WO2012160406A1 - Procédé de réalisation d'une batterie à flux d'oxydoréduction tout vanadium et système de mise en œuvre - Google Patents

Procédé de réalisation d'une batterie à flux d'oxydoréduction tout vanadium et système de mise en œuvre Download PDF

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Publication number
WO2012160406A1
WO2012160406A1 PCT/IB2011/001141 IB2011001141W WO2012160406A1 WO 2012160406 A1 WO2012160406 A1 WO 2012160406A1 IB 2011001141 W IB2011001141 W IB 2011001141W WO 2012160406 A1 WO2012160406 A1 WO 2012160406A1
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Prior art keywords
battery
electrical
electrolyte
cell
positive
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PCT/IB2011/001141
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English (en)
Inventor
Krisada Kampanatsanyakorn
Piriyathep KACHANADUL
Suradit Holasut
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Ceased legal-status Critical Current

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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
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04186—Arrangements for control of reactant parameters, e.g. pressure or concentration of liquid-charged or electrolyte-charged reactants
    • 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
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • 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 disclosure relates to an all-vanadium redox flow battery system and in particular to a method of conducting the system over prolonged periods of time countering a number of progressive alterations and unbalances in the electrolyte solutions.
  • Redox flow battery systems or briefly redox batteries store energy in acid electrolyte solutions, namely a positive and a negative solution, that are flown through respective electrode compartments of the cells of a multi-cell electrochemical reactor during charge and discharge phases.
  • Energy storage capacity is strictly tied to storage volumes of the two distinct positive and negative electrolyte solutions.
  • the redox couples used in a flow redox battery system are typically of multivalent metals dissolved in the two respective positive and negative electrolyte solutions, typically an acid electrolyte capable of dissolving the multivalent metal or metals in all states of oxidation.
  • the above considerations are generally applicable to any multivalent metal providing a viable redox couple dissolved in an aqueous acid solution, wherein the redox couple metal ions sustain the anodic oxidation reaction and the cathodic reduction reaction, the product of which remains dissolved in the acid electrolyte solution without undergoing any phase change, both during a charging phase as well as during a electrochemical discharge phase.
  • Carbon electrodes are often used in redox flow cells because of the relative high hydrogen discharge over-voltage of carbon-base materials that helps preventing parasitic water electrolysis.
  • the electrodes or more particularly the active electrode surface thereof is generally in form of a porous felt of carbon fibers readily permeated by the flowing electrolyte solution and back-contacted by the generally planar surface of a carbon-base bipolar electrical interconnecting septum (briefly "interconnect”) defining the respective flow compartment in cooperation with the opposing permionic membrane cell separator.
  • the positive electrode of the battery behaves as anode extracting electrons from V[IV] in oxidizing vanadium to V[V] according to the reaction:
  • the negative electrode of the battery behaves as cathode giving out electrons to V[III] in reducing it to V[II] according to the reaction:
  • VCT + e V -2+
  • the negative electrolyte solution will contain only divalent vanadium while the positive electrolyte solution will contains only pentavalent vanadium.
  • the permionic membrane cell separator may be either an anionic membrane or a cationic membrane.
  • V0 2 + / VO +2 in the positive are stable and not chemically reduced or oxidized by external elements
  • V+3/V+2 in the negative electrolyte storage tank are both readily oxidized by exposure to ambient air.
  • air is allowed in the tank, a relatively fast oxidation of V+2 to V+3 and a slow oxidation of V+3 to VO+2 are experienced. Therefore, it is necessary to "blanket" the liquid content in the negative electrolyte tank with nitrogen or float wax or oil on the surface of the liquid. This is bothersome. Transfer of electrolyte through the permionic membrane
  • the H + ions migrate in the opposite direction: from the positive to the negative compartment.
  • the other positive ions in the positive electrolyte solution are V0 2 + ions and VO +2 both relatively large solvated ions that substantially do not pass through the membrane because of a steric impediment. Therefore, at the end of each cycle not only the level of the positive electrolyte tank will be higher than that of the negative electrolyte tank but also the concentration of vanadium in the positive tank will slowly increase.
  • the novel method of this disclosure consists in inverting the connections of the electrical connection terminals of the battery to the recharging electrical source and to the electrical load at intervals of time.
