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WO2006003475A1 - Materiau de stockage de gaz, procede de stockage de gaz, procede pour la fabrication de materiau de stockage de gaz, et utilisations - Google Patents

Materiau de stockage de gaz, procede de stockage de gaz, procede pour la fabrication de materiau de stockage de gaz, et utilisations Download PDF

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Publication number
WO2006003475A1
WO2006003475A1 PCT/GB2005/050105 GB2005050105W WO2006003475A1 WO 2006003475 A1 WO2006003475 A1 WO 2006003475A1 GB 2005050105 W GB2005050105 W GB 2005050105W WO 2006003475 A1 WO2006003475 A1 WO 2006003475A1
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WO
WIPO (PCT)
Prior art keywords
hydrogen
storage material
reversible hydrogen
storage
reversible
Prior art date
Application number
PCT/GB2005/050105
Other languages
English (en)
Inventor
Denis Huguenin
Olivier Bordelanne
Original Assignee
Iti Scotland Limited
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 Iti Scotland Limited filed Critical Iti Scotland Limited
Priority to CA002573240A priority Critical patent/CA2573240A1/fr
Priority to EP05756223A priority patent/EP1765491A1/fr
Publication of WO2006003475A1 publication Critical patent/WO2006003475A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04201—Reactant storage and supply, e.g. means for feeding, pipes
    • H01M8/04216—Reactant storage and supply, e.g. means for feeding, pipes characterised by the choice for a specific material, e.g. carbon, hydride, absorbent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/065—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants by dissolution of metals or alloys; by dehydriding metallic substances
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • a Gas Storage Material a Method of Gas Storage, a Process for Manufacturing Gas Storage Material and Applications thereof.
  • the present invention relates to a reversible hydrogen storage material, a method of reversible hydrogen- storage, a process for manufacturing a reversible hydrogen- storage material and applications thereof.
  • a fuel cell is an energy conversion device that is capable of producing electricity from a gas such as hydrogen stored in storage media, and oxygen from the atmospheric air.
  • a gas such as hydrogen stored in storage media
  • oxygen from the atmospheric air.
  • the use of hydrogen in this way is extremely advantageous, not least because it is the most abundant element in the universe - over 95%, but also because this is a particularly low pollutant system; the fuel cell running wastes are principally water. Thus hydrogen is considered by many to be the fuel of the future.
  • Another method involves the storage of hydrogen in liquid form.
  • hydrogen in liquid form can be obtained when the temperature is at -253 0 C.
  • maintaining hydrogen at such a temperature is very costly in energy and it needs a cumbersome cooling system.
  • magnesium can be charged under standard conditions (room temperature and atmospheric pressure), however, the reaction proceeds too slowly for practical application due to slow diffusion of hydrogen within solid magnesium hydride, and this means that much more severe charging operating conditions are, in fact, needed: a temperature of 400 0 C and a pressure of 5 bars.
  • the dissociation pressure for magnesium hydride is very low, i.e. below normal pressure (1 bar), and the desorption temperature is higher than 400 0 C, thus for desorption to operate at room temperature, the hydrogen partial pressure needs to be decreased to below 10 "4 bar.
  • such storage chemical compounds are impractical for everyday use.
  • JP-56114801 discloses that a small improvement in the hydrogen exchange kinetics can be achieved using magnesium-nickel hydride
  • WO 2004/036664 discloses the use of magnesium hydride stabilized into the fluorite structure.
  • the present invention aims to resolve these problems by offering a reversible hydrogen- storage material and a method of storing hydrogen that have low manufacturing costs, that are safe to use and which are able to store hydrogen reversibly under conditions close to the normal temperature and pressure conditions.
  • the present invention also aims to determine favourable methods of making a reversible hydrogen- storage material with the maximum hydrogen storage capacity and with the optimised hydrogen charge and discharge kinetics.
  • the present invention further aims to highlight the use of such a reversible hydrogen storage material in a wide range of commercial applications.
