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    • 专利摘要:
    REDOX FLOW CELL COMPRISING HIGH MOLECULAR WEIGHT COMPOUNDS SUCH AS REDOX PAIR AND SEMIPERMEABLE MEMBRANE FOR ELECTRIC ENERGY STORAGE The present invention provides, through the use of new materials and membranes and with very little expense, an economical and life-saving redox flow cell which, even in the event of a serious accident, causes little environmental pollution by its compounds with redox activity. According to the invention, compounds with high molecular weights such as polymers or oligomers with redox activity are provided as components with redox activity and a size exclusion membrane (3) is provided as a membrane for separating high molecular weight components with redox activity.
    公开号:BR112015002936B1
    申请号:R112015002936-1
    申请日:2013-07-25
    公开日:2021-05-11
    发明作者:Ulrich Sigmar Schubert；Martin Hager；Tobias Janoschka
    申请人:Jenabatteries GmbH；
    IPC主号:
    专利说明:

    [001] The present invention refers to a redox flow cell, in general use language, also referred to as redox flow battery, for the storage of electrical energy. The redox flow cell contains two polarity-specific chambers in each of which a chemical compound with redox activity is present in dissolved form or a chemical compound with redox activity is present in dissolved form in both chambers and is linked to a deposit of liquid. In this way, two independent circuits are formed for compounds with redox activity that dissolve in, for example, water or an organic solvent, which are separated by a membrane between the polarity-specific chambers. The ion exchange between the two chambers takes place through this membrane.
    [002] The cells are particularly suitable for stationary storage applications, for example, as a buffer battery for wind power plants or as low-equalizing power and regulatory reserves in power networks, and also as mobile power reserves, for example. , for the operation of cars and electronic devices.
    [003] Existing redox flow batteries (RFB) are electrochemical energy stores. The compounds needed to establish the potential at the electrodes are dissolved, species with redox activity that are converted to their other redox state in an electrochemical reactor during the charging or discharging process. For this purpose, electrolyte solutions (catholyte, anolyte) are taken from a tank and actively pumped into the electrodes. The anode space and the cathode space are separated in the reactor by means of an ion selective membrane which usually has a high selectivity for protons. As the electrolyte solution is pumped, power can be withdrawn. The charging process is then simply the reverse of that process. The amount of energy that can be stored in an RFB is therefore directly proportional to the size of the storage tank. The power that can be drawn, on the other hand, is a function of the size of the electrochemical reactor.
    [004] RFBs have a complex system technology (BoP - Power Plant Balance), which roughly corresponds to that of a fuel cell. Usual construction sizes of individual reactors are in the range of about 2 to 50 kW. The reactors can be combined very simply in a modular form, and the tank size can also be adapted practically at will. RFBs that operate using vanadium compounds as a redox pair on both sides (VRFB) are of particular importance here. This system was first described in 1986 (AU 575247 B) and is currently the technical standard. Other inorganic low molecular weight redox pairs have been studied, including those based on cerium (B. Fang, S. Iwasa, Y. Wei, T. Arai, M. Kumagai: "A study of the Ce(III)/Ce ( IV) redox couple for redox flow battery application", Electrochimica Acta 47, 2002, 3971-3976), ruthenium (MH Chakrabarti, E. Pelham, L. Roberts, C. Bae, M. Saleem: "Ruthenium based redox flow battery for solar energy storage", Energy Conv. Manag. 52, 2011, 2501-2508), chrome (CH. Bae, EPL Roberts, RAW Dryfe: "Chromium redox couples for application to redox flow batteries", Electrochimica Acta 48, 2002 , 279-87), uranium (T. Yamamura, Y. Shiokawa, H. Yamana, H. Moriyama: "Electrochemical investigation of uranium β-diketonates for all-uranium redox flow battery', Electrochimica Acta 48, 2002, 43-50 ), manganese (F. Xue, Y. Wang, W. Hong Wang, X. Wang: "Investigation on the electrode process of the Mn(II)/Mn(III) couple in redox flow battery", Electrochimica Acta 53, 2008 , 66366642) and iron (Y. Xu, Y., Wen, J. Cheng, G. Cao, Y. Yang: "A study of iron in aqueous solutions for redox flow battery application", Electrochimica Acta 55, 2010, 715-720 ). However, these systems are based on electrolytes that contain metals that are toxic or harmful to the environment.
