MXPA00010011A - Magnesium mechanical alloys for thermal hydrogen storage - Google Patents

Abstract

A mechanically alloyed hydrogen storage material having 75-95 atomic percent Mg, 5-15 atomic percent Ni, 0.5-6 atomic percent Mo, and at least one additional element selected from the group consisting of Al, C, Ca, Ce, Co, Cr, Cu, Dy, Fe, La, Mn, Nd, Si, Ti, V, and Zr, preferably between 1-15 atomic%. The mechanically alloyed hydrogen storage preferably contains from 3-15 atomic%C and at least one other element selected from the group consisting of Al, Ca, Ce, Cu, Dy, Fe, La, Mn, and Nd. The hydrogen storage materials are created by mechanical alloying in a milling apparatus under an inert atmosphere, such as argon, or a mixed atmosphere, such as argon and hydrogen. The speed and length of the milling are varied.

Description

MECHANICAL MAGNESIUM ALLOYS FOR THERMAL HYDROGEN STORAGE DESCRIPTION OF THE INVENTION The present invention relates to mechanical alloys for the storage of hydrogen and more specifically to mechanical magnesium alloys for the storage of hydrogen. More specifically, the present invention relates to magnesium mechanical alloys of the Mg-Ni-Mo system and their use as hydrogen storage materials. Growing energy needs have prompted specialists to become aware of the fact that traditional energy sources, such as coal, oil or natural gas, are not inexhaustible, or at least that they are becoming more expensive all the time and It is advisable to consider replacing them gradually with other sources of energy, such as nuclear energy, solar energy, or geothermal energy. Hydrogen, too, is coming into use as a source of energy. Hydrogen can be used, for example, as fuel for internal combustion engines instead of hydrocarbons. In this case, it has the advantage of eliminating air pollution through the formation of oxides of carbon or sulfur by the combustion of hydrocarbons. Hydrogen can also be used to feed air-hydrogen combustion cells for the production of electricity required for electric motors. One of the problems posed by the use of hydrogen is its storage and transportation. A number of solutions have been proposed: Hydrogen can be stored under high pressure in steel cylinders, but this proposal has the drawback of requiring dangerous and heavy containers which are difficult to handle (besides having a low storage capacity of approximately 1 % in weigh) .

Hydrogen can also be stored in cryogenic containers, but this causes the disadvantages associated with the use of cryogenic liquids; such as, for example, the high cost of the containers, which also require careful handling. There are also "evaporation" losses of approximately 2-5% per day. Another method for storing hydrogen is to store it in the form of a hydride, which is then decomposed at the appropriate time to provide hydrogen. The iron-titanium, lanthanide-nickel, vanadium, and magnesium hydrides have been used in this way, as described in French Patent No. 1,529,371. The MgH2-Mg system is the most appropriate of all known metal-metal hydride systems that can be used as reversible systems for hydrogen storage because it has the highest percentage by weight (7.65% by weight) of theoretical capacity for hydrogen storage and thus the highest theoretical energy density (2332 Wh / kg; Reilly &Sandrock, Spektrum der Wissenschaft, Apr. 1980, 53) per unit of storage material. Although it is owned and the relatively low price of magnesium makes the MgH2-Mg seem the optimal system for storage of hydrogen for transportation, ie, for vehicles driven by hydrogen, its unsatisfactory kinetics has prevented it from being used until now. It is known, for example, that pure magnesium can only become hydride under drastic conditions, and then only very slowly and incompletely. The dehydrurization rate of the resulting hydride is also unacceptable for a hydrogen storage material (Genossar &Rudman, Z. Phys Phys. Chem., Neue Folge 116, 215 [1979], and the literature cited herein). In addition, the hydrogen storage capacity of a magnesium pool decreases during the decomposition-reconstitution cycles. This phenomenon can be explained by a progressive poisoning of the surface, which during the reconstitution becomes inaccessible to the magnesium atoms located inside the reserve for hydrogen.

