EP3397794A1 - Système et procédé de génération d'hydrogène gazeux à la demande - Google Patents

Système et procédé de génération d'hydrogène gazeux à la demande

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Publication number
EP3397794A1
EP3397794A1 EP16836107.9A EP16836107A EP3397794A1 EP 3397794 A1 EP3397794 A1 EP 3397794A1 EP 16836107 A EP16836107 A EP 16836107A EP 3397794 A1 EP3397794 A1 EP 3397794A1
Authority
EP
European Patent Office
Prior art keywords
electrolytic solution
valve
deposition
fluid communication
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.)
Pending
Application number
EP16836107.9A
Other languages
German (de)
English (en)
Inventor
Federico LONGHINI
Simone LONGHINI
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.)
Individual
Original Assignee
Individual
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 Individual filed Critical Individual
Publication of EP3397794A1 publication Critical patent/EP3397794A1/fr
Pending 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
    • H01M14/00—Electrochemical current or voltage generators not provided for in groups H01M6/00 - H01M12/00; Manufacture thereof
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B5/00—Electrogenerative processes, i.e. processes for producing compounds in which electricity is generated simultaneously
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M16/00—Structural combinations of different types of electrochemical generators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M16/00—Structural combinations of different types of electrochemical generators
    • H01M16/003—Structural combinations of different types of electrochemical generators of fuel cells with other electrochemical devices, e.g. capacitors, electrolysers
    • 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
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/0656—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants by electrochemical means
    • 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
    • H01M8/22—Fuel cells in which the fuel is based on materials comprising carbon or oxygen or hydrogen and other elements; Fuel cells in which the fuel is based on materials comprising only elements other than carbon, oxygen or hydrogen
    • H01M8/225—Fuel cells in which the fuel is based on materials comprising particulate active material in the form of a suspension, a dispersion, a fluidised bed or a paste
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/16—Electrolytic production, recovery or refining of metals by electrolysis of solutions of zinc, cadmium or mercury
    • 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
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
    • 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 invention relates to a system and a method for generation of gaseous hydrogen.
  • energy- storage technologies may be essential, for example, also in view of a transition towards sustainable production of energy.
  • energy storage enables energy production to be rendered independent of energy consumption, thus reducing the need for a constant monitoring and prediction of the user peak demand.
  • Energy storage provides tangible economic benefits in so far as it enables reduction of energy production of a plant.
  • the target of production in energy terms would be that of an average demand instead of a peak demand.
  • the energy-transmission lines, along with the associated equipment, can thus be sized to meet average power demands.
  • energy storage mitigates some problems associated to the intermittence in generation of energy from renewable sources (primarily, solar energy and wind and tidal power).
  • Renewable energy sources with efficient solutions of energy storage can guide transition from the traditional centralized production of power such as that from coal-fired, gas-fired, nuclear-fired plants, which require a grid for longdistance transmission of energy, towards systems with DER (Distributed Energy Resource) systems.
  • DER Distributed Energy Resource
  • DER systems include, for example, small power generation sources located in the proximity of the place of use of the electrical energy (e.g., for domestic or professional use).
  • An efficient energy-storage solution hence provides an alternative to the costly improvement of the traditional electric-power distribution grid.
  • DER systems in fact offer users the possibility of benefiting from reduced costs, a higher reliability of the service, a higher quality of the power generated, a greater energy efficiency, as well as also energy independence.
  • renewable technologies for generation of electrical energy of a distributed type, together with the so-called “green energies”, such as wind power, solar (photovoltaic) energy, geothermal energy, energy from biomasses, or energy from hydroelectric production, can also provide a significant environmental benefit.
  • green energies such as wind power, solar (photovoltaic) energy, geothermal energy, energy from biomasses, or energy from hydroelectric production
  • Energy-distribution devices in DER systems comprise a panorama of technologies including fuel cells, micro-turbines, reciprocating motors, and technologies for reduction of the load and for energy management.
  • DER technology also includes electronic power interfaces, as well as communication and control devices for the distribution and efficient operation of the individual generation units, multiple packet systems, and aggregated supply blocks.
  • the primary fuel for many distributed generation systems is natural gas, but hydrogen is a natural candidate for future uses.
  • Gaseous hydrogen is an effective energy carrier with a very high specific energy content (approximately, 120 MJ/kg). It has been demonstrated that hydrogen can be used for transport, heating, and electric-power generation, and can replace all fuels commonly used in currently available applications.
  • Hydrogen is the lightest and most abundant element on Earth. However, unlike oxygen, hydrogen is not available in free form in nature in significant concentrations. Hydrogen is produced using both renewable energy sources and non-renewable energy sources, exploiting a wide range of process technologies.
  • the technologies available for the production of hydrogen include reforming of natural gas, gasification of carbon from biomasses, and water splitting by electrolysis, photo-electrolysis, photo-biological production, thermochemical cycles of water splitting, and high-temperature decomposition.
  • the main processes for the production of hydrogen are in general water electrolysis and reforming of natural gas.
  • the simplest technology consists in storage of gaseous hydrogen in compressed form. It is a solution that can be pursued at ambient temperature, and management of the steps of compression and release of hydrogen is likewise very simple. However, the storage density (understood in terms of energy density) is very low if compared to other processes.
  • the main problem of the above technologies consists in the weight of the material that provides the absorbent substrate.
  • a storage tank with substrate of metal hydrides would weigh approximately 600 kg, an enormous weight if compared to the 80 kg of a tank of compressed hydrogen of comparable size.
  • the object of the invention is to solve the technical problems mentioned previously.
