EP3888162A1 - Électrolyte aqueux, batterie a flux redox et leur utilisation - Google Patents

Électrolyte aqueux, batterie a flux redox et leur utilisation

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Publication number
EP3888162A1
EP3888162A1 EP19817133.2A EP19817133A EP3888162A1 EP 3888162 A1 EP3888162 A1 EP 3888162A1 EP 19817133 A EP19817133 A EP 19817133A EP 3888162 A1 EP3888162 A1 EP 3888162A1
Authority
EP
European Patent Office
Prior art keywords
redox
formula
electrolyte solution
aqueous electrolyte
active
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP19817133.2A
Other languages
German (de)
English (en)
Inventor
Ulrich Sigmar Schubert
Martin Hager
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Friedrich Schiller Universtaet Jena FSU
Original Assignee
Friedrich Schiller Universtaet Jena FSU
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Filing date
Publication date
Application filed by Friedrich Schiller Universtaet Jena FSU filed Critical Friedrich Schiller Universtaet Jena FSU
Publication of EP3888162A1 publication Critical patent/EP3888162A1/fr
Pending legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/42—Alloys based on zinc
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • H01M8/184—Regeneration by electrochemical means
    • H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the invention relates to an aqueous electrolyte and a redox flow battery containing this aqueous electrolyte.
  • Redox flow batteries also known as redox flow batteries (hereinafter also referred to as “RFB”), are used to store electrical energy based on electrochemical redox reactions.
  • a redox flow battery contains a chamber or two polarity-specific chambers (half cells) separated by a membrane, which are filled with a liquid and are fed by pumps from one or more separate tanks of any size.
  • the respective liquid contains water in which redox-active substances and an inorganic or organic salt (lead additive) are dissolved.
  • the main additive can itself be redox-active.
  • RFBs are particularly suitable as stationary energy storage devices for various performance and capacities
  • RFBs are electrochemical energy stores.
  • the substances required for setting the potential on the electrodes are liquid, dissolved or also in
  • Redox-active species appearing in particle form which are transferred to their respective other redox stage during charging or discharging in an electrochemical reactor.
  • electrolyte solutions catholyte, anolyte
  • Anode and cathode compartments are separated in the reactor by a semipermeable membrane, which usually shows a high selectivity for protons and / or which is a size exclusion membrane.
  • a semipermeable membrane which usually shows a high selectivity for protons and / or which is a size exclusion membrane.
  • RFB The amount of energy that can be stored in an RFB is directly proportional to the size of the storage tanks.
  • the power that can be extracted is a function of the size of the electrochemical reactor.
  • RFBs have a complex system technology that roughly corresponds to that of a fuel cell. Usual sizes of the individual reactors range from approximately 1 to 100 kW.
  • the reactors can be combined very easily in a modular manner, and the tank size can be adjusted almost as desired.
  • a wide variety of redox-active chemical compounds have already been proposed for use in rechargeable batteries or batteries, such as RFB.
  • RFBs are already known which contain 2, 2, 6, 6-tetrasubstituted 1-piperidinyloxy compounds as the catholyte.
  • Such RFB are also described, for example, in WO 2014/026728 A1, WO 2017/084749 A1 and WO 2017/025177 A1.
  • Further RFBs containing 2,2,6,6-tetrasubstituted 1-piperidinyloxy compounds in the electrolyte are disclosed in WO 2018/032003 A1 and US 2018/0072669 A1.
  • V-RFB vanadium RFB
  • V-RFBs are therefore limited in their application temperature or complex cooling is required. Special applications, e.g. As a replacement for diesel generators on Indian cell phone masts, V-RFBs are prevented in this way.
  • special HCI-containing electrolytes were developed, which are more temperature-stable and thus enable temperatures up to approx. 45 ° C, in exceptional cases even up to 60 ° C (see US 2012/0077067 A1). However, these electrolytes are extremely corrosive.
  • Other RFB systems have not yet been described at these comparatively high temperatures. In particular, RFBs that contain organic redox-active compounds have so far not been used at these high temperatures.
  • Electrolytes leads, which surprisingly have a high stability at elevated temperatures.
  • the use of these redox-active compounds or this combination of redox-active compounds with additives allows the production of aqueous electrolytes which are stable at elevated temperatures.
  • these electrolytes allow the production of RFB that can be operated at elevated temperatures. Higher temperatures of the electrolyte can occur when operating the RFB in environments with elevated temperatures,
  • the use of the electrolytes according to the invention makes RFBs with organic redox-active compounds accessible for “high-temperature” use. In this way, new fields of application for RFB can be opened up without the need for additional cooling.
  • the invention has for its object to provide an aqueous electrolyte containing selected redox-active organic compounds, which has sufficient stability for the operation of batteries or accumulators even at elevated temperatures.
  • Another object of the present invention is to provide a redox flow battery which can be operated at elevated temperatures without the electrolyte used experiencing any significant decomposition. This object is achieved by the provision of the aqueous electrolyte solution described in claim 1.
