Non-aqueous redox flow batteries

Patent metadata

Field	Value
Publication number	US-2019319290-A1
Application number	US-201716315289-A
Country	US
Kind code	A1
Filing date	Jul 7, 2017
Priority date	Jul 8, 2016
Publication date	Oct 17, 2019
Grant date	—

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.

First claim

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(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 or a derivative thereof is selected from benzothiadiazoles having general formula (I):

in which R 1 , R 2 , R 3 and R 4 , 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, 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 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 tetrafluoroborate (TBABF 4 ), tetrabutylammonium tetrafluoroborate (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, 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.

Assignees

• Eni Spa

Inventors

• Tacca Alessandra
• Pellegrino Andrea

Classifications

• H01M2300/0025

  Organic electrolyte · CPC title

• H01M10/627

  Stationary installations, e.g. power plant buffering or backup power supplies · CPC title

• H01M2220/10

  Batteries in stationary systems, e.g. emergency power source in plant · CPC title

• H01M10/056

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

• H01M10/36

  Accumulators not provided for in groups H01M10/05-H01M10/34 · CPC title