EP4066302A1 - Compositions aqueuses stables comprenant des quinones et leur utilisation dans des batteries à circulation - Google Patents

Compositions aqueuses stables comprenant des quinones et leur utilisation dans des batteries à circulation

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Publication number
EP4066302A1
EP4066302A1 EP20811363.9A EP20811363A EP4066302A1 EP 4066302 A1 EP4066302 A1 EP 4066302A1 EP 20811363 A EP20811363 A EP 20811363A EP 4066302 A1 EP4066302 A1 EP 4066302A1
Authority
EP
European Patent Office
Prior art keywords
acid
compound
mol
general formula
composition according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP20811363.9A
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German (de)
English (en)
Inventor
Werner SCHLEMMER
Stefan Spirk
Wolfgang Kern
Philipp Nothdurft
Melahat TAYLI
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ECOLYTE GMBH
Original Assignee
Technische Universitaet Graz
Montanuniversitaet Leoben
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Application filed by Technische Universitaet Graz, Montanuniversitaet Leoben filed Critical Technische Universitaet Graz
Publication of EP4066302A1 publication Critical patent/EP4066302A1/fr
Pending legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • H01M8/184—Regeneration by electrochemical means
    • H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/26—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/23—Oxidation
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/25—Reduction
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • H01M2300/0005—Acid electrolytes
    • H01M2300/0008—Phosphoric acid-based
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to the field of quinones and their use in redox flow batteries.
  • redox flow batteries In redox flow batteries (RFBs), the volumetric capacity is low, so that batteries of this type are currently used stationary and not mobile.
  • the electrolytes are stored in tanks and pumped through a reaction cell, where they are oxidized / reduced. It is thus possible to increase the capacity of the batteries by increasing the volume (power density approx. 40 Wh / 1).
  • Large-format redox flow batteries (RFBs) can therefore be used as buffer systems for the power grid and as a backup system for critical infrastructures.
  • One of the major disadvantages of the electrolytes currently used in RFBs is their price, sustainability and availability.
  • Hydroquinones are dihydroxyphenols that are soluble in water and several organic solvents. Recently, these compounds have come into the focus of research due to their reversible electrochemical behavior, making them attractive candidates for the development of (aqueous) RFBs.
  • quinone derivatives such as sulfonates or quinones substituted with alkyl groups and similar compounds based on naphthalene or anthracene have been described in recent years.
  • quinones in particular with groups with + M effects can enter into irreversible side reactions, which leads to performance losses in RFB applications.
  • WO 2015/023974 A1 discloses a supercapacitor, wherein the electrolyte can contain a quinone compound in a low-pH solution.
  • a solution comprising 1,4-benzoquinone and hydroquinone in aqueous sulfuric acid is disclosed therein.
  • KR 20170037296 A deals with a photovoltaic cell that can continuously generate energy.
  • 1,4-benzoquinone / hydroquinone is mentioned as a redox pair.
  • water can be used as a solvent in the electrolyte.
  • RO 120939 B1 discloses a regenerative electrochemical cell which can comprise quinone / hydroquinone redox couples.
  • CN 108593 737 A deals with electrochemical sensors based on polyimides, which can be used, for example, for the detection of catechol and hydroquinone.
  • WO 2019/158615 A1 describes substituted benzoquinones.
  • CN 102035 007 A deals with a flow battery in which dihydroxyhydroquinones can be used.
  • the present invention therefore relates to an aqueous composition
  • an aqueous composition comprising a) at least one compound with the general formula (I) and at least one compound with the general formula (II) and / or at least one compound with the general formula (III) and at least one compound with the general formula (IV) where Ri and R 2 are independently H or OR 5 and R 3 and R 4 are independently H or OR 5 , where R 5 is an alkyl or allyl radical, and b) phosphate ions and / or hydrogen phosphate ions and / or their condensates.
  • Another aspect of the present invention relates to the use of an aqueous composition according to the invention as an electrolyte in a redox flow cell or in a redox flow battery.
