WO2005014165A1

WO2005014165A1 - Material for storing hydrogen and method and apparatus for production thereof

Info

Publication number: WO2005014165A1
Application number: PCT/JP2004/009538
Authority: WO
Inventors: Hironobu Fujii; Takayuki Ichikawa; Haiyan Leng; Shigehito Isobe; Nobuko Hanada; Toyoyuki Kubokawa; Kazuhiko Tokoyoda; Keisuke Okamoto; Shinkichi Tanabe; Shigeru Matsuura; Kenji Ogawa
Original assignee: National University Corporation Hiroshima University; Taiheiyo Cement Corporation
Priority date: 2003-08-11
Filing date: 2004-07-05
Publication date: 2005-02-17

Abstract

A material for storing hydrogen which comprises a lithium imide compound precursor composite material which has been converted to have a manometer size and to form a composite having a desired structure and shape, wherein the lithium imide compound precursor composite material is prepared by a method comprising mixing a fine lithium amide powder, as a starting material, with a fine lithium powder at a prescribed ratio and treating the resultant mixture with a prescribed treating process.

Description

Specification

Hydrogen storage material, method for producing the same, and apparatus for producing the same

Technical field

The present invention relates to a hydrogen storage material for efficiently storing hydrogen as a raw material for a fuel cell and the like, a method for producing the same, a production apparatus therefor, a hydrogen generation method, and a hydrogen storage material precursor used for the hydrogen storage material The present invention relates to a hydrogen storage material filling container for filling a hydrogen storage material, a moving body equipped with the same, and a gas purification device used for absorbing and releasing hydrogen to and from the hydrogen storage material.

^ Scenic technology

[0002] Clean energy that does not emit harmful substances such as NO and SO and greenhouse gases such as CO

X X 2

Fuel cells are being actively developed as one source, and some of them have already been commercialized. An important technology that supports fuel cell technology is the technology that stores hydrogen, which is a raw material for fuel cells. As a form of hydrogen storage, compression storage using a high-pressure cylinder or cold storage as liquid hydrogen has also been proposed.

[0003] However, in the storage of hydrogen by a high-pressure gas cylinder, it is necessary to increase the hydrogen pressure in order to increase the hydrogen storage amount, which increases the weight of the container and the pressure resistance and reliability of valves and the like. There's a problem. As a method of storing hydrogen as a liquid, there is a method of storing liquid hydrogen in an insulated container.Liquid hydrogen has a very low boiling point and requires a lot of energy for liquefaction. It is said that the loss due to evaporation during the supply of liquid hydrogen is 10-20%, and that even if insulation is provided, 8% of the hydrogen evaporates, which is economically problematic.

[0004] In order to solve such a problem, attention has been paid to a hydrogen storage technology using a hydrogen storage material that is advantageous for distributed storage and transport. As described in R & D News Kansai 2002.7, pp. 38-40, as a hydrogen storage material, metal materials such as rare earth, titanium, vanadium, and magnesium, and reversible disproportionation reactions were used. Alanate (eg, NaAlH

4)) and other carbon-based materials such as carbon nanotubes and activated carbon. Of these, lightweight-based inorganic compound-based materials and carbon-based materials are light-weight materials. And these are powder-based materials.

[0005] Therefore, the development of an efficient storage technology using such a powder-based lightweight material, specifically, the development of a hydrogen storage material having a high hydrogen storage rate per unit weight, the development of a hydrogen storage rate per unit volume, and the like. There is a demand for the development of a high hydrogen storage material, the development of a hydrogen storage material that exhibits hydrogen absorption and desorption performance in a low temperature range, and the development of a hydrogen storage material with good durability.

[0006] In addition, a method and apparatus for mass-producing a powder-type hydrogen storage material, an efficient storage method of a hydrogen storage material (specifically, a method of filling a predetermined container), and a method for storing a predetermined container. A simple hydrogen release method using the filled hydrogen storage material power, and an efficient hydrogen storage method for the hydrogen storage material precursor after the hydrogen storage material has released hydrogen (or before storing hydrogen). Also, a design suitable for each hydrogen storage material is required for a method of supplying a fuel cell mainly containing hydrogen released from the hydrogen storage material to the fuel cell.

[0007] First, a conventional powder-type hydrogen storage material will be examined from the material side. Alanate-based materials such as NaAlH and LiAlH are well known and studied as lightweight hydrogen storage materials.

4 4

. The hydrogen storage method using lithium nitride represented by the following formula (1) is described in Ruff, 0., and Goerges, Η ·, Benchte der Deutschen Cnemischen eselischaft zu Berlin, Vol.44, 502-6 (1911) Has been reported to. Recently, the hydrogen storage method using lithium nitride shown in the following formula (1) was reconfirmed, and Ping Chen et al., Interaction of hydrogen with metal nitrides and imides, NATURE Vol. 420, 21 NOVEMBER 2002, Reported on P302-304.

Li N + 2H Li NH + LiH + H LiNH + 2ΠΗ

3 2 2 2 2

[0008] According to these documents, the absorption of hydrogen by lithium nitride (LiN) starts at about 100 ° C.

Three

Starting at 255 ° C for 30 minutes, hydrogen absorption of 9.3% by mass was confirmed. In addition, the release characteristics of absorbed hydrogen are as follows: two steps: 6.3% by mass at a little less than 200 ° C and 3% by mass at a temperature of 320 ° C or more by slow heating at a reduced rate. Have been reported.

[0009] That is, the reaction between lithium amide (Li NH 3) and lithium hydride (LiH) represented by the following formula (2), which corresponds to the right portion of the above formula (1), starts to proceed at a little less than 200 ° C. Left side of equation (1)

2

The reaction between lithium imide (Li NH) and LiH shown in formula (3) below It is shown to begin to progress above.

LiNH + 2LiH → Li NH + LiH + H †---(2)

2 2 2

Li NH + LiH → Li N + H ΐ… (3)

2 3 2

[0010] Fig. 1 shows that LiN was absorbed at a hydrogen pressure of 3 MPa and 200 ° C by a method similar to that of the above-mentioned literature.

Three

After the storage, the sample is heated to obtain a desorption gas emission spectrum diagram. Here, the heating rate of the sample was 5 ° C / min. The characteristic line A in FIG. 1 shows the emission spectrum line of hydrogen, and the characteristic line B in FIG. 1 shows the emission spectrum line of ammonia gas (NH (g)).

Three

are doing. As can be seen from Fig. 1, the hydrogen release characteristics of the conventional method have a wide temperature range from 200 ° C to 400 ° C, and have a large peak on the high temperature side (around 320 ° C). I have.

[0011] As described above, the technology of the above-mentioned document is an effective hydrogen storage method using a lightweight metal compound called lithium nitride, but the effective hydrogen storage rate in a temperature range as low as about 200 ° C is low. There is a problem that it is necessary to heat to a high temperature range of 320 ° C or higher in order to realize high-capacity hydrogen absorption and release. In addition, in the technology described in the above-mentioned literature, the heating rate is reduced as the peak temperature of hydrogen absorption and desorption becomes closer, and heat is applied over a long period of time. Absent.

[0012] Next, conventional technologies will be examined from the viewpoint of a method and an apparatus for producing a powder-type hydrogen storage material. For example, the present inventors have previously disclosed in Japanese Patent Application Laid-Open No. 2001-302224 that a nanostructured graphite can be obtained by mechanically pulverizing under a hydrogen atmosphere. ing. Since high energy is required for such fine grinding, Japanese Patent Application Laid-Open No. 2001-302224 describes the use of a planetary ball mill capable of mechanical grinding with high energy. Such a pulverization method can also be applied to a lithium-based material such as the above-mentioned lithium nitride and a dianate-based material.

[0013] However, although the planetary ball mill can give high energy to the material to be crushed, it has a problem that it is not suitable for mass production because it is of a gravity type, so there is a limit in increasing its size. . In addition, since the pulverization process using a planetary ball mill is dry pulverization, if pulverization proceeds and the material to be pulverized becomes finer, aggregation of particles is likely to occur, which makes pulverization difficult. . Furthermore, transfer the hydrogen storage material after the grinding process to another container. It is not easy to handle the hydrogen storage material after crushing because it is necessary to perform this work in an inert atmosphere so that it does not come into contact with air etc. depending on the specified hydrogen storage material. .

[0014] If a hydrogen storage material precursor can be obtained by a method different from the method of producing a hydrogen storage material by mechanical pulverization, there is a possibility that the hydrogen storage rate can be increased. Therefore, development of a hydrogen storage material precursor capable of increasing the hydrogen storage rate and a method for producing the same are also strongly desired.

[0015] Next, conventional techniques will be examined from the viewpoint of a method of storing a hydrogen storage material. Conventionally, hydrogen storage tanks that can store large amounts of hydrogen in small volumes have been researched and developed in place of hydrogen cylinders. As a hydrogen storage material used in such a hydrogen storage tank, a hydrogen storage alloy is being developed, and a hydrogen storage tank using the hydrogen storage alloy is proposed in Japanese Patent Application Laid-Open Nos. 2000-120996 and 2002- No. 122294, JP-A-2002-221297 and JP-A-2002-340430.

However, the hydrogen storage alloy has a low hydrogen storage rate per unit weight, and a hydrogen storage tank using a hydrogen storage alloy has not yet been put into practical use. On the other hand, lightweight powder-based hydrogen storage materials such as arylate-based materials, carbon-based materials, and lithium-based materials such as lithium nitride exhibit powder characteristics and hydrogen storage-release characteristics different from those of conventional storage alloys. Unless the filling container for filling them has a structure that meets the characteristics, it is not possible to secure a sufficient amount of hydrogen storage per unit volume. The development of such lightweight powder-based hydrogen storage material filled containers has not been sufficiently developed.

Next, conventional techniques will be examined from the viewpoint of a method of releasing hydrogen from a hydrogen storage material and a method of storing hydrogen in a hydrogen storage material precursor. The absorption and desorption of hydrogen by the powdered hydrogen storage material and the hydrogen storage material precursor can be achieved by press-contacting hydrogen into the hydrogen storage material precursor filled in the hydrogen storage material filling container to hold hydrogen as a hydrogen compound. Conversely, this was accomplished by heating the hydrogen storage material to generate hydrogen.

