NON-AQUEOUS REDOX FLOW BATTERIES

• US 20190319290A1
• Filed: 07/07/2017
• Published: 10/17/2019
• Est. Priority Date: 07/08/2016
• Status: Active Grant

• Current Assignee: Eni SPA (Eni Petroleum Company Incorporated)
• Original Assignee: Eni SPA (Eni Petroleum Company Incorporated)
• Inventors: TACCA, Alessandra, PELLEGRINO, Andrea
• Granted Patent: US 10,804,558 B2
• Time in Patent Office: Days
• CPC Class Codes: H01M 10/056 characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
• CPC Class Codes: H01M 10/36 Accumulators not provided for in groups H01M10/05-H01M10/34
• CPC Class Codes: H01M 10/627 Stationary installations, e.g. power plant buffering or backup power supplies
• CPC Class Codes: H01M 2220/10 Batteries in stationary systems, e.g. emergency power source in plant
• CPC Class Codes: H01M 2300/0025 Organic electrolyte
• CPC Class Codes: H01M 2300/0028 characterised by the solvent
• CPC Class Codes: H01M 8/184 Regeneration by electrochemical means
• CPC Class Codes: H01M 8/188 by recharging of redox couples containing fluids; Redox flow type batteries
• CPC Class Codes: H01M 8/20 Indirect fuel cells, e.g. fuel cells with redox couple being irreversible H01M8/18 takes precedence
• CPC Class Codes: Y02E 60/50 Fuel cells

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. Said non-aqueous redox flow battery (RFB) may advantageously be used in devices which require a moderate to large power output (e.g., about 100 kW-100 MW) for a number of hours (i.e. >1 hour) such as, for example, devices for storing energy derived from industrial plants or from alternative energy sources (such as, solar or wind energy) for subsequent use (for example, for domestic use) or for sale.

Claims

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 or a derivative thereof 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(NCCH₃)₄—

CF₃SO₃], copper(II) trifluoromethanesulfonate [Cu(CF₃SO₃)₂], tetrakisacetonitrile copper(I) tetrafluoroborate [Cu(NCCH₃)₄—

BF₄], or mixtures thereof.

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

4. Non-aqueous redox flow battery (RFB) according to claim 3, in which in said general formula (I), R₁, R₂, R₃ and R₄, 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 tetrafluoroborate (LiBF₄), lithium hexafluorophosphate (LiPF₆), lithium perchlorate (LiClO₄), lithium methyltrifluoromethanesulfonate (LiCF₃SO₃), lithium bis(trifluoromethylsulfonyl)imide [Li(CF₃SO₂)₂N], tetraethylammonium tetrafluoroborate (TBABF₄), tetrabutylammonium tetrafluoroborate (TBABF₄), 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, 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, membranes based on polyvinyl fluorides.