Aqueous redox flow batteries featuring improved cell design characteristics

• US 9,991,543 B2
• Filed: 05/23/2016
• Issued: 06/05/2018
• Est. Priority Date: 07/27/2012
• Status: Active Grant

• Current Assignee: Lockheed Martin Corporation (Martin Marietta Corporation)
• Original Assignee: Lockheed Martin Advanced Energy Storage, 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:
  US15/162,475
• Publication Number:
  US 20160264603A1
• Time in Patent Office: 743 Days
• CPC Class Codes: C07F 7/28 Titanium compounds
• CPC Class Codes: H01M 4/9008 Organic or organo-metallic 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 composition comprising:

a metal complex containing (a) an unsubstituted catecholate ligand, (b) a substituted catecholate ligand, and (c) a third ligand selected from the group consisting of the unsubstituted catecholate ligand, the substituted catecholate ligand, ascorbate, citrate, gluconate, lactate, glycolate, a polyol, glycinate, a hydroxyalkanoate, acetate, formate, benzoate, malate, maleate, phthalate, sarcosinate, salicylate, oxalate, a urea, a polyamine, an aminophenolate, and acetylacetonate;

wherein the metal complex comprises a metal selected from the group consisting of Ce, Co, Cr, Fe, Mg, Mo, Ti, U, W, Zn and Zr.

2. The composition of claim 1, further comprising sodium and potassium counterions forming a salt of the metal complex.

3. The composition of claim 1, wherein the substituted catecholate ligand comprises a sulfonate group.

4. The composition of claim 1, wherein the substituted catecholate ligand comprises a third hydroxy moiety.

5. The composition of claim 1, wherein the metal complex contains two unsubstituted catecholate ligands and one substituted catecholate ligand.

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

7. The composition of claim 1, wherein the metal complex comprises a metal selected from the group consisting of Co, Cr, Fe, Mo, Ti, U, W, Zn, and Zr.

8. The composition of claim 1, wherein the substituted catecholate ligand comprises at least one boric acid group or salt thereof, carboxy acid group or salt thereof, hydroxyl, nitro, sulfonate group, sulfonic acid group or salt thereof, phosphonate group, phosphonic acid group or salt thereof, or polyglycol group.

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

10. An aqueous solution comprising a composition comprising a metal complex containing (a) an unsubstituted catecholate ligand, (b) a substituted catecholate ligand, and (c) a third ligand selected from the group consisting of the unsubstituted catecholate ligand, the substituted catecholate ligand, ascorbate, citrate, gluconate, lactate, glycolate, a polyol, glycinate, a hydroxyalkanoate, acetate, formate, benzoate, malate, maleate, phthalate, sarcosinate, salicylate, oxalate, a urea, a polyamine, an aminophenolate, and acetylacetonate.

11. The aqueous solution of claim 10, wherein the metal complex has a concentration of at least about 0.5 M in the aqueous solution.

12. The aqueous solution of claim 11, wherein the substituted catecholate ligand comprises a third hydroxy moiety.

13. The aqueous solution of claim 11, wherein the metal complex contains one unsubstituted catecholate ligand and two substituted catecholate ligands.

14. The aqueous solution of claim 10, wherein the substituted catecholate ligand comprises a sulfonate group.

15. The aqueous solution of claim 10, wherein the metal complex contains two unsubstituted catecholate ligands and one substituted catecholate ligand.

16. The aqueous solution of claim 10, further comprising sodium and potassium counterions.

17. The aqueous solution of claim 10, wherein the metal complex comprises a metal selected from the group consisting of Ce, Co, Cr, Fe, Mo, Sn, Ti, U, W, Zn and Zr.

18. 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 aqueous solution of claim 10.

19. The aqueous solution of claim 10, wherein the substituted catecholate ligand comprises at least one boric acid group or salt thereof, carboxy acid group or salt thereof, hydroxyl, nitro, sulfonate group, sulfonic acid group or salt thereof, phosphonate group, phosphonic acid group or salt thereof, or polyglycol group.

20. The aqueous solution of claim 19, wherein the metal complex comprises Ti.