Materials for use in an aqueous organic redox flow battery

Patent metadata

Field	Value
Publication number	US-10934258-B2
Application number	US-201715659593-A
Country	US
Kind code	B2
Filing date	Jul 25, 2017
Priority date	Jul 25, 2016
Publication date	Mar 2, 2021
Grant date	Mar 2, 2021

Abstract

Described herein are aqueous organic redox flow batteries that include a first redox active material that can include a metallocene or a salt thereof, and a second redox active material that can include a viologen or a salt thereof. The aqueous organic redox flow batteries may further include a first aqueous electrolyte, a second aqueous electrolyte, and a separator between the first and second aqueous electrolytes. In addition, disclosed herein are methods of making the metallocene and viologen compounds.

First claim

The invention claimed is:

1. 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 (VI):

or a salt thereof, wherein:
L 3 and L 4 are each independently selected from the group consisting of bond, C 1 -C 12 alkylenyl, C 1 -C 12 alkenylenyl, C 1 -C 12 alkynylenyl, and C 1 -C 4 alkylenyl-(OCH 2 CH 2 ) m ;
R 11 is selected from the group consisting of, —NO 2 , —OR g , —N(R g ) q , —C(O)R g , —C(O)OR g , —S(O) q , —PO 3 , —S(O) q R g , —S(O) q OR g , —OP(O)(OR g ) 2 , —OCH 3 , —(CR g 2 ) m CN, substituted aryl, and substituted heteroaryl;
R 12 is selected from the group consisting of —CH 3 , —NO 2 , —OR g , —C(O)R g , —C(O)OR g , —S(O) q , —PO 3 , —S(O) q R g , —S(O) q OR g , —OP(O)(OR g ) 2 ; —OCH 3 , —(CR g 2 ) m CN, substituted aryl, and substituted heteroaryl;
R g , at each occurrence, is independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, heterocyclyl, aryl, heteroaryl, alkyl-N(R h ) q , alkyl-S(O) q , an oxygen protecting group, and a nitrogen protecting group;
R h , 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; and
q, at each occurrence, is independently 2 or 3.

2. The redox flow battery of claim 1 , wherein the viologen has formula (VI-a):

or a salt thereof, wherein:
R 13 is selected from the group consisting of —N(R g ) q , —S(O) q , —PO 3 , —S(O) q R g , —(OCH 2 CH 2 ) m —OCH 3 , and substituted aryl;
R 14 is selected from the group consisting of —CH 3 , —S(O) q , —PO 3 , —S(O) q R g , —(OCH 2 CH 2 ) m —OCH 3 , and substituted aryl;
R g , at each occurrence, is independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, heterocyclyl, aryl, heteroaryl, alkyl-N(R h ) q , alkyl-S(O) q , an oxygen protecting group, and a nitrogen protecting group;
R h , 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; and
c, at each occurrence, is independently 0, 1, 2 or 3.

3. The redox flow battery of claim 1 , wherein the viologen has formula (VI-b):

wherein:
R 13 is selected from the group consisting of —N(R g ) q , —S(O) q , —PO 3 , —S(O) q R g , —(OCH 2 CH 2 ) m —OCH 3 , and substituted aryl;
R 14 is selected from the group consisting of —CH 3 , —S(O) q , —PO 3 , —S(O) q R g , —(OCH 2 CH 2 ) m —OCH 3 , and substituted aryl;
R g , at each occurrence, is independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, heterocyclyl, aryl, heteroaryl, alkyl-N(R h ) q , alkyl-S(O) q , an oxygen protecting group, and a nitrogen protecting group;
R h , 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;
V, at each occurrence, is independently Na + , K + , Li + , NR i 4 + , F − , Cl − , Br − , I − , SO 4 2− , OH − , CO 3 2− , ClO 4 − , H 2 PO 4 − , HPO 4 2− , PO 4 3− , NO 3 − , N 3 − , CN − , N(CN) 2 − , SCN − or a combination thereof;
R i , at each occurrence, is independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, heterocyclyl, aryl, and heteroaryl;
q, at each occurrence, is independently 2 or 3;
r is 1, 2, 3 or 4;
u is 1, 2, 3 or 4; and
c, at each occurrence, is independently 0, 1, 2 or 3.

