REDOX FLOW BATTERY

• US 20200136165A1
• Filed: 07/20/2018
• Published: 04/30/2020
• Est. Priority Date: 07/20/2017
• Status: Active Grant

• Current Assignee: The Board of Trustees of Michigan State University (Michigan State University)
• Original Assignee: The Board of Trustees of Michigan State University (Michigan State University)
• Inventors: Guarr, Thomas F.
• Granted Patent: US 11,545,691 B2
• Time in Patent Office: Days
• CPC Class Codes: C07D 221/14 Aza-phenalenes, e.g. 1,8-naphthalimide
• CPC Class Codes: C07D 401/04 directly linked by a ring-member-to-ring-member bond
• CPC Class Codes: C07D 401/06 linked by a carbon chain containing only aliphatic carbon atoms
• CPC Class Codes: C07D 401/10 linked by a carbon chain containing aromatic rings
• CPC Class Codes: C07D 401/14 containing three or more hetero rings
• CPC Class Codes: C07D 417/04 directly linked by a ring-member-to-ring-member bond
• CPC Class Codes: C07D 417/06 linked by a carbon chain containing only aliphatic carbon atoms
• CPC Class Codes: C07D 417/10 linked by a carbon chain containing aromatic rings
• CPC Class Codes: C07D 417/14 containing three or more hetero rings
• CPC Class Codes: C07D 471/06 Peri-condensed systems
• CPC Class Codes: C07D 487/06 Peri-condensed systems
• CPC Class Codes: H01M 4/368 Liquid depolarisers
• CPC Class Codes: H01M 4/60 of organic compounds
• CPC Class Codes: H01M 8/188 by recharging of redox couples containing fluids; Redox flow type batteries
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y02E 60/50 Fuel cells

Abstract

A redox flow battery includes a cathode, an anode, a charge-carrying electrolyte, and an (a) oxidized and a (b) reduced form of an active material. The active material has the following formula: (D)-(L)-(A)-[(L)-(A)]_V-D_Z(F1) or (D)-(L)-(A)-(L-D)_X (F2). In these formulae, each D is covalently bonded to an L, each L is covalently bonded to an A, x is a number from 0 to 5, v is a number from 0 to 5 and z is 0 or 1. D is an electron donor compound, L is a linker, and A is an electron acceptor compound. Each of D, L, and A has a particular structure.

Claims

1. A redox flow battery comprising:

(I) a cathode;

(II) an anode;

(III) a charge-carrying electrolyte; and

(IV) an (a) oxidized and a (b) reduced form of an active material having the following formula;

(D)-(L)-(A)-[(L)-(A)]_V-D_Z 

 

(F1) or

(D)-(L)-(A)-(L-D)_X 

 

(F2)

wherein each D is covalently bonded to an L, wherein each L is covalently bonded to an A, wherein x is a number from 0 to 5, v is a number from 0 to 5 and z is 0 or 1, wherein D is an electron donor compound, L is a linker, and A is an electron acceptor compound,

wherein each D has the following structure (D1);

2. The redox flow battery of claim 1 that is free of an ion-selective membrane separating said anode and said cathode to keep reduced catholyte and oxidized anolyte from mixing.

3. The redox flow battery of claim 1 wherein X is S, each of R¹ and R² is an alkyl having 1 to 4 carbon atoms, and R³, R⁴, R⁷, R⁸, R⁹, and R¹⁰ are each hydrogen.

4. The redox flow battery of claim 1 wherein X is SO₂, each of R¹ and R² is t-butyl, and R³, R⁴, R⁷, R⁸, R⁹, and R¹⁰ are each hydrogen.

5. The redox flow battery of claim 1 wherein X is a covalent bond, each of R¹ and R² is t-butyl, and R³, R⁴, R⁷, R⁸, R⁹, and R¹⁰ are each hydrogen.

6. The redox flow battery of claim 1 wherein structure (D1) is further defined as structure (Donor 1):

7. The redox flow battery of claim 1 wherein structure (D1) is further defined as structure (Donor 2):

8. The redox flow battery of claim 1 wherein structure (D1) is further defined as structure (Donor 3):

9. The redox flow battery of claim 1 wherein (L) is —

CH₂—

CH₂—

CH₂—

.

