KR20060120033A - Hydrogen storage compositions and methods of manufacture thereof - Google Patents

Abstract

Disclosed herein is a method for making a combinatorial library comprising disposing on a substrate comprising silicon, graphite, boron, boron carbide, boron nitride, aluminum, germanium, silicon nitride, silicon carbide or silicon boride at least one reactant, wherein the reactants are lithium, magnesium, sodium, potassium, calcium, aluminum or a combination comprising at least one of the foregoing reactants; heat treating the - substrate to create a diffusion multiple having at least two phases; contacting the diffusion multiple with hydrogen; detecting any absorption of hydrogen; and/or detecting any desorption of hydrogen.

Description

HYDROGEN STORAGE COMPOSITIONS AND METHODS OF MANUFACTURE THEREOF

The present invention relates to a hydrogen storage composition and a method of making the same.

Hydrogen is a "clean fuel" because it can produce energy and water by reacting with oxygen in a hydrogen-consuming device such as a fuel cell or combustion combustion. In practice, no other reaction byproducts are produced in the exhaust. As a result, the use of oxygen as a fuel effectively solves many environmental problems associated with the use of petroleum fuels. However, safe and effective storage of hydrogen gas is essential in many applications where hydrogen can be used. In particular, minimizing the volume and weight of hydrogen storage systems is an important factor in the automotive sector.

Although several hydrogen storage methods have been used recently, they are inadequate or impractical for a wide range of automotive consumer applications. For example, hydrogen can be stored in liquid form at very low temperatures. However, hydrogen consumed in liquefied hydrogen gas is about 40% of the energy available from the hydrogen produced. In addition, a standard tank filled with liquid hydrogen will be emptied by evaporation within about one week. Thus, dormancy is also a problem. These factors make liquid hydrogen impractical in most consumer applications.

Another alternative is to store hydrogen in the cylinder under high pressure. However, a 100 pound steel cylinder can store only about 1 pound of hydrogen delivered at about 2200 psi, with a 1 weight percent hydrogen storage. More expensive composite cylinders with special compressors can store hydrogen at higher pressures of about 4,500 psi to achieve a more desirable storage ratio of about 4% by weight. Higher pressures are possible, but stability factors and the high amounts of energy consumed in achieving these high pressures have forced research into alternative hydrogen storage technologies that are safe and effective.

As mentioned above, there is a need for safer and more efficient hydrogen storage and recovery methods. There is also a need to minimize the overall system volume and weight.

Summary of the Invention

In one embodiment, a method of making a combinatorial library comprises a light metal on a substrate comprising silicon, graphite, boron, boron carbide, boron nitride, aluminum, germanium, silicon nitride, silicon carbide or silicon boride Placing the reactants; Thermally treating the substrate to produce a diffusion multiple having two or more phases; Contacting the hydrogen and a diffusion multiple; Detecting any hydrogen uptake; And / or detecting any hydrogen desorption.

In another embodiment, the method for recovering hydrogen comprises AlSi, Ca ₂ Si, CaSi, CaSi ₂ , KSi, K ₄ Si ₂₃ , Li ₂₂ Si ₅ , Li ₁₃ Si ₄ , Li ₇ Si ₃ , Li ₁₂ Si ₇ , Mg ₂ Si, NaSi, NaSi ₂ , Na ₄ Si ₂₃ , AlB ₂ , AlB ₁₂ , B ₆ Ca, B ₆ K, B ₁₂ Li, B ₆ Li, B ₄ Li, B ₃ Li, B ₂ Li, BLi, B ₆ Li ₇ , BLi ₃ , MgB ₂ , MgB ₄ , MgB ₇ , NaB ₆ , NaB ₁₅ NaB ₁₆ , AlLi, Al ₂ Li ₃ , Al ₄ Li ₉ , Al ₃ Mg ₂ , Al ₁₂ Mg ₁₇ , AlB ₁₂ , Ge ₄ K, GeK, GeK ₃ , GeLi ₃ , Ge ₅ Li ₂₂ , Mg ₂ Ge, Ge ₄ Na, GeNa, GeNa ₃ , Aluminum Doped Ge ₄ K, Aluminum Doped GeK, Aluminum Doped GeK ₃ , Aluminum Doped GeLi ₃ , aluminum doped Ge ₅ Li ₂₂ , aluminum doped Mg ₂ Ge, aluminum doped Ge ₄ Na, aluminum doped GeNa, aluminum doped GeNa ₃ , Al ₄ C ₃ , Na ₄ C ₃ , Li ₄ C ₃ , K ₄ C ₃ , LiC, LiC ₆ , Mg ₂ C ₃ , MgC ₂ , AlTi ₂ C, AlTi ₃ C, AlZrC ₂ , Al ₃ Zr ₅ C, Al ₃ Zr ₂ C ₄ , Al ₃ Zr ₂ C ₇ , KC _4, the combination comprising a NaC _4, or one or more of the above-mentioned compound Contacting at least one compound selected from the group consisting in hydrogen to form a hydrogenated compound; And recovering hydrogen by heating the hydrogenated compound.

In another embodiment, a method of regenerating hydrogen comprises contacting hydrogen with a compound having one or more of Formulas I-V to form a hydrogenated compound; And recovering hydrogen by heating the hydrogenated compound:

(Li _a , Na _b , K _c , Al _d , Mg _e , Ca _f ) _x (B, C, N, Si) _y

(Li _a , Na _b , Mg _c , K _d , Ca _e , Ge _f ) _x (Al) _y

(Li _a , Na _b , Mg _c , K _d , Ca _e , Al _f ) _x (Ge) _y

(Li _a , Na _b , K _c , Al _d , Mg _e , Ca _f ) _x (B, C, N) _y

(Li _a , Na _b , K _c , Al _d , Mg _e , Ca _f ) _x (B, N, C) _y

Where

Li is lithium, Na is sodium, Mg is magnesium, K is potassium, Ca is calcium, Al is aluminum, Ge is germanium, B is boron, C is carbon, N is nitrogen, Si is silicon, a, b, c, d, e and f can be the same or different and have a value from 0 to 1 and x and y have a value from about 1 to about 22.

In a fourth embodiment, the diffusion multiple compound has one or more of Formulas I-V:

Formula I

(Li _a , Na _b , K _c , Al _d , Mg _e , Ca _f ) _x (B, C, N, Si) _y

Formula II

(Li _a , Na _b , Mg _c , K _d , Ca _e , Ge _f ) _x (Al) _y

Formula III

(Li _a , Na _b , Mg _c , K _d , Ca _e , Al _f ) _x (Ge) _y

Formula IV

(Li _a , Na _b , K _c , Al _d , Mg _e , Ca _f ) _x (B, C, N) _y

Formula V

(Li _a , Na _b , K _c , Al _d , Mg _e , Ca _f ) _x (B, N, C) _y

Where

Li is lithium, Na is sodium, Mg is magnesium, K is potassium, Ca is calcium, Al is aluminum, Ge is germanium, B is boron, C is carbon, N is nitrogen, Si is silicon, a, b, c, d, e and f can be the same or different and have a value from 0 to 1 and x and y have a value from about 1 to about 22.

In a fifth embodiment, the composition comprises AlSi, Ca ₂ Si, CaSi, CaSi ₂ , KSi, K ₄ Si ₂₃ , Li ₂₂ Si ₅ , Li ₁₃ Si ₄ , Li ₇ Si ₃ , Li ₁₂ Si ₇ , Mg ₂ Si, NaSi, NaSi ₂ , Na ₄ Si ₂₃ , AlB ₂ , AlB ₁₂ , B ₆ Ca, B ₆ K, B ₁₂ Li, B ₆ Li, B ₄ Li, B ₃ Li, B ₂ Li, BLi, B ₆ Li ₇ , BLi ₃ , MgB ₂ , MgB ₄ , MgB ₇ , NaB ₆ , NaB ₁₅ NaB ₁₆ , AlLi, Al ₂ Li ₃ , Al ₄ Li ₉ , Al ₃ Mg ₂ , Al ₁₂ Mg ₁₇ , AlB ₁₂ , Ge ₄ K, GeK, GeK ₃ , GeLi ₃ , Ge ₅ Li ₂₂ , Mg ₂ Ge, Ge ₄ Na, GeNa, GeNa ₃ , Aluminum doped Ge ₄ K, Aluminum doped GeK, Aluminum doped GeK ₃ , Aluminum doped GeLi ₃ , Aluminum Doped Ge ₅ Li ₂₂ , Aluminum Doped Mg ₂ Ge, Aluminum Doped Ge ₄ Na, Aluminum Doped GeNa, Aluminum Doped GeNa ₃ , Al ₄ C ₃ , Na ₄ C ₃ , Li ₄ C ₃ , K ₄ C ₃ , LiC, LiC ₆ , Mg ₂ C ₃ , MgC ₂ , AlTi ₂ C, AlTi ₃ C, AlZrC ₂ , Al ₃ Zr ₅ C, Al ₃ Zr ₂ C ₄ , Al ₃ Zr ₂ C ₇ , KC ₄ , NaC ₄ , or a combination comprising at least one of the foregoing compounds Hydrides of the compounds selected.

In a sixth embodiment, the hydrogen storage composition comprises calcium, barium, titanium, chromium, manganese, iron, cobalt, copper, silicon, germanium, rhodium, rhodium, ruthenium, molybdenum, niobium, zirconium, yttrium, barium, lanthanum, hafnium, And a catalyst composition disposed over the storage composition, consisting essentially of tungsten, rhenium, osmium or iridium.

In a seventh embodiment, the hydrogen storage composition comprises calcium, barium, platinum, palladium, nickel, titanium, chromium, manganese, iron, cobalt, copper, silicon, germanium, rhodium, rhodium, ruthenium, molybdenum, niobium, zirconium, yttrium, And a catalyst composition disposed over a storage composition, comprising an alloy of barium, lanthanum, hafnium, tungsten, rhenium, osmium, iridium, or a combination comprising one or more of the metals described above.

In an eighth embodiment, the hydrogen storage method comprises calcium, platinum, palladium, nickel, barium, titanium, chromium, manganese, iron, cobalt, copper, silicon, germanium, rhodium, rhodium, ruthenium, molybdenum, niobium, zirconium, Incorporating a hydrogen storage composition comprising a catalyst composition disposed over the storage composition, the alloy comprising a alloy of yttrium, barium, lanthanum, hafnium, tungsten, rhenium, osmium or iridium, to a gas mixture comprising hydrogen; Dissociating hydrogen into atomic hydrogen; And storing the atomic hydrogen in the storage composition.