4. The redox flow battery of claim 3 , wherein:
R 13 is SO 3 − , —(OCH 2 CH 2 ) m —OCH 3 , or substituted aryl;
R 14 is SO 3 − , —(OCH 2 CH 2 ) m —OCH 3 , or substituted aryl;
V, at each occurrence, is independently Na + , K + , Cl − , Br − or a combination thereof;
r is 2, 3 or 4;
u is 1; and
c, at each occurrence, is independently 1, 2 or 3.

5. The redox flow battery of claim 1 , wherein the viologen is selected from the group consisting of

6. The redox flow battery of claim 1 , wherein the viologen has formula (VII):

or a salt thereof, wherein:
L 5 and L 6 are each independently selected from the group consisting of bond, C 1 -C 12 alkylenyl, C 1 -C 12 alkenylenyl, C 1 -C 12 alkynylenyl; and C 1 -C 4 alkylenyl-(OCH 2 CH 2 ) j ,
R 15 and R 16 are each independently selected from the group consisting of OR j , —C(O)OR j , —S(O) j , —PO 3 , —S(O) j R j , —S(O) j OR j , —OP(O)(OR j ) 2 , —(CR j 2 ) j CN, substituted aryl, and substituted heteroaryl;
R j , at each occurrence, is independently selected from the group consisting of alkyl-S(O) j , and an oxygen protecting group; and
j, at each occurrence, is independently 2 or 3.

7. The redox flow battery of claim 6 , wherein the viologen is selected from the group consisting of

or salts thereof.

8. The redox flow battery of claim 1 , 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 , quinines, anthraxquinines, K 4 [Fe(CN) 6 ], N 4 [Fe(CN) 6 ], (NH 4 ) 4 [Fe(CN) 6 ], V 5+4+ , (2,2,6,6-Tetramethylpiperidin-1-yl)oxyl (TEMPO), a derivative of TEMPO, or a combination thereof.

9. The redox flow battery of claim 8 , wherein the derivative of TEMPO has formula (VIII-a):

wherein:
R 19 , R 20 , R 21 , R 22 and R 23 are each independently selected from the group consisting of hydrogen, halogen, alkyl, cycloalkyl, heterocyclyl, aryl, heteroaryl, —CN, —NO 2 , —OR k , —SR k , -alkyl-N(R k ) w , —N(R k ) w , —C(O)R k , —C(O)OR k , —S(O) w R k , —S(O) w OR k , and —OP(O)(OR k ) 2 ;
R k , at each occurrence, is independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, heterocyclyl, aryl, heteroaryl, alkyl-N(R l ) w , an oxygen protecting group, and a nitrogen protecting group;
R l , 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;
X 2 − is Cl − , Br − , I − , SO 4 2− , —NO 3 − or a combination thereof;
n 2 is 1, 2, 3, 4, or 5; and
w, at each occurrence, is independently 2 or 3.

10. The redox flow battery of claim 8 , wherein the derivative of TEMPO has formula (VIII-b):

wherein:
R 24 , R 25 , R 26 , R 27 and R 28 are each independently selected from the group consisting of hydrogen, halogen, alkyl, c

Assignees

• Liu Tianbiao
• Hu Bo
• Debruler Camden
• Luo Jian
• Univ Utah State

Inventors

• Liu Tianbiao
• Hu Bo
• Debruler Camden
• Luo Jian

Classifications

• H01M8/04746

  Pressure; Flow · CPC title

• C07D213/22 Primary

  containing two or more pyridine rings directly linked together, e.g. bipyridyl · CPC title

• C07D211/94

  Oxygen atom, e.g. piperidine N-oxide · CPC title

• H01M8/04276

  Arrangements for managing the electrolyte stream, e.g. heat exchange · CPC title

• H01M8/188

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