  • the composition according to the invention is particularly suitable for redox flow cells.
  • the above-described photoreduction of the benzoquinones in the aqueous solution enables the production of redox flow cells or batteries, the half-cell of which can be charged by means of light (eg sunlight, UV radiation, etc.) to make connections Formula (I) to compounds according to formula (II), and compounds according to formula (III) to compounds according to formula (IV).
  • the storage stability of the composition according to the invention is also advantageous in such applications.
  • Yet another aspect of the present invention relates to a method for reducing a compound having the general formula (I) to a compound having the general formula (II) and / or for reducing a compound with the general formula (III) to a compound with the general formula where Ri and R 2 are independently H or OR 5 and R 3 and R 4 are independently H or OR 5 , where R 5 is an alkyl radical or an allyl radical, comprising the step of bringing an aqueous composition according to the invention into contact with light.
  • Fig. 1 shows side reactions in HCl: Oxidation of MHQ to MQ and accelerated by light and atmospheric oxygen Formation of the MHQMQ dimer in the absence of phosphate ions and / or hydrogen phosphate ions and / or their condensates.
  • Fig. 2 shows a 1H NMR of the MQMHQ dimer which was formed in the presence of HCl.
  • MQ / MHQ solution in 1 M H3PO4 with a scan rate of 25 mV / s for over 2 hours (100 cycles) to show the stability of the aqueous mixture.
  • 3b) shows cyclic voltammograms of the same solution at different feed rates (1000 mV / s, 800 mV / s, 500 mV / s, 300 mV / s, 150 mV / s, 100 mV / s, 50 mV / s, peak currents decrease in this order) to determine the number of electrons transferred.
  • Fig. 5 shows a galvanostatic cycling of a symmetrical MQ / MHQ U-cell.
  • the capacity was normalized to the mass of the active material used. 100 cycles with an applied current of ⁇ 10 mA (0.5C) with reversal potentials of 0.5 / -0.5 V were measured.
  • the solutions used were 0.5 or 1 mM MHQ or MQ in 0.5MH 3 PO 4 .
  • Figure 6A shows the aromatic region in 1H NMR
  • RTB redox flow battery
  • Fig. 8 shows the results of experiments that were carried out with a redox flow battery (RFB). The broken lines indicate the theoretical capacity. The experiments were carried out both potentiostatically (a) and galvoanostatically (b).
  • FIG. 11 shows a potentiostatic cyclization of a redox flow battery full cell which contains 2.7 mg of caffeic acid and 3 mg of p-hydroquinone as active materials in 35 mL of 0.5M H3PO4 each.
  • Aqueous composition refers to compositions which are more than 50% by weight, preferably more than 60% by weight, even more preferably more than 70% by weight, even more preferably more than 80% by weight, even more preferably more than 90% by weight, even more preferably more than 95% by weight % By weight, include water.
  • the aqueous composition according to the invention preferably comprises less than 20% by weight, even more preferably less than 10% by weight, even more preferably less than 5% by weight, even more preferably less than 2% by weight, even more preferably less than 1% by weight, in particular no detectable organic solvent such as aceto nitrile.
  • the substituents Ri and R2 of the compounds with the formula (I) and (II) are, independently of one another, H or OR 5 .
  • the substituents R 3 and R 4 of the compounds with the formula (III) and (IV) are, independently of one another, H or OR 5 .
  • the compounds of the general formula (I) represent oxidized forms of the compounds with the general formula (II).
  • the compounds of the general formula (III) represent oxidized forms of the compounds with the general formula (IV).
  • Substituent R5 is an alkyl radical or an allyl radical.
  • the alkyl radical is preferably a Ci to C5 alkyl radical.
  • the allyl radical is preferably a C2 to C5 allyl radical.
  • "Ci to C5 alkyl radical” and “C2 to C5 allyl radical”, as used herein, includes alkyl or allyl radicals with 1 or 2 to 5 carbon radicals, which are preferably arranged linearly (ie a linear alkyl or allyl radical) .