To expel hydrogen in conventional magnesium or magnesium / nickel reserve systems, temperatures of over 250 ° C are required, with a large power supply at the same time. The high level of temperature and the high energy requirement to expel hydrogen has the effect that, for example, a motor vehicle with an internal combustion engine can not be operated exclusively from these stores. This occurs because the energy contained in the exhaust gas, in the most favorable of cases, (full load) is sufficient to meet 50% of the hydrogen requirement of the internal combustion engine from a magnesium or magnesium warehouse /nickel. Thus, the remaining hydrogen demand must be taken from a hydride store. For example, this store can be titanium / iron hydride (a typical low temperature hydride store) which can be operated at temperatures below 0 ° C. These low temperature hydride stores have the disadvantage of having only a low hydrogen storage capacity. In the past storage materials have been developed, which have a relatively high storage capacity but from which hydrogen is however expelled at temperatures up to about 250 ° C. U.S. Patent No. 4,160,014 discloses a material for storage of hydrogen of the formula Ti [i-] Zr [X] n [2-yyz] Cr [y] V [Z), wherein x = 0.05 to 0.4, and = 0 alyz = 0 to 0.4. Up to about 2% by weight of hydrogen can be stored in an alloy. In addition to this relatively low storage capacity, these alloys also have the disadvantage that the price of the alloy is very high when using metallic vanadium. In addition, US Patent No. 4,111,689, has described an alloy for storage which comprises 31 to 46% by weight of titanium, 5 to 33% by weight of vanadium and 36 to 53% by weight of iron and / or manganese. Although alloys of this type have a higher storage capacity for hydrogen than the alloy according to US Patent No. 4,160,014, hereby incorporated herein by reference, they have the disadvantage that temperatures of at least 250 are necessary. ° C to completely expel the hydrogen. At temperatures of up to about 100 ° C, approximately 80% of the hydrogen content can be discharged in the best case. However, a high discharge capacity, particularly at low temperatures, is often necessary in the industry due to the heat required to release the hydrogen from the hydride stores which is often available only at a lower temperature level. In contrast to other metals or metal alloys, especially metal alloys containing titanium or lanthanum, magnesium is preferred for the storage of hydrogen not only because of its lower material cost, but above all, due to its specific weight more low as a storage material. However, the hybridization Mg + H2? MgH2 is, in general, more difficult to achieve with magnesium, as the magnesium surface will oxidize rapidly in the air to form stable MgO and / or surface layers of Mg (OH) 2. These layers inhibit the dissociation of hydrogen molecules as well as the absorption of hydrogen atoms produced and their diffusion from the surface of the granulated particles within the magnesium storage mass. In recent years intensive efforts have been devoted to improving the hybridization capacity of magnesium by adulterating or alloying it with individual foreign metals such as aluminum (Douglass Metall, Trans 6a, 2179 [1975]), indium (Mintz, Gavra, &; Hadari, J. Inorg. Nucí Chem. 40, 765 [1978]), or iron (Welter &Rudman, Scripta Metallurgica 16, 285 [1982]), with various foreign metals (Germán Offenlegungsschriftan 2 846 672 and 2 846 673), or with intermetallic compounds such as Mg2Ni or Mg2Cu (Wiswall, Top Appl. Phys. 29, 201 [1978] and Genossar & Rudman, op. cit.) and LaNi5 (Tanguy et al., Mater. Res. Bull. 11, 1441 [1976]).

