Ferric phosphate and methods of preparation thereof

• US 9,174,846 B2
• Filed: 09/20/2010
• Issued: 11/03/2015
• Est. Priority Date: 09/18/2009
• Status: Active Grant

• Current Assignee: A123 Systems Incorporated
• Original Assignee: A123 Systems Incorporated
• Inventors: Wang, Liya, Beck, Larry W., Soltani, Mahrokh
• Primary Examiner(s): Mayes, Melvin C
• Assistant Examiner(s): Forrest, Michael
• Application Number:
  US12/885,907
• Publication Number:
  US 20110068295A1
• Time in Patent Office: 1,870 Days
• Field of Search: None
• US Class Current: 1/1
• CPC Class Codes: C01B 25/375 of iron
• CPC Class Codes: H01M 10/052 Li-accumulators
• CPC Class Codes: H01M 4/136 Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
• CPC Class Codes: H01M 4/5825 Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y02P 70/50 Manufacturing or production processes characterised by the final manufactured product

Abstract

High-purity crystalline ferric phosphate material with desirable characteristics for use in synthesis of nano-sized LFP cathode material are described. The ferric phosphate dihydrate material has as disclosed herein has a molar ratio of phosphorous to iron is from about 1.001 to about 1.05, a surface area of from about 25 m²/g to about 65 m²/g, and is substantially free of metallic or magnetic impurities. Methods of synthesizing high-purity crystalline ferric phosphate material with desirable characteristics for use in synthesis of nano-sized LFP cathode material are also described. In some embodiments, one or more magnetic traps are used during the reaction process and/or after the formation of the final product to remove magnetic impurities. In some embodiments, a synthetic method of ferric phosphate using multiple steps is described, wherein the intermediate of the synthesis is isolated and purified to improve the purity of the ferric phosphate material. In some embodiments, an iron compound is added to an aqueous solution of phosphoric acid. The solution pH and temperature are controlled to ensure the complete dissolution of the iron compound. The desired iron phosphate crystalline material can be obtained with high purity and high crystalline phase purity by controlling the pH and temperature of the solution.

Claims

1. A method of synthesizing crystalline ferric phosphate material, comprising:

a) introducing an iron (II) salt and a phosphate salt and ammonium hydroxide into an aqueous solution to form a ferrous phosphate material;

b) collecting and washing the ferrous phosphate material to remove impurities; and

c) after washing the ferrous phosphate, oxidizing the ferrous phosphate from step b) with an oxidizing agent to form a crystalline ferric phosphate material comprising a molar ratio of phosphorus to iron is from about 1.001 to about 1.05;

wherein step c) further comprises heating ferrous phosphate at a temperature of between about 35 to about 65°

C.; and

wherein the crystalline ferric phosphate material comprises less than 100 ppm metallic or magnetic impurities and less than 700 ppm sulfate impurities.

2. The method of claim 1, wherein the ferric phosphate material comprises ferric phosphate dihydrate.

3. The method of claim 1, wherein the ferrous phosphate material compromises ferrous phosphate octahydrate.

4. The method of claim 1, further comprises:

using one or more metallic traps to remove metallic or magnetic impurities in step a), step b), step c), after step c), or any combination thereof.

5. The method of claim 4, wherein the magnetic trap comprises rare-earth magnets.

6. The method of claim 1, wherein the iron (II) salt is step a) comprises iron (II) sulfate, iron (II) chloride, iron (II) nitrate, any hydrate thereof, or a mixture thereof.

7. The method of claim 1, wherein the phosphate salt in step a) comprises diammonium phosphate.

8. The method of claim 1, wherein the pH of the resulting solution in step a) is between about 4 to about 5.

9. The method of claim 1, wherein the oxidizing agent comprises hydrogen peroxide.

10. The method of claim 1, wherein step c) further comprises adding phosphoric acid.

11. The method of claim 1, wherein the method further comprises:

heating the ferrous phosphate at a temperature of between about 85 to about 100°

C.

12. The method of claim 2, wherein the method further comprises washing the resulting crystalline ferric phosphate dihydrate to a purity level of about 95% to about 99%.

13. The method of claim 2, wherein the synthesized crystalline ferric phosphate dihydrate material comprises:

from about 28.3 wt % to about 29.6 wt % iron;

from about 16.0 wt % to about 16.9 wt % phosphorous; and

less than about 0.8 wt % sulfate ion;

wherein

the ferric phosphate dihydrate material has a surface area of from about 25 m²/g to about 65 m²/g; and

the ferric phosphate dihydrate material is substantially free of metallic or magnetic impurities.

14. A method of synthesizing crystalline ferric phosphate material, comprising:

a) combining iron (II) compound and an oxidizing agent in an aqueous solution and heating the solution at a first temperature between about 30 to about 65°

C., forming amorphous ferric phosphate wherein the iron (II) compound is formed by combining an iron (II) salt and a phosphate salt wherein the phosphate salt comprises diammonium phosphate;

b) collecting and washing the amorphous ferric phosphate to remove impurities; and

c) crystallizing the amorphous ferric phosphate from step b) to form a crystalline ferric phosphate material comprising a molar ratio of phosphorus to iron is from about 1.001 to about 1.05;

wherein step c) further comprises adding phosphoric acid and heating at a second temperature between about 85 to about 100°

C.; and

wherein the crystalline ferric phosphate material comprises less than 100 ppm metallic or magnetic impurities and less than 700 ppm sulfate impurities.

15. The method of claim 14, wherein one or more metallic traps are used to remove metallic or magnetic impurities in step a), step b), step c), after step c), or any combination thereof.

16. The method of claim 14, wherein the ferric phosphate material comprises ferric phosphate dihydrate.

17. The method of claim 15, wherein the magnetic trap comprises rare-earth magnets.

18. The method of claim 14, wherein the iron (II) salt comprises iron (II) sulfate, iron (II) chloride, iron (II) nitrate, any hydrate thereof, or a mixture thereof.

19. The method of claim 18, wherein the iron (II) salt comprises iron (II) sulfate heptahydrate.

20. The method of claim 14, wherein the oxidizing agent comprises hydrogen peroxide.

21. The method of claim 14, wherein the method further comprises washing the resulting crystalline ferric phosphate material.

22. The method of claim 16, wherein the synthesized crystalline ferric phosphate dihydrate material comprises:

from about 28.3 wt % to about 29.6 wt % iron;

from about 16.0 wt % to about 16.9 wt % phosphorous; and

less than about 0.8 wt % sulfate ion;

wherein

the ferric phosphate dihydrate material has a surface area of from about 25 m²/g to about 65 m²/g; and

the ferric phosphate dihydrate material is substantially free of metallic or magnetic impurities.