WO2000075559A1 - Procede de stockage reversible de h2 et systeme de stockage de h2 base sur des materiaux en carbone a dopage metallique - Google Patents

Procede de stockage reversible de h2 et systeme de stockage de h2 base sur des materiaux en carbone a dopage metallique Download PDF

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Publication number
WO2000075559A1
WO2000075559A1 PCT/SG2000/000058 SG0000058W WO0075559A1 WO 2000075559 A1 WO2000075559 A1 WO 2000075559A1 SG 0000058 W SG0000058 W SG 0000058W WO 0075559 A1 WO0075559 A1 WO 0075559A1
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Prior art keywords
carbon
alkali metal
doped
hydrogen
alkali
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PCT/SG2000/000058
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English (en)
Inventor
Ping Chen
Jianyi Lin
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National University Of Singapore
Tan, Kuang, Lee
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Filing date
Publication date
Priority claimed from SG9902930A external-priority patent/SG109408A1/en
Application filed by National University Of Singapore, Tan, Kuang, Lee filed Critical National University Of Singapore
Priority to AU46375/00A priority Critical patent/AU4637500A/en
Publication of WO2000075559A1 publication Critical patent/WO2000075559A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • 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
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • 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
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B01J20/205—Carbon nanostructures, e.g. nanotubes, nanohorns, nanocones, nanoballs
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28004—Sorbent size or size distribution, e.g. particle size
    • B01J20/28007—Sorbent size or size distribution, e.g. particle size with size in the range 1-100 nanometers, e.g. nanosized particles, nanofibers, nanotubes, nanowires or the like
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
    • 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
    • C01B3/0021—Carbon, e.g. active carbon, carbon nanotubes, fullerenes; Treatment thereof
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/42—Materials comprising a mixture of inorganic materials
    • 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