In a ninth embodiment, the method of hydrogen generation comprises heating a hydrogen storage composition comprising a catalyst composition disposed over the storage composition, wherein the catalyst composition comprises calcium, barium, titanium, chromium, manganese, iron, cobalt, copper, Consists essentially of silicon, germanium, rhodium, rhodium, ruthenium, molybdenum, niobium, zirconium, yttrium, barium, lanthanum, hafnium, tungsten, rhenium, osmium or iridium, or the catalyst composition is calcium, platinum, palladium, nickel, barium Alloys of titanium, chromium, manganese, iron, cobalt, copper, silicon, germanium, rhodium, rhodium, ruthenium, molybdenum, niobium, zirconium, yttrium, barium, lanthanum, hafnium, tungsten, rhenium, osmium or iridium.

In a tenth embodiment, a method of storing and recovering hydrogen comprises contacting a hydrogen storage composition with a first gas mixture comprising hydrogen at a first concentration; Dissociating hydrogen into atomic hydrogen; Storing atomic hydrogen in the storage composition; Contacting the hydrogen storage composition with a second gas mixture comprising a second concentration of hydrogen; And heating the hydrogen storage composition to a temperature effective to promote desorption of hydrogen from the hydrogen storage composition.

In an eleventh embodiment, a system for storage and recovery of hydrogen includes a hydrogen generation reactor in fluid communication with a hydride recycle reactor, wherein the hydrogen generation reactor comprises a light metal silicide, borosilicate, carbosilicide, nitro to recover hydrogen. The hydrides of silicides, aluminides, germanides, borides, borocarbide, boronides or carbides are used.

Also herein, there is provided a method comprising contacting a hydrogen mixture with a gas mixture comprising hydrogen; And irradiating the hydrogen storage composition by radio frequency irradiation or microwave irradiation in an amount effective to promote absorption, adsorption, or chemisorption of hydrogen into the hydrogen storage composition.

Also herein, there is provided a method comprising contacting a hydrogen storage composition with a first gas mixture comprising a first concentration of hydrogen; Irradiating the hydrogen storage composition by radio frequency irradiation or microwave irradiation with a first frequency in an amount effective to promote absorption, adsorption and / or chemisorption of hydrogen into the hydrogen storage composition; Contacting the hydrogen storage composition with a second gas mixture comprising a second concentration of hydrogen; And irradiating the hydrogen storage composition with radio frequency irradiation or microwave irradiation with a second frequency in an amount effective to promote desorption of hydrogen from the hydrogen storage composition.

Also disclosed herein is a system for storage and recovery of hydrogen comprising a hydrogen generation reactor that uses radio frequency irradiation and / or microwave frequency irradiation to recover hydrogen.

1 is a schematic diagram showing the arrangement of a diffuse multiple assembly in a silicon substrate.

2 is a schematic diagram showing the arrangement of a diffuse multiple assembly in an aluminum substrate.

3 is a schematic diagram showing (a) formation of binary couples of magnesium and aluminum and (b) formation of three-way diffusion triples of magnesium, lithium and aluminum.

4 is a schematic diagram showing the arrangement of a diffusion multiple assembly in a boron substrate.

FIG. 5 (herein referred to as FIG. 5 refers to both FIGS. 5A and 5B) is a schematic diagram showing the arrangement of a diffuse multiple assembly in a graphite substrate.

FIG. 6 is a schematic diagram showing how a diffusion multiple assembly is sliced for analysis purposes, with a silicon substrate shown in the figure. FIG.

7 is a periodic table of elements showing metals (+) and metals (-) that chemisorb hydrogen with a high adhesion probability.

8 is a schematic diagram showing a system for uptake and desorption (recovery) of hydrogen from a hydrogen storage composition.

9 is a schematic diagram showing a system for uptake and desorption (recovery) of hydrogen from another hydrogen storage composition.

For measuring silicides, borosilicates, carbosilicides, nitrosilicides, aluminides, germanides (germanium-containing compounds), borides, borocarbide, boronides or carbides which may be usefully used for the storage of hydrogen Disclosed herein is a method of developing a combinatorial library. Also provided herein are methods for producing silicides, borosilicates, carbosilicides, nitrosilicides, aluminides, germanides, borides, borocarbide, boronides or carbides that are subsequently hydrogenated to effectively store hydrogen. Is initiated. In addition, silicides, borosilicates, carbosilicides, nitrosilicides, aluminides, germanides, borides, which can store hydrogen for use in energy generation in fuel cell products in the automotive, home and apartment, manufacturing industries, etc. Disclosed herein are hydrogen storage compositions comprising borocarbide, boronitride or carbide. In one embodiment, such a hydrogen storage composition may comprise a catalyst composition capable of dissociating hydrogen if necessary.

If the hydrogen storage composition comprises a catalyst composition, the catalyst composition is generally disposed above the storage composition. The catalyst can dissociate molecular hydrogen into atomic or ionic hydrogen and the storage composition stores atomic hydrogen. Also disclosed herein is a method of storing hydrogen, comprising impregnating the hydrogen storage composition into hydrogen gas, and dissociating the hydrogen gas into atomic hydrogen that is subsequently stored in the storage composition.

Also disclosed herein is a method of storing hydrogen, including using electromagnetic radiation in the radio frequency (radio frequency) and microwave frequency regions. The process is useful in hydrogen storage compositions such as carbon, aluminide, carbide, silicides, nitrides, borides, oxides, oxynitrides, hydroxides, silicates, aluminosilicates, and the like, or combinations comprising one or more thereof. It can be usefully used to promote the storage of hydrogen. The use of electromagnetic energy can also usefully enhance the amount of hydrogen stored in the hydrogen storage composition. The hydrogen storage composition may be used for the recovery of hydrogen in energy generating devices such as fuel cells, gas turbines, and the like.

The stored hydrogen may then be used for recovery of hydrogen in energy generating devices such as fuel cells, gas turbines, and the like. In addition, such hydrogen storage and recovery methods include land vehicles such as cars, trains, and the like; Water vehicles such as barges, ships, submarines, etc .; Or may be usefully used in aerial vehicles or spacecraft, such as airplanes, rockets, space stations, and the like.

Tactics to develop a combinatorial library for measuring silicide, borosilicate, carbosilicide, nitrosilicide, aluminide, germanide, boride, borocarbide, boronide or carbide that may be usefully used for the storage of hydrogen The method allows for simultaneous large-scale testing of a wide variety of materials. This high efficiency method allows for rapid and systematic investigation of the bulk properties of silicides, borosilicates, carbosilicides, nitrosilicides, aluminides, germanides, borides, borocarbide, boronides or carbides in bulk samples. Promote the generation of large numbers of controlled composition variations. When used in conjunction with microanalysis techniques such as electron probe microanalysis, electron backscatter diffraction analysis, etc., this combinatorial library provides phase equilibrium, modulus, precipitation kinetics, properties and composition-phase for accelerated design of multi-component alloys and systems. Can be used additionally for efficient investigation of characteristic relationships.

Complex hydrides from which hydrogen can be obtained are generally composed of H-M complexes, where M is a metal and H is hydrogen. Such hydrides may have a bond comprising one or more combinations of ionic bonds, covalent bonds, metal bonds, or bonds of the type described above. Such hydrides have a hydrogen to metal ratio of at least about one. The reaction between the metal and hydrogen to form the hydride is generally a reversible reaction and takes place according to the following scheme.

M + (x / 2) H ₂ <-> MHx

Complex hydrides can store up to about 18 weight percent hydrogen and have a high volume storage density. The bulk storage densities of hydrides are greater than liquid or solid hydrogen, which makes them very useful in energy storage applications. Adsorption, absorption or chemisorption (hereinafter simply referred to as absorption) treatment of hydrogen stores hydrogen, while desorption treatment releases hydrogen.

In an exemplary embodiment, a composition comprising light metal silicide, borosilicate, carbosilicide, nitrosilicide, aluminide, germanide, boride, borocarbide, boronide or carbide has a relatively low temperature of about 300 ° C. or less Can be reversibly decomposed at to form a hydride capable of releasing hydrogen. Light metals are alkali metals and / or alkaline earth metals. Examples of suitable light metals are lithium, sodium, magnesium, potassium, aluminum, calcium and germanium. Silicides, borosilicates, carbosilicides and nitrosilicides have the structure of Formula I:

Formula I

(Li _a , Na _b , K _c , Al _d , Mg _e , Ca _f ) _x (B, C, N, Si) _y

Where

Li is lithium, Na is sodium, Mg is magnesium, K is potassium, Ca is calcium, Al is aluminum, Ge is germanium, B is boron, C is carbon, N is nitrogen, Si is silicon, a, b, c, d, e and f can be the same or different and have a value from 0 to 1 and x and y have a value from about 1 to about 22. The sum of a + b + c + d + e + f may be one.

Light metal aluminides have the structure of formula II, while light metal germanides have the structure of formula III:

Formula II

(Li _a , Na _b , K _c , Al _d , Mg _e , Ca _f ) _x (Al) _y

Formula III

(Li _a , Na _b , Mg _c , K _d , Ca _e , Al _f ) _x (Ge) _y

Where

Li is lithium, Na is sodium, Mg is magnesium, K is potassium, Ca is calcium, Al is aluminum, Ge is germanium, B is boron, C is carbon, N is nitrogen, Si is silicon, a, b, c, d, e and f can be the same or different and have a value from 0 to 1 and x and y have a value from about 1 to about 22. The sum of a + b + c + d + e + f may be one.

Borides, borocarbide and boronides have the structure of Formula IV:

Formula IV

(Li _a , Na _b , K _c , Al _d , Mg _e , Ca _f ) _x (B, C, N) _y

Where

Li is lithium, Na is sodium, Mg is magnesium, K is potassium, Ca is calcium, Al is aluminum, Ge is germanium, B is boron, C is carbon, N is nitrogen, Si is silicon, a, b, c, d, e and f can be the same or different and have a value from 0 to 1 and x and y have a value from about 1 to about 22. The sum of a + b + c + d + e + f may be one.

Carbide has the structure of Formula V:

Formula V

(Li _a , Na _b , K _c , Al _d , Mg _e , Ca _f ) _x (B, N, C) _y

Where

Li is lithium, Na is sodium, Mg is magnesium, K is potassium, Ca is calcium, Al is aluminum, Ge is germanium, B is boron, C is carbon, N is nitrogen, Si is silicon, a, b, c, d, e and f can be the same or different and have a value from 0 to 1 and x and y have a value from about 1 to about 22. The sum of a + b + c + d + e + f may be one.