    [005] VRFB reactors can currently be obtained in blocks from 1 to 20 kW. Higher power outputs are achieved by modular connection of these reactors. Each individual block contains a multiplicity of flat cells that are connected in series to achieve a higher voltage. This bipolar construction largely corresponds to the construction of a PEM fuel cell. A perfluorinated polymer having sulfonic acid groups, usually DuPont's Nafion ® 117, is used as a membrane. Other polymers have been described, for example, SPEEK-based polymers (Q. Luo, H. Zhang, J. Chen, D. You, C. Sun, Y. Zhang: "Nafion/SPEEK composite: Preparation and characterization of Nafion/ SPEEK layered composite membrane and its application in vanadium redox flow battery", J. Memb. Sci. 325, 2008, 553-558), PVDF (J. Qiu, J. Zhang, J. Chen, J. Peng, L. Xu , M. Zhai, J. Li, G. Wei: "Amphoteric ion exchange membrane synthesized by radiation-induced graft copolymerization of styrene and dimethylaminoethyl methacrylate into PVDF film for vanadium redox flow battery applications", J. Memb. Sci. 334, 2009 , 9-15), QPPEK (S. Zhang, C. Yin, D. Xing, D. Yang, X. Jian: "Preparation of chloromethylated/quaternized poly(phthalazinone ether ketone) anion exchange membrane materials for vanadium redox flow battery applications ", J. Memb. Sci. 363, 2010, 243 249), non-fluorinated sulfonated polyarylene (D. Chen, S. Wang, M. Xiao, Y. Meng: "Synthesis and properties of novel sulfonated poly(arylene e) ther sulfone) ionomers for vanadium redox flow battery", Energy Conv. Management 51, 2010, 2816-2824) or inorganic-organic composite materials comprising SiO2 (J. Xi, Z. Wu, X. Qiu, L. Chen: "Nafion/SiO2 hybrid membrane for vanadium redox flow battery", J. Pow. Sour. 166, 2007, 531-536), but, in contrast to Nafion membranes, they are not yet practical and commercially available. The same applies to nanofiltration membranes that allow protons from the acid electrolyte to pass through them and the vanadium salts to be retained (Hongzhang Zhang, Huamin Zhang, Li Xianfeng, Zhensheng Mai, Jianlu Zhang: "Nanofiltration (NF) ) membranes: the next generation separators for all vanadium redox flow batteries (VRBs)", Energy & Environmental Science, 2011, 4, 1676-1679). Regardless of these, the same disadvantages such as high cost and environmental pollution in case of a serious accident and also short cell life also apply here.
    [006] In the present state of the art, the use of ion-conducting membranes further limits commercialization, since standard Nafion ® membranes are expensive, contain fluorine and are mechanically weak; in addition, they swell to a great degree and are susceptible to an electrochemical short circuit due to internal diffusion of vanadium ions.
    [007] Purely organic redox compounds have been used very little so far in RFBs. Thus, low molecular weight 2,2,6,6-tetramethylpiperidinyloxy (TEMPO) and N-methylphthalimide were used in an RFB with an ion conducting membrane (Z.Li, S.Li, SQ Liu, KL Huang, D. Fang, FC Wang, S. Peng: "Electrochemical properties of an all-organic redox flow battery using 2,2,6,6-tetramethyl-1-piperidinyloxy and N-methylphthalimide", Electrochem. Solid State Lett. 14, 2011, A171-A173). Furthermore, rubren is discarded because of high costs and very low solubility, despite good electrochemical properties (cf. H. Charkrabarthi, RAW Dryfe, EPL Roberts, Jour. Chem. Soc. Pak. 2007, 29, 29, 294-300 "Organic Electrolytes for Redox Flow Batteries").
    [008] Batteries based on 2,3,6-trimethylquinoxaline also utilize expensive ion selective Nafion ® membranes (FR Brushett, JT Vaughey, AN Jansen: "An All-Organic Non-aqueous Lithium-Ion Redox Flow Battery", Adv. Energy Mater. 2012, 2, 1390-1396).
