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    • 专利摘要:
    The present invention relates to a low-cost, long-lasting redox flow cell that uses less corrosive redox-active components. the redox flow cell contains a reaction cell with two electrode chambers of catholyte and anolyte, which connect respectively to at least one liquid reservoir separated by an ion-conducting membrane and equipped with electrodes, the electrode chambers each being filled with electrolyte solutions containing redox-active components dissolved or dispersed in an electrolytic solvent, as well as optional conductive salts dissolved therein and possibly other additives. the redox flow cell is characterized in that the anolyte contains a redox-active component with one to six radicals of the formula (i) or has one to six radicals of the formula (ii) in the molecule and that the catholyte contains a redox-active component with one to six radicals of formula (iii) in the iron molecule or salts or that anolyte and catholyte contain a redox active component with one to six radicals of formula (i) or formula (ii) in combination with one to six radicals of formula (iii) in the molecule containing formula (i), formula (ii), formula (iii), in which r1 is a covalent cc bond or a bivalent bridging group, r2 and r3 are independently alkyl, alkoxy, haloalkyl, cycloalkyl, aryl, aralkyl, heterocyclyl, x is a q-valent inorganic or organic anion, b and c are independently integers from 0 to 4, q is an integer from 1 to 3, a is a number with the value 2 / q and r4, r5 , r6 and r7 are independently alkyl, cycloalkyl, aryl or aralkyl.
    公开号:BR112018002468B1
    申请号:R112018002468-6
    申请日:2016-08-03
    公开日:2021-07-06
    发明作者:Ulrich Sigmar Schubert；Tobias Janoschka；Norbert Martin
    申请人:Jenabatteries GmbH；
    IPC主号:
    专利说明:

    [0001] The invention relates to a redox flow cell, referred to in common language as a flow battery or as a redox flow battery, to store electrical energy. The redox flow cell contains two polarity-specific chambers, in which a redox-active chemical compound or a redox-active compound are respectively present in both chambers in dissolved or dispersed form in an electrolyte solvent and are in communication with a reservoir of liquid. In this way, two independent circuits are formed for redox-active compounds dissolved, for example, in water or organic solvent or present dispersed in an electrolyte solvent, which are separated by a membrane between the specific polarity chambers. An ion exchange between the two chambers takes place on this membrane.
    [0002] Cells are particularly suitable for stationary storage applications, for example, as a buffer battery for wind or solar power plants or as energy reserves and regulation for load distribution in electrical networks, and also as mobile energy stores, for example, for applications in electric cars and electronic devices.
    [0003] Redox flow batteries (RFB) are electrochemical energy stores. The compounds needed to adjust the potential in the electrodes are dissolved redox-active species that are transferred in their respective redox stage during the charge or discharge process to an electrochemical reactor. To this end, electrolyte solutions (catholyte, anolyte) are removed from a tank and actively pumped into the electrodes. The anode and cathode compartments are separated in the reactor by an ion selective membrane, which generally shows a high selectivity for cations, in particular protons (eg Nafion™). In addition, there are also membranes that passively pass negatively charged ions and block positively charged ions. In addition, size selective membranes (eg dialysis or ultrafiltration membranes) are used which allow both anions and cations to pass through.
    [0004] Cells are particularly suitable for stationary storage applications, as a buffer battery for wind or solar energy systems or as reserve capacities and balance reserves for load balancing in electrical networks, as well as a mobile energy storage, by for example, for operating electric cars and electronic equipment.
    [0005] The compartment of the anode and the cathode in the context of this invention is defined as follows: The space of the cathode contains the catholyte as electrolyte and is limited by the cathode and that membrane surface that faces the cathode. The anode compartment contains the anolyte as electrolyte and is bounded by the anode and the membrane surface facing the anode.
    [0006] In the cathode occurs during the discharge, the reduction and in the loading the oxidation of the redox-active component. At the anode, oxidation takes place during discharge and reduction of the redox-active component takes place during charging.
    [0007] Exemplary descriptions of reactions in a redox flow cell during the charging process:
    [0008] Anode
    [0009] A + e" -> A" or A" + e" -> A2- or An+ + x and" -> A(n"x)+ or An' + x and" -> A(n+X)"
    [0010] In this case A is the redox-active component and n and x can adopt a natural number >= one. Electrodes are symbolized by "and".
    [0011] Cathode
    [0012] K -> K+ + e" oder K" K + e or Kn+ - K(n+y)+ + y e" or Kn' -> K(n"y)" + y e.
    [0013] Here K is the redox-active component and n and y can assume a natural number >= one. Electrons are symbolized by and ".
    [0014] When discharging the cell, the above reactions are reversed.
    [0015] While the electrolyte solution is pumped, energy can be withdrawn (discharge) or fed to the system (charge). Thus, the amount of energy that can be stored in an RFB is directly proportional to the size of the storage tanks. Removable power, however, is a function of the size of the electrochemical reactor.
    [0016] The RFB has a complex system technology (BoP - Balance of Plant), which roughly corresponds to that of a fuel cell. Typical sizes of individual reactors range from approximately 2 to 50 kW. The reactors can be easily combined in a modular way, and the tank size can be adjusted almost arbitrarily. Of particular importance are RFBs, which work with vanadium compounds as a redox pair on both sides (VRFB). This system was first described in 1986 (AU 575247 B) and currently represents the technical standard.
    [0017] Other low molecular weight, inorganic apres redox (redox-active compounds) have been researched, inter alia, on the basis of
    [0018] • Cer (B. Fang, S. Iwasa, Y. Wei, T. Arai, M. Kumagai: "A study of the Ce(lll)/Ce(IV) redox couple for redox flow battery application", Electrochimica Minutes 47, 2002, 3971-3976),
    [0019] * Ruthenium (M.H. Chakrabarti, E. Pelham, L. Roberts, C. Bae, M. Saleem:
    [0020] *"Ruthenium based redox flow battery for solar energy storage", Energy Conv. Management 52, 2011 .2501-2508]
    [0021] • Chrom (C-H. Bae, E.P.L. Roberts, R.A.W. Dryfe: "Chromium redox couples for application to redox flow batteries", Elec-trochimica Acta 48, 2002, 279-87)
    [0022] • Uran (T. Yamamura, Y. Shiokawa, H. Yamana, H. Moriyama: "Electrochemical investigation of uranium β-diketonates for alluranium redox flow battery", Electrochimica Acta 48, 2002, 43-50)
    • Mangan (F. Xue, Y. Wang, W. Hong Wang, X. Wang: "Investigation on the electrode process of the Mn(ll)/Mn(lll) couple in redox flow battery", Electrochimica Acta 53, 2008, 6636-6642).
    • Eisen (L.W. Hruska, R.F. Savinell: "Investigation of Factors Affecting Performance of the Iron-Redox Battery", J. Electrochem. Soc, 128:1, 1981, 18-25).
    [0025] Organic and partially organic systems in aqueous solutions are also a focus of attention. Thus, in January 2014, the Anthraquinone-disulfonic acid / bromine system was published, which allows very high current densities, but by using elemental bromide, high demands are made on the materials of all battery components and on the system security (B. Huskinson, MP Marshak, C. Suh, S. Er, MR Gerhardt, CJ Galvin, X. Chen, A. Aspuru-Guzik, RG Gordon, MJ Aziz: A metal free organic-inorganic aqueous flow battery", Nature 505, 2014, 195-198). Quinones are also tested as fully organic systems in aqueous solution (B. Yang, L. Hoober-Burkhard, F. Wang, GK Surya Prakash, SR Nara-yanan: " An inexpensive aqueous flow battery for large-scale electrical energy storage based on eater-doluble organic redox couples ": J. Electrochem.Soc, 161 (9), 2014, A1361 - A 380.) However, current densities that can be usefully used in redox systems are limited to less than 5 mA / cm 2 and the maximum capacity vel is less than 10 Ah/I. The stable radical molecule 2,2,6,6-tetramethyl-1-piperidonyloxyl (TEMPO) has also been used in redox flow batteries in conjunction with /V-methylphthalimide. (Z. Li, S. Li, S. Liu, K. Huang, D. Fang, F. Wang, S. Peng: "Electrochemical properties of an all-organic redox flow battery using 2,2,6,6-Tetramethyl -1-Piperidonyloxyl and N-Methylphtalimid": Electrochemical and Solid-State Letters, 14 (12), 201 1, A171-A173) Due to the resulting potentials and solubilities of the starting materials, this material system cannot be easily used in an aqueous medium, but requires hazardous substances such as solvents such as acetonitrile. Furthermore, with this system, the possible current densities of 0.35 mA/cm 2 are at least 100 times smaller than in the material systems proposed in the invention. Other electrolyte systems such as LiPF6 and TEMPO (X., Wu Xu, M. Vijayakumar, L. Cosimbescu, T. Liu, V. Sprenkle, W. Wang: "TEMPO-based catholyte for high-energy densitiy redox flow batteries. Mater. Vol. 26, 45, p7649-7653) also require organic solvents and conductive salts, which can release toxic gases such as hydrogen fluoride in the event of a failure and thus place high demands on system safety .
    [0026] The patent document WO 2014/026728 A1 describes redox flow cells with semi-permeable membranes, in which high molecular weight compounds are used as redox couple. In the example, the catholyte used is a poly(2,6,6-tetramethylpiperidinyloxymethacrylate-co-poly (ethylene glycol methyl ether methacrylate) and, as the anolyte, a poly(4,4'-bipyridine-co-poly(ethyl) - in glycol).
    [0027] This invention aims to provide a redox flow cell with systems of selected active redox materials, which can be operated safely, cheaply and efficiently, which contains an electrolyte solution with improved pumpability, which even in cross-contamination over membrane failure points can continue to function and where, compared to known solutions, an increased level of potential can be reached. The redox-active components used according to the invention are distinguished by a significantly reduced viscosity compared to the polymeric active redox compounds known from WO 2014/026728 A1 . Compared to known polymeric redox systems, the viscosity of concentrated solutions in the case of comparable capacity (1 mol / l active redox unit) is significantly lower, so that when the solution is pumped, less pressure losses occur, resulting in in better energy efficiency. Thus, concentrated solutions of V-dimethylviologen chloride have a viscosity of 5 mPas at room temperature, while concentrated solutions of VV-methylviologen polymer have a viscosity of 20 mPas at room temperature with the same capacity. Furthermore, the material systems used according to the invention are also characterized by a lower corrosivity than acid-based electrolytes.
    [0028] The objective is achieved by the provision of redox flow cells with selected active redox material systems, which can be operated without catalysts, are very soluble in water, are inexpensive and mutually compatible. Redox-active material systems can also be used as dispersions.
    [0029] The present invention relates to a redox flow cell for storing electrical energy comprising a reaction cell with two electrode chambers for catholyte and anolyte, each communicating with at least one liquid reservoir separated by a membrane ion-conductive and equipped with electrodes, in which the electrode chambers are each filled with electrolyte solutions containing redox-active components dissolved or dispersed in an electrolyte solvent and, optionally, conductive salts dissolved therein and possibly other additives. The redox flow cell according to the invention is characterized in that the anolyte is a redox-active component which contains one to six, preferably one to four, in particular one to three and very particularly preferably one to two radicals of formula I na molecule or one to six, preferably one to four, especially one to three, and preferably contains one to two radicals of formula II in the molecule and that the catholyte is a redox-active component, which contains one to six, preferably one to four, in particular one to three and very particularly preferably one to two radicals of the formula III in the molecule either contains the iron salts or the anolyte and the catholyte is a redox-active component, which contains one to six, preferably one to four, especially one to three and very particularly preferably one to two radicals of formula I or formula II in combination with one to six, preferably one to four, in particular one to three and very particularly one to two radicals of formula III at molecule.

