Aqueous redox flow batteries featuring improved cell design characteristics

Patent metadata

Field	Value
Publication number	US-9382274-B2
Application number	US-201414164839-A
Country	US
Kind code	B2
Filing date	Jan 27, 2014
Priority date	Jul 27, 2012
Publication date	Jul 5, 2016
Grant date	Jul 5, 2016

Abstract

Provided are compositions having the formula

M n Ti(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.

First claim

What is claimed:

1. A composition having the formula M n Ti(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; and provided that when both L1 and L2 are a catecholate, L3 is not oxalate, urea, catecholate or acetylacetone.

2. The composition of claim 1 , wherein said catecholate comprises 1,2-dihydroxybenzene, 1,2,3-trihydroxybenzene, 1,2,4-trihydroxybenzene or a mixture thereof.

3. A flow battery comprising the composition of claim 1 .

4. A composition having the formula M n Ti(catecholate) 2 (hydroxycatecholate);
wherein n is 0 or an integer from 1 to 6.

5. The composition of claim 4 , wherein said hydroxycatecholate comprises 1,2,3-trihydroxybenzene or 1,2,4-trihydroxybenzene.

6. An aqueous solution comprising one or more compositions having the formula M n Ti(L1)(L2)(L3) wherein:
L1, L2, and L3 are each independently selected from catecholates, ascorbate, citrate, glycolates, polyols, gluconate, glycinate, hydroxyalkanoates, acetate, formate, benzoates, malate, maleate, phthalates, sarcosinate, salicylate, oxalate, ureas, a polyamine, aminophenolates, acetylacetone or lactate, provided that at least one of L1, L2, and L3 is a catecholate;
each M is independently Na, Li, or K;
n is 0 or an integer from 1-6; and
wherein the composition is present in a concentration greater than 0.5 M.

7. The aqueous solution of claim 6 , wherein when L1 and L2 are a catecholate, L3 is not oxalate, urea, catecholate or acetylacetone.

8. The aqueous solution of claim 6 , wherein said catecholate comprises 1,2-dihydroxybenzene, 1,2,3-trihydroxybenzene, 1,2,4-trihydroxybenzene or a mixture thereof.

9. The aqueous solution of claim 6 , wherein the composition has the formula M n Ti(catecholate) 2 (hydroxycatecholate).

10. The aqueous solution of claim 9 , wherein said hydroxycatecholate comprises 1,2,3-trihydroxybenzene or 1,2,4-trihydroxybenzene.

11. The aqueous solution of claim 6 , wherein the composition is of the formula M n Ti(catecholate) 3 .

12. The aqueous solution of claim 6 , additionally comprising a buffer.

13. The aqueous solution of claim 12 , wherein said buffer is a salt of phosphate, borate, carbonate, silicate, tris(hydroxymethyl)aminomethane (tris), 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid (HEPES), piperazine-N,N′-bis(ethanesulfonic acid) (PIPES), and combinations thereof.

14. The aqueous solution of claim 6 having a pH of 1-13.

15. The aqueous solution of claim 6 having a pH of 2-12.

16. The aqueous solution of claim 6 having a pH of 4-10.

17. The aqueous solution of claim 5 , wherein at least one of L1, L2, and L3 is a catecholate bearing a sulfonic acid or a salt thereof.

18. The aqueous solution of claim 17 , wherein at least one of L1, L2, and L3 is a catecholate bearing one sulfonic acid or a salt thereof.

19. The aqueous solution of claim 6 having a pH of about 7 to about 13.

20. The aqueous solution of claim 6 having a pH of about 9 to about 13.

Assignees

• Lockheed Martin Advanced Energy Storage Llc

Inventors

• Esswein Arthur J
• Reece Steven Y
• King Evan R
• Goeltz John
• Amadeo Desiree D

Classifications

• C07F7/28 Primary

  Titanium compounds · CPC title

• H01M4/9008

  Organic or organo-metallic compounds · CPC title

• Y02E60/528

  Cross-Sectional Technologies · mapped topic

• H01M8/20

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

• H01M8/188 Primary

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