  • the present invention relates to an aqueous electrolyte solution with a
  • R 1, R 2 , R 3 and R 4 are alkyl or in each case R 1 and R 2 and R 3 and R 4 together with the common carbon atom form a cycloaliphatic or heterocyclic radical,
  • X means -O or -S
  • Y is -CH 2 -, -O-, -S-, -SO-, -SO2-, -NR 5 - or -N + R 5 R 6 - (An m ) i / m ,
  • R 5 , R ⁇ , R 6a and R 6b are independently monovalent organic radicals, preferably alkyl and in particular C 1 -C 4 -alkyl,
  • An m is an inorganic or organic anion, and m represents an integer between 1 and 4. It has been found that hydrochloric acid and / or selected salts have a temperature-stabilizing effect on compounds containing one or more radicals of the formula (Ia). These salts are ammonium salts with inorganic or organic anions, preferably with chloride or
  • Fluoride anions, salts with tetrafluoroborate anions or salts of trifluoromethanesulfonic acid are, in particular, ammonium cations or metal cations.
  • Hydrochloric acid or ammonium halides are preferably used.
  • the latter are generally quaternary ammonium halides, especially quaternary ammonium alkyl halides.
  • the alkyl groups have in particular 1-4 carbon atoms, which are preferably substituted with a hydroxyl group.
  • Quaternary ammonium chlorides or fluorides are particularly preferably used.
  • the salts with tetrafluoroborate anions or the salts of trifluoromethanesulfonic acid are preferably salts with
  • the redox-active compounds used in the electrolyte solution according to the invention can be low-molecular organic molecules
  • Act oligomers or polymers These molecules can be dissolved in the electrolyte solution or be dispersed or suspended as particles, for example as dispersions, microgels or as nanogels.
  • the redox-active compounds contain at least one radical of the formula (Ia), (Ib) or (Ic), which has a
  • the redox-active compounds used in the electrolyte solution according to the invention are preferably those which contain the remainder of the formula (Ia), (Ib), or (Ic) water soluble. However, they can also be compounds which are dispersible in water.
  • water solubility of a compound is understood to mean a solubility of at least 1 g of the compound in 1 l of water at 25 ° C.
  • oligomeric molecules are understood to mean compounds which have two to ten recurring structural units derived from monomers, each of which has a radical of the formula (Ia), (Ib) or (Ic).
  • the residues of the formula (Ia), (Ib) or (Ic) can also be attached to the oligomer structure via spacers.
  • polymeric molecules are to be understood as meaning compounds which have more than ten, preferably eleven to fifty, repeating structural units derived from monomers, each of which has a radical of the formula (Ia), (Ib) or (Ic).
  • the radicals of the formula (Ia), (Ib) or (Ic) can also be attached to the polymer structure via spacers.
  • the electrolyte solution according to the invention contains a redox-active component with one to six, preferably one to four, in particular one to three and very particularly preferably one to two radicals of the formula (Ia), (Ib) or (Ic) in the molecule.
  • redox-active compounds used in the electrolyte according to the invention containing at least one radical of the formula (Ia), (Ib) or (Ic) can vary within wide limits.
  • Redox-active compounds containing radicals of the formula (Ia), (Ib) or (Ic) are particularly preferably used, the molar masses of which are in the range from 150 to 80,000 g / mol, preferably in the range from 250 to 50,000 g / mol and very particularly preferably in Move range from 500 to 20,000 g / mol.
  • the viscosity of the electrolyte used according to the invention is typically in the range from 1 mPas to 10 3 mPas, particularly preferably 1 to 10 2 mPas and very particularly preferably 1 to 20 mPas (measured at 25 ° C. with a rotary viscometer, plate / plate).
  • the radicals R 1, R 2 , R 3 and R 4 are alkyl, preferably C 1 -C 4 -alkyl, particularly preferably methyl or ethyl and very particularly preferably methyl, or in each case R 1 and R 2 and R 3 and R 4 together with the common carbon atom form a cycloaliphatic or heterocyclic radical.
  • the cycloaliphatic radical is a cyclopentane or in particular one
  • the heterocyclic radical is a radical with five or in particular with six ring atoms or atomic groups, one of which is selected from the group -O-, -S-, -SO-, -S0 2 -, -NR 5 - or -N + R 5 R 6 - (An m ) i / m and the remaining ring atoms are carbon atoms.
  • R5 and R6 are monovalent organic radicals, such as alkyl, cycloalkyl, aryl, aralkyl or heterocyclyl.
  • An is an m-valent inorganic or organic anion and m is an integer between 1 and 4, preferably 1 or 2.
  • Preferred anions An are selected from the group of halide ions, hydroxide ions, phosphate ions, sulfate ions, perchlorate ions, hexafluorophosphate ions or tetrafluoroborate ions.
  • Residues of the formula (Ia) or (Ib), in which R 1 and R 2 and R 3 and R 4 together with the common carbon atom form a heterocyclic radical, are particularly preferred since they have an increased solubility in water compared to cycloaliphatic radicals.
  • This also applies to radicals of the formula (Ic) in which Y is -O-, -S-, -SO-, -S0 2 -, -NR 5 - or -N + R 5 R 6 - (An m ) 1 m is.
  • X represents -O or -S, preferably -O.
  • Q is preferably -O- or -S- and in particular -O- or -Q- is preferably a covalent bond.
  • the electrolyte solution according to the invention contains water or water and an organic solvent as well as the above-mentioned redox-active compound (s) and, if appropriate, further substances dissolved therein. These substances serve
  • Substances that are responsible for charge balance are called lead additives or salts, and substances that have a positive effect on stability or performance parameters are called auxiliary additives.
