US20070092395A1 - Hydrogen storage material and method for making - Google Patents

Hydrogen storage material and method for making Download PDF

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US20070092395A1
US20070092395A1 US11/242,158 US24215805A US2007092395A1 US 20070092395 A1 US20070092395 A1 US 20070092395A1 US 24215805 A US24215805 A US 24215805A US 2007092395 A1 US2007092395 A1 US 2007092395A1
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group
catalyst
metal
matrix material
aluminum
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Job Rijssenbeek
Yan Gao
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General Electric Co
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General Electric Co
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Priority to PCT/US2006/038388 priority patent/WO2007041468A2/en
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/0005Reversible 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
    • C01B3/001Reversible 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
    • C01B3/0031Intermetallic compounds; Metal alloys; Treatment thereof
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/0005Reversible 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
    • C01B3/001Reversible 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
    • C01B3/0078Composite solid storage mediums, i.e. coherent or loose mixtures of different solid constituents, chemically or structurally heterogeneous solid masses, coated solids or solids having a chemically modified surface region
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B6/00Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
    • C01B6/24Hydrides containing at least two metals; Addition complexes thereof
    • C01B6/243Hydrides containing at least two metals; Addition complexes thereof containing only hydrogen, aluminium and alkali metals, e.g. Li(AlH4)
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/32Hydrogen storage

Definitions

  • This invention relates to the storage and production of hydrogen. More particularly, this invention relates to materials used to store and generate hydrogen in such systems, and methods for making such materials.
  • Hydrogen is a “clean fuel” because it can be reacted with oxygen in hydrogen-consuming devices, such as a fuel cell or a combustion engine, to produce energy and water. Virtually no other reaction byproducts are produced in the exhaust.
  • hydrogen as a fuel effectively solves many environmental problems associated with the use of fossil fuels. Safe and efficient storage and retrieval of hydrogen gas is, however, essential for many applications that can use hydrogen. In particular, minimizing volume and weight of the hydrogen storage systems are important factors in mobile applications.
  • One embodiment is a method for making a material.
  • the method comprises providing a metallic catalyst comprising at least one metal component and at least one Group 13 element, wherein the catalyst comprises a disordered phase; providing a matrix material; and homogenizing the catalyst with the matrix material to form a material comprising (i) the matrix material and (ii) the catalyst disposed within the matrix material.
  • the material comprises a matrix material and a metallic catalyst disposed within the matrix material, the catalyst comprising at least one metal component and at least one Group 13 element, wherein the catalyst comprises a disordered phase.
  • the hydrogen storage material has a hydrogen desorption rate of at least about 3 weight percent per hour at a temperature of about 150° C.
  • FIG. 1 is a graph illustrating hydrogen desorption rates from various materials, including materials made by the method of the present invention.
  • Complex hydrides such as, for example, hydrides containing aluminum and one or more alkali metals, have been shown to reversibly store (absorb) and release (desorb) at moderate temperatures (that is, temperatures below about 200 ° C.) when they are doped with certain catalyst compounds.
  • transition metal compounds have been reported to provide this catalyst effect, albeit with slow and unstable kinetics.
  • a number of processes for the synthesis of doped complex hydrides have been proposed, but many of these processes involve additions of salts to a hydride starting material. The salt additions ultimately detract from the overall storage capacity of the final material by consuming at least a portion of the starting material, rendering the consumed material unavailable for hydrogen storage.
  • TiAl 3 titanium aluminide
  • the titanium aluminide used in the Gross et al. method is described to be a product of the reaction of titanium chloride with aluminum metal and sodium hydride, and is further described to have the L 1 2 crystal structure.
  • This ordered structure can be envisioned as a cube where the aluminum atoms are positioned in the center of each face of the cube and the titanium atoms are positioned at the corners of the cube.
  • powders of titanium aluminide, aluminum, and sodium alanate (NaAlH 4 ) were mixed in a high-energy ball mill for 2 hours.
  • the resultant material was then hydrogenated by exposure to hydrogen gas at elevated temperature and pressure.
  • the material doped with titanium via this method showed an increase of over a factor of ten in hydrogenation kinetics over undoped material, the data reported in U.S. 2003/0165423 suggest that the rate of absorption obtained with the Gross et al. material may still be too low for many practical applications.
  • the present inventors have discovered a source of the problems causing the above shortcomings. According to this discovery, the capacity and kinetics of some complex hydrides can be significantly improved over the results noted in the prior art by doping with a catalyst component having a composition and crystal structure that closely matches that of the catalyst as it is found to exist in the doped hydride material. Without being limited to any particular explanation, it is theorized that providing a catalyst component very close in composition and structure to the catalyst found to form in the doped hydride minimizes the need for intermediate reactions and/or phase transformations during processing, thereby allowing for more efficient doping of the hydride with the catalyst.
  • the present inventors have investigated certain complex hydrides and their behavior upon doping, and after complex mechanistic studies they have found that the dopants exist as a discrete, disordered phase in a mixture with the hydrides. Disordered phases have no long-range order in the positioning of atoms within the crystal lattice; unlike the L 1 2 structure noted above, the atoms in disordered titanium aluminide are not arranged in accordance with any particular pattern.
  • the addition of a catalyst having a disordered structure will allow for improved performance of the resultant hydrogen storage material when compared to the performance of material formed by addition of a catalyst having an ordered structure.
  • one embodiment of the present invention is a method for making a material.
  • the method comprises providing a metallic catalyst comprising at least one metal component and at least one Group 13 element.
  • a matrix material is also provided, and the catalyst is homogenized with the matrix material.
  • the resultant hydrogen storage material comprises the catalyst disposed within a matrix material.
  • the provided catalyst comprises a disordered phase, such as, for example, a disordered face-centered cubic phase.
  • a disordered phase such as, for example, a disordered face-centered cubic phase.
  • the existence of the disordered phase in substantial amounts in the catalyst increases the advantageousness of the catalyst.
  • the catalyst comprises at least about 60% by volume of the disordered phase.
  • the catalyst comprises at least 75% by volume, and in particular embodiments at least 90% by volume, of the disordered phase.
  • the catalyst consists essentially of the disordered phase.