  • the present invention provides a reversible hydrogen- storage material comprising: a) an active material, and b) a catalyst material, wherein the active material comprises one or more metal oxides having a conductivity of greater than 10 "10 Siemens.m "1 .
  • metal oxides can be used to produce a reversible hydrogen-storage material. Firstly, unlike the metal hydride materials used previously, metal oxides are not capable of storing hydrogen. However, the applicant has surprisingly discovered that metal oxides can be made to be capable of storing hydrogen if they are used in the presence of a catalyst material; consequently, the presence of the catalyst material is critical to the present invention. Secondly, it is expected, from Chapter 7, by P.G. Dickens and A. Chippindale, in 'Proton Conductors', pplOl-121 Cambridge University Press - 1992, that H 2 O would be discharged from hydrogen-containing metal oxides. However, this is not the case and the Applicant has observed discharge of diatomic hydrogen.
  • the active material comprises a metal oxide compound with high conduction properties and that it has a fluorite-type crystalline structure.
  • the conductivity ( ⁇ ) of a solid is derived from the sum of two contributing factors: 1) the electronic conductivity, that is, the electron motion within the solid, and 2) the ionic conductivity of the solid, that is, the motion of the ions within the solid. Looking at the latter, ions move within a solid due to the presence of intrinsic defects such as holes or vacancies within the lattice structure, and also due to extrinsic defects such as impurities.
  • the value of ionic conductivity is, therefore, a function of the degree of crystallinity of the solid and the amount of impurities weakly bonded to the solid, such as OH and CO.
  • There are conventional methods that can be used to measure the conductivity of a solid one of which is detailed in the Examples below.
  • the conductivity is higher than 2xlO "10 Siemens.m “ ⁇ further preferably higher than 5xlO "10 Siemens.m “1 and particularly preferably higher than 1 OxIO "10 Siemens.m “1 .
  • the fluorite-type crystalline structure can arise either because this is a natural crystalline form of the metal oxide, or because it can be stabilized in the fluorite form by introducing dopants. It is particularly preferred that the fluorite-type crystalline structure is stable at room temperature.
  • the catalyst material is deposited on the outer surface of the active material, for example as a substantially complete shell or as an incomplete shell, with the active material acting as a core material. Further, it is particularly advantageous that the catalyst material is deposited, either randomly or substantially evenly over the surface of the active material to provide one or more catalytically active sites on the active material. In this arrangement, the catalyst material has at least part of its surface exposed to the hydrogen being stored and the reversible hydrogen- storage material provides an interface between the catalyst material and the active material.
  • the metal oxide compounds used in the reversible hydrogen storage material of the present invention include one or more of ThO 2 , TiO 2 , CeO 2 , ZrO 2 , UO 2 , TbO 2 , PaO 2 , HfO 2 and PrO 2
  • Preferred metal oxides include CeO 2 , PrO 2 and ThO 2
  • Particularly preferred metal oxides are CeO 2 and PrO 2
  • the catalyst materials used in the reversible hydrogen- storage material of the present invention include any metal element that reacts with gaseous hydrogen; such metal elements are extremely well known to those skilled in the art.
  • Preferred metal elements include one or more of Ir, Ni, Pd, Pt, Rh, Ru, Au, Ag, Fe and Cu, and particularly preferred metal elements include one or more of Ni, Cu, Pd and Pt.
  • the reversible hydrogen- storage material is a powdered nano-composite material with a high surface area so as to favour the interaction between the storage material and the hydrogen being stored.
  • the amount of hydrogen stored depends on the density of the active material
  • the storage capacity at the surface of the active material depends upon the surface area of the reversible hydrogen- storage material. In theory, the larger the surface area, the larger the surface storage capacity.
  • the surface area of the reversible hydrogen storage material is in the range 50m 2 /g to 400m 2 /g, preferably, 100m 2 /g to 300m 2 /g.
  • the amount of catalyst material used is chosen to allow good coverage by the catalyst material over the surface of the active material whilst maintaining the efficiency of hydrogen storage.
