Materials for flow battery energy storage and methods of using

Patent metadata

Field	Value
Publication number	US-10367222-B2
Application number	US-201715445105-A
Country	US
Kind code	B2
Filing date	Feb 28, 2017
Priority date	Feb 29, 2016
Publication date	Jul 30, 2019
Grant date	Jul 30, 2019

Abstract

The present disclosure relates to a mixture that includes a mediator having a first redox potential, a non-liquid active material having a second redox potential that is less than the first redox potential, and a cation. In addition, the non-liquid active material has a first condition that includes a first oxidation state, where the cation is intercalated within the non-liquid active material, and the non-liquid active material has a second condition that includes a second oxidation state that is higher than the first oxidation state, where the non-liquid active material is substantially free of the cation. In addition, the mediator has a first condition that includes a third oxidation state and a second condition that includes a fourth oxidation state that is higher than the third oxidation state. In addition, the non-liquid active material is capable of being reversibly cycled between its first condition and its second condition, and the mediator is capable of being reversibly cycled between its first condition and its second condition.

First claim

What is claimed is:

1. A catholyte mixture comprising:
a mediator having a first redox potential;
an cathode material having a second redox potential that is less than the first redox potential; and
a cation, wherein:
the cathode material is in a form comprising a solid particulate,
the cathode material has a first condition comprising a first oxidation state, where the cation is intercalated within the cathode material,
the cathode material has a second condition comprising a second oxidation state that is higher than the first oxidation state, where the cathode material is substantially free of the cation,
the mediator has a first condition comprising a third oxidation state and a second condition comprising a fourth oxidation state that is higher than the third oxidation state,
the cathode material is capable of being reversibly cycled between the first condition of the cathode material and the second condition of the cathode material, and
the mediator is capable of being reversibly cycled between its first condition and its second condition.

2. The catholyte mixture of claim 1 , wherein the mediator comprises an organic radical group.

3. The catholyte mixture of claim 2 , wherein the organic radical group comprises a nitroxide group.

4. The catholyte mixture of claim 1 , wherein the mediator has a molecular weight less than 10,000 g/mol.

5. The catholyte mixture of claim 1 , wherein the mediator comprises at least one of (2,2,6,6-tetramethylpiperidin-1-yl)oxyl, (1-oxyl-2,2,6,6-tetramethyl-4-hydroxypiperidine), a nitronyl nitroxide, a azephenylenyl, a percholorophenylmethyl radical, tris(2,4,6-trichlorophenyl)methyl radical, poly(2,2,6,6-tetramethylpiperidinyloxy-4-yl methacrylate), or poly[4-(nitronylnitroxyl)styrene].

6. The catholyte mixture of claim 3 , wherein, when in the first condition of the mediator, the mediator comprises

and when in the second condition of the mediator, the mediator comprises

7. The catholyte mixture of claim 3 , wherein the mediator includes a structure comprising at least one of

8. The catholyte mixture of claim 1 , wherein the cathode material further comprises a gel.

9. The catholyte mixture of claim 1 , wherein the solid particulate has a particle size between 1 nanometer and 1000 micrometers.

10. The catholyte mixture of claim 1 , wherein the cathode material comprises at least one of cobalt, nickel, manganese, aluminum, titanium, vanadium, or iron.

11. The catholyte mixture of claim 10 , wherein the cathode material further comprises at least one of an oxide or a phosphate.

12. The catholyte mixture of claim 11 , wherein the cathode material comprises at least one of a cobalt oxide, a nickel cobalt oxide, a manganese cobalt oxide, or an iron phosphate.

13. The catholyte mixture of claim 11 , wherein the cathode material comprises at least one of CoO 2 , FePO 4 , or Fe 0.5 Mn 0.5 PO 4 .

14. The catholyte mixture of claim 1 , wherein the cation comprises at least one of a Group 1 element, a Group 2 element, or a Group 13 element.

15. The catholyte mixture of claim 1 , wherein the cation comprises at least one of lithium, magnesium, aluminum, or beryllium.

16. The catholyte mixture of claim 1 , further comprising a salt, wherein the salt provides at least a portion of the cation.

17. The catholyte mixture of claim 16 , wherein the salt comprises at least one of LiPF 6 , LiBF 4 , or LiClO 4 .

18. The catholyte mixture of claim 16 , further comprising a solvent, wherein the mediator and the salt are substantially soluble in the solvent.

19. The catholyte mixture of claim 18 , wherein the mixture has an energy storage density greater than or equal to 300 Wh/L, when the cathode material is in the second condition of the cathode material, and the mediator is in the second condition of the mediator.

20. A method comprising transferring energy to a catholyte mixture by applying a voltage to the catholyte mixture, wherein:
the catholyte mixture comprises a mediator having a first redox potential, an cathode material having a second redox potential that is less than the first redox potential, a cation, and a solvent,
the cathode material is in a form comprising a solid particulate,
the voltage transforms the mediator from a first condition having a first oxidation state to a second condition having a second oxidation state that is higher than the first oxidation state, and
when in the second condition, the mediator oxidizes the cathode material, thereby transforming the cathode material from a first condition comprising a third oxidation state where the cation is intercalated within the cathode material, to a second condition comprising a fourth oxidation state that is higher than the third oxidation state where the cathode material is substantially free of the cation,
the cathode material is capable of being reversibly cycled between the first condition of the cathode material and the second condition of the cathode material, and
the mediator is capable of being reversibly cycled between the first condition of the mediator and the second condition of the mediator.

21. The method of claim 20 , further comprising applying a load to the catholyte mixture, wherein the load transforms the cathode material from the second condition of the cathode material to the first condition of the cathode material.

Assignees

• Alliance Sustainable Energy

Inventors

• Gennett Thomas
• Ban Chunmei
• Braunecker Wade A
• Dameron Arrelaine A
• Engtrakul Chaiwat

Classifications

• Y02E60/528

  Cross-Sectional Technologies · mapped topic

• H01M4/505

  of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy · CPC title

• H01M4/525

  of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy · CPC title

• H01M4/5825

  Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines · CPC title

• H01M8/188 Primary

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