Aqueous redox flow batteries featuring improved cell design characteristics

• US 10,164,284 B2
• Filed: 06/01/2016
• Issued: 12/25/2018
• Est. Priority Date: 07/27/2012
• Status: Active Grant

• Current Assignee: Lockheed Martin Energy LLC (Martin Marietta Corporation)
• Original Assignee: Lockheed Martin Energy LLC (Martin Marietta Corporation)
• Inventors: Esswein, Arthur J., Reece, Steven Y., King, Evan R., Goeltz, John, Amadeo, Desiree D.
• Primary Examiner(s): Eoff, Anca
• Application Number:
  US15/170,740
• Publication Number:
  US 20160276695A1
• Time in Patent Office: 937 Days
• CPC Class Codes: C07F 7/28 Titanium compounds
• 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: Y02E 60/50 Fuel cells

Abstract

Provided are compositions having the formula M_nTi(L1)(L2)(L3) wherein L1 is a catecholate, and L2 and L3 are each independently selected from catecholates, ascorbate, citrate, glycolates, a polyol, gluconate, glycinate, hydroxyalkanoates, acetate, formate, benzoates, malate, maleate, phthalates, sarcosinate, salicylate, oxalate, a urea, polyamine, aminophenolates, acetylacetone or lactate; each M is independently Na, Li, or K; n is 0 or an integer from 1-6. Also provided are energy storage systems.

Claims

1. A liquid aqueous solution comprising:

two or more different redox active metal ligand coordination compounds having an overall solution concentration of the two or more different redox active metal ligand coordination compounds in a range of from 0.5 M to 2 M;

wherein each of the two or more different redox active metal ligand coordination compounds contains a different combination of metal ion and coordinated ligands; and

wherein

at least one of the two or more different redox active metal ligand coordination compounds contains at least one catecholate ligand.

2. The liquid aqueous solution of claim 1, wherein a solution concentration of at least one of the two or more different redox active metal ligand coordination compounds is less than about 0.5 M.

3. The liquid aqueous solution of claim 1, wherein a solution concentration of each of the two or more redox active metal ligand coordination compounds is less than about 0.5 M.

4. The liquid aqueous solution of claim 1, wherein at least one of the two or more different redox active metal ligand coordination compounds comprises titanium.

5. The liquid aqueous solution of claim 4, wherein the metal ligand coordination compound comprising titanium contains at least one catecholate ligand.

6. The liquid aqueous solution of claim 5, wherein the metal ligand coordination compound comprising titanium contains at least one unsubstituted catecholate ligand and at least one substituted catecholate ligand.

7. The liquid aqueous solution of claim 6, wherein the at least one substituted catecholate ligand comprises a sulfonated catecholate ligand.

8. The liquid aqueous solution of claim 6, wherein the at least one substituted catecholate ligand comprises a hydroxycatecholate ligand.

9. The liquid aqueous solution of claim 5, wherein the metal ligand coordination compound comprising titanium contains two unsubstituted catecholate ligands and one substituted catecholate ligand.

10. The liquid aqueous solution of claim 5, wherein the metal ligand coordination compound comprising titanium contains three unsubstituted catecholate ligands.

11. The liquid aqueous solution of claim 5, wherein the metal ligand coordination compound comprising titanium further comprises at least one ligand selected from the group consisting of a substituted catecholate, ascorbate, citrate, glycolate, a polyol, gluconate, glycinate, a hydroxyalkanoate, acetate, formate, benzoate, malate, maleate, phthalate, sarcosinate, salicylate, oxalate, a urea, a polyamine, an aminophenolate, acetylacetonate, and lactate.

12. The liquid aqueous solution of claim 1, further comprising:

sodium and potassium counterions of the two or more different redox active metal ligand coordination compounds.

13. The liquid aqueous solution of claim 12, wherein substantially equal molar quantities of sodium and potassium counterions are present.

14. The liquid aqueous solution of claim 1, wherein at least one of the two or more different redox active metal ligand coordination compounds contains at least one unsubstituted catecholate ligand and at least one substituted catecholate ligand.

15. The liquid aqueous solution of claim 14, wherein the at least one substituted catecholate ligand comprises a sulfonated catecholate ligand.

16. The liquid aqueous solution of claim 14, wherein the at least one substituted catecholate ligand comprises a hydroxycatecholate ligand.

17. The liquid aqueous solution of claim 1, wherein at least one of the two or more different redox active metal complexes contains two unsubstituted catecholate ligands and one substituted catecholate ligand.

18. The liquid aqueous solution of claim 1, wherein at least one of the two or more different redox active metal ligand coordination compounds contains three unsubstituted catecholate ligands.

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

20. 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 electrolyte solution and the second electrolyte solution comprises the liquid aqueous solution of claim 1.

21. The flow battery of claim 20, wherein at least one of the two or more redox active metal ligand coordination compounds in the liquid aqueous solution is not a metal complex present in a half-cell opposite the half-cell containing the liquid aqueous solution.

22. The liquid aqueous solution of claim 1, further comprising a salt of phosphate, borate, carbonate, silicate, tris(hydroxymethyl)aminomethane, 4-(2-hydroxyethyl)-1-piperazine ethanesulfonic acid (HEPES), piperazine-N,N′

-bis(ethanesulfonic acid) (PIPES), or combination thereof.

23. The flow battery of claim 20, wherein the liquid aqueous solution of claim 1, further comprises a salt of phosphate, borate, carbonate, silicate, tris(hydroxymethyl)aminomethane, 4-(2-hydroxyethyl)-1-piperazine ethanesulfonic acid (HEPES), piperazine-N,N′

-bis(ethanesulfonic acid) (PIPES), or combination thereof.