DE102018009393A1 - Aqueous electrolyte, redox flow battery and their use - Google Patents

Abstract

Described is an aqueous electrolyte solution with a temperature of at least 30 ° C. containing an organic compound containing at least one redox-active group of the formula (Ia) and hydrochloric acid and / or a salt selected from the group consisting of ammonium salts with inorganic or organic anions, the salts with Tetrafluoroborate anions or the salts of trifluoromethanesulfonic acid, and / or containing b) an organic compound containing at least one redox-active group of the formula (Ib) and / or containing c) an organic compound containing at least one redox-active group of the formula (Ic) wherein R, R, Round RAlkyl or round Rund Rund R together with the common carbon atom form a cycloaliphatic or heterocyclic radical, X means -O or -S, Y means -CH-, -O-, -S-, -SO-, -SO-, - NR- or -NRR- (An), Q is -O-, -S-, -NH-, -NR, -, -NRR- (An) -PR- or -SiRR-, or -Q- is a covalent one Binding represents R, R, round Pure organic residues An is a m-valent inorganic or organic anion, and m represents an integer between 1 and 4. The electrolyte can be used in redox flow batteries and is characterized by a high stability of the redox-active compounds at elevated temperatures.

Description

The invention relates to an aqueous electrolyte and a redox flow battery containing this aqueous electrolyte. Redox flow batteries, also known as redox flow batteries (hereinafter also referred to as “RFB”), are used to store electrical energy based on electrochemical redox reactions. A redox flow battery contains a chamber or two polarity-specific chambers (half cells) separated by a membrane, which are filled with a liquid and are fed by pumps from one or more separate tanks of any size. The respective liquid contains water in which redox-active substances and an inorganic or organic salt (lead additive) are dissolved. The main additive can itself be redox-active.

Due to their excellent scalability, RFBs are particularly suitable as stationary energy stores for various performance and capacity requirements. For example, as buffer systems for renewable energies, both in the private (e.g. single or multi-family houses) and industrial sectors (e.g. wind and solar power plants). They therefore have great potential for ensuring the stability of the power grid and for decentralized energy supply. Mobile applications (electric cars, trucks or ships) are also conceivable.

Existing RFBs are electrochemical energy stores. The substances necessary for setting the potential on the electrodes are liquid, dissolved or also in particle form redox-active species, which are transferred to their other redox stage during the charging or discharging process in an electrochemical reactor. For this purpose, electrolyte solutions (catholyte, anolyte) are removed from a tank and actively pumped to the electrodes. Anode and cathode compartments are separated in the reactor by a semipermeable membrane, which usually shows a high selectivity for protons and / or which is a size exclusion membrane. As long as the electrolyte solution is being pumped, electricity can be drawn. The loading process is then simply the reverse of the process. The amount of energy that can be stored in an RFB is therefore directly proportional to the size of the storage tanks. The power that can be extracted is a function of the size of the electrochemical reactor.

RFBs have a complex system technology that roughly corresponds to that of a fuel cell. Usual sizes of the individual reactors range from approximately 1 to 100 kW. The reactors can be combined very easily in a modular manner, and the tank size can be adjusted almost as desired.

A wide variety of redox-active chemical compounds have already been proposed for use in rechargeable batteries or batteries, such as RFB. An overview of the prior art can be found, for example, in an article by Feng Pan and Quing Wang, “Redox Species of Redox Flow Batteries: A Review” in Molecules 2015, 20, 20499-20517 or in an article by Winsberg et al. in Angew. Chemistry. 2017, 56, 686-711. According to this, RFBs are already known which contain 2,2,6,6-tetrasubstituted 1-piperidinyloxy compounds as the catholyte. Such RFB are for example in the WO 2014/026728 A1 , WO 2017/084749 A1 and WO 2017/025177 A1 described.

Further RFBs containing 2,2,6,6-tetrasubstituted 1-piperidinyloxy compounds in the electrolyte are described in the WO 2018/032003 A1 and US 2018/0072669 A1 disclosed.

So far, RFBs have mainly been used in the literature at room temperature. There is little evidence in the scientific literature of investigations at elevated temperatures, e.g. from 40 to 50 ° C, as well as no systematic studies on the behavior of aqueous electrolytes containing 2,2,6,6-tetrasubstituted 1-piperidinyloxy compounds at elevated temperatures. Commercial vanadium RFB (hereinafter also referred to as “V-RFB”) is known to cause problems at temperatures above 40 ° C, since the electrolytes fail irreversibly.

V-RFBs are therefore limited in their application temperature or complex cooling is required. In this way, V-RFB is denied special applications, such as replacing diesel generators on Indian cell phone masts. For V-RFB, special HCI-containing electrolytes were developed, which are more temperature-stable and thus enable temperatures up to approx. 45 ° C, in exceptional cases even up to 60 ° C (cf. US 2012/0077067 A1 ). However, these electrolytes are extremely corrosive. Other RFB systems have not yet been described at these comparatively high temperatures.

In particular, RFBs that contain organic redox-active compounds have so far not been used at these high temperatures. This is aggravated by the fact that many electrolytes are based of organic redox-active compounds are not stable at elevated temperatures. In this context, it should also be noted that the stability of many organic redox-active materials has been wrongly assessed (M.-A. Goulet, MJ Aziz, J. Electrochem. Soc. 2018, 165, A1466-A1477). Above all, this applies to the stability when loaded. Simple charge / discharge tests carried out to date do not provide any information about the aging behavior of the electrolytes. Thus, the RFBs described as one of the most stable, which contain TEMPTMA / viologen as organic redox-active compounds, are affected by these decomposition processes. At elevated temperatures, the side reactions are accelerated and lead to a rapid loss of capacity of the RFB.

Studies have shown that many electrolytes based on redox-active organic compounds decompose faster than previously thought. In the case of 2,2,6,6-tetrasubstituted 1-piperidinyloxy compounds, the decay mechanism is believed to be via a cationic species that arises from the charged species. Furthermore, splitting off of solubilizing groups in the 4-position was observed. If you want to increase the temperature stability of the electrolyte, this cation must be stabilized or the ring opening must be avoided. There are basically two ways of doing this. On the one hand, additives can be added and, on the other hand, the redox-active material can be structurally modified.

It has now been found that certain functionalized 1-piperidinyl derivatives or that the addition of selected additives to 1-piperidinyl derivatives leads to electrolytes which surprisingly have high stability at elevated temperatures. The use of these redox-active compounds or this combination of redox-active compounds with additives allows the production of aqueous electrolytes which are stable at elevated temperatures. In addition, these electrolytes allow the production of RFB that can be operated at elevated temperatures. Higher temperatures of the electrolyte can occur during operation of the RFB in environments with elevated temperatures, for example when operating in tropical or subtropical areas, and / or also when storing electrolyte solutions at elevated temperatures and / or also when throughput of high performance during charging / Discharge in the electrode rooms.

The use of the electrolytes according to the invention makes RFBs with organic redox-active compounds accessible for “high-temperature” use. In this way, new fields of application for RFB can be opened up without the need for additional cooling.

The invention has for its object to provide an aqueous electrolyte containing selected redox-active organic compounds, which has sufficient stability for the operation of batteries or accumulators even at elevated temperatures.

Another object of the present invention is to provide a redox flow battery which can be operated at elevated temperatures without the electrolyte used experiencing any significant decomposition.

This object is achieved by the provision of the aqueous electrolyte solution described in claim 1.

1. a) eine organische Verbindung enthaltend mindestens eine redoxaktive Gruppe der Formel (la) und Salzsäure und/oder ein Salz ausgewählt aus der Gruppe der Ammoniumsalze mit anorganischen oder organischen Anionen, vorzugsweise mit Chlorid- oder Fluoridanionen, der Salze mit Tetrafluoroborat-Anionen oder der Salze der Trifluormethansulfonsäure,
   
   und/oder enthaltend
2. b) eine organische Verbindung enthaltend mindestens eine redoxaktive Gruppe der Formel (Ib)
   
   und/oder enthaltend
3. c) eine organische Verbindung enthaltend mindestens eine redoxaktive Gruppe der Formel (Ic)
   
   worin R₁, R₂, R₃ und R₄ Alkyl bedeuten oder jeweils R₁ und R₂ und R₃ und R₄ zusammen mit dem gemeinsamen Kohlenstoffatom einen cycloaliphatischen oder heterocyclischen Rest bilden,
   • X -O oder -S bedeutet, Y -CH₂-, -O-, -S-, -SO-, -SO₂-, -NR₅- oder -N⁺R₅R₆- (An^m-)_1/m ist,
   • Q -O-, -S-, -NH-, -NR_6a,-, -NR_6aR_6b ⁺- (An^m-)_1/m, -PR_6a- oder -SiR_6aR_6b- bedeutet, oder -Q- eine kovalente Bindung darstellt,
   • R₅, R₆, R_6a und R_6b unabhängig voneinander einbindige organische Reste, vorzugsweise Alkyl und insbesondere C₁-C₄-Alkyl sind,
   • An ein m-wertiges anorganisches oder organisches Anion bedeutet, und m eine ganze Zahl zwischen 1 und 4 darstellt.