  • the substituent R5 is a methyl radical, an ethyl radical, a vinyl radical, a propyl radical, a propylene radical, a butyl radical, a butenyl radical, a pentyl radical or a pentenyl radical, with substituent R5 being particularly preferably a methyl radical.
  • the alkyl radical or allyl radical can also comprise further substituents, in particular water-soluble substituents, such as, for example, acid or ester groups and sulfonate groups.
  • Examples of a compound of the formula (IV) with an acid or ester group in R5 are trans-caffeic acid (trans-3- (3,4-dihydroxyphenyl) propenoic acid) and chlorogenic acid ((IS, 3R, 4R , 5R) -3 - [(E) - 3- (3,4-dihydroxyphenyl) prop-2-enoyl] oxy-1,4,5-trihydroxycyclohexane-1-carboxylic acid).
  • the aqueous composition according to the invention comprises phosphate ions and / or hydrogen phosphate ions. These are preferably added to the composition in the form of phosphoric acid or salts. “Condensates” of phosphate ions and / or hydrogen phosphate ions can be formed by splitting off water. This results in diphosphate ions or poly- or cyclo-phosphate ions.
  • the compound of the formula (I) is preferably a 1,4-benzoquinone or 1,4-benzoquinone derivative and the compound of the formula (II) is a 1,4-hydroquinone or 1,4-hydroquinone derivative.
  • the compound of the formula (III) is preferably a 1,2-benzoquinone or 1,2-benzoquinone derivative and the compound of the formula (IV) is a catechol (1,2-dihydroxybenzene) or catechol derivative.
  • the compound of the formula (III) is trans-caffeic acid-o-quinone or chlorogenic acid-o-quinone and the compound of the formula (IV) is trans-caffeic acid or chlorogenic acid .
  • phosphate ions and / or hydrogen phosphate ions or their condensates stabilize, in particular, aqueous compositions comprising MQ, pHQ, MHQ and / or pQ.
  • the aqueous composition of the present invention preferably comprises MQ and MHQ and / or pQ and pHQ.
  • the condensates of phosphate ions and hydrogen phosphate ions are hydrogen diphosphate ions, hydrogen triphosphate ions, hydrogen oligophosphate ions or hydrogen polyphosphate ions.
  • the aqueous composition comprises a compound of the general formula (I) and a compound having the general my formula (II)
  • the aqueous composition according to a preferred embodiment of the present invention comprises 0.0001 to 1.2 mol / L, preferably 0.001 to 1 mol / L, even more preferably 0.05 to 0.75 mol / L, even more preferably 0.1 to 0.75 mol / L, even more preferably 0.2 to 0.7 mol / L, of a compound of the formula (I) and / or (II).
  • concentration data are preferably the sum of the compounds with the formulas (I) and (II) in the composition according to the invention.
  • the ratio of the compounds having the formulas I and II is preferably 1:10 to 10: 1, even more preferably 1: 5 to 5: 1, even more preferably 1: 3 to 3: 1, even more preferably 1: 2 to 2: 1, particularly preferably approx. 1: 1.
  • the aqueous composition comprises a compound of the general formula (III) and a compound of the general formula (IV)
  • the aqueous composition according to a preferred embodiment of the present invention comprises 0.0001 to 1.2 mol / L, preferably 0.001 to 1 mol / L, even more preferably 0.05 to 0.75 mol / L, even more preferably 0.1 to 0.75 mol / L, even more preferably 0.2 to 0.7 mol / L, a compound of the formula (III) and / or the (IV).
  • concentration data are preferably the sum of the compounds with the formulas (III) and (IV) in the composition according to the invention.
  • the ratio of the compounds of the formulas (III) and (IV) is preferably 1:10 to 10: 1, even more preferably 1: 5 to 5: 1, even more preferably 1: 3 to 3: 1, even more preferably 1: 2 to 2: 1, particularly preferably about 1: 1.
