JPS62136547A - Hydrogen storing material and its production - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to hydrides useful, for example, as heat pumps to transport thermal energy from a low temperature heat source to a high temperature heat reservoir for heating or cooling.

BACKGROUND OF THE INVENTION It is a worldwide trend that the depletion of fossil fuel sources for energy production continues to increase. A global energy crisis is therefore expected, as evidenced by episodes of fossil fuel scarcity, inflation, recession, and war or threat of war in fossil fuel producing countries. Furthermore, this trend has intensified the flight of industry from colder regions to warmer regions, resulting in severe economic and social tensions and disruptions. Recurrent energy crises threaten peace, stability, economic growth, and economic development.

One way to solve the energy crisis lies in recovering energy from hitherto underutilized energy sources and in making better use of the energy of existing energy sources. To this end, the present invention relates to energy recovery and conservation, pollution control, and economic growth. These objects of the invention are achieved by the development of a new hydrogen storage material particularly suitable for use in heat pumps.

Traditional heat pumps are of the compressor type. Compressors are noisy, consume a lot of power, and require frequent maintenance.
Uses fluorocarbon refrigerants, which are a source of vibration and are environmentally undesirable. Because compressor-type heat pumps have many drawbacks, research is underway to develop chemical heat pumps, particularly hydride heat pumps. For example, Cont.
Lingham U.S. Pat. No. 4,044,819 and 5i
Rovich, U.S. Pat. No. 4,200,144 and representative hydride heat pump systems;
,Rohy, T.A., ArgabrfghL and G.
D, '1lada's [Metal Hydride Heat Pump (M
etal l1ydride l1eaL Pump)
J, Proc, 17th InterSoc Ene
rgy Conv Eng Conf (1982).

These hydride heat pumps operate on the reversible hydrogen storage principle. This is explained as follows.

M+l/211t=MII+Q.

[wherein M is a hydride former].

M reacts with hydrogen to form a hydride Mlf. This process is an exothermic reaction and releases heat mQ. This amount of heat can be used effectively. On the other hand, in the reverse reaction, when heat mQ is supplied to the hydride M11, the starting hydride former M is regenerated and hydrogen is liberated or released, producing a cooling effect. This process, which produces heating and/or cooling effects, does not require a compressor as only hydrogen transfer occurs. As a result, the problems of compressor type heat pumps, ie noise, vibration and other problems, are reduced or eliminated.

In a typical hydride heat pump system, 2
Pairs of different metal alloy hydrides are used. The hydride is housed in beds that are thermally and physically separated but interconnected to create hydrogen flow. This is shown schematically in FIG. Initially, hydride A is substantially hydrogenated and hydride B is substantially unhydrogenated.

A typical heat pump cooling cycle consists of four stages as shown in FIG. According to this diagram, the cycle includes the following steps.

Step l - Isothermal process involving hydrogen desorption in A and hydrogen absorption in B.

Bed A receives and receives thermal QCA at TC. Bed B is (A
absorbs hydrogen (released from ) and releases heat-QMI3 to the surroundings in TM.

Step 2 - Conspicuous heating process.

Bed A absorbs heat QSA and is heated from TC to TM,
Bed B absorbs heat Q' SI3 and is heated from TM to Tll.

Isothermal process including hydrogen desorption in steps 3-8 and hydrogen absorption at A.

Bed B receives and takes heat (QII8) from the Tll heat source. The bed ^ absorbs the hydrogen released from the bed B and delivers the heat of TM to the hot oil.

Step 4 - Conspicuous Cooling Process.

Bed ^ releases heat -Q''SA, is cooled from TM to TC, and returns to its original state.Bed B releases heat -0SB, is cooled from T11 to TM, and returns to its original state.

Different hydrides may have different pressure versus composition (117M) curves. At a given temperature each hydride has a certain pressure at which it begins to absorb significant amounts of hydrogen. The pressure remains relatively constant until a certain amount of hydrogen is absorbed. In this regard, exposing the hydride to more hydrogen does not result in significant compositional changes. In order to prevent the flow of hydrogen from the bed containing hydride A to the bed containing hydride B in step 1, the hydride pair is heated at the above temperatures TC and TM with a suitable pressure difference between A and B. must have such characteristics that it exists. Similarly, in step 3, the hydride pairs are each placed at a temperature T11 such that hydrogen flows from bed B to bed A.
and TM such that a sufficient pressure difference exists between B and A.

