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WO2018108895A1 - Procédé de nettoyage conçu pour un électrolyte liquide d'une batterie redox - Google Patents

Procédé de nettoyage conçu pour un électrolyte liquide d'une batterie redox Download PDF

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Publication number
WO2018108895A1
WO2018108895A1 PCT/EP2017/082406 EP2017082406W WO2018108895A1 WO 2018108895 A1 WO2018108895 A1 WO 2018108895A1 EP 2017082406 W EP2017082406 W EP 2017082406W WO 2018108895 A1 WO2018108895 A1 WO 2018108895A1
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WIPO (PCT)
Prior art keywords
electrolyte liquid
cells
negative
electrolyte
tank
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Ceased
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PCT/EP2017/082406
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German (de)
English (en)
Inventor
Adam Harding Whitehead
Martin Harrer
Peter Pokorny
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Gildemeister Energy Storage GmbH
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Gildemeister Energy Storage GmbH
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Publication of WO2018108895A1 publication Critical patent/WO2018108895A1/fr
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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • 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
    • 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
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • 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
    • H01M8/20—Indirect fuel cells, e.g. fuel cells with redox couple being irreversible
    • 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 subject invention describes a method for reducing contaminants of an electrolyte fluid suitable for a redox flow battery.
  • a redox flow battery is an electrochemical-based power generation and storage system typically consisting of tanks for storing positive and negative electrolyte fluids, and pumps and lines for circulating the electrolyte fluids through one or more cell stacks, each of which is comprised of a number of cells ,
  • the cells of the cell stack are each formed by a positive half cell and a negative half cell, wherein the positive and negative half cells of a cell are separated by a semipermeable membrane, typically an ion exchange membrane.
  • the positive half cell contains a frame-mounted positive electrode through which the positive electrolyte liquid flows.
  • the negative half-cell contains a negative electrode in a frame, through which the negative electrolyte liquid flows.
  • the charged positive electrolytic liquid is vanadium having the oxidation number +4 (also referred to as V IV ) and vanadium having the oxidation number +5 (also referred to as V v ).
  • the negative electrolyte liquid consists of vanadium having the oxidation number +2 (also referred to as V ") and vanadium having the oxidation number +3 (also referred to as V 1 ") - whereby the negative electrolyte liquid is "more negative" than the positive electrolyte liquid
  • the average oxidation number of the entire electrolyte liquid (negative and positive total) is +3.5, and both the positive and the negative electrolyte liquid may contain sulfuric acid and other additives, and the positive and negative electrodes are mostly porous Gra
  • bipolar electrode plates are arranged, which are usually made of a composite material of carbon and plastic, located on the axial outer sides of the axially outer cells of the cell stack At
  • the vanadium used in a vanadium electrolytic liquid is found in chemical association with other elements.
  • impurities that improve the performance of the Vanadium redox battery influence be kept as low as possible.
  • impurities due to hydrogen catalysts such as copper (Cu), silver (Ag), gold (Au), arsenic (As), antimony (Sb) and platinum group elements in the electrolyte liquid are to be reduced as much as possible, since excessive hydrogen evolution during loading - Drives can significantly reduce the efficiency of the vanadium redox battery.
  • the starting material for the vanadium electrolyte liquid is usually V v , for example vanadium pentoxide (V 2 0 5 ) or ammonium metavanadate (NH 4 V0 3 ) is used.
  • V v vanadium pentoxide
  • NH 4 V0 3 ammonium metavanadate
  • the starting material is often chemically cleaned in order to achieve a first reduction of the impurities, as disclosed, for example, in EP 0713257 A1. Usually, this cleaning is done by setting various parameters such as pH and temperature. With this method, sulphates, hydroxides or oxides are selectively deposited, whereupon the prepurified starting material is dissolved in sulfuric acid (H 2 S0 4 ).
  • the prepurified electrolyte liquid can be filtered in order to remove particles.