  • This invention relates to a method of storing H2 in metal-doped carbon-based solid state sorbents, such as carbon nano tubes (including stacked truncated carbon nanocones), carbon nanofibers, activated carbon, carbon fibers, graphite and amorphous carbon.
  • metal-doped carbon-based solid state sorbents such as carbon nano tubes (including stacked truncated carbon nanocones), carbon nanofibers, activated carbon, carbon fibers, graphite and amorphous carbon.
  • the present invention also relates to metal-doped carbon-based sorbent materials capable of absorbing up to 25 wt% of hydrogen at moderate temperature and pressure.
  • Hydrogen has been recognized as an ideal energy carrier.
  • end-user hydrogen storage is still one of the challenging technical problems attracting increasing research interest 1"5 to make it truly useful.
  • a substantial number of research groups worldwide have put intensive effort to try to use a hydrogen based fuel cell as a power source for automobiles and other devices. These groups have encountered problems associated with high cost and low efficiency of the hydrogen storage systems.
  • liquid hydrogen storage system is of importance because it offers good solutions in terms of technology and economy, both for mobile storage systems and large-volume storage for volumes of from 100 litres to 5000 m 3 .
  • the container (dewar) should be made of super-insulating materials, which is very expensive in practice.
  • the compressed gas storage system is usually applied in underground supply systems, similar to a network of natural gas. This is an economical and simple method, but it is unsafe and not portable.
  • Cryo-adsorbing storage systems show advantages in moderate weight and volume.
  • hydrogen molecules are bound to the sorbent only by physical adsorption forces, and remain in the gaseous state.
  • the adsorbing temperature is in the range of 60 to 100 K.
  • activated carbon is used as the sorbent due to its large portion of small pores serving as arenas for storing H2.
  • the efficiency of H2 uptake is no more than 7 wt%, which is equivalent to about 20 kg H2 per cubic meter of activated carbon.
  • the disadvantages of this system relate to the low capacity and the much lower temperature required, which, similar to that of liquid hydrogen systems, makes it necessary to use suitable super- insulated containers, and thus the cost is increased.
  • M is a selected metal system.
  • Two major metal systems, i. e. Fe-Ti and Mg-Ni, have been applied as H2 storage media and have been put into use in automobiles driven by an H2/O2 fuel cell.
  • the operating temperature is 40 - 70°C for the Ti-Fe system and 250- 350 °C for the Mg-Ni system.
  • the H2 storage capacity is less than 5 wt% for Ni-Mg and 2 wt% for Fe-Ti, which corresponds to less than 70 kg H2 per cubic meter of metals.
  • metal hydride systems normally require 20-40 bar pressure to keep the hydrogen in equilibrium. This renders the container for the metal hydride too heavy and expensive, and limits the practical exploitation of these systems.
  • Embodiments of the present invention advantageously provide systems which increase H2 storage capacity relative to prior systems and also provide for hydrogen storage under practical conditions.
  • Alkali-metal based materials have been reported as being able to absorb H2.
  • Li- based materials normally in the case of an Li battery, hydrogen absorption takes place under electro-chemical conditions 1 .
  • LiH can be formed at 300-500°C, but the dissociation requires 700-900°C.
  • K-based materials it has been reported that about 160 ml of hydrogen was absorbed by 1 gram K-intercalated graphite at liquid nitrogen temperature 6 .
  • the intercalation of alkali metal into graphene layers may form a compound, CnM.
  • the present invention advantageously provides a method which increases the hydrogen storage capacity of a solid sorbent.
  • the present invention also provides a method which enables the storage of hydrogen to be reversibly performed under ambient or higher pressure and moderate temperature.
  • the present invention advantageously provides a means to economically make an efficient sorbent.
  • the above advantages may be achieved by modifying the nature of a carbon-based material which is to be used as the sorbent in a hydrogen storage system.
  • the modification according to the invention comprises the doping of the carbon-based material with a metal which doping causes a distinct change in the structural and electronic properties of the carbon-based material.
  • doping refers to the addition of metal to carbon materials with the result that the structural and electronic properties of the carbon material are changed. This contrasts with a more strict definition of doping where actual replacement of carbon atoms within the graphitic structure is assumed. Without being bound by any theory of the invention, the inventors believe that a carbon metal compound structure is formed.
  • a method of reversibly storing hydrogen comprising exposing a solid sorbent of metal-doped carbon-based material to a hydrogen atmosphere at a temperature of from about 250 K to about 973 K under ambient or higher H2 pressure, preferably from about 1 to about 200 arm, more preferably from about 1 to about 100 atm and most preferably from about 1 to about 5 arm.
  • a method of reversibly storing hydrogen comprising pre-treatment of a solid sorbent comprising a metal- doped carbon-based material in an inert atmosphere at high temperature before exposing a solid sorbent of metal-doped carbon-based material to a hydrogen atmosphere at a lower temperature under ambient or higher H2 pressure.
  • a method of preparing an alkali metal-doped carbon-based material for use in reversibly storing hydrogen comprising mixing a carbon material with an alkali metal salt and calcining the mixture under an atmosphere of inert or reductive gases.
  • FIG. 1 is a thermogravimetric analysis (TGA) profile of a reversible H2 sorption on Li-doped carbon nanotubes.
  • TGA thermogravimetric analysis