    [009] Pyrazine-based cyanoazacarbons (US 8,080,327 B1) have been used both as an anolyte and a catholyte, with ion-conducting membranes based on cation exchangers and anion exchangers being used to separate the spaces between the electrodes. These membranes are expensive and in each case permeable only to a particular class of ions. This is reflected, in particular, in the construction of a disadvantageous system that has to use an electrolyte reservoir between the anolyte circuit and the catholyte circuit. This is necessary to ensure charge/mix equalization of the anions that diffuse through the anion exchange membrane into the reservoir and of the cations that diffuse through the cation exchange membrane into the reservoir.
    [0010] In addition to the redox organic compounds, they are described with low molecular weight organometallic stations (MH Chakrabartia, RAW Dryfe, EPL Roberts: "Evaluation of electrolytes for redox flow battery applications", Electrochimica Acta, 52, 2007, 21892195) . Here, organic binders which complex with inorganic salts of metals are used. Such linkers are, for example, bipyridyl, terpyridyl, phenanthroline or imidazoles (US 2012/0171541 A1). For such systems, too, expensive ion-conducting membranes such as Nafion ® or amine-functionalized polystyrene derivatives have to be used. The same applies to redox flow batteries based on low molecular weight ruthenium-bipyridine complexes which, for example, employ Neocepta ® anion exchange membranes. Other membranes are, on the contrary, permeable to these complexes and lead to a low battery efficiency in the present case (Y. Matsuda, K. Tanaka, M. Okada, Y. Takasu, M. Morita, T. Matsumura-Inoue: " A rechargeable redox battery utilizing ruthenium complexes with nonaqueous organic electrolyte", J. Applied Electrochem. 18, 1988, 909914).
    [0011] It is an objective of the invention to provide, through the use of new materials and membranes and with very little expense, an economical and long-lived redox flow cell that, even in the case of an eventual serious accident, causes little environmental pollution by its compounds with redox activity.
    [0012] This objective is achieved according to the invention by a redox flow cell for energy storage, containing a reaction cell that has two chambers specific to polarity 1, 2 for catholyte and anolyte, which are each connected to a reservoir for liquid and are separated by an ion exchange membrane, in which chambers 1, 2 are each filled with components with redox activity present undiluted, in dissolved or dispersed form in an electrolyte solvent, and also conductive salts dissolved in the solvent and possibly other additives, as a result of the fact that high molecular weight compounds are provided as components with redox activity and a size 3 exclusion membrane is provided as a membrane to separate the high molecular weight components with redox activity present undiluted, dissolved or dispersed form.
    [0013] Preference is given to redox flow cells in which chambers 1, 2 are each filled with components with redox activity that are present in undiluted form or as a solution in water or an organic solvent.
    [0014] For the purposes of this description, the term "size exclusion membrane" refers to a membrane that has at least the following functionalities: • separation of the space between anode and cathode • retention of high molecular weight components with redox activity • permeability for the conducting salts of the electrolyte that serve for charge equalization, that is, for anions and cations of the conducting salt.
    [0015] The retention principle of the membrane used according to the invention is based on the principle of size exclusion, that is, the membrane distinguishes between components with redox activity and conductive salt ions based on their size, which can be described, for example, by the molar mass (number average), the number of repeating units, ionic radius and/or inertial radius.
    [0016] For the purposes of this description, selectivity is the separation threshold at which molecules can no longer pass through the membrane efficiently. This means that under a given molecular weight of the molecule at least 90% of the molecules are retained by the membrane.
    [0017] The proposed size exclusion membrane, for example a semipermeable membrane or a dialysis membrane, preferably separates these high molecular weight components with redox activity in the two chambers with a selectivity of at least 500 g/mol , particularly preferably of at least 550 g/mol, where organic or organometallic materials with redox activity, polymers or oligomers which consequently have a molar mass greater than the selectivity of the size exclusion membrane are used as high mole weight components - eyepieces.
    [0018] The size exclusion membrane employed according to the invention performs separation by means of a physical (mechanical) membrane separation process. Here, the size exclusion principle is used, that is, all particles in the polarity-specific chambers for catholyte and anolyte that are larger than the membrane pores are retained by the membrane.
