High solubility iron hexacyanides

Patent metadata

Field	Value
Publication number	US-9997799-B2
Application number	US-201615166178-A
Country	US
Kind code	B2
Filing date	May 26, 2016
Priority date	Aug 15, 2012
Publication date	Jun 12, 2018
Grant date	Jun 12, 2018

Abstract

Stable solutions comprising high concentrations of charged coordination complexes, including iron hexacyanides are described, as are methods of preparing and using same in chemical energy storage systems, including flow battery systems. The use of these compositions allows energy storage densities at levels unavailable by other iron hexacyanide systems.

First claim

What is claimed is the following:

1. A solution comprising:
an aqueous solvent;
a dissolved iron hexacyanide complex having a concentration in the aqueous solvent ranging between about 1 M and about 3 M at a temperature of about 20° C. to about 25° C.; and
at least two different counterions forming a salt of the dissolved iron hexacyanide complex, the at least two different counterions comprising a first counterion and a second counterion;
wherein the solution has a pH of about 13 or less, and a molar ratio of the first counterion to the second counterion ranges between about 1:10 and about 10:1;
wherein the dissolved iron hexacyanide complex is interconvertible between a ferricyanide state and a ferrocyanide state without forming a precipitate in either state; and
wherein a concentration of the dissolved iron hexacyanide complex in the solution is at least 10% higher than the solubility limit of the complex in a solution containing only one of the at least two different counterions.

2. The solution of claim 1 , wherein the molar ratio of the first counterion to the second counterion ranges between about 0.9:1 and about 1.1:1.

3. The solution of claim 1 , wherein the first counterion and the second counterion comprise different alkali metal cations.

4. The solution of claim 3 , wherein the first counterion comprises a sodium cation and the second counterion comprises a potassium cation.

5. The solution of claim 1 , wherein the aqueous solvent is free of a co-solvent.

6. The solution of claim 1 , wherein the solution has a pH ranging between about 8 and about 13.

7. The solution of claim 1 , wherein the solution has a pH ranging between about 9 and about 13.

8. The solution of claim 1 , wherein the solution has a pH ranging between about 8 and about 12.

9. The solution of claim 1 , wherein the solution has a pH ranging between about 9 and about 12.

10. The solution of claim 1 , wherein the at least two different counterions comprise a mixture of monovalent cations.

11. The solution of claim 10 , wherein the mixture of monovalent cations comprises a mixture of sodium cations and potassium cations.

12. The solution of claim 1 , wherein the dissolved iron hexacyanide complex comprises a mixture of iron (II) hexacyanide and iron (III) hexacyanide.

13. The solution of claim 1 , further comprising:
one or more of a viscosity modifier, a wetting agent, a buffering agent, and a supporting electrolyte.

14. A flow battery comprising:
a first half-cell containing a first electrolyte solution; and
a second half-cell containing a second electrolyte solution;
wherein at least one of the first half-cell and the second half-cell contains the solution of claim 1 .

15. The flow battery of claim 14 , wherein the solution exhibits a charge/discharge density ranging between about 32 A-h/L and about 80 A-h/L.

16. The flow battery of claim 14 , wherein the first counterion comprises a sodium cation and the second counterion comprises a potassium cation.

17. The flow battery of claim 14 , wherein the solution has a pH ranging between about 8 and about 12.

18. The flow battery of claim 14 , wherein the solution has a pH ranging between about 9 and about 12.

Assignees

• Lockheed Martin Advanced Energy Storage Llc

Inventors

• Esswein Arthur J
• Goeltz John
• Amadeo Desiree

Classifications

• H01M8/188 Primary

  by recharging of redox couples containing fluids; Redox flow type batteries · CPC title

• H01M2300/0002

  Aqueous electrolytes · CPC title

• C01C3/12 Primary

  Simple or complex iron cyanides · CPC title

• H01M8/20

  Indirect fuel cells, e.g. fuel cells with redox couple being irreversible (H01M8/18 takes precedence) · CPC title

• H01M8/08

  Fuel cells with aqueous electrolytes · CPC title