Materials for high-performance aqueous organic redox flow batteries

Patent metadata

Field	Value
Publication number	US-2018097249-A1
Application number	US-201715723071-A
Country	US
Kind code	A1
Filing date	Oct 2, 2017
Priority date	Sep 30, 2016
Publication date	Apr 5, 2018
Grant date	—

Abstract

Quinones and related compounds for use in flow batteries are provided. Many of these compounds are found to mitigate the effects of crossover in a flow battery. Other structure for improving battery performance is provided.

First claim

What is claimed is:

1 . A flow battery comprising:
a positive electrode; a positive electrode electrolyte including water and a first redox couple, the positive electrode electrolyte flowing over and contacting the positive electrode, the first redox couple including an organic compound having formula I and a reduction product of the organic compound, the organic compound having formula I being reduced during discharge: a negative electrode; and a negative electrode electrolyte including water and a second redox couple, the negative electrode electrolyte flowing over and contacting the positive electrode, the second redox couple also includes the organic compound having formula I, a reduction product of the organic compound having formula I being oxidized during discharge:

wherein:
p is 0, 1, 2, 3, or 4;
o is 0, 1, 2, or 3;
r is 0, 1, 2, or 3;
R 1 , R 2 , R 3 are each independently —SO 3 H, —SO 3 Na, —SO 3 K, —CO 2 H, —CO 2 Na, —CO 2 K, —OH, —OMe, alkyl, (CH 2 CH 2 O) n OMe, NH 2 , NMe 2 , I, Cl, Br, F, —CF 3 , —CF 2 H, —NO 2 , —N(R) 3 + X 1 − , CCl 3 , —CN, —PO 3 H 2 , —COOH, —O − M + 2 , —SO 3 − M + , —PO 3 2− M + 2 , —COO − M + , —COOR, —CHO, or —COR where R is H or C 1-10 alkyl, M + is a positively charged counter-ion, and X 1 − is a negatively charge counter-ion;
X is —(CH 2 ) n , —(CH 2 OCH 2 ) n , C 4-15 branched alkyl chains or other substituted alkyl chains; and
n is 1 to 10.

2 . The flow battery of claim 1 wherein the R 3 are each independently H, —NO 2 , —CF 3 , or —SO 3 H.

3 . The flow battery of claim 1 wherein 1, 2, or 3 of the R 3 are each independently electron withdrawing groups.

4 . The flow battery of claim 1 wherein the R 3 are each independently —NO 2 , —N(R) 3 + X − , —CF 3 , CCl 3 , —CN, —SO 3 H, —PO 3 H 2 , —COOH, —OH, —O − M + , —SO 3 − M + , —PO 3 2− M + , —COO − M + , —COOR, F, Cl, Br, —CHO, or —COR where R is H or C 1-10 alkyl, M + is a positively charged counter-ion (e.g., Na + , K + , and the like).

5 . The flow battery of claim 1 wherein the R 1 , R 2 each independently include one or more electron donating group.

6 . The flow battery of claim 1 wherein the R 1 , R 2 each independently C 1-10 alkyl, NH 2 , —NHR, —N(R) 2 , —O − M + 2 , —NHCOR 2 , —OR 2 , —CH 3 , —C 2 H 5 , or phenyl where R is H or C 1-10 alkyl and M + is a positively charged counter ion.

7 . The flow battery of claim 1 wherein at least one of R 1 , R 2 , R 3 is a functional group that increases water solubility.

8 . The flow battery of claim 1 wherein the R 1 , R 2 , R 3 are each independently —SO 3 H, —PO 3 H 2 , —COOH, —OH, —O − M + , —SO 3 − M + , —PO 3 2− M + 2 , —COO − M + , pyridinyl, imidazoyl, or pyrroyl, where M + is a positively charged counter ion.

9 . The flow battery of claim 1 further comprising an ion exchange membrane interposed between the positive electrode and the negative electrode.

10 . The flow battery of claim 9 wherein the ion exchange membrane has an equivalent weight greater than 1000 with respect to protogenic groups.