    [0019] The size exclusion membrane used according to the invention can consist of a variety of materials, provided that the aforementioned functionalities are ensured. The size exclusion membrane materials may, depending on the particular application, consist of plastics, ceramics, glasses, metals or sheet-shaped textile structures. Examples of materials are organic polymers such as cellulose or modified cellulose, for example cellulose ethers or cellulose esters, polyether sulfone, polysulfone, polyvinylidene fluoride, polyesters, polyurethanes, polyamides, polypropylene, polyvinyl chloride, polyacrylonitrile, polystyrene, polyvinyl alcohol, polyphenylene oxide, polyimides, polytetrafluorethylene and their derivatives, or ceramics, glass or felts. Size exclusion membranes consisting of a multiplicity of materials (composites) are also possible.
    [0020] Size exclusion membranes can be used in various forms of load elements. Examples of these membranes are flat membranes, bag filters and hollow fiber modules. Such embodiments are known to the person skilled in the art. Preference is given to the use of flat membranes.
    [0021] The size exclusion membrane used according to the invention can be supported to allow better stability.
    [0022] The thickness of the size exclusion membrane used in accordance with the invention can vary within a wide range. Typical thicknesses are in the range of 1 µm to 5 mm, particularly preferably 10 µm to 200 µm.
    [0023] The redox active high molecular weight components used according to the invention can be any compounds that can be present in at least two different stable oxidation states and with molecular weights such that they cannot cross the exclusion membrane by size employed in accordance with the invention.
    [0024] High molecular weight components with redox activity can be polymers or oligomers; here, the term oligomers refers to compounds that have a molar mass of 500 to 5,000 g/mol (number average) and the term polymers refers to compounds that have a molar mass greater than 5,000 g/mol (number average) .
    [0025] Typical redox-active components used in accordance with the invention are oligomers or polymers that have a polymer backbone containing one or more active units. These active units can be coupled to the polymer backbone in a variety of ways. Covalent bonding of active units to the polymer backbone may be present, i.e. the active moieties covalently bond as side groups to the polymer backbone, for example via CC bonds or by bridging groups such as -O- , -S-, -NH-, CO-, -CONH- or -COO-. However, the active moieties can also form a component of the polymer backbone and are then covalently incorporated into the polymer backbone, for example, via CC bonds or by bridging groups such as -O-, -S-, - NH-, CO-, -CONH- or -COO-. Finally, the active units can also be coordinated with the polymer backbone or linked to the polymer backbone through supramolecular interactions, eg via hydrogen bonds, ionic interactions, pi-pi interactions or as Lewis acid, with groups that have Lewis base properties which in turn bind to the polymer backbone, or as a Lewis base with groups that exhibit Lewis acid properties which in turn bind to the backbone of polymer.
    [0026] Examples of compounds that can form the main polymer chain are polymers derived from ethylenically unsaturated carboxylic acids or their esters or amides, for example, polymethacrylates, polyacrylates or polyacrylamide, polymers derived from ethylenically unsaturated aryl compounds for example polystyrene, polymers derived from vinyl esters of saturated carboxylic acids or derivatives thereof, for example polyvinyl acetate or polyvinyl alcohol, polymers derived from bicyclic or polycyclic olefins or olefins, for example polyethylene, polypropylene or polynorbornene, polyimides derived from tetracarboxylic acids which form imides and diamines, polymers derived from naturally occurring polymers and their chemically modified derivatives, eg cellulose or cellulose ethers, and also polyurethanes, polyvinyl ethers, polythiophenes , polyacetylene, polyalkylene glycols, poly-7-oxanorbornene, polysiloxanes, pol ialkylene glycol and its derivatives, for example its ethers, preferably polyethylene glycol and its derivatives. Particularly preferred classes of materials used which form the polymer backbone are polymethacrylates, polyacrylates, polystyrene, polyalkylene glycols and polyvinyl ethers.