    [0030]
    [0031] ras of formulas I and II and the lines leaving position 4 in the structure of formula III represent covalent bonds connecting the structures of formulas I, II and III with the rest of the molecule,
    [0032] R1 is a covalent CC bond or a bivalent bonding group, in particular a covalent CC bond, an arylene group or a heteroarylene group, and more preferably a covalent CC bond, a phenylene group, a biphenylene group or a group thiophenediyl.
    [0033] R 2 and R 3, independently of one another, are alkyl, alkoxy, haloalkyl, cycloalkyl, aryl, aralkyl, heterocyclyl, halogen, hydroxyl, amino, nitro or cyano,
    [0034] X denotes a q-valent inorganic or organic anion or a mixture of such anions,
    [0035] b and c are independently integers from 0 to 4, preferably 0, 1 or 2,
    [0036] q is an integer from 1 to 3,
    [0037] a is a number with the value 2 / q, and
    [0038] R4, R5, R6 and R independently of one another are alkyl, cycloalkyl, aryl or aralkyl, in particular C1-C6 alkyl and very particularly preferably ethyl or methyl.
    [0039] The redox-active components preferably used in the anolyte contain one to four radicals of formula Ia and/or of formula IIa in the molecule

    [0040] where
    [0041] the lines that leave the nitrogen atoms in the structures of formulas Ia and IIa represent covalent bonds linking the structures of formulas Ia and IIa with the rest of the molecule, and
    [0042] R2, R3, X, a, b, c and q have the meaning defined above.
    The active redox components preferably used in the anolyte are compounds of the formulas Ib, IIb, IV, V, VII, Vlla, Vllb VIII, Villa, VIIIb, IX, IXa, IXb, X, Xa, Xb, XI, XIa, Xlb, XII, Xlla and Xllb



    [0044] where
    [0045]R1, R2, R3, R4, R5, R6, R7 and X have the meaning defined above,
    [0046] R8 and R10 independently of one another mean hydrogen, optionally substituted with a carboxylic acid ester group, carboxylic acid amide group, carboxylic acid group, sulphonic acid or substituted amino, optionally with aryl substituted with an acid ester group carboxylic acid, carboxylic acid amide group, carboxylic acid, sulfonic acid or amino group, aryl optionally substituted by a carboxylic acid ester, carboxylic acid amide, carboxylic acid, sulfonic acid or amino group, especially C1-C6-alkyl, C1-C6 alkyl substituted with a carboxylic acid ester group, C1-C6 alkyl substituted with a carboxylic acid amide group, C1-C6 alkyl substituted with a carboxylic acid group, C1-C6 alkyl substituted with a sulfonic acid group, or C1 -C6 alkyl substituted with an amino group, and quite especially preferably propionate, isobutionate, ethyl or methyl.
    [0047] R9 is a bivalent to hexavalent group, especially bivalent to tetravalent organic bridging group,
    [0048] R12 is a covalent bond or a bivalent to hexavalent organic bridging group, in particular bivalent to tetravalent organic bridging group,
    [0049] R14 is a covalent bond or a bivalent organic bridging group,
    [0050] R15 is a di- to hexavalent organic bridging group, especially a di-tetravalent organic bridging group.
    [0051] R18 is a 0-fold positively charged di-tetravalent organic radical, which is covalently bonded to the nitrogen atom of the bipyridyl radical through a carbon atom, in particular a bivalent to tetravalent quaternary ammonium radical, a bivalent quaternary phosphonium radical a tetravalent, a bivalent or trivalent ternary sulfonic radical or a positively charged bivalent to hexavalent, o-fold heterocyclic radical, in particular with a bivalent to tetravalent heterocyclic radical.
    [0052] R19 is an o-fold charged bivalent organic radical, preferably simply positively charged, covalently bonded to the nitrogen atom of the bipyridyl radical through a carbon atom, in particular a quaternary ammonium radical, a quaternary phosphonium radical , a ternary sulfonium radical or a 0-fold bivalent heterocyclic radical, preferably once positively charged. R20 and R21 independently mean hydrogen, optionally alkyl substituted with a sulfonic or amino acid group, carboxylic acid, carboxylic acid amide, carboxylic acid ester, optionally cycloalkyl substituted with a carboxylic acid ester group, carboxylic acid amide, carboxylic acid, sulfonic acid or amino group, optionally aryl substituted with a carboxylic acid ester group, carboxylic acid amide, carboxylic acid, sulfonic acid or amino group or optionally aralkyl substituted with a carboxylic acid ester group, carboxylic acid amide, carboxylic acid, sulfonic acid or amino group or two groups R20 and R21 together form a C1-C3-alkylene group, especially C1-C6-alkyl, C1-C6-alkyl substituted with a carboxylic acid ester group, C1-C6-alkyl substituted with a carboxylic acid amide group, C1-C6-alkyl substituted with a carboxylic acid group, C1-C6-alkyl substituted with an á group sulfonic acid, or C1C6 alkyl substituted with an amino group or together means ethylene, and quite especially preferably means propionate, isobutionate, ethyl or methyl or together ethylene.
    [0053] R22 is a bivalent organic bridging group,
    [0054] R23 is a negatively charged bivalent to tetravalent, bivalent to hexavalent organic radical, in particular, which is covalently bonded to the nitrogen atom of the bipyridyl radical through a carbon atom, especially an alkylene radical substituted with one or two carboxyl groups or sulfonic acid, a phenylene radical substituted with one or two carboxyl groups or sulfonic acid, or a bivalent heterocyclic radical substituted with one or two carboxyl groups or sulfonic acid.
    [0055] R24 is a 0-fold or once negatively charged, preferably monosubstituted, bivalent organic radical covalently bonded to the nitrogen atom of the bipyridyl radical through a carbon atom, in particular an alkylene radical substituted with a group carboxyl acid or sulfonic acid, a phenylene radical substituted with a carboxyl group or sulfonic acid, or a bivalent heterocyclic radical substituted with a carboxyl group or sulfonic acid.
    [0056] a, b, c and q have the meaning defined above,
    [0057] d is an integer from 1 to 5, preferably from 1 to 3,
    [0058] and is a number with the value (2 + 2d + 2t) / q,
    [0059] g is an integer from 1 to 5, preferably from 1 to 3
    [0060] h is an integer from 1 to 5, preferably from 1 to 3,
    [0061] When the sum of g and h is an integer from 2 to 6, preferably from 2 to 4,
    [0062] a is a number with the value 2h / q,
    [0063] j is an integer from 1 to 5, preferably from 1 to 3,
    [0064] k is a number with the value of (2 + 2j) / q,
    [0065] o is an integer from 1 to 4,
    [0066] p is a number with the value (o + 2h) / q,
    [0067] r is a number with the value (3 + 3j) / q,
    [0068] t is 0 or, if R9 is a bivalent organic bridging group, 0 or 1,
    [0069] u is an integer from 1 to 4,
    [0070] z is a number with the value 2 / q,
    [0071] z1 is a number with the value (o + 2) / q
    [0072] y for the case that 2h - u or 2 (2 - u) - u is greater than 0, a v- or x -valent inorganic or organic anion or a mixture of these anions, or in the case of 2h-u or 2(2-u) -u is less than 0, a v-or x-valent inorganic or organic cation or a mixture of such cations,
    [0073] v is an integer from -1 to -3 or from +1 to +3,
    [0074] x is an integer from -1 to -3 or from +1 to +3,
    [0075] w is 0 or a positive number with the value (-u + 2h) / v,
    [0076] y is 0 or a positive number with the value (2-u) (j + 1) / x,
    [0077] y1 in case 2 - 2u is less than 0, means an x1-valent inorganic or organic cation or a mixture of such cations,
    [0078] x1 is an integer from -1 to -3 or from +1 to +3, and
    [0079] y1 is 0 or a positive number with the value (2 - 2u) / x1.
    The particularly preferred Redox active components used in the anolyte are compounds of the formulas IVa, Va, VIIc, VIIIc, IXc and Xc


    [0081] where
    [0082] R2, R3, R4, R5, R6, R7, R8, R9, R10, R12, R14, R15 and X have the meaning defined above, and b, c, d, e, g, h, i, jkeq have the meaning defined above.
    The redox-active components preferably used in the catholyte are compounds of the formulas IIIa, IIIb, IIIc, VI, Via and/or VIb and the formulas VII, VIIa, VIIb.VIII, VIIIb, VIII, VIIIa, VIIIb, VIII, defined above Xa and / or Xb


    [0084] where
    [0085] R4, R5, R6, R7, X, o, u and q are as defined above,
    [0086] R11 is a bivalent to tetravalent organic bridging group,
    [0087] R13 is hydrogen, alkyl, alkoxy, haloalkyl, cycloalkyl, aryl, aralkyl, heterocyclyl, halogen, hydroxy, amino, nitro or cyano and
    [0088] R 16 is a monovalent organic radical 0-fold, preferably once positively charged, in particular a quaternary ammonium radical, a quaternary phosphonium radical, a ternary sulfonium radical or a monovalent heterocyclic radical 0-fold, preferably once positively charged, and
    [0089] R 17 is a positively charged bivalent to tetravalent organic radical, in particular bivalent to tetravalent quaternary ammonium, a bivalent to tetravalent quaternary phosphonium radical, a bivalent to tetravalent ternary sulfonic radical or a bivalent to tetravalent heterocyclic radical m-times positively charged.
    [0090] R25 is a monovalent u-fold, preferably once negatively charged radical, in particular a carboxylic acid or sulfonic acid radical or a single negatively charged monovalent heterocyclic radical.
    [0091] R26 is a negatively charged m-fold bivalent to tetravalent organic radical, especially an alkylene radical substituted with one or two carboxyl acid or sulfonic acid groups, or a phenylene radical substituted with one or two carboxyl acid or sulfonic acid groups or radical bivalent heterocyclic substituted with one or two carboxylic acid or sulfonic acid groups,
    [0092] Z denotes a q-valent inorganic or organic cation or a mixture of such cations,
    [0093] f is an integer from 1 to 3,
    [0094] I is a number with the value o / q or u / q,
    [0095] m is an integer from 1 to 4, and
    [0096] n indicates a number with the value m / q.
    The particularly preferred redox-active components used in the catholyte are compounds of the formulas VI, Via, VIIc, VIIIc, IXc and/or Xc as defined above.
    The very particularly preferred redox-active compounds used according to the invention are those of the formulas Ib, IIb, VIId, VIII, VIII and/or VIII


    [0099] where
    [0100] R2, R3, R4, R5, R6, R7, R8, R10, R14, R19 and X have the meaning defined above,
    [0101] R20 and R21 independently of each other are hydrogen, optionally signify alkyl substituted with a carboxylic acid ester group, carboxylic acid amide group, carboxylic acid, sulfonic acid or amino group, optionally cycloalkyl substituted with an ester group of carboxylic acid, carboxylic acid amide group, carboxylic acid, sulfonic acid or amino group, optionally aryl substituted with carboxylic acid ester group, carboxylic acid amide group, carboxylic acid, sulfonic acid or amino group or optionally aralkyl substituted with a carboxylic acid ester group, carboxylic acid amide group, carboxylic acid group, sulfonic acid group or amino group or two radicals R20 and R21 together form a C1-C3 alkylene group, especially C1-C6-alkyl, C1-C6 alkyl substituted with a carboxylic acid ester group, C1-C6 alkyl substituted with a carboxylic acid amide group, C1-C6 alkyl substituted with m a carboxylic acid group, C1C6 alkyl substituted with a sulfonic acid group or C1-C6 alkyl substituted with an amino group or together form ethylene, and mean especially preferably propionate, isobutionate, ethyl or methyl or together ethylene,
    [0102] a, b, c and q have the meaning defined above and
    [0103] s is a number with the value 3 / q.
    Of these compounds which are particularly preferably used, those of the formulas Ib, IIb, VIId, VIII, VIII and / or VIII in the anolyte and those of the formulas VIId, VIII, VIII and / or VIIIll in the catholyte are used.
