EP3999770A2 - Dispositif de stockage d'hydrogène - Google Patents

Dispositif de stockage d'hydrogène

Info

Publication number
EP3999770A2
EP3999770A2 EP20751203.9A EP20751203A EP3999770A2 EP 3999770 A2 EP3999770 A2 EP 3999770A2 EP 20751203 A EP20751203 A EP 20751203A EP 3999770 A2 EP3999770 A2 EP 3999770A2
Authority
EP
European Patent Office
Prior art keywords
hydrogen storage
storage device
thermally conducting
hydrogen
conducting network
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
EP20751203.9A
Other languages
German (de)
English (en)
Inventor
Luke SPERRIN
Enass Abo Hamed
Peter ITALIANO
Kieran O'DONNELL
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.)
H2GO Power Ltd
Original Assignee
H2GO Power Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by H2GO Power Ltd filed Critical H2GO Power Ltd
Publication of EP3999770A2 publication Critical patent/EP3999770A2/fr
Pending legal-status Critical Current

Links

Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C11/00—Use of gas-solvents or gas-sorbents in vessels
    • F17C11/005—Use of gas-solvents or gas-sorbents in vessels for hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
    • C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
    • C01B3/0031—Intermetallic compounds; Metal alloys; Treatment thereof
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2221/00—Handled fluid, in particular type of fluid
    • F17C2221/01—Pure fluids
    • F17C2221/012—Hydrogen
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2250/00—Accessories; Control means; Indicating, measuring or monitoring of parameters
    • F17C2250/06—Controlling or regulating of parameters as output values
    • F17C2250/0605—Parameters
    • F17C2250/0631—Temperature
    • 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
    • Y02E60/32—Hydrogen storage

Definitions

  • the present invention relates to hydrogen storage devices.
  • Hydrogen is an environmentally-attractive alternative fuel to fossil fuels. Importantly, hydrogen can be produced without the use of fossil fuels, such as by the electrolysis of water using renewable energy. Hydrogen has a relatively high density of energy per unit mass and is effectively non-polluting since the main combustion product is water.
  • a first aspect provides a hydrogen storage device comprising: a pressure vessel, having a first fluid inlet and/or a first fluid outlet, having therein a thermally conducting network optionally thermally coupled to a first heater and/or a first cooler; wherein the pressure vessel is arranged to receive therein a hydrogen storage material in thermal contact, at least in part, with the thermally conducting network; wherein the thermally conducting network preferably has a lattice geometry, a gyroidal geometry and/or a fractal geometry in two and/or three dimensions, comprising a plurality of nodes, having thermally conducting arms therebetween, with voids between the arms; and wherein the thermally conducting network comprises fluidically interconnected passageways therein, for example within the arms and/or the nodes thereof, for flow therethough of a fluid.
  • a second aspect provides a charging station for charging a hydrogen storage device according to the first aspect.
  • a third aspect provides a charging station assembly comprising a charging station according to the second aspect and a hydrogen storage device according to the first aspect.
  • a fourth aspect provides a method of storing hydrogen comprising passing hydrogen gas into a hydrogen storage device according to the first aspect, optionally comprising cooling the thermally conducting network.
  • a fifth aspect provides a method of providing hydrogen comprising releasing hydrogen gas from a hydrogen storage device according to the first aspect, optionally comprising heating the thermally conducting network.
  • a hydrogen storage device as set forth in the appended claims.
  • a charging station for a hydrogen storage device and a charging station assembly comprising a hydrogen storage device and a charging station.
  • a method of charging a hydrogen storage device and a method of releasing hydrogen from a hydrogen storage device is also provided.
  • the first aspect provides a hydrogen storage device comprising: a pressure vessel, having a first fluid inlet and/or a first fluid outlet, having therein a thermally conducting network optionally thermally coupled to a first heater and/or a first cooler; wherein the pressure vessel is arranged to receive therein a hydrogen storage material in thermal contact, at least in part, with the thermally conducting network; wherein the thermally conducting network preferably has a lattice geometry, a gyroidal geometry and/or a fractal geometry in two and/or three dimensions, comprising a plurality of nodes, having thermally conducting arms therebetween, with voids between the arms; and wherein the thermally conducting network comprises fluidically interconnected passageways therein, for example within the arms and/or the nodes thereof, for flow therethough of a fluid.
  • control for charging and/or release of hydrogen from the hydrogen storage device is improved because the flow of the fluid through the interconnected passageways in the thermally conducting network provides for faster, more homogenous, more accurate and/or more precise heating and/or cooling of the thermally conducting network and in turn, the hydrogen storage material in thermal contact therewith. Additionally and/or alternatively, in this way, storing and/or release of the hydrogen may be accelerated since heat generated or required, respectively, may be provided by the flow of the fluid through the interconnected passageways in the thermally conducting network.
  • the hydrogen storage device comprises and/or is a first hydrogen storage device of a set of hydrogen storage devices, for example including a plurality of hydrogen storage devices.
  • a modular assembly for example a stackable assembly, of hydrogen storage devices may be provided.
  • the first hydrogen storage device refers also to the hydrogen storage device and vice versa.
  • the pressure vessel comprises and/or is a first pressure vessel of a set of pressure vessels, for example including a plurality of pressure vessels.
  • a modular assembly of pressure vessels for example a stackable assembly, may be provided.
  • the first pressure vessel also known as a first hydrogen storage vessel
  • the pressure vessel also known as a hydrogen storage vessel
  • the pressure vessel also known as a hydrogen storage vessel
  • the first hydrogen storage device has a hydrogen storage density of at least 0.01 wt.%, at least 0.1 wt.%, at least 1 .0 wt.%, at least 1 .8 wt.%, preferably at least 2.4 wt.%, more preferably at least 3.3 wt.%, most preferably at least 5.5 wt.%, by wt.% of the first hydrogen storage vessel.
  • the first hydrogen storage device has a hydrogen storage density of at most 50 wt.%, at most 40 wt.%, at most 30 wt.%, at most 25 wt.%, preferably at most 20 wt.%, more preferably at most 15 wt.%, most preferably at most 12.5 wt.%, by wt.% of the first hydrogen storage vessel.
  • the hydrogen storage density may exceed energy storage in a Li-ion polymer battery (about 1 .8 wt.% hydrogen storage density equivalent) and may exceed hydrogen storage density in a conventional compressed hydrogen cylinder at 300 bar.
  • the first hydrogen storage device has a hydrogen storage capacity in a range from 1 g to 2,500 g, preferably in a range from 5 g to 1 ,000 g, more preferably in a range from 20 g to 500 g.
  • 1 kg hydrogen may provide about 16.65 kWh of electrical energy, assuming a 50% efficiency in converting from chemical energy of the hydrogen to electrical energy, for example via a fuel cell.
  • the first hydrogen storage device may provide an amount of electrical energy, via a fuel cell for example, in a range from 0.01665 kWh to 41.625 kWh, preferably in a range from 0.08325 kWh to 16.65 kWh, more preferably in a range from 0.333 kWh to 8.325 kWh.
  • the first hydrogen storage device comprises the pressure vessel, having the first fluid inlet and/or the first fluid outlet.
  • the pressure vessel is designed according to a relatively low operating pressure of at most 100 bar, preferably at most 75 bar, more preferably at most 50 bar, even more preferably at most 25 bar, most preferably at most 10 bar.
  • a conventional pressure vessel for high pressure storage of hydrogen i.e. 350 bar to 700 bar
  • a shape of the pressure vessel may be varied, while still maintaining an integrity and/or safety factor thereof.
  • the pressure vessel may be cuboidal such as a square based prism, thereby increasing space utilisation and/or enabling stacking thereof.
  • the pressure vessel may shaped aerodynamically (for example, for aircraft and land craft) or hydrodynamically (for water craft).
  • the first hydrogen storage device for example the pressure vessel, has at most two planes of symmetry, preferably having a shape arranged to reduce drag (i.e. shaped aerodynamically or hydrodynamically), in use.
  • the pressure vessel has a moment of inertia / > / 2 MR 2 about its central axis, where M is the mass of the pressure vessel and R is the mean radius of the pressure vessel, normal to the central axis.
  • the pressure vessel comprises an insulating layer, arranged to thermally insulate the pressure vessel. In this way, control of a temperature of the pressure vessel is improved.
  • the pressure vessel comprises a double wall (i.e. an inner pressure wall and an outer wall, for example an outer skin). In this way, a gap between the double wall may provide an insulating layer and/or comprise an insulating layer.
  • the outer wall may be shaped aerodynamically or hydrodynamically and/or the inner wall is cylindrical, having dished ends.
  • the pressure vessel comprises a passageway arranged, for example axially, to receive the first heater therein.
  • the passageway is a blind passageway.
  • the passageway is a through passageway.
  • the first heater comprises a Joule heater, for example a cartridge heater, and/or a recirculating heater, for example recirculating liquid, and the pressure vessel is arranged, for example comprising a passageway, to interchangeably receive the Joule heater and the recirculating heater therein and/or thereon.
  • the pressure vessel may comprise a through passageway, arranged to receive a cartridge heater inserted therein through an end of the passageway and the opposed end of the passageway may be closed, for example with an insulating plug.
  • the cartridge heater and the plug may be removed and fluid couplings instead fitted to the ends, such that a recirculating liquid, such as heated coolant (i.e. a heating fluid) from a fuel cell to heat the thermally conducting network, may be pumped therethrough.
  • a recirculating liquid such as heated coolant (i.e. a heating fluid) from a fuel cell to heat the thermally conducting network
  • the first hydrogen storage device comprises a passageway, wherein the first hydrogen storage device is arrangeable in: a first configuration to receive a Joule heater in the passageway; and a second configuration to receive a flow of a liquid through the passageway.
  • the first fluid inlet and the first fluid outlet are for the inlet of hydrogen into the pressure vessel and outlet of hydrogen from the pressure vessel, respectively, such as provided, at least in part, by a perforation (i.e. an aperture, a passageway, a hole) through a wall of the pressure vessel.
  • the first fluid inlet and the first fluid outlet are a gas inlet and a gas outlet, respectively.
  • the first fluid inlet and the first fluid outlet are provided by and/or via the same perforation.
  • the pressure vessel has a plurality of gas inlets and/or gas outlets, including the first gas inlet and the first gas outlet respectively.
  • the first fluid inlet and the first fluid outlet comprise releasable couplings, thereby providing coupling thereto and uncoupling therefrom, for example repeatedly, of corresponding couplings.
  • Suitable releasable couplings include push-fit fittings, bayonet fittings, quick connect fittings, cylinder connections to BS341 or DIN 477, hose end fittings, pipe end fittings, tube end fittings and screw fittings. Other releasable couplings are known.
  • the first hydrogen storage device comprises one or more of a thermocouple, a thermowell, a valve, a flashback arrestor, a filter such as a sorbent protection filter, a pressure sensor and a mass flow controller (MFC), for example inline with the first releasable fluid inlet coupling.
  • a valve is generally movable between an open position in which hydrogen can enter or exit the vessel, and a closed position in which the vessel is sealed.
  • the valve is electrically and/or pneumatically actuatable. In this way, the valve may be actuated remotely, for example via a controller.
