EP2759006A1 - Procédé de fonctionnement de piles à métal-brome - Google Patents

Procédé de fonctionnement de piles à métal-brome

Info

Publication number
EP2759006A1
EP2759006A1 EP11781871.6A EP11781871A EP2759006A1 EP 2759006 A1 EP2759006 A1 EP 2759006A1 EP 11781871 A EP11781871 A EP 11781871A EP 2759006 A1 EP2759006 A1 EP 2759006A1
Authority
EP
European Patent Office
Prior art keywords
bromine
bromide
zinc
electrolyte solution
cell
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.)
Withdrawn
Application number
EP11781871.6A
Other languages
German (de)
English (en)
Inventor
Mira Bergstein Freiberg
Iris Ben David
Ben-Zion Magnes
Eli Lancry
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.)
Bromine Compounds Ltd
Original Assignee
Bromine Compounds Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Bromine Compounds Ltd filed Critical Bromine Compounds Ltd
Publication of EP2759006A1 publication Critical patent/EP2759006A1/fr
Withdrawn legal-status Critical Current

Links

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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H01M10/365—Zinc-halogen accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/70—Arrangements for stirring or circulating the electrolyte
    • H01M50/77—Arrangements for stirring or circulating the electrolyte with external circulating path
    • 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
    • Y02E60/10—Energy storage using batteries
    • 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 invention relates to a method for generating elemental bromine in electrolyte solutions used for operating metal- bromine cells, such as zinc-bromine batteries.
  • Zinc-bromine rechargeable cell contains two chemically non- reactive electrodes and a suitable separator located between the electrodes (e.g., an ion exchange membrane);
  • the electrolyte used in the cell is an aqueous solution of zinc bromide, which is generally fed to the two compartments of the cell from two separate external reservoirs, utilizing a suitable circulation system.
  • the term "anode” is used herein to indicate the electrode where metal zinc is formed (during charge) and oxidized (during discharge) .
  • cathode is used herein to indicate the electrode where elemental bromine evolves (during charge) and reduced (during discharge) .
  • the charge and discharge states of zinc-bromine battery will now be described in more detail.
  • the aqueous electrolyte solution which circulates through the cathodic side during the cell charge contains a complexing agent which is capable of readily forming a liquid phase upon complexing with elemental bromine.
  • a complexing agent which is capable of readily forming a liquid phase upon complexing with elemental bromine.
  • the elemental bromine generated at the cathodic side during cell charge reacts almost instantaneously with the complexing agent, to form an oily phase.
  • the dense bromine- containing oily phase tends to settle at the bottom of the reservoir used for holding the catholyte.
  • the recirculation of the bromine-containing medium is prevented using suitable mechanical means, thus allowing the accumulation of elemental bromine in the catholyte reservoir. In this way, bromine is produced and stored in a reservoir outside the electrode .
  • Figure 1 provides a schematic illustration of an example of a zinc-bromine cell, wherein numerals la and lc indicate the anode and cathode, respectively, and numeral 2 represents the separator positioned between the electrodes.
  • a reservoir 3c contains the catholyte, which consists of two liquid phases: an upper, aqueous solution of zinc bromide and a lower, dense organic phase comprising the elemental bromine in a form of a complex.
  • the flow paths allowing the circulation of the anolyte and catholyte are respectively indicated by arrows (the streams are driven by pumps Pa, Pc) .
  • a suitable valve (v) allows injection of bromine into the flow path of the catholyte on discharge only.
  • the introduction of a small amount of bromine to the anolyte, the catholyte or both, e.g., between about 0.05% and 2%, and more specifically between 0.3% and 0.7% by w/w (relative to the weight of the anolyte or the catholyte) is considered to be beneficial.
