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WO2013086100A1 - Système de batterie à flux au bromure d'hydrogène pour applications d'échelle distribuée utilisant des cellules à pression équilibrée - Google Patents

Système de batterie à flux au bromure d'hydrogène pour applications d'échelle distribuée utilisant des cellules à pression équilibrée Download PDF

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Publication number
WO2013086100A1
WO2013086100A1 PCT/US2012/068120 US2012068120W WO2013086100A1 WO 2013086100 A1 WO2013086100 A1 WO 2013086100A1 US 2012068120 W US2012068120 W US 2012068120W WO 2013086100 A1 WO2013086100 A1 WO 2013086100A1
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Prior art keywords
electrolyte
chamber
pressure
hydrogen
electrolyte chamber
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PCT/US2012/068120
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English (en)
Inventor
Jonathan Andrew HAMEL
Thomas M. MADDEN
Oleg Grebenyuk
Curtis S. WARRINGTON
Timothy Banks GREJTAK
Matthew Dorson
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Sun Catalytix Corp
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Sun Catalytix Corp
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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
    • H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
    • H01M8/04104—Regulation of differential pressures
    • 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
    • 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
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M2008/1095—Fuel cells with polymeric electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • 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
    • H01M8/04201—Reactant storage and supply, e.g. means for feeding, pipes
    • H01M8/04208—Cartridges, cryogenic media or cryogenic reservoirs
    • 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

  • This disclosure relates to flow batteries and methods of operating the same, especially those flow batteries comprising hydrogen bromide.
  • Efficient and cost-effective energy storage is critical to avoid the high costs of providing backup electricity in areas where the electrical grid is highly unreliable.
  • the needs for base transceiver station applications are especially pressing, due to the high uptime required and the high costs of deploying traditional diesel power generator set technologies.
  • Hydrogen bromide is among the flow battery technologies that seem to have significant merit. Advantages of this system include the high degree of reversibility of the reactions at both electrodes, the gas-liquid phases of the reactants, and the potential for high power densities. However, to date, practical constraints as to the use of hydrogen bromide systems have limited their widespread use.
  • Various embodiments of the present invention provide methods of charging a flow battery having at least one cell, said cell having: (a) a hydrogen chamber further having a hydrogen electrode and comprising an outlet coupled to a control device capable of maintaining a predetermined pressure within the hydrogen chamber; (b) an electrolyte chamber having a bromine electrode, a volume of working electrolyte, an inlet for addition of fresh electrolyte into said electrolyte chamber, and an outlet for removal of reacted electrolyte out of said electrolyte chamber, said working, fresh, and reacted electrolytes comprising hydrogen bromide; and (c) a solid electrolyte membrane disposed between said chambers; each method comprising passing current through the cell during charging to produce a partial pressure of hydrogen in the hydrogen chamber in a range of about 50 psig to about 250 psig, and controlling the total pressure in the electrolyte chamber so as to be substantially similar to or less than the total pressure of the hydrogen chamber.
  • the entire fluidic loop is maintained to be at the same or substantially similar pressure as, or at a pressure differential to, the pressure of the electrolyte chamber.
  • only a portion of the fluidic loop is maintained to be at the same or substantially similar pressure as, or at a predetermined pressure differential to, the pressure of the electrolyte chamber.
  • the electrolyte chamber may be maintained to be at a specific pressure differential, and the pressure in an associated loop tank is not so controlled.
  • the pressure in the electrolyte chamber is maintained so as to be substantially similar to the generated pressure in the hydrogen chamber.
  • the pressure of the electrolyte chamber is maintained at a pressure less than the pressure of the hydrogen chamber.
  • the pressure of the electrolyte chamber may be maintained at a predetermined pressure differential or pressure differential range, relative to the total pressure the hydrogen chamber.
  • the pressure differential may be achieved through a passive pressure transmitting device - for example, through the use of a free floating piston, a flexible diaphragm, or a combination thereof between the hydrogen and electrolyte chambers, or pipes, tanks, etc. associated therewith - or may be achieved through an active pressure controlling device - e.g., use of hydraulics or addition of an inert gas to the electrolyte chamber or loop - or a combination of active controlling and passive pressure transmitting devices.