  • a suitable ratio of the number of moles of the catalyst material (metal) / number of moles of the active material (in its oxide form) is in the range 1 - 0.05, and preferably in the range 0.5 - 0.1.
  • the preferred reversible hydrogen- storage materials of the present invention comprise an active material selected from one or more of cerium dioxide and praseodymium dioxide, and a catalyst material selected from one or more of nickel metal and copper metal.
  • the invention also provides a method of reversible hydrogen- storage using a reversible hydrogen- storage material comprising: a) an active material, and b) a catalyst material, wherein the active material comprises one or more metal oxides having a conductivity of greater than 10 ⁇ 10 Siemens.m "1 .
  • a suitable reversible hydrogen- storage material for use in this method of hydrogen storage is as described above.
  • the present invention further provides a process for manufacturing a reversible hydrogen- storage material such as the one previously described, characterized by the fact that it comprises an activation phase of the storage material.
  • the present invention provides a process for manufacturing the reversible hydrogen- storage material comprising:
  • reaction catalysts are conventionally prepared by depositing active catalyst metal particles onto a chemical substrate with a high surface area.
  • the most widely used preparative methods are performed in liquid media, for example, impregnation, equilibrium adsorption, coprecipitation, a sol gel procedure, an inverse micelle method, deposition precipitation and spray drying.
  • Alternative methods include mechanical mixing using a mortar and pestle or ball mill and a hydrogen arc plasma method.
  • aqueous precipitation also known as coprecipitation
  • aqueous precipitation is a convenient process for preparing the inactive precursor form of the reversible hydrogen- storage material used in the present invention. Such a process is described in some detail in WO 98/45212.
  • conducting the coprecipitation process in a microreactor is an excellent way to obtain the target material on a commercial scale.
  • coprecipitation produces hydrous hydroxides in water using acid-base neutralisations or ion exchange reactions.
  • the starting materials are soluble metal salts, frequently including nitrates, carbonates and halides, which are dissolved together in distilled water, preferably at a total salt concentration of 10OgL "1 to 20OgL "1 ; the resulting solution is 'neutralised' by adding it to an aqueous alkali, for example an aqueous ammonium solution or a potassium hydroxide solution, to give a co-precipitate product which is then filtered and washed.
  • an aqueous alkali for example an aqueous ammonium solution or a potassium hydroxide solution
  • the coprecipitate product comprises a metal oxide active material core with a catalyst material in the form of a metal oxide / oxyhydroxide, deposited thereon.
  • a preferred coprecipitate process uses cerium nitrate (Ce(NOs) 3 -OH 2 O) and nickel nitrate (Ni(NO 3 ) 2 .6H 2 O) as the starting materials.
  • the product of the formation step is preferably heat treated in an optional firing step. This is to clean the product by eliminating all the physisorbed and weakly chemisorbed species.
  • the optional firing step should be carried out prior to the activation step.
  • the firing temperature has a direct effect on the ability of the final reversible hydrogen- storage material to store hydrogen. If the firing temperature is too high then it is observed that the conductivity of the metal oxide reduces, and this consequently reduces hydrogen storage in the final reversible hydrogen- storage material.
  • the maximum firing temperature can be defined as the highest temperature before which the conductivity of the metal oxide active material drops.
  • a suitable firing temperature range is from 150 0 C to below 600 0 C, preferably from 200 0 C to 550 0 C, further preferably from 200 0 C to 500 0 C, and particularly preferably from 200 0 C to 450 0 C. Conveniently, the resulting product is very stable in air and may be stored at normal temperatures.
  • the purpose of the activation step is to 'activate' the inactive precursor form of the reversible hydrogen- storage material, that is to say to make it capable of reversibly absorbing or fixing a large quantity of hydrogen under temperature and pressure conditions close to normal conditions, i.e. around 25°C and around 1 bar.
  • the activation step involves 2 separate phases. During a first phase, the inactive precursor form of the reversible hydrogen- storage material is heated to an activation temperature under a reducing atmosphere, for example under carbon monoxide, hydrogen or an atmosphere containing hydrogen diluted with an inert gas, at a heating rate of 10 0 CnUn "1 .