For detailed papers on thermodynamic problems, see A.

Abclson and J. S. Lorowitz, “Thermodynamics of metal hydride heat pumps about 1 fr (A Th
Ermodynamic analysis or
a Metal l1ydride l1cat I'
ump) J, ＾rgonneNational Lab
oratory No. 809427 is cited as a reference.

Continuous cooling of the load can be achieved by using a combination of multiple pairs of hydrides tuned to TII for alternating operation.

It is also possible to use hydride heat pumps as heating devices by utilizing the exothermic reaction of hydrogen absorption.

Additionally, hydride heat pumps may use any heat source. For example, gas, electricity, solar heat, waste heat, underground water, etc. can be used. Therefore, more effective and flexible heat utilization is possible. These systems also have good packability because the hydride systems are modular, solid state, and hydrogen gas is the only working medium.

Solid hydrides suitable for reversible hydrogen storage for use in heat pumps must have several properties. For example, the effective capacity (capacity) at a given operating temperature
The hydrogen absorption pressure and desorption properties of the material are high, the hydrogen absorption/desorption kinetics are good, the material is structurally stable to ensure long cycle life, the hydrogen absorption pressure and desorption of the material are Small hysteresis between separation pressure and
The thermal conductivity of the material is moderately high, and the cost is low and profitable.
It is necessary to satisfy the following requirements. When a material lacks either of these properties, it is not suitable for large scale commercial use.

Relatively low desorption temperatures are necessary for effective utilization of waste heat obtained from vehicles, vehicles, machinery, or other similar equipment.

Reversibility of the hydrogen storage material is necessary so that absorption-desorption cycles can be repeated without significant reduction in the hydrogen storage capacity of the hydrogen storage material. In order to absorb or desorb hydrogen in a relatively short time, it is necessary to have favorable dynamic characteristics, ie, a relatively high absorption or desorption rate.

Although considerable progress has been made in the equipment design of hydride heat pump systems, the development of hydride materials has lagged behind. No prior art hydride material meets all the requirements necessary for commercial use in heat pump systems.

The most popular material systems in the field of hydrogen storage materials are based on bimetallic or ternary metal hydride alloys of mono-phase quality.

However, such prior art binder materials do not even meet the minimum requirements for large-scale commercial use. A fundamental limitation of many prior art crystalline materials is their low hydrogen storage capacity relative to the weight of the material.

Another limitation is that many of these materials have material desorption temperatures that are too high for many applications.

Additionally, many of the prior art crystalline materials are susceptible to contamination when exposed to contaminants in hydrogen gas or from the surrounding environment. For example, many crystalline materials become contaminated even in the presence of low concentrations of oxygen, at ppm levels.

Once contaminated, the storage properties of the material are significantly reduced so that the material cannot be used unless it is reactivated, which is costly and complex.

The density of hydrogen storage sites, that is, interstitial sites, is also
The phase is constrained by the unique chemistry of the crystalline host structure. The sites of catalytic activity in single-phase crystalline host materials are relatively small in number and result from incidental surface irregularities that interrupt the periodicity of the single-phase quality structure. A few examples of such surface irregularities are dislocation sites, crystal edges, surface impurities, and foreign absorbents. These irregularities typically occur relatively little at the surface of the monocrystalline material and not throughout the bulk of the material.

The density of catalytic active sites can be increased to a limited extent by mechanically breaking the single-phase crystalline structure and forming a powder from the structure to increase surface area. Powders have problems in their use. This is because when the stored hydrogen is later released from the hydride, powder particles or subdivided fragments thereof are carried away along with the hydrogen gas as it is pumped to the location where it is used as fuel. It is from.