In one embodiment, a method of developing a combinatorial library to measure the hydrogen storage capacity of silicide, borosilicate, carbosilicide, nitrosilicide, aluminide, germanide, boride, borocarbide, boronide or carbide Is due to the use of diffusion multiples. Diffusion multiple refers to the interdiffusion reaction formed between the first reactant and the second reactant when both the first reactant and the second reactant are each spaced apart from each other and are heated to a temperature effective to effect interdiffusion. Compound that is a product. The temperature effective to enable interdiffusion is the temperature that can overcome the activation energy of diffusion and achieve some degree of interdiffusion of reactants within a manageable time. Such temperatures are generally from about 200 to about 2000 ° C. depending on the reactants.

Diffusion multiplexing generally includes placing a reactant on a substrate to form a diffusion multiplex assembly; Optionally treating the diffusion multiple assembly with hot equilibrium pressurization; Heat treating the diffusion multiple assembly to promote cross diffusion between reactants and / or cross diffusion between reactants and the substrate; Optionally cutting, polishing, and polishing the diffusion multiple; Determining the elemental composition of the various phases present in the diffusion multiple; And filling the diffusion multiples with hydrogen by contacting the diffusion multiples with a hydrogen rich gas mixture and measuring the hydrogen absorbed phase.

1 shows an exemplary embodiment of a diffuse multiple assembly comprising light metal silicides. In FIG. 1, the light element is located in a hole drilled in the silicon substrate. Other substrates that can be used are silicon boride (SiB ₄ ), silicon carbide (SiC) or silicon nitride (Si ₃ N ₄ ) substrates. Holes generally terminate at half the thickness of the block. Some holes are spaced apart from each other during heat treatment such that there is only one reactant that reacts with the substrate material to form a binary couple and binary solid solution. If the substrate comprises silicon boride, silicon carbide or silicon nitride, ternary triples may be formed.

In another way of making a ternary triple, the holes have adjacent pairs of spacing between each other, as shown in FIG. Such an arrangement, in which the holes have spacing in pairs adjacent to each other, can be used to create a three-way diffusion triple (also called a ternary compound and / or ternary solid solution) when heat treating the diffusion multiple assembly. The reactants are generally located in loosely shaped holes (ie they do not need to match exactly).

The following silicides can be obtained from the diffusion multiple assembly shown in FIG. 1, which can be used for the determination of hydrogen potential: AlSi, Ca ₂ Si, CaSi, CaSi ₂ , KSi, K ₄ Si ₂₃ , Li ₂₂ Si ₅ , Li ₁₃ Si ₄ , Li ₇ Si ₃ , Li ₁₂ Si ₇ , Mg ₂ Si, NaSi, NaSi ₂ , Na ₄ Si _23, etc., or a combination comprising one or more of the silicides described above. General ternary silicides and in particular ternary silicides including the silicides described above may be useful for hydrogenation and hydrogen production. In addition, borosilicate, carbosilicide and nitrosilicide of lithium, magnesium, calcium, sodium, potassium and aluminum can be used for hydrogenation and hydrogen production.

Silicides, borosilicates, carbosilicides and nitrosilicides generally have one or more of potassium, lithium, magnesium or sodium. The presence of potassium, lithium, magnesium and sodium enhances affinity for hydrogen. On the other hand, silicon has a low affinity for hydrogen, which is believed to be offset by the hydrogen affinity exhibited by potassium, lithium, magnesium and / or sodium. Without being bound by theory, elements of a diffusion multiple that have a high affinity for hydrogen generally promote the uptake of hydrogen, while elements such as silicon that have a low affinity for hydrogen generally promote the desorption of hydrogen. It is thought to make.

2 illustrates an exemplary embodiment of a diffuse multiple assembly comprising light metal aluminide. In FIG. 2, a diffusion multiple is produced by drilling holes in an aluminum substrate. The following aluminides and germanides can be obtained from the diffusion multiple assembly shown in FIG. 2 and can be used for the determination of hydrogen potential: AlLi, Al ₂ Li ₃ , Al ₄ Li ₉ , Al ₃ Mg ₂ , Al ₁₂ Mg ₁₇ , Ge ₄ K, GeK, GeK ₃ , GeLi ₃ , Ge ₅ Li ₂₂ , Mg ₂ Ge, Ge ₄ Na, GeNa, GeNa _3, etc., or a combination comprising one or more of the aluminides and germanides described above water. In addition, the aforementioned germanides may be doped with aluminum if necessary.

When aluminum is used as the substrate, ternary triples can be formed. Ternary triples include aluminum and lithium and magnesium, aluminum and lithium and germanium, aluminum and sodium and germanium, aluminum and magnesium and germanium, and aluminum and germanium and potassium. Aluminides and germanides generally have one or more of potassium, lithium, magnesium or sodium. The presence of potassium, lithium, magnesium and sodium increases the affinity for hydrogen. Aluminum and germanium, on the other hand, have a low affinity for hydrogen, and this feature is offset by the hydrogen affinity represented by potassium, lithium, magnesium and / or sodium. Without being bound by theory, elements of a diffusion multiple that have a high affinity for hydrogen generally promote the uptake of hydrogen, while elements such as aluminum and germanium that have a low affinity for hydrogen generally desorb hydrogen. It is believed to promote.

In FIG. 3, a diffusion multiple is produced by drilling holes in the boron substrate. The following borides can be obtained from the diffusion multiple assembly shown in FIG. 3 and can be used for the determination of hydrogen potential: AlB ₂ , AlB ₁₂ , B ₆ Ca, B ₆ K, B ₁₂ Li, B ₆ Li, B ₄ Li, B ₃ Li, B ₂ Li, BLi, B ₆ Li ₇ , BLi ₃ , MgB ₂ , MgB ₄ , MgB ₇ , NaB ₆ , NaB ₁₅ NaB ₁₆ or a combination comprising one or more of the foregoing borides Water etc. General ternary borides and in particular ternary borides including the aforementioned borides may be useful for hydrogenation and hydrogen production. In addition, borocarbide and boronide of lithium, magnesium, calcium, sodium, potassium and aluminum can be used for hydrogenation and hydrogen production. In addition, diffusion triples of the reactants can be prepared by drilling holes adjacent to each other, as can be seen in FIG. 3. Ternary triples include boron and magnesium and aluminum, boron and sodium and aluminum, boron and magnesium and potassium, boron and lithium and aluminum, boron and sodium and magnesium, boron and sodium and potassium, boron and lithium and sodium, boron and lithium and Magnesium, boron and lithium and potassium, and boron and sodium and aluminum.

Borides, borocarbide and boronides generally have one or more of potassium, lithium, magnesium or sodium. The presence of potassium, lithium, magnesium and sodium enhances affinity for hydrogen. Boron, on the other hand, has a low affinity for hydrogen, which is believed to be offset by the hydrogen affinity exhibited by potassium, lithium, magnesium and / or sodium.

In FIG. 4, a diffusion multiple is produced by drilling holes in the graphite substrate. The following carbides can be obtained from the diffusion multiple assembly shown in FIG. 4 and can be used for the determination of hydrogen potential: Al ₄ C ₃ , Na ₄ C ₃ , Li ₄ C ₃ , K ₄ C ₃ , LiC, LiC ₆ , Mg ₂ C ₃ , MgC ₂ , AlTi ₂ C, AlTi ₃ C, AlZrC ₂ , Al ₃ Zr ₅ C, Al ₃ Zr ₂ C ₄ , Al ₃ Zr ₂ C ₇ , KC ₄ , NaC ₄ , or the like described above Combination comprising at least one of the carbides. General ternary carbides and in particular ternary carbides, including those described above, may be useful for hydrogenation and hydrogen production. In addition, borocarbide and nitrocarbide of lithium, magnesium, calcium, sodium, potassium and aluminum can be used for hydrogenation and hydrogen production.

The presence of potassium, lithium, magnesium and sodium enhances affinity for hydrogen. On the other hand, carbon has a low affinity for hydrogen, which is believed to be offset by the hydrogen affinity exhibited by potassium, lithium, magnesium and / or sodium. Without being bound by theory, elements of a diffusion multiple that have a high affinity for hydrogen generally promote the uptake of hydrogen, while elements such as carbon that have a low affinity for hydrogen generally promote the desorption of hydrogen. It is thought to make.

When the substrate is made of a single element, the number of holes drilled in the substrate generally corresponds to the minimum number of diffusion multiples desired. Thus, for example, if a binary diffusion couple is required in a substrate made from a single element such as silicon, aluminum, boron, etc., one hole is drilled in the substrate, whereas if a three-way diffusion triple is required, two holes are Perforations in the substrate adjacent to each other. As mentioned above, another method of making a ternary triple involves drilling a single hole in a substrate made of an alloy. The hole is about 1 to about 10 millimeters in diameter. Exemplary diameter is about 5 millimeters. The thickness of the substrate is generally about 5 to about 25 millimeters in diameter. Exemplary substrate thickness is about 25 millimeters.

The distance “d” between the holes in the substrate is kept as close as possible to the holes drilled in pairs. The distance d is generally about 0.1 to about 2000 micrometers. Within this range, it is generally desirable to use a distance of about 400 micrometers or less. In one embodiment, it is desirable to use a distance of about 200 micrometers or less, while in other embodiments it is desirable to use a distance of about 100 micrometers or less.

In an exemplary embodiment, in one embodiment, the diffusion multiple assembly comprises the silicon substrate shown in FIG. 1. Silicon substrates are used to make combinatorial libraries from alkali metals and / or alkaline earth metals. That is, the alkali metal and / or alkaline earth metal are located in the holes of the substrate to form a diffusion multiple. The substrate has a diameter of 2.0 inches and the hole containing the reactant is drilled to a depth of 0.5 inches. Reactants selected to be located in the holes of the substrate are potassium, lithium, sodium, magnesium, aluminum and calcium. As shown in FIG. 1, the reactants sodium, potassium, lithium and aluminum are located in separate holes of the substrate. These can be used to make binary diffusion couples of silicon and reactants.

The three-way diffusion triples of the reactants can also be prepared by drilling holes adjacent to each other as shown in FIG. 1. Ternary triples include silicon and lithium and sodium, silicon and lithium and potassium, silicon and sodium and potassium, silicon and lithium and aluminum, and silicon and sodium and aluminum.

The operation of placing the light metal in the hole of the substrate is carried out in a well controlled environment, such as a glove box filled with pure argon to prevent oxidation of the light metal. The amount of light element in each hole is usually less than one quarter of the volume of the hole so that there is no pure light element remaining after the interdiffusion / heat treatment step. The silicon substrate with light-elements in the hole is then transferred to the furnace or reactor. The furnace or reactor is in a vacuum or in a protective environment, such as argon. The substrate is then heated at an elevated temperature so that significant interdiffusion can occur between the element of the hole and the silicon substrate.