  • electrolyte solvents water or mixtures of water with alcohols (e.g. ethanol), carbonic acid esters (e.g. propylene carbonate), nitriles (e.g. acetonitrile), amides (e.g. dimethylformamide, dimethylacetamide), sulfoxides (e.g. dimethyl sulfoxide), ketones (e.g. acetone), lactones ( e.g. gamma-butyrolactone), lactams (e.g. A / methyl-2-pyrrolidone), nitro compounds (e.g. nitromethane), ethers (e.g. tetrahydrofuran), chlorinated hydrocarbons (e.g. dichloromethane),
  • alcohols e.g. ethanol
  • carbonic acid esters e.g. propylene carbonate
  • nitriles e.g. acetonitrile
  • amides e.g. dimethylformamide
  • Carboxylic acids e.g. formic acid, acetic acid
  • mineral acids e.g. sulfuric acid, hydrogen halide or halogen acid
  • the main additives are usually organic or inorganic salts or hydrochloric acid.
  • these are salts, the anions selected from the group consisting of halide ions (such as fluoride ion or chloride ion), hydroxide ions,
  • Anions of inorganic acids eg., Phosphate ion, sulfate ion, nitrate ion, Hexafluorophosphationen, tetrafluoroborate, perchlorate ions, chlorate ions, Hexafluoroantimonationen, Hexafluoroarsenationen, cyanide ions
  • anions of organic acids eg acetate, formate, Trifluoroessigklaklareionen, trifluoromethanesulfonate, Pentafluorethansulfonationen, Nonafluorbutansulfonat- ion, Butyrationen, Citrations, fumarations, glutarations, lactations,
  • Chloride and fluoride ions, hydroxide ions, phosphate ions, sulfate ions, perchlorate ions, hexafluorophosphate ions and tetrafluoroborate ions are particularly preferred; as well as cations selected from the group of hydrogen ions (H + ), alkali or alkaline earth metal cations (e.g. lithium, sodium, potassium, magnesium, calcium), zinc, iron, and substituted or unsubstituted ammonium cations (e.g.
  • Hydrogen ions
  • Lithium ions, sodium ions, potassium ions, tetrabutylammonium ions and mixtures thereof are particularly preferred.
  • the conductive salts NaCI, KCl, LiPF 6 , LiBF 4 , NaBF 4 , NaPF 6 , NaCI0 4 , NaOH, KOH, Na 3 P0 4 , K 3 P0 4 , Na 2 S0 4 , NaS0 3 CF 3 , LiS0 3 CF 3 , (CH 3 ) 4 NOH, n-Bu 4 NOH, (CH 3 ) 4 NCI, n-Bu 4 NCI, (CH 3 ) 4 NBr, n-Bu 4 NBr, n- Bu 4 NPF 6 , n- Bu 4 NBF , n-Bu 4 NCI0 , NH 4 CI and their mixtures where n-Bu stands for the n-butyl group
  • Particularly preferred electrolyte solutions according to the invention contain a
  • Lead additive the anions selected from the group of halide ions,
  • phosphate ions or tetrafluoroborate ions in particular a lead additive composed of these anions and cations selected from the group of Hydrogen ions, alkali or alkaline earth metal cations, and the substituted or unsubstituted ammonium cations.
  • auxiliary additives are surfactants, viscosity modifiers, pesticides, buffers, stabilizers, catalysts, lead additives, antifreeze, temperature
  • Surfactants can be nonionic, anionic, cationic or amphoteric.
  • Nonionic surfactants e.g. polyalkylene glycol ethers, fatty alcohol propoxylates, alkyl glucosides, alkyl polyglucosides, octylphenol ethoxylates,
  • Nonylphenol ethoxylates Nonylphenol ethoxylates, saponins, phospholipids.
  • buffers are carbonic acid bicarbonate buffer, carbonic acid silicate buffer, acetic acid acetate buffer, phosphate buffer, ammonia buffer, citric acid or citrate buffer, tris (hydroxymethyl) aminomethane, 4- (2-hydroxyethyl) -1 - piperazinethanesulfonic acid , 4- (2-hydroxyethyl) piperazin-1-propanesulfonic acid, 2- (N-morpholino) ethanesulfonic acid, barbital acetate buffer).
  • the electrolyte solutions according to the invention have an elevated temperature. These can occur when using the electrolyte solution in certain areas of the battery or the accumulator, for example only in the electrode chambers during charging and / or discharging processes and / or when storing the electrolyte solution in external memories.
  • aqueous electrolyte solutions that contain at least one
  • Aqueous electrolyte solutions containing at least one conductive salt are particularly preferred, in particular those salts which are contained in highly concentrated salt solutions (sols).
  • aqueous electrolyte solutions according to the invention between 14% by weight up to the saturation limit.
  • Saturated salt solutions are often used, with some of the salts being in a precipitated form.
  • the state of charge is a characteristic value for the state of charge of the electrolyte solution or a battery containing this electrolyte solution.
  • the value for the state of charge indicates the still available capacity of an electrolyte solution or a battery in relation to the nominal value.
  • the state of charge is given as a percentage of the fully charged state.
  • the state of charge can be determined, for example, by the open circuit voltage (VOC).
  • VOC open circuit voltage
  • the open circuit voltage depends on the state of charge; this increases with increasing state of charge.
  • the cell voltage is "open
  • Circuit measured, i.e. it is the cell voltage that results for a given state of charge without an external load.