  • the composition comprises a total of 0.01 to 0.75 mol / L, preferably 0.05 to 0.7 mol / L, even more preferably 0.1 to 0.6 mol / L, even more preferably 0.15 to 0.5 mol / L, phosphate ions and / or hydrogen phosphate ions and / or their condensates.
  • the composition additionally comprises at least one acid with a pKa value of -7.5 to 8, preferably -3.5 to 8, even more preferably 1.5 to 8, even more preferably from 2 to 7.5, even more preferably from 4.2 to 6.8, even more preferably from 4.5 to 6.
  • the composition preferably comprises an acid with a pKa of less than 8.
  • the acid is an organic or inorganic acid, wherein the inorganic acid is preferably selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, and the organic acid is preferably selected from the group consisting of formic acid, citric acid, acetic acid, propionic acid, butyric acid, glyoxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, citric acid, trimesic acid, trimellitic acid and half esters thereof.
  • the inorganic acid is preferably selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid
  • the organic acid is preferably selected from the group consisting of formic acid, citric acid, acetic acid, propionic acid, butyric acid, glyoxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, citric acid, trimesic acid, trimellitic acid and
  • the composition comprises 0.001 to 5 mol / L, preferably 0.005 to 3 mol / L, acid.
  • the composition has a pH of less than 7, preferably from 1 to 6.9.
  • the composition comprises at least one electrolyte selected from the group consisting of the group of alkali and alkaline earth metal chlorides, preferably NaCl, KCl or CaCl2, from the group of alkali and alkaline earth metal sulfates, preferably Na 2 SC> 4 or K 2 SO 4 , and the group of alkali and alkaline earth metal salts of carboxylic acids, dicarboxylic acids and tricarboxylic acids, preferably before sodium acetate, sodium citrate, calcium citrate or sodium oxalate.
  • the group of alkali and alkaline earth metal chlorides preferably NaCl, KCl or CaCl2
  • the group of alkali and alkaline earth metal sulfates preferably Na 2 SC> 4 or K 2 SO 4
  • the group of alkali and alkaline earth metal salts of carboxylic acids, dicarboxylic acids and tricarboxylic acids preferably before sodium acetate, sodium citrate, calcium citrate or sodium o
  • composition according to the invention can be used as an electrolyte solution in redox flow cells or batteries.
  • the composition according to the invention therefore comprises at least one electrolyte.
  • the composition comprises at least one electrolyte in a concentration range from 0.001 to 1.5 mol / L.
  • Another aspect of the present invention relates to the use of an aqueous composition according to the invention as an electrolyte in a redox flow cell.
  • Yet another aspect of the present invention relates to a redox flow cell comprising an aqueous composition according to the invention.
  • Redox flow cells also referred to as redox flow batteries or redox flow batteries, can be used to store electrical energy.
  • Redox flow cells contain two polarity-specific chambers, in each of which a redox-active chemical compound or a redox-active compound is present in dissolved form in both chambers and is connected to a fluid reservoir. In this way, two independent circuits are formed for the redox-active compounds dissolved, for example, in water or organic solvents, which are separated by a membrane between the polarity-specific chambers. An exchange of ions takes place between the two chambers via this membrane.
  • the cells are particularly suitable for stationary storage applications, for example as a buffer battery for wind turbines or as power and control reserves for load balancing in power grids, but can also be used as mobile energy storage devices, for example for the operation of electric cars and electronic devices .
  • the compounds required to adjust the potential at the electrodes are dissolved, redox-active compounds which are converted into their respective other redox stage during the charging or discharging process in an electrochemical reactor.
  • the electrolyte solutions (catholyte, anolyte) are taken from a tank and actively pumped to the electrodes.
  • the anode and cathode compartments are separated in the reactor by an ion-selective membrane, which is usually a shows high selectivity for protons.
  • an ion-selective membrane which is usually a shows high selectivity for protons.
  • the pumping process is usually reversed. This means that the amount of energy that can be stored in a redox flow cell is directly proportional to the size of the storage tank.