  • the metal component of the metallic catalyst comprises at least one transition metal element.
  • Suitable examples of transition metal elements include, but are not limited to titanium, vanadium, iron, niobium, zirconium, yttrium, scandium, and combinations of these.
  • the catalyst also comprises at least one Group 13 element (i.e., boron, aluminum, gallium, indium, or thallium).
  • Aluminum is an advantageous element in that it is quite common and is the lightest of the Group 13 elements. Therefore, in particular embodiments, the at least one Group 13 element of the metallic catalyst comprises aluminum.
  • the molar ratio of the Group 13 element to the metallic component in certain embodiments, is in the range from about 0.01:1 to about 100:1. In particular embodiments, this range is from about 0.01 to about 3:1. In a specific embodiment, this range is about 3:1.
  • the at least one metal component comprises titanium and the at least one Group 13 metal comprises aluminum.
  • the metallic catalyst comprises a disordered phase of titanium aluminide. This disordered phase, in certain embodiments, is face-centered cubic.
  • disordered phase of titanium aluminide refers to an atomically disordered phase of any compound of titanium and aluminum and is not limited to one particular compound.
  • the disordered titanium aluminide will have any of a range of possible compositions, including TiAl 3 , TiAl, Ti 3 Al, or even non-stoichiometric formulations.
  • providing the metallic catalyst comprises providing a primary metal and transforming the primary metal into the metallic catalyst.
  • Providing the primary metal comprises, in some embodiments, providing a material comprising a transition metal element (such as titanium), a Group 13 element (such as aluminum), or combinations of both (including compounds of both, such as, for example, titanium aluminide).
  • the primary metal is provided as a combination or compound of materials in a predetermined molar ratio.
  • the primary metal comprises aluminum and titanium in a predetermined molar ratio. The particular ratio selected is determined based upon the desired phase to be formed during the transforming step.
  • the molar ratio is in the range from about 0.01:1 to about 100:1, in terms of moles aluminum to moles titanium. In certain embodiments, this range is from about 0.01 to about 3:1. In a specific embodiment, this range is about 3 : 1 , such as, for instance, where the primary metal comprises TiAl 3 .
  • phase transformation includes any change to the crystal structure of the material, even where no change in chemical composition occurs.
  • An example of such a transformation is a change in crystal structure in TiAl 3 from an ordered crystal structure to a disordered face-centered cubic structure.
  • Inducing such a transformation in some embodiments, is achieved by subjecting the primary metal to stress, strain, heat, or any combination of these. Ball milling, grinding, shot peening, mixing, crushing, swaging, extruding, and cold working are all suitable methods for inducing a phase transformation in accordance with embodiments of the present invention.
  • Quenching the primary metal from a high temperature to a low temperature can also be used in certain situations to elicit the required transformation.
  • Thermal spraying, rapid solidification, and atomization are suitable techniques because the rapid cooling of the material is often sufficient to induce phase transformations.
  • condensing material from a gas or plasma, as in, for example, sputtering is another potentially suitable technique for transforming the primary metal into the metallic catalyst.
  • the particular technique chosen will depend upon several factors, such as, for example, the composition of the primary metal, the quantities being processed, and the desired metallic catalyst to be synthesized.
  • transforming comprises ball milling the primary metal for at least 2 hours, such as via a high-energy ball milling apparatus used commonly in the art.
  • the transforming step is continued until the desired amount of primary metal has been transformed. In some cases substantially all of the primary metal is transformed, while in alternative embodiments, only a portion of the primary metal is transformed. In these latter alternatives, then, the metallic catalyst will comprise some disordered material and some ordered material. In the former embodiments, the metallic catalyst comprises substantially 100% disordered material.
  • the surface area of provided catalyst is an important factor in ensuring efficient incorporation of the catalyst into the end material.
  • the size of the powder particles is often a consideration, because a comparatively small particle size generally creates a comparatively large surface area to volume ratio.
  • providing the catalyst comprises providing a powder having a mean particle size of up to about 1 micrometer.
  • the mean particle size is less than about 100 nanometers. In particular embodiments, the mean particle size is less than about 20 nanometers.
  • a matrix material is provided for homogenization with the metallic catalyst.
  • the matrix material comprises a hydrogen storage material, such as a complex hydride, that will benefit from doping with the metallic catalyst.
  • the matrix material comprises multiple materials.
  • the matrix material in certain embodiments, comprises a hydride, a metal, a semi-metal, or a combination of these.
  • the hydride of the matrix material comprises a material having the general chemical formula A n (MH z ) x , wherein
  • A is at least one element selected from the group consisting of elements from Groups 1, 2, 3, 4, and 12 of the Periodic Table;
  • M is at least one element selected from the group consisting of the Group 13 elements
  • n is a number in the range from about 1 to about 3;
  • z is a number in the range from about 4 to about 6;
  • x a number in the range from about 1 to about 6.
  • M comprises aluminum.
  • the hydride comprises an alanate compound, and thus n is about 1 and z is about 4.
  • a particular example of such a compound is sodium alanate, NaAlH 4 , mentioned previously, although it will be clear from the above description that embodiments of the present invention contemplate the application of this method to a wide variety of compounds.
  • n is about 3 and z is about 6.
  • the matrix material comprises a combination of a hydride and aluminum.
  • the aluminum serves the function of a reactant during the hydrogen storage process, reacting with the hydride in the presence of hydrogen and the catalyst to form a different hydride having desirable storage and/or desorption properties .
  • the hydride comprises Na 3 AlH 6 .
  • the hydride comprises sodium hydride, NaH.
  • Such hydrides in the presence of the catalyst, can react with the aluminum and hydrogen to form sodium alanate, for example.
  • the metal of the matrix material comprises at least one of the first-row transition metal elements (i.e., scandium through zinc), at least one of the Group 13 elements, or combinations of any of these.
  • the matrix material in some embodiments, comprises a mixture of sodium hydride and aluminum. As described above, this particular mixture can be reacted to form sodium alanate.
  • the catalyst and matrix materials are provided and are homogenized. In many cases the relative amounts of these species present during homogenization is a factor in determining the properties of the final material.