  • the object of the invention is to provide an effective and economic solution for energy storage aimed at the production of hydrogen, also with recharging cycles that will be characterized by a high energy-storage density and that will likewise enable release of hydrogen on demand.
  • a system for generating gaseous hydrogen on demand including:
  • first electrolytic solution including water and a first alkaline electrolyte
  • At least one deposition electrolytic cell which includes an anode and a cathode and is configured for processing a flow of the first electrolytic solution supplied, during operation, by means of said first supply unit;
  • a second storage environment configured for collecting a metal that, during operation, is deposited at the cathode of the at least one deposition electrolytic cell
  • At least one generation galvanic cell configured for processing a flow of a second electrolytic solution and metal collected in the second storage environment and releasing gaseous hydrogen and electrical energy.
  • the object of the invention is moreover achieved by a method for generating gaseous hydrogen on demand, the method comprising: - a step of supply of a first electrolytic solution from a first storage environment to at least one deposition electrolytic cell, said first electrolytic solution including a first alkaline electrolyte and water, each deposition electrolytic cell including an anode and a cathode and being controlled for processing said first electrolytic solution to obtain deposition of a metal, in particular zinc, on said cathode;
  • FIG. 1 is a schematic block diagram of a system according to the invention.
  • Figures 2A and 2B are two schematic circuit representations of two sections of the system according to the invention, where Figure 2B is the prosecution of Figure 2 A starting from the reference A marked with a dashed-and- dotted line in Figure 2A;
  • FIG. 3 is a schematic sectioned perspective view of an deposition electrolytic cell of the system according to the invention.
  • Figure 4 is cross-sectional view corresponding to that of Figure 3;
  • FIG. 5 is a schematic sectioned perspective view of a generation galvanic cell of the system according to the invention.
  • Figure 6 is cross-sectional view corresponding to that of Figure 5;
  • FIG. 10A and Figure 10B illustrate schematic cross-sectional views of a component of Figure 9;
  • FIG. 11 illustrates an exploded perspective view of a galvanic cell used in yet a further embodiment of the system according to the invention.
  • FIG. 12 is a cross-sectional view of the cell of Figure 11;
  • FIG. 12A illustrates a variant of the circuit associated to a specific embodiment of the galvanic cells
  • FIG. 13 is a schematic view of a battery (the so-called stack) of galvanic cells of the type of Figure 12;
  • FIG. 14 is a schematic view of an embodiment of an electrode of the cell of Figures 11 to 13;
  • FIG. 15 is an equivalent electrical diagram of a generation section including a stack made up, by way of example, of four generation cells.
  • the reference SY in Figure 1 identifies a system for the generation of gaseous hydrogen on demand according to various embodiments of the invention.
  • the system SY includes an energy-storage section designated by the reference ST and a section for generation of hydrogen and electrical energy designated by the reference GE.
  • the energy-storage section is supplied with a first electrolytic solution taken from a first storage environment designated by the reference 1.
  • the first storage environment 1 is supplied, albeit not necessarily in an exclusive way, by means of the products of reaction of the generation unit GE.
  • the storage section ST releases gaseous oxygen into the atmosphere and releases as product of reaction a second electrolytic solution and a metal in substantially pure form, which can be stored, in combination or alternatively, in a second storage environment designated by the reference 2.
  • the second storage environment 2 provides the supply for the generation section GE, which yields electrical energy, gaseous hydrogen that supplies a fuel cell FC (or in general a user device, such as a boiler or an internal-combustion engine), and a third electrolytic solution, which preferably has the same composition as the first electrolytic solution (substantially there is a reintegration of electrolyte, and hence a reintegration of the first electrolytic solution) and supplies the first storage environment 1.
  • the fuel cell FC releases water (H 2 0), which is preferentially supplied again into the storage section ST (as an alternative to the generation section GE) to constitute or reintegrate the first electrolytic solution (in this case as solvent, and not as electrolyte).
  • the generation section ST includes the first storage environment 1 for the first electrolytic solution.
  • the first electrolytic solution is an aqueous solution including water and a first alkaline electrolyte, in particular potassium zincate (K 2 Zn(OH) 4 ).
  • the first storage environment 1 is preferentially a service tank, in which a certain amount of the first electrolytic solution is accumulated. This amount may possibly be integrated with the contribution of an external tank of larger size, separate from the system SY.
  • the first storage environment 1 is in fluid communication with a first supply unit PI, in particular a pump, the intake port of which is in fluid communication with an outlet port of the storage environment 1.
  • a first supply unit PI in particular a pump
  • the storage section ST further includes at least one deposition electrolytic cell, which is configured for processing the first electrolytic solution coming from the tank 1.
  • at least one deposition electrolytic cell is present, in the preferred embodiment illustrated herein there are present a plurality of electrolytic cells (three in this case) CI, C2, Cn, where the last reference Cn indicates that the number may even be different from (greater or smaller than) three, which is the number represented.
  • each cell CI is a cell CI
  • C2 is an electrolytic cell, which includes an anode AN_C, in this case a positive electrode, and a cathode CT C, in this case a negative electrode, and preferably has a cylindrical geometry.
  • anode AN C is obtained as an elongated cylindrical element surrounded by a cylindrical shell constituting the cathode.
  • the anode AN C may be made of nickel, nickel alloys, nickel-based composite materials (e.g., activated carbon + powdered nickel + PTFE as binder, or else Raney nickel + PTFE as binder), or stainless steel. As an alternative, it may comprise a support (e.g., made of steel), applied on which are metals such as platinum and/or palladium, having the function of catalytic components.
  • the cathode CT C may be made, for example, of zinc, stainless steel, or nickel or its alloys. More in general, the cathode CT C is made of a conductive material resistant to the alkaline solution and on which the zinc will have low adherence.