    [0027] Examples of compounds that can form the active unit are compounds that form nitroxide radicals or 2,2-diphenyl-1-picrylhydrazyl radicals, Wurster salts, quinones, compounds that can form galvinoxyl radicals, phenoxyl radicals, triarylmethyl radicals , polychlorotriphenylmethyl radicals, phenalenyl radicals, cyclopentadienyl radicals, iminoxyl radicals, verdazyl radicals, nitronylnitroxide radicals or thiazil radicals, indigo, disulfides, disulfides, thiafulvalenes, thioethers, thiolanes, thiophenes, viologen, tetracetopiperazine, trino[4] arene, anthraquinonyl sulfide, phthalazine, cinoline, ferrocene, carbazol, polyindole, polypyrrole, polyaniline, polythiophene, poly-N,N'-dialyl-2,3,5,6-tetracetopiperazine, 2,5-di-esters tert-butyl-4-methoxyphenoxypropyl, poly-2-phenyl-1,3-dithiolane, poly[methanetetryltetrathiomethylene], poly-2,4-dithiopentanylene, polyethene-1,1,2,2-tetrathiol, poly-3,4 -ethylenedioxythiophene, 5,5-bismethylthio-2,2-bitiophene, poly- 1,2,4,5-tetrakispropylthiobenzene, poly-5-amino-1,4-dihydrobenzo[d]-1'2'-dithiadiene-coaniline, poly-5,8-dihydro-1H,4H-2, 3,6,7-tetratia-anthracene, polyanthra[1',9',8'-b,c,d,e] [4',10',5'-b',c',d',e' ]bis[1,6,6a6a-SIV-trithia]pentalene, polyene-oligosulphide, poly-1,2-bisthiophenylmethyldisulfane, poly-3-thienylmethyl-cobenzyl disulfide, polytetrathionaphthalene, polynaphtho[1,8-cd] [ 1,2]-dithiol, poly-2,5-dimercapto-1,3,4-thiadiazole, polysulfide, polythiocyanogen, polyazulene, polyfluorene, polynaphthalene, polyanthracene, polyfuran, tetratiafulvalene or polyoxyphenazine and isomers and derivatives of these compounds.
    [0028] The active units are preferably covalently bonded to the polymer backbone. However, polymer addition products can also be used.
    [0029] Particular preference is given to the use of polymers that contain groups that form nitroxide radicals, verdazil radicals or nitronyl nitroxide radicals, viologens or quinones as components with redox activity.
    [0030] Examples of groups which form nitroxide radicals are piperidines, in particular the 2,2,6,6-tetra-alkyl-substituted derivatives and particularly preferably the 2,2,6,6-tetraalkyl-derivatives 4-amino-substituted or the 2,2,6,6-tetraalkyl-4-hydroxy-substituted derivatives.
    [0031] Examples of viologens are bipyridyl derivatives, in particular the 4,4'-bipyridyl derivatives which are, in particular, alkyl-substituted at the 4,4' position. It may also be advantageous to use "extended" violins; these are oligomers made up of arylene, alkylene, alkylene ether or thiophene units which are incorporated between the pyridine units and are covalently linked to the latter.
    [0032] Examples of quinones are oxidation products of phenols, for example, of hydroquinone, anthraquinone or 1,4-dihydroxynaphthalene. 1,4-Benzoquinone and 1,4 naphthoquinone are preferred.
    [0033] Very particular preference is given to polymers having a polymer backbone selected from the group consisting of polymethacrylates, polyacrylates, polystyrenes, polyalkylene glycols and polyvinyl ethers and having components with redox activity selected from the group consisting of groups that form nitroxide radicals, verdazil radicals or nitronyl nitroxide radicals, violagens and quinones covalently bonded to this polymer backbone.
    [0034] Examples of polymers that have a polymethacrylate backbone or groups that carry a polyacrylate backbone that form nitroxide radicals covalently bonded to that chain are polymethacrylates or polyacrylates that carry 2,2,6,6-tetra-alkyl -substituted piperidines which bind via an oxygen atom 4 to the carboxyl groups of the polymethacrylate or polyacrylate. A particularly preferred example of such a polymer is poly(2,2,6,6-tetramethylpiperidinyloxymethacrylate-co-poly(ethyleneglycol)methyl ether methacrylate).
    [0035] Examples of polymers having a polyalkylene glycol backbone carrying copolymerized violet radicals are polyethylene glycols with copolymerized 4,4'-bipyridyl radicals that bind via pyridyl nitrogen atoms to ethylene glycol carbon atoms. A particularly preferred example of such a polymer is poly(4,4'-bipyridine-copoly(ethylene glycol)).
    [0036] The average molar mass (number average) of the high molecular weight component with redox activity is typically at least 500 g/mol, preferably at least 550 g/mol, particularly preferably at least 1,000 g µg/mol, and is particularly preferably 1,000 to 500,000 g/mol, and in particular 1,000 to 50,000 g/mol.
    [0037] Polymers containing components with redox activity can be present as linear polymers or as branched polymers, for example, as comb or star polymers, dendrimers, conductive polymers, cyclic polymers, polycatenans or polyrotaxanes.