    [0105] More preferably, the catholyte contains compounds of formulas IIIa, IIIb or Nie defined above, and the anolyte contains compounds of formulas Ib or IIb defined above.
    [0106] In particular, the catholyte contains compounds of the formula IIIb defined above and the anolyte contains the compounds of the formula Ib defined above.
    [0107] Examples of preferred compounds of formula IIIb are 2,2,6,6-tetramethylpiperidine-4-(N,N,N-trialkylammonium) salts, in particular 2,2,6,6,tetramethylpiperidine-4 salts - (N,N,N-trimethylammonium), and more particularly 2,2,6,6-tetramethylpiperidine-4-(N,N,N-trimethylammonium) chloride.
    [0108] Examples of preferred compounds of the formula Ib are salts of N,N'-dialkylviologen, in particular salts of N,N'-dimethylviologen and especially N,N'-dialkylviologen chloride.
    Particularly preferred redox active compounds are those of the above-defined formulas VII, VIIa, VIIb, VIIc, VIId, VIII, VIII, VIIIa, VIIIb, VIIIc, VIIId, VIII, IX, IXa, IXb, IXc, X, Xa , Xa and Xc. These contain electroactive bipyridyl radicals and electroactive nitroxide radicals and can be used in both the catholyte and the anolyte, preferably in both chambers, the same compounds.
    [0110] The redox-active compounds of the formulas VII, VIIa, VIIb, VIIc, VIId, VIII, VIII, VIIIc, VIIIb, VIIIc, VIIId, VIII, IX, IXb, IXc, X, Xa, Xb and Xc defined above are combined positive and negative redox-active unit molecules (TEMPO and viologen). Until now, these redox-active units have only ever been used in the form of two different substances. Particularly preferred combination molecules according to the invention can be both oxidized and reduced. One of the resulting advantages is that the solutions are no longer irreversibly damaged when mixed caused, for example, by membrane defects. Potentials can also be adjusted by selecting the two redox-active units and therefore optimized for different application scenarios.
    [0111] If one of the radicals R2, R3, R4, R5, R6, R7, R8, R10, R13, R20 and/or R21 is alkyl, then the alkyl group may be branched and unbranched. An alkyl group typically contains one to twenty carbon atoms, preferably one to ten carbon atoms. Examples of alkyl groups are: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, butyl, pentyl, n-hexyl, n-heptyl, 2-ethylhexyl, noctyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl or eicosyl. Alkyl groups having one to six carbon atoms are particularly preferred. Alkyl groups may optionally be substituted, for example with carboxyl groups or sulphonic acid, with carboxyl ester or ester groups of sulphonic acid, with carboxylamide groups or amide groups of sulphonic acid, with hydroxyl groups or amino groups or with halogen atoms.
    [0112] If one of the radicals R2, R3 and/or R3 is alkoxy, the alkoxy group may consist of an alkyl moiety which may be branched and unbranched. An alkoxy group typically contains one to twenty carbon atoms, preferably one to ten carbon atoms. Examples of alkoxy groups are:
    [0113] Methoxy, ethoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, pentyloxy, n-hexyloxy, n-heptyloxy, 2-ethylhexyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-Tridecyloxy, n-tetradecyloxy, n-pentadecyloxy, n-hexadecyloxy, n-octadecyloxy or eicosyloxy. Particularly preferred are alkoxy groups having one to six carbon atoms.
    [0114] If one of the radicals R2, R3 and/or R13 is haloalkyl, then the haloalkyl group may be branched and unbranched. A haloalkyl group typically contains from one to twenty carbon atoms, which in turn are independently substituted with one or more halogen atoms, preferably one to ten carbon atoms. Examples of halogen atoms are fluorine, chlorine, bromine or iodine. Preference is given to fluorine and chlorine. Examples of haloalkyl groups are:
    [0115] Trifluoromethyl, difluoromethyl, fluoromethyl, bromodifluoromethyl, 2-chloroethyl, 2-bromoethyl, 1,1-difluoroethyl, 2,2,2-trifluoroethyl, 1, 1, 2,2-tetrafluoroethyl, 2-chloro-1 ,1,2-trifluoroethyl, pentafluoroethyl, 3-bromopropyl, 2,2,3,3-tetrafluoropropyl, 1, 1, 2,3,3,3-hexafluoropropyl, 1,1,1,3,3,3-hexafluoropropyl , 3-bromo-2-methylpropyl, 4-bromobutyl, perfluoropentyl.
    [0116] If one of the radicals R2, R3, R4, R5, R6, R7, R8, R10, R13, R20 and/or R2 is cycloalkyl, the cycloalkyl group is typically a cyclic group containing from three to eight, preferably five, six or seven ring carbon atoms, each of which can 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 another ring. Examples of cycloalkyl groups are cyclopropyl, cyclopentyl or cyclohexyl.
    [0117] Cycloalkyl groups can optionally be substituted, for example, with carboxyl groups or sulfonic acid, with carboxyl ester or sulfonic acid ester groups, with carboxylamide or amide groups of sulfonic acid, with hydroxyl or amino groups or with atoms of halogen.
    [0118] When one of R2, R3, R4, R5, R6, R7, R5, R10, R13, R20 and/or R21 is aryl, the aryl group is typically a cyclic aromatic group containing five to fourteen carbon atoms each one can be replaced independently of the other. Examples of substituents are alkyl groups or two alkyl groups which together with the ring carbon atoms to which they are attached can form an additional ring. Examples of aryl groups are phenyl, biphenyl, anthryl or phenantolyl. Aryl groups can optionally be substituted, for example, with carboxyl groups or sulfonic acid, with carboxyl ester groups or sulfonic acid, with amide groups of carboxamide acid or sulfonic acid, with hydroxyl or amino groups or with halogen atoms.
    [0119] If one of the radicals R2, R3 and/or R3 is heterocyclyl, the heterocyclic group may typically have a cyclic group with four to ten ring carbon atoms and at least one ring heteroatom, each of which may be substituted independently of each other. Examples of substituents are alkyl groups or two alkyl groups which together with the ring carbons to which they are attached can form an additional ring. Examples of heteroatoms are oxygen, nitrogen, phosphorus, boron, selenium or sulfur. Examples of heterocyclyl groups are furyl, thienyl, pyrrolyl or imidazolyl. Heterocyclyl 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 carboxamide or sulfonamide groups, with hydroxyl or amino groups or with halogen atoms.
    [0120] One of the radicals R2, R3, R4, R5, R6, R7, R8, R10, R13, R20 and/or aryl R21, the aralkyl group is typically an aryl group, where aryl has already been defined before which an alkyl group is covalently attached. The aralkyl group can be substituted on the aromatic ring, for example with alkyl groups or with halogen atoms. An example of an aralkyl group is benzyl.
    [0121] Aralkyl groups can optionally be substituted, for example, with carboxyl or sulfonic acid groups, with carboxyl ester or sulfonic acid ester groups, with carboxylamide or sulfonamide groups, with hydroxyl or amino groups or with halogen atoms.
    [0122] If one of the radicals R2, R3 and/or R3 is amino, the amino group may be unsubstituted or carry one or two or three substituents, preferably alkyl and/or aryl groups. Alkyl substituents can be branched and unbranched. A mono or dialkylamino group typically contains one or two alkyl groups of one to twenty carbon atoms, preferably one to six carbon atoms. Examples of monoalkylamino groups are methylamino, ethylamino, propylamino or butylamino. Examples of dialkylamino groups are: di-ethylamino, di-propylamino or di-butylamino.
    [0123] Examples of trialkylamino groups are: triethylamino, tripropylamino or tri-butylamino.
    [0124] If one of the radicals R2, R3 and/or R13 means halogen, this is to be understood as meaning a covalently bonded fluorine, chlorine, bromine or iodine atom. Preference is given to fluorine or chlorine.
    [0125] R1 is a bivalent bridging group, this is to be understood as meaning a bivalent inorganic or organic radical. Examples of divalent inorganic radicals are -O-, -S-, -SO-, -SO2-, -OP(O)O- or -NH-. Examples of bivalent organic radicals are alkylene, cycloalkylene, arylene, aralkylene or heterocyclylene.
    [0126] When R14 and R22 are a bivalent organic bridging group, they are understood to mean an organic radical that is linked to the rest of the molecule through two covalent bonds. Examples of bivalent organic radicals R14 or R22 are alkylene, alkyleneoxy, poly(alkyleneoxy), alkyleneamino, poly(alkyleneamino), cycloalkylene, arylene, aralkylene or heterocyclylene
    [0127] Alkylene groups can be branched and 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 carboxamide or sulfonamide groups, with hydroxyl or amino groups or with halogen atoms.
    [0128] Alkyleneoxy and poly(alkyleneoxy) groups may contain both branched and unbranched alkylene groups. An alkylene group occurring in an alkyleneoxy group 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 poly(alkyleneoxy) groups can vary widely. Typical numbers of repeating units range from 2 to 50. Examples of alkyleneoxy groups are: ethyleneoxy, propyleneoxy and butyleneoxy. Examples of poly(alkyleneoxy) groups are: poly(ethyleneoxy), poly(propylenoxy) and poly(butylenoxy).
    [0129] Alkyleneamino and poly(alkyleneamino) groups can contain both branched and unbranched alkylene groups. An alkylene group occurring in an alkyleneamino group or in a poly(alkyleneamino) group typically contains two to four carbon atoms, preferably two or three carbon atoms. The number of repeating units in poly(alkyleneamino) groups can vary widely. Typical numbers of repeating units range from 2 to 50. Examples of alkyleneamino groups are: ethylene-amino, propyl-diamino and butyleneamino. Examples of poly(alkyleneamino) groups are: poly(ethylene-amino), poly(propyleneamino) and poly(butyleneamino).
    [0130] Cycloalkylene groups typically contain five, six or seven ring carbon atoms, each of which may 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 another ring. An example of a cycloalkylene group is cyclohexylene. Cycloalkylene groups can optionally be substituted, for example, with carboxyl or sulfonic acid groups, with carboxyl ester or sulfonic acid ester groups, with carboxamide or sulfonamide groups, with hydroxyl or amino groups or with halogen atoms.
    [0131] Arylene groups are typically cyclic aromatic groups containing five to fourteen carbon atoms, each of which can be independently substituted. Examples of arylene groups are o-phenylene, m-phenylene, p-phenyl, o-biphenylyl, m-biphenylyl, p-biphenylyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanolyl, 2-phenantolyl, 3 -phenantolyl, 4-phenantolyl or 9-phenantolyl.
    [0132] Arylene groups can optionally be substituted, for example, with carboxyl or sulfonic acid groups, with carboxyl ester or sulfonic acid ester groups, with carboxamide or sulfonic acid amide groups, with hydroxyl or amino groups or with halogen atoms . Other examples of substituents are alkyl groups or two alkyl groups which together with the ring carbon atoms to which they are attached can form an additional ring.
    [0133] Heterocyclyl groups are typically cyclic groups having four to ten ring carbon atoms and at least one ring heteroatom, each of which may be independently substituted. Examples of heteroatoms are oxygen, nitrogen, phosphorus, boron, selenium or sulfur. Examples of heterocyclylene groups are furandiyl, thiophenediyl, pyrrolidinyl or imidazolediyl. Heterocyclylene groups are preferably aromatic. Heterocyclyl groups can optionally be substituted, for example, with carboxyl acid or sulfonic acid groups, with carboxyl ester or sulfonic acid ester groups, with carboxylamide or sulfonamide groups, with hydroxyl or amino groups or with haloaromatic groups. Other examples of substituents are alkyl groups or two alkyl groups which together with the ring carbons to which they are attached can form an additional ring.