  • anode AN C and the cathode CT C are moreover connected to an electric- power supply source, in particular a voltage generator, preferentially an electronically controlled voltage generator.
  • the terms used herein are not to be understood in an exclusive or limiting way with respect to the technical function thereof.
  • the supply manifold Ml and the discharge manifold M2 may occasionally reverse their function depending upon the step of the method of generation of hydrogen that is in progress.
  • the first supply manifold Ml comprises a first working port Mi l configured for receiving a flow of the first electrolytic solution from the first supply unit PI and further includes a plurality of second working ports Ml 2, present in which is one port M1 2 for each cell CI, C2, Cn.
  • Each working port M1 2 is in particular in fluid communication with the reaction volume VC and is configured for conveying the first electrolytic solution into the corresponding deposition electrolytic cell.
  • the first discharge manifold M2 in turn includes a first working port M2 1 for each deposition electrolytic cell CI, C2, Cn, where each working port M2 1 is configured for receiving a flow of product of reaction from the deposition cells CI, C2, Cn.
  • the product of reaction of the cells CI, C2, Cn includes a second electrolytic solution, which in turn includes water and a second alkaline electrolyte (potassium hydroxide - KOH), as will be described hereinafter.
  • the first discharge manifold M2 further includes a second working port M2 2 configured for discharging the flow of product of reaction of the deposition cells CI, C2, Cn.
  • the first working port Mi l of the first supply manifold Ml and the first supply unit PI are in fluid communication regulated by a first valve VI, which can be switched between an open position and a closed position.
  • the second working port M2 2 of the first discharge manifold M2 is in fluid communication with a circuit node J, and the fluid communication of the port M2 2 with the circuit node J is regulated by a second valve V2, which can be switched between an open position and a closed position.
  • the first discharge manifold M2 further includes a third working port
  • a third valve V3 which can be switched between an open position and a closed position.
  • the first supply manifold Ml in turn includes a third working port
  • a fourth valve V4 which can be switched between an open position and a closed position.
  • the circuit node J is moreover in fluid communication with:
  • the storage unit ST further includes a filter element Fl set downstream of the circuit node J, in particular set between the circuit node J and the fifth valve V5, and the circuit node J and the sixth valve V6.
  • the filter element Fl is substantially located upstream of a bifurcation that starts therefrom and connected to which are the valves V5 and V6.
  • the generation section GE includes at least one generation galvanic cell configured for release of gaseous hydrogen and electrical energy. Even though embodiments may be envisaged that include just one generation galvanic cell, in the preferred embodiment illustrated herein a plurality of galvanic cells are present (three in this case) Dl, D2, Dn, where the last reference Dn indicates that the number may also be different from three (either greater or smaller), which is the number represented.
  • each generation galvanic cell includes an anode AN D (in this case a negative electrode) and a cathode CT D (in this case a positive electrode) and is configured for processing an electrolytic solution including an alkaline electrolyte and a metal dispersed therein, corresponding to the metal deposited by electrolysis in the reaction cells CI, C2, Cn. Following upon processing, each cell is configured for releasing gaseous hydrogen, electrical energy, and a third electrolytic solution.
  • anode AN D is physically and functionally constituted at the moment of introduction of zinc (or in general of a metal deposited on the cathode CT C and subsequently removed) within the cell, it being defined by the zinc itself.
  • the flow of chemical species that supplies the cells Dl, D2, Dn corresponds to a number of products of reaction of the deposition electrolytic cells, and in particular those stored in the storage environment 2 (i.e., not only the metal deposited by electrolysis, but also the second electrolytic solution of water and potassium hydroxide - KOH), the third electrolytic solution has the same composition as the first and functions as reintegration of the electrolytic solution in the first storage environment 1.
  • the cells Dl, D2, Dn are cylindrical cells that include a hollow cylindrical shell and an elongated cylindrical element that is coaxial to the cylindrical shell and defines the cathode CT D.
  • the cathode CT D is preferably obtained from a porous element made of nickel foam (or else a nickel mesh, or a stainless-steel mesh) (the so-called “hydrogen evolving electrode”).
  • the cylindrical shell functions as current collector and may be made of metal material or even of plastic material, with application of a copper plate within it, preferably enriched with tip collectors BR.
  • the cells Dl, D2, Dn are moreover closed at a base by a blind bottom plate BT.
  • Set in the toroidal volume comprised between the cathode CT D and the cylindrical shell is a cylindrical porous membrane PM, preferentially a polymeric membrane.
  • the membrane PM is porous in regard to liquids and gases, but withholds the powdered zinc.
  • the anode AN D may be constituted, which corresponds to a toroidal volume of powdered zinc contained within the volume VD1.
  • the second supply manifold M3 includes a first working port M3 1 in fluid communication with the second storage environment 2, in particular with an outlet port thereof, where the fluid communication is regulated by a seventh valve V7, which can be switched between an open position and a closed position.
  • the second supply manifold M3 further includes a second working port M3 2 for each generation cell Dl, D2, Dn, configured for supplying the corresponding generation cell with the electrolytic solution and the metal dispersed therein, in the embodiment illustrated the second electrolytic solution and the metal stored in the environment 2.
  • each working port M3 2 is in fluid communication with the volume VD1, as illustrated in Figures 5 and 6.
  • conductive electrolyte KOH
  • a "mechanical” solution may be adopted, by inserting a device for physical separation between the manifold and the cells, such as a rotary feed tube distributor of the type illustrated in US 6,162,555 (which can in general be applied regardless of the geometry of the cells, but is preferably applied in the case of plane cells, which will be described hereinafter), or else an "electrical" solution using the so-called shunt resistors.