    [0038] Preference is given to the use of branched polymers, in particular comb or star polymers, dendrimers, conductive polymers, cyclic polymers, polycatenans or polyrotaxanes. These types are characterized by a higher solubility and the viscosity of the obtained solutions is generally lower than in the case of corresponding linear polymers.
    [0039] The viscosity of the electrolytes used according to the invention is typically in the range of 1 mPas to 106 mPas, particularly preferably 102 to 104 mPas (measured at 25°C using a rotating, plate/plate viscometer) .
    [0040] The solubility of polymers containing components with redox activity that are used according to the invention can also be improved by copolymerization or functionalization, for example, with polyethylene glycol, polymethacrylic acid, polyacrylic acid, poly-2-methyloxazoline or sulfonate of polystyrene.
    [0041] The polymers used according to the invention and which comprise components with redox activity can be prepared by the usual polymerization processes. Examples of these are bulk polymerization, solution polymerization, precipitation polymerization or emulsion or suspension polymerization, and also polymer-analogous functionalizations. These procedures are known to the person skilled in the art.
    [0042] Components with redox activity can be used as such, ie without solvent, if they are liquid at the temperature used. However, components with redox activity are preferably used together with a solvent.
    [0043] The redox flow cell of the present invention may also contain other elements or components that are customary for these cells, in addition to the components described above. Some of these components are required, while other components can be used if this is the case.
    [0044] Examples of components that are necessarily present are: • electrodes such as graphite electrodes, graphite non-woven, graphite paper, carbon nanotube mats or graphene • energy output conductors such as conductors made of graphite or of metals • electrolytes containing conductive salts dissolved in them; these can be liquid polymers with redox activity or a solution, emulsion or suspension composed of polymers with redox activity and electrolyte solvents • examples of electrolyte solvents are water or organic solvents such as acetonitrile, organic carbonates, alcohols, dimethylformamide, dimethyl sulfoxide, dimethylacetamide, dichloromethane, nitromethane, tetrahydrofuran, preferably water, acetonitrile and organic carbonates • examples of conductive electrolytic salts are salts containing anions selected from the group consisting of PF6, BF4, SbF6, AsF6, CIO4 , CF3SO3, SO2C2F5, C4F9SO3, (CF3SO3)N2, OH, SO4, F, Cl, Br and I, and also cations selected from the group consisting of H, alkali metal cations and alkaline earth metal cations, and cations of substituted or unsubstituted ammonium • means of transport such as pumps and also tanks and tubes for the transport and storage of components with redox activity.
    [0045] Examples of components that are optionally present are: • electrolytes additionally containing electrolytic additives in addition to the conductive salts dissolved in them • examples of electrolyte additives are surfactants, viscosity modifiers, pesticides, buffers, stabilizers, catalysts, conductive additives, antifreeze, thermal stabilizers.
    [0046] The components of high molecular weights with redox activity present undiluted, in dissolved or dispersed form, in the two chambers and the separation of the flow circuits thereof, having the above-mentioned selectivity, made it possible to create a cell of redox flux that does not contain any expensive and toxic or dangerous electrolytes that in case of damage could escape and pollute the environment.
    [0047] The separation membrane between the two separate flow paths can also be produced and used with comparatively little expense. It advantageously consists of organic material and is advantageously configured as a polymer membrane.
    [0048] Studies so far on the redox flow cell of the present invention, in particular experiments involving several repeated charge/discharge cycles, indicate a significant increase in life and lower production costs during its application compared to the systems described above .
    [0049] The redox flow cell of the present invention can be used in a variety of fields. These can be in the broadest sense electrical energy storage for mobile and stationary applications. The invention also provides the use of the redox flow cell for these purposes.
    [0050] Examples of applications are uses in the field of electromobility, for example, as energy storage in land, air and water vehicles, uses as stationary energy storage for emergency power supply, peak load equalization and o temporary storage of electricity from renewable energy sources, especially in the photovoltaic and wind energy sector.
    [0051] The redox flow cell of the present invention is preferably used as stationary storage for electrical energy.
    [0052] The redox flow cells of the present invention can be connected to each other in series or in parallel, in a manner known per se.