  • the catalyst is provided in an amount up to about 10 mole percent relative to the amount of matrix material provided. In certain embodiments, the amount of catalyst is in the range from about 0.1 to about 2 mole percent relative to the amount of matrix material.
  • Homogenization may be accomplished by any of the methods described previously for transforming primary metal into metallic catalyst. In particular embodiments, homogenizing comprises ball milling for at least about 15 minutes. The actual time, temperature, and other selected conditions for homogenizing will depend on the characteristics of the materials being homogenized.
  • one embodiment of the present invention is a method for making a material.
  • the method comprises providing a primary metal comprising at least one material selected from the group consisting of titanium, aluminum, TiAl 3 , and combinations of any of the foregoing; ball-milling the primary metal to form a metallic catalyst, wherein the metallic catalyst consists essentially of a disordered face-centered cubic phase of titanium aluminide; providing a matrix material comprising at least one material selected from the group consisting of a hydride, aluminum, and combinations thereof; and ball milling the matrix material with the catalyst.
  • Hydrogen storage materials synthesized by the methods described above can be hydrogenated in accordance with any suitable method to produce a hydrogen storage material.
  • the homogenized material may be removed to a reactor vessel capable of exposing the material to elevated hydrogen pressure.
  • the reactor may be capable of temperature control to allow exposure of the material to hydrogen at elevated temperature and pressure.
  • suitable hydrogenation can be achieved by exposing the material to hydrogen pressures of above 50 atm at temperatures above 100° C. for times ranging from about a minute to a few days, depending on the desired level of hydrogenation and the rate at which the hydrogenation reaction takes place under the given conditions.
  • hydrogen release desorption is simply achieved by heating hydrogenated material in hydrogen-lean environments. The temperature selected for desorption will depend on the material being heated and the desired rate of hydrogen release.
  • embodiments of the present invention produce materials having markedly and unexpectedly improved hydrogen storage and release characteristics than similar materials made using prior art methods. Consequently, embodiments of the present invention also include thehydrogen storage materials made by the methods described above.
  • a hydrogen storage material comprises the matrix material and the metallic catalyst disposed within the matrix material.
  • the compositional alternatives for the matrix material and the catalyst are as described above for the method embodiments.
  • the hydrogen storage material of the present invention has a hydrogen desorption rate of at least about 3 weight percent per hour at a temperature of about 150° C. This rate is significantly higher than that reported for other hydrogen storage materials of similar type, and better enables the use of such materials in practical systems for fuel storage and retrieval.
  • a 5 gram quantity of TiAl 3 having a D 0 22 ordered crystal structure as received from the manufacturer, was milled in a ball mill for 8 hours to yield the disordered TiAl 3 alloy.
  • the disordered alloy was then milled for 30 minutes with NaH and Al in a 0.02 TiAl 3 :1 NaH:1Al molar ratio, resulting in a hydrogen storage material comprising the disordered titanium aluminide disposed in a matrix material made of sodium hydride and aluminum This material was then hydrogenated at 120° C. C under 130 bars of hydrogen gas pressure.
  • FIG. 1 illustrates the results of the work described above, and compares the performance of the material of the present invention 10 with that of undoped material 20 (source: Sandrock et al., J. Alloys Compounds 339 (2002) 299-308), material doped using titanium trichloride 30 (source: Ibid.), and the material doped in accordance with Gross et al. using an ordered L 1 2 TiAl 3 catalyst (curve 40 ; source: U.S. 2003/0165423, FIG. 4).
  • the rate for the material of the present invention 10 was also significantly higher than that reported by Gross et al. 40 for ordered TiAl 3 catalyst. For example, at about 150° C., the rate of desorption (about 8 wt. % per hour as calculated from the least square fit to the data) is an order of magnitude higher than the data reported by Gross et al.
  • materials of the present invention have hydrogen capacities approximately 0.5 wt % greater than those of the halide doped materials 30 .

Abstract

A material for storage and retrieval of hydrogen is provided. The material comprises a matrix material and a metallic catalyst disposed within the matrix material, the catalyst comprising at least one metal component and at least one Group 13 element, wherein the catalyst comprises a disordered phase. The hydrogen storage material has a hydrogen desorption rate of at least about 3 weight percent per hour at a temperature of about 150° C. A method for making the material is also provided. The method comprises The method comprises providing a metallic catalyst comprising at least one metal component and at least one Group 13 element, wherein the catalyst comprises a disordered phase; providing a matrix material; and homogenizing the catalyst with the matrix material to form a material comprising (i) 43the matrix material and (ii) the catalyst disposed within the matrix material.

Description

    BACKGROUND
  • This invention relates to the storage and production of hydrogen. More particularly, this invention relates to materials used to store and generate hydrogen in such systems, and methods for making such materials.
  • Hydrogen is a “clean fuel” because it can be reacted with oxygen in hydrogen-consuming devices, such as a fuel cell or a combustion engine, to produce energy and water. Virtually no other reaction byproducts are produced in the exhaust. As a result, the use of hydrogen as a fuel effectively solves many environmental problems associated with the use of fossil fuels. Safe and efficient storage and retrieval of hydrogen gas is, however, essential for many applications that can use hydrogen. In particular, minimizing volume and weight of the hydrogen storage systems are important factors in mobile applications.
  • Several methods of storing hydrogen are currently used but these are either inadequate or impractical for widespread mobile consumer applications. For example, hydrogen can be stored in liquid form at very low temperatures, but liquefying the gas consumes significant amounts of energy, and evaporation of the hydrogen poses a considerable problem. Moreover, storing compressed gaseous hydrogen presents problems of capacity. Ordinary compressed gas tanks hold only about 1% of hydrogen gas by weight. More expensive composite cylinders with special compressors can store hydrogen at higher pressures to achieve a more favorable storage ratio of about 10% by weight. Although even higher pressures are possible, safety factors and the high amount of energy consumed in achieving such high pressures have compelled a search for alternative hydrogen storage technologies that are both safe and efficient.