  • the MFC is electrically actuatable. In this way, the MFC may be actuated remotely, for example via a controller, to control flow of hydrogen therethrough.
  • the pressure vessel is arranged to receive therein the hydrogen storage material in thermal contact, at least in part, with the thermally conducting network.
  • hydrogen storage materials As an alternative to storage of hydrogen as a compressed gas or as a liquid, certain metals and alloys permit reversible storage and release of hydrogen (i.e. hydrogen storage materials). These hydrogen storage materials, due to their high hydrogen-storage efficiency, including low hydrogen loss during cycling and/or reduced heat loss between cycles (thermal efficiency), are considered superior to conventional methods of hydrogen storage. Particularly, by storing hydrogen as a solid hydride, a greater volumetric storage density may be achieved than possible for hydrogen as a compressed gas or as a liquid. In addition, hydrogen storage as a solid hydride presents a reduced safety risk compared with storing hydrogen as a compressed gas or as a liquid. In one example, the hydrogen storage material comprises and/or is a solid hydride.
  • solid-phase metal or alloy materials can store large amounts of hydrogen by absorbing hydrogen with a high density and by forming a metal hydride under a specific temperature/pressure or electrochemical conditions, and hydrogen can be released by changing these conditions.
  • an efficiency of exchange of hydrogen into and out of such storage materials may be enhanced or inhibited by their respective heat transfer capabilities.
  • hydriding also known as hydrogen absorption
  • dehydriding also known as hydrogen desorption
  • moving heat within such storage materials or maintaining preferred temperature profiles across and through volumes of such storage materials becomes a crucial factor in such metal or alloy hydride hydrogen storage materials.
  • release of hydrogen from the crystal structure of a metal hydride requires input of some level of energy, normally heat. Placement of hydrogen within the crystal structure of a metal, metal alloy, or other storage system generally releases energy, normally heat, providing a highly exothermic reaction of hydriding or placing hydrogen atoms within the crystal structure of the hydrideable alloy.
  • the hydrogen storage devices described herein allow for rapid charging and discharging of hydrogen gas while may also be relatively compact. Typically, heat is applied to discharge hydrogen gas, and heat is released and needs to be absorbed (for example, cooling applied) during hydrogen charging.
  • the hydrogen storage devices allow for rapid heating and/or cooling, particularly via the thermally conducting network, which means less heat is wasted to the surroundings during operation, since the charging and discharging times are relatively short.
  • the hydrogen storage devices also enable highly targeted heating, which avoids unnecessary heat loss and associated wasted energy.
  • the hydrogen storage material in the device of the invention can be a compound that is a metal hydride.
  • the elemental metal reacts with hydrogen to form a metal hydride, for example:
  • the hydrogen storage material comprises one or more selected from: a metal for example an alkaline metal, an alkaline earth metal and/or a transition metal; and/or a hydride salt of a metal for example a hydride salt of an alkaline metal, an alkaline earth metal and/or a transition metal and/or a complex salt thereof; and/or a borohydride salt of a metal for example an alkaline metal, an alkaline earth metal and/or a transition metal; and/or a borohydride salt of ammonium and/or alkyl ammonium; and/or mixtures thereof.
  • a metal for example an alkaline metal, an alkaline earth metal and/or a transition metal
  • a hydride salt of a metal for example a hydride salt of an alkaline metal, an alkaline earth metal and/or a transition metal
  • a borohydride salt of ammonium and/or alkyl ammonium and/or mixtures thereof.
  • the hydrogen storage material comprises and/or is an AB X alloy, wherein A is at least one selected from a group consisting of La, Ce, Pr, Nd, Ca, Y, Zr, and Mischmetal, wherein B is at least one selected from a group consisting of Ni, Co, Mn, Al, Cu, Fe, B, Sn, Si, Ti, and x is in a range from 4.5 to 5.5.
  • the hydrogen storage material comprises and/or is an AB/A 2 B alloy, wherein A is at least one selected from a group consisting of Ti and Mg, and B is at least one selected from a group consisting of Ni, V, Cr, Zr, Mn, Co, Cu, and Fe.
  • the hydrogen storage material comprises and/or is an AB 2 alloy, wherein A is at least one selected from a group consisting of Ti, Zr, Hf, Th, Ce and rare earth metals, and B is at least one selected from a group consisting of Ni, Cr, Mn, V, Fe, Mn and Co.
  • the hydrogen storage material comprises an AB x alloy, an AB/A 2 B alloy, an AB 2 alloy, a hydride and/or a mixture thereof, as described above and/or below.
  • the hydrogen storage material comprises at least one selected from a group consisting of Pd, Pt, Ni, Ru, and Re.
  • the hydrogen storage material comprises one or more metal hydrides selected from a group consisting of: lithium hydride (LiH), sodium hydride (NaH), potassium hydride (KH), beryllium hydride (BeFh), magnesium hydride (MgFh), calcium hydride (CaFh), strontium hydride(SrH2), titanium hydride (T1H2), aluminum hydride (AIH3), boron hydride(BH3), lithium borohydride (LiBFU), sodium borohydride (NaBFU), magnesium borohydride (Mg(BH4)2), calcium borohydride (Ca(BH4)2), lithium alanate (LiAIFU), sodium alanate (NaAIFU), magnesium alanate (Mg(AIH4)2), calcium alanate (Ca(AIH4)2), and mixtures thereof.
  • metal hydrides selected from a group consisting of: lithium hydride (LiH), sodium hydride (Na
  • the hydrogen storage material comprises and/or is one or more metal hydrides selected from MgFh, NaAIFU, LiAIFU, LiH, LaNUHe, TiFeH 2 , palladium hydride PdH x , LiNH 2 , LiBH 4 and NaBH 4 .
  • MgH 2 , NaAIH 4 , LiAIH 4 , LiH and/or LaNUHe are preferred.
  • the hydrogen storage material comprises a mixture of two or more of these metal hydrides. These different metal hydrides may have different storage and/or release rates.
  • the hydrogen storage material comprises a dopant such as a catalyst and/or an additive.
  • a dopant such as a catalyst and/or an additive.
  • Ti and/or Zr may be used as catalytic dopants to improve kinetics of hydrogen storage and/or release, such as of sodium alanate.
  • alkali metal alanates were known as non-reversible‘chemical hydrides’, catalysed reversibility offers the possibility of a new family of low-temperature hydrides.
  • the alkali metal alanate-complex hydride, NaAIH4 readily releases and absorbs hydrogen when doped with a TiCb or Ti-alkoxide catalysts.
  • any appropriate transition or rare-earth metal can be used as catalysts, for example Ti, Zr, V, Mn, Fe, Ni, Co, Cr, Nb, Ge, Ce, La, Nd, Pd, Pr, Zn, Al, Ag, Ga, In and/or Cd.
  • Additives include C, which improves thermal transfer of the hydrogen storage material.
  • the hydrogen storage material is provided as particles (for example, in a powder form).
  • the particles are microparticles, having a D50 or a D90 of at most 500 pm, at most 250 pm, at most 100 pm or at most 50 pm. In one example, the particles are microparticles having a D50 or a D10 of at least 1 pm, at least 5 pm, at least 10 pm or at least 25 pm. In one example, the particles are nanoparticles having a D50 or a D90 of at most 500 nm, at most 250 nm, at most 100 nm or at most 50 nm. In one example, the particles are nanoparticles having a D50 or a D10 of at least 1 nm, at least 5 nm, at least 10 nm or at least 20 nm.
  • the particles are a mixture of particles of different sizes, for example a mixture of microparticles and nanoparticles, thereby having a bimodal particle size distribution.
  • a packing efficiency for example a density and/or a surface area of the particles may be increased, thereby increasing storage of hydrogen and/or a rate of storage of hydrogen respectively.
  • the hydrogen storage material is processed, for example by attrition such as ball milling, to reduce a particle size thereof and/or a particle size distribution thereof and/or to incorporate a dopant and/or an additive.
  • hydrogen storage materials As an alternative to storage of hydrogen as a compressed gas or as a liquid, certain unsaturated organic compounds permit reversible storage and release of hydrogen (i.e. hydrogen storage materials). These hydrogen storage materials, due to their high hydrogen- storage efficiency, including low hydrogen loss during cycling and/or reduced heat loss between cycles (thermal efficiency), are considered superior to conventional methods of hydrogen storage. Particularly, by storing hydrogen as a LHOC, a greater volumetric storage density may be achieved than possible for hydrogen as a compressed gas or as a liquid, for example as a cryogenic liquid. In addition, hydrogen storage as a LOHC presents a reduced safety risk compared with storing hydrogen as a compressed gas or as a liquid. In one example, the hydrogen storage material comprises and/or is a LOHC.
  • unsaturated organic compounds can store large amounts of hydrogen by absorbing hydrogen with a high density and by forming saturated organic compounds under a certain temperature/pressure conditions, and hydrogen can be released by changing these conditions.
  • an efficiency of exchange of hydrogen into and out of such storage materials may be enhanced or inhibited by their respective heat transfer capabilities.
  • hydrogenation loading of LOC to LOHC, thereby storing hydrogen
  • dehydrogenation unloading of LOHC to LOC, thereby releasing hydrogen
  • moving heat within such storage materials or maintaining preferred temperature profiles across and through volumes of such storage materials becomes a crucial factor in such hydrogen storage materials.
  • the hydrogen storage devices described herein allow for rapid charging and discharging of hydrogen gas while may also be relatively compact.
  • the hydrogen storage devices allow for rapid heating and cooling, particularly via the thermally conducting network, which means less heat is wasted to the surroundings during operation, since the charging and discharging times are relatively short.
  • the hydrogen storage devices also enable highly targeted heating, which avoids unnecessary heat loss and associated wasted energy.
  • the LOHC comprises and/or is a saturated cycloalkene, aromatic, heterocyclic aromatic and/or a mixture thereof.
  • LOHC generally refers to the hydrogenated (i.e. loaded, saturated) liquid organic compound while LOC generally refers to the dehydrogenated (i.e. unloaded, unsaturated) liquid organic compound.
  • a given molecular name may be used interchangeably to refer to both, with the correct meaning understood by the skilled person in the given context.
  • N-ethylcarbazole N-ethylcarbazole (NEC) may be referred to commonly as a LOHC yet is unsaturated.
  • N-Ethylcarbazole is a well-known LOHC but many other LOHCs are known. With a wide liquid range between -39 °C (melting point) and 390 °C (boiling point) and a hydrogen storage density of 6.2 wt.%, dibenzyltoluene is ideally suited as LOHC material. Formic acid has been suggested as a promising hydrogen storage material with a 4.4 wt.% hydrogen capacity. Using LOHCs relatively high gravimetric storage densities can be reached (about 6 wt.%) and the overall energy efficiency is higher than for other chemical storage options such as producing methane from the hydrogen.
  • the LOHC comprises and/or is N-ethylcarbazole (NEC), monobenzyltoluene (MBT), dibenzyltoluene (DBT), 1 ,2-dihydro-1 ,2-azaborine (AB), toluene (TOL), naphthalene (NAP), benzene, phenanthrene, pyrene, pyridine, chinoline, flurene, carbazole, methanol, formic acid, phenazine, ammonia and/or mixtures thereof.