The present invention relates to an aqueous electrolyte solution having a temperature of at least 30 ° C, preferably at least 40 ° C

1. a) an organic compound containing at least one redox-active group of the formula (Ia) and hydrochloric acid and / or a salt selected from the group of the ammonium salts with inorganic or organic anions, preferably with chloride or fluoride anions, the salts with tetrafluoroborate anions or the salts trifluoromethanesulfonic acid,
   
   and / or containing
2. b) an organic compound containing at least one redox-active group of the formula (Ib)
   
   and / or containing
3. c) an organic compound containing at least one redox-active group of the formula (Ic)
   
   in which R ₁ , R ₂ , R ₃ and R _{4 are} alkyl or in each case R ₁ and R ₂ and R ₃ and R ₄ together with the common carbon atom form a cycloaliphatic or heterocyclic radical,
   • X denotes -O or -S, Y denotes -CH ₂ -, -O-, -S-, -SO-, -SO ₂ -, -NR ₅ - or -N ⁺ R ₅ R ₆ - (An ^m- ) _{1 / m} is
   • Q -O-, -S-, -NH-, -NR _6a , -, -NR _6a R _6b ⁺ - (An ^m- ) _{1 / m} , -PR _6a - or -SiR _6a R _6b - means, or - Q- represents a covalent bond,
   • R ₅ , R ₆ , R _6a and R _{6b are} independently monovalent organic radicals, preferably alkyl and in particular C ₁ -C ₄ alkyl,
   • An m is an inorganic or organic anion, and m represents an integer between 1 and 4.

It has been found that hydrochloric acid and / or selected salts exert a temperature-stabilizing effect on compounds containing one or more radicals of the formula (Ia). These salts are ammonium salts with inorganic or organic anions, preferably with chloride or fluoride anions, salts with tetrafluoroborate anions or salts of trifluoromethanesulfonic acid. Cations of these BF ₄ ^- or trifluoromethanesulfonic acid salts are, in particular, ammonium cations or metal cations.

Hydrochloric acid or ammonium halides are preferably used. The latter are generally quaternary ammonium halides, especially quaternary ammonium alkyl halides. The alkyl groups have in particular 1-4 carbon atoms, which are preferably substituted with a hydroxyl group.

Quaternary ammonium chlorides or fluorides are particularly preferably used. The salts with tetrafluoroborate anions or the salts of trifluoromethanesulfonic acid are preferably salts with alkali metal cations, alkaline earth metal cations or ammonium cations, in particular with sodium, potassium, magnesium or calcium cations, or with quaternary ammonium cations.

The redox-active compounds used in the electrolytic solution according to the invention can be low-molecular organic molecules, oligomers or polymers. These molecules can be dissolved in the electrolyte solution or be dispersed or suspended as particles, for example as dispersions, microgels or as nanogels. The redox-active compounds contain at least one radical of the formula (Ia), (Ib) or (Ic) which is connected to the rest of the molecule via a bridge group -Q- or via a covalent bond.

The redox-active compounds containing the rest of the formula (Ia), (Ib) or (Ic) used in the electrolyte solution according to the invention are preferably water-soluble. However, they can also be compounds which are dispersible in water.

In the context of this description, 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.

In the context of this description, low molecular weight molecules are to be understood as meaning compounds which have no recurring structural units derived from monomers and which have at least one, preferably one to six, particularly preferably one to four, in particular one to three and very particularly preferably one or two radicals of the formula (la), (Ib) or (Ic) included.

In the context of this description, oligomeric molecules are understood to mean compounds which have two to ten recurring structural units derived from monomers, each of which has a radical of the formula (Ia), (Ib) or (Ic). The residues of the formula (Ia), (Ib) or (Ic) can also be attached to the oligomer structure via spacers.

In the context of this description, polymeric molecules are to be understood as meaning compounds which have more than ten, preferably eleven to fifty, repeating structural units derived from monomers, each of which has a radical of the formula (Ia), (Ib) or (Ic). The radicals of the formula (Ia), (Ib) or (Ic) can also be attached to the polymer structure via spacers.

In a preferred embodiment, the electrolyte solution according to the invention contains a redox-active component with one to six, preferably one to four, in particular one to three and very particularly preferably one to two radicals of the formula (Ia), (Ib) or (Ic) in the molecule.

Examples of preferred low molecular weight, oligomeric and polymeric redox-active compounds are listed below.

The molecular weights of the redox-active compounds used in the electrolyte according to the invention containing at least one radical of the formula (Ia), (Ib) or (Ic) can vary within wide limits. Redox-active compounds containing radicals of the formula (Ia), (Ib) or (Ic) are particularly preferably used, the molar masses of which are in the range from 150 to 80,000 g / mol, preferably in the range from 250 to 50,000 g / mol and very particularly preferably in Move range from 500 to 20,000 g / mol.

The viscosity of the electrolyte used according to the invention is typically in the range from 1 mPas to 10 ³ mPas, particularly preferably 1 to 10 ² mPas and very particularly preferably 1 to 20 mPas (measured at 25 ° C. with a rotary viscometer, plate / plate).

The radicals R ₁ , R ₂ , R ₃ and R ₄ denote alkyl, preferably C ₁ -C ₄ alkyl, particularly preferably methyl or ethyl and very particularly preferably methyl, or in each case form R ₁ and R ₂ and R ₃ and R ₄ together with the common carbon atom, a cycloaliphatic or heterocyclic radical. The cycloaliphatic radical is a cyclopentane or in particular a cyclohexane radical. The heterocyclic radical is a radical with five or in particular with six ring atoms or atomic groups, one of which is selected from the group -O-, -S-, -SO-, -SO ₂ -, -NR ₅ - or -N ⁺ R ₅ R ₆ - (An ^m- ) _{1 / m} and the remaining ring atoms are carbon atoms.

R ₅ and R ₆ are monovalent organic radicals, such as alkyl, cycloalkyl, aryl, aralkyl or heterocyclyl. Alkyl, in particular C ₂ -C ₄ -alkyl, and very particularly preferably ethyl, are preferred.

An is an m-valent inorganic or organic anion and m is an integer between 1 and 4, preferably 1 or 2.

Preferred anions An are selected from the group of halide ions, hydroxide ions, phosphate ions, sulfate ions, perchlorate ions, hexafluorophosphate ions or tetrafluoroborate ions.

Residues of the formula (Ia) or (Ib) in which R ₁ and R ₂ and R ₃ and R ₄ together with the common carbon atom form a heterocyclic radical are particularly preferred since these have an increased water solubility in comparison with cycloaliphatic radicals. This also applies to radicals of the formula (Ic) in which Y is -O-, -S-, -SO-, -SO ₂ -, -NR ₅ - or -N ⁺ R ₅ R ₆ - (An ^m- ) _{1 / m} is.

X represents -O or -S, preferably -O.

Q is preferably -O- or -S- and in particular -O- or -Q- is preferably a covalent bond.

The electrolyte solution according to the invention contains water or water and an organic solvent as well as the above-mentioned redox-active compound (s) and, if appropriate, further substances dissolved therein. These substances serve to balance the charge while charging or discharging the battery or have a positive influence on the stability or performance parameters of the battery. Substances that are responsible for charge balance are called lead additives or salts, and substances that have a positive effect on stability or performance parameters are called auxiliary additives.

Examples of electrolyte solvents are water or mixtures of water with alcohols (e.g. ethanol), carbonic acid esters (e.g. propylene carbonate), nitriles (e.g. acetonitrile), amides (e.g. dimethylformamide, dimethylacetamide), sulfoxides (e.g. dimethyl sulfoxide), ketones (e.g. acetone), lactones ( e.g. gamma-butyrolactone), lactams (e.g. N-methyl-2-pyrrolidone), nitro compounds (e.g. nitromethane), ethers (e.g. tetrahydrofuran), chlorinated hydrocarbons (e.g. dichloromethane), carboxylic acids (e.g. formic acid, acetic acid), mineral acids (e.g. sulfuric acid, Hydrogen halides or hydrohalic acids). Water or mixtures of water with carbonic acid esters (e.g. propylene carbonate) or with nitriles (e.g. acetonitrile) are preferred. Water is particularly preferred.