Prior art metal-hosted single-phase quality hydrogen storage materials include magnesium, magnesium-nickel, J<su')ram, iron-titanium, lanthanum pentane, and others. However, none of such prior art materials meet the required properties necessary for large-scale commercial use of hydride heat pump media, such as effective storage capacity at operating temperatures, adequate adsorption/desorption kinetics (rates), etc. ) etc. for example,
Theoretically, crystalline magnesium hydride has the formula storage percent = +t/(lI+M) [where II
is the weight of the stored hydrogen and M is the weight of the storage material], approximately 7.6% by weight of hydrogen can be stored. (All storage percentages hereinafter are calculated based on this formula). However, other hydrogen storage properties of magnesium do not qualify for large-scale use as a heat pump material.

Magnesium is an extremely difficult substance to activate. For example, US Pat. No. 3,479,165 discloses that activation of magnesium requires removal of the surface barrier. To obtain adequate conversion (90%) to the hydride state, activation of the magnesium must be carried out at a temperature of 400 DEG C. to 425 DEG C. and a pressure of 1000 psi over several days. Additionally, such hydride desorption typically requires heating at relatively high temperatures before hydrogen desorption begins. According to the patent, the Mg1lt material needs to be heated to a temperature of 277° C. before desorption begins. Higher temperatures and longer times are required to reach acceptable operation and output.

Due to its high desorption temperature, magnesium hydride has many applications,
In particular, it is unsuitable for applications where it is desired to utilize waste heat, such as waste heat from a combustion engine, for de-scanning. Hydrogen storage (cha-rging)
The high temperatures and pressures required in the process also limit the use of magnesium in many applications.

Other single-phase quality materials mentioned above also fail to meet commercial requirements. For example, MgJil 14 has only six combination pairs with suitable pressure composition curves to extract sufficient hydrogen at the operating conditions used in heat pumps. Vl+,
and LaNjslle are too expensive for commercial use. Another drawback of certain materials of the prior art is the inability to fill the material with hydrogen within a reasonable amount of time. In short, no prior art hydrogen storage material has all the desired properties necessary for commercial use.

One alloy system utilized as a hydrogen storer is an alloy system containing titanium, vanadium, manganese, and iron in various combinations. In this regard, see, for example, U.S. Reissue Patent No. 30.083 to Relly et al.
No. 4,353,316 to Liu et al., US Pat. No. 4,457,891 to Thernaucr et al., and US Pat. No. 4,488,906 to Gondo et al. All of these references teach the use of alloys with either titanium or manganese as the main phase and little or no vanadium. U.S. Patent No. 4446 to Bcrnauer et al.
No. 101 discloses materials with higher vanadium content.

However, there is no explanation whatsoever regarding the structure of the material or its behavior versus pressure (II-c1).

hydrogen storage
Metal l1ydride) J, 5cient
ific American, Vol, 242, No.
, 2, pp. 118-129. February 1980), it is possible to overcome many of the drawbacks of prior art materials by using a different type of material, a disordered hydrogen material. For example, Gucnter Yin-stel's U.S. Pat.
No. 265720 [Hydrogen storage material (Sto-rage M
materials for Ilydrogcn) J are amorphous or microcrystalline Uinely crys
talline) describes a silicon hydrogen storage body. The silicon is preferably a thin film applied to a substrate in combination with a suitable catalyst.

Japanese Patent Application No. 55-1674 of Ma/sumoto et al.
No. 01 [Hydrogen storage material (Ilydrogen Stor)]
Age Material) J discloses bi- or tri-element hydrogen storage materials containing at least 50% by volume of amorphous structure. The first element is Cas Mg, T
selected from i5Zrs or, v, Nb, Ta, Y and lanthanides. The second element is AI, Cr,
Fe.

Selected from the group Go, Ni, Cu, Mn and St.

A third element selected from the group B1C5P and Ge may optionally be present. According to the teachings of No. 55-167,401, an amorphous structure is necessary to overcome the high desorption or dissociation temperatures that are a drawback of many crystalline systems. High desorption temperatures (eg, above 150° C.) severely limit the applications of the system. For example, heat pumps used as air conditioners need to operate at room temperature. MaSumO
The materials suggested by tO, etc. do not have suitable combination pairs with suitable pressure versus composition curves.

According to Ma/sumoto et al., materials with an amorphous structure of 50% or more have at least some degree of amorphous structure at relatively low temperatures because the bond energies of individual atoms are not uniform and distributed over a wide range, unlike crystalline materials. Can desorb hydrogen.