  • the power that can be drawn is a function of the size of the electrochemical reactor.
  • the aqueous composition according to the invention can be used as an electrolyte in redox flow cells.
  • the electrolyte reservoir comprising the aqueous composition according to the invention at least translucent, preferably UV-permeable, in order to regenerate, ie reduce, the compounds with the general formula (I) to compounds with the general formula (II ) or the compounds with the general formula (III) to compounds with the general formula (IV) to enable chen.
  • composition according to the invention is preferably used as a catholyte in redox flow cells.
  • the composition according to the invention can also be used as an anolyte with the corresponding opposite side.
  • aqueous compositions comprising anthraquinones (sulfonated, alkylated and / or acylated), naphthaquinones (sulfonated, alkylated and / or acylated), viologens, 2,2,6,6-tetramethylpiperidinyloxyl (TEMPO) and derivatives thereof are also suitable , redox-active polymers, especially polyanillin with Violog-, Pyridinyl and / or quinone structures, natural quinones, in particular tannins, tannic acid, gallic acid, caffeic acid and / or chlorogenic acid, porphyrins and / or pyrroles as anolytes.
  • TEMPO 2,2,6,6-tetramethylpiperidinyloxyl
  • Another aspect of the present invention relates to a method for reducing a compound having the general formula (I) to a compound having the general formula (II) and / or for reducing a compound with the general formula (III) to a compound with the general formula (IV) where Ri and R 2 are independently H or OR 5 and R 3 and R 4 are independently H or OR 5 , where R 5 is an alkyl radical or an allyl radical, comprising the step of bringing an aqueous composition according to the invention into contact with light.
  • the inventive method ie the reduction of a compound of the general formula (I) to a compound of the general formula (II) and or the reduction of a compound of the general formula (III) to a compound of the general formula (IV), may be carried out in the presence of light in the composition according to the invention.
  • This makes it possible to charge a redox flow cell by exposure to light (e.g. sunlight / light in the visible range and / or UV radiation).
  • the introduced light preferably has a wavelength from 190 to 800 nm, preferably from 190 to 400 nm, even more preferably from 350 to 400 nm.
  • the light is sunlight and / or UV light.
  • the reduction is preferably carried out in a redox flow cell, but in particular not in the electrode area but, for example, in a storage tank in which the composition is stored so that the regeneration reaction, ie the reduction, does not affect the generation of electricity.
  • the present invention also relates to an aqueous composition
  • an aqueous composition comprising a) at least one compound having the general formula and at least one compound with the general formula where R-6, R7 and Rs are 0, H or OR5 and Rg, Rio and Rn are OH, H or OR5, where R6 is 0 and R9 OH, R7 0 and Rio is OH or Rs 0 and Rn is OH, where R 5 is a Is an alkyl or allyl radical, and b) phosphate ions and / or hydrogen phosphate ions and / or their condensates.
  • one of the substituents R 6 , R 7 and Rs of the compound represented by the formula (V) is 0 (oxygen). Accordingly, one of the substituents Rg, Rio and Rn of the compound with the formula (VI) at the corresponding point is OH. Therefore, R 6 is 0 when R 9 is OH, R 7 is 0 when Rio is OH, and Rs is 0 when Rn is OH.
  • R ⁇ , R7, R9 and Rio in formula (V) and formula (VI) are preferably H or OR5.
  • the compounds of the general formula (V) are preferably oxidized forms of the compounds with the general formula (VI).
  • the substituent R 6 is preferably identical to the substituent Rg
  • the substituent R 7 is preferably identical to the substituent Rio and / or substituent Rs is preferably identical to the substituent Rn, provided that these are H and / or OR 5 .
  • At least one of the substituents R ⁇ , R 7 and Rs is an oxygen atom (0), so that the compound with the formula (V) has at least two oxo groups. Accordingly, the compound with the general formula (VI) has two hydroxyl groups in the same positions. If one of the substituents R 6 , R7 and Rs is an O atom, this substituent is bonded to the corresponding carbon atom of the ring by means of a double bond.