  • the flow battery is operated such that the electrolyte chamber is substantially full of liquid working electrolyte.
  • the electrolyte chamber may be operated with a small or appreciable gaseous or vapor headspace above the liquid working electrolyte at any temperature within the operating or contemplated temperature range of operation.
  • FIG. 1 is a schematic diagram of an exemplary HBr flow battery system.
  • FIG. 2 illustrates an exemplary balanced pressure stack embodiment comprising a fully-hydraulic pressurization system.
  • FIG. 3 illustrates another exemplary balanced pressure stack embodiment using a differential head pump, with system configuration in charging (energy storage) mode.
  • FIG. 4 illustrates another exemplary balanced pressure stack embodiment using external compression with an inert gas, with system configuration in charging (energy storage) mode.
  • FIG. 5 illustrates another exemplary balanced pressure stack embodiment using pressure communication between storage tanks, with the system configured in charging (energy storage) mode.
  • This disclosure relates to flow battery systems, especially HBr flow battery systems, that utilize the same cell(s) for both energy storage and energy generation, during the respective charging and discharging operations.
  • the electrolyte comprises aqueous hydrogen bromide / bromine.
  • the formation of tribromide ion in the presence of bromine and bromide is given by equation 2:
  • an electrolyte described herein as comprising aqueous HBr or HBr/Br 2 necessarily comprises a mixture of HBr, Br 3 ⁇ (and higher polybromide anions), and Br2.
  • FIG. 1 illustrates a schematic diagram of an exemplary HBr flow battery system.
  • the system comprises two circulation loops - one for the aqueous HBr/Br 2 electrolyte 10 and one for the hydrogen 15 - which are separated by a solid electrolyte membrane, said electrolyte membrane contained within an electrochemical cell comprising separate electrolyte and hydrogen chambers. Multiple cells may be configured into a cell stack, as is known in the art.
  • the electrolyte circulation loop comprises an electrolyte tank 25, the electrolyte chamber(s), and one or more electrolyte-compatible circulation pumps 30, for circulating the aqueous HBr/Br2 electrolyte through the electrolyte chamber during both charge and discharge stages.
  • This electrolyte circulation loop may also comprise one or more valves, additional tanks, sensors, monitors, pressure regulators, looped feedback control devices, a pressure equalizing line, or any combination thereof.
  • the hydrogen loop 15 comprises of a hydrogen tank 35, the hydrogen chamber(s), an optional hydrogen purifier 45, an optional liquid absorber 50, and an optional recycle blower 60.
  • the hydrogen loop may also comprise additional pumps, tanks, one or more valves, sensors, monitors, pressure regulators, looped feedback control devices, a gas circulation ejector, or any combination thereof.
  • the hydrogen loop also comprises a gas compressor. In other embodiments it does not. It should be appreciated that the specific positioning of the various optional elements are illustrative of a single configured embodiment and may be positioned differently in other embodiments as desired.
  • bromine (Br2) forms at the positive bromine electrode (the bromine electrode is always at a potential more positive than the hydrogen electrode), which is converted to tri- and polybromide complex ions form, as described above.
  • the HBr/Br 2 (typically bromide-rich) electrolyte is pumped or otherwise flows from the electrolyte tank into the electrolyte chamber(s) through an electrolyte chamber inlet and the bromide (or polybromide) is therein oxidized to bromine.
  • Charged electrolyte is then removed from the electrolyte chamber(s) through an electrolyte chamber outlet and returned to the electrolyte tank 25, or may be transferred to a separate storage tank While shown in FIG. 1 as a single tank, it should be appreciated that multiple tanks, including separate tanks for charged and discharged electrolytes, may be used.
  • the electrolyte may be moved through the electrolyte chamber(s) in continuous or batch-wise fashion.
  • hydrogen is produced at the hydrogen electrode in the hydrogen chamber(s) of the cell(s) or cell stack.
  • hydrogen may then be captured within a hydrogen pressure vessel 35.