  • the inactive precursor form of the hydrogen- storage material is held at the activation temperature, for several hours, for example from 1 to 24 hours, preferably at least 6 hours.
  • the activation temperature can be defined as the temperature sufficient to remove the oxygen atom of the metal oxide / oxyhydroxide catalyst material in the inactive precursor form of the reversible hydrogen- storage material.
  • a suitable activation temperature to obtain a final reversible hydrogen- storage material with optimum storage capacity is up to 500 0 C, preferably in the range from 200 0 C to 500 0 C, particularly from 250 0 C to 450 0 C.
  • the first phase of the activation step is completed by maintaining the reducing atmosphere, and gradually reducing the temperature down to room temperature, around 25°C, for example at a cooling rate of 20 0 CnUn "1 .
  • the heated inactive precursor form of the reversible hydrogen- storage material obtained from the first phase is further heated to a discharging temperature under an atmosphere empty of hydrogen or oxidant species.
  • the purpose of this second phase is to ensure that the heated inactive precursor form of the reversible hydrogen- storage material obtained from the first phase is discharged of all hydrogenated species absorbed during the first phase, and to obtain a final reversible hydrogen-storage material that is ready to be charged with hydrogen.
  • an atmosphere empty of hydrogen or oxidant species include an atmosphere of argon or helium or a vacuum.
  • the heated inactive precursor form of the reversible hydrogen- storage material obtained from the first phase is heated at a heating rate of 10 0 CmIn "1 , up to a discharging temperature.
  • a suitable discharging temperature is less than 600 0 C, preferably below 550 0 C, further preferably below 500 0 C, and particularly preferably below 450 0 C.
  • the discharging temperature is maintained for a period of time sufficient to desorb the hydrogen bearing species that were absorbed during the first phase, for example from 1 hour to 24 hours.
  • the resulting reversible hydrogen- storage material is cooled to room temperature at a cooling rate of 20 0 CnUn "1 , under an atmosphere empty of hydrogen or oxidant species.
  • hydrogen is stored by the reversible hydrogen- storage material using a charging operation comprising heating the reversible hydrogen- storage material to a storage temperature under a dihydrogen containing atmosphere; preferably, the storage temperature is less than the activation temperature, and a suitable storage temperature lies between O 0 C and the activation temperature.
  • a charging operation comprising heating the reversible hydrogen- storage material to a storage temperature under a dihydrogen containing atmosphere; preferably, the storage temperature is less than the activation temperature, and a suitable storage temperature lies between O 0 C and the activation temperature.
  • Excellent hydrogen storage can be achieved when the reversible hydrogen- storage material of the present invention is charged using the above storage operation at atmospheric pressure, however, it is particularly advantageous that during the storage operation, the reversible hydrogen- storage material is subjected to a pressure in the range from 0.5 bar to 10 bar, preferably 0.5 to 5 bar. Notwithstanding this, even if the storage operation takes some time, the energy required for the storage operation is favourably very low.
  • hydrogen is discharged from the reversible hydrogen storage material using a hydrogen discharging operation comprising heating the reversible hydrogen storage material charged with hydrogen to a discharging temperature, under vacuum or under an atmosphere empty of hydrogen species.
  • a suitable discharging temperature is less than 600 0 C, preferably below 550 0 C, further preferably below 500 0 C and particularly preferably below 450 0 C.
  • the present invention also provides for the use of the reversible hydrogen- storage material described above, in a wide range of commercial applications; some of these are mentioned below. All of the applications described, below capitalise on the ability of the reversible hydrogen- storage material of the present invention to fix and absorb hydrogen. For example:
  • the reversible hydrogen- storage material of the present invention can be used either to store hydrogen in tanks or by some other means, for example, to facilitate the use of hydrogen to power fuel cell devices and combustion engines; in the field of gas purification; the reversible hydrogen- storage material of the present invention can be used either as a trapping system to capture traces of hydrogen in a neutral gas such as argon, helium or nitrogen, or as a hydrogen filtering medium, such as a membrane, that can be used to extract hydrogen from a gaseous mixture. in the field of Ultra High Vacuum; the reversible hydrogen- storage material of the present invention can be used to trap any remaining hydrogen molecules to maintain the vacuum in sealed environments.