Although these attempts somehow improved the kinetics, certain essential disadvantages have not yet been eliminated from the resulting systems. The preliminary hybridization of the adulterated magnesium with a foreign metal or intermetallic compound still demands drastic reaction conditions, and the kinetics of the system will be satisfactory and the high content of hydrogen reversible only after many cycles of hybridization and dehybridization. Considerable percentages of extraneous metal or expensive intermetallic compounds are also necessary to improve kinetic properties. In addition, the storage capacity of such systems is generally well below what would theoretically be expected for MgH2. It is known that the storage quality of magnesium and magnesium alloys can also be improved by the addition of materials that can help break stable magnesium oxides. For example, an alloy is Mg2Ni, in which Ni appears to form unstable oxides. In this alloy, the thermodynamic tests indicate that the surface reaction Mg2Ni + 02? 2MgO + Ni extended over the inclusions of the nickel metal which catalyzes the dissociation-absorption reaction of hydrogen. Reference may be made to A. Seiler et al., Journal of Less-Common Metals 73, 1980, pages 193 et seq. A possibility for the catalysis of the dissociation-absorption reaction of hydrogen on the magnesium surface also consists of the formation of a two-phase alloy, wherein one phase is a hydride former, and the other phase is a catalyst. Thus, it is known to employ galvanically nickel plated magnesium as a hydrogen storage, with reference to F. G. Eisenberg et al. Journal of Less-Common Metals 74, 1980, pages 323 et seq. However, problems were encountered during the adhesion and distribution of nickel on the magnesium surface. To obtain an extremely dense phase and a catalyst of good adhesion under the isolated formation of the equilibrium phases, it is also known that for the storage of hydrogen a eutectic mixture of magnesium can be used as a hydride-forming phase together with copper-magnesium ( Mg2Cu), with reference to J. Genossar et al., Zeitschrift fur Physikalische Chemie Neue Folge 116, 1979, pages 215 et seq. The volume storage capacity of working material that is achieved through this magnesium-containing granulate does not, however, satisfy any high demand due to the amount of copper-magnesium required for the eutectic mixture. Scientists of this era looked at various materials and postulated that a particular crystal structure is required for the storage of hydrogen, see, for example, "Hydrogen Storage in Metal Hydride," Scientific American, Vol. 242, No. 2, p. 118-129, February, 1980. It was found that it is possible to overcome many of the disadvantages of prior art materials by using a different class of materials, materials for storage of disordered hydrogen. For example, U.S. Patent No. 4,265,720 to Guenter Winstel for "Storage Materials for Hydrogen" describes a body for storage of amorphous or finely crystalline silicon hydrogen. The silicon is preferably a thin film in combination with a suitable catalyst and on a substrate. Japanese Patent Application Laid-open No. 55-167401, "Hydrogen Storage Material" in the name of Matsumato et al, discloses materials for storage of two or three element hydrogen of at least 50 volume percent amorphous structure. The first element is chosen from the group of Ca, Mg, Ti, Zr, Hf, V, Nb, Ta, Y and lanthanides, and the second group of Al, Cr, Fe, Co, Ni, Cu, Mn and Si. A third element of group B, C, P and Ge may optionally be present. According to the teaching of No. 55-167401, the amorphous structure is needed to overcome the problem of the unfavorably high desorption temperature characteristic of most crystalline systems. A high desorption temperature (cited above, eg, 150 ° C) severely limits the uses to which the system can be put. According to Matsumoto et al, material of at least 50% amorphous structure will be able to desorb at least some of hydrogen at relatively low temperatures because the binding energies of individual atoms are not uniform, as in the case of crystalline material, but they are distributed over a wide range. Matsumoto et al. claim a material of at least 50% amorphous structure. While Matsumoto et al. does not provide any additional teaching about the meaning of the term "amorphous". The scientifically accepted definition of the term encompasses a maximum short-range order of about 20 Angstroms or less. The use by Matsumato et al of amorphous structure materials to achieve better desorption kinetics