  • Several different metal hydrides have been extensively studied as potential solid-state storage media for hydrogen fuel systems. For example, hydrides of aluminum with alkali metals such as sodium, potassium, and lithium have been shown to release hydrogen at temperatures that often fall within a practical range for mobile consumer applications (e.g., below about 200° C.). However, these materials tend to behave irreversibly within this practical temperature range; that is, they release hydrogen in considerable amounts, but do not absorb (store) hydrogen with practical efficiency at these temperatures. Therefore, there is a need to provide materials having a high gravimetric hydrogen storage capacity and the ability both to store and produce hydrogen at practical temperatures. There is also a need for methods for the production of such materials.
  • BRIEF DESCRIPTION
  • Embodiments of the present invention meet these and other needs. One embodiment is a method for making a material. The method comprises providing a metallic catalyst comprising at least one metal component and at least one Group 13 element, wherein the catalyst comprises a disordered phase; providing a matrix material; and homogenizing the catalyst with the matrix material to form a material comprising (i) the matrix material and (ii) the catalyst disposed within the matrix material.
  • Another embodiment is a hydrogen storage material. The material comprises a matrix material and a metallic catalyst disposed within the matrix material, the catalyst comprising at least one metal component and at least one Group 13 element, wherein the catalyst comprises a disordered phase. The hydrogen storage material has a hydrogen desorption rate of at least about 3 weight percent per hour at a temperature of about 150° C.
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • These and other features, aspects, and advantages of the present invention will become better understood when the following detailed description is read with reference to the accompanying drawings in which like characters represent like parts throughout the drawings, wherein:
  • FIG. 1 is a graph illustrating hydrogen desorption rates from various materials, including materials made by the method of the present invention.
  • DETAlLED DESCRIPTION
  • Complex hydrides, such as, for example, hydrides containing aluminum and one or more alkali metals, have been shown to reversibly store (absorb) and release (desorb) at moderate temperatures (that is, temperatures below about 200° C.) when they are doped with certain catalyst compounds. For example, in Bogdanovic et al., U.S. Pat. No. 6,106,801, transition metal compounds have been reported to provide this catalyst effect, albeit with slow and unstable kinetics. A number of processes for the synthesis of doped complex hydrides have been proposed, but many of these processes involve additions of salts to a hydride starting material. The salt additions ultimately detract from the overall storage capacity of the final material by consuming at least a portion of the starting material, rendering the consumed material unavailable for hydrogen storage.
  • A recent process reported by Gross et al. in U.S. 2003/0165423 eliminates the use of salts as vehicles for introduction of transition metals into complex hydrides. In the method of Gross et al., titanium aluminide (TiAl3) powder is mixed with aluminum and a simple alkali hydride, such as sodium hydride, to form a titanium-doped complex alkali metal/aluminum hydride. The titanium aluminide used in the Gross et al. method is described to be a product of the reaction of titanium chloride with aluminum metal and sodium hydride, and is further described to have the L1 2 crystal structure. This ordered structure can be envisioned as a cube where the aluminum atoms are positioned in the center of each face of the cube and the titanium atoms are positioned at the corners of the cube. In an example described by Gross et al., powders of titanium aluminide, aluminum, and sodium alanate (NaAlH4) were mixed in a high-energy ball mill for 2 hours. The resultant material was then hydrogenated by exposure to hydrogen gas at elevated temperature and pressure. Although the material doped with titanium via this method showed an increase of over a factor of ten in hydrogenation kinetics over undoped material, the data reported in U.S. 2003/0165423 suggest that the rate of absorption obtained with the Gross et al. material may still be too low for many practical applications.
  • The present inventors have discovered a source of the problems causing the above shortcomings. According to this discovery, the capacity and kinetics of some complex hydrides can be significantly improved over the results noted in the prior art by doping with a catalyst component having a composition and crystal structure that closely matches that of the catalyst as it is found to exist in the doped hydride material. Without being limited to any particular explanation, it is theorized that providing a catalyst component very close in composition and structure to the catalyst found to form in the doped hydride minimizes the need for intermediate reactions and/or phase transformations during processing, thereby allowing for more efficient doping of the hydride with the catalyst.
  • The present inventors have investigated certain complex hydrides and their behavior upon doping, and after complex mechanistic studies they have found that the dopants exist as a discrete, disordered phase in a mixture with the hydrides. Disordered phases have no long-range order in the positioning of atoms within the crystal lattice; unlike the L1 2 structure noted above, the atoms in disordered titanium aluminide are not arranged in accordance with any particular pattern. Thus, according to the discovery of the present inventors, the addition of a catalyst having a disordered structure will allow for improved performance of the resultant hydrogen storage material when compared to the performance of material formed by addition of a catalyst having an ordered structure.
  • Accordingly, one embodiment of the present invention is a method for making a material. The method comprises providing a metallic catalyst comprising at least one metal component and at least one Group 13 element. A matrix material is also provided, and the catalyst is homogenized with the matrix material. The resultant hydrogen storage material comprises the catalyst disposed within a matrix material.
  • The provided catalyst comprises a disordered phase, such as, for example, a disordered face-centered cubic phase. The existence of the disordered phase in substantial amounts in the catalyst increases the advantageousness of the catalyst. In some embodiments, the catalyst comprises at least about 60% by volume of the disordered phase. In certain embodiments, the catalyst comprises at least 75% by volume, and in particular embodiments at least 90% by volume, of the disordered phase. In a specific embodiment, the catalyst consists essentially of the disordered phase.
  • As noted above, transition metal elements appear to be effective dopants for certain complex hydride systems. In some embodiments, the metal component of the metallic catalyst comprises at least one transition metal element. Suitable examples of transition metal elements include, but are not limited to titanium, vanadium, iron, niobium, zirconium, yttrium, scandium, and combinations of these.
  • The catalyst also comprises at least one Group 13 element (i.e., boron, aluminum, gallium, indium, or thallium). Aluminum is an advantageous element in that it is quite common and is the lightest of the Group 13 elements. Therefore, in particular embodiments, the at least one Group 13 element of the metallic catalyst comprises aluminum. The molar ratio of the Group 13 element to the metallic component, in certain embodiments, is in the range from about 0.01:1 to about 100:1. In particular embodiments, this range is from about 0.01 to about 3:1. In a specific embodiment, this range is about 3:1.
