Flow batteries incorporating active materials containing doubly bridged aromatic groups

Patent metadata

Field	Value
Publication number	US-12062795-B2
Application number	US-202117147585-A
Country	US
Kind code	B2
Filing date	Jan 13, 2021
Priority date	Nov 23, 2016
Publication date	Aug 13, 2024
Grant date	Aug 13, 2024

Abstract

Electrolyte solutions for flow batteries and other electrochemical systems can contain an active material that is capable of transferring one or more electrons per molecule during an oxidation-reduction cycle. Doubly bridged aromatic groups or their coordination compounds can be particularly suitable active materials. Flow batteries can include a first half-cell containing a first electrolyte solution, and a second half-cell containing a second electrolyte solution, in which at least one of the first electrolyte solution and the second electrolyte solution contains an active material having at least two aromatic groups doubly bridged by a carbonyl moiety and a bridging moiety containing a bridging atom selected from carbon, nitrogen, oxygen, sulfur, selenium and tellurium. Such bridged compounds can directly function as the active material, or coordination compounds containing the bridged compounds as at least one ligand can serve as the active material.

First claim

What is claimed is:

1. A composition comprising a coordination compound of the following formula:
D g M(L 1 )(L 2 )(L 3 )
wherein:
M is a transition metal;
D is ammonium, tetraalkylammonium, or an alkali metal ion;
g is an integer in a range of from 0 to 6: and
L 1 , L 2 and L 3 are ligands, wherein at least one of L 1 , L 2 and L 3 is a bridged compound having a formula of Structure 1:

or a salt thereof, wherein:
Ary 1 is a substituted aromatic ring or a substituted heteroaromatic ring, wherein the aromatic or heteroaromatic ring of Ary 1 is substituted with one or more of an alkyl substituted with one or more of hydroxyl, carboxyl, or amine, C 2 -C 6 polyol; OR 3 ; SR 3 ; S(═O)R 3 ; S(═O) 2 R 3 ; NR 9 R 10 ; Ch 2 (OCH 2 CH 2 )xOCH 3 ; C(═O)R 4 ; and/or sulfonyl;
Ary 2 is an unsubstituted aromatic ring, an unsubstituted heteroaromatic ring, a substituted aromatic ring, or a substituted heteroaromatic ring, wherein when substituted, the aromatic or heteroaromatic ring of Ary 1 or Ary 2 is substituted with one or more of an alkyl substituted with one or more of hydroxyl, carboxyl, amine, or sulfonyl; C 2 -C 6 polyol; OR 3 ; SR 3 ; S(═O)R 3 ; S(═O) 2 R 3 ; NR 9 R 10 ; CH 2 (OCH 2 CH 2 )xOCH 3 ; C(═O)R 4 ; and/or sulfonyl; and
Z is CR 1 R 2 , NR 8 , or S(═O);
R 1 is H; unsubstituted or substituted alkyl; C 2 -C 6 polyol; OR 3 ; SR 3 ; S(═O)R 3 ; S(═O) 2 R 3 ; NR 9 R 10 ; CH 2 (OCH 2 CH 2 )xOCH 3 ; or C(═O)R 4 ;
R 2 is an alkyl substituted with one or more of hydroxyl, carboxyl, amine, or sulfonyl; C 2 -C 6 polyol; OR 3 ; SR 3 ; S(═O)R 3 ; S(═O) 2 R 3 ; NR 9 R 10 ; CH 2 (OCH 2 CH 2 )xOCH 3 ; or C(═O)R 4 ;
R 3 is H; an alkyl substituted with one or more of hydroxyl, carboxyl, amine, or sulfonyl; (CH 2 CH 2 O)xCH 3 ; C(═O)NR 5 R 6 ; or C(═O)R 7 ;
R 4 is R 5 , OR 5 , or NR 5 R 6 ;
R 5 and R 6 are, independently, H; an alkyl substituted with one or more of hydroxyl, carboxyl, amine, or sulfonyl; (CH 2 CH 2 O)xCH 3 ; or CH 2 (OCH 2 CH 2 CH 2 )xOCH 3 ;
R 7 is OH or an alkyl substituted with one or more of hydroxyl, carboxyl, amine, or sulfonyl;
R 8 is H; an alkyl substituted with one or more of hydroxyl, carboxyl, amine, or sulfonyl; (CH 2 CH 2 O)xCH 3 ; CH 2 (OCH 2 CH 2 )xOCH 3 ; C(═O)R 5 ; C(═O)OR 5 ; or C(═O)NR 5 R 6 ;
R 9 and R 10 are, independently, H; an alkyl substituted with one or more of hydroxyl, carboxyl, amine, or sulfonyl; (CH 2 CH 2 O)xCH 3 ; or CH 2 (OCH 2 CH 2 )xOCH 3 ; and
x is an integer ranging between 0 and 100.

