Extending the lifetime of organic flow batteries via redox state management

Patent metadata

Field	Value
Publication number	US-11557786-B2
Application number	US-201917281767-A
Country	US
Kind code	B2
Filing date	Oct 1, 2019
Priority date	Oct 1, 2018
Publication date	Jan 17, 2023
Grant date	Jan 17, 2023

Abstract

The invention provides flow batteries including an anthraquinone and methods of discharging the batteries that reduce loss of capacity. The loss of capacity of anthraquinones may be mitigated by controlling the state of charge and/or oxidizing the negolyte.

First claim

What is claimed is:

1. A method of discharging a battery comprising the steps of:
a) providing a flow battery comprising a negolyte comprising an anthrahydroquinone in aqueous solution or suspension in contact with a first electrode, a posolyte comprising a redox active species in contact with a second electrode, and a barrier separating the negolyte and posolyte; and
b) discharging the flow battery so that the anthrahydroquinone is oxidized to an anthraquinone and the redox active species is reduced, wherein an oxidizing agent is provided to the discharged negolyte.

2. The method of claim 1 , wherein the anthraquinone is of formula (I):

wherein each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 is independently selected from H; halo; optionally substituted C 1-6 alkyl; oxo; optionally substituted C 3-10 carbocyclyl; optionally substituted C 1-9 heterocyclyl having one to four heteroatoms independently selected from O, N, and S; optionally substituted C 6-20 aryl; optionally substituted C 1-9 heteroaryl having one to four heteroatoms independently selected from O, N, and S; —CN; —NO 2 ; —OR a ; —SR a ; —N(R a ) 2 ; —C(═O)R a ; —C(═O)OR a ; —S(═O) 2 R a ; —S(═O) 2 OR a (e.g., SO 3 H); —P(═O)R a2 ; and —P(═O)(OR a ) 2 ; or any two adjacent groups selected from R 1 , R 2 , R 3 , and R 4 are joined to form an optionally substituted 3-6 membered ring, or an ion thereof, wherein each R a is independently H; C 1-6 alkyl; optionally substituted C 3-10 carbocyclyl; optionally substituted C 1-9 heterocyclyl having one to four heteroatoms independently selected from O, N, and S; optionally substituted C 6-20 aryl; optionally substituted C 1-9 heteroaryl having one to four heteroatoms independently selected from O, N, and S; an oxygen protecting group; or a nitrogen protecting group.

3. The method of claim 1 , wherein the redox active species comprises bromine, chlorine, iodine, molecular oxygen, vanadium, chromium, cobalt, iron, aluminum, manganese, cobalt, nickel, copper, or lead.

4. The method of claim 1 , wherein the oxidizing agent is molecular oxygen.

5. The method of claim 4 , wherein the molecular oxygen is provided in gaseous form.

6. A flow battery comprising:
i) a negolyte comprising an anthrahydroquinone in aqueous solution or suspension in contact with a first electrode;
ii) a posolyte comprising a redox active species in contact with a second electrode;
iii) a barrier separating the negolyte and posolyte; and
iv) a source of oxidizing agent in fluid communication with the negolyte and/or a gas dispersion element in the negolyte.

7. The flow battery of claim 6 , wherein the anthraquinone is of formula (I):

wherein each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 is independently selected from H; halo; optionally substituted C 1-6 alkyl; oxo; optionally substituted C 3-10 carbocyclyl; optionally substituted C 1-9 heterocyclyl having one to four heteroatoms independently selected from O, N, and S; optionally substituted C 6-20 aryl; optionally substituted C 1-9 heteroaryl having one to four heteroatoms independently selected from O, N, and S; —CN; —NO 2 ; —OR a ; —SR a ; —N(R a ) 2 ; —C(═O)R a ; —C(═O)OR a ; —S(═O) 2 R a ; —S(═O) 2 OR a (e.g., SO 3 H); —P(═O)R a2 ; and —P(═O)(OR a ) 2 ; or any two adjacent groups selected from R 1 , R 2 , R 3 , and R 4 are joined to form an optionally substituted 3-6 membered ring, or an ion thereof, wherein each R a is independently H; C 1-6 alkyl; optionally substituted C 3-10 carbocyclyl; optionally substituted C 1-9 heterocyclyl having one to four heteroatoms independently selected from O, N, and S; optionally substituted C 6-20 aryl; optionally substituted C 1-9 heteroaryl having one to four heteroatoms independently selected from O, N, and S; an oxygen protecting group; or a nitrogen protecting group.

8. The flow battery of claim 6 , wherein the redox active species comprises bromine, chlorine, iodine, molecular oxygen, vanadium, chromium, cobalt, iron, aluminum, manganese, cobalt, nickel, copper, or lead.

9. A method of reducing loss of capacity in a flow battery comprising the steps of:
a) providing a flow battery comprising a negolyte in aqueous solution or suspension in contact with a first electrode, a posolyte in contact with a second electrode, and a barrier separating the negolyte and posolyte; and
b) oxidizing the negolyte after discharge, wherein the oxidizing agent is molecular oxygen.

10. The method of claim 9 , wherein the negolyte comprises an organic redox active compound or an organometallic redox active compound.

11. The method of claim 9 , wherein the negolyte comprises an anthraquinone.

12. The method of claim 11 , wherein the anthraquinone is of formula (I):

wherein each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 is independently selected from H; halo; optionally substituted C 1-6 alkyl; oxo; optionally substituted C 3-10 carbocyclyl; optionally substituted C 1-9 heterocyclyl having one to four heteroatoms independently selected from O, N, and S; optionally substituted C 6-20 aryl; optionally substituted C 1-9 heteroaryl having one to four heteroatoms independently selected from O, N, and S; —CN; —NO 2 ; —OR a ; —SR a ; —N(R a ) 2 ; —C(═O)R a ; —C(═O)OR a ; —S(═O) 2 R a ; —S(═O) 2 OR a (e.g., SO 3 H); —P(═O)R a2 ; and —P(═O)(OR a ) 2 ; or any two adjacent groups selected from R 1 , R 2 , R 3 , and R 4 are joined to form an optionally substituted 3-6 membered ring, or an ion thereof, wherein each R a is independently H; C 1-6 alkyl; optionally substituted C 3-10 carbocyclyl; optionally substituted C 1-9 heterocyclyl having one to four heteroatoms independently selected from O, N, and S; optionally substituted C 6-20 aryl; optionally substituted C 1-9 heteroaryl having one to four heteroatoms independently selected from O, N, and S; an oxygen protecting group; or a nitrogen protecting group.

13. The method of claim 9 , wherein the posolyte comprises a redox active species comprises bromine, chlorine, iodine, molecular oxygen, vanadium, chromium, cobalt, iron, aluminum, manganese, cobalt, nickel, copper, or lead.

14. The method of claim 9 , wherein the molecular oxygen is provided in gaseous form.

Assignees

• Harvard College

Inventors

• Goulet Marc-Antoni
• Gordon Roy G
• Aziz Michael J
• Tong Liuchuan

Classifications

• H01M8/188 Primary

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

• H01M8/225 Primary

  Fuel cells in which the fuel is based on materials comprising particulate active material in the form of a suspension, a dispersion, a fluidised bed or a paste · CPC title

• H01M8/18

  Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells · CPC title

• Y02E60/50

  Fuel cells · CPC title