The main additives are usually organic or inorganic salts or hydrochloric acid. Examples of these are salts, the anions selected from the group consisting of halide ions (such as fluoride ion or chloride ion), hydroxide ions, anions of inorganic acids (e.g. phosphate ions, sulfate ions, nitrate ions, hexafluorophosphate ions, tetrafluoroborate ions, perchlorate ions, chlorine ions, hexafluoroantimonate ions, hexafluoroarsenate ions, cyanide ions ) or anions of organic acids (e.g. acetations, formations, trifluoroacetic acid ions, trifluoromethanesulfonate ions, pentafluoroethanesulfonate ions, nonafluorobutanesulfonate ions, butyrate ions, citrate ions, fumarate ions, glutarate ions, lactate ions, malate ions, malonate ions, oxalate ions, pyruvate ions). Chloride and fluoride ions, hydroxide ions, phosphate ions, sulfate ions, perchlorate ions, hexafluorophosphate ions and tetrafluoroborate ions are particularly preferred; as well as cations selected from the group of hydrogen ions (H ⁺ ), alkali or alkaline earth metal cations (e.g. lithium, sodium, potassium, magnesium, calcium), zinc, iron, and substituted or unsubstituted ammonium cations (e.g. tetrabutylammonium, tetramethylammonium, tetraethylammonium), the Substituents in general can be alkyl groups. Hydrogen ions, lithium ions, sodium ions, Potassium ions, tetrabutylammonium ions and mixtures thereof are particularly preferred. In particular, the conductive salts: NaCI, KCl, LiPF ₆ , LiBF ₄ , NaBF ₄ , NaPF ₆ , NaClO ₄ , NaOH, KOH, Na ₃ PO ₄ , K ₃ PO ₄ , Na ₂ SO ₄ , NaSO ₃ CF ₃ , LiSO ₃ CF ₃ , (CH ₃ ) ₄ NOH, n-Bu ₄ NOH, (CH ₃ ) ₄ NCl, n-Bu ₄ NCl, (CH ₃ ) ₄ NBr, n-Bu ₄ NBr, n-Bu ₄ NPF ₆ , n- Bu ₄ NBF ₄ , n-Bu ₄ NClO ₄ , NH ₄ Cl and their mixtures where n-Bu stands for the n-butyl group

Particularly preferred electrolyte solutions according to the invention contain a lead additive which contains anions selected from the group of halide ions, hydroxide ions, phosphate ions, sulfate ions, perchlorate ions, hexafluorophosphate ions or tetrafluoroborate ions, in particular a lead additive composed of these anions and cations selected from the group of hydrogen ions, alkali metal or alkaline earth metal cations , as well as the substituted or unsubstituted ammonium cations.

Examples of auxiliary additives are surfactants, viscosity modifiers, pesticides, buffers, stabilizers, catalysts, lead additives, antifreeze, temperature stabilizers and / or foam breakers.

Surfactants can be nonionic, anionic, cationic or amphoteric. Nonionic surfactants (e.g. polyalkylene glycol ethers, fatty alcohol propoxylates, alkyl glucosides, alkyl polyglucosides, octylphenol ethoxylates, nonylphenol ethoxylates, saponins, phospholipids) are particularly preferred.

Examples of buffers are carbonic acid bicarbonate buffer, carbonic acid silicate buffer, acetic acid acetate buffer, phosphate buffer, ammonia buffer, citric acid or citrate buffer, tris (hydroxymethyl) aminomethane, 4- (2-hydroxyethyl) -1-piperazinethanesulfonic acid, 4- (2-hydroxyethyl) piperazin-1-propanesulfonic acid, 2- (N-morpholino) ethanesulfonic acid, barbital acetate buffer).

The electrolyte solutions according to the invention have an elevated temperature. These can occur when the electrolyte solution is used in certain areas of the battery or the accumulator, for example only in the electrode chambers during charging and / or discharging processes and / or when the electrolyte solution is stored in external stores.

Aqueous electrolyte solutions with a temperature of 30 to 90 ° C., preferably 40 to 80 ° C., are preferred.

Aqueous electrolyte solutions which contain at least one conductive salt are also preferred.

Aqueous electrolyte solutions containing at least one conductive salt are particularly preferred, in particular those salts which are contained in highly concentrated salt solutions (sols).

The concentration of the conductive salts in the aqueous electrolyte solutions according to the invention is very particularly preferably between 14% by weight up to the saturation limit. Saturated salt solutions are often used, with some of the salts being in a precipitated form.

Particularly preferred electrolyte solutions according to the invention have a state of charge of less than 90%, in particular up to 80% and very particularly preferably from 70 to 80%. These electrolyte solutions are characterized by a particularly good temperature stability of the redox-active compounds described above or their combinations with selected additives. Of course, electrolyte solutions with a charge level of 100% are also possible.

The state of charge (SOC) is a characteristic value for the state of charge of the electrolyte solution or a battery containing this electrolyte solution. The value for the state of charge indicates the still available capacity of an electrolyte solution or a battery in relation to the nominal value. The state of charge is given as a percentage of the fully charged state.

The state of charge can be determined, for example, by the open circuit voltage (VOC). The open circuit voltage depends on the state of charge; this increases with increasing state of charge. The cell voltage is measured in the "open circuit", i.e. it is the cell voltage that results for a given state of charge without an external load.

Particularly preferred aqueous electrolyte solutions contain a compound having at least one redox-active radical of the formula (Ia), (Ib) or (Ic) which is covalently linked to a polymer backbone which is selected from the group of the polymethacrylates, polyacrylates, polystyrenes, polyalkylene glycols, Polyalkyleneimines or the polyvinyl ether, the polymer backbone preferably having 5 to 100 groups of the formula (Ia), (Ib) or (Ic).

worin

• ME eine von einem polymerisierbaren Monomer abgeleitete wiederkehrende Struktureinheit ist,
• BG eine kovalente Bindung oder eine Brückengruppe ist,
• Pip einen Piperidinylrest der Formel (la), (Ib) oder (Ic) darstellt, und
• r eine ganze Zahl von 2 bis 150, vorzugsweise von 2 bis 80 und ganz besonders bevorzugt von 8 bis 40 ist.

Very particularly preferred aqueous electrolyte solutions contain oligomers or polymers containing the recurring structural units of the formula (II) and, if appropriate, further structural units derived from solubilizing comonomers

wherein

• ME is a recurring structural unit derived from a polymerizable monomer,
• BG is a covalent bond or a bridging group,
• Pip represents a piperidinyl radical of the formula (Ia), (Ib) or (Ic), and
• r is an integer from 2 to 150, preferably from 2 to 80 and very particularly preferably from 8 to 40.

The repeating units ME and BG form the backbone of the oligomer or polymer, which contains several units of the redox-active unit of the formula (Ia), (Ib) or (Ic) defined above.

Examples of classes of substances which can form the backbone of the oligomer or polymer are polymers derived from ethylenically unsaturated carboxylic acids or their esters or amides, such as polymethacrylate, polyacrylate, polymethacrylamide or polyacrylamide, polymers derived from ethylenically unsaturated aryl compounds, such as polystyrene, from vinyl esters polymers derived from saturated carboxylic acids or their derivatives, such as polyvinyl acetate or polyvinyl alcohol, polymers derived from olefins or bi- or polycyclic olefins, such as polyethylene, polypropylene or polynorbornene, polyimides derived from imide-forming tetracarboxylic acids and diamines, from naturally occurring polymers and their chemically modified Derivatives-derived polymers, such as cellulose or cellulose ethers, and also polyurethanes, polyvinyl ethers, polythiophenes, polyacetylene, polyalkylene glycols and their derivatives, such as their ethers, for example polyethylene glycol or polyethylene glycol methyl ether, Poly-7-oxanorbornene, polysiloxanes, polyalkyleneimines and their derivatives, such as their amines, for example polyethyleneimines or N, N, N ', N'-tetramethyl-polyethyleneimines.