  • Particularly preferred aqueous electrolyte solutions contain a compound having at least one redox-active radical of the formula (Ia), (Ib) or (Ic) which is covalently linked to a polymer backbone which is selected from the group of Polymethacrylates, polyacrylates, polystyrenes, polyalkylene glycols, polyalkyleneimines or the polyvinyl ether, the polymer backbone preferably 5 to 100
  • Very particularly preferred aqueous electrolyte solutions contain oligomers or polymers containing the recurring structural units of the formula (II) and, if appropriate, further structural units derived from solubilizing comonomers
  • BG is a covalent bond or a bridging group
  • Pip represents a piperidinyl radical of the formula (Ia), (Ib) or (Ic), and
  • r is an integer from 2 to 150, preferably from 2 to 80 and very particularly preferably from 8 to 40.
  • the repeating units ME and BG form the backbone of the oligomer or polymer, which contains several units of the redox-active unit of the formula (Ia), (Ib) or (Ic) defined above.
  • classes of substances which can form the backbone of the oligomer or polymer are polymers derived from ethylenically unsaturated carboxylic acids or their esters or amides, such as polymethacrylate, polyacrylate, polymethacrylamide or polyacrylamide, polymers derived from ethylenically unsaturated aryl compounds, such as polystyrene, from vinyl esters polymers derived from saturated carboxylic acids or their derivatives, such as polyvinyl acetate or polyvinyl alcohol, of
  • Polymers derived from olefins or bi- or polycyclic olefins such as poly- ethylene, polypropylene or polynorbornene, polyimides derived from imide-forming tetracarboxylic acids and diamines, from naturally occurring polymers such as their chemically modified derivatives, such as polymers such as cellulose or cellulose ethers, and polyurethanes, polyvinyl ethers, polythiophenes, polyacetylene, polyalkylene glycols and their derivatives, and the like thereof Ethers, for example
  • polyethyleneimines or N, N, N ' , N ' -tetramethyl-polyethyleneimines are examples of combinations of the structural units ME and the bridge groups BG for some of the substance classes mentioned above. It refers to
  • Substance classes which are particularly preferred and which form the backbone of the oligomer or polymer are polymethacrylates, polyacrylates, polymethacrylamides, polyacrylamides, polystyrene, polyethyleneimines and polyvinyl ethers.
  • the redox-active units of the formulas (la), (Ib) or (Ic) are covalently linked to the polymer backbone.
  • the polymers containing redox-active components can be in the form of linear polymers or they can be comb and star polymers, dendrimers, conductor polymers, ring-shaped polymers, polycatenanes and polyrotaxanes.
  • Comb and star polymers, dendrimers, ladder polymers, ring-shaped polymers, polycatenanes and polyrotaxanes are preferably used. These types are characterized by increased solubility and the viscosity of the solutions obtained is generally lower than that of corresponding linear polymers.
  • the solubility of the polymers containing redox-active components used according to the invention can furthermore be determined by co-polymerization or functionalization tion, eg with polyethylene glycol, polymethacrylic acid, polyacrylic acid or polystyrene sulfonate, can be improved.
  • Preferred solubilizing comonomers are vinyl acetate, methyl vinyl ether, methacrylic acid, acrylic acid, alkyl methacrylate, ethyl acrylate,
  • Methacrylic acid amide acrylic acid amide, vinyl sulfonate, vinyl phosphonic acid or styrene sulfonate.
  • redox-active compounds used according to the invention can be prepared by customary processes. Oligomers and polymers can be produced using the usual polymerization processes. Examples of this are polymerization in bulk, polymerization in solution or emulsion or suspension polymerization. These procedures are known to the person skilled in the art.
  • Low molecular weight compounds containing one or more radicals of the formula (Ia), (Ib) or (Ic) typically have the following structure
  • Pip-R 7 - (Pip) n where Pip is a piperidinyl radical of the formula (Ia), (Ib) or (Ic),
  • n an integer from 0 to 5, preferably from 0 to 3
  • R 7 represents a one- to six-bonded organic radical.
  • Preferred aqueous electrolyte solutions contain a redox-active compound of the formula (purple) or (IIIb)
  • Ri, R 2 , R3 and R4 have the meaning defined above, o is an integer from 1 to 3,
  • R g is a two- to four-bond organic residue.
  • Particularly preferred aqueous electrolyte solutions contain a redox-active compound of the formula (IV), (V), (VI), (VII) or (VIII)
  • Ri, R 2 , R 3 , R 4 , Rg, X, Y, Q, ME, BG, r and o have the meaning defined above, and
  • p is 0 or 1.
  • Very particularly preferred aqueous electrolyte solutions contain a redox-active compound of the formula (purple), in which
  • Re is a group of the formula -0- (C s Fl2s) -FG or -S- (C s H 2s ) -FG,
  • s is an integer from 2 to 4, in particular is 2,
  • FG is a functional group selected from -OH, -SH, -N0 3 , -NO 2 , - CN, -OR 14 ,
  • R 14 C 1 -C 4 alkyl, preferably methyl
  • R15 is hydrogen or C1-C4 alkyl, preferably hydrogen or methyl, and in particular hydrogen,
  • R16, R17 and Ria independently of one another are hydrogen or alkyl, preferably C1-C4 alkyl, and in particular methyl, ethyl, propyl or butyl, cat is a q-valent cation,
  • q represents an integer between 1 and 4,
  • t is an integer between 2 and 5
  • o is an integer from 1 to 50, preferably from 3 to 20.
