Aqueous redox flow batteries comprising metal ligand coordination compounds

Patent metadata

Field	Value
Publication number	US-10707513-B2
Application number	US-201715682728-A
Country	US
Kind code	B2
Filing date	Aug 22, 2017
Priority date	Jul 27, 2012
Publication date	Jul 7, 2020
Grant date	Jul 7, 2020

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.

First claim

What is claimed:

1. A flow battery comprising:
a first aqueous electrolyte comprising a first redox active material;
a second aqueous electrolyte comprising a second redox active material;
wherein the first and second redox active materials comprise a different metal or metalloid;
a first electrode in contact with said first aqueous electrolyte;
a second electrode in contact with said second aqueous electrolyte and
a separator disposed between said first aqueous electrolyte and said second aqueous electrolyte;
wherein the first or second redox active material, or both the first and second redox active materials comprise a metal ligand coordination compound having a formula comprising M(L1) x (L2) y (L3) z m , where M is independently a non-zero valent metal or metalloid of Groups 2-16, including lanthanides and actinides,
wherein x, y, and z are independently 0, 1, 2, or 3, wherein x, y, and z are selected from the group consisting of (a) x=3, y=z=0; (b) x=2, y=1, z=0; (c) x=1, y=1, z=1;
m is independently −5, −4, −3, −2, −1, 0, 1, 2, 3, 4, or 5; and
L1, L2, and L3 are each independently ascorbate, citrate, a glycolate, gluconate, glycinate, α-hydroxyalkanoate, β-hydroxyalkanoate, γ-hydroxyalkanoate, malate, maleate, phthalate, a polyol, sarcosinate, salicylate, lactate, or a compound having structure according to Formula I, or an oxidized or reduced form thereof:

wherein
Ar is a 5-20 membered aromatic moiety, optionally comprising one of more O, N, or S heteroatoms;
X 1 and X 2 are independently —OH, —NHR′, —SH, or an anion thereof, X 1 and X 2 being positioned ortho to one another;
R 1 is independently at each occurrence H, C 1-6 alkoxy, C 1-6 alkyl, C 1-6 alkenyl, C 1-6 alkynyl, 5-6 membered aryl or heteroaryl, a boric acid or a salt thereof, carboxy acid or a salt thereof, C 2-6 carboxylate, cyano, halo, hydroxyl, nitro, sulfonate, sulfonic acid or a salt thereof, phosphonate, phosphonic acid or a salt thereof, or a polyglycol;
R′ is independently H or C 1-3 alkyl; and
n is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.

2. The flow battery of claim 1 , wherein both the first and second redox active materials comprise a metal ligand coordination compound.

3. The flow battery of claim 1 , wherein the first, the second, or both the first and second metal-ligand coordination compound comprises at least one ligand having a structure according to Formula I.

4. The flow battery of claim 1 , wherein the first, the second, or both of the redox-active metal ligand coordination compounds comprises at least one ligand having a structure according to Formula IA, IB, or IC:

wherein
X 1 and X 2 are independently —OH, —NHR′, —SH, or an anion thereof;
R 1 is independently at each occurrence H, C 1-6 alkoxy, C 1-6 alkyl, a boric acid or a salt thereof, carboxy acid or a salt thereof, C 2-6 carboxylate, cyano, halo, hydroxyl, nitro, sulfonate, sulfonic acid or a salt thereof, phosphonate, phosphonic acid or a salt thereof, or a polyglycol;
R′ is independently H or C 1-3 alkyl; and
n is 0-4.

5. The flow battery of claim 4 , wherein
X 1 and X 2 are both OH or an anion thereof;
R 1 is independently H, C 1-3 alkoxy, C 1-3 alkyl, a boric acid or a salt thereof, carboxy acid or a salt thereof, C 2-6 carboxylate, cyano, halo, hydroxyl, nitro, sulfonate, sulfonic acid or a salt thereof, phosphonate, phosphonic acid or a salt thereof, or a polyglycol; and
n is 1.

6. The flow battery of claim 1 , where the first, the second, or both of the redox-active metal ligand coordination compounds comprises at least one ligand of Formula I, IA, IB, or IC.

7. The flow battery of claim 6 , where the at least one ligand of Formula I, IA, IB, or IC is a catechol or pyrogallol ligand.

8. The flow battery of claim 1 , wherein either the first or the second or both the first and second metal-ligand coordination compound comprises Al, Ca, Ce, Co, Cr, Fe, Mg, Mn, Mo, Si, Sn, Ti, W, Zn, or Zr.

9. The flow battery of claim 1 , wherein one of the first or the second metal-ligand coordination compound comprises the metal ligand coordination compound having the formula comprising M(L1) x (L2) y (L3) z m , and the other comprises a cyano compound of chromium, iron, manganese, molybdenum, or ruthenium.

10. The flow battery of claim 9 , wherein the metal-ligand coordination compound is a chromium, iron, or manganese hexacyanide compound.

11. The flow battery of claim 10 , wherein the metal-ligand coordination compound is an iron hexacyanide compound.

12. The flow battery of claim 9 , wherein either or both of the first or the second metal-ligand coordination compound are present in the first or second electrolyte, respectively, at a concentration in a range of from 0.5 to 1 M.

13. The flow battery of claim 1 , wherein the first and second metal-ligand coordination compounds each exhibits substantially reversible electrochemical kinetics.

14. The flow battery of claim 1 , wherein the separator has a thickness of about 100 micron or less.

15. A system comprising a flow battery of claim 1 , and further comprising:
(a) a first chamber containing the first aqueous electrolyte and a second chamber containing the second aqueous electrolyte;
(b) at least one electrolyte circulation loop in fluidic communication each electrolyte chamber, said at least one electrolyte circulation loop comprising storage tanks and piping for containing and transporting the electrolytes;
(c) control hardware and software; and
(d) an optional power conditioning unit.

16. The system of claim 15 , wherein the system is connected to an electrical grid.

Assignees

• Lockheed Martin Energy Llc

Inventors

• Goeltz John
• Amadeo Desiree
• Esswein Arthur J
• Jarvi Thomas D
• King Evan R
• Reece Steven Y
• Tyagi Nitin

Classifications

• Y02E60/50

  Fuel cells · CPC title

• H02J7/00

  Circuit arrangements for charging or discharging batteries or for supplying loads from batteries · CPC title

• 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

• H01M8/08

  Fuel cells with aqueous electrolytes · CPC title