Such amorphous materials do not have the flat hysteresis curves (pressure isotherms) characteristic of crystalline materials. Therefore, at least some hydrogen is desorbed at relatively low temperatures.

Ma/'sumoLo etc. are more than 50% amorphous (
Materials containing an amorphous structure are claimed.

Ma/sumoLo et al. do not specifically explain the meaning of the term "amorphous," but the scientifically accepted definition of this term is that it includes maximum short-range order of less than about 20 Å. That's one thing.

MaI! to achieve improved desorption dynamics due to non-flat hysteresis curves! The use of amorphous materials such as SUmO1O is an incomplete and only partial solution.

Another problem encountered with crystalline hydrogen storage materials is their small size, especially at room temperature.

However, it is difficult to modify (or modify or change) disordered (irregular) and stable hydrogen storage materials.
Full utilization of t 1on) can lead to improved hydrogen storage properties, i.e., extended cycle life, increased physical strength, reduced absorption/desorption temperatures and pressures, improved reversibility and resistance to chemical contamination, etc. It will be done. The disordered (disordered) (1 is structurally lVi stable hydrogen storage material is 5tan-ford, I
i, 0vshinskySKrishna 5apru
, Krystyna Dec and Kuochih I
US Pat. No. 4,431,561 to Long
ge Materials and Methods
f Making the Same) J. The patent states that a disordered hydrogen storage material characterized by a chemically modified and thermodynamically metastable structure is a desirable hydrogen storage material suitable for widespread commercial use. Can be prepared on request. The modified hydrogen storage material is designed to have a higher hydrogen storage capacity than the mono-phase quality host material. The bond strength between hydrogen and storage sites in these modified materials can be tailored to obtain a wide range of binding barrels. Chemically modified and thermodynamically stable (disordered) hydrogen storage materials also have a markedly increased density of catalytic active sites, which reduces the hydrogen storage dynamics. The characteristics (adsorption/desorption rate) and contamination resistance are improved.

The synergistic effect of multiple selective modifiers incorporated into selected host matrices creates a degree and quality of structural stability that stabilizes the chemical, physical, and electronic structures and conformations that are capable of hydrogen storage. and chemical modification are obtained.

The structure of the modified hydrogen storage material is a lightweight host matrix. The host matrix is structurally modified with selective modifying elements that provide the disordered material with a local chemical environment that provides the required hydrogen storage properties.

Another advantage of the host matrix described by Ovschtnsky et al. is that it can be modified with varying percentages of modifying elements in a virtually continuous range. To this end, the host matrix can be treated with modifiers to prepare or process hydrogen storage materials with properties suitable for specific applications. This is in contrast to multicomponent single-phase host crystalline materials, which generally have a very limited range of usable stoichiometry. Such crystalline materials do not allow continuous range control of chemical and structural modification of their thermodynamic and kinetic properties.

A further advantage of these disordered hydrogen storage materials is that they have extremely high resistance to contamination.

As mentioned above, these materials have extremely high densities of catalytically active sites. Therefore, even if a given number of such sites are sacrificed to the effects of contaminating species or catalyst host species, a large number of uncontaminated active sites remain and continue to provide the desired hydrogen storage kinetics.

Another advantage of these disordered (irregular) materials is that they can be engineered to have higher mechanical flexibility than single-phase crystalline materials. For example, disordered (irregular) materials can undergo greater strain during expansion and contraction, and
The mechanical stability in the absorption-desorption cycle is improved.

Second, according to the present invention, it is possible to provide a modified disordered hydrogen storage material with improved hydrogen storage capacity and improved hydrogen storage properties. These materials are particularly suitable for use in hydride heat pump systems.

According to the present invention, a novel class of disordered (irregular) multicomponent multiphase polycrystalline quality hydrogen storage materials is provided.

These materials have multiple phases, with compositional and structural order in each application and compositional and structural disorder between each phase. The resulting disordered (irregular) multicomponent multiphase polycrystalline material has high water/water storage capacity and high reversibility. In a preferred embodiment the material has at least two phases:
That is, a main phase containing an extremely large amount of V, and a main phase containing Ti, V and Fe
It has an interparticle phase containing a relatively large amount of. A further inclusion phase may optionally be present, for example highly enriched in Ti.