Silicon substrates with light metals located in the holes are heat treated to a temperature of about 580 to about 900 ° C. to allow melting of the reactants or eutectic compounds thereof. Also, the heat treatment forming the diffusion couple is generally carried out in a convection furnace. The heat treatment to form the diffusion couple may also include the use of irradiation heating and / or convection heating, if necessary. The molten reactant diffuses and reacts with the silicon substrate to form the silicide, doped phase and solid solution composition.

When silicon carbide is used as the substrate, the heat treatment is generally carried out at a temperature of about 580 to about 1,250 ° C. such that the formation of the diffusion multiple is promoted in a timely manner. An exemplary temperature in heat treatment is 600 ° C.

When silicon nitride is used as the substrate, the heat treatment is generally carried out at a temperature of about 600 to about 1,250 ° C. such that the formation of the diffusion multiple is promoted in a timely manner. An exemplary temperature in heat treatment is 600 ° C.

When silicon boride is used as the substrate, the heat treatment is generally carried out at a temperature of about 580 to about 1,250 ° C. such that the formation of the diffusion multiple is promoted within an appropriate time. An exemplary temperature in heat treatment is 600 ° C.

If aluminum or germanium is used as the substrate, the substrate is heat treated to a temperature of about 400 to about 600 ° C. to allow melting of the reactants or their eutectic compositions. The molten reactant diffuses and reacts with the aluminum substrate to form aluminide, germanide, doped phase and solid solution compositions. An exemplary temperature in heat treatment is 450 ° C.

The boron substrate is heat treated to a temperature of about 600 to about 1000 ° C. to enable melting of the reactants or eutectic compositions thereof. When boron carbide is used as the substrate, the heat treatment is generally carried out at a temperature of about 660 to about 1,250 ° C. such that the formation of the diffusion multiple is promoted in a timely manner. An exemplary temperature in heat treatment is 700 ° C.

When boron nitride is used as the substrate, the heat treatment is generally carried out at a temperature of about 660 to about 1,250 ° C. such that the formation of the diffusion multiple is promoted in a timely manner. An exemplary temperature in heat treatment is 700 ° C.

In one embodiment, in one method of making a diffusion multiple comprising borocarbide, the boron substrate having the desired reactant is heat treated in a carbonaceous atmosphere. Diffusion multiples are generally ternary triples containing borocarbide. The heat treatment temperature in the production of borocarbide is from about 660 to about 2000 ° C.

The diffuse multiple assembly comprising the graphite substrate is heat treated to a temperature of about 500 to about 1000 ° C. to allow melting of the reactants or eutectic compositions thereof. An exemplary temperature in heat treatment is 670 ° C.

When boron carbide is used as the substrate, the heat treatment is generally carried out at a temperature of about 500 to about 1,000 ° C. such that the formation of the diffusion multiple is promoted within a suitable time. An exemplary temperature in heat treatment is 670 ° C. In one embodiment, the diffusion multiple assembly is heat treated in a nitrogen atmosphere to form a diffusion multiple (binary couple and ternary triple) comprising carbonitride. Heat treatment in nitrogen is generally carried out at a temperature of about 550 to about 1000 ° C. Exemplary temperature is about 670 ° C.

Suitable times for heat treatment of the diffusion multiple assemblies are about 5 to about 100 hours. In one embodiment, it is preferred to heat treat the diffusion multiples for about 10 to about 75 hours. In other embodiments, it is desirable to heat treat the diffusion multiples for about 15 to about 50 hours. In another embodiment, it is desirable to heat treat the diffusion multiple for about 17 to about 40 hours. An exemplary heat treatment time is about 24 hours.

An embodiment illustrating the formation of a diffusion couple or triple is disclosed in FIG. 5. 5A illustrates the formation of diffusion couples in an aluminum substrate. In FIG. 5A, magnesium was used as a reactant to create a binary diffusion couple. The block is heated to 450 ° C. for 24 hours, allowing interdiffusion between the aluminum substrate and the magnesium reactant. Although the melting point of magnesium is about 650 ° C., the interaction of aluminum with magnesium produces a eutectic composition with a melting point of 437 ° C. The molten elements diffuse and react with each other to form aluminides of various compositions illustrated by FIG. 5. In FIG. 5, it can be seen that the aluminide formed away from the boundary of the original hole of the aluminum substrate has a higher aluminum fraction compared to the magnesium fraction. In a similar manner, FIG. 5B shows the formation of diffusion triples comprising using magnesium and lithium as reactants in an aluminum substrate. The block was heated to 450 ° C. for 24 hours. Many different binary aluminides are formed at the interface of lithium or magnesium and aluminum. Examples of such aluminides formed at the interface of aluminum and lithium are AlLi, Al ₂ Li ₃ or Al ₄ Li ₉ , while examples of aluminides formed at the interface of aluminum and magnesium are Al ₃ Mg ₂ and Al ₁₂ Mg ₁₇ . Many different ternary compositions including aluminum, lithium and magnesium are formed at the interface between aluminum, magnesium and lithium.

After the heat treatment to form the diffusion multiple, the slicing operation is performed in the diffusion multiple assembly. The slicing step is designed to expose different compositions / solid solutions formed at different locations of the diffusion multiple assembly as shown in FIG. 6. Slicing operations are generally carried out using mechanical cutting using a saw or wire discharge electro-machining (EDM). After slicing, the individual slices can be optionally polished and polished if necessary. After optional polishing and polishing operations, samples are tested prior to testing for the ability of light metal silicide, borosilicate, carbosilicide, nitrosilicide, aluminide, germanide, boride, borocarbide, boronide or carbide for hydrogenation. Electron microprobe analysis and electron backscatter diffraction (EBSD) analysis are performed to identify phases and compounds. Identification of a phase or compound as defined herein means locating and / or analyzing the phase or compound.

After electron microprobe and EBSD analysis of light metal silicide, borosilicate, carbosilicide, nitrosilicide, aluminide, germanide, boride, borocarbide, boronide or carbide, the resulting diffusion multiples are exposed to hydrogen Or by hydrogenation.

Diffusion multiples, including light metal silicides, borosilicates, carbosilicides, nitrosilicides, aluminides, germanides, borides, borocarbide, boronides or carbides are generally tested for their hydrogen absorption and desorption capacity. Can be. The composition gradient formed during diffusion multiple preparation can serve as a combinatorial library that determines whether a particular composition can absorb and desorb hydrogen.

The ability of light metal diffusion multiples to reversibly absorb and desorb hydrogen can be detected by various analytical techniques. In general, the procedure for the absorption of hydrogen into silicides, borosilicates, carbosilicides, nitrosilicides, aluminides, germanides, borides, borocarbide, boronides, or carbides is characterized by crystal structure changes and / or volumetric The expansion causes a change in appearance. In addition, the absorption of hydrogen into silicides, borosilicates, carbosilicides, nitrosilicides, aluminides, germanides, borides, borocarbide, boronides or carbides is generally accompanied by exothermic, but desorption of hydrogen is generally Is achieved by heating. Analytical techniques that can be used to measure changes in diffusion multiples include time of flight secondary mass ion spectrometry (ToF-SIMS), tungsten oxide (WO3) coating, and thermography. There is. In addition, silicides, borosilicates, carbosilicides, nitrosilicides, aluminides, germanides, borides, borocarbide, boronides or carbides are hydrogenated since the hydrogenated phase (ie, hydrides) is generally comminuted. It can then be screened by observing the diffusion multiples.

ToF-SIMS has the ability to detect the uptake and desorption of all elements, including hydrogen, which is useful for determining compositions present in light metal diffusion multiples that can be readily used for storage of hydrogen. This technique can be performed at temperatures of about -100 to 600 ° C. and is highly sensitive to hydrogen, making it a useful tool for studying combinatorial libraries produced by diffusion multiplexes. Therefore, ToF-SIMS can be effectively used to map the absorption temperature and reaction conditions during the hydrogenation process.

In general, tungsten oxide (WO ₃ ) changes color when reacted with hydrogen. In order to use tungsten oxide as a detector for hydrogen absorption in diffusion multiples of various compositions, the diffusion multiples are coated with WO ₃ after the hydrogenation reaction. When the diffusion multiple is heated to release hydrogen, the WO ₃ color changes as the hydrogen is released from the diffusion multiple.

Thermography or thermal imaging (infrared imaging) can also be used to measure the absorption and desorption of hydrogen. When the phase of the diffusion multiple absorbs hydrogen, the local temperature rises, while when the hydrogen is desorbed, the local temperature decreases. Therefore, thermography can be used to image compounds that absorb or desorb hydrogen.

In one embodiment, the diffusion multiples disclosed above, such as light metal silicide, borosilicate, carbosilicide, nitrosilicide, aluminide, germanide, boride, borocarbide, boronide or carbide may be coated with a catalyst composition And may be used as a hydrogen system. The diffusion multiple acts as a storage composition upon which the catalyst composition is disposed. Generally the catalyst composition comprises a metal capable of chemisorbing hydrogen with a higher sticking probability. 7 shows a periodic table reflecting an element that shows a significant probability of adhesion to hydrogen. In this table, all materials with high adhesion probabilities are shown with + signs. Suitable examples of such metals are calcium, barium, titanium, chromium, manganese, iron, cobalt, copper, silicon, germanium, rhodium, rhodium, ruthenium, molybdenum, niobium, zirconium, yttrium, barium, lanthanum, hafnium, tungsten, rhenium, Osmium, iridium or a combination comprising at least one of the foregoing metals. In one embodiment, the catalyst composition comprises calcium, barium, titanium, chromium, manganese, iron, cobalt, copper, silicon, germanium, rhodium, rhodium, ruthenium, molybdenum, niobium, zirconium, yttrium, barium, lanthanum, hafnium, tungsten Consists essentially of rhenium, osmium or iridium. In other embodiments, the catalyst composition comprises calcium, barium, titanium, chromium, manganese, iron, cobalt, copper, silicon, germanium, rhodium, rhodium, ruthenium, molybdenum, niobium, zirconium, yttrium, barium, lanthanum, hafnium, tungsten, Alloys of rhenium, osmium or iridium.

As mentioned above, alloys of these metals may also be used. In one embodiment, the alloy may contain platinum. In other embodiments, the alloy may contain palladium. In other embodiments, the alloy may contain nickel. Examples of suitable metals that can be alloyed with platinum and / or palladium and / or nickel to dissociate molecular hydrogen into atomic hydrogen are calcium, barium, titanium, chromium, manganese, iron, cobalt, copper, silicon, germanium, rhodium, Rhodium, ruthenium, molybdenum, niobium, zirconium, yttrium, barium, lanthanum, hafnium, tungsten, rhenium, osmium, iridium or combinations comprising at least one of the foregoing metals.