  • EP 2576719 A1 shows a filter series which contains chelate resin.
  • platinum group elements ruthenium Ru, rhodium Rh, palladium Pd, osmium Os, iridium Ir, and platinum Pt
  • platinum group elements ruthenium Ru, rhodium Rh, palladium Pd, osmium Os, iridium Ir, and platinum Pt
  • All of the above methods have in common that with it the critical, usually metallic, impurities of the electrolyte liquid can not be reduced to a concentration of less than 1 ppm by weight.
  • the electrolyte liquid consists of a mixture of negative and positive electrolyte liquid, preferably in the ratio 50:50, and the electrolyte liquid from a first tank by negative half-cells of a Zellstacks a cleaning redox flow battery is circulated, whereby the electrolyte liquid passes through the negative half-cells, wherein a voltage to the cell stack of the cleaning redox flow battery is applied and the electrolyte liquid is reduced electrochemically in the negative half-cells and thereby at least a portion of the contaminants is coated by the electrolyte liquid on negative electrodes of the negative half-cells.
  • This effect is thermodynamically conditioned and usually undesirable in normal operation of a redox flow battery, since the impurities clogged by the deposition of the usually porous negative electrodes pores and serve as hydrogen catalysts. Impurities are substances that are undesirable in the electrolyte fluid and, if appropriate, can also impair the proper operation of a redox flow battery using the contaminated electrolyte fluid. According to the invention, however, this effect is used to clean an electrolyte fluid.
  • negative (and also positive) electrodes various suitable electrochemically sufficiently stable electrically conductive materials can be used - mats made of carbon or graphite fibers are often used.
  • the positive electrodes are used for the oxidation of the electrolyte liquid and should therefore be composed of a material with a slight overpotential, thus a more efficient electrochemical reaction and thus a faster deposition of impurities on the negative electrodes is possible, since the low overpotential higher electrical currents to the Cells of cleaning redox flow battery can be created.
  • the impurities are coated by the electrolyte liquid on the negative electrodes of the negative half cell of the cleaning redox flow battery, which frees the electrolyte fluid from the impurities.
  • the thus purified electrolyte liquid can then be used for the proper operation of a redox flow battery.
  • a conventional redox flow battery can be used as the cleaning redox flow battery.
  • the cleaning redox flow battery can be used as in charging, but no separate negative and positive electrolyte liquids are circulated through the half-cells, but a mixture of negative and positive electrolyte liquid is circulated as the electrolyte liquid to be cleaned by the negative half-cells.
  • the negative and positive electrolytic fluids (usually present before mixing) should of course be largely uncharged, since otherwise no charging process can be efficiently "simulated” during the cleaning process and also during the mixing of charged negative and positive electrolyte fluids to the purifying electrolyte liquid an undesirable thermal reaction occurs per se.
  • known methods such as inductively coupled plasma periodic mass spectrometry (ICPMS), can be used, wherein the proportion of impurities in the electrolyte liquid in the tanks or at other arbitrary point of the cycle of the cleaning redox flow battery can be measured.
  • a second in a second tank consisting of a mixture of negative and positive electrolyte liquid, preferably in the ratio 50:50 existing second electrolyte liquid is circulated by positive half-cells of the cleaning redox flow battery, whereby the second electrolyte liquid passes through the positive half-cells.
  • the impurities present can pass through the ion exchange membrane, with which impurities can pass from the second electrolyte liquid into the (first) electrolyte liquid (and vice versa). This allows impurities originally in the second electrolyte liquid to be deposited on the electrodes of the negative half cell.
  • the (first) electrolyte liquid and the second electrolyte liquid may also be continuously or batch-mixed during the cleaning process. This speeds up the process of cleaning the entire electrolyte fluid.