11 . The flow battery of claim 1 wherein the positive electrode and/or the negative electrode include multi-walled carbon nanotubes.

12 . The flow battery of claim 1 wherein the positive electrode and the negative electrode each independently includes water-soluble materials.

13 . The flow battery of claim 12 wherein the water-soluble materials include carbon and a binder material.

14 . The flow battery of claim 1 wherein the positive electrode electrolyte and the negative electrode electrolyte each independently include a molecule with different redox properties in various ranges of potentials.

15 . A flow battery comprising:
a positive electrode; a positive electrode electrolyte including water and a first redox couple, the positive electrode electrolyte flowing over and contacting the positive electrode, the first redox couple including an organic compound having formula II and a reduction product of the organic compound, the organic compound having formula II being reduced during discharge; a negative electrode; and a negative electrode electrolyte including water and a second redox couple, the negative electrode electrolyte flowing over and contacting the positive electrode, the second redox couple also including an organic compound having formula II, a reduction product of the organic compound having formula I being oxidized to the organic compound during discharge:
A-X-B  II

wherein:
A is a substituted or unsubstituted flavins with substituents, quinoxaline with and without substituents, substituted anthraquinones, and substituted naphthaquinones; and
B is a substituted quinone.

16 . The flow battery of claim 15 further comprising an ion exchange membrane interposed between the positive electrode and the negative electrode.

17 . The flow battery of claim 16 wherein the ion exchange membrane has an equivalent weight greater than 1000 with respect to protogenic groups.

18 . The flow battery of claim 15 wherein the positive electrode and/or the negative electrode include multi-walled carbon nanotubes.

19 . The flow battery of claim 15 wherein the positive electrode and the negative electrode each independently includes water-soluble materials.

20 . The flow battery of claim 19 wherein the water-soluble materials include carbon and a binder material.

21 . The flow battery of claim 15 wherein the positive electrode electrolyte and the negative electrode electrolyte each independently include a molecule with different redox properties in various ranges of potentials.

22 . A flow battery comprising:
a positive electrode; a positive electrode electrolyte including water and a first redox couple, the positive electrode electrolyte flowing over and contacting the positive electrode, the first redox couple including a first organic compound and a reduction product of the first organic compound, the first organic compound being reduced during discharge: a negative electrode; and a negative electrode electrolyte including water and a second redox couple, the negative electrode electrolyte flowing over and contacting the positive electrode, the second redox couple also including a second organic compound, a reduction product of the second organic compound being oxidized to the second organic compound during discharge, one or both of the first organic compound and the second organic compound including a compound selected from the group consisting of:

and combinations thereof
wherein R 4 , R 5 , R 6 , and R 7 are each independently H,

—SO 3 H, —SO 3 Na, —SO 3 K, —CO 2 H, —CO 2 Na, —CO 2 K, —OH, —OMe, alkyl, (CH 2 CH 2 O) n OMe, NH 2 , NMe2, I, Cl, Br, F, —CF 3 , —CF 2 H, —NO 2 , —N(R) 3 + X 1 − , CCl 3 , —CN, —PO 3 H 2 , —COOH, —O − M + 2 , —SO 3 − M + , —PO 3 2− M + 2 , —COO − M + , —COOR, —CHO, or —COR where R is H or C 1-10 alkyl, M + is a positively charged counter-ion, and X 1 − is a negatively charge counter-ion.

23 . A flow battery comprising:
a positive electrode; a positive ele

Assignees

• Univ Southern California

Inventors

• Narayan Sri
• Prakash Surya G
• Aniszfeld Robert
• Yang Bo
• Hoober-Burkhardt Lena
• Krishnamoorthy Sankarganesh
• Murali Advaith
• Nirmalchandar Archith

Classifications

• H01M2008/1095

  Fuel cells with polymeric electrolytes · CPC title

• H01M2300/0014

  Alkaline electrolytes · CPC title

• H01M2250/10

  Fuel cells in stationary systems, e.g. emergency power source in plant · CPC title

• H01M8/188 Primary

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

• H01M2300/0082

  Organic polymers · CPC title