[0018] However, in such a method, when the absorption and desorption of hydrogen are repeated, the hydrogen storage material (or the hydrogen storage material precursor) is agglomerated and closely packed in the lower part of the hydrogen storage container, and the hydrogen absorption and desorption efficiency is reduced. However, there was a problem that was reduced. Therefore, in order to solve such a problem, for example, Japanese Patent Application Laid-Open No. 62-108702 discloses a hydrogen storage container filled with an alloy powder for hydrogen storage, in which a hydrogen inlet pipe is provided at a lower portion. Disclosed is a hydrogen storage material-filled container in which a hydrogen releasing tube is provided at an upper portion to suppress agglomeration and overcrowding of the alloy powder for hydrogen storage.

However, according to the method described in Japanese Patent Application Laid-Open No. 62-108702, depending on the shape of the filling container, it is not possible to sufficiently prevent the hydrogen storage material from becoming overcrowded, or the contact between the hydrogen storage material precursor and hydrogen is insufficient. May be uniform. Another problem is that the hydrogen storage efficiency (or hydrogen storage material precursor) decreases when the hydrogen storage material (or hydrogen storage material precursor) is clogged in the hydrogen discharge port of the hydrogen discharge tube.

Next, conventional technologies will be examined from the viewpoint of fuel gas supply to the fuel cell. In conventional compression storage using a high-pressure boiler or cooling storage in which liquid hydrogenation is performed, moisture is mixed with air during the storage processing or during the handling of extracting hydrogen, and when this moisture is introduced into the fuel cell, it is removed. There was a general problem of poisoning. To cope with such a problem, Japanese Patent Application Laid-Open No. Sho 59-47599 discloses a method using a mixture of an adsorbent of a metal hydride and a molecular sieve as a removing material.

In the lithium material system represented by the above formula (1), the decomposition of LiNH

NH (g) may be generated simultaneously with hydrogen due to 2 etc., and water containing such NH (g)

3 3

When element is introduced into a fuel cell, a problem arises that the fuel cell is poisoned. Thus, a refinery has been developed to remove impurities from hydrogen coexisting with NH (g).

Three

Not shown.

Disclosure of the invention

The present invention has been made in view of such circumstances, and a first object of the present invention is to provide a hydrogen storage material capable of operating at a high efficiency and a low temperature, a method for producing the same, and a method for generating hydrogen. Is to do. A second object of the present invention is to provide a powdery hydrogen storage material having a high hydrogen storage capacity by mechanical pulverization at a mass production level, and to facilitate the handling of the hydrogen storage material after the pulverization treatment. An object of the present invention is to provide an apparatus and a method for manufacturing a material. A third object of the present invention is to provide a hydrogen storage material precursor capable of improving the characteristics of a hydrogen storage material, and a method for producing the same. The fourth object of the present invention is A hydrogen storage material-filled container that can be filled with a hydrogen storage material so that hydrogen can be absorbed and released efficiently, and that can increase the hydrogen storage rate per unit weight or unit volume. Another object of the present invention is to provide a gas purification apparatus capable of supplying a high-purity hydrogen or the like that prolongs the life of a fuel cell and a hydrogen storage material.

According to a first aspect of the present invention, there is provided a hydrogen storage material containing at least a nanostructured and organized lithium imide compound precursor complex, wherein the lithium imide compound precursor complex is a starting material A hydrogen storage material that has been nanostructured by subjecting a mixture obtained by adding a fine powder of lithium hydride to a fine powder lithium amide in a predetermined ratio to a predetermined complexing method. Is done.

[0025] According to a second aspect of the present invention, the nanostructured material is obtained by treating a mixture obtained by mixing fine powdered lithium amide and fine powdered lithium hydride at a predetermined ratio by a predetermined complexing method. And a method for producing a hydrogen storage material for obtaining an organized lithium imide compound precursor composite.

In the inventions according to the first and second aspects, “nanostructured and organized” means that each mixed particle in a sample has a nanometer size (for example, an average particle size of 10-100 nm). It means that these particles are further miniaturized, and these particles are complexed at the nanometer level to have a desired structure and shape.

[0027] In the inventions according to the first and second aspects, a mechanical milling process (hereinafter, referred to as "MeM process") in which a sample is crushed and mixed using a hard ball is used for the compounding process. Or a method using a jet mill that pulverizes and mixes a sample by spraying a pressurized gas.

[0028] In the present invention, it is most preferable to use the MeM treatment for the compounding treatment method. This is because the starting material mixture can be sufficiently nanostructured and organized by the MeM treatment, as described later. More specifically, this MeM treatment is a process in which a sample is charged into a closed container together with a grinding medium, tumbled or mechanically stirred to grind, press-contact, and knead the sample. Refers to a processing method for obtaining a material showing In other words, the MeM treatment involves mixing a mixed powder sample consisting of multiple components with steel balls as a grinding medium. In a closed container, the atmosphere inside the container is reduced or inert gas atmosphere higher than atmospheric pressure, and the container is rotated and revolved to knead the sample to form a nanometer-sized composite. Refers to processing. In such a MeM treatment, the starting material mixture is repeatedly subjected to microscopic collision with the grinding medium, and is subjected to impact compression force, resulting in plastic deformation (forging deformation), work hardening, pulverization, and thinning. Are finally kneaded.

[0029] In the present specification, "kneading" means that when a mixed sample has a property of being easily plastically deformed, it is crushed, stretched, bent, folded, entangled, split, and further split. Mean that the mixed sample is nanostructured 'organized as a result.

[0030] In the present invention, the starting material mixture of LiNH and LiH is subjected to MeM treatment in a hydrogen atmosphere.

2

This produces a nano-structured and organized lithium imide compound precursor complex, generates hydrogen according to the reaction of the following formula (4) by heating and heating, and generates nano-structured Li NH.

2

LiNH + LiH → Li ΝΗ + Η ΐ… (4)

2 2 2

[0031] At this time, the ratio of LiH to LiNH in the starting material is determined by the regular reaction ratio (as described above).

2

It is preferable to suppress the generation of NH (g) by the reaction of the following formula (5) by making the ratio larger than the reaction ratio of the formula (4). In this case, the excess amount of LiH

It is desirable that the content be 20% by mass or less of the normal reaction amount of LiH (reaction amount represented by the above formula (4)). In other words, the total amount of LiH is the normal LiH reaction amount to LiNH (100

2

It is desirable that the content be more than 120% by mass. This suppresses the generation of NH (g)

Three

This amount is sufficient for the excess addition of LiH for the purpose, but on the other hand, exceeding this amount causes a disadvantage that the effective hydrogen storage rate decreases. Therefore, in the present invention, LiNH

The upper limit of the amount of LiH excessively added to the mixture was set to 20% by mass of the normal LiH reaction amount.

2LiNH → Li NH + NH (g) †… (5)

2 2 3

[0032] Further, B, C, Mn, Fe, Co, Ni, Pt, Pd, Rh, Li, Na, Mg, K, Ir, Nd, Nb, La, Ca, V, Ti, Cr, Cu, Zn , Al, Si, Ru, Os, Mo, W, Ta, Zr, In, Hf, Ag, one or more metals, alloys or compounds selected from the group as catalysts As a result, the reaction of the above formula (4) can proceed efficiently. The amount of catalyst added is preferably 0.5-5 mol%. If the amount of the catalyst is less than 0.5 mol%, it is difficult to uniformly disperse the catalyst in the lithium imide compound precursor composite. On the other hand, if the amount of catalyst added exceeds 5 mol%, the effective hydrogen storage rate will decrease.

[0033] Such a catalyst is mixed with LiNH and LiH at the time of preparing a lithium imide compound precursor complex by MeM treatment, and is nanostructured and organized by MeM treatment.

2

Preferably, there is. This is because if catalyst particles are separately added to the sample after the complexing treatment, it becomes difficult for the catalyst particles to newly enter the nanostructure of the lithium imide compound precursor complex.

[0034] The pressure for the compounding treatment is preferably in the range of 0.1 lOMPa. If the processing pressure is lower than the atmospheric pressure (0. IMPa), the active ingredients hydrogen and nitrogen may be lost. On the other hand, the high pressure capability limit of the MeM processing apparatus developed by the present inventors is lOMPa, and a processing pressure exceeding this is not practical.

[0035] A powder mixture of LiNH and LiH, which is a starting material, is treated with MeM to obtain a lithium imide compound.

2

After forming the precursor complex (that is, after the complexing treatment), the lithium imide compound precursor complex is heated to a predetermined temperature range to allow the nanostructured and organized LiNH and LiH to react.

2

To produce a reversible disproportionation reaction to LiNH. In this case, reversible

2

The heating temperature for such a disproportionation reaction is preferably 250 ° C or lower, more preferably 200 ° C or lower. In this specification, the term “reversible disproportionation reaction” means that the reaction proceeds reversibly and decomposes into a plurality of different components.

[0036] According to the first and second aspects of the present invention, a hydrogen storage material that uses a lightweight nonmetallic compound and that can operate at high efficiency and at low temperature is provided. Also, LiNH and Li

2

H mixed raw material in an inert gas atmosphere such as nitrogen (N), helium (He), argon (Ar)

2

Alternatively, a lithium imide compound precursor complex is prepared by MeM treatment in an atmosphere of a reactive gas such as hydrogen, and when the reaction represented by the above equation (4) proceeds by increasing the temperature, Li NH is released along with hydrogen release. Can be generated.

2

[0037] Furthermore, the ratio of LiH to LiNH was set to be 0 to 20% higher than the normal molar ratio of 1: 1.

2

By increasing the amount, the generation of NH (g) by the reaction shown in the above formula (5) is suppressed.

Three Can do.

[0038] Furthermore, B, C, Mn, Fe, Co, Ni, Pt, Pd, Rh, Li, Na, Mg, K, Ir, Nd, Nb, La, Ca, V, Ti, By adding at least one of Cr, Cu, Zn, Al, Si, Ru, Os, Mo, W, Ta, Zr, In, Hf, Ag, etc. alone, an alloy or a compound, and performing MeM treatment, The reaction represented by the above formula (4) can be efficiently advanced, and hydrogen storage can be performed more efficiently than in the prior art. For example, the hydrogen storage rate per unit weight or per unit volume can be increased, and sharp absorption and release of hydrogen can be achieved in a low temperature range, and good durability can be obtained. Furthermore, the hydrogen absorption efficiency can be improved by performing the treatment under a wide range of pressure conditions of about 11 lOMPa.

[0039] Such a hydrogen storage material can be suitably used for a fuel cell that generates power using hydrogen and oxygen as fuels. More specifically, it can be used for automobiles, home power generation, vending machines, mobile phones, and fuel cells. It can be used in a wide range of technical fields as a power source for cordless home appliances such as laptop computers, or as a power source for self-contained robots' micro machines.