  • Cycloalkanes reported as LOHCs include cyclohexane, methyl-cyclohexane and decalin.
  • the dehydrogenation of cycloalkanes is highly endothermic (63-69 kJ/mol H2), which means this process requires relatively high temperatures and/or heat inputs.
  • Dehydrogenation of decalin is the most thermodynamically favored among the three cycloalkanes, and methyl- cyclohexane is second because of the presence of the methyl group.
  • Ni, Mo and Pt based catalysts have been investigated for dehydrogenation.
  • coking is still a big challenge for catalyst's long-term stability.
  • hydrogenation and dehydrogenation of LOHCs requires catalysts. It was demonstrated that replacing hydrocarbons by hetero-atoms, like N, O etc. improves reversible de/hydrogenation properties.
  • Formic acid contains 53 g L-1 hydrogen at room temperature and atmospheric pressure. By weight, pure formic acid stores 4.3 wt.% hydrogen. Pure formic acid is a liquid with a flash point 69 °C. However, 85% formic acid is not flammable.
  • Ammonia (NH3) releases H2 in an appropriate catalytic reformer. Ammonia provides high hydrogen storage densities as a liquid with mild pressurization and cryogenic constraints: It can also be stored as a liquid at room temperature and pressure when mixed with water. Ammonia is the second most commonly produced chemical in the world and a large infrastructure for making, transporting, and distributing ammonia exists. Ammonia can be reformed to produce hydrogen with no harmful waste.
  • hydrogen may be received into the first vessel of the first hydrogen storage device via the first fluid inlet, for example from a hydrogen gas generator, as described below.
  • the first hydrogen storage device is initially in a fully discharged state.
  • a temperature of the hydrogen storage material increases due to the exothermic absorption (i.e. hydriding) reaction of the hydrogen storage, as described previously.
  • Heat from the exothermic reaction is conducted via the thermally conducting network, thereby attenuating the increase in the temperature.
  • a first cooler may be activated to further attenuate the increase in the temperature and subsequently, deactivated when a set low temperature threshold is reached (for example 20 °C).
  • a valve inline with the first fluid inlet may be opened, to admit the hydrogen, and closed, to contain the hydrogen, for example when a pressure within the first vessel reaches, for example stabilises, at predetermined operating pressure (for example 10 bar).
  • a pressure within the first vessel reaches, for example stabilises, at predetermined operating pressure (for example 10 bar).
  • kinetics of absorption may be different and thus this step of storage of the hydrogen may be modified accordingly.
  • absorption thereof may be preferred at higher temperatures, for example of at least 100 °C, to favour kinetics of hydriding.
  • a valve inline with the first fluid outlet may be opened, to allow exit of the hydrogen therethrough, for example to an electrical generator.
  • the first heater heats the thermally conducting network and hence the hydrogen storage material, for example as activated by a temperature measurement of the thermally conducting network using a thermocouple.
  • the first heater may be deactivated once a set high temperature threshold is reached (for example 80 °C).
  • the valve may be then closed when the pressure reaches, for example stabilises at, a predetermined pressure is reached (for example 1 bar).
  • the first hydrogen storage device comprises and/or is a static first hydrogen storage device.
  • a predetermined volume of LOHC (for example, corresponding with at most an open volume of the first vessel) is received in the first vessel through the first fluid inlet and heated, via the thermally conducting network, thereby releasing hydrogen gas, which exits the first vessel via the first fluid outlet.
  • LOC liquid organic carrier
  • a predetermined volume of liquid organic carrier, LOC is received in the first vessel through the first fluid inlet together with hydrogen gas and heated and cooled, via the thermally conducting network, thereby storing the hydrogen gas in the LOC as the LOHC.
  • the LOHC or LOC
  • the static first hydrogen storage device comprises a mixer or stirrer, for mixing or stirring the LOHC (or LOC) therein, thereby improving an efficiency of dehydrogenation (or hydrogenation), respectively.
  • the first hydrogen storage device comprises and/or is a dynamic (also known as flow-through) first hydrogen storage device.
  • a flow of LOHC is received, for example continuously, into the first vessel through the first fluid inlet and heated, via the thermally conducting network, thereby releasing hydrogen gas, which exits the first vessel together with the LOC (i.e. the unloaded LOHC) through the first fluid outlet.
  • a pressurised flow of LOC is received in the first vessel together with a flow of hydrogen gas and heated and cooled, via the thermally conducting network, thereby storing the hydrogen gas in the loaded LOC as the LOHC, which exits the first vessel through the first fluid outlet.
  • the LOHC (or LOC) flows through the first vessel while releasing (or charging, respectively) the hydrogen.
  • the first hydrogen storage device comprises a pump arranged to flow the hydrogen storage material through the first vessel.
  • the first hydrogen storage device comprises, is and/or is known as a reactor.
  • the pressure vessel comprises a lid (also known as a cover or a blanking plate, for example for an access hatch or an aperture in a wall of the pressure vessel) sealing coupled thereto and/or thereon, thereby providing a sealed pressure vessel around the thermally conducting network.
  • the hydrogen storage material is advantageously added, generally in powder form, before the lid is sealing coupled to the pressure vessel.
  • the powder may be poured between arms of the thermally conducting network and optionally, into a foam to partially (i.e. at least 25%, preferably at least 35%, more preferably at least 45% by volume of voids), in a majority (i.e.
  • the hydrogen storage device comprises an agitator, for example a vibrator, mechanically coupled to the pressure vessel and/or the thermally conductive network, arranged to agitate, for example vibrate, the pressure vessel and/or the thermally conductive network to thereby increase a filling efficiency of the pressure vessel with the hydrogen storage material.
  • an agitator for example a vibrator, mechanically coupled to the pressure vessel and/or the thermally conductive network, arranged to agitate, for example vibrate, the pressure vessel and/or the thermally conductive network to thereby increase a filling efficiency of the pressure vessel with the hydrogen storage material.
  • hydrogen may be received into the pressure vessel of the first hydrogen storage device via the first fluid inlet, for example from a hydrogen gas generator, as described below.
  • the first hydrogen storage device is initially in a fully discharged state.
  • a temperature of the hydrogen storage material increases due to the exothermic absorption (i.e. hydriding) reaction of the hydrogen storage, as described previously.
  • Heat from the exothermic reaction is conducted via the thermally conducting network, thereby attenuating the increase in the temperature.
  • a first cooler may be activated to further attenuate the increase in the temperature and subsequently, deactivated when a set low temperature threshold is reached (for example 20 °C).
  • a valve inline with the first fluid inlet may be opened, to admit the hydrogen, and closed, to contain the hydrogen, for example when a pressure within the pressure vessel reaches, for example stabilises, at predetermined operating pressure (for example 10 bar).
  • a pressure within the pressure vessel reaches, for example stabilises, at predetermined operating pressure (for example 10 bar).
  • kinetics of absorption may be different and thus this step of storage of the hydrogen may be modified accordingly.
  • absorption thereof may be preferred at higher temperatures, for example of at least 100 °C, to favour kinetics of hydriding.
  • a valve inline with the first fluid outlet may be opened, to allow exit of the hydrogen therethrough, for example to an electrical generator.
  • the first heater heats the thermally conducting network and hence the hydrogen storage material, for example as activated by a temperature measurement of the thermally conducting network using a thermocouple.
  • the first heater may be deactivated once a set high temperature threshold is reached (for example 80 °C).
  • the valve may be then closed when the pressure reaches, for example stabilises at, a predetermined pressure is reached (for example 1 bar).
  • the pressure vessel comprises therein the thermally conducting network thermally coupled to the first heater.
  • a face of the thermally conducting network is in thermal contact (and hence thermally coupled to) the first heater.
  • the first heater is integrally formed with and/or in the thermally conducting network, at least in part.
  • the first heater may be embedded within (i.e. internal to) the thermally conducting network.
  • the thermally conducting network may be formed from any suitable thermally conducting material for example a metal such as aluminium, copper, respective alloys thereof such as brass or bronze alloys of copper and/or stainless steel. Preferred materials also do not react with and/or are not embrittled by hydrogen and/or the hydrogen storage material, while having sufficient strength to maintain a structural integrity of the thermally conducting network.
  • the thermally conducting network comprises a coating to reduce reaction with and/or embrittlement by hydrogen.
  • the thermally conducting network has a lattice geometry, a gyroidal geometry and/or a fractal geometry in two and/or three dimensions.
  • the thermally conducting network has a lattice geometry, a gyroidal geometry and/or a fractal geometry in two and/or three dimensions (i.e. mutually orthogonal dimensions).
  • a gyroid is an infinitely connected triply periodic minimal surface, similar to the lidnoid which is also within the scope of the first aspect.
  • the gyroid separates space into two oppositely congruent labyrinths of passages, through which the hydrogen storage material may flow. It should be understood that such geometries comprise a plurality of nodes, having thermally conducting arms (i.e. generally elongated members) therebetween, with voids (i.e. gaps, space) between the arms.
  • the fractal geometry is selected from a group consisting of a Gosper Island, a 3D H-fractal, a Quadratic Koch Island, a Quadratic Koch surface, a Von Koch surface, a Koch Snowflake, a Sierpinski carpet, a Sierpinski tetrahedron, a Mandelbox, a Mandelbulb, a Dodecahedron fractal, a Icosahedron fractal, a Octahedron fractal, a Menger sponge and a Jerusalem cube.
  • an effective density (also known as lattice volume ratio) of the lattice geometry is uniform in one, two or three dimensions (i.e. mutually orthogonal dimensions). In one example, an effective density of the lattice geometry is non-uniform in one, two or three dimensions (i.e. mutually orthogonal dimensions).
  • a uniform effective density in a particular dimension provides a constant void fraction, between arms of the lattice geometry, in the particular dimension.
  • a non-uniform effective density in a particular dimension provides a non-constant void fraction, between arms of the lattice geometry, in the particular dimension.
  • a higher effective density will lead to faster heat conduction due to a higher thermally conducting material content.
  • the effective density may increase or decrease in the particular dimension, for example radially.
  • the thermally conducting network may be designed, for example optimised, for a particular pressure vessel geometry so as to improve, for example optimise, heat transfer to and/or from the hydrogen storage material via the thermally conducting network.
  • an effective density of the lattice geometry is uniform in a first dimension, for example axially, and non-uniform in mutually orthogonal second and third dimensions, for example radially. While the surface area to volume ratios of lattice geometries, for example square lattice geometries such as three-dimensional cages, are relatively lower than of fractal geometries having the same volumes, forming and/or fabrication of lattice geometries is relatively less complex and/or costly and hence may be preferred.