  • Rmi, Rmo are the shunt resistances of the inlet manifold (M3) and discharge manifold (M4); Ri, Ro are the shunt resistances of the channels at inlet to and outlet from the cells Dl, D2, D3, Dn; and
  • Rc is the internal resistance of the cell (Vo is the voltage to the electrodes of the cell; LD is the electrical load applied to the stack of cells).
  • the second discharge manifold M4 includes a first working port M4 1 for each generation cell Dl, D2, Dn, which is configured for receiving gaseous hydrogen and the third electrolytic solution from the corresponding cell.
  • the membrane PM is permeable in regard to the electrolytic solution that supplies the galvanic cell, but is impermeable in regard to the metal dispersed in the electrolytic solution itself, which in this way remains confined between the cylindrical shell and the membrane PM.
  • the electrolytic solution can, instead, traverse the membrane PM and invade the volume VD2.
  • the anode AN D and the cathode CT D of the galvanic cells Dl, D2, Dn are preferentially electrically connected together by means of two-position switches (open/closed, see switch SW1 in Figure 7) or rheostatic switches (see switch SW2 in Figure 8), which can be activated by the user, according to the demand for electrical energy, by means of an ordinary manual or electronic command.
  • switches SW1 in Figure 7 open/closed, see switch SW1 in Figure 7
  • rheostatic switches see switch SW2 in Figure 8
  • the cylindrical shell of the cells Dl, D2, Dn is moreover preferentially provided, on part or all of its inner surface, with an array of tip electrodes BR, which, as will be seen hereinafter, are configured for conveying within the anode AN_D the electricity that enters the cell itself.
  • the second discharge manifold M4 further includes a second working port M4 2 configured for discharging the third electrolytic solution towards an intake environment of a second supply unit P2, which in particular includes a second pump, which is configured for circulation of the third electrolytic solution within the generation section GE.
  • the second discharge manifold M4 includes a third working port M4 3, configured for discharging gaseous hydrogen towards the outside, regulated by a valve G2.
  • a valve G2 To the valve G2 there may preferentially be connected the inlet of the fuel cell FC.
  • the second supply unit P2 in particular a delivery port of the corresponding second pump, is moreover in fluid communication with the first working port M3 1 of the second supply manifold M3, where the fluid communication is regulated by an eighth valve V8, which can be switched between an open position and a closed position.
  • the supply unit P2 in particular a delivery port of the corresponding second pump, is in fluid communication with the first storage environment 1, in particular the inlet port thereof.
  • the fluid communication is regulated by a ninth valve V9, which can be switched between an open position and a closed position.
  • the first electrolytic solution stored within the first storage environment 1 is a certain amount of the first electrolytic solution, which in the preferred embodiment considered herein includes water and a first alkaline electrolyte consisting of potassium zincate (K 2 Zn(OH) 4 ).
  • the method for generation of gaseous hydrogen on demand comprises a first step of supply of the first electrolytic solution from the first storage environment 1 to the one or more deposition electrolytic cells CI, C2, Cn.
  • valves VI, V2 and V5 are kept in the open position, whereas the valves V3, V4 and V6 are kept in the closed position.
  • an obligate path is defined for the electrolytic solution, set in circulation by means of the supply unit PI, which envisages traversal of the valve VI, invasion of the manifold Ml through the port Mi l, and entry into the cells CI, C2, Cn, through the ports Ml_2.
  • the electrolytic solution that enters the volume VC of the cells CI, C2, Cn is then subjected to electrolysis.
  • the cells CI, C2, Cn are electrically supplied with a voltage applied between the anode AN C and the cathode CT C so as to trigger the following reaction:
  • a second product of reaction is (basically) pure metallic zinc, which deposits on the cathode in the spongy aggregate form of metal particles.
  • a third product of reaction is water (H 2 0), which, together with potassium hydroxide (KOH), will provide - according to the modalities that will be described shortly - the second electrolytic solution referred to above.
  • KOH potassium hydroxide
  • a fourth product of reaction is gaseous oxygen (0 2 ), which is released into the atmosphere through the port M2 4 and the valve Gl .
  • operation of the cells CI, C2, Cn envisages an axial flow (either purely axial or with a prevalently axial component) from one end to the other end of the cells.
  • the supply (ports M1 2) is preferably from beneath, and the outlet of the liquid products of reaction (second electrolytic solution) and gaseous products of reaction (oxygen) through the ports M2 1 is consequently from above.
  • the reaction of electrolysis occurs substantially in a regime of permanent flow.
  • the circulation of the electrolytic solution of potassium zincate (K 2 Zn(OH) 4 ) through the cells CI, C2, Cn yields a second electrolytic solution, which, owing to its recirculation through the cells CI, C2, Cn by the unit PI, is progressively richer in potassium hydroxide (KOH) and progressively poorer in potassium zincate (K 2 Zn(OH) 4 ).
  • the reaction referred to above, and therewith the supply of the electrolytic solution (originally, first electrolytic solution, progressively, second electrolytic solution) by the supply unit PI to the cells CI, C2, Cn proceeds as long as the concentration of potassium zincate (K 2 Zn(OH) 4 ) in the second electrolytic solution (with evolving concentrations of the chemical species) that supplies the cells CI, C2, Cn reaches minimum values, in particular lower than a threshold value.
  • the criterion for determining the threshold value is of an energy nature. The expenditure in terms of energy per mass of zinc deposited increases as the concentration of zincate ions (Zn(OH) 4 2+ ) decreases.
  • the threshold value is chosen for the purpose of limiting the specific energy expenditure below a given value.