  • Preferred cations Kat are hydrogen cations, alkali metal cations, alkaline earth metal cations or ammonium cations, in particular hydrogen cations, sodium, potassium, magnesium or calcium cations, or quaternary ammonium cations.
  • Preferred anions An are selected from the group of halide ions, hydroxide ions, phosphate ions, sulfate ions, perchlorate ions, hexafluorophosphate ions or tetrafluoroborate ions.
  • Very particularly preferred aqueous electrolyte solutions contain a redox-active compound containing one or more radicals of the formula (Ia) and one
  • stabilizing additive selected from the group of quaternary Ammonium alkyl halides, especially the quaternary ammonium alkyl chlorides or fluorides, or the alkali metal, alkaline earth metal or ammonium, in particular the sodium, potassium, magnesium, calcium or quaternary ammonium tetrafluoroborates or trifluoromethanesulfonates
  • radicals denotes a monovalent organic radical, it can be alkyl, cycloalkyl, aryl, aralkyl or heterocyclyl, which are linked to the rest of the molecule via a covalent bond. These radicals can be substituted with one or more, in particular with one or two,
  • one of the radicals is a two- to six-bonded organic radical, this can be alkyl, cycloalkyl, aryl, aralkyl or heterocyclyl which are connected to the rest of the molecule via two to six covalent bonds.
  • These radicals can be substituted with one or more, in particular with one or two, for example with hydroxy, amino, carboxyl, sulfonyl,
  • Carboxylic acid ester carboxylic acid amide, sulfonic acid ester, sulfonic acid amide or halogen.
  • Preferred monovalent organic radicals R7 or Re are Ci-C4-alkyl, in particular methyl, ethyl, propyl or 2-hydroxyethyl, Ci-C4-alkoxy, in particular methoxy, ethoxy or propoxy, mono-, di-, tri- or qateralkylamino with Ci -C 4 -alkyl radicals, especially with methyl, ethyl or propyl, poly (ethyleneoxy), cyclohexyl, phenyl, phenoxy or benzyl.
  • anions are for the
  • Rg as a two- to four-bonded organic group is to be understood as an organic radical which is connected to the rest of the molecule via two, three or four covalent bonds.
  • divalent organic radicals are alkylene, alkyleneoxy, poly (alkyleneoxy), alkyleneamino, poly (alkyleneamino), cycloalkylene, arylene, aralkylene or heterocyclylene.
  • Alkylene groups can be either branched or unbranched.
  • An alkylene group typically contains one to twenty carbon atoms, preferably two to four carbon atoms. Examples of alkylene groups are: methylene, ethylene, propylene and butylene.
  • Alkylene groups can optionally be substituted, for example with carboxyl or sulfonic acid groups, with carboxyl ester or sulfonic acid ester groups, with carboxylamide or sulfonic acid amide groups, with hydroxyl or amino groups or with halogen atoms.
  • Alkyleneoxy and poly (alkyleneoxy) groups can contain both branched and unbranched alkylene groups.
  • An alkylene group occurring in an alkyleneoxy or in a poly (alkyleneoxy) group typically contains two to four carbon atoms, preferably two or three carbon atoms.
  • the number of repeating units in the poly (alkyleneoxy) groups can vary widely. Typical numbers of repeat units range from 2 to 50.
  • Examples of alkyleneoxy groups are: ethyleneoxy, propyleneoxy and butyleneoxy.
  • Examples of poly (alkyleneoxy) groups are: poly (ethyleneoxy),
  • Alkylenamino and poly (alkylenamino) groups can contain both branched and unbranched alkylene groups.
  • An alkylene group occurring in an alkylene amino or in a poly (alkylene amino) group typically contains two to four carbon atoms, preferably two or three carbon atoms.
  • the number of repeating units in the poly (alkylenamino) groups can vary widely. Typical numbers of repeating units are in the range from 2 to 50.
  • alkylene amino groups are: ethylene amino, propylene amino and butylene amino.
  • poly (alkylene amino) groups are: poly (ethylene amino), poly (propylene amino) and poly (butylene amino).
  • Cycloalkylene groups typically contain five, six or seven ring carbon atoms, which can each be independently substituted. Examples of substituents are alkyl groups or two alkyl groups which, together with the ring carbons to which they are attached, can form a further ring. An example of a cycloalkylene group is cyclohexylene. Cycloalkylene groups can optionally be substituted, for example with carboxyl or
  • Carboxylamide or sulfonamide groups with hydroxyl or amino groups or with halogen atoms.
  • Arylene groups are typically cyclic aromatic groups containing five to fourteen carbon atoms, each independently
  • arylene groups are o-phenylene, m-phenylene, p-phenyl, o-biphenylyl, m-biphenylyl, p-biphenylyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1- Phenantolyl, 2-phenantolyl, 3-phenantolyl, 4-phenantolyl or 9-phenantolyl.
  • Arylene groups can optionally be substituted, for example with carboxyl or sulfonic acid groups, with carboxyl ester or sulfonic acid ester groups, with carboxylamide or sulfonic acid amide groups, with hydroxyl or amino groups or with halogen atoms.
  • substituents are alkyl groups or two alkyl groups which, together with the ring carbon atoms to which they are attached, can form a further ring.