  • the lattice geometry is Bravais lattice for example a triclinic lattice such a primitive triclinic lattice; a monoclinic lattice such as a primitive triclinic lattice or a base-centred triclinic lattice; an orthorhombic lattice such as a primitive orthorhombic lattice a base-centred orthorhombic lattice, a body-centred orthorhombic lattice or a face-centred orthorhombic lattice; a tetragonal lattice such as a primitive tetragonal lattice or a body-centred tetragonal lattice; a hexagonal lattice such as a primitive hexagonal lattice or a rhombohedral primitive lattice; or a cubic lattice such as a primitive cubic lattice, a body- centred cubic lattice
  • the thermally conducting arms have a cross sectional dimension (for example a diameter or a width) in a range from 0.1 mm to 10 mm, preferably in a range from 0.25 mm to 5 mm, more preferably in a range from 0.5 mm to 2.5 mm and/or a length in range from 0.5 mm to 50 mm, preferably in a range from 1 mm to 25 mm, more preferably in a range from 2 mm to 10 mm.
  • heat transfer of the thermally conducting network may be controlled by selecting an effective density and/or a surface area of the thermally conducting network.
  • the thermally conducting network is formed, at least in part, by 3D printing (i.e. additive manufacturing), for example by selective laser melting (SLM), thereby enabling forming of complex shapes in three dimensions having internal voids, for example.
  • the thermally conducting network is formed, at least in part, by casting such as investment casting, moulding such as injection moulding and extrusion. Other additive manufacturing processes are known.
  • the thermally conducting network is formed, at least in part, by fabrication and/or machining such as milling, turning or drilling. Other subtractive manufacturing processes are known.
  • the thermally conducting network comprises fluidically interconnected passageways therein, for example within the arms and/or the nodes thereof, for flow therethough of a fluid, such as a heating fluid and/or a coolant, preferably a liquid for example a recirculating liquid.
  • a fluid such as a heating fluid and/or a coolant, preferably a liquid for example a recirculating liquid.
  • control for charging and/or release of hydrogen from the hydrogen storage device is improved because the flow of the fluid through the interconnected passageways in the thermally conducting network provides for faster, more homogenous, more accurate and/or more precise heating and/or cooling of the thermally conducting network and in turn, the hydrogen storage material in thermal contact therewith. Additionally and/or alternatively, in this way, storing and/or release of the hydrogen may be accelerated since heat generated or required, respectively, may be provided by the flow of the fluid through the interconnected passageways in the thermally conducting network.
  • the fluidically interconnected passageways are within, for example wholly within, the thermally conducting network, for example within the arms and/or the nodes thereof, such that at least some of the arms and/or the nodes thereof are tubular (i.e. having lumens therein) or shells (i.e. having cavities therein, hollow), respectively. That is, the passageways are internal to the thermally conducting network.
  • the voids (i.e. gaps, space) between the arms, as described above, are external to the thermally conducting network.
  • at least some of the arms comprise tubular arms and/or at least some of the nodes comprise shells.
  • walls of the arms and/or the nodes comprise no perforations therethrough.
  • a wall thickness of the arms and/or the nodes is in a range from 0.01 mm to 5 mm, preferably in a range from 0.1 mm to 2.5 mm, more preferably in a range from 0.25 mm to 1 .5 mm.
  • the fluidically interconnected passageways define a flowpath (for example, a single flowpath) or a plurality of flowpaths (for example, parallel flowpaths), for example for recirculation of the fluid.
  • the fluidically interconnected passageways define a capillary flowpath.
  • the nodes provide bifurcations for the flow.
  • the fluid is a liquid, selected for compatibility with a material of the thermally conducting network.
  • the liquid may include one or more additives, such as corrosion inhibitors, to enhance compatibility with the material.
  • the liquid may be water, optionally comprising one or more corrosion inhibitor.
  • surfaces of the fluidically interconnected passageways comprise a coating, for example to inhibit corrosion of the material of the thermally conducting network.
  • the hydrogen storage device comprises a pump for pumping the fluid through the fluidically interconnected passageways.
  • the hydrogen storage comprises a reservoir for the fluid, fluidically coupled to the fluidically interconnected passageways and optionally the pump.
  • the first heater is arranged to heat the fluid.
  • the first cooler is arranged to cool the fluid.
  • the hydrogen storage device comprises a thermally-conducting foam, for example a metal foam, attached and/or attachable to (i.e. thermally coupled to, in thermal contact with, thermally coupleable to) the thermally conducting network.
  • a foam aids heat transfer to and from the hydrogen storage material. It is known that such a foam has a high internal surface area.
  • the foam comprises and/or is an open-celled foam, preferably an open-celled metal foam (also known as a metal sponge. Open-cell metal foams are generally manufactured by foundry or powder metallurgy. In the powder method,“space holders” are used; they occupy the pore spaces and channels.
  • foam In casting processes, foam is typically cast with an open-celled polyurethane foam skeleton.
  • the inventors have found that the hydrogen storage material may be placed in the spaces (i.e. voids, lumens, pores, cells) in the foam and the hydrogen storage material retains its ability to store and release hydrogen whilst at the same time benefiting from the enhanced rate of thermal transfer brought about by the high surface area of the foam.
  • a foam pore size i.e. cell size
  • a ratio of the foam pore size to a particle size is at least 5:1 , for example at least 10:1 , for example 20:1 , wherein sizes (i.e.
  • the foam comprises and/or is a metal foam, preferably an open-celled metal foam, formed from aluminium, copper, stainless steel, nickel or zinc (or combination alloys including those metals). Aluminium foam is especially preferred.
  • the thermally conducting network preferably contains metal foam in the spaces in the network. The voids in the metal foam contain the hydrogen storage material. It has been found that the metal foam in the fractal network provides excellent transfer of heat to and from the thermoelectric heater/cooler and the hydrogen storage material.
  • the hydrogen storage device is arranged to be oriented horizontally or vertically, in use.
  • the thermally conducting network partially fills an internal volume of the pressure vessel, of at least 50%, preferably of at least 60%, more preferably of at least 70% by volume of the pressure vessel, thereby defining an unfilled volume, for example above the thermally conducting network.
  • the volume of the thermally conducting network is the gross volume thereof, defined by an envelope thereof, and thus includes the volume of the voids therein in addition to the volume of the arms and nodes thereof.
  • the unfilled volume acts as a buffer, providing a reservoir of hydrogen during charging and similarly during release, for example to account for kinetics thereof.
  • the pressure vessel comprises a mesh or a perforated sheet, arranged to cover an open area of the thermally conducting network (i.e. not thermally coupled to the pressure vessel, for example), to thereby retain the hydrogen storage material in the voids defined within the thermally conducting network.
  • the hydrogen storage device is arrangeable, for example repeatedly, in: a first arrangement wherein the thermally conducting network is within the pressure vessel; and a second arrangement wherein the thermally conducting network is outside the pressure vessel; optionally wherein the pressure vessel comprises a circumferential releasable joint.
  • the first arrangement is the in use arrangement and the second arrangement is, for example, an assembly arrangement.
  • the first inlet and/or the first outlet is arranged, for example sized, to permit insertion and/or removal of the thermally conducting network therethrough.
  • the pressure vessel comprises a releasable port for insertion and/or removal of the thermally conducting network therethrough.
  • the pressure vessel comprises a circumferential releasable joint, such that the pressure vessel may be parted to allow insertion and/or removal of the thermally conducting network.
  • a circumferential joint includes a peripheral joint (i.e. around a periphery of the pressure vessel) and hence applies also to non-cylindrical pressure vessels.
  • the pressure vessel comprises a longitudinal releasable joint, such that the pressure vessel may be parted to allow insertion and/or removal of the thermally conducting network. More generally, in one example, the pressure vessel comprises a releasable joint, such that the pressure vessel may be parted to allow insertion and/or removal of the thermally conducting network.
  • the releasable joint comprises a mechanical fastener, for example a threaded joint, a bolted joint, a clamped joint.
  • the releasable joint comprises a gasket.
  • the pressure vessel comprises a sealable joint, such that the pressure vessel may be manufactured in two or more parts to allow insertion of the thermally conducting network and the sealable joint subsequently sealed, for example permanently.
  • the thermally conducting network comprises an expandable thermally conducting network.
  • the thermally conducting network may be inserted through the first inlet and/or the first outlet into the pressure vessel and subsequently expanded, for use.
  • nodes of the thermally conducting network may be moveable nodes and/or arms of the thermally conducting network may be extensible arms.
  • the thermally conducting network comprises an contractable thermally conducting network. In this way, the thermally conducting network may be removed through the first inlet and/or the first outlet into the pressure vessel by contracting the thermally conducting network and removing the contracted thermally conducting network, for use.
  • nodes of the thermally conducting network may be moveable nodes and/or arms of the thermally conducting network may be contractable arms.
  • the thermally conducting network comprises a foldable, such as a foldable tessellated, structure of nodes and arms.
  • the hydrogen storage device optionally comprises the set of heaters including the first heater.
  • the hydrogen storage device comprises the set of heaters including the first heater and the thermally conducting network is thermally coupled to the first heater. By heating the first heater, heat is transferred to the thermally conducting network thermally coupled thereto. In turn, heat is transferred to the hydrogen storage material in thermal contact, at least in part, with the thermally conducting network. In this way, the hydrogen storage material is heated by the first heater, via the thermally conducting network, thereby causing hydrogen to be released from the hydrogen storage material.
  • the first heater is positioned inside the pressure vessel. In one example, the first heater is positioned outside of the pressure vessel.
  • the first heater comprises and/or is a thermoelectric heater and/or a Joule heater, and/or a recirculating heater, for example recirculating liquid
  • the first vessel is arranged, for example comprising a passageway, to interchangeably receive the Joule heater and the recirculating heater therein and/or thereon.
  • the first vessel may comprise a through passageway, arranged to receive a cartridge heater inserted therein through an end of the passageway and the opposed end of the passageway may be closed, for example with an insulating plug.
  • the cartridge heater and the plug may be removed and fluid couplings instead fitted to the ends, such that a recirculating liquid, such as heated coolant (i.e. a heating fluid) from a fuel cell to heat the thermally conducting network, may be pumped therethrough.
  • a recirculating liquid such as heated coolant (i.e. a heating fluid) from a fuel cell to heat the thermally conducting network
  • the first hydrogen storage device comprises a passageway, wherein the first hydrogen storage device is arrangeable in: a first configuration to receive a Joule heater in the passageway; and a second configuration to receive a flow of a liquid through the passageway.
  • Other heaters are known.
  • the hydrogen storage device comprises a thermocouple connected to the first heater, for example via a proportional-integral-derivative (PID) control.
  • PID proportional-integral-derivative
  • the first heater comprises and/or is a cartridge heater or an insertion heater.
  • cartridge heaters are elongated cylinders including electrical resistive wire, for example embedded in magnesium oxide. Suitable cartridge heaters and insertion heaters are available from Watlow (MO, USA).
  • the first heater is inserted into a passageway formed in and/or provided by the thermally conducting network.
  • the first heater is integrated into the thermally conducting network, for example integrally formed therewith. In this way, a heating efficiency of the thermally conducting network is improved.
  • the hydrogen storage device comprises a battery, preferably a rechargeable battery for example a Li-ion polymer battery, arranged to provide electrical power to the first heater.
  • the first hydrogen storage device comprises a set of heater/coolers, including the set of heaters, including a first heater/cooler, comprising the first heater.
  • the first heater/cooler By cooling the first heater/cooler, heat is transferred from the thermally conducting network thermally coupled thereto. In turn, heat is transferred from the hydrogen storage material in thermal contact, at least in part, with the thermally conducting network.
