Granted Patent B2

US 12,655,111 · App. 17/799,879 · Granted Jun 16, 2026

Inventors: Peter Geigle (Alzenau, DE); Jan Hartwig (Alzenau, DE); Eduard Baal (Offenbach, DE); Isabel Scheibel (Alzenau, DE); Evgeny Larionov (Hanau, DE); Olga Ekkert (Hanau, DE); Doris Neumann (Offenbach, DE); Christian Schneider (Aschaffenburg, DE)

Assignee: CMBlu Energy AG

C07D241/16H01M8/18H01M2300/0025

Abstract

Claims (117)

1 . A redox flow battery, comprising a first half cell comprising an electrolyte solution comprising a composition comprising at least one or at least two substituted phenazine compounds of Formula (I)(a) or Formula (I)(b)

wherein:

R 1 is positioned at ring position 7 or 8 and is —NHR x , —NR x R y , or —N(H)C(═O)R x , wherein Rx and Ry independently represent C 1 -C 4 alkyl optionally substituted with —CO 2 H, ═O, —SO 3 H, —OH, substituted or unsubstituted aryl, or —NH 2 ;

R 2 is —H, —OH, —SO 3 H, alkyl, or —CO 2 H;

R 3 is —H, —OH, —NHR x , —NR x R y , or —N(H)C(═O)R x

m is selected from any number of 0, 1, 2, and 3;

p is selected from any number of 0, 1, 2, 3, and 4;

or a salt thereof; and

a solvent, and, optionally, at least one further substituted low molecular weight aromatic redox active compound other than the substituted phenazine compounds of Formula (I)(a) or Formula (I)(b); and

a second half-cell comprising an electrolyte solution comprising a redox active species.

2 . The redox flow battery of claim 1 ,

wherein:

R 1 is —NR x R y or —N(H)C(═O)R x , and/or

R 2 is —OH, —SO 3 H, alkyl or —CO 2 H.

3 . The redox flow battery claim 1 , wherein:

The redox flow battery of

R 1 is —NR x R y .

4 . The redox flow battery of claim 1 , wherein:

R x and R y independently represent optionally substituted C 1 -C 3 alkyl.

5 . The redox flow battery of claim 1 , wherein:

R x and R y independently represent optionally substituted methyl or optionally substituted ethyl.

6 . The redox flow battery of claim 1 , wherein:

R 2 is —OH, —SO 3 H, methyl or —CO 2 H.

7 . The redox flow battery of claim 1 , wherein:

m is 0 or 1.

8 . The redox flow battery of claim 1 , wherein

p is 0, 1, 2 or 3.

9 . The redox flow battery of claim 1 , wherein

m is 0 or 1; and

p is 1, 2 or 3.

10 . The redox flow battery of claim 1 , wherein

p is 1 or 2; and

R 2 is positioned at positions 2 and/or 3.

11 . The redox flow battery of claim 1 , wherein

m is 0 or 1; and

when m is 1, R 3 is positioned at position 7 or position 8.

12 . The redox flow battery of claim 1 , wherein

m is 1 ;

R 3 is positioned at ring position 7 or 8;

p is 2; and

R 2 is positioned at ring positions 2 and 3.

13 . The redox flow battery of claim 1 , wherein

m is 0;

p is 2; and

R 2 is positioned at ring positions 2 and 3.

14 . The redox flow battery of claim 1 , wherein

R 2 is —SO 3 H.

15 . The redox flow battery of claim 1 , wherein

m is 1;

R 3 is —OH and is positioned at ring position 7 or 8.

16 . The redox flow battery of claim 1 , wherein

R 1 is —NHR x or —NR x R y ;

wherein R x and R y independently represent C 1 -C 4 alkyl optionally substituted with —CO 2 H, ═O, —SO 3 H, —OH, substituted or unsubstituted phenyl, or —NH 2 ;

p is 1 or 2 and R 2 is methyl, —SO 3 H or —CO 2 H;

m is 1; and

R 3 is positioned at position 7 or position 8, and is —NHR x or —NR x R y .

17 . The redox flow battery of claim 1 , wherein

R 1 is —NR x R y wherein

R x is substituted C 1 -C 4 alkyl; and

R y is unsubstituted C 1 -C 4 alkyl.

18 . The redox flow battery of claim 1 , wherein

R 1 is —NR x R y wherein

R x is substituted methyl or ethyl; and

R y is methyl.

19 . The redox flow battery of claim 1 , wherein

R 1 is —NR x R y wherein at least one of R x and R y is a substituted C 1 -C 4 alkyl, and wherein the substituent on the C 1 -C 4 alkyl is a terminal substituent.

20 . The redox flow battery substituted phenazine compound of claim 19 , wherein the C 1 -C 4 alkyl is substituted with —CO 2 H or —SO 3 H.

21 . The redox flow battery substituted phenazine compound of claim 1 , wherein

m is 1;

R 1 and R 3 are the same and are —NHR x , —NR x R y , or —N(H)C(═O)R x .