due to the non-planar hysteresis curve is an inadequate and partial solution. The other problems encountered in crystalline materials for hydrogen storage, particularly low useful storage capacity of hydrogen at moderate temperature, remain. However, even better results can be realized for hydrogen storage, ie, long life cycle, good physical resistance, low temperatures and absorption / desorption pressures, reversibility, and resistance to chemical poisoning, if full advantage of the modification is taken of disordered metastable hydrogen storage materials. Modification of structurally disordered metastable hydrogen storage materials is described in U.S. Patent No. 4,431,561 to Stanford R. Ovshinsky et al. for "Hydrogen Storage; Materials and Methods of Making the Same. "As described herein, disordered hydrogen storage materials, characterized by a chemically modified thermodynamically metastable structure, can be custom-made to possess all desirable characteristics for hydrogen storage for a Wide range of commercial applications The modified material for hydrogen storage can be manufactured to have a larger capacity for hydrogen storage than the single phase crystalline host materials The bond strengths between the hydrogen and the storage sites of these modified materials they can be tailored to provide a spectrum of bonding possibilities to obtain desired desorption absorption characteristics The disordered materials for storage of hydrogen that have a chemically modified structure, thermodynamically targets Table can also have a greatly increased density of catalytically active sites for improved hydrogen storage kinetics and increased resistance to poisoning. The synergistic combination of selected modifiers incorporated into a selected host matrix provides a degree and quality of structural and chemical modification that stabilizes the chemical, physical and electronic conformations and conformations of hydrogen storage. The structure for modified materials for storage of hydrogen is a light weight host matrix. The host matrix is modified structurally with selected modifying elements to provide a messy material with local chemical environments which result in the properties required for hydrogen storage. Another advantage of the host matrix described by Ovshinsky, et al is that it can be modified in a substantially continuous range of various percentages of modifying elements. This capability allows the host matrix to be manipulated by modifiers to design or tailor hydrogen storage materials with suitable characteristics for particular applications. This is in contrast to multi-component single-phase crystalline host materials which generally have a very limited range of available stoichiometry. Therefore a continuous range of control of chemical and structural modification of the thermodynamics and kinetics of such crystalline materials is not possible. Yet an additional advantage of these disordered materials for hydrogen storage is that they are much more resistant to poisoning. As stated above, these materials have a much higher density of catalytically active sites. Thus, a certain number of such sites can be sacrificed for the effects of poisonous species, while the large number of non-poisoned active sites still remain to continue to provide the desired kinetics of hydrogen storage. Another advantage of these disordered materials is that they can be designed to be mechanically more flexible than single-phase crystalline materials. Disordered materials are thus capable of more distortion during expansion and contraction allowing greater mechanical stability during the absorption and desorption cycles. A disadvantage of these disordered materials is that, in the past, some of the Mg-based alloys have been difficult to produce. Particularly those materials that did not form solutions in the fusion. Also, the most promising materials (ie, magnesium-based materials) were extremely difficult to manufacture in bulky form. That is, while fine film spraying techniques could manufacture small quantities of those disordered alloys, there was no bulky preparation technique. So, in the mid-1980s, two groups developed mechanical alloying techniques to produce bulky materials for storage of unordered magnesium alloy hydrogen. It was found that the mechanical alloy facilitates the alloying of elements with widely differing vapor pressures and melting points (such as Mg with Fe or Ti etc.), especially when there are no stable intermetallic phases. It has been found that conventional techniques such as fusion induction are inadequate for such purposes. The first of the two groups was a team of French scientists who investigated the mechanical alloying of Ni-Mg system materials and their properties for hydrogen storage. See Senegas, et al., "Phase Characterization and Hydrogen Diffusion Study in the Mg-Ni-H System," Journal of the Less-Common Metals, Vol. 129, 1987, pp. 317-326 (binary mechanical alloys of Mg and Ni that incorporate 0, 10, 25 and 55% by weight of Ni); and also, Song et al. "Hydriding and Dehydriding Characteristics of Mechanically Alloyed Mixtures Mg-xwt.