  • this latter operation i.e., capturing the hydrogen gas at pressure in a hydrogen pressure vessel - requires the use of compression pumps, in order to provide the necessary pressure lift for practical gas storage.
  • compressing the hydrogen to pressures which are commercially useful is expensive, and contributes significantly to the cost of operating such systems.
  • the flow battery is designed also to operate in a discharge mode wherein the thermodynamically "downhill” recombination of 3 ⁇ 4 and B3 ⁇ 4 to give HBr (in the reverse reactions of Equation 1, 1a, and lb) generates electrical power for external use as needed.
  • the HBr/Br 2 (typically bromine-rich) electrolyte flows from the electrolyte tank 25 into the cell(s) or stacks and the bromine is therein reduced to bromide (reverse reaction of Equations 1 and lb).
  • electrolyte from the fuel cell stacks is returned to the electrolyte tank 25, or into separate tanks holding discharged electrolyte.
  • pressure may be maintained on the hydrogen side to a predetermined pressure using a passive regulator attached to a pressurized hydrogen container or through use of a hydrogen injector, in each case the regulator or injector providing fresh (non-recycled) hydrogen.
  • a passive regulator attached to a pressurized hydrogen container or through use of a hydrogen injector, in each case the regulator or injector providing fresh (non-recycled) hydrogen.
  • some portion of the excess hydrogen may be captured in a separate accumulation tank, where it is held until required, at which point it may be returned to the hydrogen cell.
  • the hydrogen and electrolyte chambers of each cell are separated by a membranes which are generally categorized as either solid (non-porous) or porous membranes / separators.
  • the membranes / separators form durable, electrically non-conductive mechanical barriers between the hydrogen and electrolyte chambers and facilitate the transport of protons therethrough.
  • all of the cell components must be capable of resisting the system chemistries associated with the electrolyte systems employed therein, and in the case of HBr flow batteries or cells must be capable of resisting corrosion associated with aqueous hydrobromic acid / bromine systems.
  • Non-porous membranes (alternatively called polymer electrolyte membranes)
  • PEM proton exchange membranes
  • ion-conducting membranes typically, but not exclusively, comprise highly fluorinated and most typically perfluorinated polymer backbones, for example copolymers of tetrafluoroethylene and one or more fluorinated, acid- functional co- monomers, containing pendant functional groups, such as sulfonate groups, carboxylate groups, or other functional groups that form acids when protonated.
  • TFE tetrafluoroethylene
  • Non-fluorinated non-porous membranes may also be used. These membranes comprise polymers with substantially aromatic backbones— e.g., poly-styrene, polyphenylene, bi-phenyl sulfone, or thermoplastics such as polyetherketones or polyethersulfones— that are modified with sulfonic acid or similar acid groups.
  • polymers with substantially aromatic backbones e.g., poly-styrene, polyphenylene, bi-phenyl sulfone, or thermoplastics such as polyetherketones or polyethersulfones— that are modified with sulfonic acid or similar acid groups.
  • Porous membranes are non-conductive membranes which allow charge transfer between two electrodes via open channels filled with conductive electrolyte. Because these contain no inherent proton conduction capability, they must be impregnated with acid in order to function. These membranes are typically comprised of a mixture of a polymer, and inorganic filler, and open porosity.
  • Preferred polymers include those chemically compatible with hydrogen bromide and/or bromine, including high density polyethylene, polypropylene, polyvinylidene difluoride, or polytetrafluoroethylene.
  • Preferred inorganic fillers include silicon carbide or other carbide matrix materials, titanium dioxide, silicon dioxide, among others.
  • Layers of refractory ceramic powders may also be used into which an acid can be imbibed. These powders form very small, hydrophilic pores that retain acid by virtue of very high capillary forces, and exhibit high corrosion resistance.
  • Preferred embodiments include silicon carbide and nanoporous carbon powders that be imbibed with a variety of acids, including hydrogen bromide acid.
  • Porous membranes are easily permeable to liquid or gaseous chemicals. This permeability increases probability of chemicals passing through porous membrane from one electrode to another causing cross-contamination and/or reduction in cell energy efficiency.