  • FIG. 2 is a TGA profile of a reversible H2 sorption on K-doped carbon nanotubes.
  • FIGS. 3a-3d are schematic representations of various generic nanotube (FIGS. 3a,
  • FIGS. 4a-4d are schematic representations of the cross-sections of the nanotube
  • FIGS. 4a, 4b and 4d and nanofiber (FIG.4c) structures illustrated in FIGS. 3a-3d.
  • a single walled nanotube in (b) a multi-walled nanotube, in (c) stacked nanocones and in (d) stacked truncated nanocones are illustrated.
  • the alkali-doped carbon based materials are sensitive to oxygen or moisture.
  • the carbon material of the carbon-based material is selected from carbon nanotubes (including but not limited to stacked truncated carbon nanocones), activated carbon, carbon powder, amorphous or disordered carbon, carbon fibers, carbon nanofibers and graphite, and the metal is an alkali metal.
  • Graphite is commercially available and has a layered structure, high crystallinity and low surface area.
  • the typical graphite interplanar distance is 0.335 nm.
  • Carbon fibers are commercially available and made of carbon with a graphite-like structure.
  • One way of making carbon fibers commercially is by catalytic decomposition of hydrocarbons.
  • the diameter of carbon fibers is on the order of microns up to centimeters.
  • Carbon nanofibers are similar to carbon fibers in that they are made of carbon with a graphite-like structure 8 . However, the diameter is much smaller in that it is on the order of nanometers. The smaller diameter may be related to the manufacturing process such as using a smaller sized catalyst 9 .
  • Carbon fibers and carbon nanofibers have slender solid structure.
  • One special type of carbon nanofiber structure is the so-called herringbone structure consisting of stacked nanocones (FIGS.3c and 4c). Carbon nanocones may be visualized as graphene sheets rolled into conical shells. When the conical shells are stacked up (FIG. 3c) they form nanofibers with so-called herringbone structures as shown in FIG. 4c. When the conical shells are truncated and are stacked up they form nanotubes as shown in FIG. 3d with a schematic cross-sectional representation as in FIG. 4d.
  • Active carbon is commercially available.
  • the activity of activated carbon is related to its large surface area, porosity and low crystallinity.
  • Amorphous carbon is commercially available carbon with low crystallinity.
  • the first type of carbon nanotubes has walls parallel to the longitudinal axis of the tubular structure.
  • the walls have similar structure as that of graphite, but with graphene sheets arranged as nested concentric cylinders.
  • These carbon nanotubes can be either single-wall (FIGS. 3a and 4a) or multi-wall (FIGS. 3b and 4b) depending on whether a single or multiple graphene sheets are arranged as nested concentric cylinders around each other.
  • These carbon nanotubes can be made from catalytic disproportionation of CO, as previously reported 10 or by other methods well known in the art.
  • the outer diameter of these single- or multi-wall carbon nanotubes ranges from 1 to 35 nm with an average of 15 nm.
  • the second type of carbon nanotubes are made from CH 4 decomposition over the Ni-, Co- or Fe-based catalyst as previously reported 10 .
  • the structure of stacked truncated carbon nanocones shows certain differences when compared with carbon nanotubes and graphite.
  • the truncated conical shells may be visualized as graphene sheets arranged into the shape of a frustrum with open ends (FIG.3d).
  • the truncated conical shells pile up or stack up to form a hollow tubular shape with lengths varying from several microns up to several hundred microns.
  • the outer diameter varies from 10 to 60 nm (average 30 nm) and the inner diameter varies from 0.1 to 10 nm depending on the conditions during catalytic decomposition of CH4.
  • carbon nanotubes or nanofibers are used which have been prepared by catalytic disproportionation of CO (first type nanotube) or decomposition of CH4 (second type nanotube) on a Ni-based catalyst. After purification, more than 75 % , typically more than 85 % and, more typically, 90 % or more of the product is advantageously in the form of nanotubes.
  • the structural properties of carbon nanotubes and nanofibers are similar to that of graphite, but with greater interlayer distance: 0.345 nm for both types of nanotubes, compared with 0.335 nm for graphite. Both nanotubes and nanofibers can reach several microns in length.
  • the nanotubes have the a stacked truncated nanocone structure as illustrated in FIG. 3d, a cross-sectional view of which appears in FIG. 4d.
  • the metal-doped carbon-based material is an alkali metal-doped carbon- based material.
  • the alkali metal may be, for example, Li, Na, K, Rb or Cs. Mixtures of alkali metals can be used. For example, two or three different metals can be used, preferably a mixture of Li and one additional alkali metal. An exemplary mixture is of Li and K.
  • the temperature for hydrogen absorption is in the range of 400-900 K for Li-doped carbon materials, preferably between 500 and 670 K, and 200-700 K for Na- or K-doped carbon materials, preferably between 300 and 470 K.
  • the pressure for the absorption process is preferably as high as practical. The higher charging pressure results in saturation in a shorter time. Typically, the charging pressure is between 1 and 100 atm, more typically between 1 and 30 atm, most typically between 1 and 5 arm.
  • Figure 1 and 2 are the TGA spectra of Li-doped and K-doped carbon nanotubes, respectively, in the hydrogen uptake process.
  • the Li-doped sample, prepared as in Example 2 was preheated in-situ at 873 K for 1 hour in a flow of purified hydrogen (99.99%) to remove absorbed water and contaminants, then gradually cooled down from 873 to 300 K and then heated up to 873 K again linearly (2 degrees/min). From Figure 1 , it can be seen that the H2 uptake began at temperatures around 772 K and ended at 423 K. When the temperature was increased again, the sample further increased its weight, reaching a maximum value at around 673 K.