  • Several of the more commonly known complex hydrides, including the alanates, contain aluminum. Moreover, the work of the present inventors and others indicates that compounds of transition metals, particularly titanium, with aluminum are effective catalysts for use in alanate systems. Accordingly, in certain embodiments the at least one metal component comprises titanium and the at least one Group 13 metal comprises aluminum. In particular embodiments the metallic catalyst comprises a disordered phase of titanium aluminide. This disordered phase, in certain embodiments, is face-centered cubic. However, it will be appreciated that “disordered phase of titanium aluminide” as used herein refers to an atomically disordered phase of any compound of titanium and aluminum and is not limited to one particular compound. For example, depending on the relative amounts of titanium and aluminum present, the disordered titanium aluminide will have any of a range of possible compositions, including TiAl3, TiAl, Ti3Al, or even non-stoichiometric formulations.
  • In many cases, a catalyst comprising a disordered phase is not readily available and therefore must be synthesized prior to homogenizing with the matrix material. In these instances, providing the metallic catalyst comprises providing a primary metal and transforming the primary metal into the metallic catalyst. Providing the primary metal comprises, in some embodiments, providing a material comprising a transition metal element (such as titanium), a Group 13 element (such as aluminum), or combinations of both (including compounds of both, such as, for example, titanium aluminide). Often the primary metal is provided as a combination or compound of materials in a predetermined molar ratio. For instance, in some embodiments the primary metal comprises aluminum and titanium in a predetermined molar ratio. The particular ratio selected is determined based upon the desired phase to be formed during the transforming step. In some embodiments, the molar ratio is in the range from about 0.01:1 to about 100:1, in terms of moles aluminum to moles titanium. In certain embodiments, this range is from about 0.01 to about 3:1. In a specific embodiment, this range is about 3:1, such as, for instance, where the primary metal comprises TiAl3.
  • The primary metal is transformed into the metallic catalyst. In certain embodiments, transforming comprises inducing a phase transformation within the primary metal to form the disordered phase of the catalyst. As used herein, “phase transformation” includes any change to the crystal structure of the material, even where no change in chemical composition occurs. An example of such a transformation is a change in crystal structure in TiAl3 from an ordered crystal structure to a disordered face-centered cubic structure. Inducing such a transformation, in some embodiments, is achieved by subjecting the primary metal to stress, strain, heat, or any combination of these. Ball milling, grinding, shot peening, mixing, crushing, swaging, extruding, and cold working are all suitable methods for inducing a phase transformation in accordance with embodiments of the present invention. Quenching the primary metal from a high temperature to a low temperature can also be used in certain situations to elicit the required transformation. Thermal spraying, rapid solidification, and atomization are suitable techniques because the rapid cooling of the material is often sufficient to induce phase transformations. Moreover, condensing material from a gas or plasma, as in, for example, sputtering, is another potentially suitable technique for transforming the primary metal into the metallic catalyst. The particular technique chosen will depend upon several factors, such as, for example, the composition of the primary metal, the quantities being processed, and the desired metallic catalyst to be synthesized. In particular embodiments, transforming comprises ball milling the primary metal for at least 2 hours, such as via a high-energy ball milling apparatus used commonly in the art. The transforming step is continued until the desired amount of primary metal has been transformed. In some cases substantially all of the primary metal is transformed, while in alternative embodiments, only a portion of the primary metal is transformed. In these latter alternatives, then, the metallic catalyst will comprise some disordered material and some ordered material. In the former embodiments, the metallic catalyst comprises substantially 100% disordered material.
  • In certain embodiments of the present invention, the surface area of provided catalyst is an important factor in ensuring efficient incorporation of the catalyst into the end material. Thus, where the catalyst is provided as a powder, the size of the powder particles is often a consideration, because a comparatively small particle size generally creates a comparatively large surface area to volume ratio. In some embodiments, providing the catalyst comprises providing a powder having a mean particle size of up to about 1 micrometer. In certain embodiments, the mean particle size is less than about 100 nanometers. In particular embodiments, the mean particle size is less than about 20 nanometers.
  • A matrix material is provided for homogenization with the metallic catalyst. In certain embodiments the matrix material comprises a hydrogen storage material, such as a complex hydride, that will benefit from doping with the metallic catalyst. In alternative embodiments, the matrix material comprises multiple materials. The matrix material, in certain embodiments, comprises a hydride, a metal, a semi-metal, or a combination of these.
  • In some embodiments, the hydride of the matrix material comprises a material having the general chemical formula An(MHz)x, wherein
  • A is at least one element selected from the group consisting of elements from Groups 1, 2, 3, 4, and 12 of the Periodic Table;
  • M is at least one element selected from the group consisting of the Group 13 elements;
  • n is a number in the range from about 1 to about 3;
  • z is a number in the range from about 4 to about 6; and
  • x a number in the range from about 1 to about 6.
  • In certain embodiments, M comprises aluminum. In particular embodiments, the hydride comprises an alanate compound, and thus n is about 1 and z is about 4. A particular example of such a compound is sodium alanate, NaAlH4, mentioned previously, although it will be clear from the above description that embodiments of the present invention contemplate the application of this method to a wide variety of compounds. In some embodiments, n is about 3 and z is about 6. A particular example of such a compound, though again not limiting, is Na3AlH6.
  • In certain embodiments, the matrix material comprises a combination of a hydride and aluminum. In many of these embodiments, the aluminum serves the function of a reactant during the hydrogen storage process, reacting with the hydride in the presence of hydrogen and the catalyst to form a different hydride having desirable storage and/or desorption properties . For example, in some embodiments, the hydride comprises Na3AlH6. In some embodiments, moreover, the hydride comprises sodium hydride, NaH. Such hydrides, in the presence of the catalyst, can react with the aluminum and hydrogen to form sodium alanate, for example.
  • The metal of the matrix material, in some embodiments, comprises at least one of the first-row transition metal elements (i.e., scandium through zinc), at least one of the Group 13 elements, or combinations of any of these. The matrix material, in some embodiments, comprises a mixture of sodium hydride and aluminum. As described above, this particular mixture can be reacted to form sodium alanate.