  • the electrode that is functioning as anode in a flow compartment of the cell (all similarly polarized electrodes in case of a multi-cell stack) during the current phase of operation, for example during a charging phase, will be polarized as cathode, and vice versa for the other electrode of the cell or cells.
  • the interval between successive inversions of the battery polarity may correspond to the total duration of a number of charge/discharge cycles that may be set in consideration of the prevailing working conditions of the energy storage system.
  • a re-conditioning, in an inverted polarity the two electrolyte solutions, making them ready for undergoing a new ordinary charge phase of the battery system (as would have happened without effecting the inversion) represents a necessary remake of the normal "initial investment" charge of the redox flow battery system at a fresh start-up, and its cost in terms of electrical energy consumption may be in the order of about 35-65% of the total charge/discharge energy storage capacity of the system.
  • the cost of restoring optimal working conditions and energy conversion performance according to this disclosure can be considered negligible or in any case insignificant compared to cost of maintenance work for clearing the positive electrolyte flow compartments of the cells and felt electrodes from likely cloggings and/or periodically rebalancing volumes and vanadium content in the two distinct electrolyte solutions.
  • cost in terms of electrical energy and duration of re-charging phase that would need to be carried out at every changeover of polarity of the battery according to the novel method of the applicants can be reduced down to a residual proportion of the above-discussed amounts.
  • the energy storage system will be back to a condition of ability to deliver electrical energy to a load in a similarly shortened time after the switch over of polarity of the battery.
  • the circulation pipelines of the two electrolyte solutions from the respective storage tanks to the respective flow compartments of the cells of a multi-cell battery stack and similarly the return pipeline to the storage tanks are functionally duplicated and path selecting electro valves allows to exchange the source and destination tank, simultaneously to the inversion of polarity of the battery.
  • the amount of electrolyte solutions that will undergo full discharge, re-conditioning in an inverted state of charge will be the total volumes of solutions contained in the flow compartments of the multi- cell stack and in the circulation pipelines upstream and downstream of the set of path-selecting electro-valves in the return lines and in the feed lines of the two solutions.
  • Figure 1 is a scheme of a flow redox battery system according to a first embodiment the method of this disclosure.
  • Figure 2 is a scheme of a flow redox battery system according to an alternative embodiment.
  • FIG. 1 A classic functional scheme of an all vanadium redox flow battery system normally employing a multi-cell battery stack B, symbolically illustrated, having electrical connection terminals Tl and T2 at extreme end electrodes of a bipolar arrangement of cells in series, is shown in Fig. 1.
  • the energy storage system may include several multi-cell battery stacks B, interconnected according to a series-parallel arrangement best suited for the intended use of the energy storage system, in order to increase peak power and voltage ratings.
  • the scheme clearly illustrates the two distinct hydraulic circuits each including a storage tank of the respective positive and negative electrolyte solution and the circulating pumps that force the solutions to flow in parallel or in series through the respective flow compartments of the individual cells composing the multi-cell stack B.
  • the above described method of conducting the energy storage system found by the present applicants is implemented by introducing in the electrical connection of the two terminals Tlan T2 of the battery B to a DC source POWER CHARGER, for charging the redox flow battery system, and for connecting the same terminals Tl and T2 to an electrical circuit LOAD, supplied by the battery, inverting switches Iswl and Isw2, respectively.
  • the polarity notation +(-) and -(+) at the terminal ends of the battery B signify the periodically effected polarity inversion of the battery according to the method of conduction of this disclosure.
  • Fig. 2 depicts the basic functional scheme of the all vanadium redox flow battery system of Fig. 1. according to an alternative and in many respect preferred embodiment that avoids a complete reconditioning and recharging of the entire volume of each of the two distinct electrolyte solutions circulating in the respective hydraulic circuits and cell compartments.
  • the method found by the applicants besides offering a simple way of preventing accumulation of precipitated vanadium pentoxide, and periodically correcting unbalances of the state of charge of the two electrolyte solutions, makes the use of less expensive, durable and less resistive cationic membranes unplagued by the phenomenon of progressive volumetric and mass disproportionation, being the phenomenon reversible and correctable with the method of conduction of this disclosure, whenever it surpasses a tolerable measure.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Fuel Cell (AREA)