  • the hydrogen storage material is cooled by the first heater/cooler, via the thermally conducting network, thereby allowing hydrogen to be stored in the hydrogen storage material.
  • the first heater/cooler can, in a space-efficient manner, enable heat to be removed from the hydrogen storage material during the hydrogen storage phase, and heat to be supplied to the hydrogen storage material during hydrogen release.
  • the first heater/cooler is positioned inside the pressure vessel. In one example, the first heater/cooler is positioned outside of the pressure vessel. Positioning the first heater/cooler outside the pressure vessel simplifies certain aspects of the assembly of the device and allows simpler access for electrical wiring.
  • Thermoelectric heater and/or cooler devices can be very closely controlled (i.e. accurately, precisely and/or responsively), which providing control to a high degree of accuracy, precision and/or short response times.
  • the heater of the first heater/cooler may be as described above with respect to the first heater.
  • the cooler of the first heater/cooler comprises and/or is a heat sink, optionally with active cooling by air propelled by a fan or by a cooling fluid (e.g.
  • the first heater/cooler comprises and/or is a Peltier device or other device that makes use of thermoelectric cooling and heating.
  • Devices of this type are commonly referred to as a Peltier heat pump, a solid state refrigerator, or a thermoelectric cooler (TEC).
  • TEC thermoelectric cooler
  • a thermoelectric heater and cooler device may be used together with a heat sink with optional active cooling (e.g. active cooling by air propelled by a fan or active cooling by a cooling fluid (e.g. water) being propelled by a pump).
  • active cooling e.g. active cooling by air propelled by a fan or active cooling by a cooling fluid (e.g. water) being propelled by a pump.
  • Application of heat or removal of heat on the side of the thermoelectric device that is not thermally coupled to the thermally conducting network enhances the ability of the thermoelectric device to heat and cool the thermally conducting network.
  • the first heater/cooler e.g. a thermoelectric heater and cooler
  • the thermally conducting network As the two are in thermal contact, heat can efficiently be passed from one to the other. The heat can pass in either direction - heating the thermally conducting network or cooling it.
  • the contact between the heater/cooler module and the thermally conducting network need not be direct physical contact.
  • the first hydrogen storage device comprises one or more of thermoelectric heaters and/or coolers on a base to provide a Peltier heater/cooler assembly, wherein the thermally conducting network is thermally coupled (for example, attached) to the Peltier heater/cooler assembly.
  • the thermally conducting network may be 3D printed onto the heater/cooler assembly.
  • foam for example metal foam, as described below
  • the foam may be attached by a physical bond for example by soldering, brazing and/or welding the thermally conducting network and foam together.
  • solder and/or filler it is preferred for the solder and/or filler to have high thermal conductivity, which is the case for most solder and filler materials.
  • the first heater comprises a Joule heater and/or a recirculating heater, preferably wherein the first hydrogen storage device, for example the pressure vessel, is arranged to interchangeably receive the Joule heater and the recirculating heater therein and/or thereon, as described above.
  • the first hydrogen storage device comprises a phase change material (PCM) in thermal contact, at least in part, with the thermally conducting network.
  • PCMs phase change material
  • heat arising during hydrogen storage may PCMs are materials having high heats of fusion and which, upon changing phase at respective phase change temperatures such as by melting and solidifying, are capable of storing and/or releasing large amounts of energy.
  • PCMs may be classified as latent heat storage (LHS) units.
  • LHS latent heat storage
  • Latent heat storage can be achieved through liquid-solid, solid-liquid, solid-gas and liquid-gas phase changes. However, only solid-liquid and liquid-solid phase changes are generally practical for PCMs.
  • the PCM is a solid-liquid (and liquid-solid) PCM.
  • the first hydrogen storage device comprises a phase change material (PCM) in thermal contact, at least in part, with the thermally conducting network.
  • PCM phase change material
  • the PCM comprises at least one of an organic PCM, an inorganic PCM, an eutectic PCM, a hygroscopic PCM, a solid-solid PCM and a thermal composite.
  • a PCM one or more of the following properties may be desirable: phase change temperature in a desired operating temperature range, high latent heat of fusion per unit volume, high specific heat, high density and high thermal conductivity, small volume change on phase transformation, small vapour pressure at operating temperatures, congruent melting, high nucleation rate to avoid supercooling of a liquid phase, high rate of crystal growth, chemical stability, reversibility of phase change, absence of degradation due to phase change, non-corrosiveness, non-toxic, non-flammable, low cost and/or availability.
  • Organic PCMs include, for example, paraffins (C n H2n+2), carbohydrates and lipid-derived materials. Beneficial properties of organic PCMs may include freezing without much undercooling, melting congruently, self-nucleation, compatibility with conventional material of construction, no or little segregation, chemically stability, high heat of fusion, safe and nonreactivity and/or recyclability.
  • carbohydrate and lipid based PCMs may be produced from renewable sources.
  • organic PCMs may have low solid thermal conductivities, require high heat transfer rates during the freezing cycle, low volumetric latent heat storage capacities and/or flammabilities. To obtain reliable phase change points, manufacturers typically provide technical grade paraffins, which are essentially paraffin mixture(s) and are completely refined of oil.
  • Inorganic PCMs include salt hydrates (MPH S O), for example. Beneficial properties of inorganic PCMs may include high volumetric latent heat storage capacity, availability, low cost, sharp melting point, high thermal conductivity, high heat of fusion and/or non-flammability. However, inorganic PCMs may have high changes of volume, super cooling in solid-liquid transition and/or nucleating agents may be required.
  • Organic and inorganic PCMs are available from Rubitherm Technologies GmbH (Berlin, Germany), for example, having phase change temperatures in a range of from -9 °C to 90 °C. Heat storage capacities of these PCMs range typically from 150 kJ/kg to 290 kJ/kg.
  • Eutectic PCMs include, for example, c-inorganic and inorganic-inorganic compounds. Beneficial properties of eutectic PCMs may include sharp melting point and/or improved volumetric storage density compared with organic PCMs.
  • Hygroscopic PCMs include, for example, natural building materials such as wool insulation and earth/clay render finishes, that can absorb and release water.
  • Solid-solid PCMs undergo solid/solid phase transitions with associated absorption and release of large amounts of heat, having latent heats comparable with solid/liquid PCMs. Nucleation may not be required to prevent supercooling.
  • the temperature range of solid-solid PCMs are available having phase change temperatures in a range of from 25°C to 180°C.
  • a phase change temperature of the PCM corresponds with a desorption temperature of the hydrogen storage material, in use.
  • hydrated salt S58 available from PCM Products Ltd, UK
  • the phase change temperature is within 20°C, preferably within 10°C, more preferably within 5°C of a desorption temperature of the hydrogen storage material. In one example, the phase change temperature is at most 20°C, preferably at most 10°C, more preferably at most 5°C above a desorption temperature of the hydrogen storage material.. In this way, an efficiency of heat storage and release by the PCM is improved, since hysteresis is reduced.
  • the PCM has a heat storage capacity in a range of from 100 kJ/kg to 1000 kJ/kg, preferably of from 150 kJ/kg to 500 kJ/kg, more preferably of from 200 kJ/kg to 300 kJ/kg, for example 230 kJ/kg.
  • the first phase change temperature of the PCM may be a determining factor in selection, thereby limiting candidate PCMs.
  • the PCM comprises an encapsulated PCM.
  • Encapsulation of the PCM may be required for PCMs undergoing solid - liquid phase transformations.
  • Example of encapsulation include macro-encapsulation, micro-encapsulation and molecular encapsulation. Macro-encapsulation with large volume containment may be unsuitable for PCMs having low thermal conductivity, since such PCMs tend to solidify at edges of the macro-encapsulation, thereby preventing effective heat transfer.
  • Micro-encapsulation generally allows PCMs to be incorporated into construction materials, for example by coating a microscopic sized PCM with a protective coating. Molecular-encapsulation allows a very high concentration of PCM within a polymer compound.
  • the encapsulated PCM is divided into cells.
  • the cells may be arranged to reduce static head. Walls of the cells may provide effective heat transfer, restrict passage of water through the walls, resist leakage and/or corrosion and/or may be chemically compatible with the PCM.
  • Cell wall material examples include stainless steel, polypropylene and polyolefin.
  • the PCM comprises an additive arranged to increase a thermal conductivity of the PCM. Some PCMs, for example some organic PCMs, may have high heats of fusion but low thermal conductivities. By including additives within the PCM, the thermal conductivity of the PCM may be increased, thereby improving heat absorption of the PCM, for example.
  • the additives may include, for example, particles, fibres or wires, having high thermal conductivities.
  • the second aspect provides a charging station for charging a hydrogen storage device according to the first aspect.
  • the charging station is arranged to charge a plurality of hydrogen storage devices, for example simultaneously.
  • the charging station comprises a manifold coupleable to a plurality of hydrogen storage devices.
  • the charging station comprises a cooling system, arranged to cool a hydrogen storage device during charging thereof.
  • the cooling system comprises a fan, a bath, a cooling jacket and/or a recirculating coolant system.
  • the third aspect provides a charging station assembly comprising a charging station according to the second aspect and a hydrogen storage device according to the first aspect.
  • the fourth aspect provides a method of storing hydrogen comprising passing hydrogen gas into a hydrogen storage device according to the first aspect, optionally comprising cooling the thermally conducting network, for example by flowing the fluid through the fluidically interconnected passageways.
  • the method comprises cooling the fluid.
  • the method comprises pumping the fluid.
  • the fifth aspect provides a method of providing hydrogen comprising releasing hydrogen gas from a hydrogen storage device according to the first aspect, optionally comprising heating the thermally conducting network, for example by flowing the fluid through the fluidically interconnected passageways.
  • the method comprises heating the fluid.
  • the method comprises pumping the fluid.
  • the term“comprising” or“comprises” means including the component(s) specified but not to the exclusion of the presence of other components.
  • the term“consisting essentially of or“consists essentially of means including the components specified but excluding other components except for materials present as impurities, unavoidable materials present as a result of processes used to provide the components, and components added for a purpose other than achieving the technical effect of the invention, such as colourants, and the like.
  • Figure 1 is a CAD axial cross-section of a hydrogen storage device according to an exemplary embodiment
  • Figure 2 is a CAD axial cross-section of the hydrogen storage device of Figure 1 ;
  • Figure 3 schematically depicts a cutaway, perspective view of a simulation of the of the hydrogen storage device of Figure 1 ;
  • Figure 4A is a schematic axial cross-section of a hydrogen storage device according to an exemplary embodiment and Figures 4B to 4D are schematic transverse cross-sections of the hydrogen storage device of Figure 4A;
  • FIGS. 5A to 5C schematically depict thermally conducting networks for a hydrogen storage device according to an exemplary embodiment
  • Figure 6A is a photograph of a foam for a hydrogen storage device according to an exemplary embodiment
  • Figure 6B is a schematic view of a hydrogen storage device according to an exemplary embodiment, in more detail
  • Figure 7A is a plan elevation view of a hydrogen storage device according to an exemplary embodiment
  • Figure 7B is a side cross-sectional view of the hydrogen storage device of Figure 7A;
  • Figure 8 is a CAD cutaway perspective view of a hydrogen storage device according to an exemplary embodiment
  • Figure 9 is a CAD axial cross-section of the hydrogen storage device of Figure 10.