  • The catalyst and matrix materials are provided and are homogenized. In many cases the relative amounts of these species present during homogenization is a factor in determining the properties of the final material. In some embodiments, the catalyst is provided in an amount up to about 10 mole percent relative to the amount of matrix material provided. In certain embodiments, the amount of catalyst is in the range from about 0.1 to about 2 mole percent relative to the amount of matrix material. Homogenization may be accomplished by any of the methods described previously for transforming primary metal into metallic catalyst. In particular embodiments, homogenizing comprises ball milling for at least about 15 minutes. The actual time, temperature, and other selected conditions for homogenizing will depend on the characteristics of the materials being homogenized.
  • In order to fully capitalize on the advantages provided by the method described above, one embodiment of the present invention is a method for making a material. The method comprises providing a primary metal comprising at least one material selected from the group consisting of titanium, aluminum, TiAl3, and combinations of any of the foregoing; ball-milling the primary metal to form a metallic catalyst, wherein the metallic catalyst consists essentially of a disordered face-centered cubic phase of titanium aluminide; providing a matrix material comprising at least one material selected from the group consisting of a hydride, aluminum, and combinations thereof; and ball milling the matrix material with the catalyst.
  • Hydrogen storage materials synthesized by the methods described above can be hydrogenated in accordance with any suitable method to produce a hydrogen storage material. For instance, the homogenized material may be removed to a reactor vessel capable of exposing the material to elevated hydrogen pressure. Moreover, the reactor may be capable of temperature control to allow exposure of the material to hydrogen at elevated temperature and pressure. As a non-limiting example, for alanates and other complex hydrides, suitable hydrogenation can be achieved by exposing the material to hydrogen pressures of above 50 atm at temperatures above 100° C. for times ranging from about a minute to a few days, depending on the desired level of hydrogenation and the rate at which the hydrogenation reaction takes place under the given conditions. On the other hand, hydrogen release (desorption) is simply achieved by heating hydrogenated material in hydrogen-lean environments. The temperature selected for desorption will depend on the material being heated and the desired rate of hydrogen release.
  • The methods provided in accordance with embodiments of the present invention produce materials having markedly and unexpectedly improved hydrogen storage and release characteristics than similar materials made using prior art methods. Consequently, embodiments of the present invention also include thehydrogen storage materials made by the methods described above.
  • In accordance with embodiments of the present invention, a hydrogen storage material comprises the matrix material and the metallic catalyst disposed within the matrix material. The compositional alternatives for the matrix material and the catalyst are as described above for the method embodiments. In stark contrast to conventional hydrogen storage materials of similar chemical composition, the hydrogen storage material of the present invention has a hydrogen desorption rate of at least about 3 weight percent per hour at a temperature of about 150° C. This rate is significantly higher than that reported for other hydrogen storage materials of similar type, and better enables the use of such materials in practical systems for fuel storage and retrieval.
  • EXAMPLES
  • In order to more fully illustrate and describe the methods and materials disclosed herein, the following examples are provided. However, it should be appreciated that these examples are not intended to limit the invention in any way.
  • A 5 gram quantity of TiAl3, having a D0 22 ordered crystal structure as received from the manufacturer, was milled in a ball mill for 8 hours to yield the disordered TiAl3 alloy. The disordered alloy was then milled for 30 minutes with NaH and Al in a 0.02 TiAl3:1 NaH:1Al molar ratio, resulting in a hydrogen storage material comprising the disordered titanium aluminide disposed in a matrix material made of sodium hydride and aluminum This material was then hydrogenated at 120° C. C under 130 bars of hydrogen gas pressure.
  • Desorption rate of hydrogen from the hydrogenated material described above as a function of temperature was measured by observing the desorption of hydrogen under isothermal conditions into a known volume. FIG. 1 illustrates the results of the work described above, and compares the performance of the material of the present invention 10 with that of undoped material 20 (source: Sandrock et al., J. Alloys Compounds 339 (2002) 299-308), material doped using titanium trichloride 30 (source: Ibid.), and the material doped in accordance with Gross et al. using an ordered L1 2 TiAl3 catalyst (curve 40; source: U.S. 2003/0165423, FIG. 4). The data indicate that the material doped using disordered TiAl3 in accordance with embodiments of the present invention provided desorption rates equal to or faster than the material doped using titanium trichloride 30. The rate for the material of the present invention 10 was also significantly higher than that reported by Gross et al. 40 for ordered TiAl3 catalyst. For example, at about 150° C., the rate of desorption (about 8 wt. % per hour as calculated from the least square fit to the data) is an order of magnitude higher than the data reported by Gross et al. Moreover, because there is no salt formation upon reaction of the catalyst with the alanate, materials of the present invention have hydrogen capacities approximately 0.5 wt % greater than those of the halide doped materials 30.
  • While various embodiments are described herein, it will be appreciated from the specification that various combinations of elements, variations, equivalents, or improvements therein may be made by those skilled in the art, and are still within the scope of the invention as defined in the appended claims.

Claims (67)

1. A method for making a material, the method comprising:
providing a metallic catalyst comprising at least one metal component and at least one Group 13 element, wherein the catalyst comprises a disordered phase;
providing a matrix material; and
homogenizing the catalyst with the matrix material to form a material comprising (i) a matrix material and (ii) said catalyst disposed within the matrix material.
2. The method of claim 1, wherein said disordered phase comprises a disordered face-centered cubic phase.
3. The method of claim 2, wherein said metallic catalyst comprises at least 60 percent by volume of said disordered phase.
4. The method of claim 3, wherein said catalyst consists essentially of said disordered phase.
5. The method of claim 1, wherein the at least one metal component comprises at least one transition metal element.
6. The method of claim 5, wherein the at least one transition metal element is at least one material selected from the group consisting of titanium, vanadium, iron, niobium, zirconium, yttrium, and scandium.
7. The method of claim 1, wherein the at least one Group 13 element comprises aluminum.
8. The method of claim 1, wherein the at least one metal component comprises titanium and the at least one Group 13 element comprises aluminum.
9. The method of claim 8, wherein the metallic catalyst comprises a disordered phase of titanium aluminide.
10. The method of claim 9, wherein said titanium aluminide comprises at least one compound selected from the group consisting of TiAl3, TiAl, and Ti3Al.
11. The method of claim 1, wherein providing the metallic catalyst comprises
providing a primary metal; and
transforming the primary metal into the metallic catalyst.