Generally, platinum and / or palladium and / or nickel may be present in an amount from about 0.1 to about 75 weight percent based on the total weight of the catalyst composition. In one embodiment, the platinum and / or palladium and / or nickel is preferably present in an amount of about 0.5 to about 70 weight percent based on the total weight of the catalyst composition. In other embodiments, the platinum and / or palladium and / or nickel is preferably present in an amount of about 3 to about 65 weight percent based on the total weight of the catalyst composition. In another embodiment, the platinum and / or palladium and / or nickel is preferably present in an amount of about 5 to about 50 weight percent based on the total weight of the catalyst composition.

The catalyst composition is disposed above the storage composition. The storage composition usefully facilitates storage of atomic hydrogen. Suitable examples of materials that can be used in the preparation composition are carbon, carbide, silicide, sulfide, nitride, oxide, oxynitride, hydroxide, silicate, alanate, aluminosilicate, borosilicate, carbosilicide, nitro Silicides, aluminides, germanides, borides, borocarbide, boronides or combinations comprising one or more of the foregoing.

Exemplary forms of carbon that can be used in the storage composition are those having high surface areas such as carbon black and / or carbon nanotubes. Suitable carbon nanotubes are vapor grown carbon fibers, single wall carbon nanotubes and / or multiwall carbon nanotubes.

Suitable oxides that may be used in the storage compositions are silicon dioxide (eg, dry silica), alumina, ceria, titanium dioxide, zirconium oxide, tungsten oxide, vanadium pentoxide, and the like, or combinations comprising one or more of the foregoing oxides. Generally, metal oxides can be prepared using aerogel technology. Generally, metal oxides include tungsten oxide (WO ₃ ), nickel oxide (NiO ₂ ), cobalt oxide (CoO ₂ ), manganese oxide (Mn ₂ O ₄ and MnO ₂ ), vanadium oxide (VO ₂ and V ₂ O ₅ ), Molybdenum oxide (MoO ₂ ), or the like, or combinations comprising at least one of the foregoing oxides.

In general, the storage composition preferably has a surface area of at least about 10 m ² / gm. In one embodiment, the storage composition preferably has a surface area of at least about 50 m ² / gm. In other embodiments, the storage composition preferably has a surface area of at least about 100 m ² / gm.

In one embodiment, the storage composition may comprise nanoparticles. The nanoparticles may have a size of about 1 to about 200 nanometers, on which the catalyst composition may be disposed. In one embodiment, the particle size is about 3 to about 150 nanometers. In other embodiments, the particle size is about 5 to about 100 nanometers. In yet another embodiment, the particle size is about 10 to about 80 nanometers.

Generally, the catalyst composition is deposited in the storage composition through sputtering, chemical vapor deposition from a solution or the like. In one embodiment, the catalyst composition may completely cover about 1 to about 100% surface area of the total surface area of the storage composition. In one embodiment, the catalyst composition may cover about 5 to about 90% surface area of the total surface area of the storage composition. In other embodiments, the catalyst composition may cover about 10 to about 75% surface area of the total surface area of the storage composition. In another embodiment, the catalyst composition may cover about 15 to about 50% of the surface area of the total composition of the storage composition.

If the catalyst composition does not cover 100% of the surface area of the storage composition, it may be desirable for the catalyst composition to be disposed on the surface of the storage composition as isolated particulates. There is no particular limitation on the shape of the particles. For example spherical, irregular, plate or whiskers and the like. Bimodal or higher particle size distributions may also be used. Particulates of the catalyst composition may have a radius of rotation of about 1 to about 200 nanometers (nm). In one embodiment, the particulates of the catalyst composition may have a radius of rotation of about 3 to about 150 nanometers (nm). In other embodiments, the particulates of the catalyst composition may have a radius of rotation of about 5 to about 100 nanometers (nm). In yet another embodiment, the particulates of the catalyst composition may have a radius of rotation of about 10 to about 75 nanometers (nm).

In other embodiments, nanoparticles and microparticles of a storage composition having a catalyst composition disposed over the storage composition can be fused together under reduced pressure to form a hydrogen storage composition. Generally, the storage composition is preferably present in an amount of about 30 to about 99 weight percent based on the total weight of the hydrogen storage composition. In one embodiment, the storage composition is preferably present in an amount of about 35 to about 95 weight percent based on the total weight of the hydrogen storage composition. In other embodiments, the storage composition is preferably present in an amount of about 40 to about 90 weight percent based on the total weight of the hydrogen storage composition. In another embodiment, the storage composition is preferably present in an amount of about 45 to about 85 weight percent based on the total weight of the hydrogen storage composition.

In one embodiment involving the storage of hydrogen, the hydrogen storage composition is impregnated in a hydrogen containing environment. Hydrogen in molecular structure is dissociated into atomic hydrogen by the catalyst composition and stored in the storage composition. Hydrogen is then released from the hydrogen storage composition by heating. The storage of hydrogen can be carried out in a device called an applicator. The applicator is a container for holding the hydrogen storage composition. In other embodiments, while storing hydrogen in the hydrogen storage composition, hydrogen may be introduced into the applicator under reduced pressure, or the applicator may be pressurized after hydrogen introduction. In addition, the hydrogen storage composition may be stirred during the storage process to obtain uniform storage of hydrogen into the hydrogen storage composition. Since storage of hydrogen is generally an exothermic reaction, the applicator can be cooled with water, liquid nitrogen, liquid carbon dioxide, or air as needed during storage of hydrogen.

As mentioned above, radio and microwave frequencies can be used to facilitate the recovery as well as the storage of hydrogen from the hydrogen storage composition. Coupling of dipoles and radiation present in the hydrogen storage composition is used to facilitate storage and recovery of hydrogen. In one embodiment, the frequencies of microwave and radio wave irradiation can be varied to achieve effective coupling between the radiation and the dipole of the hydrogen storage composition. Such coupling can effectively promote the storage and / or release of hydrogen. In other embodiments, the frequencies of microwave and radio wave irradiation can be varied with the temperature of the hydrogen storage composition to effectively promote storage and / or release of hydrogen.

In one embodiment, when the hydrogen storage composition is located in the electromagnetic field, the power absorbed by the composition is described by the following formula VI:

Where

P is the power absorbed per unit volume, ω is 2πf (where f is the applied frequency), ε ₀ is the permittivity of free space, ε ″ _r is the dielectric loss factor of the material, and E is applied locally From Equation VI, the absorbed power directly depends on the dielectric loss factor, which, among other factors, has many factors such as the dipole moment, temperature and frequency of irradiation of the various components present in the hydrogen storage composition. Depends on

In one embodiment, in the use of Equation VI, the dielectric loss factor in the hydrogen storage composition may be adjusted or optimized to desirably facilitate the storage and / or release of hydrogen in the hydrogen storage composition. In other embodiments, the first frequency (in the microwave or radio wave range) in the first environment may be used to facilitate storage of hydrogen in the hydrogen storage composition, while in the second environment (or the first environment) The second frequency can be used to promote recovery of hydrogen in the hydrogen storage composition. The environment defined herein refers to any formulation contained in the composition as well as the hydrogen storage composition that promotes storage and / or recovery of hydrogen when the hydrogen storage composition is coupled with radio frequency radiation and / or microwave radiation. Examples of such agents are materials having dipoles that can be heated upon treatment with radio frequency radiation and / or microwave radiation. Examples of such materials are water, alcohols, dimethylformamide, acetone, carbon, silicon carbide, and the like or combinations comprising one or more of the foregoing agents.

In general, when radio waves are used to perform storage and / or desorption of hydrogen by the hydrogen storage composition, good uniformity and significant speed in absorption and / or desorption are possible. However, when microwaves are used, mechanical agitation can be used to promote uniform absorption and / or desorption of hydrogen by the hydrogen storage composition. Non-uniform heating by microwaves can lead to heat release, which can lead to undesirable sintering of the hydrogen storage composition. Different frequencies within the electromagnetic spectrum can be used to promote the storage and recovery of hydrogen in the hydrogen storage composition simultaneously or sequentially. In one embodiment, to store hydrogen, it may be desirable to contact the hydrogen storage composition with a gas mixture containing hydrogen. In other embodiments, for the storage of hydrogen, the storage of hydrogen can occur by exposing the hydrogen storage composition to the hydrogen just formed. For example, the hydrogen storage composition may be first irradiated over a radio frequency wave for a given time and then at a microwave frequency during the hydrogen storage or recovery process. Alternatively, it may be desirable to simultaneously treat the hydrogen storage composition at both the radio frequency as well as the microwave frequency during storage and / or recovery of hydrogen. It is also contemplated that several different frequencies within the radio frequency range or microwave frequency range, or both, may be used sequentially or simultaneously to facilitate storage and recovery of hydrogen in the hydrogen storage composition.

In one embodiment, a method of storing and recovering hydrogen comprises contacting a hydrogen storage composition to a first gas mixture comprising hydrogen; Irradiating the hydrogen storage composition in an amount effective to promote absorption, adsorption, or chemisorption of hydrogen into the hydrogen storage composition via radio frequency irradiation or microwave irradiation having a first frequency; Contacting the hydrogen storage composition with a second gas mixture comprising hydrogen at a second concentration of hydrogen; And irradiating the hydrogen storage composition in an amount effective to promote desorption of hydrogen from the hydrogen storage composition via radio frequency irradiation or microwave irradiation having a second frequency.

In one embodiment, the first frequency is not the same as the second frequency, but greater or less than the second frequency. In one embodiment, radio frequencies may be used to promote storage of hydrogen in the hydrogen storage composition, while microwave frequencies may be used to promote recovery of hydrogen from the hydrogen storage composition. In other embodiments, microwave frequencies may be used to promote storage of hydrogen in the hydrogen storage composition, while radio frequencies may be used to promote recovery of hydrogen from the hydrogen storage composition. In other embodiments, the first frequency is the same as the second frequency.

In another embodiment, the first concentration of hydrogen impregnated with the hydrogen storage composition is greater than the second concentration of hydrogen impregnated with the hydrogen storage composition. In an exemplary embodiment, the process of contacting the hydrogen storage composition with an environment comprising a second concentration of hydrogen may comprise physical transfer of the hydrogen storage composition from a first location where hydrogen storage occurs to a second location where hydrogen recovery occurs. Can be. In other embodiments, the first position may be the same as the second position. In an exemplary embodiment, the first location may be a hydrogen storage composition production reactor as shown in FIG. 9, while the second location may be a hydrogen production reactor. As described above, the hydrogen stored in the hydrogen storage composition may be present in a gas mixture comprising hydrogen, or may be formed and stored directly in the hydrogen storage composition without mixing with other gases.

