 , LiH 2 PO 4 , and CH 3 CO 2 Li.

3. The method of producing a cathode active material for a lithium secondary battery according to claim 1 , wherein pH of the washing liquid containing the lithium ions is in the range of from 5 to 9.

4. The method of producing a cathode active material for a lithium secondary battery according to claim 1 , wherein the washing time is one hour or less.

5. The method of producing a cathode active material for a lithium secondary battery according to claim 1 , wherein the post-synthesis lithium metal phosphate comprises one or two kinds of elements selected from the group consisting of V and Nb.

6. The method of producing a cathode active material for a lithium secondary battery according to claim 1 , wherein a particle diameter of the post-synthesis lithium metal phosphate is in the range of from 20 to 200 nm.

7. The method of producing a cathode active material for a lithium secondary battery according to claim 1 , wherein a ratio of Li atoms number to M atoms number in a region up to depth of 2 nm from a surface of the post-synthesis lithium metal phosphate is 0.7 or more and less than 1.1.

8. The method of producing a cathode active material for a lithium secondary battery according to claim 1 , the method further comprises a step of forming a layer containing carbon on at least a portion of a surface of the lithium metal phosphate after the washing step.

9. The method of producing a cathode active material for a lithium secondary battery according to claim 8 , wherein the step of forming a layer containing carbon on at least a portion of the surface of the lithium metal phosphate after the washing step comprises:
mixing the lithium metal phosphate with a liquid in which a material containing carbon atoms is dissolved, after the washing,
removing a solvent of the liquid in which a material containing carbon atoms is dissolved after the mixing step, and
heating the mixture of the lithium metal phosphate and the material containing carbon atoms for 1 hour to 20 hours under an atmosphere containing oxygen with a concentration 1% or less at a temperature of 400° C. to 900° C., after removing the solvent of the liquid in which the material containing carbon atoms is dissolved.

10. The method of producing a cathode active material for a lithium secondary battery according to claim 1 , wherein the transition metal (M) in the LiMPO 4 is either Mn or Fe.

11. The method of producing a cathode active material for a lithium secondary battery according to claim 1 , wherein the transition metal (M) in the LiMPO 4 comprises both Mn and Fe.

12. The method of producing a cathode active material for a lithium secondary battery according to claim 1 , wherein the synthesizing step is carried out by hydrothermal synthesis method.

13. The method of producing a cathode active material for a lithium secondary battery according to claim 12 , wherein the hydrothermal synthesis is carried out by using a liquid containing water, a lithium (Li) source, one or two or more kinds of transition metal (M) source, and a phosphoric acid (PO 4 ) source as raw materials.

14. The method of producing a cathode active material for a lithium secondary battery according to claim 12 , wherein the hydrothermal synthesis is carried out by using a liquid containing water, Li 3 PO 4 , and one or two or more kinds of transition metal (M) source as raw materials.

15. The method of producing a cathode active material for a lithium secondary battery according to claim 13 , wherein the transition metal (M) source is MnSO 4 and/or FeSO 4 .

16. The method of producing a cathode active material for a lithium secondary battery according to claim 13 , wherein LiOH is used as the lithium (Li) source.

17. The method of producing a cathode active material for a lithium secondary battery according to claim 13 , wherein H 3 PO 4 is used as the phosphate (PO 4 ) source.

18. The method of producing a cathode active material for a lithium secondary battery according to claim 1 , wherein a water content with respect to the washing liquid is 94.8 mass % or more.

Assignees

• Kabe Isao
• Shirakawa Akihiko
• Oriji Gaku
• Tonegawa Akihisa
• Showa Denko Kk

Inventors

• Kabe Isao
• Shirakawa Akihiko
• Oriji Gaku
• Tonegawa Akihisa

Classifications

• C01B25/45 Primary

  containing plural metal, or metal and ammonium · CPC title

• H01M10/052

  Li-accumulators · CPC title

• H01M4/5825 Primary

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

• Y02E60/10

  Energy storage using batteries · CPC title