Polyacrylat BG = -COO-¹⁾ ME =

Polymethacrylamid BG = -CONH- ME =

Polyacrylamid BG = -CONH- ME =

Polystyrol BG = kovalente C-C-Bindung oder -CH₂- oder -NH- ME =

Polyvinylacetat BG = kovalente C-C-Bindung ME =

Polyethylen BG = kovalente C-C-Bindung ME =

Polypropylen BG = kovalente C-C-Bindung ME =

Polyvinylether BG = -O-¹⁾ ME =

Polyethylenimin BG = kovalente N-C-Bindung ME =

¹⁾ Im Falle des Restes der Formel (Ib) entspricht das Sauerstoffatom der Carbonsäureestergruppe bzw. der Vinylgruppe dem Sauerstoffatom des Piperidinylrestes in 4-Position Below are examples of combinations of the structural units ME and the bridge groups BG for some of the substance classes mentioned above. It refers to Polymethacrylate BG = -COO- ¹⁾ ME =

Polyacrylate BG = -COO- ¹⁾ ME =

Polymethacrylamide BG = -CONH- ME =

Polyacrylamide BG = -CONH- ME =

Polystyrene BG = covalent CC bond or -CH ₂ - or -NH- ME =

Polyvinyl acetate BG = covalent CC bond ME =

Polyethylene BG = covalent CC bond ME =

Polypropylene BG = covalent CC bond ME =

Polyvinyl ether BG = -O- ¹⁾ ME =

Polyethyleneimine BG = covalent NC bond ME =

¹⁾ In the case of the radical of the formula (Ib), the oxygen atom of the carboxylic acid ester group or the vinyl group corresponds to the oxygen atom of the piperidinyl radical in the 4-position

Substance classes which are particularly preferred and which form the backbone of the oligomer or polymer are polymethacrylates, polyacrylates, polymethacrylamides, polyacrylamides, polystyrene, polyethyleneimines and polyvinyl ethers.

The redox-active units of the formulas (la), (Ib) or (Ic) are covalently linked to the polymer backbone.

The polymers containing redox-active components can be in the form of linear polymers or they can be comb and star polymers, dendrimers, conductor polymers, ring-shaped polymers, polycatenanes and polyrotaxanes.

Comb and star polymers, dendrimers, ladder polymers, ring-shaped polymers, polycatenanes and polyrotaxanes are preferably used. These types are characterized by increased solubility and the viscosity of the solutions obtained is generally lower than that of corresponding linear polymers.

The solubility of the polymers containing redox-active components used according to the invention can furthermore be determined by co-polymerization or functionalization, e.g. with polyethylene glycol, polymethacrylic acid, polyacrylic acid or polystyrene sulfonate.

Preferred solubilizing comonomers are vinyl acetate, methyl vinyl ether, methacrylic acid, acrylic acid, alkyl methacrylate, ethyl acrylate, methacrylic acid amide, acrylic acid amide, vinyl sulfonate, vinyl phosphonic acid or styrene sulfonate.

The redox-active compounds used according to the invention can be prepared by customary processes. Oligomers and polymers can be produced using the usual polymerization processes. Examples of this are polymerization in bulk, polymerization in solution or emulsion or suspension polymerization. These procedures are known to the person skilled in the art.

Low molecular weight compounds containing one or more radicals of the formula (Ia), (Ib) or (Ic) typically have the following structure Pip-R ₇ - (Pip) _n , wherein Pip is a piperidinyl radical of the formula (Ia), (Ib) or (Ic), n is an integer from 0 to 5, preferably from 0 to 3, and R _{7 is} a one- to six-membered organic radical.

worin R₁, R₂, R₃ und R₄ die oben definierte Bedeutung besitzen,

• o eine ganze Zahl von 1 bis 3 ist,
• R₈ ein einbindiger organischer Rest ist, und
• Rg ein zwei- bis vierbindiger organischer Rest ist.

Preferred aqueous electrolyte solutions contain a redox-active compound of the formula (IIIa) or (Illb)

wherein R ₁ , R ₂ , R ₃ and R _{4 have} the meaning defined above,

• o is an integer from 1 to 3,
• R _{8 is} a monovalent organic radical, and
• Rg is a two- to four-bond organic residue.

worin R₁, R₂, R₃, R₄, R₉, X, Y, Q, ME, BG, r und o die oben definierte Bedeutung besitzen, und p 0 oder 1 ist.Particularly preferred aqueous electrolyte solutions contain a redox-active compound of the formula (IV), (V), (VI), (VII) or (VIII)

wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₉ , X, Y, Q, ME, BG, r and o have the meaning defined above, and p is 0 or 1.

Very particularly preferred aqueous electrolyte solutions contain a redox-active compound of the formula (IIla), in which
R _{8 is} a group of the formula -O- (C _s H _2s ) -FG or -S- (C _s H _2s ) -FG,
s is an integer from 2 to 4, in particular 2, FG is a functional group selected from -OH, -SH, -NO ₃ , -NO ₂ , - CN, -OR ₁₄ , -SR ₁₄ , - (O-CH ₂ -CH ₂ ) _o -OR ₁₅ , - (O-CH ₂ -CH ₂ ) _o -NR ₁₆ R ₁₇ R ₁₈ ⁺ (An ^q- ) _{1 / q} , -COR ₁₅ , -COO ^- (Kat ^{q +} ) _{1 / q} , -COOR ₁₅ , -SO ₃ ^- (Kat ^{q +} ) _{1 / q} , -SO ₃ R ₁₅ , -SO ₄ ^- (Kat ^{q +} ) _{1 / q} , -SO ₄ R ₁₅ , -PO ₄ ^2- (Cat ^{q +} ) _{2 / q} , -PO ₄ (R ₁₅ ) ₂ , -PO ₃ ^2- (Kat ^{q +} ) _{2 / q} , -PO ₃ (R ₁₅ ) ₂ , -NR ₁₆ R ₁₇ R ₁₈ ⁺ (An ^q- ) _{1 / q} , -N ⁺ R ₁₆ R ₁₇ -C _t H _2t -SO ₃ ^- or -NR ₁₅ -SO ₂ -R ₁₆ ,
R ₁₄ C ₁ -C ₄ alkyl, preferably methyl,
R _{15 is} hydrogen or C ₁ -C ₄ alkyl, preferably hydrogen or methyl, and in particular hydrogen,
R ₁₆ , R ₁₇ and R ₁₈ independently of one another are hydrogen or alkyl, preferably C ₁ -C ₄ alkyl, and in particular methyl, ethyl, propyl or butyl,
Kat is a q-valued cation,
An q-valued anion means ,,
q represents an integer between 1 and 4,
t is an integer between 2 and 5, and
o is an integer from 1 to 50, preferably from 3 to 20.

Preferred cations Kat are hydrogen cations, alkali metal cations, alkaline earth metal cations or ammonium cations, in particular hydrogen cations, sodium, potassium, magnesium or calcium cations, or quaternary ammonium cations.

Preferred anions An are selected from the group of halide ions, hydroxide ions, phosphate ions, sulfate ions, perchlorate ions, hexafluorophosphate ions or tetrafluoroborate ions.

Very particularly preferred aqueous electrolyte solutions contain a redox-active compound containing one or more radicals of the formula (Ia) and a stabilizing additive selected from the group of the quaternary ammonium alkyl halides, in particular the quaternary ammonium alkyl chlorides or fluorides, or the alkali metal, alkaline earth metal or ammonium, in particular the sodium, potassium, magnesium, calcium or quaternary ammonium tetrafluoroborates or trifluoromethanesulfonates

If one of the radicals denotes a monovalent organic radical, it can be alkyl, cycloalkyl, aryl, aralkyl or heterocyclyl, which are linked to the rest of the molecule via a covalent bond. These radicals can be substituted with one or more, in particular with one or two radicals, for example with hydroxy, amino, carboxyl, sulfonyl, carboxylic acid ester, carboxylic acid amide, sulfonic acid ester, sulfonic acid amide or halogen.

If one of the radicals is a two- to six-bonded organic radical, this can be alkyl, cycloalkyl, aryl, aralkyl or heterocyclyl which are connected to the rest of the molecule via two to six covalent bonds. These radicals can be substituted with one or more, in particular with one or two radicals, for example with hydroxy, amino, carboxyl, sulfonyl, carboxylic acid ester, carboxylic acid amide, sulfonic acid ester, sulfonic acid amide or halogen.

Preferred monovalent organic radicals R ₇ or R ₈ are C ₁ -C ₄ alkyl, in particular methyl, ethyl, propyl or 2-hydroxyethyl, C ₁ -C ₄ alkoxy, in particular methoxy, ethoxy or propoxy, mono-, di-, Tri- or Qateralkylamino with C ₁ -C ₄ alkyl radicals, in particular with methyl, ethyl or propyl, poly (ethyleneoxy), cyclohexyl, phenyl, phenoxy or benzyl. In the case of quateralkylamino, anions are present for the charge balance.

Rg as a two- to four-bonded organic group is to be understood as an organic radical which is connected to the rest of the molecule via two, three or four covalent bonds.