The energy generator for emitting electromagnetic radiation can be both a continuous wave or a pulse wave generator, and one of these types of generators can be used for hydrogen storage and hydrogen generation processes.

In one embodiment, a combined source of electromagnetic radiation can be used to promote the uptake and desorption of hydrogen. Such a source may be within the microwave and / or radio frequency range, or may be outside the range described above if necessary. In one exemplary embodiment, in addition to microwave and radio frequency radiation, it can also be used when other forms of electromagnetic energy such as infrared radiation, ultraviolet radiation, X-ray radiation are required.

In addition to using a combination of sources of electromagnetic radiation (ie, radio and microwave) to facilitate storage and recovery of hydrogen in the hydrogen storage composition, the energy derived from electromagnetic radiation can be converted into other forms of thermal energy such as gas combustion or electrical It may be desirable to supplement with heating induced in a heated oven or furnace. In one embodiment, the hydrogen storage composition may be heated using convective and / or conductive heating with energy derived from radio frequency or microwave radiation. In this case, other forms of heating may be used to heat the hydrogen storage composition to a predetermined desired temperature, but additional increases in temperature can be obtained through microwave and radio wave irradiation and coupling. When conventional heating by a technique such as convection is used alone, a temperature gradient where the outer surface or skin temperature is higher than the inner or central temperature is usually present in the heated material. This effect is commonly referred to as the 'skin-core' effect and generates chemical or physical gradients in the hydrogen storage composition. Thus, combinations of microwave and / or radio frequency heating as well as heating by convection or conduction can be usefully used to enhance temperature uniformity, thereby reducing chemical concentration gradients or physical property gradients in the hydrogen storage composition.

In general, radio frequencies of about 10 kilohertz (kHz) to about 300 megahertz (MHz) may be used to facilitate storage and recovery of hydrogen. In one embodiment, a frequency of about 1 MHz to about 250 MHz can be used. In other embodiments, a frequency of about 50 to about 225 MHz may be used to facilitate storage and recovery of hydrogen.

In addition, microwave frequencies of about 300 MHz to about 300 gigahertz (GHz) can be effectively used to facilitate storage and recovery of hydrogen. In one embodiment, a frequency of about 400 MHz to about 280 GHz may be used. In other embodiments, frequencies of about 600 MHz to about 260 GHz can be used to facilitate storage and recovery of hydrogen. In another embodiment, frequencies of about 750 MHz to about 250 GHz can be used to facilitate storage and recovery of hydrogen. The frequencies of both microwave irradiation and radio frequency irradiation can be tuned to promote the absorption, adsorption, chemisorption or desorption of hydrogen. In general, the electromagnetic energy delivered to the hydrogen storage composition is generally sufficient to be able to be stored without any sintering. Such energy may be from about 0.001 watts / gram to about 1,000 watts / gram of hydrogen storage composition. The frequency can be modulated to promote hydrogen absorption, adsorption, chemisorption or desorption.

In one embodiment, during storage of hydrogen in the hydrogen storage composition, radio frequency or microwave energy may be introduced into the applicator or waveguide after the hydrogen storage composition is positioned at the desired location in the applicator. Hydrogen gas may then be introduced into the applicator. Hydrogen may optionally be introduced into the applicator under pressure, and the applicator may optionally be pressurized after the introduction of hydrogen. The pressure of the applicator after the introduction of hydrogen is generally maintained at about 1 kg / cm ² to about 100 kg / cm ² . An exemplary pressure value of the applicator is about 30 kg / cm ² .

Hydrogen can be introduced into the applicator along with other non-reactive gases to facilitate the storage process. This combination of hydrogen and other gases is referred to as a gas mixture. Exemplary non-reactive gases are inert gases. When other gases are introduced with hydrogen, the hydrogen content is generally about 50 to about 99 weight percent based on the total weight of the gas mixture.

Radio frequency radiation or microwave radiation may be applied to the applicator in the form of combustion waves or pulse waves. In addition, the hydrogen storage composition can be stirred during the storage process to obtain uniform storage of hydrogen into the composition. Since storage of hydrogen is generally an exothermic reaction, during storage of hydrogen, the applicator can be cooled with water, liquid nitrogen, liquid carbon dioxide, or air if necessary.

During hydrogen recovery, heat may be supplied to the hydrogen storage composition to produce hydrogen. Therefore, radio frequency radiation and microwave radiation can be applied to heat the hydrogen storage composition. Heating of the composition may be accomplished by a combination of convective heating and radio frequency irradiation and / or microwave frequency irradiation. While recovering hydrogen, the pressure of the applicator can be arbitrarily lowered. During hydrogen recovery, the applicator pressure is about 1 to about 300 millimeters of mercury (mm of Hg).

In one exemplary method of generating and storing hydrogen by using a hydrogen storage composition and radio frequency waves (radio waves) and / or microwaves, the system shown in FIG. 9 is a hydrogen generation reactor (a second at a second location). An optional hydrogen storage composition reactor (first applicator in a first location) upstream of and in fluid communication with the applicator). As described above, if desired, the first applicator may be different from the second applicator, and the first position may be different from the second position. In other embodiments, the first applicator can be the same as the second applicator and the first position can be the same as the second position. The hydrogen storage composition reactor uses radio waves and / or microwaves to regenerate the hydrogen storage composition used to generate hydrogen in the hydrogen production reactor. The hydrogen storage composition may be in the form of a slurry if necessary.

At least a portion of the hydrogen storage composition in the hydrogen generation reactor is used to recover hydrogen from the hydrogen storage composition. When a hydrogen storage composition releases hydrogen, it is said to consume a hydrogen storage composition. Hydrogen generation reactors use radio waves and / or microwaves to produce hydrogen. The hydrogen generation reactor may also use convection heating, conduction heating, PEM fuel cell exhaust heat, etc., in addition to microwaves and radio waves for heating the hydrogen storage composition for the purpose of hydrogen generation. In addition, the hydrogen generation reactor is upstream of and in fluid communication with the optional drying and separation reactor, and the spent hydrogen storage composition is optionally transferred to the drying and separation reactor. At least a portion of the spent hydrogen storage composition produced in the hydrogen generation reactor is optionally recycled to the drying and separation reactor. Optionally, the hydrogen generation reactor is supplied with water. The optional drying and separation reactor separates any reusable fluid, such as water, from the spent hydrogen storage composition and recycles the fluid to the optional hydrogen storage composition reactor. The hydrogen storage composition is then recycled to the hydrogen storage composition reactor for mixing and regeneration with the recycled carrier liquid. In addition to the hydrogen storage composition, other materials, such as carbon, alanate, and the like, can be used to generate hydrogen in the hydrogen generation reactor.

In one embodiment, the hydrogen storage composition may be hydrogenated by treating it with a mixture of gases comprising hydrogen. As mentioned above, hydrogen storage compositions generally release heat while absorbing hydrogen. Desorption of hydrogen often requires a thermal cycle. This thermal cycle can be obtained by applying an electric field or by passing a current through the desired material. This can be accomplished because most hydrogenated hydrogen storage compositions are electrically conductive. The resistance of these materials varies with the extent of hydrogen storage.

In one embodiment, desorption of stored hydrogen can be facilitated by the use of an electromagnetic field. Microwave energy may be directly applied to the hydrogenated hydrogen storage composition or a suitable medium mixed with the hydrogenated hydrogen storage composition, such as water, alcohol, or the like, to enable local release of hydrogen under controlled conditions without heating the entire system. This method provides for high efficiency desorption, which generally occurs at temperatures lower than the temperatures achieved due to conduction and / or heating by convection. This phenomenon occurs because of the local excitation of the bonds in the hydrogen storage composition by microwaves. Desorption can be carried out by two different methods. The first of these involves the use of microwaves to achieve the release of the total hydrogen content. The second method only initiates the desorption process which can then be continued in a much easier manner than when heated by conduction and / or convective heating at lower temperatures and only by conduction and / or convective heat from the start of the process. And using microwave processing to accomplish this.

In another embodiment, hydrogen desorption can be induced by heat generated by electrical resistance embedded in the hydrogen storage composition. The current energy flowing to the resistor is converted to heat by the Joule effect. The amount of heat generated locally by the current flow is particularly high in the case of compressed powder silicide materials with hot spots, in which case the hot spots are generated in the current path between powder particles with a very high resistivity. In extreme cases, powder bonding may occur at hot spots. Therefore, the thermal parameters must be properly adjusted to prevent sintering or powder bonding. Depending on the conditions of the process, the hydrogen storage composition may be heated directly or may be heated by the use of multiple resistors described above.

In another embodiment, the hydrogen uptake and desorption mixes the fine particle hydrogen storage composition with an appropriate amount of another chemical composition having a higher thermal conductivity to conduct heat to the hydrogenated compound for faster hydrogen release. Is achieved by In another embodiment, hydrogen desorption is accomplished by using exhaust heat released from a proton exchange membrane (PEM) fuel cell to heat the hydrogenated hydrogen storage composition.

In another embodiment, dopants comprising elements from titanium, vanadium, zirconium, yttrium, lanthanum, nickel, manganese, cobalt, silicon, gallium, germanium and lanthanides can be added to catalyze the desorption of hydrogen. The dopant may be added in an amount up to about 20% by weight of the total hydrogen storage composition prior to storage of hydrogen. Generally, it is desirable to add the dopant in an amount up to about 15% by weight of the total hydrogen storage composition. In one embodiment, the dopant may be added in an amount up to about 10 weight percent based on the total weight of the hydrogen storage composition, while in other embodiments the dopant is about 5 weight based on the total weight of the hydrogen storage composition. It may be added in an amount of up to%.

Hydrogen released from silicide, borosilicate, carbosilicide, nitrosilicide, aluminide, germanide, boride, borocarbide, boronide or carbide is about 1 to about 8 weight based on the total weight of the hydrogen storage composition May be%. In one embodiment, the desorbed hydrogen is at least about 4% by weight based on the total weight of the hydrogen storage composition. In other embodiments, the desorbed hydrogen is at least about 5% by weight based on the total weight of the hydrogen storage composition. In yet another embodiment, the desorbed hydrogen is at least about 6% by weight based on the total weight of the hydrogen storage composition.

As described above, the combined method of measuring hydrogen absorption and desorption probability of light metal silicide, borosilicate, carbosilicide, nitrosilicide, aluminide, germanide, boride, borocarbide, boronide or carbide is rapid and Efficient Light metal silicides, borosilicates, carbosilicides, nitrosilicides, aluminides, germanides, borides, borocarbide, boronides or carbides measured as absorbing and desorbing hydrogen are fuel cells, gases for storage of energy It can be used in a turbine or the like.