    [0053] The invention will be illustrated in more detail below with the aid of a redox flow cell schematically represented in the drawing as an exemplary embodiment.
    [0054] The redox flow cell consists of two structurally identical half-cells 1 and 2 produced as hollow Teflon bodies, wherein half-cell 1 acts as anolyte chamber and half-cell 2 acts as catholyte chamber .
    The two half-cells 1, 2 (shown in exploded view for clarity) are joined here by means of a size 3 exclusion membrane which has an exclusion limit of 1000 g/mol.
    [0056] Each half-cell 1, 2 has an inlet port 4 and an outlet port 5 by means of which the half-cells 1, 2 are connected by hoses to a respective storage container (liquid storage) containing the anolytes or the catholytes for the corresponding half-cell 1 or 2 (not shown in the drawing for clarity).
    [0057] The anolyte or catholyte is (in each case as a separate liquid circuit by means of the half-cells 1 and 2 of the redox flow cell) pumped by means of a pump (also not shown for clarity) of the respective storage container via the appropriate half-cell 1 or 2 (indicated by arrows on the inlet and outlet ports 4, 5) during the loading/unloading process.
    [0058] Each half-cell 1, 2 has an internal electrode made of graphite/graphite felt in which an electrode reaction known per se occurs in the respective half-cell 1, 2. These internal electrodes are in each case conducted as polarity dependent power output conductors 6 for electrical connection of half cells 1, 2.
    [0059] A solution (10 mg/ml) of poly(2,2,6,6-tetramethyl-piperidinyloxymethacrylate-copoly(ethylene glycol) methyl ether methacrylate) in propylene carbonate is used as the catholyte. A solution (10 mg/ml) of poly(4,4'-bipyridine-copoly(ethylene glycol)) in propylene carbonate is used as the anolyte. Tetrabutylammonium hexafluorophosphate (0.1 mol/l) is added as conducting salt to both solutions. The cell thus obtained could be repeatedly charged and discharged with a constant current of 500 µA and had a discharge voltage of about 1.1 V.
    [0060] List of used reference numerals 1 ,2 - Half-cell 3 - Size exclusion membrane 4 - Input port 5 - Output port 6 - Power output conductor
    权利要求:
    Claims (14)
    [0001]
    1. Redox flow cell, for electrical energy storage, containing a reaction cell that has two polarity-specific chambers (1, 2) for catholyte and anolyte, which are each connected to a reservoir for liquid and are separated by an ion exchange membrane, in which the chambers (1, 2) are each filled with components with redox activity present undiluted, in dissolved or dispersed form in an electrolyte solvent, and also conductive salts dissolved in the solvent and possibly other additives, characterized by the fact that high molecular weight compounds are provided as components with redox activity and a size exclusion membrane (3) is provided as a membrane to separate the high molecular weight components with redox activity present in undiluted , in dissolved form or in dispersed form in which the size exclusion membrane has a selectivity of at least 500 g/mol and the components of and high molecular weights with redox activity have a corresponding molar mass greater than 500 g/mol.
    [0002]
    2. Redox flow cell according to claim 1, characterized in that the chambers (1, 2) are each filled with components with redox activity that are present in undiluted form or as a solution in water or a organic solvent.
    [0003]
    3. Redox flow cell according to claim 1, characterized in that a semipermeable membrane is provided as a size exclusion membrane.
    [0004]
    4. Redox flow cell according to claim 1, characterized in that a dialysis membrane is provided as a size exclusion membrane.
    [0005]
    5. Redox flow cell according to claim 1, characterized in that the size exclusion membrane consists of plastics, ceramics, glass, metals, composites or textile structures in sheet form or combinations of these materials, preferably polymers organics, in particular cellulose or modified cellulose, polyether sulfone, polysulfone, polyvinylidene fluoride, polyesters, polyurethanes, polyamides, polypropylene, polyvinyl chloride, polyacrylonitrile, dextran, lignin, polypropylene oxide, polyethyleneimine, polyacrylic acid, polystyrene , polyvinyl alcohol, polyphenylene oxide, polyimides, polytetrafluoroethylene or derivatives thereof.
    [0006]
    6. Redox flow cell according to claim 1, characterized in that the size exclusion membrane consists of organic material and is, in particular, configured as a polymer membrane.
