• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    To reactivate a redox flow battery, at least parts of the flow paths of the electrolyte of one of the half cells of the flow battery are temporarily purged with the electrolyte of the respective other half cell.
    公开号:AT514391A1
    申请号:T50387/2013
    申请日:2013-06-13
    公开日:2014-12-15
    发明作者:Martin Dipl Ing Fh Harrer；Whitehead Adam Dr Harding
    申请人:Cellstrom Gmbh；
    IPC主号:
    专利说明:

    1
    FW-3 540 AT
    Redox flow battery and method of reactivation
    The invention relates to a method for reactivating a redox flow battery, wherein at least parts of the flow paths of the electrolyte of one of the half cells of the flow battery are temporarily purged with a reactivation liquid. Furthermore, the invention also relates to a redox flow battery for carrying out such a method, with at least one consisting of two, separated by an ion-selective membrane half-cell flow cell, and with one electrolyte circuit per half-cell, in which via switching elements, if necessary, lockable lines an electrolyte tank via a pump connect to the half cell.
    The cell or stack resistance of a redox flow battery (for example, a Va-nadium redox flow battery) may be known to increase over time, for example as a result of accumulation of organic deposits on the electrodes or deactivation of these electrodes, resulting in an increase hydro-phobicity and gas retention. It is therefore necessary to occasionally clean or reactivate the flow battery, for which various methods are known. In US Pat. No. 3,540,934 it is suggested that the flow cells be briefly electrically overloaded, which leads to their cleaning but does not benefit the stability of the bipolar plates. From WO 12160406 A1 a reverse polarization of the electrical connections of the cells is known, but this poses difficulties with the regulation of the state of charge in the cells (which are not flushed during this process), which leads to overloading by overcharging and destroying the bipolar plates can. It also requires additional high-current electrical circuits and controls.
    It is also known from JP 3425060 B2, JP 2000200615 A2 or WO 12167542 A1 to treat the flow cells with different rinsing solutions as cleaning and reactivating liquid (for example 3M and 6M H2S04 or distilled water), but in all these known cases the reactivating liquids be kept ready in separate rinse tanks, which requires additional effort and thus additional costs and an increase in the total battery. From the JP 2004079229 A2, organic rinsing or cleaning solutions have become known in the last-mentioned context, which, however, also increases the complexity of the overall system and additionally brings safety risks, since most of these organic solutions are combustible. 2/11 2
    FW-3 540 AT
    The object of the present invention is to improve a redox flow battery and a method for reactivating it so that, with simple means and without appreciably increasing the complexity of the system, occasionally necessary cleaning and reactivation can be carried out.
    This object is achieved in a method according to the present invention in that for the reactivation of one of the half-cells as the reactivation liquid, the electrolyte of the respective other half-cell is used and passed in parallel through both half-cells.
    The redox flow battery according to the invention has for this purpose in at least one of the electrolyte circuits via switching elements, if necessary, openable connection lines to at least a portion of the flow paths in the other electrolyte circuit. The possible cleaning and reactivation is very simple and requires very little additional equipment expense compared to the above-mentioned prior art. In principle, both the use of the positive electrolyte for purifying and reactivating the negative half cell, and the use of the negative electrolyte for purifying and reactivating the positive half cell are possible - both electrolytes can dissolve solid deposits from the electrodes - V205 dissolves, for example, in the negative but not in the positive electrolyte whereas organic or metallic deposits tend to be better dissolved in the positive electrolyte. However, it is preferred that the positive electrolyte is flushed through at least parts of the flow paths of the negative half-cell, as this has proven to be more effective.
    In a preferred, further embodiment of the invention, it is provided that the temporary flushing for reactivation via a switching of the flow paths of the electrolyte used in each case takes place to the other half-cell, wherein the electrical connections of the half-cells remain unchanged. After the same electrolyte is present in both half cells of the flow cell during the reactivation phase, the cell voltage drops to about 0 volts, whereby no power can be taken from the respective flow cell. The reactivation can therefore only be carried out if power is available from another source (for example for driving the pumps). However, other power sources may also be formed by other flow cells with independent electrolyte circuits or by an external power supply.
    In the case of a battery comprising a plurality of flow cells, only a portion of the flow cells is preferably reactivated at the same time, while the other flow cells remain in normal operation. In this way, electrical power can continue to be drawn from the overall system, albeit at a level reduced by the respectively reactivated flow cells. Also, the currently remaining in normal operation through 3/11 3
    FW-3 540 AT flow cells provide the necessary power for reactivation regardless of external connections.
    The reactivation can either be initiated manually by appropriate operators or, depending on certain monitored cell parameters, automatically executed. In the case of automatic execution preferably automatically controlled valves can be used with appropriate actuators, which start and duration of cleaning or reactivation can proceed according to predetermined criteria. For example, a fixed period of time since the last reactivation may serve to trigger a renewed reactivation. Also, a change in the cell resistance after exceeding a certain value can trigger a reactivation. Monitored can also be the evolution of hydrogen, which after a certain increase, a reactivation can be initiated. It would also be possible to monitor the state of charge and, depending thereon, to initiate or carry out a reactivation.