12. The method of claim 11, wherein providing the primary metal comprises providing a material comprising at least one selected from the group consisting of a transition metal element, a Group 13 element, and combinations and compounds. thereof.
13. The method of claim 12, wherein providing the primary metal comprises providing a material selected from the group consisting of titanium, aluminum, titanium aluminide, and combinations of any of the foregoing.
14. The method of claim 13, wherein the primary metal comprises titanium and aluminum in a predetermined molar ratio.
15. The method of claim 14, wherein the molar ratio, in terms of moles aluminum to moles titanium, is in the range from about 0.01:1 to about 100:1.
16. The method of claim 15, wherein the molar ratio, in terms of moles aluminum to moles titanium, is in the range from about 0.01:1 to about 3:1.
17. The method of claim 16, wherein the molar ratio, in terms of moles aluminum to moles titanium, is about 3:1.
18. The method of claim 17, wherein the primary metal comprises TiAl3.
19. The method of claim 11, wherein transforming comprises inducing a phase transformation within the primary metal to form the disordered phase of the catalyst.
20. The method of claim 19, wherein inducing comprises subjecting the primary metal to at least one environmental condition selected from the group consisting of stress, strain, and heat.
21. The method of claim 19, wherein transforming comprises subjecting the primary metal to at least one operation selected from the group consisting of ball milling, grinding, shot peening, mixing, crushing, swaging, extruding, cold working, quenching, condensing, sputtering, thermal spraying, rapid solidification, atomization, and combinations thereof.
22. The method of claim 21, wherein transforming comprises ball milling the primary metal for at least 2 hours.
23. The method of claim 1, wherein the matrix material comprises at least one material selected from the group consisting of a hydride, a metal, a semi-metal, and combinations thereof.
24. The method of claim 23, wherein the hydride comprises a material having the chemical formula An(MHz)x, wherein
A is at least one element selected from the group consisting of elements from Groups 1, 2, 3, 4, and 12;
M is at least one element selected from the group consisting of the Group 13 elements;
n is a number in the range from about 1 to about 3;
z is a number in the range from about 4 to about 6; and
x a number in the range from about 1 to about 6.
25. The method of claim 24, wherein M comprises aluminum.
26. The method of claim 25, wherein n is about 1 and z is about 4.
27. The method of claim 26, wherein the hydride comprises sodium alanate.
28. The method of claim 25, wherein n is about 3 and z is about 6.
29. The method of claim 28, wherein the hydride comprises Na3AlH6.
30. The method of claim 24, wherein the matrix material comprises a combination of the hydride and aluminum.
31. The method of claim 30, wherein the hydride comprises Na3AlH6.
32. The method of claim 23, wherein the hydride comprises sodium hydride.
33. The method of claim 23, wherein the metal comprises at least one element selected from the group consisting of the Group 13 elements and the first-row transition metal elements.
34. The method of claim 33, wherein the metal comprises aluminum.
35. The method of claim 34, wherein the matrix material comprises sodium hydride and aluminum.
36. The method of claim 1, wherein providing the metallic catalyst comprises providing an amount of catalyst of up to about 10 mole percent relative to the amount of matrix material.
37. The method of claim 36, wherein the amount of catalyst is in the range from about 0.1 to about 2 mole percent relative to the amount of matrix material.
38. The method of claim 1, wherein providing the catalyst comprises providing a powder having a mean particle size of up to about 1 micrometer.
39. The method of claim 38, wherein the mean particle size is less than about 100 nanometers.
40. The method of claim 39, wherein the mean particle size range is less than about 20 nm.
41. The method of claim 1, wherein homogenizing comprises subjecting a mixture of the catalyst and the matrix material to at least one operation selected from the group consisting of ball milling, grinding, shot peening, mixing, crushing, swaging, extruding, cold working, quenching, condensing, sputtering, thermal spraying, rapid solidification, atomization, and combinations thereof.
42. The method of claim 41, wherein homogenizing comprises ball milling for at least about 15 minutes.
43. The material made in accordance with the method of claim 1.
44. A method for making a material, the method comprising:
providing a primary metal comprising at least one material selected from the group consisting of titanium, aluminum, TiAl3, and combinations of any of the foregoing;
ball-milling the primary metal to form a metallic catalyst, wherein the metallic catalyst consists essentially of a disordered face-centered cubic phase of titanium aluminide;
providing a matrix material comprising at least one material selected from the group consisting of a hydride, aluminum, and combinations thereof; and
ball milling the matrix material with the catalyst to form a material comprising (i) a matrix material and (ii) said catalyst disposed within the matrix material.
45. The material made in accordance with the method of claim 44.
46. A hydrogen storage material comprising:
a matrix material; and
a metallic catalyst disposed within said matrix material, said catalyst comprising at least one metal component and at least one Group 13 element, wherein said catalyst comprises a disordered phase;
wherein said hydrogen storage material has a hydrogen desorption rate of at least about 3 weight percent per hour at a temperature of about 150° C.
47. The material of claim 46, wherein said disordered phase comprises a disordered face-centered cubic phase.
48. The material of claim 46, wherein said metallic catalyst comprises at least 60 percent by volume of said disordered phase.
49. The material of claim 48, wherein said catalyst consists essentially of said disordered phase.
50. The material of claim 46, wherein the at least one metal component comprises at least one transition metal element.
51. The material of claim 50, wherein the at least one transition metal element is at least one material selected from the group consisting of titanium, vanadium, iron, niobium, zirconium, yttrium, and scandium.
52. The material of claim 46, wherein the at least one Group 13 element comprises aluminum.
53. The material of claim 46, wherein the at least one metal component comprises titanium and the at least one Group 13 element comprises aluminum.
54. The material of claim 53, wherein the metallic catalyst comprises a disordered phase of titanium aluminide.
55. The material of claim 54, wherein said titanium aluminide comprises at least one compound selected from the group consisting of TiAl3, TiAl, and Ti3Al.
56. The material of claim 46, wherein the matrix material comprises at least one material selected from the group consisting of a hydride, a metal, a semi-metal, and combinations thereof.