  • Heterocyclylene groups are typically cyclic groups with four to ten ring carbon atoms and at least one ring heteroatom, which can each be independently substituted.
  • heteroatoms are oxygen, nitrogen, phosphorus, boron, selenium or sulfur.
  • Heterocyclylene groups are furandiyl, thiophendiyl, pyrroldiyl or imidazole diyl. Heterocyclylene groups are preferably aromatic. Heterocyclyl groups can optionally be substituted, for example with carboxyl or sulfonic acid groups, with carboxyl ester or sulfonic acid ester groups, with carboxylamide or sulfonic acid amide groups, with hydroxyl or amino groups or with halogen atoms. Further examples of substituents are alkyl groups or two alkyl groups which, together with the ring carbons to which they are attached, can form a further ring.
  • Aralkylene groups are typically aryl groups to which one or two alkyl groups are covalently attached. Aralkyl groups can be covalently linked to the rest of the molecule via their aryl radical and their alkyl radical or via two alkyl radicals.
  • the aralkylene group can, for example, on the aromatic ring
  • Alkyl groups or substituted with halogen atoms are Alkyl groups or substituted with halogen atoms.
  • aralkylene groups are benzylene or dimethylphenylene (xylylene).
  • R g examples of R g as a three-membered organic radical are alkyltriyl, alkoxytriyl, tris-poly (alkyleneoxy), tris-poly (alkylenamino), cycloalkyltriyl, aryltriyl, aralkyltriyl or heterocyclyltriyl. These residues correspond to the double-bonded residues already described in detail above, with the difference that these are linked to the rest of the molecule by three covalent bonds instead of two covalent bonds.
  • Rg examples of Rg as a four-bonded organic radical are alkylquaternyl, alkoxyquaternyl, quater-poly (alkyleneoxy), quater-poly (alkylenamino), cycloalkylquaternyl, arylquaternyl, aralkylquaternyl or heterocyclylquaternyl.
  • alkylquaternyl alkoxyquaternyl, quater-poly (alkyleneoxy), quater-poly (alkylenamino), cycloalkylquaternyl, arylquaternyl, aralkylquaternyl or heterocyclylquaternyl.
  • the invention relates to a first type of redox flow battery for storing electrical energy, comprising a reaction cell with two electrode chambers for catholyte and anolyte, each of which is connected to at least one liquid store, the electrode chambers being separated by a membrane, are equipped with electrodes and are each filled with electrolyte solutions that contain redox-active components in liquid form, dissolved or dispersed in an aqueous electrolyte solvent, and, if appropriate, conductive salts dissolved therein and possibly other additives.
  • This 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 an aqueous electrolyte solution as defined above.
  • the electrolyte solutions in the electrode chambers can be treated with paraffin oil
  • Preferred redox flow batteries of this first type also contain an aqueous electrolyte solution according to the definition given above in the liquid store (s).
  • Redox flow batteries of this first type are preferred, in which the anolyte contains a compound containing one or more bipyridiyl groups in the molecule
  • the lines extending from the nitrogen atoms in the structures of the formulas IX and X represent covalent bonds which connect the structures of the formulas IX and X to the rest of the molecule
  • Rio and Rn independently of one another denote alkyl, alkoxy, haloalkyl, cycloalkyl, aryl, aralkyl, heterocyclyl, halogen, hydroxy, amino, nitro or cyano,
  • b and c are independently integers from 0 to 4, preferably 0, 1 or 2, in particular 0,
  • q is an integer from 1 to 4, and
  • a is a number with the value 2 / q.
  • the compounds containing one or more bipyridiyl groups in the molecule as a redox-active component can be low-molecular organic molecules, oligomers or polymers. These preferably contain
  • the redox-active compounds containing the radical of the formula (IX) or of the formula (X) are preferably water-soluble. However, they can also be compounds which are dispersible in water.
  • anions An q are halide ions (fluoride ion, chloride ion, bromide ion, iodide ion), hydroxide ions, anions of inorganic acids (e.g. phosphate ions, sulfate ions, nitrate ions, hexafluorophosphate ions, tetrafluoroborate ions,
  • Perchlorate ions chlorate ions, hexafluoroantimonate ions, hexafluoroarsenate ions, cyanide ions
  • anions of organic acids e.g. acetate ions, formate ions, trifluoroacetic acid ions, trifluoromethane sulfonate ions, pentafluoroethane sulfonate ions, nonafluorobutane sulfonate ions, butyrate ions, citrate ions, fumarate ions
  • Preferred anions An q are chloride and fluoride ions, hydroxide ions,
  • Redox-active components used with preference in the anolyte are compounds of the formulas IXa or Xa
  • R12 and R13 independently of one another are hydrogen, alkyl which is optionally substituted by a carboxylic acid ester, carboxamide, carboxylic acid, sulfonic acid or amino group, for example a 2-trialkylammonium ethyl group, optionally substituted with a carboxylic acid ester, carboxylic acid amide, carboxylic acid, sulfonic acid or amino group, cycloalkyl, optionally substituted with a carboxylic acid ester, carboxylic acid amide, carboxylic acid, sulfonic acid or amino group or optionally with a carboxylic acid ester, carboxylic acid amide, carboxylic acid - mean sulfonic or amino group substituted aralkyl, especially -C 6 alkyl, substituted with a Carbonklareesteromia Ci-Ce-alkyl, with a carboxylic acid amide group substituted Ci-C 6 alkyl, substituted with a carboxylic acid group -C 6 al
  • RI 4 and R15 independently of one another are hydrogen, optionally substituted alkyl with a carboxylic acid ester, carboxylic acid amide, carboxylic acid, sulfonic acid or amino group, for example a 2-trialkylammonium ethyl group, optionally with a carboxylic acid ester, carboxylic acid amide, carboxylic acid, sulfonic acid or Amino group substituted cycloalkyl, aryl optionally substituted with a carboxylic acid ester, carboxylic acid amide, carboxylic acid, sulfonic acid or amino group or aralkyl optionally substituted with a carboxylic acid ester, carboxylic acid amide, carboxylic acid, sulfonic acid or amino group or two radicals R 12 and R 13 together form a CrC ß alkylene group, in particular Ci-C 6 alkyl, Ci-C 6 alkyl substituted with a carboxylic acid ester group, Ci-C 6 alkyl substitute
  • Examples of particularly preferably used compounds are N, N ' -Di-Ci-C 4 - alkylbipyridyl cations with any anions for charge balancing, for example N, N ' -Dimethylbipyridylhalogenide, such as N, N ' -Di-methylbipyridylchloride.