  • a moderate capacity unit operating at lOOkW'h contains about one ton of an electrolyte solution, and therefore, a few kilograms of bromine are to be added to the anodic half-cell prior to charging.
  • the initial amount of bromine reguired prior to starting a new unit charge cycle is up to 100 kg.
  • elemental bromine is an easily volatile liquid with a strong, disagreeable odor an irritating effect. Therefore, the transportation and storage of elemental bromine must satisfy stringent requirements, and employing liquid bromine in populated areas requires the application of stringent safety measures and trained personal.
  • the present invention provides a safe method for generating elemental bromine in-situ in a bromide-containing electrolyte solution suitable for use in a metal bromine cell, and more specifically in a zinc bromine cell, which method comprises chemically oxidizing bromide (Br " ) in said electrolyte solution in an acidic environment, to produce elemental bromine.
  • the in-situ generation of elemental bromine according to the method of the present invention may facilitate the operation of various zinc-bromine rechargeable cells, including the zinc bromine cell having separate streams of anolyte and catholyte circulating in the cell, as shown in Figure 1 (known as "flow battery”) .
  • the present invention provides a method for operating a metal bromine cell (e.g., zinc bromine cell) containing an electrolyte solution, comprising generating elemental bromine in-situ by means of chemically oxidizing bromide (Br " ) in an acidic environment, thereby supplying elemental bromine to the electrolyte solution of said cell.
  • a metal bromine cell e.g., zinc bromine cell
  • bromine chemically oxidizing bromide
  • the present invention provides a method for operating a zinc-bromine rechargeable cell having an anolyte and catholyte circulating therein, comprising generating elemental bromine in-situ by means of chemically oxidizing bromide (Br-) in an acidic environment, thereby supplying elemental bromine to said anolyte, catholyte or both, and charging or discharging the cell.
  • the elemental bromine is generated at a concentration in the range from 0.05 to 2.0% by weight relative to the weight of the anolyte, catholyte or both.
  • An electrolyte solution which is suitable for use according to the invention is an aqueous, concentrated solution of zinc bromide, as commonly employed for operating zinc bromine rechargeable batteries.
  • concentration of the zinc bromide in the aqueous electrolyte solution is not less than 1.0M, and preferably between 2.0 and 3.0M (prior to cell charge) .
  • the electrolyte solution may optionally contain one or more other halide salts, such as zinc chloride (zinc ions source usually 0.5M), sodium chloride or potassium chloride , and also sulfate salts (both are conductivity enhancers up to 3M) .
  • the total concentration of these secondary water-soluble salts, which may be optionally present in the electrolyte solution can be up to 3.5 M, e.g., between 0.5-3.5 M.
  • the electrolyte solution further comprises at least one water soluble complexing agent which is capable of forming a liquid phase upon complexing with elemental bromine.
  • Quaternary ammonium salts especially halide salts and specifically bromide salts, are suitable for use as complexing agents.
  • the cationic portion of said salts contains a nitrogen atom, which is bonded to four organic groups, (e.g., alkyl groups which may be the same or different).
  • the tetracoordinate nitrogen may also be a member of a ring, namely, a heterocyclic ring, which heterocyclic ring may optionally contain a further heteroatom other than said tetracoordinate nitrogen.
  • the cationic portion of said salts may also contain a positively charged nitrogen atom which is a member of a heteroaromatic ring.