  • This mixing during the cleaning process can be carried out by recycling (continuously or batchwise) a portion, preferably 10%, of the (first) electrolyte liquid after passing through the negative half-cells into the second tank and a portion, preferably 10% of the second electrolyte liquid after Passing through the positive half-cells is returned to the first tank.
  • This method is easy to implement, so the reduction of contamination is continuous and can take some time and many changes.
  • the first electrolytic liquid and the second electrolytic liquid can be mixed together.
  • a heat exchanger which serves the dissipation of thermal energy, which arises during the cleaning process.
  • the electrolyte liquid can be circulated from a first tank through the negative half-cells, sulfuric acid being separated from a first tank.
  • a second tank is circulated through the positive half cells and an increased voltage, which is greater than the usual voltage, preferably 2.5 V per cell, is applied to the positive half cells and the negative half cells.
  • a catalyst for reducing an existing overpotential may be provided in the context of an oxygen evolution. This accelerates the oxidation, which allows a faster reaction rate and thus cleaning rate.
  • a lower voltage can be applied to the cell stack, thus reducing the possibility of overloading components of the cell stack.
  • This catalyst may, for example, consist of platinum Pt, iridium (IV) oxide Ir0 2 , lead (IV) oxide Pb02, etc. So it is the entire electrolyte liquid pumped from a tank through the negative half-cells and reduced. The applied voltage oxidizes the sulfuric acid in the positive half-cells. This increases the efficiency of the process and requires fewer recirculations than when the electrolyte liquid is pumped through the negative half cells and the second electrolyte liquid through the positive half cells. Thus, the total duration of the cleaning process can be reduced by about a factor of 10.
  • the electrolyte liquid may be circulated from a first tank through the negative half cells, with pure electrolyte liquid consisting of a mixture of negative and positive electrolyte liquid, preferably in the ratio 50:50, circulated by a second tank through the positive half cells.
  • pure electrolyte liquid instead of the sulfuric acid, it is not necessary to apply an increased voltage to the cell stacks.
  • a commonly used voltage that can otherwise be used to charge the redox flow battery typically 1, 0-1, 6V per cell in each cell stack, is sufficient.
  • the electrolyte liquid can also be pumped from a first tank through the negative half cells of the cell stack, pumped from the negative half cells into a second tank and pumped further and from the second tank through the positive half cells of the cell stack.
  • the (to be cleaned) electrolyte liquid is circulated alternately through the negative half-cells and through the positive half-cells.
  • a single recirculation may be sufficient to reduce the electrolyte fluid contaminants to the desired level.
  • the electrolyte liquid can be oxidized and thus raised to the desired redox potential to produce a positive electrolyte liquid. This can be done for example by dilution with water or sulfuric acid.
  • the cleaned electrode can rolyttellkeit be reduced chemically or electrochemically. Methods for oxidizing and reducing electrolyte liquids are well known and will therefore not be described further here.
  • the negative electrodes of the negative half cells of the cleaning -Redox flow-through battery to be cleaned to remove the coated impurities. This can therefore be carried out after the execution of the cleaning process of the electrolyte liquid or during an interruption of the cleaning process.
  • This cleaning of the negative electrodes can be carried out chemically, for example using an oxidizing agent such as, for example, a positively charged electrolyte liquid, hydrogen peroxide H 2 O 2 , or electrochemically.
  • the purge redox flow battery must be idle.
  • the, preferably pure, positive electrolyte liquid naturally picks up the impurities. Of course, this can only take place until the positive electrolyte liquid has a certain degree of impurities, whereupon the positive electrolyte liquid can be subjected to purification, or even disposed of.
  • the cleaning method described above primarily removes metallic contaminants by coating them on the negative electrodes.
  • the cleaning process can be carried out until the proportion of the impurities in the electrolyte liquid reaches or falls below one or more of the following limits: 0.5 mass ppm Cu; 1 mass ppm As, Pb, Sb; 0.1 mass ppm Rh, Ru, Au, Ag and other elements of the Pt group.