  • a neutral gas such as argon, helium or nitrogen
  • a hydrogen filtering medium such as a membrane
  • the reversible hydrogen- storage material of the present invention can be used in the design of hydrogen selective sensors. in the field of the reaction catalyst manufacture; the reversible hydrogen- storage material of the present invention can provide a 3D source of active hydrogen for hydrogenation reactions.
  • the reversible hydrogen storage material may comprise a refractory oxide support such as alumina, zirconia, titania, silica, zinc oxide and zeolites.
  • the process for manufacturing the reversible hydrogen- storage material of the present invention involves a formation step, an activation step, and optionally, a firing step. These steps will now be described in some detail.
  • the formation step is conveniently carried out using a co-precipitation method to produce an inactive precursor form of the reversible hydrogen- storage material of the present invention.
  • catalyst metal nitrate and active material metal nitrate salts are dissolved in distilled water (150 ml) (total salt concentration catalyst material metal + active material metal is in the range 100 g.L 1 to 200 g.L 1 ).
  • This solution is then added drop-wise to a basic solution of triethylamine (400 ml) under moderate stirring at 6O 0 C.
  • a white/orange co-precipitate forms and this changes rapidly into a brown/olive co- precipitate that is kept at 6O 0 C under stirring for one hour.
  • the solution is cooled to room temperature and maintained under moderate stirring overnight.
  • the resulting brown precipitate is filtered using a sintered disk funnel with a water jet- aspirator, to give a solid that is washed, first with pure ethanol (800 ml) to remove traces of triethylamine and then with boiling distilled water (approx. 1.51) until the filtrate washing solution has a neutral pH, i.e. a pH of about 7.
  • the washed precipitated powder is then collected in a PTFE beaker and suspended in ethanol (200 ml).
  • the obtained suspension is stirred in a sonicator for three hours and the stirring is maintained overnight without ultrasound.
  • the aim of this step is to perfectly disperse the suspended precipitate in ethanol.
  • the brown/orange suspension is returned to the sonicator for one hour.
  • the resulting suspension is then cooled using a lyophilization method, in order to get a solid with high surface area, by placing the PTFE beaker into a polystyrene box and pouring liquid nitrogen onto the suspension.
  • the polystyrene box is then filled with liquid nitrogen (11) and closed for about twenty minutes. During this time, the suspension freezes to produce a solid lump.
  • this solid lump is dried, by placing it in a desiccator under vacuum at room temperature, using a liquid nitrogen trap to condense the ethanol. After two days and two nights under vacuum, a dried brown/orange powder is obtained of a co-precipitate containing metal oxide active material and metal oxide/oxyhydroxide catalyst material.
  • the surface area of the powder is from 50m 2 /g to 400m 2 /g.
  • the inactive precursor of the reversible hydrogen- storage material produced in each of Examples 1-6 by the above formation step is in the form of a co-precipitate that contains an active material of metal oxide and a catalyst material of metal oxide/oxyhydroxide. These materials were then treated to a firing temperature of 150 0 C for 1 hour under vacuum to clean the product by eliminating all physisorbed and weakly chemisorbed species.
  • firing temperature has a marked effect on the ability if the final reversible hydrogen- storage material to store hydrogen.
  • the applicants have observed that when the firing temperature is too high, the conductivity of the active material is reduced. It is clear, therefore, that the conductivity must be maintained above a certain level to preserve hydrogen storage capability.
  • a co-precipitate containing an active material of metal oxide and a catalyst material of metal oxide/oxyhydroxide was subjected to firing under air for 1 hour at different temperatures from 150 0 C to 950 0 C. The conductivity values were measured at 25°C under air and are reported in Table 2 below.