  • Figure 10 is a CAD radial cross-section of the hydrogen storage device of Figure 10;
  • Figure 11 is an alternative CAD radial cross-section of the hydrogen storage device of Figure 10.
  • Figure 12 is a CAD cutaway perspective view of a hydrogen storage device according to an exemplary embodiment
  • Figure 13 is a CAD axial cross-section of the hydrogen storage device of Figure 12;
  • Figure 14 is a CAD radial cross-section of a thermally conducting network of the hydrogen storage device of Figure 12;
  • Figure 15 schematically depicts Brumble lattices for a thermally conducting network
  • Figure 16 is a CAD perspective view of a hydrogen storage device according to an exemplary embodiment
  • Figure 17 is a CAD axial cross-section of the hydrogen storage device of Figure 16;
  • Figure 18 is a CAD axial cross-section of a hydrogen storage device according to an exemplary embodiment
  • Figure 19 is a CAD perspective view of a charging station assembly according to an exemplary embodiment
  • Figure 20 shows the periodic table of elements, showing suitability of elements for hydrogen storage according to HHI Production, HHI Reserve and Abundance of the elements, where HHI is the Herfindahl-Hirschman index, a commonly accepted measure of market concentration, has been calculated from geological data (known elemental reserves) and geopolitical data (elemental production) for much of the periodic table;
  • Figure 21 shows a chart of gravimetric H2 density (wt.%) as a function of volumetric H2 density (kg H2 / m 3 ) for metal hydrides, chemical hydrogen and absorbents;
  • Figure 22 shows a chart of observed H2 capacity (wt.%) as a function of temperature, showing H2 sorption temperature (°C) and temperature for observed H2 release (°C), for metal hydrides, chemical hydrogen and absorbents;
  • Figure 23A is a CAD perspective view of a hydrogen storage device according to an exemplary embodiment
  • Figure 23B is a CAD perspective semi-transparent view of the hydrogen storage device of Figure 23A
  • Figure 23C is a CAD axial cross-section view of the hydrogen storage device of Figure 23A;
  • Figure 24A is a cutaway perspective view of a hydrogen storage device according to an exemplary embodiment
  • Figure 24B is a cutaway perspective exploded view of a related hydrogen storage device
  • Figure 25 is a cutaway perspective view of a hydrogen storage device according to an exemplary embodiment
  • Figure 26A is a CAD partial cutaway perspective view of a hydrogen storage device according to an exemplary embodiment
  • Figure 26B is a CAD longitudinal perspective cross- sectional view of the hydrogen storage device
  • Figure 26C is a CAD perspective view of the thermally conducting network, in more detail
  • Figure 27A is a CAD partial cutaway perspective view of a hydrogen storage device according to an exemplary embodiment
  • Figure 27B is a CAD transverse cross-sectional view of the hydrogen storage device
  • Figure 28A is a CAD partial cutaway perspective view of a hydrogen storage device according to an exemplary embodiment
  • Figure 28B is a CAD partial cutaway perspective view of the hydrogen storage device, in more detail
  • Figure 28C is a CAD exploded perspective view of a part of the hydrogen storage device, in more detail
  • Figure 29A is a CAD partial cutaway perspective view of a hydrogen storage device according to an exemplary embodiment
  • Figure 29B is a CAD longitudinal cross-sectional view of the hydrogen storage device
  • Figure 30 is a CAD partial cutaway exploded perspective view of a hydrogen storage device according to an exemplary embodiment
  • Figure 31 is a CAD transverse cross-sectional view of a hydrogen storage device according to an exemplary embodiment.
  • Figure 32 is a CAD partial cutaway perspective view of a hydrogen storage device according to an exemplary embodiment.
  • FIG. 1 is a CAD axial cross-section of a hydrogen storage device 100A.
  • Figure 2 is a CAD axial cross-section of the hydrogen storage device 100A of Figure 1 .
  • the hydrogen storage device 100A comprises: a pressure vessel 230A, having a first fluid inlet 210A and/or a first fluid outlet 220A, having therein a thermally conducting network 240A optionally thermally coupled to a first heater and/or a first cooler; wherein the pressure vessel 230A is arranged to receive therein a hydrogen storage material in thermal contact, at least in part, with the thermally conducting network 240A; wherein the thermally conducting network 240A preferably has a lattice geometry, a gyroidal geometry and/or a fractal geometry in two and/or three dimensions, comprising a plurality of nodes, having thermally conducting arms therebetween, with voids between the arms; and wherein the thermally conducting network 240A comprises fluidically interconnected passageways therein, for example
  • the first hydrogen storage device 100A comprises a passageway 250A, wherein the first hydrogen storage device 200A is arrangeable in: a first configuration to receive a Joule heater in the passageway 250A; and a second configuration to receive a flow of a liquid through the passageway 250A.
  • a cartridge heater (not shown) is insertable into the passageway 250A through an end thereof and the opposed end of the passageway 250A is closed, with an insulating plug 260A.
  • the cartridge heater and the plug 260A are removed and fluid couplings 270A, 280A instead fitted to the ends, such that a recirculating liquid, such as coolant from a fuel cell, may be pumped therethrough.
  • the hydrogen storage device 100A is arranged to be oriented horizontally, in use.
  • the pressure vessel 230A is generally cylindrical, having dished ends.
  • the passageway, provided by a tube having a circular cross- section extends between the dished ends longitudinally, offset from an axis of the pressure vessel 230A.
  • the thermally conducting network 240A partially fills an internal volume of the pressure vessel 230A, particularly a region of the internal volume extending across about 75% of a diameter the pressure vessel, thereby completely surrounding the tube, such that an unfilled volume UV above the thermally conducting network 240A is defined.
  • the thermally conducting network 240A is thermally coupled to at least a part of an internal surface of the pressure vessel 230A and an external surface of the tube.
  • the unfilled volume UV acts as a buffer, providing a reservoir of hydrogen during charging and similarly during release, for example to account for kinetics thereof.
  • FIG. 3 schematically depicts a cutaway, perspective view of a simulation, particularly by finite element analysis (FEA) the hydrogen storage device of Figure 1 .
  • the pressure vessel is generally cylindrical, having a wall thickness of 2 mm, and hemispherical dished ends, having a wall thickness of 1 .5 mm.
  • the pressure vessel is formed from a material having a yield stress at 100° C of 181 MPa.
  • a maximum stress at an operating pressure of 20 bar is 61 MPa, giving a safety factor of about 3.
  • a maximum stress at an operating pressure of 5 bar is 15.2 MPa, giving a safety factor of about 1 1 .9.
  • the deformed pressure vessel 230A’ and deformed passageway 240A’ following simulated yield.
  • Figure 4A is a schematic axial cross-section of a hydrogen storage device 200 according to an exemplary embodiment and Figures 4B to 4D are schematic transverse cross- sections of the hydrogen storage device 200 of Figure 4A.
  • FIGS 4A - 4D show the hydrogen storage device 200.
  • the hydrogen storage device 200 comprises a hollow metal cylinder (outer cylindrical vessel wall (1)) and along with two metallic end-caps (2), providing the pressure vessel. Inside this volume exists the hydrideable metal/metal alloy (5), an aluminium fractal structure (4) with metallic foam in contact with it (not shown in figure). Both end-caps (2) contain an internal cavity for the location of multiple peltier devices (6) and heat/cold sinks (7).
  • the outer cylindrical vessel wall (1) there are three gas inlets (10) and three gas outlets (1 1) allow for heating/cooling gas (air) access to this internal cap cavity to add/remove heat.
  • the end-caps In one of the end-caps four ports (holes) are included, allowing access into the pressure vessel; they are a hydrogen gas inlet (8), a hydrogen gas outlet (9), a pressure sensor connection (15) and a temperature sensor connection (14).
  • the end-caps are held in place and form a seal through a thread and o-ring arrangement (3).
  • the end-caps can be removed for easy access to the pressure vessel.
  • the end-caps have covers (13) which can be removed for easy access to the heating/cooling gas containment volume within them.
  • the hydrogen storage device 200 comprises: a pressure vessel 1 , having a first fluid inlet 8 and/or a first fluid outlet 9, having therein a thermally conducting network 4 optionally thermally coupled to a first heater and/or a first cooler; wherein the pressure vessel 1 is arranged to receive therein a hydrogen storage material in thermal contact, at least in part, with the thermally conducting network 4; wherein the thermally conducting network 340 has a fractal geometry in two dimensions, comprising a plurality of nodes, having thermally conducting arms therebetween, with voids between the arms; and wherein the thermally conducting network 4 comprises fluidically interconnected passageways therein, within the arms and the nodes thereof, for flow therethough of a fluid.
  • FIG. 5A to 5C schematically depict thermally conducting networks for a hydrogen storage device according to an exemplary embodiment.
  • Figure 5 shows there are shown three alternative fractal networks (A) Gosper Island; (B) ‘Snowflake’ design; and (C) Koch Snowflake for the thermally conducting network of the hydrogen storage device 200.
  • the 2D radially symmetric fractal patterns extend axially. Axial cross-sections, midpoint radial cross-sections and perspective views for the fractal networks are shown.
  • Figure 6A is a photograph of a foam for a hydrogen storage device according to an exemplary embodiment
  • Figure 6B is a schematic view of a hydrogen storage device according to an exemplary embodiment, in more detail.
  • Figure 6A shows a photograph of voids (i.e. open space) in a metal foam, particularly aluminium foam.
  • the aluminium foam is produced from 6101 aluminium alloy, retaining 99% purity of the parent alloy.
  • the foam has a reticulated structure in which cells (i.e. pores) are open and have a dodecahedral shape.
  • the foam has a bulk density of 0.2 g/cm3; a porosity of 93% porosity and about 8 pores/cm.
  • Figure 6B schematically depicts a metal hydride powder included and/or in contact with a metal foam which in turn is thermally coupled to a thermally conducting network.
  • Figure 7A is a plan elevation view of a hydrogen storage device 200’ according to an exemplary embodiment and Figure 7B is a side cross-sectional view of the hydrogen storage device 200’ of Figure 7A.
  • FIGS 7A and 7B schematically depict a compact design of a hydrogen storage device 200’.
  • the hydrogen storage device 200’ comprises a hydrogen gas containment volume formed from a cuboid-based container vessel (1) with square-planar lid (2).
  • the lid (2) is secured through the use of four axial-corner screws in screw fixings (7) and it is sealed by an O-ring (3) positioned between the vessel (1) and the lid (2).
  • the hydrogen containment volume has within it a hydrideable metal/metal alloy (5) and metal foam (not shown).
  • a Peltier device (6) thermally coupled to the thermally conducting network (4) and outside of the vessel (1) acts as a heater/cooler.