57. The material of claim 56, wherein the hydride comprises a material having the chemical formula An(MHz)x, wherein
A is at least one element selected from the group consisting of elements from Groups 1, 2, 3, 4, and 12;
M is at least one element selected from the group consisting of the Group 13 elements;
n is a number in the range from about 1 to about 3;
z is a number in the range from about 4 to about 6; and
x a number in the range from about 1 to about 6.
58. The material of claim 57, wherein M comprises aluminum.
59. The material of claim 58, wherein n is about 1 and z is about 4.
60. The material of claim 59, wherein the hydride comprises sodium alanate.
61. The material of claim 57, wherein n is about 3 and z is about 6.
62. The material of claim 61, wherein the hydride comprises Na3AlH6.
63. The material of claim 56, wherein the matrix material comprises a mixture of a hydride and a metal.
64. The material of claim 63, wherein the metal comprises aluminum.
65. The material of claim 46, wherein the metallic catalyst is present in said hydrogen storage material an amount of up to about 10 mole percent relative to the amount of matrix material.
66. The material of claim 65, wherein the amount of catalyst is in the range from about 0.1 to about 2 mole percent relative to the amount of matrix material.
67. A hydrogen storage material comprising:
a catalyst disposed in a matrix material, wherein said catalyst consists essentially of a disordered phase of titanium aluminide, and
said matrix material comprises at least one material selected from the group consisting of a hydride, a metal, a semi-metal, and combinations thereof,
wherein said hydrogen storage material has a hydrogen desorption rate of at least about 3 weight percent per hour at a temperature of about 150° C.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100221137A1 (en) * 2007-04-18 2010-09-02 University Of Virginia Patent Foundation Hydrogen Storage Material with Intermediate Bond Strength and Process for Making the Same
CN112755989A (en) * 2021-02-08 2021-05-07 烟台大学 Hydrogen storage material catalyst, hydrogen storage material containing the catalyst and preparation method

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5616432A (en) * 1994-06-14 1997-04-01 Ovonic Battery Company, Inc. Electrochemical hydrogen storage alloys and batteries fabricated from Mg containing base alloys
US6106801A (en) * 1995-07-19 2000-08-22 Studiengesellschaft Method for the reversible storage of hydrogen
US6471935B2 (en) * 1998-08-06 2002-10-29 University Of Hawaii Hydrogen storage materials and method of making by dry homogenation
US20030053948A1 (en) * 2000-03-16 2003-03-20 Borislav Bogdanovic Method for reversibly storing hydrogen on the basis of alkali metals and alumium
US6589312B1 (en) * 1999-09-01 2003-07-08 David G. Snow Nanoparticles for hydrogen storage, transportation, and distribution
US20030143154A1 (en) * 2002-01-29 2003-07-31 Gross Karl J. Direct synthesis of catalyzed hydride compounds
US20030165423A1 (en) * 2002-01-29 2003-09-04 Gross Karl J. Direct synthesis of hydride compounds using a titanium aluminate dopant
US20040009121A1 (en) * 2002-07-10 2004-01-15 Jensen Craig M. Methods for hydrogen storage using doped alanate compositions
US20040105805A1 (en) * 2002-11-01 2004-06-03 Ragaiy Zidan Complex hydrides for hydrogen storage
US20040247521A1 (en) * 2001-12-21 2004-12-09 Borislav Bogdanovic Reversible storage of hydrogen using doped alkali metal aluminum hydrides
US20050032641A1 (en) * 2003-07-17 2005-02-10 Ragaiy Zidan Hydrogen storage material and process using graphite additive with metal-doped complex hydrides
US20050054525A1 (en) * 2003-09-10 2005-03-10 Ovshinsky Stanford R. High capacity hydrogen storage material based on catalyzed alanates

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5616432A (en) * 1994-06-14 1997-04-01 Ovonic Battery Company, Inc. Electrochemical hydrogen storage alloys and batteries fabricated from Mg containing base alloys
US6106801A (en) * 1995-07-19 2000-08-22 Studiengesellschaft Method for the reversible storage of hydrogen
US6471935B2 (en) * 1998-08-06 2002-10-29 University Of Hawaii Hydrogen storage materials and method of making by dry homogenation
US6589312B1 (en) * 1999-09-01 2003-07-08 David G. Snow Nanoparticles for hydrogen storage, transportation, and distribution
US6814782B2 (en) * 2000-03-16 2004-11-09 Studiengesellschaft Kohle Mbh Method for reversibly storing hydrogen on the basis of alkali metals and aluminum
US20030053948A1 (en) * 2000-03-16 2003-03-20 Borislav Bogdanovic Method for reversibly storing hydrogen on the basis of alkali metals and alumium
US20040247521A1 (en) * 2001-12-21 2004-12-09 Borislav Bogdanovic Reversible storage of hydrogen using doped alkali metal aluminum hydrides
US20030143154A1 (en) * 2002-01-29 2003-07-31 Gross Karl J. Direct synthesis of catalyzed hydride compounds
US20030165423A1 (en) * 2002-01-29 2003-09-04 Gross Karl J. Direct synthesis of hydride compounds using a titanium aluminate dopant
US20040009121A1 (en) * 2002-07-10 2004-01-15 Jensen Craig M. Methods for hydrogen storage using doped alanate compositions
US20040105805A1 (en) * 2002-11-01 2004-06-03 Ragaiy Zidan Complex hydrides for hydrogen storage
US20050032641A1 (en) * 2003-07-17 2005-02-10 Ragaiy Zidan Hydrogen storage material and process using graphite additive with metal-doped complex hydrides
US20050054525A1 (en) * 2003-09-10 2005-03-10 Ovshinsky Stanford R. High capacity hydrogen storage material based on catalyzed alanates

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100221137A1 (en) * 2007-04-18 2010-09-02 University Of Virginia Patent Foundation Hydrogen Storage Material with Intermediate Bond Strength and Process for Making the Same
US8551396B2 (en) 2007-04-18 2013-10-08 University Of Virginia Patent Foundation Hydrogen storage material with intermediate bond strength and process for making the same
CN112755989A (en) * 2021-02-08 2021-05-07 烟台大学 Hydrogen storage material catalyst, hydrogen storage material containing the catalyst and preparation method

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