  • Tetra-alkyl ammonium bromides, and the bromide salts of ⁇ , ⁇ -dialkyl morpholinium, N,N-d.ialkyl pyrrolidinium and N-alkyl pyridinium salts are suitable for use in the method provided by the present invention, wherein the alkyl groups are C1-C7 straight or branched alkyl groups, which may be the same or different from one another.
  • a suitable electrolyte solution which may be used in zinc bromine batteries has the following composition: from 2.0 to 3.0 M ZnBr 2 , from 0.5 to 1.0 M ZnCl 2 and from 0.5 to 1.0 M total concentration of N-methyl-N-ethyl pyrrolidinium bromide (MEP) and N-methyl-N-ethyl morpholinium bromide (MEM) as the complexing agent.
  • MEP N-methyl-N-ethyl pyrrolidinium bromide
  • MEM N-methyl-N-ethyl morpholinium bromide
  • one or more water soluble salts may be present in the electrolyte solution at a concentration ranging from 0.5 to 3 M.
  • the method according to the invention involves the chemical oxidation of bromide in the electrolyte solution in an acidic environment. Accordingly, a bromide source, an oxidant and an acid are combined in the electrolyte described above in order to accomplish the reaction.
  • auxiliary bromide source may be added to the solution in order to supply the bromide.
  • a useful auxiliary bromide source may be, for example, hydrobromic acid, which may be applied in the form of an aqueous solution (e.g., of 48% w/w concentration) .
  • One or more water soluble bromide salts may also be used as the auxiliary bromide source. Suitable examples of such salts include - but are not limited to - sodium bromide (NaBr) , potassium bromide (KBr) and ammonium bromide (NH 4 Br) .
  • the aforementioned oxidizers may be used in the electrolyte solution in the following weight concentration ranges: from 0.1 to 5% of Zn0 2 , e.g., about 0.3%, or from 0.2 to 10.0% of Zn0 2 /ZnO (about 1:1 mixture or any mixture compositions), e.g., about 0.6% of said mixture.
  • the relevant chemical reactions are as follows:
  • bromate salts Another class of utilizable oxidants includes bromate salts.
  • chemical oxidation of bromide using bromate as an oxidizing agent in an acidic environment is represented by the following chemical equation (3) :
  • Bromate salts which can be used as oxidizing agents in the practice of the present invention may be selected from the group consisting of potassium bromate (KBr0 3 ) , sodium bromate (NaBrC>3) and zinc bromate (Zn(Br03) 2 ) .
  • potassium bromate KBr0 3
  • sodium bromate NaBrC>3
  • zinc bromate Zn(Br03) 2
  • the weight concentration of the bromate salt oxidizer in the electrolyte solution can be in the following ranges: from 0.1 to 5% KBr0 3 , e.g., about 0.2%; from 0.1 to 10% NaBr0 3 , e.g., about 0.3%; or from 0.1 to 10% Zn(Br0 3 ) 2 , e.g., about 0.3%.
  • Other useful oxidants include hypohalites.
  • Specific hypohalite salts which can be used as oxidizing agents in the practice of the present invention may be selected from the group consisting of hypochlorites, e.g., NaClO.
  • the oxidation reaction proceeds at room temperature (in the range between 20 and 30°C) under stirring, and the desired amount of elemental bromine is generally formed after 1 to 24 hours.
  • the measurement of the bromine content of the electrolyte solution can be carried out using acceptable titration techniques.
  • the reaction mixture may be periodically sampled and subjected to iodometric titration. Spectroscopy techniques may also be employed for monitoring the progress of the reaction and for measuring the amount of bromine formed, since the absorption of the reaction mixture correlates nicely with the concentration of bromine.
  • the method of the present invention may be used for the in-situ generation of elemental bromine at the discharge or charge state of various zinc-bromine batteries utilizing flowing electrolyte, including batteries arranged in the form of serially connected bipolar electrodes (a stack arrangement, in which a plurality of bipolar electrodes and separators interposed therebetween are positioned between two terminal electrodes is described, for example, in US 4,615,108).
  • the battery may be subsequently charged or discharged according to methods known in the art (e.g., US 5,459,390 and US 6,036,937).
  • Oxidizer zinc peroxide (as Zn0 2 /ZnO mixture)