Examples of divalent organic radicals are alkylene, alkyleneoxy, poly (alkyleneoxy), alkylene amino, poly (alkylene amino), cycloalkylene, arylene, aralkylene or heterocyclylene.

Alkylene groups can be either branched or unbranched. An alkylene group typically contains one to twenty carbon atoms, preferably two to four carbon atoms. Examples of alkylene groups are: methylene, ethylene, propylene and butylene. Alkylene groups can optionally be substituted, for example with carboxyl or sulfonic acid groups, with carboxyl ester or sulfonic acid ester groups, with carboxylamide or sulfonic acid amide groups, with hydroxyl or amino groups or with halogen atoms.

Alkyleneoxy and poly (alkyleneoxy) groups can contain both branched and unbranched alkylene groups. An alkylene group occurring in an alkyleneoxy or in a poly (alkyleneoxy) group typically contains two to four carbon atoms, preferably two or three carbon atoms. The number of repeating units in the poly (alkyleneoxy) groups can vary widely. Typical numbers of repeat units range from 2 to 50. Examples of alkyleneoxy groups are: ethyleneoxy, propyleneoxy and butyleneoxy. Examples of poly (alkyleneoxy) groups are: poly (ethyleneoxy), poly (propyleneoxy) and poly (butyleneoxy).

Alkylenamino and poly (alkylenamino) groups can contain both branched and unbranched alkylene groups. An alkylene group occurring in an alkylene amino or in a poly (alkylene amino) group typically contains two to four carbon atoms, preferably two or three carbon atoms. The number of repeating units in the poly (alkylenamino) groups can vary widely. Typical numbers of repeating units are in the range from 2 to 50. Examples of alkylene amino groups are: ethylene amino, propylene amino and butylene amino. Examples of poly (alkylene amino) groups are: poly (ethylene amino), poly (propylene amino) and poly (butylene amino).

Cycloalkylene groups typically contain five, six or seven ring carbon atoms, 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 a further 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 carboxylamide or sulfonic acid amide groups, with hydroxyl or amino groups or with halogen atoms.

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-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1- Phenantolyl, 2-phenantolyl, 3-phenantolyl, 4-phenantolyl or 9-phenantolyl. Arylene groups can optionally be substituted, for example with carboxyl or sulfonic acid groups, with carboxyl ester or sulfonic acid ester groups, with carboxylamide or sulfonic acid amide groups, with hydroxyl or amino groups or with halogen atoms. Further examples of substituents are alkyl groups or two alkyl groups which, together with the ring carbon atoms to which they are attached, can form a further ring.

Heterocyclylene groups are typically cyclic groups with four to ten ring carbon atoms and at least one ring heteroatom, which can each be independently substituted. Examples of heteroatoms are oxygen, nitrogen, phosphorus, boron, selenium or sulfur. Examples of heterocyclylene groups are furandiyl, thiophendiyl, pyrroldiyl or imidazole diyl. Heterocyclylene groups are preferably aromatic. Heterocyclyl groups can optionally be substituted, for example with carboxyl or sulfonic acid groups, with carboxyl ester or sulfonic acid ester groups, with carboxylamide or sulfonic acid amide groups, with hydroxyl or amino groups or with halogen atoms. More examples of Substituents are alkyl groups or two alkyl groups which, together with the ring carbons to which they are attached, can form a further ring.

Aralkylene groups are typically aryl groups to which one or two alkyl groups are covalently attached. Aralkyl groups can be covalently linked to the rest of the molecule via their aryl radical and their alkyl radical or via two alkyl radicals. The aralkylene group on the aromatic ring can be substituted, for example, with alkyl groups or with halogen atoms. Examples of aralkylene groups are benzylene or dimethylphenylene (xylylene).

Examples of Rg as a three-bonded organic radical are alkyltriyl, alkoxytriyl, tris-poly (alkyleneoxy), tris-poly (alkylenamino), cycloalkyltriyl, aryltriyl, aralkyltriyl or heterocyclyltriyl. These residues correspond to the double-bonded residues already described in detail above, with the difference that these are linked to the rest of the molecule by three covalent bonds instead of two covalent bonds.

Examples of R ₉ as a four-bonded organic radical are alkylquaternyl, alkoxyquaternyl, quater-poly (alkyleneoxy), quater-poly (alkylenamino), cycloalkyl-quaternyl, aryl-quaternyl, aralkylquaternyl or heterocyclylquaternyl. These residues correspond to the double-bonded residues already described in detail above, with the difference that these are connected to the rest of the molecule by four covalent bonds instead of two covalent bonds.

Aqueous electrolyte solutions containing a compound having at least one redox-active radical of the formula (Ic), in which Y is -O-, - S-, -SO-, -SO ₂ -, -NR ₅ - or -N ⁺ R ₅ R, are very particularly preferred ₆ - (An ^m- ) _{1 / m} is. Compared to compounds with Y = -CH ₂ - these have an increased water solubility. These compounds have a particularly favorable combination of water solubility and temperature stability.

In a further embodiment, the invention relates to a first type of redox flow battery for storing electrical energy, comprising a reaction cell with two electrode chambers for catholyte and anolyte, each of which is connected to at least one liquid reservoir, the electrode chambers being separated by a membrane, are equipped with electrodes, and are each filled with electrolyte solutions that contain redox-active components in liquid form, dissolved or dispersed in an aqueous electrolyte solvent, as well as any conductive salts and possibly other additives dissolved therein. This redox flow battery is characterized in that the anolyte contains a water-soluble redox-active component and that the catholyte in the electrode chamber contains an aqueous electrolyte solution as defined above.

The electrolyte solutions in the electrode chambers can be covered with paraffin oil in order to minimize the diffusion of oxygen.

Preferred redox flow batteries of this first type also contain an aqueous electrolyte solution according to the definition given above in the liquid store (s).

Redox flow batteries of this first type are preferred in which the anolyte contains a compound containing one or more bipyridiyl groups in the molecule as the redox-active component.

worin

• die von den Stickstoffatomen in den Strukturen der Formeln IX und X abgehenden Linien kovalente Bindungen darstellen, welche die Strukturen der Formeln IX und X mit dem Rest des Moleküls verbinden,
• R₁₀ und R₁₁ unabhängig voneinander Alkyl, Alkoxy, Haloalkyl, Cycloalkyl, Aryl, Aralkyl, Heterocyclyl, Halogen, Hydroxy, Amino, Nitro oder Cyano bedeuten,
• An ein q-wertiges anorganisches oder organisches Anion bedeutet,
• b und c unabhängig voneinander ganze Zahlen von 0 bis 4, vorzugsweise 0, 1 oder 2, insbesondere 0 sind,
• q eine ganze Zahl von 1 bis 4 ist, und
• a eine Zahl mit dem Wert 2/q ist.

These are typically compounds containing at least one redox-active radical of the formula (IX) or of the formula (X) in the molecule, preferably one to six, in particular one to four, very particularly preferably one to three and very preferably one to two radicals of Formula (IX) or formula (X) in the molecule

wherein

• the lines extending from the nitrogen atoms in the structures of the formulas IX and X represent covalent bonds which connect the structures of the formulas IX and X to the rest of the molecule,
• R ₁₀ and R ₁₁ independently of one another denote alkyl, alkoxy, haloalkyl, cycloalkyl, aryl, aralkyl, heterocyclyl, halogen, hydroxy, amino, nitro or cyano,
• An q-valued inorganic or organic anion means
• b and c are independently integers from 0 to 4, preferably 0, 1 or 2, in particular 0,
• q is an integer from 1 to 4, and
• a is a number with the value 2 / q.

The compounds containing one or more bipyridiyl groups in the molecule as a redox-active component can be low-molecular organic molecules, oligomers or polymers. These preferably contain at least one radical of the formula (IX) or of the formula (X) which is connected to the rest of the molecule via the covalent bonds.

The redox-active compounds containing the radical of the formula (IX) or of the formula (X) are preferably water-soluble. However, they can also be compounds which are dispersible in water.

Examples of anions An ^q- are halide ions (fluoride ion, chloride ion, bromide ion, iodide ion), hydroxide ions, anions of inorganic acids (for example phosphate ions, sulfate ions, nitrate ions, hexafluorophosphate ions, tetrafluoroborate ions, perchlorate ions, chlorine ions, hexafluoroantimonate ions, hexafluoroarsenate ions or cyanide ions) organic acids (e.g. acetations, formations, trifluoroacetic acid ions, trifluoromethanesulfonate ions, pentafluoroethanesulfonate ions, nonafluorobutanesulfonate ions, butyrate ions, citrate ions, fumarate ions, glutarate ions, lactate ions, malate ions, malonate ions, oxalate ions, pyruvate ions, tartrate ions).