  • the degree of this cross-contamination depends on, among other features, the size (the effective diameter and channel length), and character (hydrophobicity / hydrophilicity) of the pores, the nature of the electrolyte, and the degree of wetting between the pores and the electrolyte).
  • MEAs membrane electrode assemblies
  • Typical MEAs used in HBr systems comprise a polymer electrolyte membrane (PEM) within a four or five layer structure, said structure also including hydrogen and bromine catalysts layers positioned on opposite sides of the PEM, and one or more fluid transport layers (FTL) or gas diffusion layers (GDL's).
  • PEM polymer electrolyte membrane
  • FTL fluid transport layers
  • GDL's gas diffusion layers
  • Each catalyst layer may include at least one electrochemical catalyst, typically including platinum and/or other precious or non-precious metal or metals.
  • electrochemical catalyst typically including platinum and/or other precious or non-precious metal or metals.
  • the terms "catalyst layer,” “hydrogen catalyst layer” and “bromine catalyst layer” refer to layers of such a catalyst material capable of improving the efficiency of the respective electrochemical conversion, under the appropriate electrochemical conditions. Such catalysts are known by those skilled in the art.
  • Various embodiments of the present invention provide methods of charging a flow battery having at least one cell, said cell having: (a) a hydrogen chamber further having a hydrogen electrode and comprising an outlet coupled to a control device capable of maintaining a predetermined pressure within the hydrogen chamber; (b) an electrolyte chamber having a bromine electrode, a volume of working electrolyte, an inlet for addition of fresh (pre-charged) electrolyte into said electrolyte chamber, and an outlet for removal of reacted (charged) electrolyte out of said electrolyte chamber, said working, fresh, and reacted electrolytes comprising hydrogen bromide; and (c) a solid electrolyte membrane disposed between said chambers; each method comprising passing current through the cell during charging to produce a partial pressure of hydrogen in the hydrogen chamber in a range of about 50 psig to about 250 psig, and controlling the total pressure in the electrolyte chamber so as to be substantially similar to or less than the total pressure of the hydrogen chamber.
  • the entire fluidic loop is maintained to be at the same or substantially similar pressure as, or at a pressure differential to, the pressure of the electrolyte chamber.
  • only a portion of the fluidic loop is maintain to be at the same or substantially similar pressure as, or at a predetermined pressure differential to as the pressure of the electrolyte chamber.
  • the electrolyte chamber may be maintained to be at a specific pressure differential, while the pressure in an associated loop tank(s) is/are not so controlled.
  • outlet of the hydrogen chamber is fluidicly coupled to a gas tank suitable for storing hydrogen gas at the elevated pressure produced in the hydrogen chamber.
  • hydrogen electrode refers to the working electrode on which hydrogen, H 2 is formed (by a reduction reaction) during the charging operation or on which 3 ⁇ 4 is consumed (oxidized) during the discharge operation.
  • hydrogen electrode is sometimes also called the “negative electrode” in these systems, since the hydrogen electrode potential is always negative relative to the potential of the bromine electrode regardless of whether the cell is charging or discharging.
  • bromine electrode refers to the working electrode on which bromine is formed (oxidizing a bromide or polybromide anion) during the charging operation, or on which Br 2 is reduced to a bromide (or polybromide) anion during the discharging operation.
  • bromine electrode is sometimes also called the “positive electrode” in these systems, since the bromine electrode potential is always positive relative to the potential of the hydrogen electrode regardless of whether the cell is charging or discharging.
  • fresh electrolyte refers to the "pre-charged" electrolyte composition entering the electrolyte chamber, the term
  • working electrolyte refers to the electrolyte occupying the electrolyte chamber during the passage of electrical current during charging
  • reactive electrolyte refers to the "charged” electrolyte leaving the electrolyte chamber, having been already subject to the passage of electric current while within the electrolyte chamber. It should be appreciated that, in the context of a typical charging operation, bromide ion is converted to bromine while in the electrolyte chamber, such that the concentration of bromide ion (or polybromide equivalent) in the electrolyte entering the electrolyte chamber (the fresh electrolyte) is higher than that leaving the chamber (the reacted electrolyte).