[0040] According to a third aspect of the present invention, there is provided a hydrogen storage material that includes a metal hydride and ammonia and generates hydrogen by a reaction between the two.

[0041] According to a fourth aspect of the present invention, there is provided a hydrogen generation method for generating hydrogen by reacting a metal hydride with ammonia.

According to the third and fourth inventions, the hydrogen generation temperature can be lowered to near room temperature, and a sufficient amount of hydrogen can be obtained.

According to a fifth aspect of the present invention, there is provided a hydrogen storage material having a mixture, complex, or reactant of a metal hydride and a metal amide compound, wherein at least two of these metal species are used. Is done.

[0044] According to a sixth aspect of the present invention, a metal hydride, a metal amide compound, and a catalyst that enhances the ability to absorb and release hydrogen are used under an inert gas atmosphere or a hydrogen atmosphere, or an inert gas and hydrogen. A step of mixing the catalyst so that the metal hydride and the metal amide compound are supported in a mixed gas atmosphere, wherein the metal hydride and the metal amide compound are composed of two or more metal components. A method for producing a hydrogen storage material is provided.

[0045] According to a seventh aspect of the present invention, a metal hydride and a metal amide compound are mixed with an inert gas. Mixing in an atmosphere or a hydrogen atmosphere or in a mixed gas atmosphere of an inert gas and hydrogen; and supporting a catalyst that enhances hydrogen absorption / desorption ability on the object to be processed obtained after the mixing step; And a method for producing a hydrogen storage material, wherein the metal hydride and the metal amide compound comprise two or more metal components.

[0046] According to an eighth aspect of the present invention, a step of supporting a catalyst for increasing hydrogen absorption / desorption ability on at least one of a metal hydride and a metal amide compound, and a metal hydride and a metal on which the catalyst is supported, respectively. An amide compound, or a metal hydride supporting the catalyst and a metal amide compound not supporting the catalyst, or a metal amide compound supporting the catalyst and a metal hydride not supporting the catalyst In an inert gas atmosphere, a hydrogen atmosphere, or a mixed gas atmosphere of an inert gas and hydrogen, and a metal component constituting the metal hydride and the metal amide compound. A method for producing a hydrogen storage material, wherein

According to a ninth aspect of the present invention, there is provided a hydrogen storage material having a mixture, a complex, or a reactant of a metal hydride and a metal amide compound, wherein these metal species are two kinds of lithium and magnesium. Is provided.

According to the inventions according to the fifth to ninth aspects, it is possible to obtain a hydrogen storage material in which the hydrogen generation temperature and the hydrogen release peak temperature are set to be lower than those in the related art.

[0049] According to a tenth aspect of the present invention, there is provided a method for producing a hydrogen storage material which comprises a metal hydride and a metal amide compound and generates hydrogen by a reaction between the metal hydride and the metal amide. To produce a metal amide compound, and a step of mixing a metal hydride with the metal amide compound obtained in the synthesis step.

[0050] According to the invention according to the tenth aspect, a metal amide compound having high purity can be easily produced by itself, and therefore, for example, the metal constituting the metal hydride and the metal amide compound are formed. Even when different metals are used, the hydrogen storage material can be manufactured with high purity. Further, a mixture of a plurality of types of metal amide compounds can be easily obtained.

[0051] According to an eleventh aspect of the present invention, a hydrogen storage material obtained by pulverizing a mixture, complex, or reaction product of lithium hydride and lithium amide by a predetermined mechanical pulverization treatment. And a hydrogen storage material having a BET specific surface area of 15 m ² / g or more.

[0052] According to a twelfth aspect of the present invention, there is provided a hydrogen storage material obtained by pulverizing a mixture, complex or reaction product of lithium hydride and magnesium amide by a predetermined mechanical pulverization treatment, A hydrogen storage material having a specific surface area of 7.5 m ² Zg or more.

[0053] According to a thirteenth aspect of the present invention, there is provided a hydrogen storage material obtained by pulverizing a mixture, complex, or reaction product of magnesium hydride and lithium amide by a predetermined mechanical pulverization process, A hydrogen storage material having a specific surface area of 7.5 m ² Zg or more.

[0054] According to a fourteenth aspect of the present invention, there is provided a hydrogen storage material having a hydrogenated lithium imide, wherein the hydrogen storage material has a specific surface area of 10 m ² / g or more by a BET method.

[0055] According to a fifteenth aspect of the present invention, there is provided a hydrogen storage material obtained by hydrogenating a mixture, a composite, or a reaction product of magnesium nitride and lithium imide, and has a specific surface area of 5 m ² / g or more by a BET method. A hydrogen storage material, which is:

[0056] According to a sixteenth aspect of the present invention, there is provided a hydrogen storage material having a mixture, a complex, or a reactant containing a metal hydride, a metal amide compound, and a catalyst that enhances the ability to absorb and release hydrogen. Is a hydrogen storage material comprising nanoparticles.

According to a seventeenth aspect of the present invention, there is provided a hydrogenated hydrogen storage material containing a metal imide compound and a catalyst for enhancing the ability to absorb and release hydrogen, wherein the catalyst is hydrogen comprising nanoparticles. Storage material is provided.

[0058] According to the inventions according to the eleventh to seventeenth aspects, a hydrogen storage material having a lower hydrogen release temperature than conventional ones can be obtained. As a result, the energy required for heating for releasing hydrogen from the hydrogen storage material is reduced, and restrictions on the material and structure of a container or the like for filling the hydrogen storage material are relaxed.

[0059] According to an eighteenth aspect of the present invention, a hydrogen storage comprising two or more types of catalysts that releases hydrogen by the reaction of a metal hydride and a metal amide compound and promotes the hydrogen release reaction. A method for producing a material, comprising: adding one kind of a catalyst and a predetermined easily crushable inorganic substance to one of a metal hydride and a metal amide compound, and crushing and mixing; Adding the remaining one of the metal hydride and the metal amide compound to the object to be treated obtained as described above, and another type of catalyst that promotes the hydrogen release reaction, and pulverizing and mixing the hydrogen storage material. And a method for producing the same.

[0060] According to a nineteenth aspect of the present invention, a method for producing a hydrogen storage material containing two or more types of catalysts that releases hydrogen by reacting a metal hydride with a metal amide compound and promotes the hydrogen release reaction A step of adding one kind of catalyst and a predetermined easily crushable inorganic substance to either one of the metal hydride and the metal amide compound, and crushing and mixing the metal hydride and the metal amide compound. A method for producing a hydrogen storage material, comprising: a step of adding another type of catalyst to one of the remaining components and crushing and mixing; and a step of crushing and mixing the objects to be processed obtained in the two mixing steps. Is done.

[0061] Conventional methods for supporting a plurality of catalysts on a hydrogen storage material include a method in which a plurality of catalysts are added to the hydrogen storage material at the same time and a pulverizing treatment is performed, and a method in which a plurality of catalysts are staggered in the hydrogen storage material. And then pulverizing. However, when a plurality of types of catalysts are supported on a hydrogen storage material by such a method for supporting a catalyst, the expected effect of improving characteristics has not been obtained. According to the inventions according to the eighteenth and nineteenth aspects, a hydrogen storage material having a high hydrogen release rate and a low hydrogen release start temperature can be obtained by exhibiting the functions of a plurality of catalysts.

[0062] According to a twentieth aspect of the present invention, a cylindrical pulverizing container in which a hydrogen storage material is pulverized, and the pulverizing container so that the inside of the pulverizing container can be maintained in a hydrogen atmosphere. A hydrogen introduction section for introducing hydrogen into the inside; a hydrogen storage material introduction section capable of introducing a hydrogen storage material into the grinding vessel while maintaining the hydrogen atmosphere in the grinding vessel; A hydrogen storage material discharge unit that discharges the hydrogen storage material, a plurality of grinding rollers arranged along the inner wall of the grinding container while matching the longitudinal direction of the rotation axis with the longitudinal direction of the grinding container, and the grinding container. A drive mechanism for causing relative rotation between the plurality of crushing rollers and rotation of the plurality of crushing rollers, wherein the inside of the crushing container is set to a hydrogen atmosphere, and the hydrogen storage material is supplied to the crushing container. Introduced within An apparatus for producing a hydrogen storage material, wherein a hydrogen storage material is mechanically pulverized by a compressive force and a shearing force between an inner wall of the pulverizing container and the pulverizing roller to produce a hydrogen storage material.

[0063] According to a twenty-first aspect of the present invention, a pulverizing container having an inner cylinder and an outer cylinder coaxially provided, and an annular pulverization chamber formed between the inner cylinder and the outer cylinder, A hydrogen introduction unit for introducing hydrogen into the annular grinding chamber so that the annular grinding chamber can be maintained in a hydrogen atmosphere; and a hydrogen storage material in the annular grinding chamber while maintaining the hydrogen atmosphere in the annular grinding chamber. , A hydrogen storage material discharge portion for discharging the hydrogen storage material in the annular grinding chamber, and a drive for causing relative rotation between the inner cylinder and the outer cylinder. A hydrogen atmosphere in the annular grinding chamber, introducing a hydrogen storage material and a grinding medium into the annular grinding chamber, and causing relative rotation between the inner cylinder and the outer cylinder. And mechanically pulverize the hydrogen storage material to produce a hydrogen storage material. An apparatus for producing a hydrogen storage material to be produced is provided.

[0064] According to a twenty-second aspect of the present invention, a rotatable cylindrical pulverizing vessel for pulverizing a hydrogen storage material therein, and the rotatable cylindrical pulverizing vessel so that the inside of the pulverizing vessel can be maintained in a hydrogen atmosphere. A hydrogen introduction unit that introduces hydrogen into the grinding container, a hydrogen storage material introduction unit that can introduce a hydrogen storage material into the grinding container while maintaining the hydrogen atmosphere in the grinding container, A hydrogen storage material discharge section for discharging the hydrogen storage material, an impeller provided in the pulverizing container with the longitudinal direction of the rotating shaft coinciding with the longitudinal direction of the pulverizing vessel, the pulverizing vessel and the impeller. And a drive mechanism for rotating the impeller in a direction opposite to each other, and the inside of the pulverizing container is set to a hydrogen atmosphere, and a hydrogen storage material material and a pulverizing medium are filled in the pulverizing container. In the opposite direction An apparatus for producing a hydrogen storage material, which mechanically pulverizes a hydrogen storage material by rotating to produce a hydrogen storage material, is provided.

