Aqueous redox flow batteries comprising metal ligand coordination compounds

• US 9,991,544 B2
• Filed: 05/27/2016
• Issued: 06/05/2018
• Est. Priority Date: 07/27/2012
• Status: Active Grant

• Current Assignee: Lockheed Martin Energy LLC (Martin Marietta Corporation)
• Original Assignee: Lockheed Martin Advanced Energy Storage, LLC (Martin Marietta Corporation)
• Inventors: Goeltz, John, Amadeo, Desiree, Esswein, Arthur J., Jarvi, Thomas D., King, Evan R., Reece, Steven Y., Tyagi, Nitin
• Primary Examiner(s): Raymond, Brittany
• Application Number:
  US15/167,930
• Publication Number:
  US 20160276694A1
• Time in Patent Office: 739 Days
• CPC Class Codes: H01M 8/08 Fuel cells with aqueous electrolytes
• CPC Class Codes: H01M 8/188 by recharging of redox couples containing fluids; Redox flow type batteries
• CPC Class Codes: H01M 8/20 Indirect fuel cells, e.g. fuel cells with redox couple being irreversible H01M8/18 takes precedence
• CPC Class Codes: H02J 7/00 Circuit arrangements for charging or depolarising batteries or for supplying loads from batteries
• CPC Class Codes: Y02E 60/50 Fuel cells

Abstract

This invention is directed to aqueous redox flow batteries comprising redox-active metal ligand coordination compounds. The compounds and configurations described herein enable flow batteries with performance and cost parameters that represent a significant improvement over that previous known in the art.

Claims

1. An aqueous solution comprising:

a metal complex containing at least one substituted catecholate ligand; and

a supporting electrolyte comprising an ammonium salt or a phosphonate salt.

2. The aqueous solution of claim 1, wherein the ammonium salt comprises an alkylammonium salt or an arylammonium salt.

3. The aqueous solution of claim 1, wherein the metal complex has a concentration of at least about 0.5M in the aqueous solution.

4. The aqueous solution of claim 1, wherein the at least one substituted catecholate ligand comprises a sulfonated catecholate ligand.

5. The aqueous solution of claim 1, wherein the at least one substituted catecholate ligand comprises a hydroxycatecholate ligand.

6. The aqueous solution of claim 1, wherein the metal complex contains two unsubstituted catecholate ligands and one substituted catecholate ligand.

7. The aqueous solution of claim 1, wherein the metal complex contains one unsubstituted catecholate ligand and two substituted catecholate ligands.

8. The aqueous solution of claim 1, wherein the metal complex comprises a metal selected from the group consisting of Al, Ca, Ce, Co, Cr, Fe, Mg, Mo, Sn, Ti, U, W, Zn and Zr.

9. The aqueous solution of claim 8, wherein the metal complex comprises Ti.

10. The aqueous solution of claim 1, wherein the aqueous solution has a pH ranging between about 9 to about 13.

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

12. The aqueous solution of claim 1, wherein the metal complex contains at least one unsubstituted catecholate ligand and at least one substituted catecholate ligand.

13. A flow battery comprising:

a first half-cell containing a first aqueous electrolyte solution; and

a second half-cell containing a second aqueous electrolyte solution;

wherein at least one of the first aqueous electrolyte solution and the second aqueous electrolyte solution comprises an aqueous solution comprising a metal complex containing at least one catecholate ligand, and a supporting electrolyte comprising an ammonium salt or a phosphonate salt.

14. The flow battery of claim 13, wherein the ammonium salt comprises an alkylammonium salt or an arylammonium salt.

15. The flow battery of claim 13, wherein the metal complex contains at least one unsubstituted catecholate ligand and at least one substituted catecholate ligand.

16. The flow battery of claim 15, wherein the at least one substituted catecholate ligand comprises a sulfonated catecholate ligand.

17. The flow battery of claim 15, wherein the at least one substituted catecholate ligand comprises a hydroxycatecholate ligand.

18. The flow battery of claim 15, wherein the metal complex contains two unsubstituted catecholate ligands and one substituted catecholate ligand.

19. The flow battery of claim 15, wherein the metal complex contains one unsubstituted catecholate ligand and two substituted catecholate ligands.

20. The flow battery of claim 13, wherein the metal complex contains three unsubstituted catecholate ligands.

21. The flow battery of claim 13, wherein the metal complex comprises Ti.

22. The flow battery of claim 13, wherein the metal complex has a concentration of at least about 0.5M in the aqueous solution.

23. The flow battery of claim 13, wherein the metal complex contains at least one unsubstituted catecholate ligand and at least one substituted catecholate ligand.