Non-aqueous redox flow batteries

Patent metadata

Field	Value
Publication number	US-10804558-B2
Application number	US-201716315289-A
Country	US
Kind code	B2
Filing date	Jul 7, 2017
Priority date	Jul 8, 2016
Publication date	Oct 13, 2020
Grant date	Oct 13, 2020

Abstract

Non-aqueous redox flow battery (RFB) comprising: a positive compartment in which a positive electrode is positioned and in which a positive non-aqueous liquid electrolyte is caused to flow; a negative compartment in which a negative electrode is positioned and in which a negative non-aqueous liquid electrolyte is caused to flow; an ion-exchange membrane positioned between the positive compartment and the negative compartment in which: said positive non-aqueous liquid electrolyte comprises a solution of copper triflate or tetrafluoroborate complexes [Cu(I) or Cu(II)] in at least one organic solvent; said negative non-aqueous liquid electrolyte comprises a solution of at least one benzothiadiazole or a derivative thereof in at least one organic solvent.

First claim

The invention claimed is:

1. Non-aqueous redox flow battery (RFB) comprising:
a positive compartment in which a positive electrode is positioned and in which a positive non-aqueous liquid electrolyte is caused to flow;
a negative compartment in which a negative electrode is positioned and in which a negative non-aqueous liquid electrolyte is caused to flow;
an ion-exchange membrane positioned between the positive compartment and the negative compartment in which:
said positive non-aqueous liquid electrolyte comprises a solution of copper triflate or tetrafluoroborate complexes [Cu(I) or Cu(II)] in at least one organic solvent;
said negative non-aqueous liquid electrolyte comprises a solution of at least one benzothiadiazole in at least one organic solvent.

2. Non-aqueous redox flow battery (RFB) according to claim 1 , in which said copper triflate or tetrafluoroborate complexes [Cu(I) or Cu(II)] are selected from: tetrakisacetonitrile copper(I) triflate [Cu(NCCH 3 ) 4 .CF 3 SO 3 ], copper(II) trifluoromethanesulfonate [Cu(CF 3 SO 3 ) 2 ], tetrakisacetonitrile copper(I) tetrafluoroborate [Cu(NCCH 3 ) 4 .BF 4 ], or mixtures thereof.

3. Non-aqueous redox flow battery (RFB) according to claim 1 , in which said benzothiadiazole is selected from benzothiadiazoles having general formula (I):

in which R 1 , R 2 , R 3 and mutually identical or different, represent a hydrogen atom, or a halogen atom; or represent one of the following groups: —CN, —NO 2 , —COOH, —SO 3 H, —SH; or are selected from: linear or branched, saturated or unsaturated C 1 -C 10 alkyl groups, linear or branched, saturated or unsaturated C 1 -C 10 alkoxy groups, carboxylic: esters having general formula R′—COO—R″ in which R′ and R″, mutually identical or different, are selected from linear or branched, saturated or unsaturated C 1 -C 10 alkyl groups, sulfonic esters having general formula R′—OSO 2 —R″ in which R′ and R″ have the same meanings described above, thioesters having general formula R′—SO—R″ in which R′ and R″ have the same meanings described above, —(O—CH 2 —CH 2 ) n —OH groups in which n is an integer ranging from 1 to 4, —(O—CH(CH 3 )—CH 2 ) n —OH groups in which n is an integer ranging from 1 to 4, optionally substituted aryl groups, or optionally substituted heteroaryl groups.

4. Non-aqueous redox flow battery (RFB) according to claim 3 , in which in said general formula (I), R 1 , R 2 , R 3 and R 4 , mutually identical, represent a hydrogen atom.

5. Non-aqueous redox flow battery (RFB) according to claim 1 , in which said electrolytes comprise at least one supporting electrolyte selected from lithium tetrafluoroborate (LiBF 4 ), lithium hexafluorophosphate (LiPF 6 ), lithium perchlorate (LiClO 4 ), lithium methyltrifluoromethanesulfonate (LiCF 3 SO 3 ), lithium bis(trifluoromethylsulfonyl)imide [Li(CF 3 SO 2 ) 2 N], tetraethylammonium tetrafluorborate (TBABF 4 ), tetrabutylammonium tetrafluorborate (TBABF 4 ), or mixtures thereof.

6. Non-aqueous redox flow battery (RFB) according to claim 1 , in which said organic solvent is selected from acetonitrile, dimethylacetamide, diethyl carbonate, dimethyl carbonate, γ-butyrolactone (GBL), propylene carbonate (PC), ethylene carbonate (EC), N-methyl-2-pyrrolidone (NMP), fluoroethylene carbonate, N,N-dimethylacetamide, or mixtures thereof.

7. Non-aqueous redox flow battery (RFB) according to claim 1 , in which said ion-exchange membrane is selected from the following polymeric membranes:
anion-exchange membranes selected from: membranes based on a styrene-divinylbenzene copolymer or on a chloromethylstyrene-divinylbenzene copolymer containing amino groups, membranes based on poly(ether ether ketones), membranes based on a divinylbenzene-vinylpyridine copolymer containing a quaternary pyridine group; membranes based on an aromatic polysulfonic copolymer containing a chloromethyl group and amino groups, or membranes based on polytetrafluoroethylene (PTFE);
cation-exchange membranes selected from: membranes based on a fluoropolymer-copolymer based on tetrafluoroethylene sulfonate, membranes based on poly(ether ether ketones), membranes based on polysulfones, membranes based on polyethylene, membranes based on polypropylene, membranes based on ethylene-propylene copolymers, membranes based on polyimides, or membranes based on polyvinyl fluorides.

Assignees

• Eni Spa

Inventors

• Tacca Alessandra
• Pellegrino Andrea

Classifications

• Y02E60/50

  Fuel cells · CPC title

• H01M10/056

  characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes · CPC title

• H01M8/188 Primary

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

• H01M2300/0025

  Organic electrolyte · CPC title

• H01M8/20

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