Hybrid Flow Battery for Storing Electrical Energy and Use Thereof

Patent metadata

Field	Value
Publication number	US-2018331363-A1
Application number	US-201615777076-A
Country	US
Kind code	A1
Filing date	Nov 14, 2016
Priority date	Nov 18, 2015
Publication date	Nov 15, 2018
Grant date	—

Abstract

Disclosed is a redox flow battery which is of simple construction, inexpensive and long-lasting.
The redox flow battery for storing electrical energy comprises a reaction cell having two electrode chambers for catholyte and anolyte, which are each connected to at least one store for liquid and are separated by a semipermeable membrane that is impermeable for the redox pair in the catholyte, and which are equipped with electrodes, wherein the electrode chambers are each filled with electrolyte solutions comprising redox-active components in liquid state, dissolved or dispersed in an aqueous electrolyte solvent, and optionally conducting salts dissolved therein and optionally further additives.
The redox flow battery is characterized in that the anolyte comprises a zinc salt as redox-active component and that the catholyte comprises as a redox-active component a compound comprising at least one residue of formula I in the molecule

wherein
the line going off the 4-position in the structure of formula I represents a covalent bond connecting the structure of formula I with the remainder of the molecule, and
R 1 , R 2 , R 3 and R 4 independently of one another represent alkyl, cycloalkyl, aryl or aralkyl.

First claim

1 . Redox flow battery for storing of electrical energy comprising a reaction cell having two electrode chambers for catholyte and anolyte, which are each connected to at least one store for liquid and are separated by a semipermeable membrane that is impermeable for the redox pair in the catholyte, and which are equipped with electrodes, wherein the electrode chambers are each filled with electrolyte solutions comprising redox-active components in liquid state, dissolved or dispersed in an aqueous electrolyte solvent, as well as optionally conducting salts dissolved therein and optionally further additives, wherein the anolyte comprises zinc salt as redox-active component and wherein the catholyte comprises as a redox-active component a compound comprising at least one residue of formula I in the molecule

wherein
the line going off the 4-position in the structure of formula I represents a covalent bond connecting the structure of formula I with the remainder of the molecule, and
R 1 , R 2 , R 3 and R 4 independently of one another represent alkyl, cycloalkyl, aryl or aralkyl.

2 . The redox flow battery according to claim 1 , wherein the electrolyte comprises water or water and an organic solvent, in which additional compounds are dissolved.

3 . The redox flow battery according to claim 1 , wherein the redox-active component in the catholyte comprises one to six residues of formula I in the molecule.

4 . The redox flow battery according to claim 3 , wherein the redox-active component in the catholyte comprises one to three residues of formula I in the molecule.

5 . The redox flow battery according to claim 4 , wherein the redox-active component in the catholyte is a compound of formulae Ia, Ib, Ic, Id, Ie and/or If

wherein
R 1 , R 2 , R 3 and R 4 have the meaning defined in claim 1 ,
X is a q-valent inorganic or organic anion or a mixture of such anions,
q is an integer from 1 to 3,
o is an integer from 1 to 4,
u is an integer from 1 to 4,
R 8 is a two- to four-valent organic bridge group,
R 5 is hydrogen, alkyl, alkoxy, haloalkyl, cycloalkyl, aryl, aralkyl, heterocyclyl, halogen, hydroxy, amino, nitro or cyano, and
R 6 is an o-times, preferably a single positively charged monovalent organic residue, in particular a quaternary ammonium residue, a quaternary phosphonium residue, a ternary sulfonium residue, or an o-times, preferably a single positively charged monovalent heterocyclic residue,
R 9 is an m-times positively charged two-to four-valent organic residue, in particular a two-to four-valent quaternary ammonium residue, a two-to four-valent quaternary phosphonium residue, a two-to-three-valent ternary sulfonium residue or an m-times positively charged two to four-valent heterocyclic residue,
R 7 is an u-times, preferably a single negatively charged monovalent residue, in particular a carboxyl or sulfonic acid residue or an u-times, preferably a single negatively charged monovalent heterocyclic residue,
R 10 is an m-times negatively charged two-to-four-valent organic residue, in particular an alkylene residue substituted with one or two carboxyl groups or sulfonic acid groups, or a phenylene residue substituted with one or two carboxyl groups or sulfonic acid groups, or a two-valent heterocyclic residue substituted with one or two carboxyl groups or sulfonic acid groups,
Z is a q-valent inorganic or organic cation or a mixture of such cations,
f is an integer from 1 to 3,
l is a number with the value o/q or u/q,
m is an integer from 1 to 4, and
n is a number with the value m/q.