% Ni (x = 5, 10, 25 and 55)", Journal of the Lesser-Common Metals, Vol. 131, 1897, p. 71-79 (binary mechanical alloys of Mg and Ni that incorporate 5, 10, 25 and 55% by weight of Ni). The second of the two groups was a team of Russian scientists who investigated the properties for hydrogen storage of binary mechanical alloys of magnesium and other metals. See, Ivanov, et al., "Mechanical Alloys of Magnesium - New Materials for Hydrogen Energy", Doklady Physical Chemistry (English Translation) vol. 286: 1-3, 1986, pp. 55-57, (binary mechanical alloys of Mg with Ni, Ce, Nb, Ti, Fe, Co, Si and C); as well; Ivanov, et al. "Magnesium Mechanical Alloys for Hydrogen Storage", Journal of the Less-Common Metals, vol. 131, 1987, pp. 25-29 (binary mechanical alloys of Mg with Ni, Fe, Co, Nb and Ti); and Stepanov, et al., "Hydriding Properties of Mechanical Alloys of Mg-Ni", Journal of the Less-Common Metals, vol. 131, 1987, pp. 89-97 (binary mechanical alloys of Mg-Ni systems). See also the collaborative work between the French and Russian groups Konstanchuck, et al., "The Hydriding Properties of the Mechanical Alloy With Composition Mg-25% Fe", Journal of the Less-Common Metals, vol. 131, 1987, pp. 181-189 (mechanical binary alloy of Mg and 25% by weight of Fe). Later, in the late '80s and early' 90s, a group of Bulgarian scientists (sometimes in collaboration with the group of Russian scientists) investigated the hydrogen storage properties of mechanical magnesium alloys and metal oxides. . See Khrussanova, et al., "Hydriding Kinetics of Mixtures Containing Some 3d-Transition Metal Oxides and Magnesium" Zeitschrift für Physikalische Chemie Neue Folge, München, vol. 164, 1989, pp. 1261-1266 (comparing binary mixtures and mechanical alloys of Mg with Ti02, V2O5 and Cr203); and Peshev, et al., "Surface Composition of Mg-Ti02 Mixtures for Hydrogen Storage, Prepared by Different Methods," Materials Research Bulletin, vol. 24, 1989, pp-207-212 (comparing conventional mixtures and mechanical alloys of Mg and Ti02). See also Khrussanova, et al., "On the Hydriding of a Mechanically Alloyed Mg (90%) -V205 (10%) Mixture," International Journal of Hydrogen Energy, vol. 15, No. 11, 1990, pp. 799-805 (investigating the hydrogen storage properties of a binary mechanical alloy of Mg and V205); and Khrussanova, et al., "Hydriding of Mechanically Alloyed Mixtures of Magnesium With Mn02, Fe203, and NiO", Materials Research Bulletin, vol. 26, 1991, pp. 561-567 (investigating the storage properties of hydrogen of binary mechanical alloys of Mg with and Mn02, Fe203, and NiO). Finally, see also Khrussanova, et al., "The Effect of the Electron Concentration on the Absorption Capacity of Some Systems for Hydrogen Storage", Materials Research Bulletin, vol. 26, 1991, pp. 1291-1298 (investigating the effects of d-electron concentration on the hydrogen storage properties of materials, including mechanical alloys of Mg and 3-d metal oxides); and Mitov, et al., "A Mossbauer Study of a Hydrided Mechanically Alloyed Mixture of Magnesium and Iron (III) Oxide", Materials Research Bulletin, vol. 27, 1992, pp. 905-910 (investigating the hydrogen storage properties of a binary mechanical alloy of Mg and Fe203). More recently, a group of Chinese scientists have investigated the hydrogen storage properties of some mechanical alloys of Mg with other metals. See Yang et al., "The Thermal Stability of Amorphous Hydride Mg5oNi50H54 and Mg30Ni70H45", Zeitschrift für Physikalische Chemie, München, vol. 183, 1984, pp. 141-147 (investigating the storage properties of hydrogen of the mechanical alloys MgsoNiso and Mg3rjNi70); and Lei, et al., "Electrochemical Behavior of Some Mechanically Alloyed Mg-Ni-based Amorphous Hydrogen Storage Alloys", Zeitschrift für Physikalische Chemie, München, vol. 183, 1994, pp. 379-384 (investigating the electrochemical properties [ie Ni-MH battery] of some mechanical alloys of Mg-Ni with Co, Si, Al, and Co-Si). Research on mechanical Mg alloys with other metals for use as