Applications of low-cost, thermal and electrochemically stable organic compounds as high performance redox active materials in redox flow batteries

Patent metadata

Field	Value
Publication number	US-11271238-B2
Application number	US-201916695826-A
Country	US
Kind code	B2
Filing date	Nov 26, 2019
Priority date	Nov 27, 2018
Publication date	Mar 8, 2022
Grant date	Mar 8, 2022

Abstract

Described herein are redox active materials based on functionalization of 2,5-di(pyridine-4-yl)thiazolo-[5,4-d]thiazole (Py2TTz). Also described herein are aqueous organic redox flow batteries that include a first redox active material and a second redox active material comprising a viologen compound or a salt thereof.

First claim

What is claimed is:

1. A compound of formula (I):

or a salt thereof, wherein:
m is 1, 2, or 3;
each A is independently selected from arylene or heteroarylene;
L 1 and L 2 are C 1 -C 10 -alkyl;
n, at each occurrence, is independently 1, 2, or 3;
R 1 and R 2 are independently selected from the group consisting of —NO 2 , —OR a , —C(O)R b , —C(O)OR c , —S(O) q , —PO 3 , —S(O) q R d , —S(O) q OR e , —OP(O)(OR f ) 2 ; —OCH 2 , —P(O)(OR g ) 2 , —CHO, —(CR h 2 ) q CN, —N(R i ) q , and —P(R j ) r ;
each R a , R b , R c , R d , R e , R f , R g , R h , R i and R j are independently selected from the group consisting of hydrogen, C 1 -C 4 alkyl, cycloalkyl, heterocyclyl, aryl, heteroaryl, C 1 -C 4 alkyl-N(R k ) w , C 1 -C 4 alkyl-S(O) w , an oxygen protecting group, and a nitrogen protecting group;
R k , at each occurrence, is independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, heterocyclyl, aryl, heteroaryl, an oxygen protecting group, and a nitrogen protecting group;
q, at each occurrence, is independently 2 or 3;
r, at each occurrence, is independently 2, 3, or 4; and
w, at each occurrence, is independently 2 or 3;
wherein each aryl, heteroaryl, arylene, heteroarylene, cycloalkyl, and heterocyclyl is independently unsubstituted or substituted.

2. A compound of claim 1 , wherein A is selected from the group consisting of:

3. The compound of claim 1 , wherein m is 2 and A is a five-membered or six-membered arylene or heteroarylene.

4. The compound of claim 1 , wherein A is selected from the group consisting of:

5. The compound of claim 1 , wherein R 1 and R 2 are independently selected from the group consisting of —S(O) q , —PO 3 , —S(O) q R d , and —N(R i ) q .

6. The compound of claim 1 , wherein each R a , R b , R c , R d , R e , R f , R g , R h , R i and R j are independently selected from hydrogen and C 1 -C 4 alkyl.

7. The compound of claim 1 , wherein the compound is a salt of fluoride, chloride, bromide, iodide, hydroxide, sulfate, carbonate, chlorate, perchlorate, phosphate, dihydrogen phosphate, hydrogen phosphate, nitrate, nitride, nitrile, dicyanamide, thiocyanate, bis(trifluoromethane)sulfonamide, hexafluorophosphate, tetrafluorophosphite, or a combination thereof.

8. A redox flow battery comprising:
a first redox active material; and
a second redox active material comprising a viologen or a salt thereof, wherein the viologen has formula (I):

wherein:
m is 1, 2, or 3;
each A is independently selected from arylene or heteroarylene;
L 1 and L 2 are C 1 -C 10 -alkyl;
n, at each occurrence, is independently 1, 2, or 3;
R 1 and R 2 are independently selected from the group consisting of —CH 3 , —NO 2 , —OR a , —C(O)R b , —C(O)OR c , —S(O) q , —PO 3 , —S(O) q R d , —S(O) q OR e , —OP(O)(OR f ) 2 ; —OCH 2 , —P(O)(OR g ) 2 , —CHO, —(CR h 2 ) q CN, —N(R i ) q , and —P(R j ) r
each R a , R b , R c , R d , R e , R f , R g , R h , R i and R j are independently selected from the group consisting of hydrogen, C 1 -C 4 alkyl, cycloalkyl, heterocyclyl, aryl, heteroaryl, C 1 -C 4 alkyl-N(R k ) w , C 1 -C 4 alkyl-S(O) w , an oxygen protecting group, and a nitrogen protecting group;
R k , at each occurrence, is independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, heterocyclyl, aryl, heteroaryl, an oxygen protecting group, and a nitrogen protecting group;
q, at each occurrence, is independently 2 or 3;
r, at each occurrence, is independently 2, 3, or 4; and
w, at each occurrence, is independently 2 or 3;
wherein each aryl, heteroaryl, arylene, heteroarylene, cycloalkyl, and heterocyclyl is independently unsubstituted or substituted.

