Aqueous electrolyte, redox flow battery and use thereof

Patent metadata

Field	Value
Publication number	US-12261337-B2
Application number	US-201917297763-A
Country	US
Kind code	B2
Filing date	Nov 27, 2019
Priority date	Nov 29, 2018
Publication date	Mar 25, 2025
Grant date	Mar 25, 2025

Abstract

An aqueous electrolyte solution can comprise a redox-active compound, wherein the redox-active compound is a functionalized ferrocene containing solubility-facilitating groups attached to a cyclopentadienyl ring via spacers, the spacers having two to four carbon atoms.
The electrolyte solution may be used in redox flow batteries and is characterized by high stability of the redox active compound at elevated temperatures of 30° C. or above.

First claim

The invention claimed is:

1. An aqueous electrolyte solution comprising a redox-active compound with at least one redox-active residue of formula (I)
(X—C 5 H 4 )Fe(Y—C 5 H 3 —Z)  (I),

wherein X is a residue of formula —(C n H 2n )-FG or of formula —(C n H 2n )-Sp-(C n H 2n )-FG or of formula —(C n H 2n )-Brgp-,
Y is hydrogen or a residue of formula —(C n H 2n )-FG or of formula —(C n H 2n )-Sp-(C n H 2n )-FG,
Z is hydrogen or a covalent bond, which links the residue of formula (I) with a remainder of the compound,
FG is a functional group selected from —OH, —SH, —NO 3 , —NO 2 , —CN, —OR 1 , —SR 1 , —(O—CH 2 —CH 2 ) o —OR 2 , —(O—CH 2 —CH 2 ) o —NR 3 R 4 R 5 + (An m− ) 1/m , —COR 2 , —COO − (Kat m+ ) 1/m , —COOR 2 , —SO 3 − (Kat m+ ) 1/m , —SO 3 R 2 , —SO 4 − (Kat m+ ) 1/m , —SO 4 R 2 , —PO 4 2− (Kat m+ ) 2/m , —PO 4 (R 2 ) 2 , —PO 3 2− (Kat m+ ) 2/m , —PO 3 (R 2 ) 2 , —NR 3 R 4 R 5 + (An m− ) 1/m -N + R 3 R 4 —C t H 2t —SO 3 − or —NR 2 —SO 2 —R 3 ,
Brgp is a divalent bridging group which links the residue of formula (I) with the remainder of the compound,
Sp is —O—, —S—, —SO— or —SO 2 —,
R 1 is C 1 -C 4 alkyl,
R 2 is hydrogen or C 1 -C 4 alkyl,
R 3 , R 4 and R 5 independently of one another represent hydrogen or alkyl,
Kat is an m-valent inorganic or an organic cation,
An is an m-valent inorganic or an organic anion,
m is an integer between 1 and 4,
n represents an integer between 2 and 4,
t is an integer between 2 and 5, and
is an integer from 1 to 50,
and wherein the aqueous electrolyte solution has a temperature from 30° C. to 90° C.

2. The aqueous electrolyte solution according to claim 1 , wherein the aqueous electrolyte solution comprises at least one conducting salt.

3. The aqueous electrolyte solution according to claim 1 , wherein the aqueous electrolyte solution is contained in a redox flow battery and has a charge state of less than 90%.

4. The aqueous electrolyte solution according to claim 1 , wherein Y is hydrogen and m is 1 or 2.

5. The aqueous electrolyte solution according to claim 1 , wherein FG is a functional group selected from
(O—CH 2 —CH 2 ) o —OR 2 , —COR 2 , —COO − (Kat m+ ) 1/m ), —SO 3 − (Kat m+ ) 1/m , —SO 4 − (Kat m+ ) 1/m , —PO 4 2− (Kat m+ ) 2/m , —PO 3 2− (Kat m+ ) 2/m or —NR 3 R 4 R 5 + (An m− ) 1/m .

6. The aqueous electrolyte solution according to claim 1 , wherein Kat is selected from a hydrogen cation, an alkali metal cation, an alkaline earth metal cation, an ammonium cation, or a quaternary ammonium cation.

7. The aqueous electrolyte solution according to claim 1 , wherein An is selected from a halide ion, a hydroxide ion, a phosphate ion, a sulfate ion, a perchlorate ion, a hexafluorophosphate ion or a tetrafluoroborate ion.