hydrogen storage materials has continued and outstanding results have been achieved with the mechanical magnesium alloys described herein. The current invention discloses mechanically alloyed hydrogen storage materials having 75-95 atomic% Mg, and the remainder includes Ni, Mo, and at least one additional element selected from the group consisting of Al, C, Ca, Ce, Co , Cr, Cu, Dy, Fe, La, Mn, Nd, Si, Ti, V and Zr. Preferably the alloy contains 5-15% atomic Ni and 0.5-6% atomic Mo. The additional elements are preferably pre in a range of about 1-15% total atomic. Preferably the mechanical alloy comprises a multi-phase material, which includes at least one amorphous phase. Hydrogen storage materials were created by mechanical alloying in a ball mill apparatus under an inert atmosphere such as argon. The speed and length of the milling are varied. Certain new hydrogen storage materials have been discovered primarily for use in hydrogen thermal storage applications. The particular materials developed are mechanical alloys of the Mg-Ni-Mo system which includes one or more additional elements selected from the group consisting of Al, C, Ca, Ce, Co, Cr, Cu, Dy, Fe, La, Mn, Nd, Si, Ti, V, and Zr. Hydrogen storage materials are manufactured by a mechanical alloying process. The initial materials for the Mg-Ni-Mo system can be pure powders of Mg, Ni and Mo together with powders of the additional elements. The initial materials may also include Ni, Mo alloys and the additional elements. The initial materials were milled in a ball mill apparatus for various times at different speeds under an argon atmosphere. Since there are many such processes, two such processes have been used. One process uses a high energy ball mill where the rubbing is carried out in a stainless steel jug on 0.4762 centimeter (3/16 inch) stainless steel balls under an argon atmosphere. The mass ratio of the medium to the charge to be alloyed was approximately 100: 1. Typically 4 lbs of medium was used in a jar of 750 cc in volume. The second method involves the use of a planetary ball mill. Unlike the grinder in which the jug is stationary, in the planetary ball mill the jars rotate on a horizontal plane around its own central axis. Preliminary experiments indicate that to alloy samples that are sour and in the form of large pieces (5-10 mm in size), it is preferable to use grinding media of tungsten carbide of approximately 3 mm in diameter. When the initial material is of a smaller particle size, 0.01 mm or less), the stainless steel grinding media of approximately 0.4762 centimeters (3-16 of an inch) or less works best. In any of these systems, grinding media can be used. These grinding media help keep the components of the alloy from being entrained in the inert gas under which the materials are generally milled. Also, the spraying agent helps to promote the total production of useful particles of the alloy having a particular size of less than about 45 microns. It has been found that ethane is a useful spraying agent. The mechanically alloyed samples do not need any crushing since the final product is in powder form. However, to eliminate the effects due to particle size, the materials were placed through a sieve to obtain particles of fairly uniform size. For activation, samples were typically exposed to hydrogen gas at approximately 500 psi at temperatures between 250 ° C and 350 ° C overnight after the reactor had been evacuated to 10 ~ 3 Torr. To fully activate the samples, they underwent at least more than three absorption / desorption cycles. The storage capacity of hydrogen, and kinetics of hybridization and dehybridization and pressure-composition isotherms were determined by combinations of volumetric and manometric methods. The change of pressure against time during the hybridization and dehybridization processes was read dynamically using a computer. The phase analysis in a scanning electron microscope (SEM) was performed on a mounted and polished sample to minimize the effect of the topography. The sample was photographed in the secondary electron image mode (SEI) which mainly shows the topography, and the backscattered electron image mode (BEI) shows the contrast by atomic number. The areas of higher atomic number in the BEI appear clearer than the lower atomic number areas. After identifying the regions of different composition, a chemical analysis of the stain is performed by dispersive energy x-ray spectroscopy (EDS). All ESD results were analyzed with pure element patterns. The x-ray diffraction was made for the structural