  • sulfur dioxide S0 2 of the electrolyte liquid is reduced, but not by deposition on the negative electrodes, but by oxidation, or reduction.
  • Sulfur dioxide S0 2 leads in a vanadium electrolyte liquid during operation also to increased hydrogen formation, which is why the reduction of sulfur dioxide S0 2 represents an advantageous effect.
  • the cleaning method can be applied in particular to a vanadium electrolyte liquid.
  • the vanadium electrolyte liquid is thus by the electrochemical
  • electrolyte fluids such as iron-chromium electrolyte fluids (thus suitable for an iron-chromium redox flow-through battery) may also be cleaned in the manner described. It is important that the positive and negative electrolyte liquid are miscible, ie are chemically substantially similar or have only a different oxidation state (such as V 2+ and V 3+ , V0 2+ and V0 2 + in the case of the vanadium redox flow battery ).
  • a cell stack 2 of a redox flow battery 1 comprises a plurality of cells 4. Each cell is formed from a positive half-cell 42 and a negative half-cell 41, so there are 2 positive half-cells 42 and negative half-cells 41 arranged alternately in the cell stack. Between the positive half cell 42 and the negative half cell 41 of a cell 4, a semipermeable membrane 6, typically an ion exchange membrane (cation and / or anion exchange membrane, eg Nafion®), is arranged in each case. Between two adjacent cells 4, an electrode plate 7, for example a bipolar plate, is arranged.
  • a positive electrode 422 are respectively arranged, in the frame 401 of the negative half-cells 41 each negative electrodes 412 are arranged.
  • the positive electrodes 422 and negative electrodes 412 are usually designed as mats of carbon or graphite fibers.
  • About recesses 80 in the frame 401 of the half-cells 40, or cells 4 are pumped in normal operation by means of the pumps 71, 72 electrically differently charged electrolyte liquids through the cells 4, wherein in a cell 4, or the respective positive half-cell 42 respectively the positive Electrode 422 is flowed through by the positive electrolyte liquid and the negative electrode 412 of the negative half cell 41 by the negative electrolyte liquid.
  • redox Flow batteries 1 such as a vanadium redox flow battery or a vanadium polyhalite battery
  • the two electrolyte liquids are chemically similar or have only a different oxidation state (eg V 2+ and V 3+ , V0 2+ and V0 2 + ).
  • FIG. 1 also shows the tanks 91, 92 of a redox flow battery 1, in which usually the electrolyte liquids are stored for operation.
  • the electrolyte liquids are circulated using the pumps 71, 72 between the negative half-cells 41 and positive half-cells 42 and the negative and positive tanks 91, 92, respectively.
  • the negative or positive tanks 91, 92 may be spatially separate containers, but may also be formed, for example as two compartments divided by a dividing wall, in a common container.
  • the cell stack 2 is completed at the two axial ends by an end plate 60, for example made of plastic.
  • the end plates 60 are driven by tensioning means 4, e.g.
  • an electrical connection 19 can be provided on the end plates 60, via which the current collectors 3 in the interior of the redox flow battery 1 can be connected to an external circuit on both sides of the redox flow battery 1.
  • the electrical connection 19 is shown only in FIG. 1, and the connection between the current collector 3 and the electrical connection 19 can not be seen in the figures.
  • the electrolyte liquid connections for the supply and removal of the electrolyte liquids are provided on the end plates 60.
  • a positive inflow 921 is used to supply the positive half-cells with electrolyte liquid (in normal operation, ie positive electrolyte liquid) and a positive outflow 922 to return the electrolyte liquid after flowing through the positive half-cells 42 into the respective negative or positive tank 91, 92.
  • Analog serves a negative inflow 91 1 to the negative half-cells 41 with electrolyte liquid (in normal operation so negative electrolyte liquid) to supply and a negative outflow 912 to return the electrolyte liquid after flowing through the negative half-cells 41 in the respective negative or positive tank 91, 92.