  • additional individual embodiments include those methods which provides that current is passed through the cell during charging of the flow battery so as to produce a partial pressure of hydrogen in the hydrogen cell in a range having a lower limit of about 50 psig, about 75 psig, about 100 psig, about 125 psig, about 150 psig, about 175 psig, and about 200 psig, and an upper limit in a range of about range of about 250 psig, about 225 psig, about 200 psig, about 175 psig, and about 150 psig.
  • Exemplary, non-limiting embodiments then, provide that the current is passed through the cell during charging of the flow battery to produce a partial pressure of hydrogen in a range of about 50 psig to about 250 psig, about 150 psig to about 250 psig, about 175 psig to about 250 psig, about 175 psig to about 225 psig, or about 200 psig to about 250 psig.
  • psig refers to pounds per square inch (psi) gauge, or psi above ambient external pressure (i.e., 0 psig is ambient external pressure), as is commonly understood by the engineering community.
  • the total pressure of the hydrogen chamber may be higher than the partial pressure of the hydrogen generated by the charging of the flow battery.
  • the presence of an additional gas or vapor pressure of a liquid within the hydrogen chamber may provide for this incrementally higher pressure.
  • any additional gas or vapor be either chemically inert or practically chemically inert toward high pressure hydrogen.
  • the invention also provides embodiments wherein the pressure in the electrolyte chamber is maintained so as to be substantially similar to the generated pressure in the hydrogen chamber.
  • the term "substantially similar” is intended to mean equal to or as nearly equal to as practically controllable.
  • Several exemplary methods for maintaining the pressure of the electrolyte chamber are described below.
  • the pressure of the electrolyte chamber is maintained at a pressure less than the pressure of the hydrogen chamber.
  • the pressure of the electrolyte chamber is maintained at a predetermined pressure differential or pressure differential range, relative to the total pressure the hydrogen chamber.
  • the maintenance of a substantially similar or deliberate pressure differential may be achieved through a passive pressure transmitting device - for example, through the use of a free floating piston, a flexible diaphragm, or a combination thereof between the hydrogen and electrolyte chambers, or pipes, tanks, etc. associated therewith— or may be achieved through an active pressure controlling device - e.g., use of hydraulics or addition of an inert gas to the electrolyte chamber or loop - or a combination of active controlling and passive pressure transmitting devices.
  • a passive pressure transmitting device for example, through the use of a free floating piston, a flexible diaphragm, or a combination thereof between the hydrogen and electrolyte chambers, or pipes, tanks, etc. associated therewith— or may be achieved through an active pressure controlling device - e.g., use of hydraulics or addition of an inert gas to the electrolyte chamber or loop - or a combination of active controlling and passive pressure transmitting devices.
  • the pressure differential between the hydrogen and electrolyte chambers (or pipes, tanks, etc. associated therewith) may be practically zero (i.e., when “substantially similar"), small (e.g., when the pressures are within about 50 psi, within about 25 psi, within about 10, or within about 5 psi or less of one another), or large (e.g., when the pressure differential is greater than about 50 psi, greater than about 75 psi, greater than about 100 psi, greater than about 125 psi, greater than about 150 psi, greater than about 175 psi, or greater than about 200 psi), such that the pressure of the electrolyte chamber (or pipes, tanks, etc. associated therewith) is at least 0 psig. Small or substantially similar pressure differentials between the hydrogen side and the electrolyte side minimize the physical stresses experienced by the interposed membrane or membrane assembly.
  • the flow battery is operated such that the electrolyte chamber is substantially full of liquid working electrolyte - i.e., there is no appreciable gaseous or vapor headspace above the working electrolyte.
  • the pressure in the electrolyte chamber can be maintained hydraulically.
  • separate pump systems may be used decouple the flow of electrolyte through the electrolyte chamber from the maintenance of the pressure within that chamber. That is, a first pump or pump system may maintain circulation of the electrolyte through the electrolyte chamber at a controlled rate of feed, while a second pump or pump system provides incremental changes in the overall (hydraulic) pressure within the electrolyte chamber. The operation of the second pump or pump system may be coupled and controlled relative to the pressure of the hydrogen chamber. Such configurations may provide reduced power requirements of each pump relative to other control mechanisms. See, e.g., FIG. 2.