  • R5 is identical both in the compound with the formula (V) and in the compound with the formula (VI).
  • Yet another aspect of the present invention relates to a method for reducing a compound having the general formula to a compound with the general formula where R-6, R7 and Rs 0, H or OR5 and Rg, Rio and Rn OH, H or OR5, where R60 and R9 OH, R70 and Rio OH or Rs 0 and Rn OH, where R 5 is an alkyl or allyl radical, and comprising the step of bringing an aqueous composition according to the invention into contact with light.
  • R-6, R7 and Rs 0, H or OR5 and Rg, Rio and Rn OH, H or OR5, where R60 and R9 OH, R70 and Rio OH or Rs 0 and Rn OH, where R 5 is an alkyl or allyl radical and comprising the step of bringing an aqueous composition according to the invention into contact with light.
  • MQ and MHQ are relatively unstable. While MQ and MHQ individually show hardly any side reactions in acidic, aqueous solution, mixtures of the two have a strong tendency to degradation. The most common side reactions are dimerization. MHQ acts as a nucleophile and MQ as an electrophile. It is particularly problematic that MHQ tends to oxidize to MQ in acidic media, which did heavily influenced. Light also has a strong influence on stability: MQ can be converted into a (reactive) excited state by absorption. This means that radical side reactions cannot be ruled out.
  • Equations 1 and 2 show the calculation of the number of electrons transferred by means of CV (cyclic voltammetry). This includes the diffusion coefficient D [cm 2 s 1 ], the electrode surface A [cm 2 ], the Faraday constant F [C / mol], the feed rate v [Vs -1 ] the peak current iP [mA], the number of electrons transferred n [], the concentration c [mol ml-1], the ideal gas constant R [Jmol -1 K _1 ] and the temperature T [K].
  • the corresponding measurements were carried out in the 3-electrode structure described above; the scan rates were 50, 100, 150, 300, 500 and 1000 mV / s in potential ranges between -1 and 1 V.
  • Equation (2) Measurements at different pH values support the 2 e hypothesis, since the shift of the redox potential in quinones is usually around -22 mV / pH for 1 e and -59 mV / pH for 2 e transitions (see AJ Bard, "Electrochemical methods: fundamentals and applications”; Allen J. Bard, Larry R. Faulkner, Wiley, New York, 1980).
  • Example 3 Tests of MQ / MHQ based whole cells
  • MQ / MHQ had a redox potential of approx. 0.33 V vs. Ag / AgCl at pH 0.5 to 1.
  • a redox flow cell When using a commercially available quinone (eg a monosulfonated p-benzoquinone) with a redox potential of approx. 0 V vs. Ag / AgCl or NADH with a potential of approx. -0.5 vs. Ag / AgCl at pH 1 on the opposite side A redox flow cell would achieve a voltage difference of 0.35 V or 0.8 V in the cell.
  • quinone eg a monosulfonated p-benzoquinone
  • Iron salts such as V 3+ / V 2+ with a redox potential of approx. -480 mV against Ag / AgCl can be used, which would result in a net voltage of approx. 0.8 V.
  • the resulting volumetric energy density also depends on the solubility of the quinones in the medium in question. With a (classic for quinones) solubility of approx. 0.7 mol / 1 in acidic solution, an energy density of approx. 30 Wh / 1 would result.
  • a similar charge / discharge scheme as in the sandwich cell can be observed in glass cells without flow and stirring with (after the first cycles) low losses (see FIG. 4).
  • 10 mg MQ or 10 mg MHQ were dissolved in 3 mL 0.5M H3PO4 each.
  • Two glass tubes (3 mm diameter, 6 cm length) were bent at right angles in the middle and separated by a Nafion 211 membrane. Then the MQ and the MHQ solutions were poured into the respective side.
  • the measurements were carried out in the potentiostatic mode ( ⁇ 0.75 V vs. counter electrode, 1 h / charge / discharge), carbon paper electrodes contacted by steel were used as electrodes.