[0065] According to the twenty-third aspect of the present invention, the hydrogen storage material raw material is crushed therein, and the hydrogen storage material discharge port for discharging the crushed hydrogen storage material to the outside is provided at the lower portion of the side wall. Cylindrical crushing container having a bottom, a housing for accommodating the crushing container and maintaining the inside of the crushing container in a predetermined gas atmosphere, and having a cylindrical curved surface, the curved surface and a side wall of the crushing container One or more inner pieces arranged so as to have a predetermined gap between the inner surface, a holding member for holding the inner piece, and a gap width between the milling vessel and the inner piece are substantially equal. A container rotating mechanism for rotating the milling container and / or the holding member so as not to change, wherein the housing has a gas introducing portion for introducing hydrogen into the inside thereof, and holds the inside thereof in a hydrogen atmosphere. A hydrogen storage material introduction unit for introducing a hydrogen storage material into the grinding container while keeping the hydrogen storage material discharged from the grinding container through the hydrogen storage material discharge port; A hydrogen storage material discharge unit that discharges a part of the hydrogen storage material discharged from the grinding container through the hydrogen storage material discharge port into the grinding container; A hydrogen atmosphere in the housing, introducing a hydrogen storage material into the pulverizing container, and mechanically converting the hydrogen storage material by a compressive force and a shearing force between a side wall of the pulverizing container and the inner piece. And an apparatus for producing a hydrogen storage material that is subjected to mechanical pulverization to produce a hydrogen storage material.

[0066] According to a twenty-fourth aspect of the present invention, a jet nozzle for injecting a predetermined processing gas containing hydrogen at high pressure, and a high-pressure processing gas injected from the jet nozzle are introduced into the inside thereof, A pulverizing container having a predetermined shape for pulverizing the hydrogen storage material by the gas flow; a hydrogen storage material source introduction unit capable of introducing the hydrogen storage material into the pulverization container while maintaining the gas atmosphere in the pulverization container; A hydrogen storage material discharge unit for discharging the hydrogen storage material in the pulverizing container, and introducing the hydrogen storage material into the pulverizing container by setting the atmosphere in the pulverizing container to an atmosphere containing hydrogen. The hydrogen storage material is mechanically pulverized by collision or grinding of the hydrogen storage material on the jet of the high-pressure processing gas or by shearing force applied from the high-pressure processing gas. An apparatus for producing a hydrogen storage material that crushes to produce a hydrogen storage material is provided.

According to a twenty-fifth aspect of the present invention, a hydrogen storage material is introduced into the above-mentioned pulverization container while the inside of the cylindrical pulverization container is kept in a hydrogen atmosphere, and the hydrogen storage material is introduced into the pulverization container and the inner wall of the pulverization container. Hydrogen storage by the relative rotational movement between the plurality of crushing rollers provided along and the compressive and shearing forces generated between the inner wall of the crushing container and the crushing rollers due to the rotation of the plurality of crushing rollers. Mechanically pulverize raw materials to produce hydrogen storage materials And a method for producing a hydrogen storage material.

[0068] According to a twenty-sixth aspect of the present invention, an annular grinding chamber formed between the inner cylinder and the outer cylinder of a grinding vessel having an inner cylinder and an outer cylinder provided coaxially is set to a hydrogen atmosphere. Meanwhile, a grinding medium and a hydrogen storage material are introduced into the annular grinding chamber, and a relative rotational movement is caused between the inner cylinder and the outer cylinder to mechanically pulverize the hydrogen storage material to perform a hydrogen storage material. And a method for producing a hydrogen storage material.

[0069] According to a twenty-seventh aspect of the present invention, a pulverizing medium and a hydrogen storage material are filled in the pulverizing container while the inside of the cylindrical pulverizing container is in a hydrogen atmosphere. A method for producing a hydrogen storage material, wherein a hydrogen storage material is mechanically pulverized by rotating an impeller provided in a pulverization container in directions opposite to each other to mechanically pulverize the hydrogen storage material.

[0070] According to a twenty-eighth aspect of the present invention, a hydrogen storage material is introduced into the crushing vessel while the inside of the bottomed cylindrical crushing vessel is in a hydrogen atmosphere, and the cylinder provided in the crushing vessel is provided. The inner piece and the inner piece are formed by rotating the inner piece or rotating the milling vessel so that the gap width between the cylindrical curved surface of the inner piece having a curved surface and the side wall of the milling vessel does not substantially change. Provided is a method for producing a hydrogen storage material, wherein a hydrogen storage material is mechanically pulverized by a compressive force and a shear force generated between the hydrogen storage material and the side wall of the container to produce a hydrogen storage material.

[0071] According to a twenty-ninth aspect of the present invention, while a high-pressure injection of a predetermined processing gas containing hydrogen is performed on the pulverizing container, the hydrogen storage material is so supplied as to ride on the gas flow of the processing gas generated in the pulverizing container. Is introduced into the milling vessel, and the hydrogen storage material is mechanically pulverized by collision or grinding of the hydrogen storage material in the gas stream or by shearing force given by the gas stream. A method for producing a hydrogen storage material for producing hydrogen.

[0072] According to the present invention according to the twentieth to twenty-ninth aspects, a hydrogen storage material that exhibits a hydrogen storage function by granulation by mechanical pulverization in a hydrogen atmosphere is pulverized with high energy. Therefore, a hydrogen storage material having a high hydrogen storage capacity can be obtained. In addition, the industrialization is possible because the grinding mechanism does not limit the amount of grinding like a planetary ball mill. Therefore, it can sufficiently cope with mass production. Also, in producing a hydrogen storage material using a hydrogen storage function material that exhibits a hydrogen storage function by mechanically pulverizing under a hydrogen atmosphere, a metal component having a function of dissociating hydrogen molecules into hydrogen atoms. Is added during the mechanical pulverization of the hydrogen storage function material, the metal component can be supported in a highly dispersed state without the metal component being thickly covered with the hydrogen storage function material. High hydrogen storage capacity is obtained by the action of the metal component.

[0073] According to a thirtieth aspect of the present invention, a cylindrical pulverizing container for pulverizing a hydrogen storage material therein, and a slurry comprising the hydrogen storage material and a predetermined solvent are placed in the pulverization container. A slurry supply unit to be introduced, a slurry discharge unit to discharge the slurry in the grinding container, a grinding ball filled in a predetermined amount in the grinding container, and a stirring device for rotating the grinding ball in the grinding container, An apparatus for producing a hydrogen storage material comprising:

[0074] According to a thirty-first aspect of the present invention, a grinding container, which is held in a liquid-tight manner, is filled with a milling ball and a slurry comprising a hydrogen storage material and a solvent, and the grinding container is filled in the grinding container. A method for producing a hydrogen storage material is provided, wherein the raw material for hydrogen storage material is mechanically pulverized by collision of the ground balls by rotating an impeller provided to produce a hydrogen storage material.

[0075] According to the inventions according to the thirtieth and thirty-first aspects, since the object to be ground is ground by wet grinding, aggregation of the ground particles is suppressed. Thereby, fine graining can be efficiently promoted, and a fine hydrogen storage material having a high hydrogen storage rate can be obtained. In addition, continuous grinding is easy, and high mass productivity can be obtained. Further, by filling the hydrogen storage material after the pulverization treatment into a predetermined container or the like, it becomes easy to store and transport the hydrogen storage material.

According to a thirty-second aspect of the present invention, there is provided a hydrogen storage material precursor having a metal imide compound which changes into a hydrogen storage material containing a metal hydride and a metal amide compound by reacting with hydrogen. And a hydrogen storage material precursor, wherein the metal imide compound is synthesized without undergoing a reaction between the metal hydride and the metal amide compound. [0077] According to a thirty-third aspect of the present invention, there is provided a hydrogen storage material precursor which reversibly changes into a hydrogen storage material capable of releasing hydrogen by reacting with hydrogen, the heat of a metal amide compound being A hydrogen storage material precursor having a metal imide compound generated by decomposition is provided.

[0078] According to a thirty-fourth aspect of the present invention, there is provided a method for producing a hydrogen storage material precursor having a metal imide compound which reversibly changes into a hydrogen storage material capable of releasing hydrogen by reacting with hydrogen. hand,

A method for producing a hydrogen storage material precursor that obtains the metal imide compound by thermally decomposing a metal amide compound is provided.

According to the inventions according to the thirty-second to thirty-fourth aspects, a hydrogen storage material having a high hydrogen release rate can be obtained based on the obtained hydrogen storage material precursor. Further, a hydrogen storage material having a low hydrogen release start temperature can be obtained.

[0080] According to a thirty-fifth aspect of the present invention, the function of occluding or releasing hydrogen at a temperature of 80 ° C or higher is activated, and the hydrogen occluding and releasing of the hydrogen occluding material is enhanced. A hydrogen storage material-filling container for filling a solid hydrogen storage material containing a catalyst containing the hydrogen storage material, the container being filled with the hydrogen storage material, and a flow of hydrogen flowing inside the container. A hydrogen storage material-filled container comprising: a flow path forming member for forming a path; and heating means for heating the hydrogen storage material to a temperature of 80 ° C. or higher.

[0081] According to the invention of the thirty-fifth aspect, when the hydrogen storage material is heated by the heating means, the function of occluding or releasing hydrogen of the hydrogen storage material is activated. It can store and release hydrogen. As a result, it is possible to provide a hydrogen storage material filled container that is particularly suitable for a lithium-based material. Further, since the lithium-based material has a higher hydrogen storage rate per unit weight than the hydrogen storage alloy or the like, the hydrogen storage rate per mass of the filled container can be increased. As a result, this hydrogen storage material-filled container can be used for a hydrogen supply device mounted on a fuel cell vehicle, etc., and a storage tank system for a buffer tank hydrogen station for stationary fuel cells. It can be applied to all hydrogen storage devices in the hydrogen energy society. [0082] Further, according to the hydrogen storage material-filled container according to the thirty-fifth aspect, the hydrogen storage material can be efficiently heated, so that the storage and release of hydrogen can be performed in a short time. Further, the surface area of the gas flow pipe can be increased, and the efficiency of the hydrogen storage material storing or releasing hydrogen can be increased.

[0083] According to a thirty-sixth aspect of the present invention, there is provided a moving object equipped with the hydrogen storage material-filled container according to the thirty-fifth aspect.

[0084] According to the moving object according to the thirty-sixth aspect, for example, a lightweight fuel cell vehicle or a hydrogen engine vehicle capable of traveling over a long distance with one replenishment can be realized.