  • the space between the electrodes AN C and CT C during deposition tends to decrease on account of the growth of the layer of zinc. It is necessary to prevent shorting between the electrodes and prevent the passageway by the flow of electrolyte from being blocked (in addition to preventing detachment of the zinc during deposition).
  • the next step is that of storage of the metallic zinc deposited on the cathode CT C in the second storage environment 2.
  • the valves VI, V2, and V6 are switched into the closed position, whereas the valves V3, V4, and V5 are switched into the open position.
  • the manifold M2 that receives a flow of the second electrolytic solution with a low concentration of potassium zincate (K 2 Zn(OH) 4 ) and a high concentration of potassium hydroxide (KOH) through the valve V3 and the port M2 3.
  • the aforesaid electrolytic solution invades the manifold M2 and through the ports M2 1 invades the cells CI, C2, Cn with an axial flow (from top to bottom) opposite to the axial flow (from bottom to top) with which the electrolytic cells are supplied for the reaction of electrolysis.
  • the supply of electricity to each of the cells CI, C2, Cn is interrupted.
  • Circulation of the second electrolytic solution with low concentration of potassium zincate (K 2 Zn(OH) 4 ) and high concentration of potassium hydroxide (KOH) within the cells CI, C2, Cn will provide flushing of the cathode CT C, with consequent detachment of the layer of spongy metallic zinc deposited thereon.
  • a mechanical system for detachment of zinc for example an ultrasound vibration system.
  • the zinc flushed off in this way is then collected, together with the second electrolytic solution with a low concentration of potassium zincate (K 2 Zn(OH) 4 ) and a high concentration of potassium hydroxide (KOH), within the manifold Ml, and from this sent on through the valve V4 and the circuit node J into the filter Fl, where the spongy metallic zinc deposits.
  • the filter Fl separates the solid fraction constituted by metallic zinc from the liquid fraction (water, KOH, K 2 Zn(OH) 4 ).
  • the valves are switched back into the initial configuration (VI, V2, V5 open, V3, V4, V6 closed), and the step of supply of the electrolytic solution restarts, which ceases when the concentration of potassium zincate (K 2 Zn(OH) 4 ) reaches values that render it no longer exploitable, with a further switching of the valves (VI, V2 and V6 closed, V3, V4 and V5 open) and a subsequent step of discharge of the zinc into the filter Fl in addition to the zinc that was deposited previously.
  • the aqueous solution obtained following upon this step corresponds to the second electrolytic solution, including water and potassium hydroxide (KOH) (in addition to minimum amounts of potassium zincate - K 2 Zn(OH) 4 ), i.e., in which the evolution of the concentrations of potassium hydroxide (KOH) and potassium zincate (K 2 Zn(OH) 4 ) has reached a condition that renders it exploitable in another process within the system SY, in particular in the generation section GE.
  • KOH potassium hydroxide
  • the storage section ST and the generation section GE can be installed in different places.
  • the storage environment 2 is obtained as energy storage tank that can be separated and transferred in a completely safe way for a subsequent use as supply for the galvanic cells Dl, D2, Dn.
  • the tank 2 does not contain any gas under pressure, and in particular does not contain gaseous hydrogen under pressure (which would be highly inflammable). Instead, the tank 2 contains an inert material, such as zinc, which is moreover perfectly eco-compatible.
  • the zinc can be then transferred elsewhere in the tank 2 for use in the generation section GE with the only addition - at the moment of installation in the section GE - of water and an alkaline electrolyte, preferably potassium hydroxide (KOH), which already constitutes the second electrolytic solution.
  • an alkaline electrolyte preferably potassium hydroxide (KOH)
  • KOH potassium hydroxide
  • potassium hydroxide is a compound commercially available at a low cost and in a form that is easily transportable (pellets or powder). Water may normally be taken from the water mains so that it is possible to recreate separately the same conditions of supply proper to the system SY when there exists physical integration (in addition to functional integration) between the two sections ST and GE, i.e., when both the metallic zinc and the second electrolytic solution are stored inside the tank 2.
  • the above process envisages in general a step of supply of the metal (zinc) stored in the second storage environment 2 and of the second electrolytic solution - whether it is already present in the environment 2 or added subsequently - to the one or more generation galvanic cells Dl, D2, Dn.
  • the zinc hence remains concentrated in the toroidal volume VDl and is in contact with the current collector (cylindrical metal shell or copper plate with tip collector BR), which is configured for conveying the flow of electrical charges within the layer of zinc.
  • the current collector cylindrical metal shell or copper plate with tip collector BR
  • the third electrolytic solution continues, progressively enriching itself with potassium zincate (K 2 Zn(OH) 4 ) as it is recirculated to the supply of the galvanic cells Dl, D2, Dn, whereas potassium hydroxide (KOH), as a result, converts by reaction with the zinc to form, among other things, potassium zincate (K 2 Zn(OH) 4 ).
  • the third electrolytic solution invades the second discharge manifold M4 through the ports M4 1, and gaseous hydrogen is released through the port M4 3 and the valve G2, whereas the electrolytic solution is recirculated to intake of the unit P2 through the port M4 2.
  • the presence of the bottom plate BT moreover determines a semi -toroidal flow of chemical species in the cells Dl, D2, Dn, (preferably) with inlet from above and outlet from below.
  • the third electrolytic solution substantially has the same composition as the first electrolytic solution, and - above all - substantially has the same concentration of potassium zincate (K 2 Zn(OH) 4 ) that characterizes the first electrolytic solution in the tank 1 (in addition to minimal amounts of potassium hydroxide - KOH).