determination. Table 1 summarizes examples of alloys in the Mg-Ni-Mo system, as well as their nominal composition, and the maximum hydrogen storage capacity (H / M) obtained therefrom at 350 or 300 ° C. The samples, prepared by mechanical alloying, are typically multi-phase with at least one main amorphous phase as revealed by the XRD study. Among the list of additional elements listed above, carbon (C) is particularly useful. It can be added to the alloy in an amount of about 3-15% atomic. The carbon can be combined with at least one other element selected from the group consisting of Al, Ca, Ce, Cu, Dy, Fe, La, Mn, and Nd. In addition to being an alloying ingredient, carbon is also an excellent grinding medium and can be used alone or in conjunction with the heptane described hereinbefore. It should be noted that while the mechanical alloys of the present invention can be mactured by mechanically alloying the Mg with other elements that are prealloyed, they are also included within the scope of the invention by alloying Mg with elemental powders of other elements or prealloying the Mg with the elements under melting point and then mechanically alloying the prealloyed Mg with elemental powders or other prealloyment of high melting point elements. Also, while the materials can be mechanically alloyed under an inert atmosphere, the alloy under a mixture of inert gas and hydrogen or pure hydrogen is included within the scope of the invention. Finally, while the present invention has been described in the context of hydrogen thermal storage, these materials or modifications thereof can find many other applications, such as electrochemical storage of hydrogen, use for heat pump or as a storage material of fuel cell. Therefore, while the invention has been described along with the preferred embodiments and procedures, it should be understood that it is not intended to limit the invention to the described embodiments and methods. On the contrary, it is intended to cover all alternatives, modifications and equivalences which may be included within the spirit and scope of the invention as defined by the appended claims in the following.

Claims (13)

1. CLAIMS 1. A mechanically alloyed hydrogen storage material characterized in that it has 75-95 atomic percent Mg, 5-15 atomic percent Ni, 0.5-6 atomic percent Mo, and at least one additional element selected from the group consisting of Al, C, Ca, Ce, Co, Cr, Cu, Dy, Fe, La, Mn, Nd, Si, Ti, V, and Zr.
2. 2. The material for storage of mechanically alloyed hydrogen according to claim 1, characterized in that at least one element in the alloy in the range of 1-15 atomic% is additionally included.
3. 3. The mechanically alloyed hydrogen storage material according to claim 1, characterized in that the mechanical alloy comprises a multiple phase material. .
4. The mechanically alloyed hydrogen storage material according to claim 1, characterized in that the mechanical alloy includes at least one amorphous phase.
5. 5. The material for storage of mechanically alloyed hydrogen according to claim 1, characterized in that at least one additional element comprises C.
6. 6. The material for storage of mechanically alloyed hydrogen according to claim 5, characterized in that the alloy contains 3-15% atomic% C.
7. The material for storage of mechanically alloyed hydrogen according to claim 5, characterized in that it additionally includes at least one other element selected from the group consisting of Al, Ca, Ce, Cu, Dy, Fe , La, Mn and Nd.
8. 8. The material for storage of mechanically alloyed hydrogen according to claim 3, characterized in that at least one additional element comprises C.
9. 9. The material for storage of mechanically alloyed hydrogen according to claim 8, characterized in that the alloy contains 3-15% atomic% C.
10. The material for storage of mechanically alloyed hydrogen according to claim 8, characterized in that it additionally includes at least one other element selected from the group consisting of Al, Ca, Ce, Cu, Dy, Fe , La, Mn and Nd.
11. The material for storage of mechanically alloyed hydrogen according to claim 4, characterized in that at least one additional element comprises C.
12. 12. The material for storage of mechanically alloyed hydrogen according to claim 11, characterized in that the alloy contains 3-15% atomic% C. The material for storage of mechanically alloyed hydrogen according to claim 11, characterized in that it additionally includes at least one other element selected from the group consisting of Al, Ca, Ce, Cu, Dy, Fe , La, Mn, and Nd.