[0085] According to a thirty-seventh aspect of the present invention, a plurality of independent storage chambers filled with a powder-based hydrogen storage material, openings provided on floors of the plurality of storage chambers, A hydrogen introduction line communicating with the plurality of storage chambers through openings, wherein the hydrogen storage material does not occlude hydrogen and the hydrogen is introduced into the hydrogen storage material. The hydrogen storage material is scattered in each storage chamber by being introduced from the outside through the line and ejected from the opening into the plurality of storage chambers so that the hydrogen storage material and the hydrogen are brought into contact with each other. And a hydrogen storage material-filled container for storing the hydrogen.

[0086] According to the invention of the thirty-seventh aspect, agglomeration of a hydrogen storage material (a hydrogen storage material precursor in a state in which the hydrogen storage material has absorbed hydrogen and is in a state of absorbing hydrogen) in the hydrogen storage container. · Because overcrowding is reduced, hydrogen can be efficiently filled in the hydrogen storage material precursor. In addition, since the ability to release hydrogen from the hydrogen storage material can be increased, the supply efficiency of hydrogen energy can be increased.

[0087] According to a thirty-eighth aspect of the present invention, hydrogen containing ammonia and / or water vapor, or a mixed gas of hydrogen and one or more selected from the group consisting of He, Ne, Ar, and N is used.

2

There is provided a gas purification apparatus characterized in that a filter containing an alkali metal hydride and a Z or alkaline earth metal hydride is provided in a flow path.

[0088] According to the invention of the thirty-eighth aspect, ammonia and Z or water poisoning the fuel cell can be efficiently removed from these gases suitably used for the fuel cell and the like by reducing the residual concentration. It can be removed by the PPM order.

Brief Description of Drawings

[Figure 1] Gas of desorption gas from a conventional hydrogen storage material starting from lithium nitride (Li N)

Three

FIG.

FIG. 2 is a gas emission spectrum diagram showing the results of mass number analysis of desorbed gas accompanying a rise in temperature in Comparative Example 1.

FIG. 3 is a gas emission spectrum diagram showing the results of mass number analysis of desorbed gas accompanying a rise in temperature in Comparative Example 2.

FIG. 4A is an enlarged schematic cross-sectional view showing an initial kneaded state of the MeM treatment.

FIG. 4B is an enlarged schematic cross-sectional view showing a kneaded state in the middle stage of the MeM treatment.

FIG. 4C is an enlarged schematic cross-sectional view showing a kneaded state in the latter half of the MeM treatment.

FIG. 5 is a gas emission spectrum diagram showing the result of mass number analysis of desorbed gas accompanying a rise in temperature in Example 1.

FIG. 6 is a gas emission spectrum diagram showing the results of mass spectrometry of desorbed gas accompanying temperature rise in Example 2.

FIG. 7 is a gas emission spectrum diagram showing the results of mass spectrometry of desorbed gas accompanying a rise in temperature in Example 3.

FIG. 8 is a characteristic diagram showing a change in a gas release spectrum line and a change in mass loss at the time of temperature rise when hydrogen release and hydrogen storage are repeated with the hydrogen storage material according to the present invention.

FIG. 9 is a graph showing the hydrogen release rate of each sample of Example 4-1-24 in a predetermined temperature range.

FIG. 10 is a graph showing the relationship between the reaction temperature and the hydrogen release rate of each sample of Examples 31 to 34.

FIG. 11 is an XRD chart diagram after a hydrogen generation reaction in Example 35.

FIG. 12 is a graph showing emission spectra of desorbed hydrogen in Example 41 and Comparative Examples 41 and 42 as the temperature was increased by the TG-MASS apparatus.

FIG. 13 is a graph showing emission spectra of desorbed hydrogen with temperature rise by the TG-MASS apparatus of Examples 51 and 52 and Comparative Examples 51 and 52.

FIG. 14 is a diagram showing an example of a DTA curve of a hydrogen storage material composed of lithium hydride and lithium amide. FIG. 15 is a graph showing the relationship between the specific surface area, the hydrogen release temperature, and the hydrogen release rate of a hydrogen storage material composed of lithium hydride and lithium amide.

FIG. 16 is a graph showing a relationship between a specific surface area of a hydrogen storage material composed of lithium hydride and magnesium amide, and a hydrogen release temperature and a hydrogen release rate.

FIG. 17 is a graph showing a relationship between a specific surface area of a hydrogen storage material composed of magnesium hydride and lithium amide, and a hydrogen release temperature and a hydrogen release rate.

FIG. 18 is a graph showing the relationship between the specific surface area of a hydrogen storage material composed of hydrogenated lithium imide, the hydrogen release temperature, and the hydrogen release rate.

FIG. 19 is a graph showing a relationship between a specific surface area, a hydrogen release temperature, and a hydrogen release rate of a hydrogen storage material obtained by hydrogenating a pulverized mixture of magnesium nitride and lithium imide.

FIG. 20 is a hydrogen release spectrum chart of Example 81 and Comparative Example 81.

FIG. 21 is a hydrogen release spectrum chart of Example 82 and Comparative Example 82.

FIG. 22 is a flowchart showing a production process of a hydrogen storage material in which two or more types of catalyst are supported.

FIG. 23 is a flow chart showing another production process of a hydrogen storage material carrying two or more types of catalysts.

FIG. 24 is a flow chart showing still another production process of a hydrogen storage material carrying two or more types of catalysts.

FIG. 25 is a graph showing the relationship between the temperature of the hydrogen storage material and the amount of released hydrogen in Examples 91-93 and Comparative Examples 91-93.

FIG. 26A is a horizontal sectional view showing a schematic structure of a first manufacturing apparatus.

FIG. 26B is a vertical sectional view showing a schematic structure of the first manufacturing apparatus.

FIG. 27 is a sectional view showing a schematic structure of a second manufacturing apparatus.

FIG. 28 is a diagram schematically showing a pulverizing operation by a second manufacturing apparatus.

FIG. 29 is a perspective view showing a schematic structure of a third manufacturing apparatus with a part cut away.

FIG. 30 is a sectional view showing a schematic structure of a fourth manufacturing apparatus.

FIG. 31 is a diagram showing a pulverization mode in a fourth manufacturing apparatus.

FIG. 32 is a sectional view showing a schematic structure of a fifth manufacturing apparatus. FIG. 33 is a graph showing the relationship between the milling time and the average particle size of the hydrogen storage material in Examples 101-104 and Comparative Example 101.

FIG. 34 is an enlarged view of the relationship between the milling time in FIG. 33 and the average particle size of the hydrogen storage material.

FIG. 35 is a graph showing the relationship between the milling time and the hydrogen storage amount in Examples 101-104 and Comparative Example 101.

FIG. 36 is a graph showing the relationship between the retention time at 250 ° C. and the hydrogen storage amount (cumulative value) in Examples 105-109 and Comparative Example 102.

FIG. 37 is a sectional view showing a schematic configuration of a sixth manufacturing apparatus.

FIG. 38 is a cross-sectional view showing a schematic configuration of a manufacturing apparatus in which the sixth manufacturing apparatus is transformed into a form capable of continuous processing.

FIG. 39 is a cross-sectional view showing a schematic configuration of another manufacturing apparatus in which the sixth manufacturing apparatus is transformed into a form capable of continuous processing.

FIG. 40 is a graph showing the relationship between the heating time and temperature and the hydrogen storage rate in Example 111 and Comparative Example 111.

FIG. 41 is a graph showing the relationship between the temperature and the hydrogen release amount in Example 121 and Comparative Example 121.

FIG. 42 is a graph showing the relationship between the temperature and the hydrogen release amount in Examples 122 and 123 and Comparative Examples 122 and 123.

FIG. 43 is a cross-sectional view showing a schematic structure of a first hydrogen storage material-filled container.

FIG. 44 is a cross-sectional view showing a schematic structure of a second hydrogen storage material-filled container.

FIG. 45 is a cross-sectional view showing a schematic structure of a third hydrogen storage material-filled container.

FIG. 46 is a sectional view showing a schematic structure of a fourth hydrogen storage material-filled container.

FIG. 47 is a view showing a schematic configuration of a moving body equipped with a hydrogen storage material-filled container.

FIG. 48 is a perspective view showing a schematic structure of a fifth hydrogen storage material filled container.

FIG. 49 is a diagram showing a configuration in which a gas purification device is combined with a hydrogen storage material-filled container. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings.

First, a hydrogen storage material containing at least a lithium imide compound precursor composite that has been nanostructured and organized will be described. Metallic and non-metallic compounds The hydrogen storage capacity is related to the nanometer-scale structure / structure, and high-performance hydrogenated materials can be produced by nanostructure / structure control, that is, nanostructure / structuring at the nanometer scale.

[0091] One of the methods of nanostructuring and organizing a powder material is MeM treatment. In this method, a hard ball called a crushing medium and a raw material are placed in a closed container, and the raw material is crushed, pressed, and kneaded by rolling or mechanical stirring to obtain a material having physical properties different from those of the starting material. Is the way. An example of a procedure for producing a nanostructured-structured hydrogen storage material by MeM treatment performed by the present inventors will be described below. Needless to say, the specific method and conditions of the MeM processing are not limited to the examples shown here.

[0092] Starting from LiNH and LiH, the reversible inequality of Eq. (4) shown above (repeated below)

2

Attention was paid to a hydrogen absorption / desorption reaction using a chemical reaction.

LiNH + LiH → Li ΝΗ + Η ΐ… (4)

2 2 2

According to this reaction, 6.5% by mass of hydrogen as a theoretical value can be reversibly absorbed and released. At this time, the standard enthalpy of the hydrogenation reaction is Δ Η = _44.5 (kj / mol H),

2

Hydrogen absorption and desorption at low temperature is also expected from a mechanical point of view.

[0094] (Comparative Example 1)

Therefore, first, commercially available LiNH and LiH are weighed at a ratio of 1: 1 by the number of molecules, and then weighed in an agate mortar.

2

Mix for a few minutes. The mixture thus obtained (that is, the sample according to Comparative Example 1) was heated at a heating rate of 5 ° C./min, and mass number analysis of desorbed gas accompanying the heating was performed.