  • the third electrolytic solution will not have the same composition as the first electrolytic solution of potassium zincate (K 2 Zn(OH) 4 ) for the simple reason that the sodium hydroxide that is consumed gives rise to sodium zincate (Na 2 Zn(OH) 4 ).
  • the aim is to use the third electrolytic solution as reintegration of the first electrolytic solution without envisaging further treatment stages, it is necessary for the alkaline metal in the electrolyte (zincate) of the first electrolytic solution to coincide with the alkaline metal of the electrolyte (hydroxide) of the second electrolytic solution.
  • a utilizer for example the fuel cell FC
  • a further energy integration can be obtained between the utilizer (FC) and the system SY by sending the oxygen released from the manifold M2 to the supply of the utilizer itself.
  • This second reaction leads to formation of zinc oxide (ZnO), water, and hydroxide ions OH " .
  • the aim is to keep the zinc within the zincate ion, preventing the reaction from proceeding: in this way, there is obtained formation of a supersaturated solution of zincate ions.
  • the advantage over allowing the reaction to proceed is the following: the limit of solubility of zinc oxide (ZnO) in alkaline solutions of potassium hydroxide (KOH) is in the region of 60 g/1 of Zn, whereas it is possible to obtain concentrations even 3-4 times higher for the solubility of zincate (Zn(OH) 4 2" ) (formation of supersaturated solutions of zincate with even 300 g/1 of Zn).
  • the energy is stored without gas under pressure and without hydrogen-retention substrates.
  • the energy is simply stored, so to speak, in the form of a precursor consisting of metallic zinc.
  • Zinc presents no difficulties or restrictions to transport, is eco- compatible, and can be easily be combined with an electrolytic solution obtained at the moment of use on a generation section GE located elsewhere with respect to the storage section ST.
  • the system may moreover present different power levels according to the size and/or the number of the cells CI, C2, Cn that define the maximum power that can be stored.
  • the electric power at output depends instead upon the size of the hydrogen-evolving electrode that constitutes the cathode CT D of each cell Dl, D2, Dn.
  • the capacity of the system i.e., the amount of energy storable per unit time depends, instead, solely upon the size of the tank 1, which defines the amount of the first electrolytic solution circulating in the system.
  • the rate of the electrochemical reaction within the galvanic cells Dl, D2, Dn can be significantly improved with a preheating of the second electrolytic solution to a temperature of approximately 40-80°C, which is a preheating temperature that can be typically obtained by means of integration of the system SY with a thermal solar plant, or else by means of exploitation of the waste heat of the fuel cell FC.
  • Cn enables minimization of the size of the machine since the usable current density (as regards peak values; in steady-state conditions, the values are lower) is of approximately 30-40 A/dm 2 ; consequently, it is possible to obtain cells with smaller electrodes.
  • the maximum usable current density would be approximately one order of magnitude lower (3-4 A/dm 2 ), beyond which complete electrolysis would be obtained, with generation of hydrogen.
  • the zinc can be left immersed in the electrolytic solution (KOH + H 2 0) without this producing hydrogen, especially if the zinc is pure. It is possible to resume zinc deposition subsequently, and it is moreover possible to store zinc and electrolytic solution even together in the cells CI, C2, Cn. This would be impossible in an acid environment since this would erode the zinc.
  • the solution according to the invention affords an economic advantage: in the aforesaid known solutions, there is the need to increase the number of cells to increase the capacity of the system, whereas in the solution according to the invention it is sufficient to increase the size of the tank.
  • the metal that functions as precursor for energy storage is zinc
  • other metals for example iron or manganese
  • the storage section ST' includes the tank 1 for the first electrolytic solution, once again an aqueous solution including water and a first alkaline electrolyte, in particular potassium zincate (K 2 Zn(OH) 4 ).
  • the tank 1 is in fluid communication with the pump PI, in particular a pump the intake port of which is in fluid communication with an outlet port of the tank l .
  • the storage section ST' further includes at least one deposition electrolytic cell, which is configured for processing the first electrolytic solution coming from the tank 1.
  • at least one deposition electrolytic cell which is configured for processing the first electrolytic solution coming from the tank 1.
  • a plurality of electrolytic cells are present (three in this case) CI ', C2', Cn', where the last reference Cn indicates that the number may also be different from (greater or smaller than) three, which is the number represented.
  • the electrolytic cells CI ', C2', Cn' are immersed in a containment volume VS, which in this embodiment is functionally equivalent to the storage environment (or tank) 1 for the section ST.
  • the volume VS includes a supply port C IN, which receives fluid from the pump PI, and a discharge port C OUT, which is configured for disposing of the (solid and fluid) products contained in the volume VS.
  • a supply port C IN which receives fluid from the pump PI
  • a discharge port C OUT which is configured for disposing of the (solid and fluid) products contained in the volume VS.
  • the port C OUT is in fluid communication with the inlet port of the second storage environment 2, where the fluid communication is regulated by the valve V6, as described previously.
  • each cell CI ', C2', Cn' has the same structure as the cells CI, C2, Cn (electrolytic cell including the anode AN C, positive, and the cathode CT C, negative, and preferably having a cylindrical geometry). Consequently, the corresponding description already presented in regard to the aforesaid cells altogether applies here, provided that this does not regard aspects that are manifestly incompatible.
  • each deposition electrolytic cell CI ', C2', Cn' Operatively associated to each deposition electrolytic cell CI ', C2', Cn' is an impeller EVIl, EVI2, EVIn housed in a corresponding control volume and functionally constituting a supply unit configured for circulation of the first electrolytic solution through the corresponding deposition electrolytic cell CI ', C2', Cn'.
  • the function of the impellers EVIl, EVI2, EVIn is similar to that of the pump PI in the section ST.