In one exemplary embodiment of generating and storing hydrogen from a hydride of a light metal silicide, borosilicate, carbosilicide, nitrosilicide, aluminide, germanide, boride, borocarbide, boronide or carbide, FIG. The system shown in 8 includes an optional slurry generation reactor upstream of and in fluid communication with the hydrogen production reactor. The slurry generation reactor regenerates the metal hydride slurry used to generate hydrogen in the hydrogen production reactor. At least a portion of the metal hydride in the hydrogen generation reactor is oxidized to the metal hydroxide while recovering hydrogen from the light metal hydride. Hydrogen generation reactors use electromagnetic radiation, convection heating, PEM fuel cell exhaust heat, and the like, to heat hydrides for hydrogen production. In addition, the hydrogen generation reactor is upstream of and in fluid communication with the optional drying and separation reactor, and the metal hydroxide is transferred to the drying and separation reactor. At least a portion of the metal hydroxide produced in the hydrogen generation reactor is recycled to the drying and separation reactor. Optionally, the hydrogen generation reactor is supplied with water. The optional drying and separation reactor separates any reusable fluid, such as water, from the metal hydroxide and recycles the fluid to the optional hydrogen storage composition reactor. The system also includes a hydride recycle reactor downstream of and in fluid communication with the drying and separation reactor. Dry metal hydroxides from the drying and separation reactors are regenerated as metal hydrides in the hydride recycle reactor by contacting a mixture of gases comprising hydrogen. The hydride recycle reactor is supplied with carbon and oxygen in an effective amount to regenerate the metal hydride. The regenerated metal hydride is then recycled to the slurry production reactor for mixing with the recycled carrier liquid.

In other embodiments related to storage and recovery of hydrogen from a hydrogen storage system containing a catalyst composition, the hydrogen storage composition first comprises a first comprising a first concentration of hydrogen at a first location, such as the hydrogen storage composition reactor of FIG. 9. Contact with the gas mixture. In the first position, hydrogen is dissociated into atomic hydrogen and stored in the storage composition. The hydrogen storage composition which now contains hydrogen is then contacted with a second gas mixture comprising a second concentration of hydrogen at a second location, such as the hydrogen production chamber of FIG. 9. Wherein the hydrogen storage system is heated to a temperature effective to promote the desorption of hydrogen from the hydrogen storage composition. In one embodiment, the first concentration of hydrogen is greater than the second concentration. In other embodiments, the first position may be the same as the second position. In another embodiment, the first position may be different from the second position.

This hydrogen storage and recovery method can be useful for board recovery of hydrogen in fuel cells installed in small vehicles such as automobiles weighing less than about 2,500 kg. In addition, such hydrogen storage and recovery methods include land vehicles such as cars, trains, and the like; Water vehicles such as barges, ships, submarines, etc .; Or may be usefully used in aerial vehicles or spacecraft, such as airplanes, rockets, space stations, and the like. It can also be used for the recovery of hydrogen in fuel cells used in power generators used in residential applications, factories, office buildings, and the like.

Although the invention has been described with reference to exemplary embodiments, various changes may be made and equivalents may be substituted for elements of the invention without departing from the scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the present invention not be limited to the particular embodiments described as the best mode contemplated for carrying out the invention, but that all embodiments fall within the scope of the appended claims.

Claims (63)