In particularly preferred embodiments, the multi-component, multi-phase, polycrystalline material has a nominal charge composition TiaVbMncFca (Equation 9
It has the formula % 1.31 and 1.6<b+d<2.0). The main crystalline phase has the stoichiometric formula TiaVbMnaFedC, where 12<a<18.53<'b<59.9<c<
11 and 17<d<21). The continuous interparticle phase has the stoichiometric formula TisVbMncPedC, where 31
<a<36.23<b<26.10<C<12
and 29<d<34).

These materials can reversibly store relatively large amounts of hydrogen, such as greater than about 1.45% by weight. The material is further characterized as having advantageous pressure-temperature-rate hydrogen absorption-desorption kinetics.

Unlike prior art materials, the materials of the present invention have a disordered polycrystalline structure, whether crystalline or amorphous.

Thermochemical heat pumps utilizing hydride materials of the type of the present invention are included within the scope of the present invention. The heat pump includes at least one pair of hydride beds with connectors between the beds to allow hydrogen to be transferred between the beds. At least one of the beds is comprised of the multicomponent, multiphase, polycrystalline material of the present invention.

The invention will be explained below based on the accompanying drawings.

The material of the present invention is a disordered (irregular) multicomponent multiphase polycrystalline hydrogen storage material. The term “Mutetsuni or 1 rule” is
It refers to a material in which there is no compositional or structural order among the phases, but in which there is a functional order.

The material may be either amorphous or polycrystalline (but without compositional long-range order) or microstructured, or it may be a homogeneous mixture containing any combination of these phases. The novel class of hydrogen storage materials disclosed in the present invention is a multiphase structure that primarily includes a polycrystalline structure. The term "iron-free order" means the absence of long-range structural and compositional order between the phases. The term "polycrystalline" means that the material has local structural order and the crystallite size of the main phase is in the range of 300 Å or more.

In preferred embodiments, the local structural order and crystallite size range from 5 to 100 microns. In particularly preferred embodiments, the crystallite size is between 10 and 15 microns.

The materials of the present invention are multiphase, comprising at least one predominant crystalline phase substantially surrounded by an intergranular phase. Furthermore, 1
More than one inclusion phase may be present. The inventors believe that the interparticle phase that substantially surrounds the crystallites acts as a hydrogen transport conduit for transporting hydrogen into and out of the crystallites during absorption and desorption processes, and that one or more inclusion phases It is thought that it functions to catalytically assist the absorption and desorption of hydrogen from hydrides. However, I do not intend to adhere to this view.

The main crystal prephase is surrounded by the interparticle phase. Two different inclusion phases may occur scattered throughout the material.

The samples described herein can be prepared by induction melting. The nominal composition of the sample is shown in Table ■ below. Powdered laboratory grade constituent elements, titanium, vanadium,
The manganese and iron are thoroughly mixed and heated in an induction furnace until completely molten and then cooled to form a solidified ingot. The ingot is then subdivided in conventional manner to form the material of the invention.

Table 1 Sample # Nominal composition Hydrogen weight% 108
Ti:+sMntoV4tFQto 1.80
110 TiffJn+oV4. Fct+
1.85116 Tia+Mrl++V+oFO
t* 1.60115 TisaMn+oV
a7PO+o 2.80117 Ti3+M
n++Va7Fe, 2.9 optionally, the powdered material may be activated by applying hydrogen under pressure to the powdered material. 1
In one preferred embodiment, activation is carried out under a hydrogen atmosphere at a pressure of 450 psi or higher for at least 30 minutes at room to ambient temperature. According to another preferred embodiment, the pressure 2
Activation is performed at a temperature of at least 200° C. under a hydrogen atmosphere of 00 psi or higher. This high temperature activation requires at least 10 minutes.

In particularly preferred embodiments, the multi-component, multi-phase polycrystalline material comprises:
Nominal composition TiaVbMnaPe, 1 (where 0.5<
a<0.75.1.15<b<1.65.0.9
<a+c<1.31 and 1.6<b+d<2.0
). The main cohesive phase has the stoichiometric formula TiaVbMn
cFcdC, where 12<a<18, S3<b<
59.9<c<11 and 17<d<21). The continuous interparticle phase is stoichiometric TiaVbMnaFe
In the dC formula, '31<a<36.23<b<26
．． 10<c<12 and 29<d<34).