Preferred anions An ^q- are chloride and fluoride ions, hydroxide ions, phosphate ions, sulfate ions, perchlorate ions, hexafluorophosphate ions and tetrafluoroborate ions.

worin

• R₁₀, R₁₁, An, a, b, c und q die oben definierte Bedeutung besitzen,
• R₁₂ und R₁₃ unabhängig voneinander Wasserstoff, gegebenenfalls mit einer Carbonsäureester-, Carbonsäureamid-, Carbonsäure-, Sulfonsäure- oder Aminogruppe substituiertes Alkyl, beispielsweise eine 2-Trialkylammoniumethylgruppe, gegebenenfalls mit einer Carbonsäureester-, Carbonsäureamid-, Carbonsäure-, Sulfonsäure- oder Aminogruppe substituiertes Cycloalkyl, gegebenenfalls mit einer Carbonsäureester-, Carbonsäureamid-, Carbonsäure-, Sulfonsäure- oder Aminogruppe substituiertes Aryl oder gegebenenfalls mit einer Carbonsäureester-, Carbonsäureamid-, Carbonsäure-, Sulfonsäure- oder Aminogruppe substituiertes Aralkyl bedeuten, insbesondere C₁-C₆-Alkyl, mit einer Carbonsäureestergruppe substituiertes C₁-C₆-Alkyl, mit einer Carbonsäureamidgruppe substituiertes C₁-C₆-Alkyl, mit einer Carbonsäuregruppe substituiertes C₁-C₆-Alkyl, mit einer Sulfonsäuregruppe substituiertes C₁-C₆-Alkyl, oder mit einer Aminogruppe substituiertes C₁-C₆-Alkyl, und ganz besonders bevorzugt Propionat, Isobutionat, Ethyl oder Methyl, und
• R₁₄ und R₁₅ unabhängig voneinander Wasserstoff, gegebenenfalls mit einer Carbonsäureester-, Carbonsäureamid-, Carbonsäure-, Sulfonsäure- oder Aminogruppe substituiertes Alkyl, beispielsweise eine 2-Trialkylammoniumethylgruppe, gegebenenfalls mit einer Carbonsäureester-, Carbonsäureamid-, Carbonsäure-, Sulfonsäure- oder Aminogruppe substituiertes Cycloalkyl, gegebenenfalls mit einer Carbonsäureester-, Carbonsäureamid-, Carbonsäure-, Sulfonsäure- oder Aminogruppe substituiertes Aryl oder gegebenenfalls mit einer Carbonsäureester-, Carbonsäureamid-, Carbonsäure-, Sulfonsäure- oder Aminogruppe substituiertes Aralkyl bedeuten oder zwei Reste R₁₂ und R₁₃ zusammen eine C₁-C₃-Alkylengruppe bilden, insbesondere C₁-C₆-Alkyl, mit einer Carbonsäureestergruppe substituiertes C₁-C₆-Alkyl, mit einer Carbonsäureamidgruppe substituiertes C₁-C₆-Alkyl, mit einer Carbonsäuregruppe substituiertes C₁-C₆-Alkyl, mit einer Sulfonsäuregruppe substituiertes C₁-C₆-Alkyl, oder mit einer Aminogruppe substituiertes C₁-C₆-Alkyl sind oder zusammen Ethylen bedeuten, und ganz besonders bevorzugt Propionat, Isobutionat, Ethyl oder Methyl oder zusammen Ethylen bedeuten.

Redox-active components used with preference in the anolyte are compounds of the formulas IXa or Xa

wherein

• R ₁₀ , R ₁₁ , An, a, b, c and q have the meaning defined above,
• R ₁₂ and R ₁₃ independently of one another are hydrogen, optionally substituted alkyl with a carboxylic acid ester, carboxamide, carboxylic acid, sulfonic acid or amino group, for example a 2-trialkylammoniumethyl group, optionally with a carboxylic acid ester, carboxamide, carboxylic acid, sulfonic acid or amino group Aryl substituted, optionally substituted with a carboxylic acid ester, carboxylic acid amide, carboxylic acid, sulfonic acid or amino group or aryl optionally substituted with a carboxylic acid ester, carboxylic acid amide, carboxylic acid, sulfonic acid or amino group, in particular C ₁ -C ₆ alkyl , substituted with a Carbonsäureestergruppe C ₁ -C ₆ alkyl, substituted with a carboxamide group C ₁ -C ₆ alkyl, substituted with a carboxylic acid group, C ₁ -C ₆ alkyl, substituted with a sulfonic acid C ₁ -C ₆ alkyl, or C ₁ -C ₆ alkyl substituted with an amino group, and very particularly preferably P ropionate, isobutionate, ethyl or methyl, and
• R ₁₄ and R ₁₅ independently of one another are hydrogen, optionally substituted alkyl with a carboxylic acid ester, carboxylic acid amide, carboxylic acid, sulfonic acid or amino group, for example a 2-trialkylammoniumethyl group, optionally with a carboxylic acid ester, carboxylic acid amide, carboxylic acid, sulfonic acid or amino group substituted cycloalkyl, aryl optionally substituted with a carboxylic acid ester, carboxylic acid amide, carboxylic acid, sulfonic acid or amino group or aralkyl optionally substituted with a carboxylic acid ester, carboxylic acid amide, carboxylic acid, sulfonic acid or amino group or two radicals R ₁₂ and R ₁₃ together form a C ₁ -C ₃ alkylene group, in particular C ₁ -C ₆ alkyl, C ₁ -C ₆ alkyl substituted with a carboxylic acid ester group, C ₁ -C ₆ alkyl substituted with a carboxamide group, C ₁ - substituted with a carboxylic acid group C ₆ alkyl, C ₁ -C ₆ alkyl substituted with a sulfonic acid group, or with a Amino group substituted C ₁ -C ₆ alkyl or together are ethylene, and very particularly preferably propionate, isobutionate, ethyl or methyl or together are ethylene.

Examples of particularly preferably used compounds are N, N'-di-C ₁ -C ₄ -alkylbipyridyl cations with any anions for charge balancing, for example N, N'-dimethylbipyridyl halides, such as N, N'-dimethylbipyridyl chlorides.

Preferred redox flow batteries of the first type contain as the anolyte an aqueous electrolyte solution, which is preferably covered with paraffin oil, at a temperature of at least 30 ° C., preferably from 30 to 90 ° C., and in particular from 30 to 50 ° C. contains a redox-active compound containing at least one radical of the formula (IXa) or of the formula (Xa).

In further preferred redox flow batteries of this first type, the electrode chambers for the catholyte and anolyte are separated by a semipermeable membrane which is impermeable to the redox couple in the catholyte, and the anolyte contains zinc salt as the redox-active component.

In a further embodiment, the invention also relates to a second type of redox flow battery for storing electrical energy, comprising a reaction cell with an electrode chamber for an electrolyte solution, which is connected to at least one liquid storage device, the electrode chamber being equipped with a cathode and an anode is, and is filled with electrolytic solution containing redox-active components in liquid form, dissolved or dispersed in an aqueous electrolytic solvent, and optionally conductive salts dissolved therein and possibly other additives. This redox flow battery is characterized in that the electrolyte solution contains an aqueous electrolyte solution according to the definition given above and zinc salt as a further redox-active component.

Redox flow batteries of this second type are distinguished by the fact that they only have to have a liquid reservoir and that no membrane has to be used to separate the reaction cell in the anode and cathode compartments.

Preferred redox flow batteries of this second type also contain an aqueous electrolyte solution according to the definition given above in the liquid store.

Redox flow batteries of this second type are preferred, in which a zinc solid anode with the redox pair zinc (II) / zinc (0) is used.

Examples of zinc salts for the redox flow batteries of the first and second type are zinc chloride, zinc fluoride, zinc bromide, zinc iodide, zinc nitrate, zinc nitrite, zinc hydrogen carbonate, zinc sulfate, zinc perchlorate, zinc tetrafluoroborate and zinc hexafluorophosphate. In addition to zinc salts with inorganic anions, zinc salts with organic anions can also be used, for example zinc acetate, zinc oxalate or zinc formate.

In the second type and in a preferred embodiment of the first type of the redox flow battery according to the invention zinc is used as the redox active anode material. Of particular note are the different physical states that zinc can assume within the battery.

During the charging process, zinc (II) cations dissolved in the electrolyte on the anode surface are reduced to elemental zinc (0). For this two electrons have to be taken up. The active material zinc is found in the battery in both dissolved and solid form.