  • the doping of alkali metals to the carbon materials may be achieved by solid state reaction between the carbon materials and alkali metal salts.
  • the solid state reaction method preferably involves thoroughly mixing the carbon materials with the alkali metal salt, then subjecting the mixture to high temperature treatment under inert gases, such as He, N2, Ar, etc. or reductive gases such as H2, etc.
  • the alkali-doped carbon based materials are sensitive to oxygen or moisture. Exposure to oxygen during or after the calcination process greatly reduces the ability of the sorbent material to take up hydrogen. It is therefore preferred to use a salt lacking in oxygen in the calcination process. If the ability of hydrogen uptake of the alkali-doped carbon-based material is impaired by exposure to oxygen or moisture, this impairment can be reversed by a pre-treatment at an elevated temperature under an inert atmosphere (e.g. Ar, N2) or a reducing atmosphere (e.g. H2) for a period of time before charging the doped material with hydrogen.
  • an inert atmosphere e.g. Ar, N2
  • a reducing atmosphere e.g. H2
  • a pre-treatment at elevated temperature is performed on the doped material at temperatures ranging between 373 and 1073 K under an inert atmosphere such as Ar or N before charging the doped material with H 2 at a lower temperature.
  • the subrange between 573 and 973 K is typically chosen.
  • the subrange between 673 and 1023 K is typically chosen.
  • the alkali metal salts may include carbonates, nitrates, hydroxides, halogenides, acetates, hydrides, nitrites, or the like.
  • the molar ratio of alkali metal to the carbon materials in the reaction is preferably from about 1 : 50 to 1 : 1 , more preferably from 1 : 10 to
  • the temperature for the chemical reaction is preferably in the range of from 473 to 1273 K according to the alkali metal salts selected. Typical conditions are 473-1073 K, more typically 773 to 1073 K for doping with Li under hydrogen or an inert gas, and 573-1273 K, more typically 623 to 973 K for doping with Na and K under hydrogen.
  • the abnormal capability for reversible H2 sorption by the alkali metal-doped carbon materials according to embodiments of the invention is derived from the doping of alkali metal into the carbon materials.
  • the electronic structure of the carbon material is changed significantly due to the alkali metal doping, as revealed by our XPS and UPS studies.
  • Alkali metal in the alkali metal-doped carbon-based materials transfers a near unity charge to carbon, resulting in an M + state and a significant increase in free electron density in the graphene layers . In the valence band region the alkali metal doping creates an extra density of states at the Fermi edge.
  • This alkali metal-derived Fermi-level band shifts the Fermi level closer toward the instrument vacuum level and plays a particularly important role in reducing the activation energy for the dissociative hydrogen chemisorption.
  • Other mechanisms of reversible hydrogen sorption, such as physical adsorption, are possible.
  • the hydrogen dissociative absorption on carbon is a slow activated process, with an activation energy corresponding to an above-zero-energy crossing between the dissociated H-atoms and H2 molecular potential curves. Few molecules may have high enough energy to surmount this intrinsic energy barrier, resulting in minimal sticking taking place on carbon at ambient pressure and moderate temperatures without metal-doping. Energetically the key step for this process is the weakening and the final breaking of the H-H bond. Band-structure calculations indicate that the half-filled Fermi level band created by the alkali metal doping is formed by the hybridization of the alkali metal outermost s orbital with a low-lying bonding C ⁇ band.
  • the cyclable hydrogen binding capacity of the alkali metal-doped carbon material of the invention is at least 5 % , more preferably at least 15 % of the weight of the unabsorbed material. More preferably, the cyclable hydrogen binding capacity is at least 20% , still more preferably up to 25% of the weight of the unabsorbed material, most preferably the cyclable capacity ranges from 20% to 25 % of the weight of the unabsorbed alkali-doped carbon-based material.
  • Example 2 After maintaining the sample at room temperature for 60 min and purging with H2, maintaining an H2 atmosphere at 30 psi to drive away the air left in the sample chamber, the temperature was increased from room temperature to 973K at a rate of 20 K/min, and maintained at 973K for 1 h to outgas the absorbed water and volatile contaminants. Then, the sample was cooled to 623K at a rate of 20 K/min, and maintained for 2 h. A weight increase of 20 % due to hydrogen uptake was achieved after this process.
  • Example 2 Example 2
  • TGA system The system was heated to 673K to remove absorbed water and volatile contaminants, and then cooled down to 298K and maintained for 2 h. A weight increase of about 5 % was achieved after such a process.
  • Li-doped carbon nanotubes multi-wall, first type nanotubes
  • Ni catalyst 100 mg was pre-reduced at 700 °C in a flow of purified hydrogen in a tubular reactor for 1 hour.
  • the hydrogen gas was then replaced by purified CH4 as the feed-gas and the reaction system was maintained at 700 °C for 1 hour to let CH 4 decompose on the Ni catalyst.
  • the CH4 gas supply was then turned off and the catalyst together with the material formed was allowed to cool down to room temperature under ambient pressure.
  • the material collected comprises truncated stacked carbon nanocones with metal catalyst attached, formed by decomposition of CH4 on the Ni catalyst.
  • the H2-rechargeability of Li- and K-doped samples was tested by TGA.
  • Li- doped samples carbon nanotubes and graphite
  • the saturated H2 uptake was measured at 653K after each complete deso ⁇ tion at 823 K
  • K-doped carbon materials it was measured at 298 K after each run of deso ⁇ tion at 773 K.
  • the results show that after more than 20 cycles of abso ⁇ tion-deso ⁇ tion, the capacities of H2 uptake are reduced by less than 10% for both systems.