    [0134] Aralkylene groups are typically aryl groups to which one or two alkyl groups are covalently bonded. Aralkyl groups can be covalently bonded via their aryl radical and their alkyl radical or via two alkyl radicals to the rest of the molecule. The aralkylene group can be substituted on the aromatic ring, for example, with alkyl groups or with halogen atoms. Examples of aralkylene groups are benzyl or dimethylphenylene (xylylene).
    [0135] If one of the radicals R9, R11, R12 or R15 is a bivalent or hexavalent organic bridging group, this is to be understood as meaning an organic radical, which through two, three, four, five or six covalent bonds is attached to the remainder of the molecule.
    [0136] Examples of bivalent organic radicals are alkylene, alkyleneoxy, poly(alkyleneoxy), alkyleneamino, poly(alkyleneamino), cycloalkylene, arylene, aralkylene or heterocyclyls. These radicals have already been described in detail above.
    [0137] Examples of trivalent organic radicals are alkyltriyl, alkoxytriyl, tris-poly(alkyleneoxy), tris-poly(alkyleneamino), cycloalkyltriyl, aryltriyl, aralkyltriyl or heterocyclyltrile. These radicals correspond to the bivalent radicals already described in detail above with the difference that they are attached to three covalent bonds instead of two covalent bonds to the rest of the molecule.
    [0138] Examples of tetravalent organic radicals are alkylquaternyl, alkoxyquaternyl, Quater-poly (alkyleneoxy), Quater-poly (alkyleneamino), cycloalkylquaternyl, aryl-quaternyl, aralkylquaternyl or heterocyclylquaternyl. These radicals correspond to the bivalent radicals already described in detail above with the difference that they are attached to four covalent bonds instead of two covalent bonds to the rest of the molecule.
    [0139] Examples of pentavalent organic radicals are alkylquinkinyl, alkoxyquinquinyl, quinquipenyl (alkyleneoxy), quinquipenyl (alkyleneamino), cycloalkylquinquinyl, arylquinquinyl, aralkylquinquinyl or heterocyclylquinquinyl. These radicals correspond to the bivalent radicals already described in detail above with the difference that they are attached to five covalent bonds instead of two covalent bonds to the rest of the molecule.
    [0140] Examples of organic hexahydric radicals are alkylhexyl, alkoxyhexyl, hexylpoly(alkyleneoxy), hexylpoly(alkyleneamino), cycloalkylhexyl, arylhexyl, aralkylhexyl or heterocyclylhexyl. These radicals correspond to the divalent radicals already described in detail above with the difference that they are attached to six covalent bonds instead of two covalent bonds to the rest of the molecule.
    [0141] R16 is a 0-fold positively charged monovalent organic radical, preferably once positively charged. These are generally alkyl, alkoxy, haloalkyl, cycloalkyl, aryl, aralkyl, or heterocyclyl, which contain one to four positively charged radicals, in particular quaternary ammonium groups, quaternary phosphonium radicals, ternary sulfonic radical or a heterocyclyl radical. one to four times charged monovalent rocyclic. The charge equalization takes place via one or more anions Xq". The attachment of the 0-fold positively charged piperidine-1-oxyl radical is preferably done via the heteroatom of the 0-fold positively charged radical. Particularly preferred examples of R- 16 are the radicals N + R26R27R28, P + R26R27R28, -S + R26R27 or -Het wherein R26, R27 and R28 independently represent hydrogen, alkyl, cycloalkyl, aryl, aralkyl or heterocyclyl, especially C1-C6-alkyl, cyclohexyl, phenyl or benzyl, and Het is a monovalent, once positively charged heterocyclic radical which has one to three ring nitrogen atoms or one ring nitrogen atom and one to two oxygen atoms on the ring or ring sulfur atoms, particularly preferably a monovalent imidazolium radical, pyridinium, guanidinium, uronium, thiouronium, piperidinium or morpholinium.
    [0142] R 19 is a 0-fold positively charged bivalent organic radical, preferably a once positively charged bivalent organic radical. In this case it is generally alkylene, haloalkylene, cycloalkylene, arylene, aralkylene or heterocyclylene containing one to four positively charged radicals, in particular one to four quaternary ammonium radicals, one to four quaternary phosphonium radicals, one to four sulphonium radicals ternary or a one to four times positively charged divalent heterocyclic radical. Charge compensation takes place via the anion(s) Xq-. The attachment of the positively charged radical 0-fold to the piperidine-oxyl radical is preferably effected via the heteroatom of the positively charged radical. The bond between R19 and the nitrogen atom of the bipyridyl radical is via a carbon atom of the R19 radical. Particularly preferred examples of R19 radicals are the radicals -N + R26R27R29-, -P + R26R27R29-, -S + R26R29- or -Het + -, wherein R26 and R27 independently of one another represent hydrogen, alkyl, cycloalkyl, aryl, aralkyl or heterocyclyl, in particular C1-C6-alkyl, cyclohexyl, phenyl or benzyl, R29 represents a bivalent organic radical and Het represents a bivalent and once positively charged heterocyclic radical containing one to three ring nitrogen atoms or one ring nitrogen atom and one to two ring oxygen atoms or ring sulfur atoms, more preferably, a monovalent imidazolium, pyridinium, guanidinium, uronium, tioterium, piperidinium or morpholinium radical.
    [0143] R17 is a positively charged bivalent to tetravalent organic radical m-fold. In this case, it is an organic radical, which has m-times positively charged groups and which through two, three or four covalent bonds is linked with the rest of the molecule. Examples of positively charged radicals are quaternary ammonium, quaternary phosphonium, ternary sulfonium or an m-times charged divalent to tetravalent heterocyclic radical. The attachment of the m-fold positively charged radical to the piperidine-1-oxyl radical preferably occurs via the heteroatoms of the m-fold positively charged radical. Particularly preferred examples of radicals R17 are the radicals -N + R30R31- [R32-N + R30R31] f-, -P + R30- [R24-S + R30] f- or [Hetm +,] f- where R30 and R31 are independently alkyl, cycloalkyl, aryl, aralkyl or heterocyclyl, in particular C1-C6 alkyl, cyclohexyl, phenyl or benzyl, f has the meaning defined above, R32 represents an f + 1-valent organic radical and Het represents a bivalent to tetravalent and m-fold positively charged heterocyclic radical having one to three ring nitrogen atoms or one ring nitrogen atom and one to two ring oxygen atoms or ring sulfur atoms, particularly preferably an imidazolium, pyridinium, guanidinium, uronium, thiouronium, pyridinium, or morpholinium radical.
    [0144] R 18 is a 0-fold positively charged bivalent to tetravalent organic radical. This is an organic radical with positively charged groups and is linked through two, three or four covalent bonds with the rest of the molecule. R18 is covalently bonded to the nitrogen atom of the bipyridyl radical(s) through a carbon atom. Examples of positively charged radicals are quaternary ammonium, quaternary phosphonium, ternary sulfonium or an o-fold charged divalent to tetravalent heterocyclic radical. The attachment of the positively charged radical o-fold piperidine-1-oxyl radical preferably occurs via the heteroatoms of the o-fold positively charged radical. Particularly preferred examples of R18 radicals are the radicals - [N + R30R31] g- [R33-N + R30,R 31] h-, - [P + R30R31] g- [R33-PR30R31] h-, - [S + R30 g- [R33-S + R30] h- or [Hetm +,] g + h-, where R30 and R31, independently of one another, are alkyl, cycloalkyl, aryl, aralkyl or heterocyclyl, in particular C1- C6-alkyl, cyclohexyl, phenyl or benzyl z, g and h are as defined above, R33 is a valid g + h organic radical and Het is a positively charged divalent to tetravalent heterocyclic radical containing one to three ring nitrogen atoms or a ring nitrogen atom and contains one to two ring oxygen atoms or ring sulfur atoms, particularly preferably a bivalent radical to tetravalent imidazolium, pyridinium, guanidinium, uronium, thionium, piperidinium or morpholinium.
    [0145] Examples of bivalent organic radicals R29, R32 and R33 are alkylene, cycloalkylene, arylene, aralkylene or heterocyclic. These radicals have already been described in detail above.
    [0146] Examples of trivalent organic radicals R32 and R33 are alkyltriyl, cycloalkyltriyl, aryltriyl, aralkyltriyl or heterocyclyltrile. These radicals correspond to the bivalent radicals already described in detail above with the difference that they are linked by three covalent bonds, rather than two covalent bonds, to the rest of the molecule.
    [0147] Examples of tetravalent organic radicals R32 and R33 are alkyltriyl, cycloalkyltriyl, aryltriyl, aralkyltriyl or heterocyclyltrile. These radicals correspond to the divalent radicals already described in detail above with the difference that they are linked by three covalent bonds, instead of two covalent bonds, to the rest of the molecule.
    [0148] R23 is a negatively charged u-fold bivalent to tetravalent organic radical. This is an organic radical that has negatively charged groups and that through two, three or four covalent bonds it is linked with the remaining molecule. R23 is covalently bonded to the nitrogen atom of the bipyridyl radical(s) through a carbon atom. Examples of negatively charged radicals are alkylene radicals or arylene radicals which are substituted by carboxylic acid or sulfonic acid radicals, hydrocarbon moieties of alkylene radicals or various arylene radicals being interrupted by one or more -O-, -CO-O groups -, -CO-NH- or -NH- or a bivalent to tetravalent heterocyclic radical substituted with up to two carboxylic acid or sulfonic acid radicals. Attachment of the negatively charged radical u-fold to the piperidine-1-oxyl radicals preferably occurs via carbon atoms of the negatively charged radical u-fold. Particularly preferred examples of R23 radicals are alkylene radicals or arylene radicals which are substituted by one or two carboxylic acid or sulfonic acid radicals.
    [0149] R24 is a u-fold negatively charged bivalent organic radical, preferably a negatively charged bivalent organic radical once. In this case, it is generally an alkylene, haloalkylene, cycloalkylene, arylene, aralkylene or heterocyclylene, which contains one to four uniquely negatively charged radicals, in particular an alkylene radical or arylene radical with one to four carboxylic acid or sulfonic acid substituents, being that the hydrocarbon moieties of alkylene radicals or various arylene radicals may be interrupted by one or more groups -O-, -CO-O-, -CO-NH- or -NH-, or a negatively charged one to four times divalent heterocyclic radical . Charge compensation occurs via the anion(s) Xq- or via the cation(s) Yx +. The attachment of the negatively charged radical u-fold to the piperidine-1-oxyl radical preferably occurs via a carbon atom of the negatively charged radical u-fold. The bond of R24 and the nitrogen atom of the bipyridyl radical through a carbon atom of the R24 radical.
    [0150] R25 is a u-fold negatively charged monovalent organic radical, preferably once negatively charged. In this case it is generally an alkyl, alkoxy, haloalkyl, cycloalkyl, aryl, aralkyl or heterocyclyl, which contain one to four radicals once negatively charged, in particular one to four carboxylic acid radicals or one to four sulfonic acid radicals or one monovalent heterocyclic radical substituted with one to four carboxylic acid radicals or with one to four sulfonic acid radicals. Charge compensation takes place via one or more Zq + cations. Attachment of the negatively charged radical u-times to the piperidine-1-oxyl radical preferably occurs via a carbon atom of the negatively charged radical.
    [0151] The redox-active components used according to the invention with one to six radicals of formula I or with one to six radicals of formula II in the molecule present counterions Xq-. Through which the ionic charges that result during charging or discharging are compensated for. In the case of Xq- counterions, they may be inorganic or organic q-valent anions.
    [0152] Examples of inorganic anions Xq- are ions of halide, such as fluoride, chloride, bromide or iodide, or hydroxide ions, or anions of inorganic acids, such as phosphate, sulfate, nitrate, hexafluorophosphate, tetrafluoroborate, perchlorate, chlorate, hexafluoroantimonate, hexafluoroarsenate, cyanide.
