Method for the synthesis of iron hexacyanoferrate

Patent metadata

Field	Value
Publication number	US-9546097-B2
Application number	US-201414472228-A
Country	US
Kind code	B2
Filing date	Aug 28, 2014
Priority date	Mar 28, 2012
Publication date	Jan 17, 2017
Grant date	Jan 17, 2017

Abstract

A method is provided for synthesizing iron hexacyanoferrate (FeHCF). The method forms a first solution of a ferrocyanide source [A 4 Fe(CN) 6 .P H 2 O] material dissolved in a first solvent, where “A” is an alkali metal ion. A second solution is formed of a Fe(II) source dissolved in a second solvent. A reducing agent is added and, optionally, an alkali metal salt. The first and second solutions may be purged with an inert gas. The second solution is combined with the first solution to form a third solution in a low oxygen environment. The third solution is agitated in a low oxygen environment, and A X+1 Fe 2 (CN) 6 .Z H 2 O is formed, where X is in the range of 0 to 1. The method isolates the A X+1 Fe 2 (CN) 6 .Z H 2 O from the third solution, and dries the A X+1 Fe 2 (CN) 6 .Z H 2 O under vacuum at a temperature greater than 60 degrees C.

First claim

We claim:

1. A method for synthesizing iron hexacyanoferrate (FeHCF), the method comprising:
forming a first solution of a ferrocyanide source [A 4 Fe(CN) 6 .P H 2 O] material dissolved in a first solvent,
where “A” is selected from the group consisting of alkali metal ions;
where p is in a range of 0 to 10;

forming a second solution of a Fe(II) source dissolved in a second solvent;
adding a reducing agent to a solution selected from the group consisting of the first solution, the second solution, and both the first and second solutions;
combining the second solution with e first solution to form a third solution in a low oxygen environment;
agitating the third solution in a low oxygen environment; and,
forming a A X+1 Fe 2 (CN) 6 .Z H 2 O material,
where x is in a range of 0 to 1; and,
where z is in a range of 0 to 7.

2. The method of claim 1 where in the reducing agent is a sulfur-containing material.

3. The method of claim 2 wherein the sulfur-containing material is selected from the group consisting of thiosulfate (S 2 O 3 ) 2− , sulfite (SO 3 ) 2− , bisulfite (HSO 3 ) − , metabisulfite (S 2 O 5 ) 2− , and combinations thereof.

4. The method of claim 1 wherein “A” is selected from the group consisting of lithium (Li + ), sodium (Na + ), potassium (K + ), cesium (Cs + ), and combinations thereof.

5. The method of claim 1 where the Fe(II) source is selected from the group consisting of Fe(II) acetate, Fe(II) bromide, Fe(II) chloride, Fe(II) nitrate, Fen oxalate, Fe(II) phosphate, Fe(II) sulfate, Fen salts, Fe(II) complexes, and combinations thereof.

6. The method of claim 1 wherein the first and second solvents are independently selected from the group consisting of deoxygenated water, alcohols, and polar solvents.

7. The method of claim 1 further comprising:
adding an alkali metal salt to a solution selected from the group consisting of the first solution, the second solution, and both the first and second solutions.

8. The method of claim 7 wherein the alkali metal salt includes an alkali metal ion selected from the group consisting of Li + , Na + , K + , Cs + , and combinations thereof.

9. The method of claim 7 wherein the alkali metal salt is selected from the group consisting of alkali metal acetates (CH 3 CO 2 − ), ascorbates, bromides (Br − ), citrates, chlorides (Cl − ), formates (HCO 2 − ), iodides (I − ) nitrates (NO 3 − ), oxalates (C 2 O 4 2− ) phosphates (PO 4 3− ), sulfates (SO 4 2− ), and combinations thereof.

10. The method of claim 1 wherein agitating the third solution in a low oxygen environment includes an environment containing 10 parts per million (ppm) or less of oxygen.

11. The method of claim 1 further comprising:
isolating the A X+1 Fe 2 (CN) 6 .Z H 2 O material from the third solution; and,
drying the A X+1 Fe 2 (CN) 6 .Z H 2 O material under vacuum at a temperature greater than 60 degrees C.

12. The method of claim 1 further comprising:
prior to combining the first and second solutions, purging the first and second solutions with an inert gas.

13. A method for fabricating a battery electrode, the method comprising:
providing a current collector;
forming an electrode material as follows:
forming a first solution of a ferrocyanide source [A 4 Fe(CN) 6 .P H 2 O] material dissolved in a first solvent,
where “A” is selected from the group consisting of alkali metal ions;
where p is in a range of 0 to 10;

forming a second solution of a Fe(II) source dissolved in a second solvent;
adding a reducing agent to a solution selected from the group consisting of the first solution, the second solution, and both the first and second solutions;
combining the second solution with the first solution to form a third solution in a low oxygen environment;
agitating the third solution in a low oxygen environment;
forming a A X+1 Fe 2 (CN) 6 .Z H 2 O electrode material,
where X is in a range of 0 to 1;
where z is in a range of 0 to 7;

isolating the A X+1 Fe 2 (CN) 6 .Z H 2 O electrode material from the third solution;
drying the A X+1 Fe 2 (CN) 6 .Z H 2 O electrode material under vacuum at a temperature greater than 60 degrees C.;

adding conductive carbon materials to the A X+1 Fe 2 (CN) 6 .Z H 2 O electrode material;
adding a binder material to form an electrode mixture;
forming the electrode mixture overlying the current collector; and,
drying the electrode mixture overlying the current collector under vacuum at a temperature of greater than 60 degrees C.

14. The method of claim 13 wherein the ratio of A X+1 Fe 2 (CN) 6 .Z H 2 O material in the electrode mixture is in a range of 60 to 95% by weight (wt %).

15. The method of claim 13 wherein the ratio of conductive carbon materials in the electrode mixture is in a range of 0 to 30 wt %.

16. The method of claim 13 wherein the ratio of binder material in the electrode mixture is in a range of 3 to 20 wt %.

17. The method of claim 13 wherein the binder material includes a polymer.

Assignees

• Sharp Laboratories America Inc

Inventors

• Vail Sean
• Lu Yuhao
• Lee Jong-Jan

Classifications

• Y02E60/122

  Cross-Sectional Technologies · mapped topic

• H01M4/622

  being polymers · CPC title

• H01M4/136

  Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy · CPC title

• H01M4/58

  of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates · CPC title

• H01M4/1397

  of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy · CPC title