Method for preparing lithium metal phosphor oxide

Patent metadata

Field	Value
Publication number	US-10752504-B2
Application number	US-201314419289-A
Country	US
Kind code	B2
Filing date	May 10, 2013
Priority date	Aug 10, 2012
Publication date	Aug 25, 2020
Grant date	Aug 25, 2020

Abstract

The present invention relates to a method for preparing a lithium metal phosphor oxide, the method including: mixing an iron salt solution and a phosphate solution in a reactor; applying a shearing force to the mixed solution in the reactor during the mixing to form a suspension containing nano-sized iron phosphate precipitate particles; obtaining the nano-sized iron phosphate particles from the suspension; and mixing the iron phosphate with a lithium raw material and performing firing, and the lithium metal phosphor oxide according to the present invention has an Equation of LiM n FePO 4 . Herein, M is selected from the group consisting of Ni, Co, Mn, Cr, Zr, Nb, Cu, V, Ti, Zn, Al, Ga, and Mg, and n is in a range of 0 to 1. According to the present invention, since calcination is performed at a temperature that is lower than that of another existing method, there is an effect of reducing a process cost, and the obtained lithium metal phosphor oxide prepared according to the method of the present invention has an olivine structure type.

First claim

The invention claimed is:

1. A method for preparing a lithium metal phosphor oxide, the method comprising:
introducing an iron salt solution and a phosphate solution through separate inflow paths into a reactor, the reactor including a chamber into which the inflow paths ultimately flow and a distributor, the chamber containing an agitator in a form of a rotatable packed bed on a vertically positioned rotation shaft, the packed bed having a cylindrical shape and including one mesh layer, the distributor existing at a central portion in a cylinder of the packed bed, and the iron salt solution and the phosphate solution are supplied to an internal surface of the packed bed through the distributor;
mixing the iron salt solution and the phosphate solution to form a mixed solution in the reactor;
applying a shearing force to the mixed solution in the reactor during the mixing, applying the shearing force including agitating the mixed solution by the agitator, whereby a flow condition having a Reynolds number of 8,000 to 100,000 is formed in the distributor of the reactor to form a suspension containing nano-sized iron phosphate precipitate particles;
optionally doping a dissimilar metal into the nano-sized iron phosphate precipitate particles, the dissimilar metal being selected from the group consisting of Ni, Co, Mn, Cr, Zr, Nb, Cu, V, Ti, Zn, Al, Ga, and Mg,
obtaining nano-sized iron phosphate particles from the suspension; and
mixing the nano-sized iron phosphate particles with a lithium raw material and performing firing to form the lithium metal phosphor oxide such that the lithium metal phosphor oxide has the following Equation I
LiM n FePO 4   Equation I

where M is selected from the group consisting of Ni, Co, Mn, Cr, Zr, Nb, Cu, V, Ti, Zn, Al, Ga, and Mg, and n is in a range of 0 to 1.

2. The method of claim 1 , wherein the iron salt solution includes one kind or more selected from the group consisting of an iron (III) acetate salt, an iron (III) halide salt, an iron (III) nitrate salt, an iron (III) sulfate salt, and a hydrate and a mixture thereof.

3. The method of claim 1 , wherein the iron salt solution includes one kind or more selected from the group consisting of an iron (II) acetate salt, an iron (II) halide salt, an iron (II) nitrate salt, an iron (II) sulfate salt, iron (II) hydroxide, and a hydrate and a mixture thereof.

4. The method of claim 1 , wherein the applying of the shearing force is performed under a condition where at least one of nano-sized amorphous iron phosphate and crystalline iron phosphate particles is formed.

5. The method of claim 1 , wherein the nano-sized iron phosphate particles have a narrow particle size distribution having a steepness of less than 3.

6. The method of claim 1 , wherein mixing of the iron salt solution and the phosphate solution is performed under a condition where intermediate iron phosphate species are not formed.

7. The method of claim 1 , wherein the nano-sized iron phosphate particles are amorphous.

8. The method of claim 7 , further comprising: aging the suspension under a condition where crystalline iron phosphate particles are formed.

9. The method of claim 7 , further comprising: aging the nano-sized amorphous iron phosphate particles.

10. The method of claim 9 , further comprising: applying a shearing force to a mixture containing the nano-sized amorphous iron phosphate particles and adjusting the shearing force and a condition in the mixture to form crystalline nano-sized iron phosphate particles, during the aging.

11. The method of claim 10 , further comprising: isolating the crystalline iron phosphate particles from the mixture containing the nano-sized iron phosphate particles; and drying the crystalline iron phosphate particles to form a crystalline iron phosphate powder.

12. The method of claim 10 , further including doping the dissimilar metal while forming the crystalline nano-sized iron phosphate particles, to form a metal-doped crystalline iron phosphate having the following Equation: MFePO 4 where M is selected from the group consisting of Ni, Co, Mn, Cr, Zr, Nb, Cu, V, Ti, Zn, Al, Ga, and Mg.

13. The method of claim 12 , wherein a molar ratio of [Fe] and [M] is 1-x:x, and herein, x is 0.01 to 0.05.

14. The method of claim 1 , wherein a firing temperature is 500° C. to 700° C.

15. The method of claim 1 , wherein one kind or more selected from the group consisting of LiOH, Li 2 CO 3 , and LiCl are included as the lithium raw material.

16. The method of claim 10 , wherein the crystalline iron phosphate and the lithium raw material are mixed such that a molar ratio of the crystalline iron phosphate to the lithium raw material is 1:0.5 to 1.5.

17. The method of claim 11 , wherein mixing the nano-sized iron phosphate particles with the lithium raw material includes mixing the crystalline iron phosphate with the lithium raw material wherein in the mixing of the crystalline iron phosphate and the lithium raw material, a carbon-coated raw material selected from sucrose or glucose is further included.

18. The method of claim 12 , wherein the metal-doped crystalline iron phosphate and the lithium raw material are mixed such that a molar ratio of doped crystalline iron phosphate to the lithium raw material is 1:0.5 to 1.5.

19. The method of claim 12 , wherein mixing the nano-sized iron phosphate particles with the lithium raw material includes mixing the metal-doped crystalline iron phosphate with the lithium raw material wherein in the mixing of the metal-doped crystalline iron phosphate and the lithium raw material, a carbon-coated raw material selected from sucrose or glucose is further included.

Assignees

• Samsung Sdi Co Ltd

Inventors

• Song Hyun A
• Chang Dong Gyu
• Yang Woo Young

Classifications

• Y02E60/10

  Energy storage using batteries · CPC title

• C01D15/00 Primary

  Lithium compounds · CPC title

• C01G49/00

  Compounds of iron · CPC title

• B01J19/24

  Stationary reactors without moving elements inside (B01J19/08, B01J19/26 take precedence; with stationary particles B01J8/02) · CPC title

• B01J6/00

  Heat treatments such as} Calcining; Fusing {; Pyrolysis (furnaces F27D) · CPC title