    [0007]
    7. Redox flow cell according to claim 1, characterized in that the thickness of the size exclusion membrane is in the range of 1 μm to 5 mm, particularly preferably from 10 μm to 200 μm.
    [0008]
    8. Redox flow cell, according to claim 1, characterized in that organic or organometallic materials with redox activity, oligomers or polymers are used as components of high molecular weights.
    [0009]
    9. Redox flow cell, according to claim 1, characterized in that polymers containing groups that form nitroxide radicals, verdazil radicals or nitronyl nitroxide radicals, viologens or quinones are used as components with redox activity.
    [0010]
    10. Redox flow cell, according to claim 9, characterized in that polymers that have a main polymer chain selected from the group consisting of polymethacrylates, polyacrylates, polystyrenes, polyalkylene glycols and polyvinyl ethers and that have components with redox activity selected from the group consisting of groups that form nitroxide radicals, verdazil radicals or nitronyl nitroxide radicals, violagens and quinones covalently bonded to this polymer backbone are used as components with redox activity.
    [0011]
    11. Redox flow cell, according to claim 1, characterized in that polymers that are present as linear polymers or as branched polymers, in particular as comb or star polymers, dendrimers, conductive polymers, cyclic polymers, polycatenans or polyrotaxanes are used as components with redox activity.
    [0012]
    12. Redox flow cell according to claim 1, characterized in that the viscosity of the electrolytes used is in the range of 1 mPas to 106 mPas, particularly preferably from 102 to 104 mPas (measured at 25°C using a rotary viscometer, plate/plate).
    [0013]
    13. Use of the redox flow cell as defined in claim 1, characterized in that it is for the storage of electrical energy for mobile and stationary applications.
    [0014]
    14. Use according to claim 13, characterized by the fact that the redox flow cell is used in the field of electromobility, in particular as energy storage in land, air and water vehicles, or by the fact that the Redox flow cell is used as stationary energy storage for emergency power supply, peak load equalization and temporary storage of electrical energy from renewable energy sources, especially in the photovoltaic and wind energy sector.
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    同族专利:
    公开号 | 公开日
    SI2785442T1|2016-01-29|
    HUE028376T2|2016-12-28|
    US20150207165A1|2015-07-23|
    CA2880997C|2020-08-25|
    DK2785442T3|2016-01-25|
    BR112015002936A2|2017-08-08|
    RS54512B1|2016-06-30|
    JP2015532764A|2015-11-12|
    HRP20160057T1|2016-02-12|
    SG11201500701SA|2015-04-29|
    WO2014026728A1|2014-02-20|
    RU2015109007A|2016-10-10|
    JP6302468B2|2018-04-11|
    CN104582820A|2015-04-29|
    US9905876B2|2018-02-27|
    MX2015001996A|2015-09-29|
    PT2785442E|2016-01-20|
    MY170328A|2019-07-17|
    AU2013304341A1|2015-02-26|
    PL2785442T3|2016-04-29|
    EP2785442B1|2015-10-21|
    IL237059A|2019-02-28|
    KR20150044922A|2015-04-27|
    ES2555475T3|2016-01-04|
    EP2785442A1|2014-10-08|
    AU2013304341B2|2018-03-08|
    CA2880997A1|2014-02-20|
    HK1205043A1|2015-12-11|
    MX354025B|2018-02-07|
    SMT201500324B|2016-02-25|
    CY1117069T1|2017-04-05|
    KR102091385B1|2020-03-20|
    RU2653356C2|2018-05-08|
    CN104582820B|2019-01-11|
    ZA201500337B|2015-12-23|
    DE102012016317A1|2014-02-20|
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    法律状态:
    2018-03-06| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-03-13| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-03-20| B06I| Publication of requirement cancelled [chapter 6.9 patent gazette]|Free format text: ANULADA A PUBLICACAO CODIGO 6.6.1 NA RPI NO 2462 DE 13/03/2018 POR TER SIDO INDEVIDA. |
    2019-10-08| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-03-30| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-05-11| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 25/07/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    DE102012016317.7A|DE102012016317A1|2012-08-14|2012-08-14|Redox flow cell for storing electrical energy|
    DE102012016317.7|2012-08-14|
    PCT/EP2013/002206|WO2014026728A1|2012-08-14|2013-07-25|Redox flow cell comprising high molecular weight compounds as redox pair and semipermeable membrane for storage of electrical energy|
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