    The switching elements may be formed in a preferred embodiment of the invention of 3-way valves, which are switchable for temporary flushing of the respective half-cells, which further simplifies the arrangement in a flow battery according to the invention.
    The invention will be explained in more detail below with reference to the schematic drawings. Fig. 1 shows an arrangement according to the prior art known, and Fig. 2 and 3 show embodiments of redox flow batteries according to the present invention.
    According to FIG. 1, a stack 1 of a known redox flow battery consisting of a plurality of flow cells, not shown in detail, is connected to an electrolyte tank 4, 5 via an electrolyte circuit 2, 3 for the two half cells of each flow cell separated by an ion-selective membrane. In each case an electrolyte pump 6, 7 and optionally further, not shown additional switching elements is circulated in operation of the flow battery positive electrolyte in one and negative electrolyte in the other of the electrolyte circuits 2, 3. As a result of the ion selectivity of the membrane separating the two half cells of each flow cell, a directed charge exchange between the half cells can take place, whereby electrical power can be taken from the electrodes and electrical connections of the flow cells or the stack 1, not shown here, or supplied to the battery for recharging.
    Within the stack 1, the two electrolytes can not freely mix but are separated by means of ion-selective exchange membranes on one side of the porous, usually felt-like electrodes and bipolar plates on the other side of the electrodes. At 4/11 4
    FW-3540 AT now to occasionally required cleaning and reactivation of the flow battery to be able to temporarily flush at least parts of the flow paths in the electrolyte circuits 2, 3 of one of the half-cells with reactivation, are in the inventive arrangement of Figure 2 via switching elements 8, 9,10, 11 as required openable connecting lines 12, 13 provided to at least a portion of the flow paths in the other electrolyte circuit. Assuming that 2 is the positive electrolyte circuit and 4 is the positive electrolyte tank (corresponding to 3 the negative electrolyte circuit and 5 the negative electrolyte tank) there are thus the following operating modes for the arrangement according to FIG.
    With open switching elements 8 and 11 and closed switching elements 10 and 13, the standard operation takes place - positive electrolyte circulates in the electrolyte circuit 2 and negative electrolyte circulates in the electrolyte circuit 3rd
    With closed switching elements 8 and 11 and opened switching elements 9 and 10 positive electrolyte from the electrolyte tank 4 is pumped not only by the positive electrolyte circuit 2 but also in parallel through the electrolyte circuit 3, whereby the reactivation of the flow battery according to the invention using the positive electrolyte for both half-cells each Flow cell takes place.
    With open switching elements 9 and 11 and closed switching elements 8 and 10, the liquid level in the two electrolyte tanks 4 and 5, if necessary, be compensated again.
    It is clear that other combinations of switching elements could be used in the invention - for example, the switching elements 8 and 9 could be replaced by a single 3-way valve. The above-mentioned liquid compensation (with pump delivery from the positive electrolyte tank 4 to the negative electrolyte tank 5) is suitable for stacks with cation exchange membranes. In order to be able to pump from the negative electrolyte tank 5 into the positive electrolyte tank, if necessary, additional switching elements and / or connecting lines would have to be provided.
    In the embodiment according to the invention according to FIG. 3, negative electrolyte can be pumped out of the tank 5 through the positive electrolyte pump 6, which has the advantage of dissolving V205 deposits in the positive electrolyte pump 6 in a Vana-dium redox flow battery. The various operations of the arrangement of Fig. 3 are as follows:
    With open switching elements 15 and 17 and closed switching element 16 in the connecting line 14, the standard operation is carried out with completely separate electrolyte circuits.
    With open switching elements 16 and 17 and closed switching element 15, a reactivation or cleaning of the negative side takes place. 5/11 5
    FW-3 540 AT
    When switching element 17 is closed and switching elements 15 and 16 open, cleaning or reactivation of the positive side takes place.
    When the switching elements 15, 16 and 17 are opened, a compensation of the liquid levels in the electrolyte tanks 4 and 5 takes place again as required.
    Not shown in the drawings are the various monitoring and control units with which, if necessary, an automatic cleaning and reactivation can take place. In all cases, it is provided that the cleaning and reactivation takes place solely by various possible switching and diversion of the existing electrolyte te or electrolyte circuits and thus without consuming separate supply of reactivation and no costly electrical switching at the terminals of the flow battery. 6/11
    权利要求:
    Claims (7)
    [1]
    1. A method for reactivating a redox flow battery, wherein at least parts of the flow paths of the electrolyte of one of the half cells of the flow battery are temporarily rinsed with a reactivation liquid, characterized in that used as reactivation liquid, the electrolyte of the other half cell and is passed in parallel through both half-cells.