Abstract

La précipitation accidentelle de pentoxyde de vanadium, le déséquilibre progressif de la teneur en vanadium dans les deux solutions d'électrolyte, le transfert d'une solution d'électrolyte à travers la membrane permionique lors de l'utilisation d'une membrane cationique comme séparateur de cellules sont des effets délétères de différents mécanismes électro-chimico-physiques qui sont actifs lors de la réalisation d'un cycle d'une batterie à flux d'oxydoréduction tout vanadium comme système de stockage d'énergie. A cet effet, pour remédier efficacement à certains ou à la totalité de ces inconvénients, l'invention porte sur un procédé, qui comprend une étape consistant à inverser les connexions des bornes de connexion électrique de la batterie avec la source électrique de recharge et avec la charge électrique par intervalles de temps. Dans la pratique, l'électrode qui joue le rôle d'anode dans un compartiment de circulation de la cellule pendant la phase de fonctionnement en cours sera polarisée en cathode, et inversement pour l'autre électrode de la ou des cellules.
PCT/IB2011/001141 2011-05-26 2011-05-26 Procédé de réalisation d'une batterie à flux d'oxydoréduction tout vanadium et système de mise en œuvre Ceased WO2012160406A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/IB2011/001141 WO2012160406A1 (fr) 2011-05-26 2011-05-26 Procédé de réalisation d'une batterie à flux d'oxydoréduction tout vanadium et système de mise en œuvre

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PCT/IB2011/001141 WO2012160406A1 (fr) 2011-05-26 2011-05-26 Procédé de réalisation d'une batterie à flux d'oxydoréduction tout vanadium et système de mise en œuvre

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103219530A (zh) * 2013-04-03 2013-07-24 胡国良 钒电池碳毡电极的处理方法
WO2014198546A1 (fr) 2013-06-13 2014-12-18 Cellstrom Gmbh Batterie redox à flux et son procédé de réactivation
DE102014221148A1 (de) * 2014-10-17 2016-04-21 Bayerische Motoren Werke Aktiengesellschaft Betriebsverfahren eines Redox-Flow-Systems und eines Kraftfahrzeuges sowie Redox-Flow-System und Kraftfahrzeug mit einem Redox-Flow-System
JP2016517137A (ja) * 2013-03-15 2016-06-09 ユナイテッド テクノロジーズ コーポレイションＵｎｉｔｅｄ Ｔｅｃｈｎｏｌｏｇｉｅｓ Ｃｏｒｐｏｒａｔｉｏｎ 酸化溶液に曝すことによるフローバッテリ電極の再活性化
DE102019106588A1 (de) * 2018-11-16 2020-05-20 H2, Inc. Verfahren zum entfernen eines präzipitats einer redox-flow-batterie und dieses umfassende redox-flow-batterie
CN112909301A (zh) * 2021-03-26 2021-06-04 苏州辉美汽车科技有限公司 一种液流电池及其充电再生循环系统
US11056698B2 (en) 2018-08-02 2021-07-06 Raytheon Technologies Corporation Redox flow battery with electrolyte balancing and compatibility enabling features
CN113270624A (zh) * 2021-04-14 2021-08-17 上海交通大学 具备催化剂管理与电解液容量再平衡的液流电池子系统
CN114156516A (zh) * 2021-12-01 2022-03-08 湖南汇锋高新能源有限公司 一种钒电解液电解生产方式及其装置
US11271226B1 (en) 2020-12-11 2022-03-08 Raytheon Technologies Corporation Redox flow battery with improved efficiency
CN116601806A (zh) * 2020-12-22 2023-08-15 环球油品有限责任公司 反向极性刷新方法和氧化还原液流电池系统
CN117393810A (zh) * 2023-12-12 2024-01-12 江苏美淼储能科技有限公司 钒电池在线恢复容量和在线抑制钒离子跨膜扩散的办法

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JPS61173468A (ja) * 1985-01-28 1986-08-05 Mitsui Eng & Shipbuild Co Ltd 電解または電池装置
JPS62163270A (ja) * 1986-01-10 1987-07-20 Sumitomo Electric Ind Ltd １液式レドツクスフロ−電池の充放電方法
JPH01146267A (ja) * 1987-12-03 1989-06-08 Chiyoda Corp レドツクスフロー電池の運転方法
JP2002216833A (ja) * 2001-01-19 2002-08-02 Kansai Electric Power Co Inc:The レドックス電池
US20030143456A1 (en) * 1995-05-03 2003-07-31 Michael Kazacos High energy density vanadium electrolyte solutions, methods of preparation thereof and all-vanadium redox cells and batteries containing high energy vanadium electrolyte solutions