FIG. 2 shows a gas emission spectrum diagram showing the results of mass number analysis of desorbed gas accompanying the temperature rise of the sample of Comparative Example 1. In FIG. 2, the horizontal axis represents temperature (° C.), and the vertical axis represents gas emission spectrum intensity (arbitrary unit) by mass number (MASS) analysis of desorbed gas accompanying temperature rise. In addition, a characteristic line C in FIG. 2 represents a hydrogen emission spectrum line, and a characteristic line D represents an emission spectrum line of ammonia gas (NH (g)). As is evident from Figure 2,

Three

In the sample of Comparative Example 1, a large amount of NH (g) was released simultaneously with the release of hydrogen. this is,

Three

It is thought to be due to the thermal decomposition reaction of LiNH shown in equation (5) shown above (reprinted below).

2

It is. 2LiNH → Li NH + NH (g) †… (5)

2 2 3

[0096] This result indicates that when LiNH and LiH make microscopic contact, LiN

2

It supports that the hydrogen release reaction by H and LiH is occurring. LiNH and LiH

In the case where 2 2 makes microscopic contact, the decomposition reaction of equation (5) takes precedence before the reaction of equation (4) proceeds, so the thermal decomposition of LiNH alone Only reaction occurs,

2

As a result, a large amount of NH (g) is released.

Three

(Comparative Example 2)

Therefore, it is said that the microscopic contact between LiNH and LiH is increased to suppress the release of NH (g).

twenty three

For the purpose, LiNH and LiH are weighed in a ratio of 1: 2 in the number ratio of molecules and mixed in an agate mortar for several minutes.

2

A mixed mixture (sample of Comparative Example 2) was prepared, and the obtained sample was subjected to the same mass number analysis of desorbed gas accompanying temperature rise as in Comparative Example 1.

[0098] Fig. 3 is a gas release spectrum diagram showing the results of mass number analysis of desorbed gas accompanying the temperature rise of the sample of Comparative Example 2. A characteristic line E in FIG. 3 indicates an emission spectrum line of hydrogen, and a characteristic line F indicates an emission spectrum line of N H (g). As is evident from Figure 3, the comparison

Three

In the sample of Example 2, the release of NH (g) was observed at the same time as the release of hydrogen, but compared with Comparative Example 1.

Three

It was found that the release of NH (g) was suppressed. From this result, this reaction system (reaction

Three

In the hydrogen storage system in Eq. (4), it was found that the structure at the nanoscale is a parameter that largely controls the absorption and desorption characteristics of hydrogen.

[0099] (Example 1)

Therefore, as Example 1, the purpose was to achieve overlapping microscopic contact of LiNH and LiH,

2

LiNH fine powder and LiH fine powder are weighed at a ratio of 1: 1 in number of molecules, and MeM treatment is performed for 2 hours.

2

Carried out. Both the LiNH fine powder and the LiH fine powder have an average particle size of several tens of m (20 4

2

0 μm) of each reagent.

[0100] Specifically, in the MeM treatment, a powder obtained by mixing a mixed powder sample LiNH and LiH at a ratio of 1: 1 and a small amount of a catalyst are placed in a steel pot (30 cc internal volume). Grams and steel

2

20 balls (diameter: 7 mm) are charged, and the inside of the container is rotated and revolved at a rotation speed of 400 rpm with a reducing gas atmosphere such as hydrogen or an inert gas atmosphere such as argon (Ar). A few micron-sized nanometer-sized composite of LiNH and LiH.

2 Powder particles were obtained. The MeM processing apparatus used was a P7 planetary ball mill manufactured by Fritsch (Germany).

Here, the microscopic effect of the MeM processing will be described with reference to FIGS. 4A to 4C. The mixed sample sealed in the hermetically sealed container undergoes impact compression force due to repeated collisions with hard steel balls (pulverizing medium), undergoes plastic deformation (forging deformation), work hardens, is pulverized, and becomes thin. And finally kneaded. The kneading of such a mixed sample proceeds stepwise as follows.

[0102] In the initial stage of kneading, as shown in Fig. 4A, the sample particles 502 are sandwiched between the steel balls 504 and crushed by a compressive impact force as shown in Fig. 4A. It is. In the middle stage of kneading, the sample particles 502 are further crushed, stretched, flaked and laminated as shown in FIG. 4B. Furthermore, at the latter stage of the kneading, as shown in FIG. Become like In this way, nanostructured and organized mixed powder particles having a size on the order of several microns are obtained.

[0103] The mixture obtained by such a MeM treatment was subjected to mass number analysis of desorbed gas accompanying the temperature increase in the same manner as in Comparative Examples 1 and 2. FIG. 5 shows a gas emission spectrum diagram showing the mass number analysis result of the desorbed gas accompanying the temperature rise of the sample of Example 1. In FIG. 5, a characteristic line G indicates an emission spectrum line of hydrogen, and a characteristic line H indicates an emission spectrum line of NH (g).

As is clear from FIG. 5, the sample of Example 1 has remarkably suppressed NH (g) emission as compared with Comparative Examples 1 and 2 mixed with the agate mortar described above. That is, in the above equation (4)

Three

It has been found that MeM treatment plays a very effective and important role in hydrogen storage systems using disproportionation reactions. However, the release of NH (g) is still recognized

Three

(Example 2)

Next, a method for producing a hydrogen storage material to which metal particles are added as a catalyst will be described. By using the MeM treatment, it is possible to easily add a catalyst that increases the reaction rate of hydrogen absorption and desorption. Lmol% Ni particles with respect to the number of moles of Li in a molar ratio of 1: 1 Mixed with the mixed mixture of LiNH and LiH and subjected to the same MeM treatment as in Example 1 above.

2

A sample was prepared. At this time, the average particle size of both LiNH fine powder and LiH fine powder is

2

Those with a diameter of several tens of μΐη were used. Ni nanoparticles having an average particle diameter of 20 nm were used as the Ni particles.

For the obtained sample, mass number analysis of desorbed gas accompanying temperature rise was performed in the same manner as in Example 1 and the like. FIG. 6 shows a gas emission spectrum diagram showing the result of mass number analysis of the desorbed gas accompanying the temperature rise of the sample of Example 2. In FIG. 6, the characteristic line indicated by a solid line indicates the emission spectrum line of hydrogen, and the characteristic line indicated by a broken line indicates the emission spectrum line of NH (g).

Three

As is clear from comparison between FIG. 5 and FIG. 6, it can be seen that the addition of the catalyst sharpens the hydrogen release statue. Further, in the sample according to Example 2, hydrogen release was almost completed between 150 ° C and 300 ° C at a heating rate of 5 ° C / min, and NH ( g) with the release of hydrogen was observed.

Three

The peak height of the emission spectrum of NH (g) with respect to the peak height of the spectrum

Three

Compared to 1, you can see that it is lower. In other words, the generation of NH (g) is suppressed.

Three

To work hard.

(Example 3)

Next, a method for producing a hydrogen storage material to which a metal compound particle catalyst has been added will be described. Here, too, by using the MeM treatment, it is possible to easily add a catalyst that increases the reaction rate of hydrogen absorption and desorption. Lmol% titanium trichloride (Ti C1) particles (average particle size: 2-4 μ μη) with respect to the number of moles of Li are mixed in a 1: 1 ratio of the number of molecules to a mixture of LiNH and LiH.

A sample was prepared which was mixed with the 32 merging and subjected to the same MeM treatment as in Example 1 above.

[0109] The mass number analysis of the desorbed gas accompanying the temperature rise was performed on the obtained sample in the same manner as in Example 1 above. FIG. 7 shows a gas emission spectrum diagram showing the mass number analysis result of the desorbed gas accompanying the temperature rise in Example 3. In FIG. 7, the characteristic! ^ Indicated by a solid line indicates the emission spectrum line of hydrogen, and the characteristic line K indicated by the broken line indicates the emission spectrum line of NH (g). Figure

Three

As is clear from the comparison between FIG. 5 and FIG. 7, it can be seen that the addition of the catalyst sharpens the hydrogen emission total. At a rate of 5 ° C / min, Hydrogen release was completed at 300 ° C, and no NH (g) release was measured during the measurement.

Three

became.

[0110] When TiCl is added, TiCl is separated by the subsequent heating of the hydrogen storage material.

33, it is presumed that the metal titanium exists in the lithium imide compound precursor complex in the form of Ti.

[0111] (Cycle test and its evaluation results)

Next, the cycle characteristics of the lithium imide compound precursor complex containing TiCl as a catalyst

Three

explain about. Lmol% TiCl particles are mixed in a molar ratio of 1: 1 based on the number of moles of Li.

Three

Sample mixed with mixed LiNH and LiH and treated with MeM as in Example 1.

2

Is the first cycle sample. Then, the first cycle sample was degassed under vacuum at 220 ° C for 12 hours, and then the sample obtained by reacting with hydrogen at 180 ° C under a hydrogen pressure of 3 MPa for 12 hours was used as the second cycle sample. A sample obtained by performing the same treatment one more time was used as a third cycle sample.

[0112] FIG. 8 shows a gas release outside line representing the results of a temperature programmed desorption gas analysis performed on the three types of samples thus obtained, and a mass loss line representing the results of thermogravimetric measurement. In Fig. 8, the characteristic line P1 is the gas emission spectrum line of the first cycle sample, the characteristic line Q1 is the gas emission spectrum line of the second cycle sample, and the characteristic line R1 is the gas emission spectrum of the third cycle sample. Lines are shown. The characteristic line P2 in Fig. 8 shows the mass loss line of the first cycle sample, the characteristic line Q2 shows the mass loss line of the second cycle sample, and the characteristic line R2 shows the mass loss line of the third cycle sample. Show me.

[0113] As is clear from Fig. 8, the second and third cycle samples show some characteristic deterioration in terms of hydrogen release temperature and hydrogen release amount as compared with the first cycle sample. This is thought to be due to the fact that the material became a stable substance that did not participate in the storage and release of hydrogen during the third heating process, which was considered to have originally been included in the carohydrate (catalyst) or raw material. It is. However, there is no significant difference between the second cycle sample and the third cycle sample, so the cycle characteristics are considered to be very good. Furthermore, when desorption gas analysis is performed at a heating rate of 1 ° C / min, the peak position of the desorption curve decreases to 200 ° C or less, and hydrogen storage and release at 200 ° C or less may be possible. confirmed. [0114] Note that all of the hydrogen storage experiments described above were performed under a pressure condition of about 3MPa. From the viewpoint of improving the absorption efficiency of hydrogen and hydrogen, it can be performed under a wide range of pressure conditions of about 11 lOMPa. Of course.

[0115] The improvement of the hydrogen release characteristics (sharpening of the emission spectrum and lowering of the release temperature) by the addition of the catalyst to the catalyst is similar to that of the Ni particles and TiCl particles described above.