8. The aqueous electrolyte solution according to claim 1 , wherein Z is a covalent bond which connects the at least one redox-active residue of the formula (I) to a polymer backbone selected from the group of polymethacrylates, polyacrylates, polystyrenes, polyalkylene glycols, polyalkylene imines or polyvinyl ethers, and wherein the polymer backbone includes 5 to 100 residues of the formula (I).

9. The aqueous electrolyte solution according to claim 1 , wherein the aqueous electrolyte solution comprises oligomers or polymers with recurring structural units of the formula (II) and optionally further structural units derived from solubility-facilitating comonomers

wherein
ME is a recurring structural unit derived from a polymerizable monomer,
BG is a covalent bond or a bridging group,
FC represents a residue of formula (X—C 5 H 4 )F (Y—C 5 H 3 —Z),
X, Y and Z have the meanings defined in claim 1 , and
r is an integer from 2 to 150.

10. The aqueous electrolyte solution according to claim 1 , wherein the redox-active compound is a compound of formula (II)
(X—C 5 H 4 )Fe(Y—C 5 H 4 )  (II),

wherein X and Y have the meaning defined in claim 1 .

11. The aqueous electrolyte solution according to claim 1 , wherein the redox-active compound is a compound of formula (III)
[(X—C 5 H 4 )Fe(Y—C 5 H 3 —)]—R 7 —[(—C 5 H 3 —Y)Fe(C 5 H 4 —X)] p   (III),

wherein X and Y have the meaning defined in claim 1 ,
R 7 is a two-to four-valent organic group, and
p represents an integer from 1 to 4.

12. The aqueous electrolyte solution according to claim 1 , wherein n is 2.

13. A redox flow battery for storing electrical energy comprising a reaction cell with two electrode chambers for a catholyte and an anolyte, which are each connected to at least one liquid reservoir, the two electrode chambers being separated by a membrane, being equipped with electrodes, and each being filled with electrolyte solutions which contain redox-active components in liquid form dissolved or dispersed in an aqueous electrolyte solvent, as well as, optionally comprising conducting salts dissolved therein, and wherein the redox flow battery is characterized in that the anolyte contains a water-soluble redox-active component and that the catholyte in the electrode chamber contains the aqueous electrolyte solution according to claim 1 .

14. The redox flow battery according to claim 13 , wherein the redox-active component of the anolyte contains a compound comprising one or more bipyridiyl groups.

15. The redox flow battery according to claim 13 , wherein the electrode chambers for catholyte and anolyte are separated by a semipermeable membrane impermeable to the redox couple in the catholyte, and the redox-active component of the anolyte contains a zinc salt.

16. A redox flow battery for storing electrical energy, comprising a reaction cell with an electrode chamber for an electrolyte solution, which is connected to at least one liquid reservoir, the electrode chamber being equipped with a cathode and an anode, and the electrode chamber being filled with the aqueous electrolyte solution of claim 1 , wherein the aqueous electrolyte solution further comprises a zinc salt as a further redox-active component.

17. The redox flow battery according to claim 13 , wherein the redox flow battery comprises a zinc solid anode with a redox pair zinc (II)/zinc (0).

18. The redox flow battery according to claim 13 , wherein a charge state of the catholyte or of the catholyte and the anolyte is less than 90%.

19. The redox flow battery according to claim 13 , wherein the redox flow battery is adapted for a storage of electrical energy for mobile and stationary applications, wherein the storage includes stationary storage for emergency power supply, for peak load balancing, or for intermediate storage of electrical energy from renewable energy sources.

20. The aqueous electrolyte solution of claim 1 , wherein the aqueous electrolyte solution has a temperature of at least 40° C.

21. A redox flow battery comprising the aqueous electrolyte solution according to claim 1 , wherein the redox-active compound is a compound of formula (II)
(X—C 5 H 4 )Fe(Y—C 5 H 4 )  (II),

wherein X and Y have the meaning defined in claim 1 .

Assignees

• Univ Jena Friedrich Schiller

Inventors

• Schubert Ulrich Sigmar

Classifications

• H01M2300/0005

  Acid electrolytes · CPC title

• H01M4/60

  of organic compounds · CPC title

• H01M4/38

  of elements or alloys · CPC title

• Y02E60/10

  Energy storage using batteries · CPC title

• Y02E60/50

  Fuel cells · CPC title