    [0153] Examples of Xq- organic anions are anions of mono- or polyvalent carboxylic acids or mono- or polyvalent sulfonic acids, in which these acids can be saturated or unsaturated. Examples of organic acid anions are acetate, formate, trifluoroacetate, trifluoromethanesulfonate, pentafluoroethanesulfonate, no-nofluorobutanesulfonate, butyrate, citrate, fumarate, glutarate, lactate, malate, malonate, oxalate, pyruvate or tartrate.
    [0154] In addition, the redox-active components used according to the invention may contain inorganic cations, such as mono- or polyvalent metal ions, or organic cations, such as ammonium, imidazolium, pyridinium, guanidinium, urnium, tioternium, piperidinium , morpholinium or phosphonium. Charge compensation is performed by the Xq- anions.
    [0155] In some cases, the active redox components used according to the invention carry one or more negative charges. Here, charge compensation takes place via Yx or Zq + counterions. However, there may also be cases where the redox-active components have a zwitterionic structure and do not require other anions or cations for charge compensation.
    [0156] In the case of the Yx- anions it can be inorganic or organic valent x anions. Examples of Yx- anions correspond to the examples given above for Xq- anions.
    [0157] In the case of Yx + cations they can be inorganic or organic x-valent cations. Examples of these are x-valent metal ions, or x-valent organic cations, such as ammonium, imidazolium, pyridinium, guanidinium, uronium, thiouronium, piperidinium, morpholinine or phosphonium. Preference is given to the use of mono- or divalent metal ions, in particular alkali metal or alkaline earth metal cations.
    [0158] Zq + cations can be inorganic or organic q-valent cations. Examples of these are q-valent metal ions or q-valent organic cations such as ammonium, imidazolium, pyridinium, guanidinium, uronium, tioteronium, piperidinium, morpholinium or phosphonium. Preference is given to the use of mono- or divalent metal ions, in particular alkali metal or alkaline earth metal cations.
    [0159] Preferably used in redox flow cells are compounds containing halide ions, hydroxy ions, phosphate ions, sulfate ions, perchlorate ions, hexafluorophosphate ions or tetrafluoroborate ions and preferably cations selected from the group of hydrogen ions (H +), alkali and alkaline earth metal cations (eg lithium, sodium, potassium, magnesium, calcium), as well as substituted or unsubstituted ammonium cations (eg tetrabutylammonium, tetramethylammonium, tetraethylammonium), which substituents generally can be alkyl groups.
    [0160] Preference is given to the use of active redox compounds containing one to four, in particular one to two structural units of formula I or II wherein R1 is a covalent CC bond or -O-, -NH-, arylene or heteroarylene , and fully particularly preferred is a covalent CC bond, phenylene, biphenylene or thiophenediyl.
    [0161] Other redox active compounds preferably used are those containing one to four structural units, in particular one to two structural units of the formula I and/or II, in particular those of the formulas Ia or IIa and very particularly preferred those of the formulas Ib , IIb, IV, V VII, VIII, IX, IXa, X or Xa, and more preferably those of the formulas IVa, Va, VIIa, VIIb, VIIc, VIId, Villa, VIIIb, VIIIc, VIIId, IXa, IXb, Xa or Xb, where b and c is zero or where b and c are 1 or 2 and R2 and R3 are respectively methyl, ethyl, methoxy, ethoxy, trifluoromethyl, difluoromethyl, fluoro, chloro, hydroxy, amino or nitro.
    [0162] Other active redox compounds preferably used are those of formula III, VII, VIIa, VIIb VIII, Villa, VIIIb, IX, IXa, IXb, X, Xa or Xb, in particular those of formulas IIIa, IIIb, V, Via , VIIc VII, VIII, VIII, VIII, VIII, VIII, Xc or Xc in which R4, R5, R6 and R7 respectively stand for C1-C6-alkyl and more preferably ethyl or methyl.
    The active redox compounds preferably used are those of the formula IV, V, VII, VIIa, VIIb, VIII, Villa or VIIIb, in particular those of the formulas IVa, Va, VIIc or VIIIc and very particularly preferred those of the formulas Ib, VIId, VIIe, VIIId or VIIIe, in which R8 or R8 and R10 stand for hydrogen, C1-C6 alkyl, C1-C6 alkyl substituted with a carboxylic acid alkyl ester group, C1-C6 alkyl substituted with a carboxylic acid amide group, C1-C6 alkyl substituted with a carboxylic acid group and C1-C6 alkyl substituted with a sulfonic acid group or C1-C6 alkyl substituted with an amino group and very particularly preferably hydrogen, ethyl or methyl.
    [0164] Other active redox compounds preferably used are those of formula IIb, in which R20 and R21 signify hydrogen, C1-C6-alkyl with C1-C6-alkyl substituted with an alkyl carboxylic acid ester group, with C1-C6-alkyl substituted with a carboxylic acid amide group, with a C1-C6-alkyl substituted with a carboxylic acid group, with a C1-C6-alkyl substituted with a sulfonic acid group or with a C1-C6-alkyl substituted with an amino group and totally especially preferably hydrogen, ethyl or methyl or in which the radicals R20 and R21 together form a C1-C3-alkylene group, especially ethylene.
    [0165] Other preferred redox-active compounds are those of formula IIIa, in which R13 is hydrogen, C1-C6-alkyl, C1-C6 alkoxy, C1-C6-partial- or perfluoroalkyl, C1-C6-partial- or perchloroalkyl, C1-C6 fluoroalkyl, phenyl, benzyl, fluorine, chlorine, hydroxy, amino or nitro.
    [0166] The active redox compounds preferably used are those of formula IV or V, in particular those of formula IVa or Va, wherein R9 is alkylene, poly(alkyleneamino), arylene, aryltriyl, arylquaternyl, heterocyclylene, heterocyclyltriyl or heterocyclylquaternyl , most especially preferably C2-C6 alkylene, di-(C2-C6-alkylene), tri-(C2-C6 alkylene), quater-(C2-C-alkyleneamino), phenylene, phenyltriyl or phenylquaternyl.
    [0167] Other redox-active compounds preferably used are those of the formula VII or VIII, in particular those of the formulas VIIc or VIIIc, in which R 12 is alkylene, alkyltriyl, alkylquaternyl, alkyloxyyl, alkyloxytriyl, alkyloxyquaternyl, arylene, aryltriyl, arylquaternyl, heterocyclylene, heterocyclyltriyl or heterocyclylquaternyl, very particularly preferably C2-C6 alkylene, such as ethylene or propylene, or C2-C6-alkoxytyl, such as 1,2-dioxyethylene or 1,3-dioxypropylene, or C3-C6-alkoxytriyl , such as a 1,2, 3-propanetriol radical or a trimethylolpropane radical, or a C4-C6-alkoxyquaternyl radical, such as a pentaerythritol, or phenylene, phenyltriyl or phenylquaternyl radical.
    [0168] Other active redox compounds preferably used are those of formula IX or X, in particular those of formula VIId or VIIId, wherein R is an alkylene, alkyleneamino, poly(alkyleneamino), arylene or heterocyclic radical, very particularly preferably C2-C6-alkylene, C2-C6-alkyleneamino or phenylene.
    [0169] Other active redox compounds preferably used are those of the formula IX or X, especially those of the formulas IXc or Xc, wherein R15 is alkylene, alkyltriyl, alkylquaternyl, arylene, aryltriyl, arylquaternyl, heterocyclyl, heterocyclyltriyl or heterocyclylquaternyl, most particularly preferably C2-C6-alkylene, such as ethylene or propylene, or phenylene, phenyltriyl or phenylquaternyl.
    [0170] Other active redox compounds preferably used are those of the formula VI, wherein R is alkylene, alkyltriyl, alkylquaternyl, alkyloxyyl, alkyloxytriyl, alkyloxyquaternyl, arylene, aryltriyl, arylquaternyl, heterocyclyl, heterocyclyltriyl or heterocyclylquaternyl, very particularly preferably C 2 -C 6 -alkylene, such as ethylene or propylene, or C 2 -C 6 -alkoxytyl, such as 1,2-dioxyethylene or 1,3-dioxypropylene, or C 3 -C 6 -alkoxytriyl, such as a 1,2,3 radical - propanetriol or a trimethylolpropane radical, or a C4 C6 alkoxyquaternyl radical, such as a pentaerythritol radical, or phenylene, phenyltriyl or phenylquaternyl.
    [0171] The indices b and c are preferably each 0 or independently 1 or 2.
    [0172] Index a is preferably 1 or 2 and especially 2.
    [0173] The index q is preferably 1 or 2 and especially 1
    [0174] Index d is preferably 1 or 2 and especially 1.
    [0175] The index g is preferably 1 or 2 and especially 1.
    [0176] The h index is preferably 1 or 2 and especially 1.
    [0177] Particular preference is given to the use of compounds of the formulas VII or VIII, in particular of the formulas VIIa or Villa and very particularly preferably those of the formulas VIIc or VIIIc wherein the index g is 1 and the index h is 1 or 2 or where the g-index means 1 or 2 and the h-index means 1.
    [0178] The index i is preferably 1 or 2 and, in particular, 1.
    [0179] Index j is preferably 1 or 2 and especially 1.
    [0180] The index k is preferably 1, 2 or 4 and in particular 2 or 4.
    [0181] The index f is preferably 1 or 2 and especially 1.
    [0182] The index m is preferably 1 or 2 and especially 1.
    [0183] The index n is preferably 1/2, 1 or 2 and especially 1/2 or 1.
    [0184] Index I is preferably 1/2 or 1 and especially 1.
    [0185] The index o is preferably 1 or 2 and especially 1.
    [0186] The index p is preferably 6, 5, 4, 3, 5/2, 2 or 3/2 and especially 3 or 5.
    [0187] The index r is preferably 9, 6, 9/2 or 3 and in particular 9 or 6.
    [0188] The s index is preferably 3 or 3/2 and especially 3.
    [0189] Index t is preferably 0.
    [0190] Index u is preferably 1 or 2, in particular 1.
    [0191] The index v is preferably -1 or -2 and especially -1.
    [0192] The index x is preferably -1 or -2 and especially -1.
    [0193] The index x1 is preferably -1 or -2 and especially -1.
    [0194] The y index is preferably 1 or 2 and especially 2.
    [0195] The z-index is preferably 1 or 2 and especially 2.
    [0196] The z1 index is preferably 3 or 1, 5 and especially 1.5.
    [0197] The iron salts used according to the invention as catholyte are water-soluble iron salts in oxidation states II and / or III. Iron salts can have any anions, as long as the water solubility of these salts is not questioned.
    [0198] For the purposes of this description, the 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.
    [0199] Examples of iron salts are combinations of Fe(II) chloride with Fe(III) chloride or Fe(II) sulfate with Fe(III) sulfate. In addition to iron salts with inorganic anions, it is also possible to use iron salts with organic anions, eg Fe(II) acetate with Fe(III) acetate.
    [0200] The redox system used according to the invention presents many advantages compared to other material systems for redox flow batteries. For example, noble metal catalysts are needed as in the iron/chromium cell type, as the reaction kinetics of viologen compared to chromium is much faster. Furthermore, redox active materials (TEMPO derivatives, iron (II / III) chloride and dimethylvinyl chloride) are very easily soluble in water, even at neutral pH (more than 2 mol / L at room temperature). This results in high storage capacities (more than 53 Ah / I in 2 mol / l of active materials). The solutions can further dispense with the use of aggressive acid as an electrolyte, as is commonly used in prior art systems (eg in vanadium systems).
    [0201] The redox active materials used according to the invention are also compatible with each other, that is, a mixed solution of TEMPO derivatives and Viologen or iron chloride derivatives can be manufactured (ll / III and Viologen and derivatives this solution can be used both as an anolyte as well as as a catholyte. This significantly reduces the problem of cross contamination through membrane imperfections, which is a major issue for long term stability in other organic / partially organic flow systems. redox.