  • the hydrogen storage device 200’ comprises the pressure vessel 1 , having the first fluid inlet 8 and the first fluid outlet 9, comprising therein a thermally conducting network 4 optionally thermally coupled to the first heater (not shown), wherein the pressure vessel 1 is arranged to receive therein a hydrogen storage material (not shown) in thermal contact, at least in part, with the thermally conducting network 4, wherein the first fluid inlet 8 and/or the first fluid outlet 9 are in fluid communication with the first releasable fluid inlet coupling (not shown) and/or the first releasable fluid outlet coupling (not shown), respectively; and preferably, wherein the thermally conducting network 4 has a lattice geometry and/or a fractal geometry in two and/or three dimensions.
  • Figure 8 is CAD cutaway perspective view of a hydrogen storage device 200” according to an exemplary embodiment.
  • Figure 9 is CAD axial cross-section of the hydrogen storage device 200”of Figure 8.
  • Figure 10 is a CAD radial cross-section of the hydrogen storage device 200”of Figure 8.
  • the hydrogen storage device 200 comprises: a pressure vessel 201”, having a first fluid inlet 208” and/or a first fluid outlet 209”, having therein a thermally conducting network 204” optionally thermally coupled to a first heater and/or a first cooler; wherein the pressure vessel 201” is arranged to receive therein a hydrogen storage material in thermal contact, at least in part, with the thermally conducting network 204”; wherein the thermally conducting network 203” has a fractal geometry in two dimensions, comprising a plurality of nodes, having thermally conducting arms therebetween, with voids between the arms; and wherein the thermally conducting network 204” comprises fluidically interconnected passageways therein, within the arms and the nodes thereof, for flow therethough of a fluid.
  • the pressure vessel 201 is generally cylindrical, having a generally dished first end and a necked second end opposed thereto, and having a single aperture providing both the first fluid inlet 208” and the first fluid outlet 209”.
  • the pressure vessel 201 is bottle-shaped.
  • An inner wall portion 201 1” of the pressure vessel 201” provides an axial cylindrical, elongate blind passageway 210”, arranged to receive a first heater 206” (not shown), that extends from the first end towards the second end and that is coaxial with an outer wall portion 2010” of the pressure vessel 201”.
  • a second blind passageway in the first end is arranged to receive a thermocouple (not shown).
  • the pressure vessel has an internal volume of about 500 cm 3 , thereby providing a hydrogen storage capacity of about 25 g Fh. In this example, .
  • the thermally conducting network 204 has a lattice geometry in three dimensions.
  • an effective density of the lattice geometry is uniform in a first dimension, particularly axially, and non-uniform in mutually orthogonal second and third dimensions, particularly radially. Particularly, the effective density decreases radially outwards, such that there is faster heat transfer proximal the passageway 210” and hence the first heater.
  • the thermally conducting network 204” is formed from an aluminium alloy.
  • the thermally conducting network 204” may be formed from copper, respective alloys thereof such as brass or bronze alloys, and/or stainless steel, as described previously.
  • Figure 1 1 is an alternative CAD radial cross-section for the hydrogen storage device 200” of Figure 10.
  • a node density i.e. number of nodes per unit volume
  • a cross-sectional area of the arms is relatively larger than that of Figure 10.
  • Figure 12 is a CAD cutaway perspective view of a hydrogen storage device 200’” according to an exemplary embodiment.
  • Figure 13 is a CAD axial cross-section of the hydrogen storage device 200’” of Figure 12.
  • the pressure vessel 201”’ has an internal volume of about 50 cm 3 , thereby providing a hydrogen storage capacity of about 2.5 g H 2 .
  • Figure 14 is a CAD radial cross-section of a thermally conducting network of the hydrogen storage device of Figure 12. Generally, the lattice geometry is as described with respect to Figure 1 1 .
  • Figure 15 schematically depicts Bravais lattices for a thermally conducting network, as described above.
  • Figure 16 is a CAD perspective view of a hydrogen storage device 200B according to an exemplary embodiment, generally as described with respect to the hydrogen storage device 200A.
  • Figure 17 is a CAD axial cross-section of the hydrogen storage device 200B of Figure 16.
  • the hydrogen storage device 200B is arranged to be oriented horizontally, in use.
  • the pressure vessel 230B is generally cylindrical, having dished ends.
  • a passageway 250B provided by a tube having a circular cross-section, extends between the dished ends longitudinally, offset from an axis of the pressure vessel 230A.
  • the thermally conducting network 240B partially fills an internal volume of the pressure vessel, particularly a region of the internal volume extending across about 75% of a diameter the pressure vessel, thereby completely surrounding the tube, such that an unfilled volume above the thermally conducting network 240B is defined.
  • the thermally conducting network 240B is thermally coupled to at least a part of an internal surface of the pressure vessel 230B and an external surface of the tube.
  • the unfilled volume acts as a buffer, providing a reservoir of hydrogen during charging and similarly during release, for example to account for kinetics thereof.
  • Figure 18 is a CAD axial cross-section of a hydrogen storage device 240C according to an exemplary embodiment, generally as described with respect to Figures 16 and 17, having a relatively longer axial length and a relatively smaller diameter.
  • FIG 19 is a CAD perspective view of a charging station assembly 1 according to an exemplary embodiment.
  • the charging station assembly 1 comprises a charging station 2 and a hydrogen storage device 200.
  • the charging station 2 is arranged to receive eight hydrogen storage devices, arranged in a bank of 4 x 2 hydrogen storage devices.
  • the charging station 2 is arranged to charge a plurality of hydrogen storage devices 200, for example simultaneously.
  • the charging station 2 comprises a manifold 3 coupleable to the plurality of hydrogen storage devices 200.
  • the charging station 2 comprises a cooling system 4, arranged to cool a hydrogen storage device during charging thereof.
  • the cooling system 2 comprises a plurality of fans.
  • Figure 23A is a CAD perspective view of a hydrogen storage device 300 according to an exemplary embodiment
  • Figure 23B is a CAD perspective semi-transparent view of the hydrogen storage device 300 of Figure 23A
  • Figure 23C is a CAD axial cross-section view of the hydrogen storage device 300 of Figure 23A.
  • the hydrogen storage device 300 comprises: a pressure vessel 330, having a first fluid inlet 310 and/or a first fluid outlet 320, having therein a thermally conducting network 340 optionally thermally coupled to a first heater and/or a first cooler; wherein the pressure vessel 330 is arranged to receive therein a hydrogen storage material in thermal contact, at least in part, with the thermally conducting network 340; wherein the thermally conducting network 340 has a fractal geometry in two dimensions, comprising a plurality of nodes 341 , having thermally conducting arms 342 therebetween, with voids V between the arms 342; and wherein the thermally conducting network 340 comprises fluidically interconnected passageways 343 therein, within the arms 342 and the nodes 341 thereof, for flow therethough of a fluid.
  • the hydrogen storage device 300 is generally as described with respect to the hydrogen storage device 100A of Figure 1 .
  • FIG. 24A is a cutaway perspective view of a hydrogen storage device 200 according to an exemplary embodiment.
  • the hydrogen storage device 200 comprises a pressure vessel 230, having a first fluid inlet 210 and a first fluid outlet 220, comprising therein a thermally conducting network 240 thermally coupled to a first heater 300A, wherein the pressure vessel 230 is arranged to receive therein a hydrogen storage material (not shown) in thermal contact, at least in part, with the thermally conducting network 240, wherein the first fluid inlet 210 and/or the first fluid outlet 220 are in fluid communication with the first releasable fluid inlet coupling (not shown) and/or the first releasable fluid outlet coupling (not shown), respectively; and wherein the thermally conducting network 240 has a lattice geometry in three dimensions.
  • the pressure vessel 230 is generally cylindrical, having a generally internally dished first end and a flanged second end opposed thereto, and having a single aperture providing both the first fluid inlet 210 and the first fluid outlet 220.
  • the pressure vessel 230 is can-shaped.
  • An inner wall portion 230I of the pressure vessel 230 provides an axial cylindrical, elongate blind passageway P, arranged to optionally receive a second heater 300B (not shown) of the set of heaters 300, particularly a cartridge heater (not shown), that extends from the first end towards the second end and that is coaxial with an outer wall portion 2300 of the pressure vessel 230.
  • Blind passageways in the second end are arranged to receive thermocouples TC.
  • the first heater 300A is provided by a recirculating heater, for example heated using waste heat from a fuel cell coupled thereto, and includes a double helix heating tube 350, having an inlet 310 and an outlet 320, in thermal contact with the thermally conducting network 240, which is arranged between the inner 350I and outer 3500 helices of the heating tube 350.
  • the double helix heating tube 350 extends from the second end towards the first end is coaxial with an outer wall portion 2300 of the pressure vessel 230.
  • the inner 350I and outer 3500 helices of the double helix heating tube 350 are directly in thermal contact with the inner wall portion 230I and the outer wall portion 2300 of the pressure vessel 230, respectively.
  • a pressure gauge PG is provided in the second end. The second end is mechanically releasably coupled to the pressure vessel 230, using mechanical fasteners.
  • the thermally conducting network 240 has a lattice geometry in three dimensions, in which generally each node is connected by four arms to four other nodes, respectively, in an axially adjacent preceding layer, such that generally each node is thus connected by eight arms to eight other nodes, four nodes in the axially adjacent preceding layer and four nodes in an axially adjacent proceeding layer. Nodes proximal the inner 350I and outer 3500 helices of the heating tube 350 are in mutual thermal contact therewith.
  • an effective density of the lattice geometry is uniform in a first dimension, particularly axially, and non-uniform in mutually orthogonal second and third dimensions, particularly radially.
  • the thermally conducting network 240 has a porosity of at least 90%.
  • the thermally conducting network 240 is formed from an aluminium alloy.
  • the thermally conducting network 240 comprises inner 240I and outer 2400 portions, having annular shapes. The outer portion 2400 is received in thermal contact with and between the inner 350I and outer 3500 helices of the double helix heating tube 350 while the inner portion 240I is received in thermal contact with and within the inner helix 350I.
  • FIG. 24B is a cutaway perspective exploded view of a related hydrogen storage device 200.
  • the thermally conducting network 240 of the hydrogen storage device 200 of Figure 24B comprises inner 240I, middle 240M and outer 2400 portions.
  • the inner portion 240I has a cylindrical shape and the middle 240M and outer 2400 portions have annular shapes.
  • the outer portion 2400 is received in thermal contact and without the outer 3500 helices of the double helix heating tube 350, the middle portion 240M is received in thermal contact with and between the inner 350I and outer 3500 helices while the inner portion 240I is received in thermal contact with and within the inner helix 350I.
  • FIG. 25 is a cutaway perspective view of a hydrogen storage device according to an exemplary embodiment.
  • the hydrogen storage device 200 is generally as described with respect to the hydrogen storage devices 200 of Figures 24A and 24B and like reference signs denote like features.
  • the hydrogen storage device 200 does not include the inner wall portion 230I of the pressure vessel 230 of Figures 24A and 24B and does not include blind passageways in the second end to receive thermocouples.
  • the thermally conducting network 240 is cylindrical, to be received in thermal contact with the outer wall portion 2300 of the pressure vessel 230.
  • the inner 350I and outer 3500 helices of the double helix heating tube 350 are integrated within the thermally conducting network 240.