  • Each control volume includes one or more ports PT in communication with the inside of the containment volume for:
  • the first direction of rotation corresponds to a step of deposition of metal on the cathode CT C of the deposition electrolytic cell
  • the second direction of rotation corresponds to a step of scavenging/washing off of the metal deposited by the cathode CT C.
  • Each of the impellers EVIl, IM2, EVIn can be driven in rotation independently of the other impellers.
  • the pump PI merely integrates operation of the impellers EVIl, EVI2, EVIn. It loses its function of circulation of the first electrolytic solution (which it possesses, instead, in the section ST) during the step of deposition or scavenging of the cells CI ', C2', Cn' for removal of the zinc, but functions as a simple pump for loading the first electrolytic solution into the volume VS.
  • the impeller or impellers are driven in the first direction of rotation, as illustrated in Figure 10A.
  • the valve V6 is in the closed position, whereas the pump PI is stationary.
  • the impellers EVIl, EVI2, EVIn are driven in rotation in the opposite direction.
  • the powdered zinc that is emptied out through the ports PT migrates towards the bottom of the volume VS by gravity, traversing the shielding filter F l '.
  • the latter prevents any re-intake of the metal powders from the bottom of the volume VS in the case where a new step of zinc deposition is set under way (provided that the concentration of zinc in the first electrolytic solution - evolving towards the composition of the second electrolytic solution - so enables).
  • the metal powders simply remain resting on the bottom, without being entrained in suspension by the motion of the fluid in the volume VS.
  • the valve V6 is switched into the open position, and the ensemble of the second electrolytic solution and the powdered zinc is emptied into the tank 2.
  • the liquid fraction can be emptied into a separate storage environment, leaving in the tank 2 just the powdered zinc as described previously.
  • the main advantage of a system SY including the generation section ST' consists in the fact that it is possible to eliminate the inlet and discharge manifolds Ml, M2, together with the corresponding valves VI to V5 (with considerable simplification), and likewise in the fact that it is possible to vary the amount of energy - or rather of precursor - stored, simply by varying the number of impellers that are simultaneously active.
  • each cell Dl ', D2', Dn' includes:
  • an inlet body CM Dl coupled to the current collector CC D and configured for receiving said second electrolytic solution and the metal (zinc) deposited in the deposition electrolytic cells, where the metal (in powder form) defines an anode AN D' of the cell;
  • CM D2 which is configured for collecting gaseous hydrogen and - according to the structure of the cathode CT D' - a second electrolytic solution, and is in fluid communication with the first working port M4 1 of the second discharge manifold M4 for release of gaseous hydrogen and the second (evolving) electrolytic solution; in certain embodiments, as will be seen hereinafter, hydrogen and the second electrolytic solution can be released in separate environments.
  • the current collector CC D is operatively associated to the inlet body
  • the collector CC D can be set within the body CM Dl in a position opposite to the membrane PM or in an intermediate position, or else again can be set in contact with or in the strict proximity of the membrane PM, in which case the collector CC D will have to provide areas of passage for the second electrolytic solution (e.g., it may be made like a copper mesh);
  • the porous membrane PM is set between the cathode CT D' and the inlet body CM Dl (in certain embodiments, the membrane PM is laminated with the cathode, see hereinafter);
  • the discharge body CM D2 is set on an opposite side of the cathode CT D' with respect to the porous membrane PM; in this way, the two bodies CM Dl and CM D2 are located in end positions of the cell.
  • the cells Dl ', D2', Dn' are well suited, as a result of their plane geometry, to the constitution of a stack of cells, which will provide not only an electrical connection in series between the galvanic cells (as on the other hand is in any case obtained in the cells Dl, D2, Dn), but also a mechanical connection.
  • the cells Dl ', D2', Dn' are functionally identical to the cells Dl, D2, Dn in so far as they perform, macroscopically, the same function.
  • the intake of the powdered zinc and of the second electrolytic solution into the volume VD1 can be done from above as illustrated in Figures 11 and 12 (e.g., from the manifold M3 through the corresponding ports M3 2, or else from a hopper that receives zinc and the second electrolytic solution from the manifold M3 or functions itself as manifold M3, with corresponding valve for supply of the cells), or else can be done by means of passages orthogonal to the plane of the cell (i.e., that have a direction that proceeds from the collector CC D to the discharge body CM D2), which themselves constitute the inlet and discharge manifolds M3, M4;
  • the current collector CC D which is plane and not cylindrical, can be installed in a slightly inclined position to favour descent of the zinc particles
  • the cathode CT D' can be obtained in a double-layered configuration, including a hydrophilic layer and a hydrophobic layer, where the hydrophilic layer faces the porous membrane PM, whereas the hydrophobic layer faces the volume VD2.
  • the cathode CT D' can be obtained with a triple-layered structure, as illustrated in Figure 14.
  • An electrode of this sort comprises, all laminated together, from right to left as viewed in the figure:
  • hydrophilic layer HF made of activated carbon, nickel, and PTFE as binder, or else Raney nickel + PTFE; this layer is permeable to the liquid (second electrolytic solution in this case) and to the gas (H 2 in this case);
  • a current collector CR (functionally the cathode CT D') made of porous nickel, which is permeable to liquid (second electrolytic solution in this case) and gas (H 2 in this case);
  • FIB hydrophobic layer FIB made of the same material as the layer HF, which is permeable only to gas (H 2 in this case);
  • the cells Dl ' D2', Dn' operate in a way similar to the cells Dl, D2, Dn.
  • the user starts the process of generation of hydrogen simply by closing the electrical circuit at the terminals of the electrodes of the individual cell (or of the series of cells).