    [2]
    2. The method according to claim 1, characterized in that the positive Eltektrolyt is flushed through at least parts of the flow paths of the negative half-cell.
    [3]
    3. The method according to claim 1 or 2, characterized in that the temporary flushing takes place via a switching of the flow paths of the electrolyte used in each case to the other half-cell, wherein the electrical connections of the half-cells remain unchanged.
    [4]
    4. The method according to one or more of claims 1 to 3, characterized in that in a flow cell consisting of a plurality of flow cells each only a portion of the flow cells is reactivated simultaneously, while the other flow cells remain in normal operation.
    [5]
    5. Redox flow battery for performing the method according to one or more of claims 1 to 4, comprising at least one of two, separated by an ion-selective membrane half-cells flow cell, and each with an electrolyte circuit (2,3) per half-cell, in the above Switching elements (8-11, 15-17), if necessary lockable lines (12-14) connect an electrolyte tank (4, 5) via a pump (6.7) to the half cell, characterized in that one of the electrolyte circuits (2, 3) Having switching elements (8-11, 15-17), if necessary, openable connecting lines (12-14) to at least a part of the flow paths in the other electrolyte circuit (2,3).
    [6]
    6. flow battery according to claim 5, characterized in that the switching elements of 3-way valves are formed, which are switchable for the temporary flushing of the respective half-cell (s).
    [7]
    7/11
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    同族专利:
    公开号 | 公开日
    AT514391B1|2015-10-15|
    US20160111744A1|2016-04-21|
    WO2014198546A1|2014-12-18|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    GB1587748A|1977-11-28|1981-04-08|Gel Inc|Energy conversion apparatus|
    US6475661B1|1998-01-28|2002-11-05|Squirrel Holdings Ltd|Redox flow battery system and cell stack|
    US20060251957A1|2005-01-28|2006-11-09|Dennis Darcy|Flowing electrolyte battery with electric potential neutralization|DE102019106588A1|2018-11-16|2020-05-20|H2, Inc.|METHOD FOR REMOVING A PRECIPITITY OF A REDOX FLOW BATTERY AND THIS COMPREHENSIVE REDOX FLOW BATTERY|CH393361A|1960-03-29|1965-06-15|Ciba Geigy|Process for the production of epoxy compounds|
    US3540934A|1967-07-11|1970-11-17|Jan Boeke|Multiple cell redox battery|
    JPH02109275A|1988-10-18|1990-04-20|Toyota Motor Corp|Metal-bromine battery|
    JPH03147278A|1989-11-01|1991-06-24|Toyota Motor Corp|Zinc-bromine battery|
    JP3425060B2|1997-05-09|2003-07-07|住友電気工業株式会社|Electrolyte flow battery with internal resistance recovery mechanism|
    JP2000200615A|1999-01-07|2000-07-18|Sumitomo Electric Ind Ltd|Reactivating method of electrode and redox-flow secondary battery|
    JP2004079229A|2002-08-12|2004-03-11|Sumitomo Electric Ind Ltd|Method of reactivating redox flow battery electrode|
    US7517608B2|2007-03-09|2009-04-14|Vrb Power Systems Inc.|Inherently safe redox flow battery storage system|
    US8785023B2|2008-07-07|2014-07-22|Enervault Corparation|Cascade redox flow battery systems|
    WO2012160406A1|2011-05-26|2012-11-29|Krisada Kampanatsanyakorn|Method of conducting an all vanadium redox flow battery and implementing system|
    CN102244286B|2011-06-07|2014-10-15|中国东方电气集团有限公司|Flow battery system and repair device thereof|EP3523851A4|2016-10-07|2020-07-15|VionX Energy Corporation|Electrochemical-based purification of electrolyte solutions, and related systems and methods|
    US11251452B2|2020-01-08|2022-02-15|Institute of Nuclear Energy Research, Atomic Energy Council, Executive Yuan, R.O.C.|Method of restoring electrolyte of vanadium redox flow battery through electrolysis|
    法律状态:
    2016-11-15| PC| Change of the owner|Owner name: GILDEMEISTER ENERGY STORAGE GMBH, AT Effective date: 20161005 |
    2018-12-15| PC| Change of the owner|Owner name: ENEROX GMBH, AT Effective date: 20181018 |
    优先权:
    申请号 | 申请日 | 专利标题
    ATA50387/2013A|AT514391B1|2013-06-13|2013-06-13|Redox flow battery and method of reactivation|ATA50387/2013A| AT514391B1|2013-06-13|2013-06-13|Redox flow battery and method of reactivation|
    US14/897,454| US20160111744A1|2013-06-13|2014-05-28|Redox flow battery and method for reactivation thereof|
    PCT/EP2014/061104| WO2014198546A1|2013-06-13|2014-05-28|Redox flow battery and method for the reactivation thereof|
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