10. The redox flow battery of claim 1 wherein (L) is phenyl.

11. The redox flow battery of claim 1 wherein structure (A1) is utilized, wherein R¹¹ is compound (P2), y is 1, and each of R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²³, and R²⁴ are hydrogen.

12. The redox flow battery of claim 1 wherein structure (A1) is utilized, wherein R¹¹ is compound (P2), y is 1, each of R¹³, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, and R²³ are hydrogen, and R¹², R¹⁴, R²¹, and R²⁴ are each methyl.

13. The redox flow battery of claim 1 wherein structure (A1) is utilized, wherein R¹¹ is compound (P2), y is 1, each of R¹³, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, and R²³ are hydrogen, and R¹², R¹⁴, R²¹, and R²⁴ are each phenyl.

14. The redox flow battery of claim 1 wherein v is 0 and z is 0.

15. The redox flow battery of claim 1 wherein v is 1 and z is 1.

16. The redox flow battery of claim 1 wherein v is 1 and x is 1.

17. The redox flow battery of claim 1 wherein structure (A2) is further defined as structure (A6):

18. The redox flow battery of claim 17 wherein each of R²⁵-R³⁶ is hydrogen.

19. The redox flow battery of claim 1 wherein y is 1 and x is 1, wherein there are two (D) electron donor compounds wherein in each (D) X is SO₂, each of R¹ and R² is t-butyl, and R³, R⁴, R⁷, R⁸, R⁹, and R¹⁰ are each hydrogen, and wherein there is a single (A) electron acceptor compound wherein structure (A1) is utilized and wherein R¹¹ is compound (P2), y is 1, each of R¹³, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, and R²³ are hydrogen, and R¹², R¹⁴, R²¹, and R²⁴ are each methyl.

20. The redox flow battery of claim 1 wherein y is 1 and x is 1, wherein there are two (D) electron donor compounds wherein in each (D) X is a covalent bond, each of R¹ and R² is t-butyl, and R³, R⁴, R⁷, R⁸, R⁹, and R¹⁰ are each hydrogen, and wherein there is a single (A) electron acceptor compound wherein structure (A1) is utilized and wherein R¹¹ is compound (P2), y is 1, each of R¹³, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, and R²³ are hydrogen, and R¹², R¹⁴, R²¹, and R²⁴ are each methyl.

21. A redox flow battery comprising:

(I) a cathode;

(II) an anode;

(III) a charge-carrying electrolyte; and

(IV) an active material comprising two or more pyridine or substituted pyridine units, any two of which are separated by 1 to 3 phenyl or substituted phenyl groups, wherein one or more of the pyridine or substituted pyridine units are linked through a nitrogen atom to a moiety having a reversible electrochemical oxidation.

22. An active material for a redox flow battery with the active material having the following formula:

(D)-(L)-(A)-[(L)-(A)]_V-D_Z 

 

(F1) or

(D)-(L)-(A)-(L-D)_X 

 

(F2)

wherein each D is covalently bonded to an L, wherein each L is covalently bonded to an A, wherein x is a number from 0 to 5, v is a number from 0 to 5 and z is 0 or 1, wherein D is an electron donor compound, L is a linker, and A is an electron acceptor compound,

wherein each D has the following structure (D1);

23. The active material of claim 22 wherein X is S, each of R¹ and R² is t-butyl, and R³, R⁴, R⁷, R⁸, R⁹, and R¹⁰ are each hydrogen.

24. The active material of claim 22 wherein X is SO₂, each of R¹ and R² is t-butyl, and R³, R⁴, R⁷, R⁸, R⁹, and R¹⁰ are each hydrogen.

25. The active material of claim 22 wherein X is a covalent bond, each of R¹ and R² is t-butyl, and R³, R⁴, R⁷, R⁸, R⁹, and R¹⁰ are each hydrogen.

26. The active material of claim 22 wherein (L) is —

CH₂—

CH₂—

CH₂—

.

27. The active material of claim 22 wherein (L) is phenyl.

28. The active material of claim 27 wherein structure (A2) is further defined as structure (A6):

29. The redox flow battery of claim 28 wherein each of R²⁵-R³⁶ is hydrogen.