  • spacers 8 may be provided between the end plates 60 in order to ensure a constant distance 8 'between the end plates 60.
  • Impurities can be As, Pb, Sb, Rh, Ru, Au, Ag, etc.
  • the cleaning method according to the invention can be carried out until the electrolyte liquid 101 as impurity 1 1 less than 0.5 mass ppm Cu and / or below 1 ppm by mass As, Pb, Sb, and / or less than 0.1 ppm by mass each of Rh, Ru, Au, Ag, and / or other platinum group elements.
  • the procedure is as follows.
  • a vanadium electrolyte liquid is used as the electrolyte liquid 101 to be cleaned.
  • the electrolyte liquid 101 consists of a ratio of V '": V IV of about 50:50, as for example, by mixing positive and negative electrolyte liquid of a vanadium redox flow battery as shown in Figure 1 arises or by the in the state of Thus, a certain degree of impurities 11 is present in the electrolyte liquid 101, which is to be lessened to a certain extent.
  • a redox flow battery 1 can be used , as described in Fig.1 and Fig.2, can be applied, whereby an otherwise commonly used for charging voltage V in the amount of, for example, 1, 6V per cell can be applied.
  • the electrolyte liquid 101 to be purified is stored in a first tank 91 'and a second electrolyte liquid 102 is stored in a second tank 92'.
  • the first tank 91 'and the second tank 92' may be the tanks of a purge redox flow battery 1 ', i. a commercial redox flow battery 1, as shown in Fig.1.
  • the electrolyte liquids stored therein can be circulated via the cleaning redox flow battery V as described below.
  • the electrolyte liquid 101 is circulated through the negative half-cells 41 of the purifying redox flow battery V via the negative inflow 91 1 and the negative flow 912, and the second electrolyte liquid 102 is circulated through the positive inflow 921 and the positive outflow 922 through the positive half-cells 42 of the cleaning redox flow battery 1 'circulated.
  • V IV is reduced electrochemically to V 1 "in the electrolyte liquid, with a subsequent reduction of a part of the V 1 " to V "by electrochemical means 0.001 M at V ", which is an indicator of the atmosphere required for cleaning.
  • the impurities 1, typically metallic are electrochemically or chemically coated on the negative electrodes 412 of the negative half-cells 41 of the cleaning redox flow battery 1 ', eg in the reaction 2V 2+ + Cu 2+ ⁇ -> 2V 3+ + Cu.
  • the reaction 2V 2+ + Cu 2+ ⁇ -> 2V 3+ + Cu As a purely electrochemical reaction, for example, Cu 2+ + 2e " -> Cu, whereby this electrochemical reaction proceeds parallel to the usual redox reaction reaction V 3+ + e " - »V 2+ .
  • the electrolyte liquid Preferably, to accelerate the cleaning process, the electrolyte liquid
  • This mixing can in principle be continuous or batchwise, whereby the rate of mixing can be regulated by a valve (not shown).
  • thermal problems may occur because the electrolytic liquid is heated by the mixing process because the electrolytic liquid 101 and the second electrolytic liquid 102 reach different redox potentials by the cleaning process.
  • a temperature of the electrolyte fluid should not exceed 40 ° C. Therefore, in the first tank 91 'and in the second tank 92', a heat exchanger 93 for discharging thermal energy may be provided as shown in the embodiment of FIG. If the negative and positive electrolytic liquid were not mixed continuously or in batches after passing through the respective half-cells, but were completely mixed with one another, a temperature rise of about 26 ° C. would be expected without the use of a heat exchanger 93.
  • the electrolyte liquid would reach a temperature of 56 ° C and thus exceed the target maximum temperature of 40 ° C.
  • preferably about 10% of the electrolyte liquid is mixed after each pass through the respective half-cells, whereby the temperature increase can be limited to about 3 ° C.
  • the target maximum temperature of 40 ° C is not reached.