  • a single pump or pump system may be employed to control both the circulation of the electrolyte through the electrolyte chamber as well as the pressure within the electrolyte chamber.
  • the pressure balance may be maintained using a gear pump or other similar pump, whose outlet pressure is matched to the increasing electrolyte pressure during charge by means of a throttle valve.
  • the pressure of the electrolyte chamber is controlled relative to the pressure of the hydrogen chamber, while the pressure in the HBr/Br 2 tank is not, and may even be separately vented.
  • This mode of operation has the advantage of simple system operation, but may require using a relatively expensive pump that is compatible with the HBr electrolyte and Br 2 reactants.
  • pressurized parts of the system are depicted by the dotted lines / outlines.
  • the flow battery may be operated such that the electrolyte chamber is not substantially full of liquid working electrolyte - i.e., there is a small or appreciable gaseous or vapor headspace above the liquid working electrolyte at any temperature within the operating or contemplated temperature range of operation.
  • the presence of vapor headspace is a concept well understood by the skilled engineer.
  • the pressure of the electrolyte chamber may be controlled by adding an inert gas to said electrolyte chamber or any portion of the fluidic loop associated with the electrolyte chamber, including the electrolyte storage tanks.
  • inert gas refers to a gas which does not chemically participate in the operation of the cell. As shown in
  • FIG. 3 for example, the pressure balance is shown to be maintained by pressurizing the headspace of both the electrolyte chamber and the connected storage tank with an inert gas.
  • the pressure of the electrolyte tank may be maintained through the use of devices capable of mechanically transmitting the pressures of the hydrogen chamber to the electrolyte chamber.
  • Such devices may include a movable piston or flexible membrane or a combination or both.
  • An example of this embodiment is shown schematically in FIG. 5, where the pressure associated with the hydrogen storage vessel (and the hydrogen chamber) is mechanically transmitted to the HBr/Br 2 storage vessel via a moving piston or flexible membrane.
  • pressurized parts of the system are depicted by the dotted lines / outlines.
  • controlling the pressure of the second, electrolyte chamber so as to be either substantially similar or at a defined pressure differential relative to the hydrogen chamber requires feedback monitoring, if control is to be maintained. Such control may be provided using the process management system(s) described above.
  • NAFION-based membranes are expected to have hydrogen crossover currents of about 2.5 mA/cm 2 at a hydrogen pressure of 200 psig on the hydrogen and ambient pressure on the bromine side. If the operating current density is 500 mA/cm 2 , then this represents a very tolerable -0.5% impact on current efficiency.
  • porous membranes will have substantially less ability to withstand pressure differentials. For example, if the electrolyte was highly wetting (contact angle of about 0 degrees) within 1-10 micron pores then the theoretical cross-pressure difference that could be sustained without gas breakthrough is in a range of about 2.5 to about 25 psi. This cross pressure will go down to the extent that the fluid is not completely wetting.
  • porous membranes will require that the degree of hydrogen over-pressure be only that which is dictated by bubble pressures with the porous membrane of interest with the liquid electrolyte of interest.
  • This cross-pressure can be roughly approximated by that given by the Young- Laplace equation using the appropriate wetting angle and fluid surface tension.

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Abstract

L'invention concerne, selon divers modes de réalisation de la présente invention, des procédés de chargement d'une batterie à flux possédant au moins une cellule, ladite cellule possédant : (a) une chambre à hydrogène possédant une électrode à hydrogène et comprenant une sortie couplée à un dispositif de commande apte à maintenir une pression prédéterminée dans la chambre à hydrogène ; (b) une chambre à électrolyte possédant une électrode de bromure, un volume d'électrolyte de travail, une entrée pour l'ajout d'électrolyte frais dans ladite chambre d'électrolyte, et une sortie pour le retrait d'électrolyte ayant réagi hors de la chambre d'électrolyte, lesdits électrolytes de travail, frais et ayant réagi comprenant du bromure d'hydrogène ; et (c) une membrane d'électrolyte solide disposée entre lesdites chambres.
