Metal (ii) phosphate powders, lithium metal phosphate powders for li-ion battery, and methods for manufacturing the same

Patent metadata

Field	Value
Publication number	US-2020165132-A1
Application number	US-202016776895-A
Country	US
Kind code	A1
Filing date	Jan 30, 2020
Priority date	Jun 17, 2011
Publication date	May 28, 2020
Grant date	—

Abstract

Metal (II) phosphate powders, lithium metal phosphate powders for a Li-ion battery and methods for manufacturing the same are provided. The lithium metal 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, Co, Ni, Cu, Cr, V, Mo, Ti, Zn, Zr, Tc, Ru, Rh, Pd, Ag, Cd, Pt, Au, Al, Ga, In, Be, Mg, Ca, Sr, B and Nb, 0.5<a≤1, the lithium metal phosphate powders are composed of plural flake powders, and a length of each of the flake powders is ranged from 50 nm to 10 μm.

First claim

What is claimed is:

1 . Lithium metal phosphate powders for a Li-ion battery, 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, Co, Ni, Cu, Cr, V, Mo, Ti, Zn, Zr, Tc, Ru, Rh, Pd, Ag, Cd, Pt, Au, Al, Ga, In, Be, Mg, Ca, Sr, B and Nb, 0.5<a≤1, the lithium metal phosphate powders are composed of plural flake powders, and a length of each of the flake powders is ranged from 50 nm to 10 μm.

2 . The lithium metal phosphate powders of claim 1 , wherein the flake 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.

3 . The lithium metal phosphate powders of claim 1 , wherein M comprises at least one metal selected from the group consisting of Mn, Co, Cu, Ni, Zn, and Mg.

4 . The lithium metal phosphate powders of claim 1 , wherein a thickness of each of the flake powders is ranged from 5 nm to 1 μm.

5 . The lithium metal phosphate powders of claim 1 , wherein M is Mn, Co, Ni or Cu, and 0.6≤a≤1.

6 . The lithium metal phosphate powders of claim 1 , represented by the following formula (II-1):
LiFe 1-a1-a2 Mn a1 M′ a2 PO 4   (II-1)
wherein M′ comprises at least one metal selected from the group consisting of Co, Cu, Ni, Zn, and Mg, 0.2≤a1≤0.8, 0.05≤a2≤0.4, and 0.5<a1+a2≤1.

7 . A method for manufacturing lithium metal phosphate powders, comprising the following steps:
(a) providing metal (II) phosphate powders represented by the following formula (I):
(Fe 1-x M x ) 3 (PO 4 ) 2 .y H 2 O  (I)

wherein M comprises at least one metal selected from the group consisting of Mn, Co, Ni, Cu, Cr, V, Mo, Ti, Zn, Zr, Tc, Ru, Rh, Pd, Ag, Cd, Pt, Au, Al, Ga, In, Be, Mg, Ca, Sr, B and Nb, 0.5<x≤1, y is an integer of 0 to 8, the metal phosphate (II) powders are composed of plural flake powders, and a length of each of the flake powders is ranged from 50 nm to 10 μm;
(b) mixing the metal (II) phosphate powders with a Li-containing precursor to obtain mixed powders; and
(c) heat-treating the mixed powders to obtain lithium metal phosphate powders 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, Co, Ni, Cu, Cr, V, Mo, Ti, Zn, Zr, Tc, Ru, Rh, Pd, Ag, Cd, Pt, Au, Al, Ga, In, Be, Mg, Ca, Sr, B and Nb, 0.5<a≤1, the lithium metal phosphate powders are composed of plural flake powders, and a length of each of the flake powders is ranged from 50 nm to 10 μm.

8 . The method of claim 7 , wherein the step (a) comprises the following steps:
(a1) providing a P-containing precursor solution, wherein the P-containing precursor solution comprises: a P-containing precursor, and a weakly alkaline compound; and (a2) adding at least one metal (II) compound into the P-containing precursor solution to obtain the metal (II) phosphate powders represented by the formula (I).

9 . The method of claim 8 , wherein the P-containing precursor is at least one selected from the group consisting of H 3 PO 4 , NaH 2 PO 4 , Na 2 HPO 4 , Mg 3 (PO 4 ) 2 , and NH 4 H 2 PO 4 .

10 . The method of claim 8 , wherein the weakly alkaline compound is at least one selected from the group consisting of Na 2 CO 3 , and NaHCO 3 .

11 . The method of claim 8 , wherein the metal (II) compound is a sulfate, a carbonate, a nitrate, an oxalate, an acetate, a chlorite, a bromide, or an iodide of Fe, Mn, Co, Ni, Cu, Cr, V, Mo, Ti, Zn, Zr, Tc, Ru, Rh, Pd, Ag, Cd, Pt, Au, Al, Ga, In, Be, Mg, Ca, Sr, B or Nb.

12 . The method of claim 7 , 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 .

13 . The method of claim 7 , wherein the metal (II) phosphate powders are mixed with the Li-containing precursor and at least one carbon-containing material to obtain the mixed powders in the step (b).

14 . The method of claim 13 , wherein the carbon-containing material is sugar, stearic acid, citric acid, lauric acid, polystyrene, polystyrene ball (PS ball), graphene oxide, glucose, or vitamin C.

15 . The method of claim 7 , wherein the mixed powders is heat-treated under an atmosphere or vacuum or with an introduced gas flow to obtain the lithium metal phosphate powders, in the step (c).

16 . The method of claim 15 , wherein the atmosphere or the introduced gas flow comprises at least one selected from the group consisting of N 2 , H 2 , He, Ne, Ar, Kr, Xe, CO, methane, Ar—H 2 mixed gas, and N 2 —H 2 mixed gas.

17 . The method of claim 7 , wherein the lithium metal phosphate powders are represented by the following formula (II-1):
LiFe 1-a1-a2 Mn a1 M′ a2 PO 4   (II-1)
wherein M′ comprises at least one metal selected from the group consisting of Co, Cu, Ni, Zn, and Mg, 0.2≤a1≤0.8, 0.05≤a2≤0.4, and 0.5<a1+a2≤1.

18 . The method of claim 7 , wherein the flake 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.

Assignees

• Univ Nat Tsing Hua

Inventors

• Chou Lih-Hsin
• Peng shao-wei
• Chang Kai-Chu

Classifications

• H01M10/0525

  Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries · CPC title

• H01M2004/021

  Physical characteristics, e.g. porosity, surface area · CPC title

• C01B25/306 Primary

  from phosphates · CPC title

• C01B25/45

  containing plural metal, or metal and ammonium · CPC title

• H01M4/5825

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