  • the rate of mixing and the performance of the heat exchanger must be coordinated so as not to reach the target maximum temperature.
  • a chemical reduction may be provided, wherein, for example, oxalic acid may be added to the second electrolyte liquid 102.
  • the second electrolyte liquid 102 which is circulated through the positive half cells 42, may be replaced by "fresh" electrolyte liquid.
  • the production of hydrogen depends primarily on how long the negative electrode 412 coated with the contaminants 11 is in contact with the Electrolyte liquid 101. Therefore, in principle a still rapid reduction of the impurities 1 1 is desirable because the process just described takes a few weeks, depending on the electrolyte liquid 101 to be cleaned.
  • FIGS. 4a and 4b A further embodiment of the cleaning method according to the invention is therefore outlined in FIGS. 4a and 4b.
  • the electrolyte liquid 101 is circulated via the negative inflow 91 1 and the negative outflow 912 from a first tank 91 'through the negative half cells 41 of the purifying redox flow battery V.
  • sulfuric acid S stored in a second tank 92 is circulated via the positive inflow 921 and the positive outflow 922.
  • an increased voltage V1 which is greater than the voltage V, is applied to the cleaning redox flow battery 1 ', ie to the positive half cells 41 and the negative half cells 42.
  • the boosted voltage V1 is about 2.5V per cell.
  • the impurities 11 are also coated on the negative electrode 412, ie, for example, the chemical reaction Cu 2 + + 2e " -> Cu occurs again Reducing one
  • pure electrolyte liquid R consisting of a mixture of negative and positive electrolyte liquid, preferably in the ratio 50:50, can be used in the cleaning process according to FIG. 4 and thus circulated by the second tank 92 through the positive half cells 42.
  • pure the same limit values of impurities as are to be achieved for the electrolyte liquid 101 can be considered here, ie 0.5 mass ppm Cu, 1 mass ppm As, Pb, Sb, 0.1 mass ppm. ppm Rh, Ru, Au, Ag and elements of the Pt group.
  • FIGS. 5a and 5b show a third embodiment of the cleaning method according to the invention.
  • the electrolyte liquid 101 is pumped from a first tank 91 'via the negative inflow 91 1 through the negative half cells 41 of the cell stack 2 of the cleaning redox flow battery V. Further, the electrolyte liquid 101 is pumped from the negative half-cells 41 via the negative drain 912 in the second tank 92 and further pumped from the second tank 92 through the positive inflow 921 in the positive half-cells 42 of the cell stack 2 of the cleaning redox flow battery V. From the positive drain 922, the electrolyte liquid 101 flows back into the first tank 91 '.
  • the pros The cleaning process corresponds to the procedure described with reference to FIG.
  • the negative electrodes 412 of the negative half cells 41 of the cleaning redox flow battery V may be subjected to cleaning to remove the impurities 1 1 coated on the negative electrodes 412.
  • the second electrolyte liquid 102 in the positive half cells 42 can be oxidized to a mixture of V IV and V v .

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Abstract

L'objectif de cette invention est de réduire la concentration d'un électrolyte liquide en impuretés de manière appropriée pour une batterie redox. A cet effet, un procédé consiste à faire circuler l'électrolyte liquide, qui est constitué d'un mélange d'un électrolyte liquide négatif et d'un électrolyte liquide positif, de préférence dans une proportion 50:50, d'un premier réservoir, à travers des demi-cellules négatives d'un empilement de cellules d'une batterie redox de nettoyage, l'électrolyte liquide parcourant ces demi-cellules négatives, une tension étant appliquée à l'empilement de cellules de la batterie redox de nettoyage, et l'électrolyte liquide étant réduit de manière électrochimique dans les demi-cellules négatives, et au moins une partie des impuretés de l'électrolyte liquide étant ainsi déposée sur des électrodes négatives des demi-cellules négatives.