The zinc solid anode can be present permanently as a metallic electrode or can only be formed in situ during the charging process of the battery on an electrically conductive surface within the chamber by the reduction of zinc cations. The zinc cations can function mainly as an active material, but also secondarily as a lead additive or as part of a lead additive mixture.

During the charging process, zinc (II) cations dissolved in the electrolyte on the anode surface are reduced to elemental zinc (0). The anode can consist of any electrically conductive material, preferably metal, in particular zinc or zinc alloys. By taking up two electrons, metallic zinc is deposited on the electrode surface. In the opposite case, metallic zinc passes from the electrode surface through the release of two electrons into zinc ions, which accumulate in the anolyte.

Particularly preferred redox flow batteries according to the invention have a zinc solid anode with the redox pair zinc (II) / zinc (0).

The advantage over the fully organic redox flow batteries described is the reduction in production costs. The zinc anode is much more cost-effective to produce than known organic anodes. On the other hand, the redox couple zinc (II)) / zinc (0) is characterized by very good stability against external environmental influences, such as sensitivity to oxygen. Conventional systems must be kept free of oxygen; this complicates the design of the battery considerably and increases the operating costs. If a zinc anode is used, this can be completely dispensed with.

Zinc also has a very high overvoltage in aqueous media and thus enables an extremely high potential window. The potential window is to be understood as the voltage (potential range) which, due to the position of the redox pairs, in the range of the electrochemical voltage series, between cathode and anode can be achieved without unwanted side reactions or decomposition of the redox-active species, the main additive, the electrolyte, or another component of the entire battery. Conventional aqueous flow batteries are limited to a potential window of around 1.2 V. Otherwise this would produce hydrogen gas. By using a zinc anode, the potential window can be expanded to more than 2 V. This leads to a considerable increase in the electrical power per cell. Zinc has a very high overvoltage compared to hydrogen, which is why, despite the high voltage of 2 V, there is no hydrogen at the anode and the battery can be operated safely.

The term “battery” is used in its broadest sense in the context of this description. This can be a single rechargeable electrochemical cell or a combination of several such electrochemical cells.

Particularly preferred redox flow batteries of the present invention have a charge state of the catholyte or of the catholyte and of the anolyte of less than 90%, in particular up to 80% and very particularly preferably from 70 to 80%. These redox flow batteries are distinguished by a particularly good temperature stability of the electrolyte and in particular the redox-active compounds described above or their combinations with selected additives. The state of charge is determined as described above. Of course, the state of charge of the catholyte or of the catholyte and the anolyte in the RFB according to the invention can also be 100%.

In addition to the components described above, the redox flow battery according to the invention can also contain further elements or components customary for such cells.

In the redox flow battery according to the invention, selected redox-active components are used in the chamber (s), which are present in the chamber (s) in dissolved, liquid or dispersed form.

The redox potential of the redox-active component can be determined, for example, using cyclic voltammetry. This method is known to the person skilled in the art (see Allen J. Bard and Larry R. Faulkner, "Electrochemical Methods: Fundamentals and Applications", 2001, 2nd edition, John Wiley &Sons; Richard G. Compton, Craig E. Banks, "Understanding Voltammetry ”, 2010, 2nd edition, Imperial College Press).

• • Trennung von Anoden- und Kathodenraum
• • Zurückhalten der redoxaktiven Komponente im Katholyten und im Anolyten, also Zurückhalten des Kathoden- und des Anoden-AktivMaterials
• • Durchlässigkeit für die Leitsalze des Elektrolyten, die zum Ladungsausgleich dienen, also für Anionen und/oder Kationen des Leitsalzes bzw. für die im Elektrolyten enthaltenen Ladungsträger allgemein.

The first type of redox flow battery according to the invention contains a semipermeable or microporous membrane. This fulfills the following functions

• • Separation of anode and cathode compartments
• • Retention of the redox-active component in the catholyte and in the anolyte, ie retention of the cathode and anode active material
• • Permeability for the conductive salts of the electrolyte, which serve to balance the charge, that is, for anions and / or cations of the conductive salt or for the charge carriers contained in the electrolyte in general.

The membrane may include a size exclusion membrane, e.g. B. a dialysis membrane, but also an ion-selective membrane. The membrane prevents the redox-active ferrocene compound from entering the anode compartment and preventing redox-active components of the anolyte from penetrating into the cathode compartment. The passage of dissolved zinc (II) cations does not have to, but can also be inhibited by the membrane.

Depending on the application, the membrane materials can consist of plastics, ceramics, glasses, metals or textile fabrics. Examples of materials are organic polymers, such as cellulose or modified cellulose, for example cellulose ethers or cellulose esters, polyether sulfone, polysulfone, polyvinylidene fluoride, polyester, polyurethanes, polyamides, polypropylene, polyvinyl chloride, polyacrylonitrile, polystyrene, polyvinyl alcohol, polyphenylene oxide, polyimides, polytetrafluoroethylene and their derivatives, or also ceramics, glasses or felts. Membranes consisting of several materials (composites) are also possible.

The membranes and the resulting redox flow batteries can be used in various forms. Examples of this are flat membranes, pocket filter construction and wound modules. These embodiments are known to the person skilled in the art. Flat membranes are preferably used.

The thickness of the membrane used according to the invention can vary over a wide range. Typical thicknesses are in the range between 0.1 µm and 5 mm, particularly preferably between 10 µm and 200 µm.

• • Fördermittel, wie Pumpen, sowie Tanks und Rohre für den Transport und die Lagerung von redoxaktiven Komponenten
• • Elektroden, bevorzugt bestehend aus oder enthaltend Graphit, Graphitvlies, Graphitpapier, Carbon-Nano-Tube-Teppichen, Aktivkohle, Russ oder Graphen
• • gegebenenfalls Stromableiter, wie z.B. aus Graphit oder aus Metallen

In addition to the redox-active components, electrolytes and optionally membranes described above, the redox flow cell according to the invention preferably contains further components. It refers to

• • Funding means, such as pumps, as well as tanks and pipes for the transport and storage of redox-active components
• • Electrodes, preferably consisting of or containing graphite, graphite fleece, graphite paper, carbon nano-tube carpets, activated carbon, carbon black or graphene
• • where appropriate, current arresters, such as those made of graphite or metals

• Edelstahl, Hastelloy oder Eisen-Chrom-Nickel-haltige Legierungen, Graphit, Graphitvlies, Graphitpapier, Carbon-Nano-Tube-Teppichen, Aktivkohle, Russ oder Graphen.

The negative electrode preferably contains zinc and can also contain the following materials, for example:

• Stainless steel, Hastelloy or iron-chromium-nickel-containing alloys, graphite, graphite fleece, graphite paper, carbon nano-tube carpets, activated carbon, carbon black or graphene.

The redox flow batteries according to the invention contain current collectors as a further optional but preferred component. These have the task of establishing the best possible electrical contact between the electrode material and the external current source or current sink.

Aluminum, aluminum alloys, copper, stainless steel, Hastelloy, iron-chromium-nickel alloys, noble metal-coated titanium or tantalum, in particular platinum and / or iridium and / or ruthenium oxide-coated titanium, can be used as current conductors in the redox flow batteries according to the invention, Niobium, tantalum, hafnium or zirconium can be used.

All components that allow the transmission of electrical current to the electrodes are referred to as current conductors. The redox reactions take place on the electrodes (cathode and anode), which are in direct contact with the electrolyte.

The redox flow batteries according to the invention can be used in a wide variety of fields. In the broadest sense, this can be the storage of electrical energy for mobile and stationary applications. The invention also relates to the use of the redox flow batteries for these purposes. Examples of applications include use as stationary storage for emergency power supply, peak load balancing, and for the temporary storage of electrical energy from renewable energy sources, in particular in the sectors of photovoltaics, hydropower and wind power, from gas, coal, biomass, tides, - and marine power plants and deployments in the field of electromobility, such as storage in land, air and water vehicles.

The redox flow batteries according to the invention can be connected to one another in a manner known per se in a serial or parallel manner.

The following examples illustrate the invention without restricting it thereto.

Example 1: Temperature stability of TEMPTMA

Es wurden geladene TMA-TEMPO-Lösungen in Wasser untersucht und bei verschiedenen Temperaturen für unterschiedliche Zeiten temperiert. Die Elektrolyte ohne Additive zeigen eine Restkapazität von 89% (nach 4 Tagen bei 40 °C). Im Gegensatz dazu zeigen Elektrolyte mit einem äquimolaren Zusatz von NH₄Cl oder von Chlorwasserstoff noch eine Restkapazität von 96%.