  • the anode AN D' constituted by the powdered zinc in the volume VD1, is gradually eroded to form an electrolytic solution progressively richer in potassium zincate (K 2 Zn(OH) 4 ), with simultaneous generation of gaseous hydrogen at the cathode CT D' and simultaneous generation of electrical energy.
  • the electrolytic solution that enters the volume VD1 wets the porous membrane PM and the metallic zinc (the anode AN D'), but only the electrolytic solution passes through the porous membrane PM.
  • the zinc thus remains concentrated in the volume VD1 and is in contact with the current collector (e.g., a copper plate with collector tips BR), which is configured for conveying the flow of electrical charges within the layer of zinc.
  • the current collector e.g., a copper plate with collector tips BR
  • the third electrolytic solution is progressively enriched with potassium zincate (K 2 Zn(OH) 4 ) as it is recirculated to the supply of the galvanic cells Dl ', D2', Dn', whereas potassium hydroxide (KOH) is consequently converted by reaction with the zinc to form, among other things, potassium zincate (K 2 Zn(OH) 4 ).
  • the third electrolytic solution enters the second discharge manifold M4 through the ports M4 1, and gaseous hydrogen is released through the port M4 3 and the valve G2, whereas the electrolytic solution is recirculated to the intake of the unit P2 through the port M4 2.
  • the second electrolytic solution that is recirculated through the cells Dl ', D2', Dn' penetrates the porous membrane PM and the cathode CT D', but in the latter only as far as the end of the hydrophilic layer.
  • the hydrophobic layer can be traversed just by the gaseous hydrogen H 2 . In this way, there will be two separate outlet ports for the products of the electrochemical reaction within the cells Dl ', D2', Dn', i.e.,
  • FIG. 12 A a circuit diagram of the generation section of the system SY is illustrated in the case of double- layered or triple-layered electrode.
  • the references that are identical to the ones previously used designate the same components.
  • the manifold M4 is split into a first manifold and a second manifold.
  • the first manifold (which maintains the simple reference M4) carries the same connections with the rest of the circuit already described.
  • the first manifold M4 loses the valve G2, and is now located on an opposite side with respect to the manifold M3.
  • the ports M4 1 now collect just the second electrolytic solution that is collected in the cavity inside the electrode CT D' and is schematically represented with a dashed line in Figure 12A.
  • the port M4 2 is regularly in fluid communication with the intake of the pump P2.
  • the second manifold identified by the reference M4' includes first working (inlet) ports M4'_l in fluid communication with the volume VD2. These ports collect the gaseous hydrogen that is discharged at the cathode CT D'.
  • the valve G2 is now located on the manifold M4' and conveys gaseous hydrogen on the outside towards a user device, for example the supply of the fuel cell FC.

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Abstract

Cette invention concerne un système (SY) et un procédé de stockage d'énergie destiné à la production ultérieure d'hydrogène gazeux et d'énergie électrique à la demande. Le système (SY) et le procédé exploitent un précurseur d'hydrogène constitué d'un métal déposé par électrolyse d'une solution alcaline dans une cellule de dépôt électrolytique (C1, C2, Cn).
EP16836107.9A 2015-12-30 2016-12-27 Système et procédé de génération d'hydrogène gazeux à la demande Pending EP3397794A1 (fr)

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ITUB2015A009792A ITUB20159792A1 (it) 2015-12-30 2015-12-30 Sistema e procedimento per la generazione di idrogeno gassoso a richiesta
PCT/IB2016/058012 WO2017115269A1 (fr) 2015-12-30 2016-12-27 Système et procédé de génération d'hydrogène gazeux à la demande

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CN114039075A (zh) * 2015-11-18 2022-02-11 英钒能源(加拿大)公司 电极组件以及电解质分布得到改进的液流电池
GB201710224D0 (en) * 2017-06-27 2017-08-09 Univ Surrey Hydrogen generator
FR3079530B1 (fr) 2018-04-03 2024-04-26 Ergosup Procede electrochimique de production d'hydrogene gazeux sous pression par electrolyse puis par conversion electrochimique
GB201811785D0 (en) * 2018-07-19 2018-09-05 Univ Surrey A continuous process for sustainable production of hydrogen
NL2022332B1 (en) * 2018-12-31 2020-07-23 Univ Delft Tech Electrolytic cell for H2 generation
EP4063538A1 (fr) * 2019-11-20 2022-09-28 Hydris Ecotech, S.L. Dispositif pour générer du gaz oxhydrique (hho) et système à cet effet qui inclut ledit dispositif
FR3123064A1 (fr) * 2021-05-19 2022-11-25 Ergosup Générateur électrique à hydrogène comportant un dispositif de stockage et de fourniture d’hydrogène amélioré

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US5208526A (en) * 1990-07-19 1993-05-04 Luz Electric Fuel Israel Ltd. Electrical power storage apparatus
US6162555A (en) * 1999-07-15 2000-12-19 Metallic Power, Inc. Particle feeding apparatus for electrochemical power source and method of making same
US6942105B2 (en) * 2002-05-17 2005-09-13 Metallic Power, Inc. In-line filtration for a particle-based electrochemical power system
AU2003272425A1 (en) * 2002-09-12 2004-04-30 Metallic Power, Inc. Improved fuel for a zinc-based fuel cell and regeneration thereof
ES2607436T3 (es) * 2009-12-14 2017-03-31 Phinergy Ltd. Batería de cinc-aire
DE102012022029A1 (de) * 2012-11-12 2014-05-15 Astrium Gmbh Verfahren und Vorrichtung zur Bereitstellung elektrischer Energie für einen Verbraucher

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