Landscapes

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

Abstract

L'invention porte sur un procédé pour la production de brome élémentaire dans une solution électrolytique contenant du bromure appropriée pour être utilisée dans une pile à métal-brome, comprenant l'oxydation chimique de bromure (Br-) dans ladite solution électrolytique dans un environnement acide, pour produire du brome élémentaire. L'invention porte également sur un procédé pour le fonctionnement d'une pile à métal-brome.
EP11781871.6A 2011-09-21 2011-09-21 Procédé de fonctionnement de piles à métal-brome Withdrawn EP2759006A1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/IL2011/000747 WO2013042103A1 (fr) 2011-09-21 2011-09-21 Procédé de fonctionnement de piles à métal-brome

Publications (1)

Publication Number Publication Date
EP2759006A1 true EP2759006A1 (fr) 2014-07-30

Family

ID=44936325

Family Applications (1)

Application Number Title Priority Date Filing Date
EP11781871.6A Withdrawn EP2759006A1 (fr) 2011-09-21 2011-09-21 Procédé de fonctionnement de piles à métal-brome

Country Status (3)

Country Link
EP (1) EP2759006A1 (fr)
CN (1) CN103947012B (fr)
WO (1) WO2013042103A1 (fr)

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9905874B2 (en) 2011-09-22 2018-02-27 Bromine Compounds Ltd. Additives for hydrogen/bromine cells
US9722272B2 (en) 2012-05-10 2017-08-01 Bromine Compounds Ltd. Additives for zinc-bromine membraneless flow cells
ES2617663T3 (es) 2013-02-07 2017-06-19 Bromine Compounds Ltd. Procesos para la preparación de bromuro de 1-alquil-3-alquil-piridinio y usos de los mismos como aditivos en celdas electroquímicas
CN103259032B (zh) * 2013-04-28 2016-06-08 单萌 一种常温热发电方法及其装置
CN104600338A (zh) * 2013-11-01 2015-05-06 上海空间电源研究所 一种锌溴液流电池电解液添加剂及其制作方法
EP3204977B1 (fr) 2014-10-06 2023-12-20 EOS Energy Technology Holdings, LLC Électrolyte pour pile électrochimique rechargeable
CN105680082A (zh) * 2014-11-17 2016-06-15 中国科学院大连化学物理研究所 一种长寿命锌溴液流电池结构及其电解液
JP2018512719A (ja) * 2015-03-19 2018-05-17 プリマス パワー コーポレイション キレート剤および金属めっき促進剤を含むフロー電池電解質組成物
KR20180005215A (ko) 2015-05-11 2018-01-15 브로민 콤파운드 리미티드 플로우 배터리용 첨가제
US11394069B2 (en) 2015-11-10 2022-07-19 Bromine Compounds Ltd. Additives for a flow battery
CN106876727A (zh) * 2015-12-13 2017-06-20 中国科学院大连化学物理研究所 一种氧化石墨烯修饰锌溴液流电池碳毡电极及其应用
US10892524B2 (en) 2016-03-29 2021-01-12 Eos Energy Storage, Llc Electrolyte for rechargeable electrochemical cell
KR20170132005A (ko) * 2016-05-23 2017-12-01 롯데케미칼 주식회사 레독스 흐름 전지
CN108134141B (zh) * 2016-12-01 2020-05-05 中国科学院大连化学物理研究所 一种无隔膜静态锌溴电池
CN106602181A (zh) * 2016-12-28 2017-04-26 西华大学 一种氯镁电池及其储能方法
CN109755618B (zh) * 2017-11-01 2021-10-29 中国科学院大连化学物理研究所 一种锌溴液流电池正极电解液在电池中的应用
CN108172878A (zh) * 2018-02-13 2018-06-15 青海百能汇通新能源科技有限公司 电解质添加剂、电解液及电解液的制备方法
WO2020185486A1 (fr) * 2019-03-13 2020-09-17 Eastman Chemical Company Procédés utiles dans la fabrication de cyclododécasulfure

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Also Published As

Publication number Publication date
CN103947012A (zh) 2014-07-23
CN103947012B (zh) 2016-07-06
WO2013042103A1 (fr) 2013-03-28

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