  • the heated inactive precursor form of the reversible hydrogen- storage material obtained from the first phase in respect of the materials of Examples 2, 4 and 6 was further heated from room temperature to 600 0 C under an atmosphere empty of hydrogen or oxidant species and analysed using mass spectrometry to determine the amount of hydrogen emitted.
  • the signal intensity results, given in Table 3, provide an indication of the amount of released hydrogen; the higher the current (signal intensity), the greater the amount of stored hydrogen being emitted.
  • the reversible hydrogen- storage material obtained at the end of the second phase is ready to be charged with hydrogen under optimum storage conditions.
  • a powdered sample of the material whose conductivity is being measured is pressed to form a disk pellet with a diameter equal to 13mm. Pressure in the 2.5 to 3.5 tonne range is applied and maintained for 15 minutes. The pellet is then placed into a conductivity cell (quartz tube) with 2 platinum electrodes connected to a complex impedance spectrometer analyser able to operate at frequencies between 0.1 Hz to 32Hz in order to measure resistances between lOm ⁇ to 100M ⁇ .
  • the applied alternative current has a maximum voltage amplitude of 300 mV.
  • the duration of the storage operation, and also the storage temperature have a marked effect on the amount of hydrogen stored; the amount of hydrogen increases as the duration of the storage operation increases, until a stable quantity of stored hydrogen, corresponding to the saturation level of the hydrogen storage material, is obtained.
  • the reversible hydrogen- storage material obtained in respect of Example 1 was subjected to a storage operation involving heating to a storage temperature of 250 0 C, under 1 bar of a dihydrogen diluted at 95% in a helium atmosphere for varying periods of time.
  • the results are summarized below in Table 4.
  • the "full" storage material is heated up to a discharging temperature of below 600 0 C under vacuum or an atmosphere empty of hydrogen. This heating induces desorption, in gas form, of the majority of the hydrogen adsorbed during the charging operation.
  • Table 5 below presents results of discharging operations conducted on a storage material sample form Example 1, "filled" during a previous storage operation. In this example, previous storage operations have been conducted for 2 hours, under a 1 bar pressure of a diluted at 95% in helium hydrogen atmosphere. Each previous storage operation has been conducted at a different storage temperature, 5O 0 C, 15O 0 C and 25O 0 C.
  • the reversible hydrogen- storage material of the present invention is able to desorb at least 0.7 g of molecular hydrogen per lOOg of material.
  • the reversible hydrogen- storage material of the present invention is able to undergo several charging/discharging cycles.

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Abstract

La présente invention a trait à un matériau de stockage d'hydrogène réversible, à un procédé de stockage de l'hydrogène réversible de l'hydrogène, à un procédé de fabrication de matériau de stockage réversible de l'hydrogène et leurs utilisations. En particulier, le matériau de stockage réversible de l'hydrogène comporte un matériau actif et un matériau catalyseur, le matériau actif comprenant un ou des oxydes.
PCT/GB2005/050105 2004-07-06 2005-07-06 Materiau de stockage de gaz, procede de stockage de gaz, procede pour la fabrication de materiau de stockage de gaz, et utilisations WO2006003475A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CA002573240A CA2573240A1 (fr) 2004-07-06 2005-07-06 Materiau de stockage de gaz, procede de stockage de gaz, procede pour la fabrication de materiau de stockage de gaz, et utilisations
EP05756223A EP1765491A1 (fr) 2004-07-06 2005-07-06 Materiau de stockage de gaz, procede de stockage de gaz, procede pour la fabrication de materiau de stockage de gaz, et utilisations

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FR0451444 2004-07-06
FR0451444A FR2872716B1 (fr) 2004-07-06 2004-07-06 Produit de stockage reversible de dihydrogene, procede de fabrication d'un tel produit, et utilisation d'un tel produit pour le stockage reversible de dihydrogene

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
CN103968231A (zh) * 2014-04-03 2014-08-06 上海华篷防爆科技有限公司 一种由铁基多孔金属材料制备的储氢装置

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CA3080734A1 (fr) * 2020-05-14 2021-11-14 Hydro-Quebec Systeme et procede de stockage et de production d'electricite

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