Method of preparing nanoparticles of lithium transition metal phosphates, lithium transition metal phosphates, and method of preparing the same
View Patent ↗Provided are lithium transition metal phosphates where the cation anti-site defects between lithium and transition metals in a lithium transition metal phosphate with a cation well-ordered olivine structure are arranged only in a 1D crystal direction, and a method of preparing the same. The method comprises adding any one selected from the group consisting of an alkali element and an element that has a valence of 5 + or any combination thereof to a solid salt comprising lithium, transition metals, and phosphorus as a starting material to produce a first intermediate material; subjecting the first intermediate to a first heat treatment at a temperature of approximately 250° C. to approximately 400° C. to produce a second amorphous material; and cooling the second intermediate material to room temperature, followed by a second heat treatment at a temperature of approximately 400° C. to approximately 800° C. to produce a final material in which the cation-distribution defect is locally clustered and the distribution has a 1D-oriented arrangement parallel to any one axis direction in the crystal.
1. A method of preparing lithium transition metal phosphate, the method comprising,
adding an alkali element, as an additive, to a solid salt comprising lithium, transition metals, and phosphorus as a starting material to produce a first intermediate material;
subjecting the first intermediate to a first heat treatment at a temperature of approximately 250° C. to approximately 400° C. to produce a second amorphous material; and
cooling the second intermediate material to room temperature, followed by a second heat treatment at a temperature of approximately 400° C. to approximately 800° C. to produce a final material in which cation-distribution defects are locally clustered and a distribution of the defects has a 1D-oriented arrangement parallel to any one axis direction in a crystal of lithium transition metal phosphate.
2. The method of claim 1 , wherein the alkali element is sodium (Na) or potassium (K).
3. The method of claim 1 , wherein the starting material is any one selected from the group consisting of carbonates, oxalates, acetates, ammonium phosphates and any combination thereof.
4. The method of claim 3 , wherein the carbonate is lithium carbonate (Li 2 CO 3 ), the oxalate is MC 2 O 4 (2H 2 O) (M=Fe, Mn, Co, Ni, Ti, Cu or any combination thereof), the acetate is M(CO 2 CH 3 ) 2 (M=Fe, Mn, Co, Ni, Ti, Cu or any combination thereof), and the ammonium phosphate is ammonium dihydrogen phosphate (NH 4 H 2 PO 4 ).
5. The method of claim 1 , wherein the alkali element is added to the starting material in an amount of greater than 0 mol % and approximately 5 mol % or less.
6. The method of claim 1 , wherein the first intermediate material has a stoichiometric composition of (Li 1-x A x )(M 1-y By)PO 4 or (LiA x )(MB y )PO 4 (A or B=Na, K or any combination thereof, M=Fe, Mn, Co, Ni, Ti, Cu, or any combination thereof, and 0<x≦0.05, and 0<y≦0.05).
7. The method of claim 1 , wherein the first and second heat treatments are carried out under a gas atmosphere of any one selected from argon (Ar), nitrogen (N2), and carbon monoxide/carbon dioxide (CO/CO 2 ) at a flow rate of approximately 100 to approximately 500 cc/min.
8. The method of claim 1 , wherein an additive for Na comprises sodium carbonate (Na 2 CO 3 ), and an additive for K comprises potassium carbonate (K 2 CO 3 ).
9. The method of claim 1 , wherein the first and second heat treatments are carried out for approximately 1 to approximately 10 hours.
10. The method of claim 1 , wherein the second heat treatment is carried out at a temperature of approximately 400° C. to approximately 800° C. for approximately 2 to approximately 10 hours.
11. The method of claim 1 , wherein the producing of the final material comprises crystallizing the second intermediate material from the amorphous state into a metastable intermediate phase.
12. A lithium transition metal phosphate, comprising:
an alkali element, as an additive, where anti-site defects between lithium and a transition metal are locally clustered in a crystal of the lithium transition metal phosphate and a distribution of the defects has a 1D-oriented arrangement parallel to any one axis direction in the crystal.
13. The phosphate of claim 12 , wherein any one axis is crystallograpically the b-axis.
14. The phosphate of claim 12 , wherein the alkali element is added in an amount of greater than 0 mol % and approximately 5 mol % or less.
15. The phosphate of claim 12 , wherein a crystal structure of the crystal is an olivine structure.
16. The phosphate of claim 12 , where the alkali element comprises at least one of Na and K.