22 . The redox flow battery of claim 21 , wherein

R 1 is at position 7 and R 3 is at position 8; or

R 1 is at position 8 and R 3 is at position 7.

23 . The redox flow battery of claim 1 , wherein

R 1 is —N(H)C(═O)R x , wherein R x is ethyl substituted on the terminal carbon with —C(═O)OH or —SO 3 H.

24 . The redox flow battery of claim 1 , wherein

R 1 is —N(CH 3 )—CH 2 —C(═O)OH, —N(CH 3 )-(CH 2 ) 2 —C(═O)OH, —N(H)-(CH 2 ) 2 —C(═O) OH, —N(CH 3 )—CH 2 —SO 3 H, —N(CH 3 )-(CH 2 ) 2 —SO 3 H, —N(H)—CH 2 —aryl, —N(H)—CH 2 —CH 2 —aryl, —N(H)—CH 2 OH, —N(H)-(CH 2 ) 2 OH, —N(H)—CH 3 , —N(H)—C 2 H 5 , —N(H)C(═O)-(CH 2 ) 2 —CO 2 H, or —N(H)C(═O)-(CH 2 ) 2 —SO 3 H.

25 . The redox flow battery substituted phenazine compound of claim 1 , wherein R 2 is —SO 3 H, and R 2 is positioned at ring position 2 and/or 3.

26 . The redox flow battery of claim 1 , wherein R 3 is —H or —OH.

27 . The redox flow battery substituted phenazine compound of claim 26 , wherein R 3 is selected from —OH and positioned at ring position 7 or 8.

28 . The redox flow battery substituted phenazine compound of claim 1 , wherein p is 2, and R 2 is selected from —SO 3 H and methyl.

29 . The redox flow battery of claim 1 , wherein p is 0, m is 1, and R 1 and R 3 are identical.

30 . The redox flow battery of claim 1 , wherein said redox flow battery comprises at least one carbon-based electrode.

31 . The redox flow battery of claim 30 , wherein the redox flow battery comprises a carbon-based electrode other than carbon felt, carbon cloth and carbon paper.

32 . The redox flow battery of claim 1 , wherein the redox active species comprised by the second half-cell comprises a salt of Fe(CN) 6 3− , Fe(CN) 6 4− or a combination thereof.

33 . The redox flow battery of claim 1 , wherein the solvent comprises water and/or an organic water-miscible solvent.

34 . The redox flow battery of claim 1 , wherein the composition has a pH value of from 6 to 13.5.

35 . A substituted phenazine compound of Formula (I) (a) or Formula (I) (b)

wherein:

R 1 is positioned at ring position 7 or 8 and is —NHR x , —NR x R y , or —N(H)C(═O)R x ,

wherein R x and R y independently represent C 1 -C 4 alkyl optionally substituted with —CO 2 H, ═O, —SO 3 H, —OH, substituted or unsubstituted aryl, or —NH 2 ;

R 2 is —H, —OH, —SO 3 H, alkyl, or —CO 2 H;

R 3 is —H, —OH, —NHR x , —NR x R y , or —N(H)C(═O)R x

m is selected from any number of 0, 1, 2, and 3;

p is selected from any number of 0, 1, 2, 3, and 4;

or a salt thereof; and

wherein R 2 is —SO 3 H, and R 2 is positioned at ring position 2 and/or 3.

36 . A substituted phenazine compound of Formula (I) (a) or Formula (I) (b)

wherein:

R 1 is positioned at ring position 7 or 8 and is —NHR x , —NR x R y , or —N(H)C(═O)R x ,

wherein R x and R y independently represent C 1 -C 4 alkyl optionally substituted with —CO 2 H, ═O, —SO 3 H, —OH, substituted or unsubstituted aryl, or —NH 2 ;

R 2 is —H, —OH, —SO 3 H, alkyl, or —CO 2 H;

R 3 is —H, —OH, —NHR x , —NR x R y , or —N(H)C(═O)R x

m is selected from any number of 0, 1, 2, and 3;

p is selected from any number of 0, 1, 2, 3, and 4;

or a salt thereof; and

wherein R 3 is selected from —OH and positioned at ring position 7 or 8.

37 . A substituted phenazine compound of Formula (I) (a) or Formula (I) (b)

wherein:

R 1 is positioned at ring position 7 or 8 and is —NHR x , —NR x R y , or —N(H)C(═O)R x ,

wherein R x and R y independently represent C 1 -C 4 alkyl optionally substituted with —CO 2 H, ═O, —SO 3 H, —OH, substituted or unsubstituted aryl, or —NH 2 ;

R 2 is —H, —OH, —SO 3 H, alkyl, or —CO 2 H;

R 3 is —H,—OH, —NHR x , —NR x R y , or —N(H)C(═O)R x

m is selected from any number of 0, 1, 2, and 3;

p is selected from any number of 0, 1, 2, 3, and 4;

or a salt thereof; and

wherein p is 2, and R 2 is selected from —SO 3 H and methyl.

Assignments (1)

Priority Claims (1)

Continuity (1)

References Cited (239)