Loaded TMA-TEMPO solutions in water were examined and tempered at different temperatures for different times. The electrolytes without additives show a residual capacity of 89% (after 4 days at 40 ° C). In contrast, electrolytes with an equimolar addition of NH ₄ Cl or hydrogen chloride still show a residual capacity of 96%.

QUOTES INCLUDE IN THE DESCRIPTION

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Patent literature cited

• WO 2014/026728 A1 [0005]
• WO 2017/084749 A1 [0005]
• WO 2017/025177 A1 [0005]
• WO 2018/032003 A1 [0006]
• US 2018/0072669 A1 [0006]
• US 2012/0077067 A1 [0008]

Claims (18)

Aqueous electrolyte solution with a temperature of at least 30 ° C. containing a) an organic compound containing at least one redox-active group of the formula (Ia) and hydrochloric acid and / or a salt selected from the group of the ammonium salts with inorganic or organic anions, the salts with tetrafluoroborate Anions or the salts of trifluoromethanesulfonic acid

and / or containing b) an organic compound containing at least one redox-active group of the formula (Ib)

and / or containing c) an organic compound containing at least one redox-active group of the formula (Ic)

wherein R ₁ , R ₂ , R ₃ and R _{4 are} alkyl or each R ₁ and R ₂ and R ₃ and R ₄ together with the common carbon atom form a cycloaliphatic or heterocyclic radical, X is -O or -S, Y is -CH ₂ -, -O-, -S-, -SO-, -SO ₂ -, -NR ₅ - or -N ⁺ R ₅ R ₆ - (An ^m- ) _{1 / m} , Q is -O-, -S -, -NH-, -NR _6a , -, -NR _6a R _6b ⁺ - (An ^m- ) _{1 / m} , -PR _6a - or -SiR _6a R _6b - means, or -Q- represents a covalent bond, R ₅ , R ₆ , R _6a and R _{6b are,} independently of one another, monovalent organic radicals, An is an m-valent inorganic or organic anion, and m represents an integer between 1 and 4. Aqueous electrolyte solution after Claim 1 , characterized in that it has a temperature of 30 to 90 ° C, preferably 30 to 50 ° C. Aqueous electrolyte solution according to at least one of the Claims 1 to 2nd , characterized in that it contains at least one conductive salt. Aqueous electrolyte solution according to at least one of the Claims 1 to 3rd , characterized in that their state of charge is less than 90%. Aqueous electrolyte solution according to at least one of the Claims 1 to 4th , characterized in that they contain a compound with at least one redox-active radical of the formula (la), (Ib) or (Ic) which is covalently linked to a polymer backbone which is selected from the group of polymethacrylates, polyacrylates, polystyrenes, polyalkylene glycols , Polyalkylenimine or the polyvinyl ether, wherein the polymer backbone preferably has 5 to 100 groups of the formula (Ia), (Ib) or (Ic). Aqueous electrolyte solution according to at least one of the Claims 1 to 4th , characterized in that these oligomers or polymers containing the recurring structural units of the formula (II) and optionally further structural units derived from solubilizing comonomers

wherein ME is a repeating structural unit derived from a polymerizable monomer, BG is a covalent bond or a bridging group, Pip represents a piperidinyl radical of the formula (Ia), (Ib) or (Ic), and r is an integer from 2 to 150. Aqueous electrolyte solution according to at least one of the Claims 1 to 4th , characterized in that it contains a redox-active compound of the formula (IIIa) or (IIIb)

wherein R ₁ , R ₂ , R ₃ and R ₄ the in Claim 1 have defined meaning, o is an integer from 1 to 3, R _{8 is} a single-bonded organic radical and Rg is a two- to four-bonded organic radical. Aqueous electrolyte solution according to at least one of the Claims 1 to 7 , characterized in that it contains a redox-active compound of formula (IV), (V), (VI), (VII) or (VIII)

wherein R ₁ , R ₂ , R ₃ , R ₄ , Q, X and Y the in Claim 1 have defined meaning, ME, BG and r the in Claim 6 have defined meaning, Rg and o the in Claim 7 have defined meaning, and p is 0 or 1. Aqueous electrolyte solution after Claim 7 , characterized in that it contains a redox-active compound of the formula (IIIa) in which R _{8 is} -O- (C _s H _2s ) -FG or -S- (C _s H _2s ) -FG, s is an integer of 2 to 4, FG means a functional group selected from -OH, -SH, -NO ₃ , -NO ₂ , - CN, -OR ₁₄ , -SR ₁₄ , - (O-CH ₂ -CH ₂ ) _o -OR ₁₅ , -COR ₁₅ , - (O-CH ₂ -CH ₂ ) _o -NR ₁₆ R ₁₇ R ₁₈ ⁺ (An ^q- ) _{1 / q} , -COO ^- (Kat ^{q +} ) _{1 / q} , -COOR ₁₅ , -SO ₃ ^- (Kat ^{q +} ) _{1 / q} , -SO ₃ R ₁₅ , -SO ₄ ^- (Kat ^{q +} ) _{1 / q} , -SO ₄ R ₁₅ , -PO ₄ ^2- (Kat ^{q +} ) _{2 / q} , -PO ₄ ( R ₁₅ ) ₂ , -PO ₃ ^2- (Kat ^{q +} ) _{2 / q} , -PO ₃ (R ₁₅ ) ₂ , -NR ₁₆ R ₁₇ R ₁₈ ⁺ (An ^q- ) _{1 / q} , -N ⁺ R ₁₆ R ₁₇ -C _t H _2t -SO ₃ ^- or -NR ₁₅ -SO ₂ -R ₁₆ , R _{14 is} C ₁ -C ₄ alkyl, R _{15 is} hydrogen or C ₁ -C ₄ alkyl, R ₁₆ , R ₁₇ and R _{18 is} independently hydrogen or alkyl, Kat is a q-valent cation, An is a q-valent anion, q is an integer between 1 and 4, t is an integer between 2 and 5, and o is an integer is from 1 to 50. Aqueous electrolyte solution according to at least one of the Claims 1 to 4th , characterized in that it contains a redox-active compound containing one or more radicals of the formula (Ia) and a stabilizing additive, the stabilizing additive being selected from the group of hydrochloric acid, the quaternary ammonium alkyl halides, in particular the quaternary ammonium alkyl chlorides or fluorides, or the alkali metal, alkaline earth metal or ammonium, especially the sodium, potassium, magnesium, calcium or quaternary ammonium tetrafluoroborates or - trifluoromethanesulfonates Redox flow battery for storing electrical energy containing a reaction cell with two electrode chambers for catholyte and anolyte, each of which is connected to at least one liquid store stand, the electrode chambers being separated by a membrane, equipped with electrodes, and each filled with electrolyte solutions containing redox-active components in liquid form, dissolved or dispersed in an aqueous electrolyte solvent, and, if appropriate, conductive salts dissolved therein and possibly other additives, thereby characterized in that the anolyte contains a water-soluble redox-active component and that the catholyte in the electrode chamber contains an aqueous electrolyte solution according to at least one of the Claims 1 to 10th contains Redox flow battery after Claim 11 , characterized in that the anolyte contains a compound containing one or more bipyridiyl groups in the molecule as a redox-active component. Redox flow battery after Claim 11 , characterized in that the electrode chambers for catholyte and anolyte are separated by a semipermeable membrane which is impermeable to the redox couple in the catholyte, and that the anolyte contains zinc salt as the redox-active component. Redox flow battery for storing electrical energy containing a reaction cell with an electrode chamber for an electrolyte solution, which is connected to at least one liquid reservoir, the electrode chamber being equipped with a cathode and an anode, and filled with electrolyte solution containing the redox-active components in contains liquid form, dissolved or dispersed in an aqueous electrolyte solvent, and, if appropriate, conductive salts dissolved therein and possibly other additives, characterized in that the electrolyte solution is an aqueous electrolyte solution according to at least one of the Claims 1 to 10th and contains zinc salt as a further redox-active component. Redox flow battery according to at least one of the Claims 11 to 14 , characterized in that it has a zinc solid anode with the redox couple zinc (II) / zinc (0). Redox flow battery according to at least one of the Claims 11 to 15 , characterized in that the electrolyte solution in the electrode chambers is covered with paraffin oil. Redox flow battery according to at least one of the Claims 11 to 16 , characterized in that the state of charge of the catholyte or the catholyte and the anolyte is less than 90%. Use of the redox flow battery according to one of the Claims 11 to 17th for the storage of electrical energy for stationary and mobile applications, in particular as stationary storage for emergency power supply, peak load balancing, for the temporary storage of electrical energy from renewable energy sources, in particular in the photovoltaic, hydropower and wind power sector, or from gas , Coal, biomass, tidal and marine power plants.