PCT/US2012/068120 2011-12-06 2012-12-06 Système de batterie à flux au bromure d'hydrogène pour applications d'échelle distribuée utilisant des cellules à pression équilibrée Ceased WO2013086100A1 (fr)

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Cited By (7)

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Publication number Priority date Publication date Assignee Title
WO2015095555A1 (fr) 2013-12-19 2015-06-25 Robert Bosch Gmbh Batterie rédox à hydrogène/brome dans laquelle de l'hydrogène est librement échangé entre deux compartiments à cellules
WO2015100216A1 (fr) * 2013-12-23 2015-07-02 Robert Bosch Gmbh Système et procédé pour renvoyer un matériau depuis le côté br2 d'un arrière de batterie à flux h2/br2 après un croisement
EP2963723A1 (fr) 2014-07-04 2016-01-06 Elestor BV Ensemble de batterie à flux hydrogène-redox
NL2030263B1 (en) 2021-12-23 2023-06-29 Elestor B V A Hydrogen-X flow battery system coupled to a hydrogen pipeline network.
WO2024044461A1 (fr) * 2022-08-22 2024-02-29 Ess Tech, Inc. Système de cellule de rééquilibrage pour batterie à flux redox
WO2025198474A1 (fr) 2024-03-22 2025-09-25 Elestor B.V. Réservoir de stockage d'électrolyte pour système de batterie à flux redox
WO2025250014A1 (fr) 2024-05-30 2025-12-04 Elestor B.V. Procédé de récupération de composés métalliques à partir d'un système de pile à circulation

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US11594749B2 (en) 2013-12-19 2023-02-28 Robert Bosch Gmbh Hydrogen/bromine flow battery in which hydrogen is freely exchanged between two cell compartments
WO2015095555A1 (fr) 2013-12-19 2015-06-25 Robert Bosch Gmbh Batterie rédox à hydrogène/brome dans laquelle de l'hydrogène est librement échangé entre deux compartiments à cellules
US20160308237A1 (en) * 2013-12-19 2016-10-20 Robert Bosch Gmbh Hydrogen/Bromine Flow Battery in which Hydrogen is Freely Exchanged between Two Cell Compartments
US10326153B2 (en) 2013-12-23 2019-06-18 Robert Bosch Gmbh System and method for returning material from the Br2 side of an H2/Br2 flow battery back after crossover
WO2015100216A1 (fr) * 2013-12-23 2015-07-02 Robert Bosch Gmbh Système et procédé pour renvoyer un matériau depuis le côté br2 d'un arrière de batterie à flux h2/br2 après un croisement
WO2016001392A1 (fr) * 2014-07-04 2016-01-07 Elestor Bv Ensemble batterie rédox à hydrogène
AU2015282903B2 (en) * 2014-07-04 2018-02-22 Elestor Bv A hydrogen-redox flow battery assembly
US10468704B2 (en) 2014-07-04 2019-11-05 Elestor Bv Hydrogen-redox flow battery assembly
EP2963723A1 (fr) 2014-07-04 2016-01-06 Elestor BV Ensemble de batterie à flux hydrogène-redox
NL2030263B1 (en) 2021-12-23 2023-06-29 Elestor B V A Hydrogen-X flow battery system coupled to a hydrogen pipeline network.
WO2023121454A1 (fr) 2021-12-23 2023-06-29 Elestor B.V. Système de batterie à circulation d'hydrogène x couplé à un réseau de conduites d'hydrogène
WO2024044461A1 (fr) * 2022-08-22 2024-02-29 Ess Tech, Inc. Système de cellule de rééquilibrage pour batterie à flux redox
WO2025198474A1 (fr) 2024-03-22 2025-09-25 Elestor B.V. Réservoir de stockage d'électrolyte pour système de batterie à flux redox
NL2037312B1 (en) 2024-03-22 2025-10-02 Elestor B V electrolyte storage tank for a redox flow battery system
WO2025250014A1 (fr) 2024-05-30 2025-12-04 Elestor B.V. Procédé de récupération de composés métalliques à partir d'un système de pile à circulation

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