9. A redox flow battery of claim 8 , wherein A is selected from the group consisting of:

10. The redox flow battery of claim 8 , wherein m is 2 and A is a five-membered or six-membered arylene or heteroarylene.

11. The redox flow battery of claim 8 , wherein A is:

12. The redox flow battery of claim 8 , wherein R 1 and R 2 are independently selected from the group consisting of —S(O) q , —PO 3 , —S(O) q R d , and —N(R i ) q .

13. The redox flow battery of claim 8 , wherein each R a , R b , R c , R d , R e , R f , R g , R h , R i and R j are independently selected from hydrogen and C 1 -C 4 alkyl.

14. The redox flow battery of claim 8 , wherein the compound is a salt of fluoride, chloride, bromide, iodide, hydroxide, sulfate, carbonate, chlorate, perchlorate, phosphate, dihydrogen phosphate, hydrogen phosphate, nitrate, nitride, nitrile, dicyanamide, thiocyanate, bis(trifluoromethane)sulfonamide, hexafluorophosphate, tetrafluorophosphite, or a combination thereof.

15. The redox flow battery of claim 8 , wherein the first redox active material comprises − [Fe(CN) 6 ] 3+/2+ , I 3 − /I − , Br 2 /Br − , S 4 − /S 2 , KBr, NaBr, NH 4 Br, KI, NaI, NH 4 I, FeCl 2 , FeBr 2 , Ce 4+/3+ , Mn 3+/2+ , PbO 2 /PbSO 4 , quinone, a derivative of quinone, anthraquinone, a derivative of anthraquinone, K 4 [Fe(CN) 6 ], N 4 [Fe(CN) 6 ], (NH 4 ) 4 [Fe(CN) 6 ], Ni(OH) 2 , V 5+/4+ , (2,2,6,6-Tetramethylpiperidin-1-yl)oxyl (TEMPO), a derivative of TEMPO, or a combination thereof.

16. The redox flow battery of claim 15 , wherein the derivative of TEMPO is selected from the group consisting of 4-trimethylammonium-(2,2,6,6-Tetramethylpiperidin-1-yl)oxy (4-N Me -TEMPO), 4-dimethyl(propyl-3-N,N,N,-trimethylammonium)-(2,2,6,6-Tetramethylpiperidin-1-yl)oxy ((4-N NPr -TEMPO), 4-hyoxyl-ammonium-(2,2,6,6-Tetramethylpiperidin-1-yl)oxy (4-OHTEMPO), 4-sulfonate-(2,2,6,6-Tetramethylpiperidin-1-yl)oxy (4-SO 3 -TEMPO), 4-amino-(2,2,6,6-Tetramethylpiperidin-1-yl)oxy (4-NH 2 -TEMPO), N,N,N,2,2,6,6-heptamethylpiperidinyloxy-4-ammonium chloride (N Me -TEMPO), and a combination thereof.

17. The redox flow battery of claim 8 , further comprising:
a first aqueous electrolyte;
a second aqueous electrolyte; and
a separator between the first and second aqueous electrolytes.

18. The redox flow battery of claim 17 , wherein the second redox active material is present in the second aqueous electrolyte at a concentration of ≥0.1 M.

19. The redox flow battery claim 17 , further comprising a first electrode in contact with the first aqueous electrolyte and a second electrode in contact with the second aqueous electrolyte.

20. The redox flow battery of claim 17 , wherein the separator is a porous separator.

21. The redox flow battery of claim 17 , wherein the separator is an anion exchange membrane or a cation exchange membrane.

22. The redox flow battery of claim 17 , wherein the first and second aqueous electrolytes each independently comprise a salt having the formula (IV):
A-B  (II),

wh

Assignees

• Liu Tianbiao
• Univ Utah State

Inventors

• Liu Tianbiao

Classifications

• H01M8/188 Primary

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

• H01M2300/0002

  Aqueous electrolytes · CPC title

• Y02E60/10

  Energy storage using batteries · CPC title

• H01M8/023

  Porous and characterised by the material · CPC title

• C07D513/04 Primary

  Ortho-condensed systems · CPC title