Ferrous phosphate powders, lithium iron phosphate powders for Li-ion battery, and methods for manufacturing the same

Patent metadata

Field	Value
Publication number	US-10029918-B2
Application number	US-201715853579-A
Country	US
Kind code	B2
Filing date	Dec 22, 2017
Priority date	Jun 17, 2011
Publication date	Jul 24, 2018
Grant date	Jul 24, 2018

Abstract

Ferrous (II) phosphate (Fe 3 (PO 4 ) 2 ) powders, lithium iron phosphate (LiFePO 4 ) powders for a Li-ion battery and methods for manufacturing the same are provided. The lithium iron phosphate powders are represented by the following formula (II):

LiFe (1-a) M a PO 4   (II)

wherein, M, and a are defined in the specification, the lithium iron phosphate powders are composed of plural flake powders, the length of each of the flake powders is 0.1-10 μm, and a ratio of the length and the thickness of each of the flake powder is in a range from 11 to 400.

First claim

What is claimed is:

1. A method for manufacturing lithium iron phosphate powders, sequentially comprising the following steps:
(a) providing ferrous (II) phosphate powders, wherein the ferrous (II) phosphate powders are represented by the following formula (I):
Fe (3-x) M x (PO 4 ) 2 .yH 2 O   (I)

wherein M comprises at least one metal selected from the group consisting of Mn, Cr, Co, Cu, Ni, V, Mo, Ti, Zn, Zr, Tc, Ru, Rh, Pd, Ag, Cd, Pt, Au, Al, Ga, In, Be, Mg, Ca, Sr, B, and Nb, 0≤x<1.5, y is an intergral of 0 to 8, the ferrous (II) phosphate powders are composed of plural flake powders, the length of each of the flake powders is 0.2-10 μm, and a ratio of the length and the thickness of each of the flake powder is in a range from 14 to 500;
(b) mixing the ferrous (II) phosphate powders with a Li-containing precursor to obtain mixed powders; and
(c) heat-treating the mixed powders to obtain lithium iron phosphate powders.

2. The method as claimed in claim 1 , wherein the lithium iron phosphate powders are represented by the following formula (II):
LiFe (1-a) M a PO 4   (II)

wherein M comprises at least one metal selected from the group consisting of Mn, Cr, Co, Cu, Ni, V, Mo, Ti, Zn, Zr, Tc, Ru, Rh, Pd, Ag, Cd, Pt, Au, Al, Ga, In, Be, Mg, Ca, Sr, B, and Nb, 0≤a<0.5, the lithium iron phosphate powders are composed of plural flake powders, the length of each of the flake powders is 0.1-10 μm, and a ratio of the length and the thickness of each of the flake powder is in a range from 11 to 400.

3. The method as claimed in claim 1 , wherein the thickness of each of the flake powder of the ferrous (II) phosphate powders is 1-50 nm.

4. The method as claimed in claim 1 , wherein the flake powders of the ferrous (II) phosphate powders are powders composed of independent flakes, flake powders that one end of each of the flake powders connects to each other, flake powders connecting to each other at the center of the flakes, or flake powders that one end of each of the flake powders connects to each other to form a connecting center.

5. The method as claimed in claim 1 , wherein the ferrous (II) phosphate powders are crystallized ferrous (II) phosphate powders.

6. The method as claimed in claim 5 , wherein the ferrous (II) phosphate powders show an X-ray diffraction pattern 2θ angles (°) having characteristic peaks at about 18.32, 19.84, 23.24, 28.24, 30.32, 33.34, 35.88, 37.20, 39.36, 40.94, and 41.82.

7. The method as claimed in claim 6 , wherein the ferrous (II) phosphate powders show an X-ray diffraction pattern 2θ angles (°) having further characteristic peaks at about 20.72, 22.12, 24.86, 27.08, 34.3, and 44.14.

8. The method as claimed in claim 1 , wherein the ferrous (II) phosphate powders have a crystallization degree of more than 10%.

9. The method as claimed in claim 2 , wherein the flake powders of the lithium iron phosphate powders are powders composed of independent flakes, flake powders that one end of each of the flake powders connects to each other, flake powders connecting to each other at the center of the flakes, or flake powders that one end of each of the flake powders connects to each other to form a connecting center.

10. The lithium iron phosphate powders as claimed in claim 1 , wherein the lithium iron phosphate powders have olivine structures.

11. The method as claimed in claim 2 , wherein the thickness of each of the flake powder of the lithium iron phosphate powders is 1-60 nm.

12. The method as claimed in claim 1 , wherein M comprises at least one metal selected from the group consisting of Mn, Cr, Co, Cu, Ni, Zn, Al, and Mg.

13. The method as claimed in claim 1 , wherein surfaces of the lithium iron phosphate powders are coated with carbon.

14. The method as claimed in claim 2 , wherein 0≤a<0.15.

15. The method as claimed in claim 1 , wherein the Li-containing precursor is at least one selected from the group consisting of LiOH, Li 2 CO 3 , LiNO 3 , CH 3 COOLi, Li 2 C 2 O 4 , Li 2 SO 4 , LiCl, LiBr, LiI, LiH 2 PO 4 , Li 2 HPO 4 , and Li 3 PO 4 .

16. The method as claimed in claim 1 , wherein the ferrous (II) phosphate powders are mixed with the Li-containing precursor and a carbon-containing material to obtain the mixed powders in the step (b).

17. The method as claimed in claim 16 , wherein an amount of the carbon-containing material is 0.1-40 wt % of a weight of the lithium iron phosphate powders.

18. The method as claimed in claim 1 , wherein the mixed powders is heat-treated under an atmosphere or with an introduced gas flow to obtain the lithium iron phosphate powders in the step (c).

19. The method as claimed in claim 18 , wherein the atmosphere or the introduced gas flow is N 2 , H 2 , He, Ne, Ar, Kr, Xe, CO, methane, N 2 —H 2 mixed gas, or a combination thereof.

20. The method as claimed in claim 1 , wherein the mixed powders are heat-treated at 300-900° C.

Assignees

• Univ Nat Tsing Hua

Inventors

• Chou Lih-Hsin
• Chen Bing-Kai
• Chu Hsin-Hsu
• Yang Yueh-Ting

Classifications

• C01P2002/74

  by peak-intensities or a ratio thereof only · CPC title

• C01B25/375

  of iron · CPC title

• C01P2004/61

  Micrometer sized, i.e. from 1-100 micrometer · CPC title

• H01M4/5825

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

• C01B25/45 Primary

  containing plural metal, or metal and ammonium · CPC title