    [0202] In particular, combination molecules that have a TEMPO functionality and a Viologen functionality bound in one molecule significantly reduce the problem of cross-contamination in all membrane defects. If cross-contamination occurs, the same substance will still be present in the anolyte and catholyte. The combined molecules thus simulate substances - mainly metal / metallic salts, which can assume at least three different redox states, as is the case, for example, with the metal vanadium.
    [0203] Another advantage is that hydrogen formation, which impairs system operation and system safety, can be suppressed because the viologen is capable of oxidizing hydrogen (CL Bird, AT Kuhn, Chem. Soc. Rev.: " Electrochemistry of the Viologens" 40, 1981, p49-82). The hydrogen produced during charging is no longer available to the battery system and therefore means a loss of battery efficiency. Viologene derivatives can therefore also be used as redox-active additives for additional redox flow battery systems. In addition, an advantage of this system is the possibility of achieving a rebalancing of capacity through light, in which the viologen molecule can be converted photoinduced into reduced form (TW Ebbe-sen, Levey G., LK Patterson "Photoreduction of methyl viologen in neutral solution without additives "Nature, 1982 vol 298, p545 - 548). In this way it is possible to save costly external external rebalancing cycles. Rebalancing is a necessary step in vanadium systems to adjust the same amount of charge carriers on the anode and cathode sides.
    [0204] Redox-active components are used in dissolved form; its use as dispersion is also implied.
    [0205] The molecular weights of the redox components used according to the invention containing radicals of formula I or II or III or of formulas I and III or II and III can vary within wide limits. Particular preference is given to the use of redox-active components containing radicals of formula I or II or III or of formulas I and III or II and III whose molar masses are less than 500 g/mol.
    [0206] The viscosity of the electrolyte used according to the invention is typically in the range of 1 mPas to 103 mPas, particularly preferably 10-2 to 102 mPas and very particularly preferably 1 to 20 mPas (measured at 25 °C with a rotating viscos meter, plate/plate).
    [0207] The manufacture of the active redox components used according to the invention can be carried out by conventional methods of organic synthesis. These procedures are known to the version in the art.
    [0208] The redox flow cell according to the invention may contain, in addition to the redox-active components described above, other elements or components usual for such cells.
    [0209] In the redox flow cell according to the invention, selected redox-active components are used in both chambers, which are separated from each other by an ion-conductive membrane and which are present in the chambers in dissolved or dispersed form .
    [0210] The electrolyte contains the redox-active components. Furthermore, an organic solvent and/or water is used. In addition, the electrolyte may contain at least one conductive salt. Furthermore, additives can still be used. Examples of these are surfactants, viscosity modifiers, pesticides, buffers, stabilizers, catalysts, conductive additives, antifreeze agents, temperature stabilizers and/or defoamers.
    [0211] Examples of electrolytic solvents are water, alcohols (eg ethanol), carbonic acid esters (eg propylene carbonate), nitriles (eg acetonitrile), amides (eg dimethylformamide, dimethylacetamide), sulfoxides (eg , dimethylsulfoxide), ketones (for example acetone). Lactones (eg gamma-butyrolactone), lactams (eg A / methyl-2-pyrrolidone), nitro compounds (eg nitromethane), ethers (eg tetrahydrofuran), chlorinated hydrocarbons (eg dichloromethane - no), carboxylic acids (eg formic acid, acetic acid) (eg sulfuric acid, hydrogen halides or hydrohalogenated acids) and mixtures thereof. Water, carbonic acid esters (eg, propylene carbonate), nitriles (eg, acetonitrile) and mixtures thereof are preferred. Water is particularly preferred.
    [0212] Examples of conductive salts are salts containing anions selected from the group of halide ions (fluoride ion, chloride ion, bromide ion, iodide ion), hydroxide ions, inorganic acid anions (eg, phosphate ions, sulfate ions, nitrate ions, hexafluorophosphate ions, tetrafluoroborate ions, perchlorate ions, chlorate ions, hexafluoroantimonate ions, hexafluoroarsenate ions, cyanide ions) or organic acid anions (eg, acetate ions, formate ions, trifluoroacetic acid ions, trifluoroacetic acid ions) trifluoromethanesulfonate, pentafluoroethanesulfonate ions, nonofluorobutanesulfonate ions, butyrate ions, citrate ions, fumarate ions, glutarate ions, lactate ions, malate ions, malonate ions, oxalate ions, pivurate ions, ions). Particularly preferred are chloride and fluoride ions, hydroxide ions, phosphate ions, sulfate ions, perchlorate ions, hexafluorophosphate ions and tetrafluoroborate ions; and cations selected from the group of hydrogen ions (H +), alkali metal or alkaline earth metal cations (eg lithium, sodium, potassium, magnesium, calcium), zinc, iron and substituted ammonium cations or unsubstituted (eg tetrabutylammonium, tetramethylammonium, tetraethylammonium) where the substituents may generally be alkyl groups. Hydrogen ions, lithium ions, sodium ions, potassium ions, tetrabutylammonium ions and their mixtures are particularly preferred. In particular, the conductive salts: NaCl, KCl, LiPF6, LiBF4, NaBF4, NaPF6, NaCIO4, NaOH, KOH, Na3PO4, K3PO4, Na2SO4, Na-SO3CF3, LiSO3CF3, (CH3)4NOH, n-Bu4NOH, (CH3)4NCI , n-Bu4NCI, (CH3)4NBr, n-Bu NBr, n-Bu4NPF6, n-Bu NBF4, n-Bu4NC10 and mixtures thereof, wherein n-Bu represents the n-butyl group.
    [0213] Examples of electrolytic additives are surfactants that can be non-ionic, anionic, cationic or amphoteric. Particular preference is given to nonionic surfactants (eg polyalkylene glycol ethers, fatty alcohol propoxylates, alkyl glucosides, alkyl polyglucosides, octylphenol ethoxylates, nonylphenol ethoxylates, saponins, phospholipids).
    [0214] Other examples of electrolyte additives are buffers (eg, carbonic acid bicarbonate buffer, carbonic acid-bicarbonate buffer, carbonic acid-acetate buffer, phosphate buffer, ammonia buffer, citric acid buffer or citrate buffer, tris (hi- droxymethyl)-aminomethane, 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid, 4-(2-hydroxyethyl)-piperazine-1-propanesulfonic acid, 2-(N-morpholino)ethanesulfonic acid, acetate-barbital buffer).
    [0215] The selection of the redox-active components is such that the redox-active component in the catholyte has a different redox potential, preferably higher, more positive than the redox-active component in the anolyte. Redox-active component is understood to mean all redox states associated with this component or all its reduction/oxidation states. The redox-active component can assume >= 2 oxidation and/or reduction states. If the active redox component > 2 assumes oxidation and/or reduction states, then the redox potential of at least two oxidation and/or reduction states will be different in that a potential difference can be established between the catholyte and the anolyte .
    [0216] According to the invention, the potential difference between the redox reactions of the active redox components that occur in the anolyte and catholyte varies between greater than 0 V and 4.0 V; preferably between 0.5 and 2.5V; more preferably between 0.9 and 1.6V.
    [0217] The redox potential of the active redox component can be determined, for example, by means of cyclic voltammetry. This method is known to those skilled in the art (see Allen J. Bard and Larry R. Faulkner, "Electrochemical Method: Fundamentals and Applications", 2001, 2nd Ed., John Wiley & Johnson, G Compton, Craig E. Banks, "Understanding Voltammetry", 2010, 2nd edition, Imperial College Press)
    [0218] The redox flow cell according to the invention contains a membrane that contains ions. This fulfills the following functions
    [0219] anode and cathode space separation
    [0220] retention of both active redox components
    [0221] permeability for conducting salts of the electrolyte, which serve for charge compensation, that is, for anions and / or cations of the electrolyte salt or for the charge carrier contained in the electrolyte in general.
    [0222] The proposed membrane, for example a membrane permeable to conductive salt ions or a dialysis membrane, separates active redox components with comparatively low molar masses in the two chambers.
    [0223] Depending on the application, the membrane materials can consist of plastics, ceramics, glass, metals or fabrics. Examples of materials are organic polymers such as cellulose or modified cellulose, for example cellulose ethers or cellulose esters, polyethersulfone, polysulfone, polyvinylidene fluoride, polyesters, polyurethanes, polyamides, polypropylene, polyvinyl chloride, polyacryltrile, polystyrene , polyvinyl alcohol, polyphenylene oxide, polyimides, polytetrafluoroethylene and their derivatives, or in addition ceramics, glass or felts. Membranes (composites) made of various materials are also possible.
    [0224] The membranes and the resulting redox flow cells can be used in a variety of ways. Examples are flat membranes, bag filter design, and well-engineered modules. These embodiments are known to those skilled in the art. Flat membranes are preferably used.
    [0225] The membrane used according to the invention can be used for better stability, for example by a plastic material or fabric in the form of a sieve or perforated.
    [0226] The thickness of the membrane used according to the invention can vary within wide limits. Typical thicknesses are in the range between 0.1 m and 5 mm, particularly preferably between 10 µm and 200 µm.
    [0227] In addition to the electroactive components, electrolytes and membranes described above, the redox flow cell according to the invention contains other components. Its about
    [0228] • conveyor means such as pumps as well as tanks and pipes for transporting and storing active redox components
    [0229] • electrodes, preferably consisting of or containing graphite, graphite wool, graphite paper, carbon nanotube screens, activated carbon, carbon black or graphene,
    [0230] • if applicable, current conductors, eg made of graphite or metals.
    [0231] The positive electrode may contain or consist of the following materials:
    [0232] titanium coated with noble metal or diamond, niobium, tungsten, graphite, silicon carbide or tantalum, in particular titanium oxide coated with platinum and / or iridium and / or ruthenium, diamond or with electrically conductive constituents, for example boron, doped diamond, vitreous carbon (Lothar Dunsch Elektrochemische Reaktionen an Glaskohlenstoff, Zeitschrift für Chemie, 14, 12, p463468, December 1974, indium oxide and lead oxide, lead alloy, lead alloy, p. eg lead alloy with 1% silver, tin, tin oxide, carbon black, spinel (as described, for example, in patent document EP 0042984), perovskites (Ca-TiO3), delafosites (containing copper and / or iron oxide), antimony, bismuth, cobalt, platinum and/or platinum black, palladium and/or palladium black, manganese, polypyrrole (as described, for example, in patent document EP 0191726 A2, EP 0206133 A1) , stainless steel, Hastelloy or alloys containing iron-chromium-nickel.
    [0233] Positive electrodes containing nickel are preferably used when the electrolyte has an alkaline pH of >=7-8.
    [0234] Coated electrode materials can employ the following known coating techniques: chemical vapor deposition (CVD), physical vapor deposition (PVD), electrodeposition, non-electrolytic deposition from a liquid solution containing the metal in dissolved form and a reducing agent and wherein the reducing agent causes the deposition of the desired metal on a surface.
    [0235] The negative electrode may contain or consist of the following materials:
    [0236] zinc, stainless steel, Hastelloy or alloys containing iron-chromium nickel, graphite, graphite nonwovens, graphite paper, carbon nanotube screens, activated carbon, carbon black or graphene.
    [0237] Negative nickel-containing electrodes are preferably used when the electrolyte has an alkaline pH of >=7-8.
    [0238] The redox flow cells according to the invention contain as another optional component, but preferred, current conductor. These are tasked with producing the best possible electrical contact between the electrode material and the external power source or current drain
    [0239] As they can be used as current conductors, aluminum, aluminum alloys, stainless steel, Hastelloy, alloys containing iron-chromium-nickel, titanium coated with noble metal or tantalum, in particular titanium oxide coated with platinum and/or iridium and/or ruthenium, niobium, tantalum, hafnium, zirconium.
    [0240] To produce coated current conductors, for example, the following known coating methods are used: chemical vapor deposition (CVD), physical vapor deposition (PVD), electrodeposition without electrostatic deposition from a liquid solution containing the metal in dissolved form it is a reducing agent and wherein the reducing agent effects the deposition of the desired metal onto a surface.