Abstract

La présente invention concerne un procédé de stockage réversible d'hydrogène consistant à exposer un matériau solide en carbone à dopage métallique à une atmosphère d'hydrogène, à une température d'environ 250 K à environ 973 K sous pression ambiante ou à sous pression plus élevée. Le matériau en carbone à dopage métallique est généralement dopé au moyen d'un métal alcalin et sa préparation est effectuée par mélange d'un matériau en carbone et d'un sel de métal alcalin et calcination du mélange sous atmosphère d'un gaz inerte ou réducteur.
PCT/SG2000/000058 1999-06-04 2000-04-25 Procede de stockage reversible de h2 et systeme de stockage de h2 base sur des materiaux en carbone a dopage metallique WO2000075559A1 (fr)

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Application Number Priority Date Filing Date Title
AU46375/00A AU4637500A (en) 1999-06-04 2000-04-25 Method of reversibly storing H2 and H2-storage system based on metal-doped carbon-based materials

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
SG9902930-8 1999-06-04
SG9902930A SG109408A1 (en) 1999-06-04 1999-06-04 Method of reversibly storing h2, and h2-storage system based on metal-doped carbon-based materials
US09/517,057 2000-03-02
US09/517,057 US6471936B1 (en) 1999-06-04 2000-03-02 Method of reversibly storing H2 and H2 storage system based on metal-doper carbon-based materials

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004048259A1 (fr) * 2002-11-21 2004-06-10 California Institute Of Technology Compositions a base de carbone pour le stockage reversible d'hydrogene
SG117426A1 (en) * 2001-10-31 2005-12-29 Univ Singapore Method for alkali hydride formation and materials for hydrogen storage
WO2006003475A1 (fr) * 2004-07-06 2006-01-12 Iti Scotland Limited Materiau de stockage de gaz, procede de stockage de gaz, procede pour la fabrication de materiau de stockage de gaz, et utilisations
US8015808B2 (en) 2001-01-09 2011-09-13 G4 Insights Inc. Power plant with energy recovery from fuel storage
US8541637B2 (en) 2009-03-05 2013-09-24 G4 Insights Inc. Process and system for thermochemical conversion of biomass
US9394171B2 (en) 2009-11-18 2016-07-19 G4 Insights Inc. Method and system for biomass hydrogasification
US10653995B2 (en) 2009-11-18 2020-05-19 G4 Insights Inc. Sorption enhanced methanation of biomass

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Publication number Priority date Publication date Assignee Title
EP0112548A2 (fr) * 1982-12-22 1984-07-04 Studiengesellschaft Kohle mbH Procédé pour la production de systèmes actifs pour l'emmagasinage de l'hydrogène par hydrures de magnésium
DE19745549A1 (de) * 1997-10-10 1999-04-15 Mannesmann Ag Gasspeicher

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0112548A2 (fr) * 1982-12-22 1984-07-04 Studiengesellschaft Kohle mbH Procédé pour la production de systèmes actifs pour l'emmagasinage de l'hydrogène par hydrures de magnésium
DE19745549A1 (de) * 1997-10-10 1999-04-15 Mannesmann Ag Gasspeicher

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8015808B2 (en) 2001-01-09 2011-09-13 G4 Insights Inc. Power plant with energy recovery from fuel storage
SG117426A1 (en) * 2001-10-31 2005-12-29 Univ Singapore Method for alkali hydride formation and materials for hydrogen storage
WO2004048259A1 (fr) * 2002-11-21 2004-06-10 California Institute Of Technology Compositions a base de carbone pour le stockage reversible d'hydrogene
WO2006003475A1 (fr) * 2004-07-06 2006-01-12 Iti Scotland Limited Materiau de stockage de gaz, procede de stockage de gaz, procede pour la fabrication de materiau de stockage de gaz, et utilisations
US8541637B2 (en) 2009-03-05 2013-09-24 G4 Insights Inc. Process and system for thermochemical conversion of biomass
US9394171B2 (en) 2009-11-18 2016-07-19 G4 Insights Inc. Method and system for biomass hydrogasification
US10190066B2 (en) 2009-11-18 2019-01-29 G4 Insights Inc. Method and system for biomass hydrogasification
US10653995B2 (en) 2009-11-18 2020-05-19 G4 Insights Inc. Sorption enhanced methanation of biomass

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