  • the inner 350I and outer 3500 helices of the double helix heating tube 350 are mutually spaced apart from and only indirectly in thermal contact with the outer wall portion 2300 of the pressure vessel 230, respectively, via the thermally conducting network 240.
  • the hydrogen storage device 200 includes a bed compression disc 231 , internal to the pressure vessel 230 proximal the first end and bed compression disc bolts 232 mechanically coupled thereto, extending through the first end, for uniaxially compressing the hydrogen storage material to improve thermal contact with the thermally conducting network.
  • O-rings 233 are arranged in the outer wall portion 2300 to prevent loss of the hydrogen storage material during compression thereof.
  • Figure 26A is a CAD partial cutaway perspective view of a hydrogen storage device 200 according to an exemplary embodiment
  • Figure 26B is a CAD longitudinal perspective cross- sectional view of the hydrogen storage device 200
  • Figure 26C is a CAD perspective view of the thermally conducting network, in more detail.
  • the hydrogen storage device 200 comprises a pressure vessel 230, having a first fluid inlet 210 and a first fluid outlet 220, comprising therein a thermally conducting network 240 thermally coupled to a first heater 300A, wherein the pressure vessel 230 is arranged to receive therein a hydrogen storage material (not shown) in thermal contact, at least in part, with the thermally conducting network 240, wherein the first fluid inlet 210 and/or the first fluid outlet 220 are in fluid communication with the first releasable fluid inlet coupling (not shown) and/or the first releasable fluid outlet coupling (not shown), respectively; and wherein the thermally conducting network 240 has a lattice geometry in three dimensions.
  • the hydrogen storage material comprises and/or is a liquid organic hydrogen carrier, LOHC.
  • the hydrogen storage device 200 is a dynamic hydrogen storage device 200.
  • the first fluid inlet 210 and the first fluid outlet 220 are mutually spaced apart at opposed ends of the first vessel 230, thereby defining, at least in part, a path for flow of the hydrogen storage material and/or hydrogen therebetween, for example via the voids of the thermally conducting network 240.
  • the first fluid inlet 210 and the first fluid outlet 220 comprise releasable couplings, thereby providing coupling thereto and uncoupling therefrom, for example repeatedly, of corresponding couplings.
  • the lattice geometry is Bravais lattice particularly a cubic lattice specifically a primitive cubic lattice.
  • the thermally conducting arms have a cross sectional dimension (for example a diameter or a width) of about 0.5 mm.
  • the thermally conducting network 240 partially fills an internal volume of the first vessel 230, of at least 90%, by volume of the first vessel 230.
  • the thermally conducting network 240 comprises a LOHC hydrogenation and/or dehydrogenation catalyst, for example provided on and/or in a surface thereof.
  • the thermally conducting network 240 has a porosity in a range from 75% to 95%, by volume of the thermally conducting network 240.
  • the thermally conducting network 240 has a specific surface area in a range from 1 nr 1 to 10 nr 1 , particularly about 7 nr 1 .
  • the thermally conducting network 240 comprises a LOHC hydrogenation and/or dehydrogenation catalyst, for example provided on and/or in a surface thereof.
  • the first heater is arranged heat the hydrogen storage material to temperature in a range from 150 °C to 300 °C.
  • the hydrogen storage device 200 comprises a pump (not shown) arranged to flow the hydrogen storage material through the first vessel 230.
  • the hydrogen storage device 200 is a reactor.
  • the first vessel 230 is an elongated cylinder formed from a Ti alloy (to withstand an operating pressure of about 2 bar at a temperature of about 260 °C for dehydrogenation), having a bore extending therethrough for the first heater, particularly a Joule cartridge heater.
  • the first fluid inlet 210 and the first fluid outlet 220 are provided with Swagelok releasable couplings.
  • the first fluid inlet 210 is arranged at an acute angle to the axis of the first vessel and the first fluid outlet is arranged parallel to the axis, to suit the particular application.
  • Figure 27A is a CAD partial cutaway perspective view of a hydrogen storage device 300 according to an exemplary embodiment
  • Figure 27B is a CAD transverse cross-sectional view of the hydrogen storage device 300.
  • the hydrogen storage device 300 is generally as described with respect to the hydrogen storage device 200 of Figures 24A and 24B.
  • Like reference signs denote like features.
  • the thermally conducting network 240 is provided by four extrusions 240A to 240D, for example of aluminium or copper or an alloy thereof (i.e. having a relatively high thermal conductivity), each disposed in a quadrant of the pressure vessel 230 and extending between opposed faces thereof, thereby maximising a length of the pressure vessel 230 benefiting from the thermally conducting network 240.
  • the four extrusions 240A to 240D each comprise 22 planar fins 241 radiating from four heating tubes 350A to 350D, as described below. Ends of the fins of an extrusion are in thermal contact with corresponding fins of an adjacent extrusion or the wall of the pressure vessel 230. Voids between the fins may be filled with a hydrogen storage material.
  • a thermally conducting network having a fractal geometry in two dimensions may similarly be provided by extrusion. In this way, the thermally conducting network 240 may be provided cost effectively, by extrusion.
  • the first heater 300A is provided by a recirculating heater, for example heated using waste heat from a fuel cell coupled thereto, and includes four heating tubes 350A to 350D, having inlets 310A to 310D and outlets 320A to 320D (not shown) respectively, in thermal contact with the thermally conducting network 240 and extending between opposed faces of the pressure vessel 230.
  • Figure 28A is a CAD partial cutaway perspective view of a hydrogen storage device 400 according to an exemplary embodiment
  • Figure 28B is a CAD partial cutaway perspective view of the hydrogen storage device 400, in more detail
  • Figure 28C is a CAD exploded perspective view of a part of the hydrogen storage device 400, in more detail.
  • the hydrogen storage device 400 is generally as described with respect to the hydrogen storage device 300 of Figures 27A to 27B.
  • Like reference signs denote like features.
  • the four extrusions 240A to 240D extend from one face of the pressure vessel 230 towards the opposed face, with a headspace H disposed thereabove proximal the opposed face for storage of hydrogen, as a buffer.
  • hydrogen may be stored in the headspace H at a relatively low pressure, for example for start up.
  • the headspace is delimited by a plate assembly 290, comprising a first plate 291 , a second plate 292 and a gasket 293 and a mesh 294 therebetween.
  • a central aperture A, covered by the mesh 294, allows hydrogen to flow therethrough while the mesh 294 retains the hydrogen storage material therebelow.
  • Figure 29A is a CAD partial cutaway perspective view of a hydrogen storage device 500 according to an exemplary embodiment
  • Figure 29B is a CAD longitudinal cross-sectional view of the hydrogen storage device 500.
  • the hydrogen storage device 500 is generally as described with respect to the hydrogen storage device 400 of Figures 28A to 28C.
  • Like reference signs denote like features.
  • the four extrusions 240A to 240D are spaced apart from both faces of the pressure vessel 230.
  • the hydrogen storage device 400 includes two U-shaped heating tubes 350A to 350B, having inlets 310A to 310B and outlets 320A to 320B respectively, in thermal contact with the thermally conducting network 240 and projecting from one face towards the opposed face of the pressure vessel 230.
  • the thermally conducting network 240 is relatively shorter.
  • FIG. 30 is a CAD partial cutaway exploded perspective view of a hydrogen storage device 600 according to an exemplary embodiment.
  • the hydrogen storage device 600 is generally as described with respect to the hydrogen storage device 400 of Figures 28A to 28C.
  • the thermally conducting network 240 comprises metal foam quadrants or wedges, for example manufactured by rolling a sheet of foam around a tubular core and subsequently, dividing the rolled foam cylinder. Thermal contact with the walls of the pressure vessel 230 arises from compression of the foam thereagainst.
  • Figure 31 is a CAD transverse cross-sectional view of a hydrogen storage device 700 according to an exemplary embodiment.
  • a hybrid thermally conducting network 240 is provided by an extrusion, as described with respect to Figures 27A and 27B, having foam, generally as described with respect to Figure 31 , arranged between the fins.
  • Figure 32 is a CAD partial cutaway perspective view of a hydrogen storage device 800 according to an exemplary embodiment.
  • the hydrogen storage device 800 is generally as described with respect to the hydrogen storage device 200 of Figures 24A and 24B.
  • Like reference signs denote like features.
  • the thermally conducting network 240 comprises an aluminium foam having a porosity of 93%.
  • the invention provides a hydrogen storage device comprising: a pressure vessel, having a first fluid inlet and/or a first fluid outlet, having therein a thermally conducting network optionally thermally coupled to a first heater and/or a first cooler; wherein the pressure vessel is arranged to receive therein a hydrogen storage material in thermal contact, at least in part, with the thermally conducting network; wherein the thermally conducting network preferably has a lattice geometry, a gyroidal geometry and/or a fractal geometry in two and/or three dimensions, comprising a plurality of nodes, having thermally conducting arms therebetween, with voids between the arms; and wherein the thermally conducting network comprises fluidically interconnected passageways therein, for example within the arms and/or the nodes thereof, for flow therethough of a fluid.
  • control for charging and/or release of hydrogen from the hydrogen storage device is improved because the flow of the fluid through the interconnected passageways in the thermally conducting network provides for faster, more homogenous, more accurate and/or more precise heating and/or cooling of the thermally conducting network and in turn, the hydrogen storage material in thermal contact therewith. Additionally and/or alternatively, in this way, storing and/or release of the hydrogen may be accelerated since heat generated or required, respectively, may be provided by the flow of the fluid through the interconnected passageways in the thermally conducting network.

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Abstract

L'invention concerne un dispositif (100A) de stockage d'hydrogène qui comprend : un récipient sous pression (230A), comportant une première entrée (210A) de fluide et/ou une première sortie (220A) de fluide possédant en son sein un réseau thermoconducteur (240A) éventuellement accouplé thermiquement à un premier dispositif chauffant et/ou à un premier refroidisseur ; le récipient sous pression (230A) étant agencé pour recevoir en son sein un matériau de stockage d'hydrogène en contact thermique, au moins en partie, avec le réseau thermoconducteur (240A) ; le réseau thermoconducteur (240A) présentant de préférence une géométrie de réseau, une géométrie gyroïdale et/ou une géométrie fractale dans deux et/ou trois dimensions, comprenant une pluralité de nœuds, ayant des bras thermoconducteurs entre eux, avec des vides entre les bras ; et le réseau thermoconducteur (240A) comprenant des passages en communication fluidique en son sein, par exemple à l'intérieur de leurs bras et/ou de leurs nœuds, pour qu'un fluide puisse s'écouler à travers ceux-ci.
EP20751203.9A 2019-07-19 2020-07-17 Dispositif de stockage d'hydrogène Pending EP3999770A2 (fr)

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GB1910411.6A GB2586578B (en) 2019-07-19 2019-07-19 Hydrogen storage device
PCT/GB2020/051726 WO2021014135A2 (fr) 2019-07-19 2020-07-17 Dispositif de stockage d'hydrogène

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IT202200005474A1 (it) * 2022-03-21 2023-09-21 Agt S R L Serbatoio per gas in pressione.
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GB2574673B (en) * 2018-06-15 2020-06-17 H2Go Power Ltd Hydrogen storage device

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GB2586578B (en) 2021-11-24

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