    [0241] The redox flow cell according to the invention can be used in a wide variety of fields. In the broadest sense, this can be electrical energy storage for mobile and stationary applications. The invention also relates to the use of the redox flow cell for these purposes.
    [0242] Examples of applications are the use of stationary storage for emergency power supply, peak load compensation, as well as for the intermediate storage of electricity from renewable energy sources, especially in the photovoltaic and wind sector, from from gas, coal, biomass, tidal and marine power plants and applications in the field of electromobility, such as storage in land, air and water vehicles.
    [0243] The redox flow cell according to the invention is preferably used as a stationary storage for electrical energy.
    [0244] The redox flow cells according to the invention can be interconnected in a way known per se, serially or parallel.
    [0245] The following examples illustrate the invention without limiting it.
    [0246] Example 1: Viologen/iron redox flow battery
    [0247] Theoretical cell potential (E ° is defined as the redox potential in water at 20°C against a silver / silver chloride reference electrode):
    [0248] E ° Fe2+ / Fe3 + = 0.77 V
    [0249] E ° MV2 + / MV + = -0.43V
    [0250] ->Cell voltage = 1.2V
    [0251] An electrolyte solution was prepared consisting of 1-mol / L of Fe-Cl2 and 1 mol / L of dimethylviologen chloride dissolved in an electrolyte solution of 2 mol / L NaCl. The substances are commercially available from Chemicals. The electrolyte solution was tested in a redox flow cell with an active area of 5 cm 2. The loading and unloading operations were carried out both statically (liquid was not pumped) and with the liquid being pumped. It was possible to achieve power densities of up to 120 mW / cm2. The storage capacity was 25 Ah / L. Considering overvoltages, a cellular voltage of approximately 1.0 V was observed
    [0252] Figure 1 plots the OCV curve of this cell as a function of its state of charge. The OCV curve shows the dependence of cell voltage on the state of charge. The cell voltage is measured in the "open circuit", ie it is the cell voltage (open circuit voltage, in short: OCV), which results in a certain state of charge with no external load. The lower these voltage values, the higher the energy content and the more efficiently the system will be operated.
    [0253] Figure 2 shows the load curve of this cell.
    [0254] Example 2:
    [0255] TEMPO-ammonium chloride / viologen redox flow battery
    [0256] theoretical cell potential:
    [0257] E ° TIME-N + / TIME-N | 2+ = 0.78V
    [0258] E ° MV2+ / MV + = -0.43V
    [0259] ->Cell voltage = 1.21V
    [0260] Two electrolyte solutions were prepared: the solution for the working electrode (battery pole-plus) was prepared from 1.0 g of TEMPO-ammonium chloride with the structure below and 0.55 g of NaCl in 10 ml of water. The solution for the counter electrode (battery pole-minus) was prepared from 1.5 g of dimethylviologen chloride and 0.55 g of NaCl in 10 ml of water. The solutions were tested in a redox flow cell with an active area of 5 cm2 (analogous to Example 1). The cell was cyclically loaded and unloaded.
    [0261] Structure of ammonium chloride TIME:

    [0262] Figure 3 plots the OCV curve of this cell as a function of its state of charge.
    [0263] Figure 4 shows that the possible level of potential of the single cell is higher if, instead of a polymeric redox system, a small molecule redox system is used. Figure 4 shows the OCV curve of a cell containing the above-described TEMPO ammonium chloride and dimethyl viologen with chloride as a counterion as active redox components (upper curve). Also shown is the OCV curve of a cell containing a polymer based on TEMPO and Viologen as the redox-active component. It can be seen that the cell voltage of the small molecule system is increased by about 0.2 V; that is, the energy density of the small molecule system is increased by more than 15%, even at the same concentration.
    [0264] Example 3: Redox flow battery TEMPO viologen TEMPO
    [0265] Theoretical potential of the cell:
    [0266] E ° MV-TEMPO 2 + / MV-TEMPO3 + = 0.68V
    [0267] E ° MV TIME 2 + / MV TIME + = -0.46V
    [0268] ->Cell voltage = 1.14V
    [0269] An electrolyte solution was prepared from 213 mg of methylviologen-TEMPO with the following structure and 235 mg of NaCl in 4 ml of water. The solution was used for both the working electrode (battery pole-plus) and the counter electrode (battery pole-minus) and tested in a redox flow cell with an active area of 5 cm 2 (analogous to Example 1, liquid not pumped). The cell was cyclically loaded and unloaded. In addition, an OCV curve was recorded.
    [0270] Methyl Viologen Structure TIME:

    [0271] Figure 5 plots the OCV curve of this cell as a function of its state of charge (SOC).
    [0272] Figure 6 shows the load curve of this cell.
    [0273] Example 4: Viologen propanoate redox flow battery - TEMPO
    [0274] Theoretical potential of the cell:
    [0275] E ° MV -TEMP02 + / MV-TEMPO3 += 0.67V
    [0276] E ° MV-TEMP0 2 + / MV-TEMPO + = -0.49V
    [0277] ->Cell voltage = 1.16V
    [0278] An electrolyte solution was prepared from 110 mg of propane-ato-viologen -TEMPO with the following structure and 117 mg of NaCl in 2 ml of water. The solution was used for both the working electrode (battery pole-plus) and the counter electrode (battery negative pole) and tested in a redox flow cell with an active area of 5 cm 2 (analogous to Example 1) . not pumped). The cell was cyclically loaded and unloaded. In addition, an OCV curve was recorded.
    [0279] Propanoate-viologen Structured

    [0280] Figure 7 plots the OCV curve of this cell as a function of its state of charge (SOC).
    [0281] Figure 8 shows the load curve of this cell.
    [0282] Synthesis Examples
    [0283] Example 5: Synthesis of Ammonium Chloride-TEMPO

    [0284] 4-Oxo-2,2,6,6-tetramethylpiperidine-1-oxyl (2)
    [0285] 20 g of 4-oxo-2,2,6,6-tetramethylpiperidine (1), 2 g of Na2WO4x2 H2O and 2 g of Na2H2EDTA were dissolved in 133 ml of water at room temperature. 26.6 ml of hydrogen peroxide (30%) were added under stirring. Reaction progress was monitored by gas chromatography (GC) and added to the complete conversion of (1) plus another 5 ml portions of hydrogen peroxide. The red reaction solution was separated from the green precipitate and washed with 150 ml of water. The aqueous phase was extracted seven times with 50 ml of dichloromethane and dried over magnesium sulphate. The solvent was removed and the product was dried (60% yield) under vacuum.
    [0286] 4-(dimethylamino)-2,2,6,6-tetramethylpiperidine-1-oxyl (3)
    [0287] 2 g of 4-oxo-2,2,6,6-tetramethylpiperidine-1-oxyl (2) was dissolved in 20 ml of dry methanol and 7.3 g of dimethylamine hydrochloride was added under argon shielding gas atmosphere. Upon cooling and stirring, the reaction mixture was treated with 444 mg of NaBH3CN. After 48 hours, it was made alkaline with sodium hydroxide solution and extracted three times with 50 ml of dichloromethane. The organic phase was dried over magnesium sulphate, the solvent removed and the crude product dried in vacuo. The resulting crude product was used further without further purification in the next step.
    [0288] 1-oxyl-A/, A, W-2,2,6,6-heptamethylpiperidine-4-ammonium chloride (4, abbreviated: ammonium chloride-TEMPO)
    [0289] The crude product 4-(dimethylamino)-2,2,6,6-tetramethylpiperidine-1-oxyl (3) was completely dissolved in 20 ml of diethyl ether, the solids were removed by filtration and a solution of 1 .42 g of methyl iodide in 5 ml of diethyl ether. After the solution was stirred at room temperature for 20 hours, the resulting precipitate was separated and washed with 20 ml of diethyl ether. The precipitate was dissolved in 50 ml of water and an ion exchange of the iodide counterion on chloride on an ion exchange resin (Dowex Marathon A2, chloride form). The resulting solution was lyophilized and the product was obtained as an orange powder (89% yield).
    [0290] Example 6: Synthesis of Methylviologen-TEMPO

    [0291] 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl-4-(chloromethyl)benzoate (7)
    [0292] To a solution of 5 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine-A/-oxyl (6) in 80 ml of dry chloroform and 8 ml of dry triethylamine were added 4.3 ml of 4-(chloromethyl)benzoyl chloride (5) was added dropwise with stirring at room temperature. After six hours, the reaction mixture was added to a mixture of 300 ml of ice water and 50 ml of 5% bicarbonate solution, stirred and extracted three times with 200 ml of chloroform. The organic phase was washed with 200 ml of water, dried over magnesium sulphate and the solvent removed under vacuum. After drying under vacuum, the crude product was obtained as an orange powder (yield 95%). The resulting crude product was used further without further purification in the next step.
    [0293] 1-(4-((1-oxy-2,2,6,6-tetramethylpiperidin-4-yl)oxy)carbonyl)benzyl)-[4,4'-bipyridin]-1-ium chloride ( 8)
    [0294] To 4.5 g of the crude product of 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl-4-(chloromethyl)benzoate (7) and 2.2 g of 4.4' - bipyridine 80 ml of acetonitrile were added and the solution was stirred at 80°C for 72 hours. The reaction mixture was precipitated into 450 ml of cold ethyl acetate, the resulting precipitate was separated and dried under vacuum. The product was obtained as an orange solid (78% yield).
    [0295] 1-(4-((1-oxyl-2,2,6,6-ethramylpiperidin-4-yl)oxy)carbonyl)benzyl)-1,-methyl[4,4'-bipyridine]-chloride 1, 1'-io (9, abbreviated: methylviologen TEMPO)
    [0296] Variant A: To a solution of 2 g of 1-(4-((((1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)oxy)carbonyl)benzyl)-[chloride] 4,4']-bipyridin]-1-yl (8) in 8 ml of water was added chloromethane (pressure 2 bar) in a pressure reactor. product was obtained as a solid (yield 95%) by lyophilization.
    [0297] Variant B: To a solution of 0.5 g of 1-(4-(((1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)oxy)carbonyl)benzyl)-chloride [4,4'-bipyridin]-1-ylium (8) in 12 ml DMSO was added 0.14 ml methyl iodide. The reaction mixture was stirred at 60°C for 6 hours and then precipitated into 150 ml of acetic ester. The precipitate was dissolved in water and the ion exchange of the iodide counter ion was carried out in chloride on an ion exchange resin (Dowex Marathon A2, chloride form). The resulting solution was lyophilized and the product obtained as an orange powder (yield 82%)
    [0298] Example 7: Synthesis of propanoatoviologen-TEMPO

    [0299] 3-(1'-(4-(((1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)oxy)carbonyl)benzyl)-[4,4'-bipyridine] chloride -1, 11-diio-1-yl) propanoate (10, abbreviated: propanoate viologen TEMPO)
    [0300] To 2 g of 1-(4-((1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)oxy)carbonyl)benzyl)-[4,4'-bipyridine]-chloride 10(8) was added in 10 ml of acetonitrile with stirring 3 ml of acrylic acid. The solution was stirred at 60°C for 30 minutes, cooled and precipitated into cold ethyl acetate. The precipitate was separated, dried under vacuum and the target product obtained as a powder (56% yield).
    [0301] Example 8: Synthesis of Multifunctionalized Viologen Viologene

    [0302] 1-Methyl-[4,4'-bipyridin]-1-yl chloride (11)
    [0303] 100 g of 4,4'-bipyridine were placed in 200 ml of acetonitrile and 200 ml of toluene in a pressure reactor. After the addition of 32.4 g of chloromethane, the solution was stirred at 70°C for 26 hours. The solvent was removed under vacuum and the product (98% yield) was obtained as a gray powder.