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61173468A (ja) * 1985-01-28 1986-08-05 Mitsui Eng & Shipbuild Co Ltd 電解または電池装置
JPS62163270A (ja) * 1986-01-10 1987-07-20 Sumitomo Electric Ind Ltd １液式レドツクスフロ−電池の充放電方法
JPH01146267A (ja) * 1987-12-03 1989-06-08 Chiyoda Corp レドツクスフロー電池の運転方法
US20030143456A1 (en) * 1995-05-03 2003-07-31 Michael Kazacos High energy density vanadium electrolyte solutions, methods of preparation thereof and all-vanadium redox cells and batteries containing high energy vanadium electrolyte solutions
JP2002216833A (ja) * 2001-01-19 2002-08-02 Kansai Electric Power Co Inc:The レドックス電池

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016517137A (ja) * 2013-03-15 2016-06-09 ユナイテッド テクノロジーズ コーポレイションＵｎｉｔｅｄ Ｔｅｃｈｎｏｌｏｇｉｅｓ Ｃｏｒｐｏｒａｔｉｏｎ 酸化溶液に曝すことによるフローバッテリ電極の再活性化
US10044058B2 (en) 2013-03-15 2018-08-07 United Technologies Corporation Reactivation of flow battery electrode by exposure to oxidizing solution
CN103219530A (zh) * 2013-04-03 2013-07-24 胡国良 钒电池碳毡电极的处理方法
WO2014198546A1 (fr) 2013-06-13 2014-12-18 Cellstrom Gmbh Batterie redox à flux et son procédé de réactivation
DE102014221148A1 (de) * 2014-10-17 2016-04-21 Bayerische Motoren Werke Aktiengesellschaft Betriebsverfahren eines Redox-Flow-Systems und eines Kraftfahrzeuges sowie Redox-Flow-System und Kraftfahrzeug mit einem Redox-Flow-System
DE102014221148B4 (de) 2014-10-17 2024-02-22 Bayerische Motoren Werke Aktiengesellschaft Betriebsverfahren eines Redox-Flow-Systems und eines Kraftfahrzeuges sowie Redox-Flow-System und Kraftfahrzeug mit einem Redox-Flow-System
US11637298B2 (en) 2018-08-02 2023-04-25 Raytheon Technologies Corporation Redox flow battery with electrolyte balancing and compatibility enabling features
US11056698B2 (en) 2018-08-02 2021-07-06 Raytheon Technologies Corporation Redox flow battery with electrolyte balancing and compatibility enabling features
DE102019106588A1 (de) * 2018-11-16 2020-05-20 H2, Inc. Verfahren zum entfernen eines präzipitats einer redox-flow-batterie und dieses umfassende redox-flow-batterie
US11271226B1 (en) 2020-12-11 2022-03-08 Raytheon Technologies Corporation Redox flow battery with improved efficiency
CN116601806A (zh) * 2020-12-22 2023-08-15 环球油品有限责任公司 反向极性刷新方法和氧化还原液流电池系统
EP4268307A4 (fr) * 2020-12-22 2025-11-26 Uop Llc Procédé de rafraîchissement de polarité inverse et système de batterie à flux redox
CN112909301A (zh) * 2021-03-26 2021-06-04 苏州辉美汽车科技有限公司 一种液流电池及其充电再生循环系统
CN113270624A (zh) * 2021-04-14 2021-08-17 上海交通大学 具备催化剂管理与电解液容量再平衡的液流电池子系统
CN113270624B (zh) * 2021-04-14 2022-03-22 上海交通大学 具备催化剂管理与电解液容量再平衡的液流电池子系统
CN114156516A (zh) * 2021-12-01 2022-03-08 湖南汇锋高新能源有限公司 一种钒电解液电解生产方式及其装置
CN114156516B (zh) * 2021-12-01 2024-05-07 湖南汇锋高新能源有限公司 一种钒电解液电解生产方式及其装置
CN117393810A (zh) * 2023-12-12 2024-01-12 江苏美淼储能科技有限公司 钒电池在线恢复容量和在线抑制钒离子跨膜扩散的办法
CN117393810B (zh) * 2023-12-12 2024-03-08 江苏美淼储能科技有限公司 钒电池在线恢复容量和在线抑制钒离子跨膜扩散的办法

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