Placing a reactant comprising a light metal on a substrate comprising silicon, graphite, boron, boron carbide, boron nitride, aluminum, germanium, silicon nitride, silicon carbide or silicon boride; Thermally treating the substrate to produce a diffuse multiple having two or more phases; Contacting the hydrogen and a diffusion multiple; Detecting any hydrogen uptake; And / or Detecting any hydrogen desorption Method of producing a combinatorial library comprising a. The method of claim 1, Wherein the light metal is an alkali metal or an alkaline earth metal, and the light metal is disposed in a hole in the substrate. The method of claim 1, The light metal is lithium, magnesium, sodium, potassium, calcium or aluminum, and the light metal is disposed in the hole of the substrate. The method according to any one of claims 1 to 3, Wherein the heat treatment is carried out at a temperature of about 200 to about 2000 ° C. The method according to any one of claims 1 to 4, Heat treatment, If the substrate is silicon, it is carried out at a temperature of about 580 to about 900 ℃, When the substrate is silicon boride, it is carried out at a temperature of about 580 to about 1250 ° C., If the substrate is silicon carbide, it is carried out at a temperature of about 580 to about 1250 ℃, When the substrate is silicon nitride, it is carried out at a temperature of about 600 to about 1250 ° C., If the substrate is aluminum or germanium, it is carried out at a temperature of about 400 to about 600 ° C., If the substrate is boron is carried out at a temperature of about 660 to about 1000 ℃, If the substrate is boron boride is carried out at a temperature of about 660 to about 1250 ℃, or If the substrate is graphite, the process is carried out at a temperature of about 500 to about 1000 ° C. The method according to any one of claims 1 to 5, At least one reactant is disposed on the substrate and forms a binary couple upon thermal treatment. The method according to any one of claims 1 to 5, At least one reactant is disposed on the substrate and forms a ternary triple upon thermal treatment. The method according to any one of claims 1 to 5, Wherein at least two reactants are disposed on the substrate and form ternary triples upon thermal treatment. The method according to any one of claims 1 to 8, And identifying and analyzing one or more phases of the diffusion couple using electronic microprobe analysis. The method according to any one of claims 1 to 9, Slicing and polishing the diffusion multiple. The method according to any one of claims 1 to 10, The method further comprises analyzing the dispersion multiple by electron microprobe analysis or electron backscatter diffraction. AlSi, Ca ₂ Si, CaSi, CaSi ₂ , KSi, K ₄ Si ₂₃ , Li ₂₂ Si ₅ , Li ₁₃ Si ₄ , Li ₇ Si ₃ , Li ₁₂ Si ₇ , Mg ₂ Si, NaSi, NaSi ₂ , Na ₄ Si ₂₃ , AlB ₂ , AlB ₁₂ , B ₆ Ca, B ₆ K, B ₁₂ Li, B ₆ Li, B ₄ Li, B ₃ Li, B ₂ Li, BLi, B ₆ Li ₇ , BLi ₃ , MgB ₂ , MgB ₄ , MgB ₇ , NaB ₆ , NaB ₁₅ NaB ₁₆ , AlLi, Al ₂ Li ₃ , Al ₄ Li ₉ , Al ₃ Mg ₂ , Al ₁₂ Mg ₁₇ , AlB ₁₂ , Ge ₄ K, GeK, GeK ₃ , GeLi ₃ , Ge ₅ Li ₂₂ , Mg ₂ Ge, Ge ₄ Na, GeNa, GeNa ₃ , Aluminum Doped Ge ₄ K, Aluminum Doped GeK, Aluminum Doped GeK ₃ , Aluminum Doped GeLi ₃ , Aluminum Doped Ge ₅ Li ₂₂ , Aluminum doped Mg ₂ Ge, aluminum doped Ge ₄ Na, aluminum doped GeNa, aluminum doped GeNa ₃ , Al ₄ C ₃ , Na ₄ C ₃ , Li ₄ C ₃ , K ₄ C ₃ , LiC, LiC ₆ , Mg ₂ C ₃ , MgC ₂ , AlTi ₂ C, AlTi ₃ C, AlZrC ₂ , Al ₃ Zr ₅ C, Al ₃ Zr ₂ C ₄ , Al ₃ Zr ₂ C ₇ , KC ₄ , NaC ₄ , or the aforementioned compounds One or more shoes selected from the group consisting of combinations comprising one or more of Contacting the mixture in hydrogen to form a hydrogenated compound; And Recovering hydrogen by heating the hydrogenated compound Recovering hydrogen comprising a. Contacting hydrogen with a compound having one or more of Formulas I-V to form a hydrogenated compound; And Recovering hydrogen by heating the hydrogenated compound Including a method for regenerating hydrogen: Formula I (Li _a , Na _b , K _c , Al _d , Mg _e , Ca _f ) _x (B, C, N, Si) _y Formula II (Li _a , Na _b , Mg _c , K _d , Ca _e , Ge _f ) _x (Al) _y Formula III (Li _a , Na _b , Mg _c , K _d , Ca _e , Al _f ) _x (Ge) _y Formula IV (Li _a , Na _b , K _c , Al _d , Mg _e , Ca _f ) _x (B, C, N) _y Formula V (Li _a , Na _b , K _c , Al _d , Mg _e , Ca _f ) _x (B, N, C) _y Where Li is lithium, Na is sodium, Mg is magnesium, K is potassium, Ca is calcium, Al is aluminum, Ge is germanium, B is boron, C is carbon, N is nitrogen, Si is silicon, a, b, c, d, e and f can be the same or different and have a value from 0 to 1 and x and y have a value from about 1 to about 22. The method according to claim 12 or 13, Wherein the heating is carried out using a combination comprising microwave irradiation, convection heating, electrical resistance heating, or one or more of the heating methods described above. The method according to any one of claims 12 to 14, Adding a dopant comprising an element selected from titanium, vanadium, zirconium, yttrium, lanthanum, nickel, magnesium, cobalt, silicon, gallium, germanium and lanthanides to the compound in an amount up to about 20% by weight of the diffusion multiple How to further include. The method according to any one of claims 12 to 15, The heating is carried out by the exhaust heat of the fuel cell. An energy generating device in which the method of any one of claims 12-16 is used for generating energy. Diffusion multiple compounds having at least one of Formulas I-V: Formula I (Li _a , Na _b , K _c , Al _d , Mg _e , Ca _f ) _x (B, C, N, Si) _y Formula II (Li _a , Na _b , Mg _c , K _d , Ca _e , Ge _f ) _x (Al) _y Formula III (Li _a , Na _b , Mg _c , K _d , Ca _e , Al _f ) _x (Ge) _y Formula IV (Li _a , Na _b , K _c , Al _d , Mg _e , Ca _f ) _x (B, C, N) _y Formula V (Li _a , Na _b , K _c , Al _d , Mg _e , Ca _f ) _x (B, N, C) _y Where Li is lithium, Na is sodium, Mg is magnesium, K is potassium, Ca is calcium, Al is aluminum, Ge is germanium, B is boron, C is carbon, N is nitrogen, Si is silicon, a, b, c, d, e and f can be the same or different and have a value from 0 to 1 and x and y have a value from about 1 to about 22. The method of claim 18, Compound in which the sum of a, b, c, d, e and f is one. AlSi, Ca ₂ Si, CaSi, CaSi ₂ , KSi, K ₄ Si ₂₃ , Li ₂₂ Si ₅ , Li ₁₃ Si ₄ , Li ₇ Si ₃ , Li ₁₂ Si ₇ , Mg ₂ Si, NaSi, NaSi ₂ , Na ₄ Si ₂₃ , AlB ₂ , AlB ₁₂ , B ₆ Ca, B ₆ K, B ₁₂ Li, B ₆ Li, B ₄ Li, B ₃ Li, B ₂ Li, BLi, B ₆ Li ₇ , BLi ₃ , MgB ₂ , MgB ₄ , MgB ₇ , NaB ₆ , NaB ₁₅ NaB ₁₆ , AlLi, Al ₂ Li ₃ , Al ₄ Li ₉ , Al ₃ Mg ₂ , Al ₁₂ Mg ₁₇ , AlB ₁₂ , Ge ₄ K, GeK, GeK ₃ , GeLi ₃ , Ge ₅ Li ₂₂ , Mg ₂ Ge, Ge ₄ Na, GeNa, GeNa ₃ , Aluminum doped Ge ₄ K, Aluminum doped GeK, Aluminum doped GeK ₃ , Aluminum doped GeLi ₃ , Aluminum doped Ge ₅ Li ₂₂ , Aluminum doped Mg ₂ Ge, Aluminum doped Ge ₄ Na, Aluminum doped GeNa, Aluminum doped GeNa ₃ , Al ₄ C ₃ , Na ₄ C ₃ , Li ₄ C ₃ , K ₄ C ₃ , LiC, LiC ₆ , Mg ₂ C ₃ , MgC ₂ , AlTi ₂ C, AlTi ₃ C, AlZrC ₂ , Al ₃ Zr ₅ C, Al ₃ Zr ₂ C ₄ , Al ₃ Zr ₂ C ₇ , KC ₄ , NaC ₄ , or any of the aforementioned compounds Hydrogen of a compound selected from the group consisting of combinations comprising at least one The composition comprises water. Essentially calcium, barium, titanium, chromium, manganese, iron, cobalt, copper, silicon, germanium, rhodium, rhodium, ruthenium, molybdenum, niobium, zirconium, yttrium, barium, lanthanum, hafnium, tungsten, rhenium, osmium or iridium And a catalyst composition disposed over the storage composition. Calcium, barium, platinum, palladium, nickel, titanium, chromium, manganese, iron, cobalt, copper, silicon, germanium, rhodium, rhodium, ruthenium, molybdenum, niobium, zirconium, yttrium, barium, lanthanum, hafnium, tungsten, rhenium, A hydrogen storage composition comprising a catalyst composition disposed over a storage composition comprising an alloy of osmium, iridium or a combination comprising at least one of the foregoing metals. The method of claim 21 or 22, Storage compositions include carbon, carbides, silicides, sulfides, nitrides, oxides, oxynitrides, hydroxides, silicates, alanates, aluminosilicates, borosilicates, carbosilicides, nitrosilicides, aluminides, germanides, A composition comprising boride, borocarbide, boronitride or a combination comprising one or more of the foregoing. The method of claim 23, wherein Wherein the carbon comprises carbon black and / or carbon nanotubes and the oxide is a metal oxide. The method of claim 24, Metal oxides include alumina, ceria, titanium dioxide, zirconium oxide, tungsten oxide (WO ₃ ), nickel oxide (NiO ₂ ), cobalt oxide (CoO ₂ ), manganese oxides (Mn ₂ O ₄ and MnO ₂ ), vanadium oxide (VO ₂ and V ₂ O ₅ ), molybdenum oxide (MoO ₂ ), or a combination comprising at least one of the foregoing oxides. The method according to any one of claims 22 to 25, A composition wherein the alloy comprises platinum, palladium and / or nickel. The method of claim 21, wherein The composition wherein the catalyst composition covers a surface area of about 1 to about 100% of the total surface area of the storage composition. The method according to any one of claims 21 to 27, Wherein the catalyst composition is disposed on the surface of the storage composition as isolated particulates. The method of claim 28, The isolated particulate has a radius of rotation of about 1 to about 200 nanometers. Calcium, platinum, palladium, nickel, barium, titanium, chromium, manganese, iron, cobalt, copper, silicon, germanium, rhodium, rhodium, ruthenium, molybdenum, niobium, zirconium, yttrium, barium, lanthanum, hafnium, tungsten, rhenium, Impregnating a hydrogen storage composition comprising a catalyst composition disposed over the storage composition, the alloy comprising osmium or iridium, to a gas mixture comprising hydrogen; Dissociating hydrogen into atomic hydrogen; And Storing atomic hydrogen in the storage composition Hydrogen storage method comprising a. A method of producing hydrogen comprising heating a hydrogen storage composition comprising a catalyst composition disposed over a storage composition, the method comprising: The catalyst composition comprises calcium, barium, titanium, chromium, manganese, iron, cobalt, copper, silicon, germanium, rhodium, rhodium, ruthenium, molybdenum, niobium, zirconium, yttrium, barium, lanthanum, hafnium, tungsten, rhenium, osmium or iridium Or consist essentially of calcium, platinum, palladium, nickel, barium, titanium, chromium, manganese, iron, cobalt, copper, silicon, germanium, rhodium, rhodium, ruthenium, molybdenum, niobium, zirconium, yttrium, A method comprising an alloy of barium, lanthanum, hafnium, tungsten, rhenium, osmium or iridium. Contacting the hydrogen storage composition with a first gas mixture comprising hydrogen at a first concentration; Dissociating hydrogen into atomic hydrogen; Storing atomic hydrogen in the storage composition; Contacting the hydrogen storage composition with a second gas mixture comprising a second concentration of hydrogen; And Heating the hydrogen storage composition to a temperature effective to promote desorption of hydrogen from the hydrogen storage composition Hydrogen storage and recovery method comprising a. The method of claim 34, wherein The first concentration of hydrogen is greater than the second concentration. 34. The method of claim 32 or 33, Contacting the hydrogen storage composition to a gas mixture comprising hydrogen at a first concentration is performed at a first location, and contacting the hydrogen storage composition at an environment comprising a second concentration of hydrogen is performed at a second location. The method of claim 34, wherein The first position is not the same as the second position. The method of claim 34, wherein The first position and the second position are the same. A hydrogen generation reactor in fluid communication with a hydride recycle reactor, wherein the hydrogen generation reactor comprises a light metal silicide, borosilicate, carbosilicide, nitrosilicide, aluminide, germanide, boride, borocarbide to recover hydrogen A system for the storage and recovery of hydrogen, using borohydride or hydride of carbide. The method of claim 37, A system in which a hydrogen generation reactor is in fluid communication with and downstream of the slurry generation reactor. The method of claim 37 or 38, A system in which the hydrogen generation reactor is in fluid communication with the drying and separation reactors upstream thereof. The method of claim 38 or 39, And the slurry generation reactor is in fluid communication with the drying and separation reactors downstream of them. The method according to any one of claims 38 to 40, A system in which a hydride recycle reactor is in fluid communication with a slurry generation reactor. The method according to any one of claims 37 to 41, The system wherein the metal hydride slurry is transferred from the slurry generation reactor to the hydrogen production reactor. The method of claim 37, The recycled metal hydride is passed from the hydride recycle reactor to the slurry production reactor. The method of claim 39, Water is introduced into the hydrogen generation reactor. The method of claim 39, The system in which hydrogen is produced in a hydrogen production reactor by the use of heat from microwave irradiation, convective heat, and exhaust heat from a fuel cell. Contacting the hydrogen storage composition with a gas mixture comprising hydrogen; And Irradiating the hydrogen storage composition by radio frequency irradiation or microwave irradiation in an amount effective to promote absorption, adsorption or chemisorption of hydrogen into the hydrogen storage composition. Storage method of hydrogen comprising a. The method of claim 46, Contacting is carried out at a pressure of about 1 to about 100 kg / cm ² . The method of claim 46, The irradiation is conducted at about 10 kilohertz to about 300 gigahertz and the irradiation imparts an energy of about 0.001 watts / g to about 1,000 watts / g to the hydrogen storage composition. Contacting the hydrogen storage composition with a first gas mixture comprising hydrogen at a first concentration; Irradiating the hydrogen storage composition by radio frequency irradiation or microwave irradiation with a first frequency in an amount effective to promote absorption, adsorption and / or chemisorption of hydrogen into the hydrogen storage composition; Contacting the hydrogen storage composition with a second gas mixture comprising a second concentration of hydrogen; And Irradiating the hydrogen storage composition by radio frequency irradiation or microwave irradiation with a second frequency in an amount effective to promote desorption of hydrogen from the hydrogen storage composition. Hydrogen storage and recovery method comprising a. The method of claim 49, The first concentration of hydrogen is greater than the second concentration. The method of claim 49, The first frequency is not equal to the second frequency. The method of claim 49, The first frequency is equal to the second frequency. The method of any one of claims 49-52, Contacting the hydrogen storage composition in a gas mixture comprising hydrogen at a first concentration is carried out at a first location and contacting the hydrogen storage composition at an environment comprising a second concentration of hydrogen is performed at a second location. . The method of claim 53 wherein The first position is not the same as the second position. The method of claim 53 wherein The first position and the second position are the same. The method of claim 51, wherein The irradiation is conducted at about 10 kilohertz to about 300 gigahertz and the irradiation imparts an energy of about 0.001 watts / g to about 1,000 watts / g to the hydrogen storage composition. The method of any one of claims 49-56, And wherein the hydrogen storage composition comprises carbon, aluminide, alanate, carbide, boride, nitride, borocarbide, boronide, silicide, borosilicate, carbosilicide or nitrosilicide. A system for the storage and recovery of hydrogen comprising a hydrogen generation reactor using radio frequency irradiation and / or microwave frequency irradiation to recover hydrogen. The method of claim 58, And wherein the hydrogen generation reactor is in fluid communication with and downstream of the hydrogen storage composition reactor. The method of claim 58, And the hydrogen generation reactor is in fluid communication with and upstream of the hydrogen storage composition reactor, and wherein the hydrogen storage composition reactor uses radio frequency irradiation and / or microwave frequency irradiation to store hydrogen. The method of claim 58, A hydrogen generation reactor in fluid communication with and upstream of the drying and separation reactor, wherein the hydrogen storage composition reactor also uses radio frequency irradiation and / or microwave frequency irradiation to store hydrogen. 62. The method of claim 61, The hydrogen storage composition reactor is in fluid communication with and downstream of the drying and separation reactor. 62. The method of claim 61, The hydrogen storage composition slurry is passed from the hydrogen storage composition reactor to the hydrogen production reactor.

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