PCT/EP2017/082406 2016-12-13 2017-12-12 Procédé de nettoyage conçu pour un électrolyte liquide d'une batterie redox Ceased WO2018108895A1 (fr)

Applications Claiming Priority (2)

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ATA51131/2016 2016-12-13
ATA51131/2016A AT519236B1 (de) 2016-12-13 2016-12-13 Reinigungsverfahren für eine Elektrolytflüssigkeit einer Redox-Durchflussbatterie

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WO2020086645A1 (fr) 2018-10-23 2020-04-30 Lockheed Martin Energy, Llc Procédés et dispositifs pour éliminer des impuretés d'électrolytes
CN114276871A (zh) * 2021-12-24 2022-04-05 雅安市中甫新能源开发有限公司 一种钒电池电堆清洗剂及其制备方法与电堆清洗方法
WO2023110799A1 (fr) * 2021-12-15 2023-06-22 Enerox Gmbh Procédé de nettoyage pour un liquide électrolytique d'une batterie à flux redox
CN117080491A (zh) * 2023-10-18 2023-11-17 液流储能科技有限公司 液流电池电解液的纯化方法
AT527309A4 (de) * 2023-11-03 2025-01-15 Enerox Gmbh Endplatte für einen Zellstack einer Redox-Durchflussbatterie

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JPH03192662A (ja) * 1989-12-21 1991-08-22 Chiyoda Corp レドックスフロー電池の電池容量回復方法
WO2004082056A1 (fr) * 2003-03-14 2004-09-23 Unisearch Limited Nouvelle batterie a flux redox d'halogenure de vanadium
WO2015126131A1 (fr) * 2014-02-20 2015-08-27 오씨아이 주식회사 Batterie à flux redox

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2019365849B2 (en) * 2018-10-23 2025-01-16 Lockheed Martin Energy, Llc Methods and devices for removing impurities from electrolytes
EP3870540A4 (fr) * 2018-10-23 2022-08-17 Lockheed Martin Energy, LLC Procédés et dispositifs pour éliminer des impuretés d'électrolytes
WO2020086645A1 (fr) 2018-10-23 2020-04-30 Lockheed Martin Energy, Llc Procédés et dispositifs pour éliminer des impuretés d'électrolytes
AU2019365849C1 (en) * 2018-10-23 2025-05-15 Lockheed Martin Energy, Llc Methods and devices for removing impurities from electrolytes
US12074353B2 (en) 2018-10-23 2024-08-27 Lockheed Martin Energy, Llc Methods and devices for removing impurities from electrolytes
WO2023110799A1 (fr) * 2021-12-15 2023-06-22 Enerox Gmbh Procédé de nettoyage pour un liquide électrolytique d'une batterie à flux redox
AT525774A1 (de) * 2021-12-15 2023-07-15 Enerox Gmbh Reinigungsverfahren für eine Elektrolytflüssigkeit einer Redox-Durchflussbatterie
AT525774B1 (de) * 2021-12-15 2023-09-15 Enerox Gmbh Reinigungsverfahren für eine Elektrolytflüssigkeit einer Redox-Durchflussbatterie
CN114276871A (zh) * 2021-12-24 2022-04-05 雅安市中甫新能源开发有限公司 一种钒电池电堆清洗剂及其制备方法与电堆清洗方法
CN117080491A (zh) * 2023-10-18 2023-11-17 液流储能科技有限公司 液流电池电解液的纯化方法
CN117080491B (zh) * 2023-10-18 2024-02-09 液流储能科技有限公司 液流电池电解液的纯化方法
AT527309B1 (de) * 2023-11-03 2025-01-15 Enerox Gmbh Endplatte für einen Zellstack einer Redox-Durchflussbatterie
AT527309A4 (de) * 2023-11-03 2025-01-15 Enerox Gmbh Endplatte für einen Zellstack einer Redox-Durchflussbatterie

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