Figures 4A and 4B show Ilragg X-ray diffraction patterns for two samples of the inventive material. Fourth
In Figures A and 4B, the main peak exists at 2θ of 43 degrees. A narrow peak width at 1/2 of the maximum intensity indicates a high degree of crystallinity of the sample.

Figures 4A and 4B further show small peaks that are characteristic of the material of the present invention. These peaks are 20 degrees, 37 degrees, 40 degrees,
It occurs at 42 degrees, 45 degrees, 62 degrees and 78.5 degrees.

Figures 3A and 3B show the absorption-desorption characteristics of two samples of the inventive material, which are P-C-7 curves. The second line shifts upward. Therefore, these curves are equimixtures of pressure versus weight percent hydrogen stored. For the materials of the present invention, the PCT curve is characterized by a hydrogen ff in the range of about 0.4-1.4 wt%
The pressure is slightly shifted upward relative to lffi%. As the weight percent of hydrogen absorbed increases, the pressure shifts slightly upward until a point is reached where hydrogen absorption substantially stops and the pressure increases rapidly.

In the reference literature such as MatsumOtO mentioned above, P-C-7 which has a similar shape as a characteristic curve of a true amorphous material.
A curve is shown. However, Matsumoto
Gradually rising P-C-7 for isomerical amorphous materials
The curve corresponds to a different phenomenon than the slightly sloped curve of the inventive material. With much longer range local order than prior art amorphous materials, the disordered materials of the present invention are multiphase and polycrystalline in nature. Such materials have many thermodynamic paths occurring at many phase boundaries: 1. , complicate 4. -6-0 characteristic dh IQ. A progressively sloping PCT curve results from the superposition of many different pressure cavities represented by various phases and phase combinations.

These plateaus are superimposed and smoothed into the curve shown.

This thermodynamically complex behavior of thermodynamically metastable polycrystalline multiphasic feeds allows them to possess a combination of properties not available with monoclonal or amorphous materials. Disordered (irregular) polycrystalline materials have a high absorption/desorption pressure, hydrogen storage capacity, reversibility, and dynamic properties (adsorption/desorption rate).
Desired combinations of various properties, such as resistance to contamination, resistance to contamination, etc., can be obtained to suit a particular application. In the case of the material according to the invention, the elements are selected such that they yield optimal properties that are particularly suitable for use as a hydrogen storage material, for example in heat pumps. Thus, materials can be prepared that have effective hydrogen storage capacity and rapid absorption-desorption kinetics and a high degree of fouling resistance, and that absorption and desorption occur rapidly at and below room temperature.

Although the samples described herein were prepared by induction melting and slow cooling as described above, other preparation methods may be used. The melting may be tri-arc) melting. Cooling may be rapid quenching such as melt spinning on a cooling surface, physical and chemical vacuum evaporation, plasma spraying, sputtering, or other known techniques.

Although the invention has been described with respect to certain preferred embodiments, it will be clear that the scope of the invention is not limited thereby in any way, but only by the claims.

[Brief explanation of drawings]

Figure 1 is a schematic diagram of a two-bed hydride heat pump, Figure 2 is an illustration of a two-pair hydride heat pump, and Figures 3A and 3B are illustrations of samples of the materials described in the text.
'CT curves, Figures 4A and 4B are Bragg X-ray diffraction patterns of samples of the materials described in the text.

Claims (17)