  • Preferred redox flow batteries of the first type contain as the anolyte an aqueous electrolyte solution, which is preferably covered with paraffin oil, with a temperature of at least 30 ° C, preferably from 30 to 90 ° C, and in particular from 30 to 50 ° C, the contains a redox-active compound containing at least one radical of the formula (IXa) or of the formula (Xa).
  • the invention also relates to a second type of redox flow battery for storing electrical energy containing one
  • Reaction cell with an electrode chamber for an electrolyte solution, which is connected to at least one liquid store, the
  • Electrode chamber is equipped with a cathode and an anode, and is filled with electrolyte solution containing redox-active components in liquid form, dissolved or dispersed in an aqueous electrolyte solvent, and
  • This redox flow battery is characterized in that the electrolyte solution contains an aqueous electrolyte solution according to the definition given above and zinc salt as a further redox-active component.
  • Redox flow batteries of this second type are distinguished by the fact that they only have to have a liquid reservoir and that no membrane has to be used to separate the reaction cell in the anode and cathode compartments.
  • Preferred redox flow batteries of this second type also contain
  • Liquid storage is an aqueous electrolytic solution as defined above.
  • Redox flow batteries of this second type are preferred, in which a zinc solid anode with the redox pair zinc (II) / zinc (0) is used.
  • Examples of zinc salts for the redox flow batteries of the first and second type are zinc chloride, zinc fluoride, zinc bromide, zinc iodide, zinc nitrate, zinc nitrite, zinc hydrogen carbonate, zinc sulfate, zinc perchlorate, zinc tetrafluoroborate and zinc hexafluorophosphate.
  • zinc salts with inorganic anions zinc salts with organic anions can also be used, for example zinc acetate, zinc oxalate or zinc formate.
  • Electrons are absorbed.
  • the active material zinc is found in the battery in both dissolved and solid form.
  • the zinc solid anode can be present permanently as a metallic electrode or can only be formed in situ during the charging process of the battery on an electrically conductive surface within the chamber by the reduction of zinc cations.
  • the zinc cations can function mainly as an active material, but also secondarily as a lead additive or as part of a lead additive mixture.
  • the anode can consist of any electrically conductive material, preferably metal, in particular zinc or zinc alloys.
  • metallic zinc is deposited on the electrode surface. In reverse In the case, metallic zinc passes from the electrode surface through the release of two electrons into zinc ions, which accumulate in the anolyte.
  • Particularly preferred redox flow batteries according to the invention have a zinc solid anode with the redox pair zinc (II) / zinc (0).
  • the advantage over the fully organic redox flow batteries described is the reduction in production costs.
  • the zinc anode is much more cost-effective to produce than known organic anodes.
  • the redox couple zinc (II)) / zinc (0) is characterized by very good stability against external environmental influences, such as sensitivity to
  • Zinc also has a very high overvoltage in aqueous media and thus enables an extremely high potential window.
  • the potential window is
  • battery is used in its broadest sense in the context of this description. This can be a single rechargeable act electrochemical cell or a combination of several such electrochemical cells.
  • Particularly preferred redox flow batteries of the present invention have a charge state of the catholyte or of the catholyte and of the anolyte of less than 90%, in particular of up to 80% and very particularly preferably of 70 to 80%.
  • These redox flow batteries are characterized by a particularly good temperature stability of the electrolyte and in particular the above be
  • Catholyte and the anolyte in the RFB according to the invention also be 100%.
  • the redox flow battery according to the invention can also contain further elements or components customary for such cells.
  • redox-active components are used in the chamber (s), which are present in the chamber (s) in dissolved, liquid or dispersed form.
  • the redox potential of the redox-active component can be, for example, by means of
  • Cyclic voltammetry can be determined. This method is known to the person skilled in the art (compare Allen J. Bard and Larry R. Faulkner, “Electrochemical Methods:
  • the first type of redox flow battery according to the invention contains a semi-permeable or microporous membrane. This fulfills the following functions
  • the membrane may include a size exclusion membrane, e.g. B. a dialysis membrane, but also an ion-selective membrane.