  • the simulated data were calculated using Winsim2002 software (see Fig. 6B).
  • Example 5 Redox flow battery The RFB experiments were carried out in a LAB-I c ⁇ cell from C-Tech Innovation Ltd. (Chester, UK) (see Figure 7). Carbon flow electrodes 5a and 5b were placed in the reaction cell 4 (AvCarb 200). A Nafion 211 proton exchange membrane was used as membrane 7. For symmetrical experiments, MHQ and MQ in 0.5M H3PO4 were used. Asymmetrical experiments were carried out with MHQ and p-benzoquinone in 0.5 M H3PO4. The solutions were stored in polypropylene tanks 2a and 2b and pumped through the reaction cell 4 by means of pumps 3a and 3b with a flow rate of 140 ml / s.
  • the scan rate was 150, 125, 100, 75, 50 and 25 mV, descending in the direction indicated by the arrow, in a range from -1 to +1 V.
  • the experiments were carried out with the help of an Arbin LBT 50 potentiostat and analyzed with the Arbin Data Watcher software. The addition of conductive salts was completely dispensed with.
  • the redox potential was between 307 and 328 mV (2-methoxyhydroquinone), 50 and 160 mV (p-benzoquinone), 270 and 320 mV (caffeic acid-o- Quinone), 350 and 450 mV (chlorogenic acid-o-quinone) against an Ag / AgCl reference electrode.
  • Example 7 Potentiostatic cycling of a full cell redox flow battery based on caffeic acid and p-hydroquinone

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Abstract

La présente demande de brevet concerne une composition aqueuse comprenant a) au moins un composé de formule générale (I) et au moins un composé de formule générale (II), et/ou au moins un composé de formule générale (III) et au moins un composé de formule générale (IV), formules dans lesquelles R1 et R2 représentent indépendamment l'un de l'autre H ou OR5 et R3 et R4 représentent indépendamment l'un de l'autre H ou OR5, R5 étant un radical alkyle ou un radical allyle, et b) des ions phosphate et/ou des ions phosphate d'hydrogène et/ou leurs condensats.
EP20811363.9A 2019-11-28 2020-11-27 Compositions aqueuses stables comprenant des quinones et leur utilisation dans des batteries à circulation Pending EP4066302A1 (fr)

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EP19212222.4A EP3828975A1 (fr) 2019-11-28 2019-11-28 Compositions aqueuses stables comprenant des quinones et leur utilisation dans des batteries à flux redox
PCT/EP2020/083575 WO2021105322A1 (fr) 2019-11-28 2020-11-27 Compositions aqueuses stables comprenant des quinones et leur utilisation dans des batteries à circulation

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EP20811363.9A Pending EP4066302A1 (fr) 2019-11-28 2020-11-27 Compositions aqueuses stables comprenant des quinones et leur utilisation dans des batteries à circulation

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RO120939B1 (ro) * 1999-05-27 2006-09-29 Savel Matache Pilă electrochimică redox, procedeu de realizare şi procedeu de regenerare a soluţiilor de electrolit
CN102035007A (zh) * 2009-09-25 2011-04-27 中国人民解放军63971部队 一种水溶性有机电对液流电池
JP2016532294A (ja) * 2013-08-15 2016-10-13 ザ リージェンツ オブ ザ ユニバーシティ オブ カリフォルニア ポリマーハイブリッドスーパーキャパシタにおける安定性及びキャパシタンスを高める多成分アプローチ
KR102003299B1 (ko) * 2015-09-25 2019-07-24 주식회사 엘지화학 광재생 전지
CA3088902A1 (fr) * 2018-02-13 2019-08-22 Cmblu Projekt Ag Composes amines derives de lignine et leurs utilisations
CN108593737A (zh) * 2018-05-07 2018-09-28 辽宁科技大学 聚酰亚胺电化学传感原件及其制备方法和传感器

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