    [0304] 1',1'''oxybis(ethane-2-diyl)) bis(1-methyl-[4',-bipyridin]-1, 1'-diyl) chloride (13)
    [0305] To 0.2 g of 1-methyl-[4,4'-bipyridin]-1-ium chloride (11) was added 61 µl of 1-bromo-2-(2-bromoethoxy) ethane (12 ), 18 mg of tetrabutylammonium iodide and 2 ml of DMSO. The reaction mixture was stirred at 110°C for 3 days, cooled and precipitated into cold ethyl acetate. The precipitate was dissolved in water and the ion exchange of the iodide counterion on chloride was performed on an ion exchange resin (Dowex Marathon A2, chloride form). The resulting solution was lyophilized and the product was obtained as an orange powder (73% yield)
    [0306] Analytical data on the target products of Examples 5 to 8
    [0307] 1H NMR spectra were recorded on a Bruker Fourier 300 (300 MHz). The TEMPO radicals were reduced with phenylhydrazine or hydrazine hydrate, so that there were no paramagnetic species that could interfere with the measurements.
    [0308] Cyclic voltammograms were measured in a 3-electrode configuration using a glassy carbon disc electrode as the working electrode, a platinum wire as the counter electrode and a silver/silver chloride electrode as the reference. The electrolyte used was an aqueous solution of sodium chloride (0.1 mol / 1).
    [0309] 1-Oxyl Chloride / V, / V, / V-2,2,6,6-heptamethylpiperidin-4-ammonium chloride (4, abbreviated: ammonium chloride - TEMPO)
    [0310] 1H NMR (DMSO, 300 MHz) δ: 3.73 (1H, m); 3.02 (9H, s); 1.99 (2H, m); 1.55 (2H, m); 1.09 (12H, d).
    [0311] Figure 9 shows a cyclic voltammogram of the substance in aqueous sodium chloride solution (0.1 mol / l), measured against a silver / silver chloride reference electrode
    [0312] 1-(4-((1-oxyl-2,1,6,6-tetramethylpiperidin-4-yl)oxy)carbonyl)benzyl)-1'-methyl-[4,4'-bipyridin] chloride -1, 1'-dio (9, abbreviated: methyl viologen TEMPO)
    [0313] 1H NMR (D20, 300 MHz) δ: 9.09 (2H, d); 8.94 (2H, d); 8.44 (4H, m); 8.01 (2H, d); 7.52 (2H, d); 5.93 (2H, s); 5.28 (1H,m); 4.40 (3H, s); 2.13 (2H, m); 1.82 (2H, m); 1.24 (12H, s).
    [0314] Figure 10 shows a voltammogram of the cyclic substance in aqueous sodium chloride solution (0.1 mol / l), measured in relation to a silver / silver chloride reference electrode
    [0315] 3-(1 4 -(((1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)oxy)carbonyl)benzyl)-[4,4'-bipyridin]-1, chloride 1' dio-1-yl) propanoate (10, abbreviated: viologen TEMPO propanoate)
    [0316] 1H NMR (D2O, 300 MHz) δ: 9.05 (4H, m); 8.43 (4H, m); 8.02 (2H, d); 7.51 (2H, d); 5.92 (2H, s); 5.31 (1H,m); 4.81 (2H,t); 2.87 (2H,t); 2.16 (2H, m); 1.84 (2H, m); 1.26 (12H, d).
    [0317] Figure 11 shows a cyclic voltammogram of the substance in aqueous sodium chloride solution (0.1 mol / l), measured against a silver / silver chloride reference electrode. The solid lines here represent the individual measure of the anodic or cathodic area, while the dashed line represents a measure of the entire area.
    [0318] 1', 1m-(oxy-bis(ethane-2,1-diyl)) bis(1-methyl-[4,4'-bipyridin]-1,1'-diyl) chloride (13)
    [0319] 1H NMR (DMSO, 300 MHz) δ: 9.09 (4H, m); 8.99 (4H, m); 8.50 (8H, m); 4.88 (4H, m); 4.45 (6H, s); 4.06 (4H, m).
    权利要求:
    Claims (16)
    [0001]
    1. Redox flow cell for the storage of electrical energy, characterized in that it comprises a reaction cell with two electrode chambers for catholyte and anolyte, which are in connection respectively with at least one liquid reservoir, which are separated by an ion-conductive membrane, and which are equipped with electrodes, and the electrode chambers are respectively filled with electrolyte solutions, which comprise redox-active components dissolved or dispersed in an electrolyte solvent, as well as optionally conducting salts there dissolved substances and optionally other additives, wherein the anolyte contains an active redox component comprising from one to six formula I residues in the molecule or comprises from one to six formula II residues in the molecule, wherein the catholyte contains an active redox component which comprises from one to six residues of formula III in the molecule, or comprises the iron salts or wherein anolyte and catholyte contain a co. redox-active component, comprising from one to six radicals of formula I or formula II in combination with one to six radicals of Formula III in the molecule
    [0002]
    2. Redox flow cell according to claim 1, characterized in that, in the anolyte, a compound of the formulas Ib, IIb, IV, V, VII, VIIa, VIIb VIII, VIlla, VIIIb, IX, IXa, IXb , X, Xa, Xb, XI, Xla, Xlb, XII, Xlla and/or Xllb is used as a redox-active component. Ra N+ 7 / + NR
    [0003]
    3. Redox flow cell according to claim 2, characterized in that a compound of the formulas IVa, Va, VIIc, VIIIc, IXc and/or Xc is used as the redox-active component in the anolyte
    [0004]
    4. Redox flow cell according to claim 1, characterized in that, in the catholyte, a compound of formulas IIIa, IIIb, IIIc, VI, VIa and/or VIb or of formulas VII, VIIa, VIIb, VIII, VIIIa, VIIIb, IX, IXa, IXb, X, Xa and/or Xb, as defined in claim 2, is used as a redox-active component
    [0005]
    5. Redox flow cell according to claim 3 or 4, characterized in that a compound of formulas VI, VIIIc, VIIIc, IXc and/or Xc defined in claim 3 or 4 is used as a redox-active compound in the catholyte .
    [0006]
    6. Redox flow cell according to claim 1, characterized in that a compound of the formulas Ib, IIb, Vlld, VIIIe, VIII and/or VIIIll is used as a redox-active compound
    [0007]
    7. Redox flow cell according to claim 1, characterized in that the catholyte contains compounds of the formulas IIIa, IIIb or Mio as defined in claim 4 and the anolyte contains compounds of the formulas Ib or IIb as defined in claim 2.
    [0008]
    8. Redox flow cell according to claim 7, characterized in that the catholyte contains a compound of formula IIIb and the anolyte contains a compound of formula Ib.
    [0009]
    9. Redox flow cell according to claim 8, characterized in that the compound of formula IIIb is a 2,2,6,6-tetramethylpiperidin-1-yloxyl-4-(N,N,N-trialkylammonium salt) ) and that the compound of formula Ib is a salt of N,N'-dialkylviologen.
    [0010]
    10. Redox flow cell according to claim 1, characterized in that compounds of the formulas VII, VIIa, VIIb, VIIc, VIId, VIIe, VIII, VIIIa, VIIIb, VIIc, are used in the catholyte and/or the anolyte, VIIId, VIIIe, IX, IXa, IXb, IXc, X, Xa, Xb or Xc as defined in claim 2, 3 or 6.
    [0011]
    11. Redox flow cell according to any one of claims 1 to 10, characterized in that compounds containing halide ions, hydroxide ions, phosphate ions, sulfate ions, perchlorate ions, hexafluorophosphate ions or tetrafluoroborate ions and, of preferably, cations selected from the group of hydrogen ions, alkali or alkaline earth metal cations, as well as substituted or unsubstituted ammonium cations.
    [0012]
    12. Redox flow cell according to any one of claims 1 to 11, characterized in that active redox compounds containing one to four structural units of formula III, VII, VIIa, VIIb VIII, VIIIa, VIIIb, IX are used , IXa, IXb, X, Xa or Xb, in particular those of formulas IIIa, IIIb, V, VIa, VIIc, VIId, VIIe, VIIIc, VIIId, VIIIe, IXc or Xc, in which R4, R5, R6 and R7 are respectively C 1 -C 6 -alkyl and particularly preferably ethyl or methyl.
    [0013]
    13. Redox flow cell according to claim 2, 3 or 6, characterized in that active redox compounds of formulas IV, V, VII, VIIIa, VIIIb, VIII, VIIIa or VIIIb are used, especially those of formulas IVa , Va, VIIIc or VIIIc and fully especially preferably those of the formulas Ib, VIIId, VIIIe, VIIId or VIIIe, in which R8 or R8 and R10 stand for hydrogen, C1-C6-alkyl, C1-C6-alkyl substituted with an alkyl ester group of carboxylic acid, C1-C6-alkyl substituted with a carboxylic acid amide group, C1-C6-alkyl substituted with a carboxylic acid group, C1-C6-alkyl substituted with a sulfonic acid group or C1-C6-alkyl substituted with a amino group, and fully especially preferably means hydrogen, propionate, isobutionate, ethyl or methyl.
    [0014]
    14. Redox flow cell according to claim 4, characterized in that active redox compounds of formula IIIa are used, in which R13 is hydrogen, C1-C6-alkyl, C1-C6-alkoxy, C1-C6-partial or perfluoroalkyl, C1-C6 - partial or perchloroalkyl, C1-C6-fluoro-chloroalkyl, phenyl, benzyl, fluoro, chloro, hydroxy, amino or nitro.
    [0015]
    15. Redox flow cell according to claim 4, characterized in that redox-active compounds of the formula VI are used, in which R11 is alkylene, alkyltriyl, alkylquaternyl, alkyloxytyl, alkyloxytriyl, alkyloxyquaternyl, arylene, aryltriyl, arylquaternyl, heterocyclylene, heterocyclyltriyl or heterocyclylquaternyl is particularly preferably C2-C6-alkylene, such as ethylene or propylene, or C2-C6-alkoxyalkyl, such as 1,2-dioxyethylene or 1,3-dioxypropylene, or C3-C6-alkoxytriyl , such as a 1,2,3-propanetriol radical or a trimethylolpropane or C4-C6-alkoxyquaternyl radical, such as a pentaerythritol, or phenylene, phenyltriyl or phenylquaternyl radical.
    [0016]
    16. Use of the redox flow cell as defined in any one of claims 1 to 15, characterized in that it is for the storage of electrical energy for stationary and mobile applications, in particular as a stationary store for the supply of emergency energy, peak load balancing, for the intermediate storage of electrical energy from renewable energy sources, in particular in the photovoltaic and wind energy sector, or from gas, coal, biomass, tidal and marine power plants and for use in the field of electromobility, such as storage in land, air and water vehicles.
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    法律状态:
    2020-02-18| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-03-30| B25C| Requirement related to requested transfer of rights|Owner name: JENABATTERIES GMBH (DE) ; FRIEDRICH-SCHILLER-UNIVERSITAET JENA (DE) Free format text: A FIM DE ATENDER A TRANSFERENCIA, REQUERIDA ATRAVES DA PETICAO NO 870200157829 DE 16/12/2020, E NECESSARIO ESCLARECER SE A CESSAO E TOTAL OU PARCIAL, POIS FOI PEDIDO CESSAO TOTAL DOS DIREITOS, MAS O DOCUMENTO DE CESSAO APRESENTADO E DE CESSAO PARCIAL. |
    2021-03-30| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-06-22| B25A| Requested transfer of rights approved|Owner name: JENABATTERIES GMBH (DE) |
    2021-07-06| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 03/08/2016, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    DE102015010083.1|2015-08-07|
    DE102015010083.1A|DE102015010083A1|2015-08-07|2015-08-07|Redox flow cell for storing electrical energy and its use|
    PCT/EP2016/001338|WO2017025177A1|2015-08-07|2016-08-03|Redox flow cell for storing electrical energy and use thereof|
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