  • a size exclusion membrane e.g. B. a dialysis membrane, but also an ion-selective membrane.
  • the membrane prevents the redox-active ferrocene compound from entering the anode compartment and preventing redox-active components of the anolyte from penetrating into the cathode compartment.
  • the passage of dissolved zinc (II) cations does not have to, but can also be inhibited by the membrane.
  • the membrane materials can consist of plastics, ceramics, glasses, metals or textile fabrics.
  • materials are organic polymers, such as cellulose or modified cellulose, for example cellulose ethers or cellulose esters, polyether sulfone, polysulfone, polyvinylidene fluoride, polyester, polyurethanes, polyamides, polypropylene,
  • the membranes and the resulting redox flow batteries can be used in various forms. Examples of this are
  • the thickness of the membrane used according to the invention can vary over a wide range. Typical thicknesses are in the range between 0.1 pm and 5 mm, particularly preferably between 10 pm and 200 pm.
  • the redox flow cell according to the invention preferably contains further components. It refers to
  • Funding means such as pumps, as well as tanks and pipes for the transport and storage of redox-active components
  • Electrodes preferably consisting of or containing graphite, graphite fleece, graphite paper, carbon nano-tube carpets, activated carbon, carbon black or graphene
  • current arresters such as made of graphite or metals
  • the negative electrode preferably contains zinc and can also contain the following materials, for example:
  • the redox flow batteries according to the invention contain current collectors as a further optional but preferred component. These have the task of ensuring the best possible electrical contact between the electrode material and the external one
  • Hafnium or zirconium can be used. All components that allow the transmission of electrical current to the electrodes are referred to as current conductors. The redox reactions take place on the electrodes (cathode and anode), which are in direct contact with the electrolyte.
  • the redox flow batteries according to the invention can be used in a wide variety of fields. In the broadest sense, it can be the
  • Act storage of electrical energy for mobile and stationary applications The invention also relates to the use of the redox flow batteries for these purposes. Examples of applications include use as stationary storage for emergency power supply, peak load balancing and for
  • the redox flow batteries according to the invention can be connected to one another in a manner known per se in a serial or parallel manner.
  • Example 1 Temperature stability of TEMPTMA

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Abstract

L'invention concerne une solution électrolytique aqueuse ayant une température d'au moins 30 °C, contenant a) un composé organique contenant au moins un groupe à activité redox selon la formule (Ia) et de l'acide chlorhydrique et/ou un sel choisi dans le groupe composé des sels d'ammonium comprenant des anions inorganiques ou organiques, des sels comprenant des anions tétrafluoroborate ou des sels d'acide trifluorométhanesulfonique, (formule Ia) et/ou contenant b) un composé organique contenant au moins un groupe à activité redox selon la formule (Ib) et/ou contenant c) un composé organique contenant au moins un groupe à activité redox selon la formule (Ic), dans laquelle R1, R2, R3 et R4 représentent un alkyle ou respectivement R1 et R2 et R3 et R4 forment ensemble avec l'atome de carbone commun un radical cycloaliphatique ou hétérocyclique, X représente -O ou -S, Y est -CH2-, -O-, -S-, -SO-, -SO2-, -NR5- ou -N+R5R6- (Anm-)1/m, Q représente -O-, -S-, -NH-, -NR6a -NR6aR6b +- (Anm-)1/m, -PR6a- ou -SiR6aR6b-, ou -Q- représente une liaison covalente, R5, R6, R6a et R6b sont des radicaux organiques monovalents, An représente un anion inorganique ou organique de valence m, et m est un nombre entier entre 1 et 4. L'électrolyte peut être utilisé dans des batteries à flux redox et est caractérisé par une grande stabilité des composé à activité redox à des températures élevées.
EP19817133.2A 2018-11-29 2019-11-27 Électrolyte aqueux, batterie a flux redox et leur utilisation Pending EP3888162A1 (fr)

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DE102018009393.0A DE102018009393A1 (de) 2018-11-29 2018-11-29 Wässriger Elektrolyt, Redox-Flow-Batterie und deren Verwendung
PCT/EP2019/000322 WO2020108786A1 (fr) 2018-11-29 2019-11-27 Électrolyte aqueux, batterie a flux redox et leur utilisation

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US8771856B2 (en) 2010-09-28 2014-07-08 Battelle Memorial Institute Fe-V redox flow batteries
DE102012016317A1 (de) 2012-08-14 2014-02-20 Jenabatteries GmbH Redox-Flow-Zelle zur Speicherung elektrischer Energie
DE102015010083A1 (de) 2015-08-07 2017-02-09 Friedrich-Schiller-Universität Jena Redox-Flow-Zelle zur Speicherung elektrischer Energie und deren Verwendung
DE102015014828A1 (de) * 2015-11-18 2017-05-18 Friedrich-Schiller-Universität Jena Hybrid-Flow-Zelle zur Speicherung elektrischer Energie und deren Verwendung
US10934258B2 (en) 2016-07-25 2021-03-02 Utah State University Materials for use in an aqueous organic redox flow battery
WO2018032003A1 (fr) 2016-08-12 2018-02-15 President And Fellows Of Harvard College Électrolytes aqueux de batterie à flux redox dotés d'une stabilité chimique et électrochimique élevée, d'une hydrosolubilité élevée et d'une faible perméabilité membranaire

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