6 . The redox flow battery according to claim 5 , wherein the redox-active component in the catholyte is a compound of formulae Ia or Id.

7 . The redox flow battery according to claim 1 , wherein X is selected from the group consisting of halogenide ions, hydroxide ions, phosphate ions, sulfate ions, perchlorate ions, hexafluorophosphate ions or tetrafluoroborate ions and wherein Z is selected from the group consisting of hydrogen ions, alkali metal cations or earth alkaline metal cations, and of the substituted or unsubstituted ammonium cations.

8 . The redox flow battery according to claim 5 , wherein redox-active compounds are used, in which R 5 is hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -partial- or perfluoroalkyl, C 1 -C 6 -partial- or perchloroalkyl, C 1 -C 6 -fluorochloroalkyl, phenyl, benzyl, fluorine, chlorine, hydroxy, amino or nitro.

9 . The redox flow battery according to claim 5 , wherein redox-active compounds of formula Id are used, in which R 8 is alkylene, alkyltriyl, alkylquaternyl, alkyloxydiyl, alkyloxytriyl, alkyloxyquaternyl, arylene, aryltriyl, arylquaternyl, heterocyclylene, heterocyclyltriyl or heterocyclylquaternyl, very preferred C 2 -C 6 -alkylene, such as ethylene or propylene, or C 2 -C 6 -alkoxydiyl, such as 1.2-dioxyethylene or 1.3-dioxypropylene, or C 3 -C 6 -alkoxytriyl, such as a 1.2.3-propanetriol residue or a trimethylolpropane residue, or C 4 -C 6 -alkoxyquaternyl, such as a pentaerithritol residue, or phenylene, phenyltriyl or phenylquaternyl.

10 . The redox flow battery according to claim 1 , wherein this contains oligomers or polymers with the recurring structural units of formula II

wherein
R 1 , R 2 , R 3 and R 4 have the meaning defined in claim 1 ,
ME is a recurring structural unit derived from a polymerisable monomer,
BG is a covalent bond or a bridge group, and
r is an integer between 2 and 150.

11 . The redox flow battery according to claim 1 , wherein R 1 , R 2 , R 3 and R 4 are C 1 -C 6 -alkyl, and preferably ethyl or methyl.

12 . The redox flow battery according to claim 1 , wherein this contains a solid matter zinc anode with the redox couple zinc(II)/zinc(0).

13 . The redox flow battery according to claim 1 , wherein this contains a 2.2.6.6-tetramethylpiperidinyloxyl-based cathode with the redox couple 2.2.6.6-tetramethylpiperidinyl-N-oxoammonium/2.2.6.6-tetramethyl-piperidinyl-N-oxyl.

14 . The redox flow battery according to claim 1 , wherein the electrolyte contains a conducting salt which comprises anions selected from the group consisting of halogenide ions, hydroxide ions, phosphate ions, sulfate ions, perchlorate ions, hexafluorophosphate ions or tetrafluoro-borate ions, preferably a conducting salt composed of these anions and of cations selected from the group consisting of hydrogen ions, alkali metal cations or earth alkaline metal cations, as well as of substituted or unsubstituted ammonium cations.

15 . Use of the redox flow battery according to claim 1 for storage of electrical energy for stationary and mobile applications, preferably as stationary repository for emergency power supply, for peak load adjustment, and for the intermediate storage of electrical energy from replenishable energy sources, especially in the sector of photovoltaics and wind power or from gas-, coal-, biomass-, tidal- or marine-power plants, and for applications in the field of electromobility, as repository in land, air and water vehicles.

16 . The use of the redox flow battery according to claim 15 , wherein

Assignees

• Univ Jena Friedrich Schiller

Inventors

• Winsberg Jan
• Janoschka Tobias
• Schubert Ulrich Sigmar
• Häupler Bernhard
• Hager Martin

Classifications

• H01M2300/0005

  Acid electrolytes · CPC title

• H01M4/38

  of elements or alloys · CPC title

• H01M4/42

  Alloys based on zinc · CPC title

• H01M8/188

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

• H01M2250/20

  Fuel cells in motive systems, e.g. vehicle, ship, plane · CPC title