Three

Other elements having a medium action, such as B, C, Mn, Fe, Co, Ni, Pt, Pd, Rh, Li, Na, Mg, K, Ir, Nd, Nb, La, Ca, V, Ti, Cr, Cu, Zn, Al, Si, Ru, Os, Mo, W, Ta

It can also be realized by a simple substance, alloy or compound containing at least one of, Zr, In, Hf and Ag. Next, the embodiment will be described.

(Examples 4-1 to 24)

Example 4 is composed of LiH and LiNH as in Example 1, but the test method is different.

2

In Example 524, as in Examples 2 and 3, various catalysts were added to LiH and LiNH.

2

Although the test method is different. As shown in Table 1 below, for Examples 5-21, LiH, LiNH, and various catalysts were set at a molar ratio of 1: 1: 0.01, and the total amount thereof was 1.3 g.

2

Was weighed in a high purity Ar glove box as described above. Further, in Example 22, as shown in Table 1, LiH, LiNH, chromium chloride (CrCl) and TiCl were used in a molar ratio of 1: 1: 0.01:

2 3 3

0.01, and weighed in a high-purity Ar glove box so that their total amount was 1.3 g. Further, in Example 23 and Example 24, as shown in Table 1, the molar ratio of LiH, LiNH, and the predetermined catalyst was set to 1: 2: 1: 0.01, and the total amount thereof was 1.3 g. So high

2

Purity Weighed in Ar glove box.

[0117] [Table 1]

Mixing (molar ratio)

Catalyst type

LiH LiNH ₂ catalyst

Example 4 1.00 1.00 0 (none)

Example 5 1.00 1.00 0.01 TiCI ₃

Example 6 1.00 1.00 0.01 CrCI ₃

Example 7 1.00 1.00 0.01 VCI ₂

Example 8 1.00 1.00 0.01 HfCI ₄

Example 9 1.00 1.00 0.01 lrCI ₃

Example 10 1.00 1.00 0.01 CoCI ₂

Example 11 1.00 1.00 0.01 NiCI ₂

Example 12 1.00 1.00 0.01 PtCI ₂

Example 13 1.00 1.00 0.01 FeCI ₃

Example 14 1.00 1.00 0.01 NdCI ₂

Example 15 1.00 1.00 0.01 PdCI ₂

Example 16 1.00 1.00 0.01 MoCI ₃

Example 17 1.00 1.00 0.01 RhCI ₃

Example 18 1.00 1.00 0.01 WCI ₄

Example 19 1.00 1.00 0.01 Co

Example 20 1.00 1.00 0.01 Fe

Example 21 1.00 1.00 0.01 Ni

Example 22 1.00 1.00 0.02 CrCI ₃ + TiCI ₃

Example 23 1.20 1.00 0.01 TiCI ₃

Example 24 1.20 1.00 0.01 CrCI ₃

Next, the weighed sample was placed in a high-chromium steel mill container with a valve (250 cm ³ ) in a high-purity Ar glove box. Subsequently, after evacuating the inside of the mill container, high-purity Ar was introduced into the mill container so that the internal pressure of the mill container became MPa, and room temperature was reduced using a planetary ball mill (Fritsch, P5). Milling was performed at 25 (kpm for 120 minutes to prepare a sample. After the inside of the mill container was evacuated and filled with Ar, the mill container was opened in a high-purity Ar glove box, and the sample was taken out. , Metal Ni, metal Co and metal Fe are samples manufactured by Vacuum Metallurgy Co., Ltd. (Ni: average particle size 20 nm BET specific surface area: 43.8 m ² / g, Co: average particle size Particle diameter 20 nm, BET specific surface area: 47.9 mg, Fe: average particle diameter 20 nm, BET specific surface area: 46.0 m ² / g). All other metal chlorides were manufactured by Aldrich (purity 95% or more).

Example 4 [0119] Each of the 24 samples was weighed in a high-purity Ar glove box in an amount of 500 mg, and filled in a SUS reaction vessel (internal volume: about 50 cm ³ ) equipped with a valve having an internal volume of 50 cm ³ . The reaction vessel is equipped with a thermocouple so that the temperature near the upper part of the sample can be measured. The reaction vessel filled with this sample was placed in a pressure sensor, a vacuum pump, and an experimental apparatus (internal volume: about 300 cm ³ ) equipped with a gas chromatograph (manufactured by Shimadzu Corporation, GC9A, TCD detector, column: Molecular Sieve 5A). After mounting and evacuating, the sample was heated to room temperature-300 ° C at a heating rate of 10 ° C / min, and discharged into the reaction vessel at room temperature, 150 ° C, 200 ° C, and 250 ° C. The gas was quantified using the attached gas chromatograph, and the hydrogen content was measured. The hydrogen release rate was a value obtained by dividing the amount of hydrogen measured in this manner by the amount of the sample before heating. Note that the hydrogen release rate was corrected by calculating the amount of hydrogen collected and lost on a gas chromatograph at each temperature.

[0120] Figure 9 shows the hydrogen release rates released in the temperature range of room temperature-150 ° C, room temperature-200 ° C, and room temperature-250 ° C. As shown in FIG. 9, each of the samples except for Examples 7, 13, and 15 showed a hydrogen release rate near lmass% at a temperature rise of room temperature to 250 ° C. The hydrogen release characteristics were shown. In Example 15, the hydrogen release rate from room temperature to 200 ° C. exceeded 0.4 mass%, indicating a high hydrogen release rate in a relatively low temperature range. In Example 7 and Example 13, the hydrogen release rate in the low temperature range from room temperature to 150 ° C exceeded 0.4 mass%, and the high hydrogen release rate was shown in the low temperature range of 150 ° C or lower.

[0121] Next, it is composed of a metal hydride (solid) and ammonia gas (NH (g)).

Three

A hydrogen storage material that generates hydrogen by a reaction will be described. Here, lithium hydride (LiH) is suitably used as the metal hydride, and the hydrogen generation reaction in this case is represented by the following formula (6). Since the reaction of the following formula (6) starts even at room temperature, hydrogen can be extracted from the hydrogen storage material at a low temperature near room temperature, which was conventionally difficult.

LiH + NH (g) → LiNH + H G-(6)

3 2 2 [0122] When the reaction temperature increases, as shown by the following formula (7), a secondary reaction in which lithium imide (Li NH) and NH (g) are generated by a decomposition reaction of the generated lithium amide (LiNH).

2 2 3

Therefore, it is preferable to control the reaction conditions so that such a reaction does not occur.

2LiNH → Li NH + NH (g) †… (7)

2 2 3

[0123] Metal hydrides other than LiH include sodium hydride (NaH) and magnesium hydride.

(MgH 2), calcium hydride (CaH 2) and the like. Hydrogen evolution reaction in the case of NaH

twenty two

Is based on the above formula (6), and in the case of MgH, it is expressed by the following formula (8). Hydrogen release in the case of CaH

twenty two

The raw reaction conforms to the following equation (8). A mixture of such multiple metal hydrides and NH

Three

Hydrogen may be generated by reacting with (g).

MgH + 2NH (g) → Mg (NH) + 2H †… (8)

2 3 2 2 2

[0124] For example, in the reaction between LiH and NH (g), a solid-phase reaction forms near the surface.

Three

Prescribed mechanical grinding treatment to prevent the reaction of NH (g) with LiH

twenty three

, It is preferable to expose unreacted LiH to NH (g).

Three

[0125] As the metal hydride, it is preferable to use a metal that supports a catalyst that promotes the hydrogen generation reaction. Such catalysts include B, C, Mn, Fe, Co, Ni, Pt, Pd, Rh, Li, Na, Mg, K, Ir, Nd, Nb, La, Ca, V, Ti, Cr, Cu , Zn, Al, Si, Ru, 〇s, Mo, W, Ta, Zr, In, Hf, Ag One or more metals or their compounds or alloys, or hydrogen storage alloys are preferred Used for

[0126] The amount of the supported catalyst is preferably from 0.1% by mass to 20% by mass of the metal hydride. When the amount of the supported catalyst is less than 0.1% by mass, the effect of accelerating the hydrogen generation reaction is not obtained. When the amount exceeds 20% by mass, the reaction between the reactants such as metal hydride is hindered. The hydrogen release rate per mass will be reduced.

[0127] In order to increase the rate of hydrogen generation by the reaction between metal hydride and NH (g), metal hydrogen

Three

Into the reaction vessel, and the Li NH phase formed near the surface by the solid-phase gas-phase reaction

2

To prevent the reaction between NH (g) and LiH, for example, the unreacted part of the metal hydride

Three

The metal hydride and NH (g) are sealed in a reaction vessel so that the H (g) can be easily contacted.

3 3

While stirring or pulverizing the metal hydride in the reaction vessel, the metal hydride and NH (g)

Three Are preferably used to generate hydrogen.

(Examples 31-34)

As shown in Table 2, LiH (purity 95%, manufactured by Sigma-Aldrich) or LiH to which titanium trichloride (TiCl; manufactured by Sigma-Aldrich) was added as a catalyst was converted to high-purity argon (

Three

Ar) In a glove box, about 0.3 g was put into a sample container with a valve made of SUS. Here, LiH in Example 31 is the reagent itself taken out of the reagent bottle. The LiH of Example 32 was prepared by using a planetary ball mill (Fritsch, Model P5) to transfer the reagent lg taken out of the reagent bottle into a high chrome steel mill container (internal volume; 250 cm ³ ) in an Ar glove box. And milled (crushed) at 250 rpm for 2 hours in an atmosphere of room temperature. In Example 33, LiH and TiCl taken out of the reagent bottle were mixed in an Ar glove box using an agate mortar.

Three

For a short time. In Example 34, as in Example 32, LiH and TiCl taken out of the reagent bottle were subjected to milling using a planetary ball mill.

Three

[0129] The sample container was attached to the reactor, and the inside of the sample container was evacuated. Thereafter, NH (g) is introduced into the sample container so that the molar ratio shown in Table 2 is obtained and the inside of the sample container is set to 0.2 MPa (absolute pressure). The temperature inside the sample container is increased by heating

Three

Was heated from room temperature to 200 ° C. at a rate of 5 ° C./min. The reaction gas was sampled from the inside of the sample container at a predetermined temperature, and the composition of the sampling gas was analyzed by gas chromatography (Shimadzu Corporation, model: GC9A, using TCD detector, column: molecular sieve 5A).