[Claims] (1) Consisting of a disordered multiphase polycrystalline material having at least one main phase surrounded by an interparticle phase, the multiphase material has a nominal composition Ti_aV_bMn_cFe_d [wherein 0.5
<a<0.75, 1.15<b<1.65, 0.9<a
+c<1.31 and 1.6<b+d<2.0],
The main crystalline phase has the stoichiometric formula Ti_aV_bMn_cFe_
d [wherein, 12<a<18, 53<b<59, 9<c<
11 and 17<d<21], and the interparticle phase has the stoichiometric formula Ti_aV_bMn_cFe_
d [wherein, 31<a<36, 23<b<26, 10<c
A multi-component hydrogen storage material having a composition represented by <12 and 29<d<34]. (2) contains at least one inclusion phase, and the at least one inclusion phase has the stoichiometric formula Ti_aV_bM
n_cFe_d [wherein, 48<a<50, 15.5<b
17.5, 6<c<8 and 26<d<29]. The hydrogen storage material according to claim 1. (3) The hydrogen storage material according to claim 1, further comprising hydrogen. (4) The hydrogen storage material according to claim 1, wherein the main crystalline phase has a crystallite size of 300 Å or more. (5) The hydrogen storage material according to claim 4, wherein the crystallite size of the main crystalline phase is in the range of 5 to 100μ. (6) The hydrogen storage material according to claim 1, wherein the material is characterized by a Bragg x-ray diffraction pattern with a main peak occurring at 43 degrees 2θ. (7) Bragg x-ray diffraction pattern has 2θ of 37 degrees and 4
The hydrogen storage material according to claim 6, having small peaks at 0 degrees, 42 degrees, 45 degrees, 62 degrees and 78.5 degrees. (8) at least one pair of hydride beds connected by a hydrogen transport connector, wherein at least one of the at least one pair of hydride beds is the multicomponent hydrogen according to any one of claims 1 to 7; A thermochemical hydride-dehydride heat pump characterized in that it includes a storage material. (9) Nominal composition Ti_aV_bMn_cFe_d [wherein, 0.5<a<0.75, 1.15<b<1.65, 0
．． 9<a+c<1.31 and 1.6<b+d<2.0]
and the main crystalline phase has the stoichiometric formula Ti_aV_bMn
_cFe_d [wherein, 12<a<18, 53<b<59
, 9<c<11 and 17<d<21], and the interparticle phase has the stoichiometric formula Ti_aV_bMn
_cFe_d [wherein, 31<a<36, 23<b<26
, 10<c<12 and 29<d<34]: (a) a first solid source of powdered titanium and a second solid source of powdered vanadium; (b) mixing appropriate amounts of each solid source to obtain a mixture of the correct stoichiometry; (c) A method comprising: melting the mixture; (d) cooling the molten mixture to form a solid ingot; and (c) subdividing the ingot to form particles. 10. The method of claim 9, further comprising the step of activating the material by exposing the material to a hydrogen atmosphere at a pressure of 400 psi or more at room temperature for 30 minutes or more. . (11) The method further comprises the step of activating the material by exposing the material to a hydrogen atmosphere at a temperature of 200°C or more and a pressure of 200 psi or more for 10 minutes or more. Method described. (12) having at least one main phase surrounded by an interparticle phase, with nominal composition Ti_aV_bMn_cFe_
d [wherein, 0.5<a<0.75, 1.15<b<1.
65, 0.9<a+c<1.31 and 1.6<b+d<
2.0], and the main crystalline phase has the stoichiometric formula Ti_aV_
bMn_cFe_d [wherein 12<a<18, 53<b<
59,9<c<11 and 17<d<21], and the interparticle phase has the stoichiometric formula Ti_aV_b
Mn_cFe_d [wherein, 31<a<36, 23<b<
26, 10 < c < 12 and 29 < d < 34]: (a) a first solid source consisting of powdered titanium and a second solid source consisting of powdered vanadium; (b) mixing appropriate amounts of each solid source; (c) melting the mixture; and (d) molten material. A method comprising the step of rapidly cooling. 13. The method of claim 12, wherein the step of rapidly quenching the material comprises melt spinning on a cooling surface. 14. The method of claim 12, wherein the step of rapidly quenching the material comprises vacuum deposition. 15. The method of claim 12, wherein the step of rapidly quenching the material comprises plasma spraying. 16. The method of claim 12, wherein the step of rapidly quenching the material comprises sputtering. (17) The method of claim 13, further comprising the step of activating the material by exposing the material to a hydrogen atmosphere at a pressure of 400 psi or more at room temperature for 30 minutes or more. . (18) Furthermore, 2
13. The method of claim 12, comprising activating the material by exposing the material to a hydrogen atmosphere at a temperature of 00C or higher and a pressure of 200 psi or higher for 10 minutes or more.