EP2759006A1 - A method of operating metal- bromine cells - Google Patents
A method of operating metal- bromine cellsInfo
- 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- Withdrawn
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)
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- 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
Description
Claims
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/IL2011/000747 WO2013042103A1 (en) | 2011-09-21 | 2011-09-21 | A method of operating metal- bromine cells |
Publications (1)
Publication Number | Publication Date |
---|---|
EP2759006A1 true EP2759006A1 (en) | 2014-07-30 |
Family
ID=44936325
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP11781871.6A Withdrawn EP2759006A1 (en) | 2011-09-21 | 2011-09-21 | A method of operating metal- bromine cells |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP2759006A1 (en) |
CN (1) | CN103947012B (en) |
WO (1) | WO2013042103A1 (en) |
Families Citing this family (18)
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 |
JP6392248B2 (en) | 2013-02-07 | 2018-09-19 | ブローミン コンパウンズ リミテッド | Process for the preparation of 1-alkyl-3-alkyl-pyridinium bromides and their use as additives in electrochemical cells |
CN103259032B (en) * | 2013-04-28 | 2016-06-08 | 单萌 | A kind of room-temperature thermal power generation and device thereof |
CN104600338A (en) * | 2013-11-01 | 2015-05-06 | 上海空间电源研究所 | Zinc-bromine flow battery electrolyte additive and production method thereof |
BR112017006815A2 (en) * | 2014-10-06 | 2017-12-26 | Eos Energy Storage Llc | rechargeable electrochemical cell electrolyte |
CN105680082A (en) * | 2014-11-17 | 2016-06-15 | 中国科学院大连化学物理研究所 | Long-lifetime zinc-bromine flow battery structure and electrolyte |
CN107980187A (en) * | 2015-03-19 | 2018-05-01 | 普里默斯电力公司 | Flow battery group electrolyte composition containing chelating agent and metal plating reinforcing agent |
AU2016261702B2 (en) | 2015-05-11 | 2021-01-28 | Bromine Compounds Ltd. | An additive for a flow battery |
WO2017081678A1 (en) | 2015-11-10 | 2017-05-18 | Bromine Compounds Ltd. | Additives for a flow battery |
CN106876727A (en) * | 2015-12-13 | 2017-06-20 | 中国科学院大连化学物理研究所 | A kind of graphene oxide modifies zinc-bromine flow battery carbon felt electrode and its application |
US10892524B2 (en) | 2016-03-29 | 2021-01-12 | Eos Energy Storage, Llc | Electrolyte for rechargeable electrochemical cell |
KR20170132005A (en) * | 2016-05-23 | 2017-12-01 | 롯데케미칼 주식회사 | Redox flow battery |
CN108134141B (en) * | 2016-12-01 | 2020-05-05 | 中国科学院大连化学物理研究所 | Static zinc-bromine battery without diaphragm |
CN106602181A (en) * | 2016-12-28 | 2017-04-26 | 西华大学 | Chlorine-magnesium battery and energy storage method thereof |
CN109755618B (en) * | 2017-11-01 | 2021-10-29 | 中国科学院大连化学物理研究所 | Application of zinc-bromine flow battery anode electrolyte in battery |
CN108172878A (en) * | 2018-02-13 | 2018-06-15 | 青海百能汇通新能源科技有限公司 | The preparation method of electrolyte additive, electrolyte and electrolyte |
WO2020185486A1 (en) * | 2019-03-13 | 2020-09-17 | Eastman Chemical Company | Processes useful in the manufacture of cyclododecasulfur |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CH554078A (en) * | 1971-08-31 | 1974-09-13 | Consiglio Nazionale Ricerche | ELECTRIC ACCUMULATOR. |
US3811945A (en) * | 1972-08-24 | 1974-05-21 | Consiglio Nazionale Ricerche | Electric battery |
US4109065A (en) * | 1977-08-10 | 1978-08-22 | General Electric Company | Rechargeable aqueous zinc-halogen cell |
EP0149448B1 (en) | 1983-12-19 | 1990-11-07 | S.E.A. Studiengesellschaft für Energiespeicher und Antriebssysteme Gesellschaft m.b.H. | Galvanic element, in particular a secondary element, and method of production |
US4818642A (en) * | 1986-03-03 | 1989-04-04 | Exxon Research And Engineering Company | Electrolyte additive for improved battery performance |
JPH0364871A (en) * | 1989-08-02 | 1991-03-20 | Meidensha Corp | Electrolyte for zinc bromide cell |
AT398142B (en) | 1991-05-24 | 1994-09-26 | Elin Energieanwendung | METHOD FOR DETERMINING THE CHARGE STATE OF A ZINC-BROM BATTERY, AND METHOD FOR CHARGING THE SAME |
AT399246B (en) | 1992-12-23 | 1995-04-25 | Elin Energieanwendung | METHOD FOR CHARGING AND DISCHARGING ZINC / BROM BATTERIES |
JPH07105992A (en) * | 1993-10-04 | 1995-04-21 | Meidensha Corp | Regenerating method for electrolyte for zinc-bromine battery |
US6036937A (en) | 1998-11-18 | 2000-03-14 | Tetra Technologies, Inc. | Method for producing zinc bromide |
-
2011
- 2011-09-21 CN CN201180074982.3A patent/CN103947012B/en not_active Expired - Fee Related
- 2011-09-21 EP EP11781871.6A patent/EP2759006A1/en not_active Withdrawn
- 2011-09-21 WO PCT/IL2011/000747 patent/WO2013042103A1/en unknown
Non-Patent Citations (2)
Title |
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None * |
See also references of WO2013042103A1 * |
Also Published As
Publication number | Publication date |
---|---|
WO2013042103A1 (en) | 2013-03-28 |
CN103947012A (en) | 2014-07-23 |
CN103947012B (en) | 2016-07-06 |
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