2. The composition of claim 1 ,
wherein at least one of L 1 , L 2 and L 3 is a bridged compound having a formula of Structure 3:

wherein:
R 11 optionally substituted alkyl, alkenyl, alkynyl, aryl, aralkyl, heterocyclyl, or heteroaryl; C 2 -C 6 polyol; OR 3 ; SR 3 ; S(═O)R 3 ; S(═O) 2 R 3 ; NR 9 R 10 ; CH 2 (OCH 2 CH 2 )xOCH 3 ; C(═O)R 4 ; halogen; nitro; cyano; sulfonyl; or perfluoroalkyl;
R 12 is H; optionally substituted alkyl, alkenyl, alkynyl, aryl, aralkyl, heterocyclyl, or heteroaryl; C 2 -C 6 polyol; OR 3 ; SR 3 ; S(═O)R 3 ; S(═O) 2 R 3 ; NR 9 R 10 ; CH 2 (OCH 2 CH 2 )xOCH 3 ; C(═O)R 4 ; halogen; nitro; cyano; sulfonyl; or perfluoroalkyl;
and
n and mare integers, independently, ranging between 0 and 14.

3. The composition of claim 1 , wherein Z is NR 8 .

4. The composition of claim 1 , wherein Z is S(═O).

5. The composition of claim 1 , wherein Z is CR 1 R 2 .

6. The composition of claim 1 ,
wherein:
Ary 1 is a substituted phenyl, naphthyl, pyridinyl, pyrazinyl, pyrimidinyl, triazinyl, quinolinyl, isoquinolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, thiophenyl, benzothiophenyl, pyrrolyl, indolyl, isoindolyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, triazolyl, benzotriazolyl, oxazolyl, benzoxazolyl, isoxazolyl, benzisoxazolyl, thiazolyl, benzothiazolyl, isothiazolyl, benzisothiazolyl, furanyl, benzofuranyl, or isobenzofuranyl; and
Ary 2 is a substituted or unsubstituted benzene, naphthyl, pyridine, pyrazine, pyrimidine, triazine, quinolone, isoquinoline, phthalazine, quinazoline, quinoxaline, thiophene, benzothiophene, pyrrole, indole, isoindole, pyrazole, indazole, imidazole, benzimidazole, triazole, benzotriazole, oxazole, benzoxazole, isoxazole, benzisoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, furan, benzofuran, or isobenzofuran ring.

7. The composition of claim 1 , wherein the transition metal is Ti.

8. The composition of claim 1 , wherein at least two of L 1 , L 2 and L 3 is the bridged compound.

9. The composition of claim 1 , wherein L 1 , L 2 and L 3 are the bridged compound.

10. The composition of claim 1 , wherein at least one of L 1 , L 2 and L 3 is a catecholate ligand or a substituted catecholate ligand.

11. The composition of claim 1 , wherein two of L 1 , L 2 and L 3 is a catecholate ligand or a substituted catecholate ligand.

12. The composition of claim 1 , wherein at least one of L 1 , L 2 and L 3 is ascorbate, citrate, glycolate, a polyol, gluconate, hydroxyalkanoate, acetate, formate, benzoate, malate, maleate, phthalate, sarcosinate, salicylate, oxalate, urea, polyamine, aminophenolate, acetylacetonate, or lactate.

13. The composition of claim 12 , wherein the ligand L 1 , L 2 and L 3 is substituted with at least one C 1-6 alkoxy, C 1-6 alkyl, C 1-6 alkenyl, C 1-6 alkynyl, 5- or 6-membered aryl, 5- or 6-membered heteroaryl, boronic acid or a derivative thereof, carboxylic acid or a derivative thereof, cyano, halide, hydroxyl, nitro, sulfonate, sulfonic acid or a derivative thereof, phosphonate, phosphonic acid or a derivative thereof, or glycol.

14. The composition of claim 13 , wherein the glycol is polyethylene glycol.

15. The composition of claim 1 , further comprising an unbound form of the bridged compound.

16. The composition of claim 1 , further comprising an aqueous solution in which the coordination compound is disposed.

Assignees

• Lockheed Martin Energy Llc

Inventors

• Millard Matthew
• Norman Zachariah M

Classifications

• H01M8/20

  Indirect fuel cells, e.g. fuel cells with redox couple being irreversible (H01M8/18 takes precedence) · CPC title

• H01M8/188 Primary

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

• H01M8/04276

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

• C07F7/28

  Titanium compounds · CPC title

• Y02E60/50

  Fuel cells · CPC title