(Example 35)

The composition of Example 35 is shown in Table 2. The LiH taken out of the reagent bottle is placed in a high chrome steel mill container (modified so that exhaust Z sealing can be performed) in the Ar glove box, and then the inside of the mill container is evacuated and placed in the mill container. Introduce a predetermined amount of NH (g) and seal the mill container.

Three

Stopped. This was milled (crushed) at 250 rpm for 30 minutes. The reaction gas was sampled from the Minore container after the milling treatment, and the composition was analyzed by gas chromatography. After milling, the powder in the mill container was identified by powder X-ray diffraction (XRD).

[0131] [Table 2] Compound molar ratio

Before hydrogen generation reaction During hydrogen generation

LiH TiCI ₃ NH ₃ milling processing Milling processing Example 31 0 None None

Example 32 0 Yes No

Example 33 0.05 None None

Example 34 0.05 Yes No

Example 35 0 No Yes

[0132] Fig. 10 is a graph showing the relationship between the reaction temperature and the hydrogen release rate for Examples 31 to 34. This hydrogen release rate is calculated by adding the mass of generated hydrogen to the sum of the initial masses of LiH and NH (g).

Three

The theoretical value is about 8.05. In all the samples of Examples 31 to 34, it was confirmed that hydrogen was generated even at room temperature, and it was confirmed that the higher the treatment temperature, the higher the hydrogen release rate. Examples 32 and 34 in which milling was performed before the reaction with NH (g)

Three

An increase in the amount of hydrogen generated was observed as compared with Examples 31 and 33 in which milling was not performed. This is thought to be because the surface area (reaction area) of LiH was increased by fine grinding of LiH. In addition, as is clear from the comparison between Example 31 and Example 33 and between Example 32 and Example 34, when the catalyst was added, an increase in the amount of hydrogen generation was observed. It was confirmed that it was promoted.

[0133] As a result of analyzing the gas composition in the mill container after the milling treatment in Example 35, it was confirmed that 70% of the collected gas was hydrogen. Since a large amount of hydrogen was obtained in a short processing time of 30 minutes, hydrogen was generated by reacting LiH with NH (g) while milling LiH.

Three

It was confirmed that the reaction could be accelerated. FIG. 11 shows an XRD image of the powder in the sample container after the hydrogen generation reaction of Example 35. From FIG. 11, it was confirmed that LiNH based on the formula (6) shown above was almost used. Note that lithium hydroxide (LiOH) was detected in FIG.

2

The reason for this was that unreacted LiH was formed by reacting with moisture in the air during the preparation of the measurement sample for XRD and during the measurement process, and it was present in the original raw material. This is probably due to the following.

[0134] Next, a mixture or complex or reaction product of a metal hydride and a metal amide compound ( Hereinafter, a hydrogen storage material having a mixture or the like and at least two or more of these metal species will be described. Here, “having a mixture, a complex, or a reactant (that is, a mixture, etc.)” means that the mixture, the complex, and the reactant do not have to have only one of the forces. Or two, and all of these. Such hydrogen storage materials include, specifically, (1) a metal constituting a metal hydride and a metal constituting a metal amide compound are different, and (2) a plurality of kinds of metals having different metal components. One containing a metal hydride and (3) one containing a plurality of metal amide compounds having different metal components.

[0135] A preferable example is lithium hydride (LiH), which has a property that the decomposition temperature is low among metal hydrides, considering only the reduction of the hydrogen release temperature, and the metal amide compound At least, it decomposes at lower temperature than LiH to produce ammonia gas (NH (g))

3 The magnesium amide (Mg (NH)) and calcium amide (Ca (NH))

2 2 2 2

Include these mixtures, and combinations that are preferred.

[0136] As can be seen by comparing Example 41 and Example 43 described below, when the metal amide compound is used alone (single component), as the atomic weight of the metal element constituting the metal amide compound increases, Hydrogen release rate decreases. Therefore, the combination of the lightest lithium amide (LiN H) and Mg (NH) or Ca (NH) for lowering the temperature has been used in practice.

2 2 2 2 2

Preferred for

[0137] In the case of a material using LiH, LiNH and Mg (NH), each substance is

2 2 2

When they are blended so as to be equivalent, each substance may be used in combination as shown in the following formula (9). In the equation (9), it is preferable that a = b + 2c. It is also possible to use lithium imide (for example, Li NH) having an equivalent force.

twenty two

aLiH + bLiNH + cMg (NH) →

2 2 2

aH † + (b + c) Li NH + cMgNH ~ (9)

twenty two

[0138] Such a mixture of a metal hydride and a metal amide compound is preferably nanostructured and organized by MeM treatment. This MeM treatment can be performed by using a planetary ball mill or the like in the case of small-scale production. In the case of mass production, various mixed Z grinding methods described later, for example, a roller mill, inner and outer cylinders, etc. Rotary mill, attritor, in It can be carried out using a nap-piece type mill, an air current milling type mill or the like.

[0139] In order to obtain a mixture or the like of a metal hydride and a metal amide compound, the mixing / crushing treatment of the metal hydride and the metal amide compound is performed using an inert gas (eg, argon (Ar), nitrogen (N)).

2 Atmosphere, hydrogen (H) atmosphere, or mixed gas atmosphere of inert gas and hydrogen

2

It is performed under insufflation. At this time, it is preferable that the atmospheric pressure (gas pressure) be equal to or higher than the atmospheric pressure. This increases the amount of hydrogen released from the mixture after the mixing / pulverization process, for unknown reasons.

[0140] A mixture of a metal hydride and a metal amide compound or the like may contain a catalyst that enhances the ability to absorb and release hydrogen. Suitable horny media include B, C, Mn, Fe, Co, Ni, Pt, Pd, Rh, Li, Na, Mg, K, Ir, Nd, Nb, La, Ca, V, Ti, Cr, One or more metals selected from Cu, Zn, Al, Si, Ru, 〇s, Mo, W, Ta, Zr, In, Hf, Ag, or their compounds or alloys, or hydrogen storage Alloys are preferably used.

[0141] The amount of such a catalyst carried is preferably 0.1% by mass or more and 20% by mass or less of a mixture of a metal hydride and a metal amide. If the amount of supported catalyst is less than 0.1% by mass, the effect of accelerating the hydrogen generation reaction cannot be obtained. If the amount exceeds 20% by mass, the reaction between the reactants such as metal hydrides is adversely affected, and The rate of hydrogen release per mass will be reduced.

[0142] One of the following three methods is used as a method for causing a mixture of a metal hydride and a metal amide compound to carry a catalyst having a hydrogen absorbing / releasing ability. That is, (a) by adding a catalyst when mixing and pulverizing a metal hydride and a metal amide compound, an object to be treated (that is, a metal hydride, a metal amide compound, a mixture thereof, or a reaction product thereof) is obtained. (B) a method in which the catalyst is supported on the object by mixing the catalyst with the object obtained by mixing and pulverizing the metal hydride and the metal amide compound, and (c) the metal hydrogen. Before mixing and pulverizing the hydride and the metal amide compound, any one of the methods in which at least one of the metal hydride and the metal amide compound is loaded with a catalyst capable of absorbing and releasing hydrogen by a mixed pulverization treatment or the like is used.

(Preparation of Various Metal Amides)

For example, Mg (NH) converts magnesium hydride (MgH) lg to high-purity Ar glove box.

2 2 2 In a tas, it is charged into a high chrome steel mill container (internal volume: 250 cm ³ ), then the inside of the mill container is evacuated, and then the molar ratio of the following formula (10) is exceeded, and Then, a predetermined amount of NH (g) was introduced into the mill container so that the inside of the mill container became 0.4 MPa or less (absolute pressure), and the mill container was sealed. It was prepared by milling at a rotational speed of for a predetermined time. From the mill vessel after milling, the generation of Mg (NH 2) was confirmed by the amount of hydrogen in the reaction gas and XRD measurement. LiNH

2 2 2, Ca (NH)

twenty two

Prepared as described above. The raw materials used for preparing each metal amide are as shown in Table 3.

MgH + 2NH (g) → Mg (NH) + 2H ΐ

3 2 2 2… (10)

2

[Table 3]

(Examples 41 to 47)

Table 4 shows the composition of the starting materials of Examples 41 to 47 described below. Table 4 shows the specified raw materials whose LiH, MgH, LiNH, Mg (NH), and Ca (NH) powers were also selected.

2 2 2 2 2 2

High-purity Ar gross so that it has a predetermined composition containing two or more metal elements and that the amount of titanium trisalt (Ti C1) is 1.0 mol% of the total molar amount of the metal components of the starting material.

Three

It was weighed in a vacuum box and charged into a mill container with a valve made of high chromium steel. Subsequently, after evacuating the inside of the mill container, high-purity hydrogen was introduced into the mill container so that the inside of the mill container became IMPa, and the planetary ball mill device (Fritsch, P5) was used. Milling was performed at 250 rpm for 2 hours in an air atmosphere. After milling, the inside of the mill container was evacuated and filled with Ar, and then removed in a high-purity Ar glove box. [0146] (Comparative Examples 41 and 42)

Table 4 shows the composition of the starting materials of Comparative Examples 41 and 42. In Comparative Example 41, LiH and LiNH were used, and in Comparative Example 42, LiH and LiNH were contained such that the metal hydride and the metal amide compound contained one metal.

MgH and Mg (NH 2) were each prepared so as to have a predetermined composition shown in Table 4, and TiCl

It was weighed in a high-purity Ar glove box and charged into a high-chromium steel valve-equipped mill vessel so that 2 2 2 3 was 1. Omol% of the total molar amount of the metal components of the starting material. Then, after evacuating the Minore container, high-purity hydrogen was introduced into the mill container so that the inside of the mill container became IMPa, and the planetary ball mill was used to rotate at 250 rpm at room temperature and in the atmosphere. Milled for 2 hours by number. After milling, the mill container was evacuated and filled with Ar, and then removed in a high-purity Ar glove box.

[Table 4]

[0148] (Sample evaluation)

The sample prepared as described above was placed in a TG-

Using a MASS device (thermogravimetric / mass spectrometer), the temperature was raised at a rate of 5 ° C / min, and the desorbed gas from each sample was sampled and analyzed.

[0149] (Result)

Figure 12 shows the emission spectrum of desorbed hydrogen with increasing temperature using the TG-MASS device. FIG. 3 is an explanatory diagram showing the relationship between the degree and the hydrogen release intensity. In FIG. 12, a characteristic line a indicates Example 41, a characteristic line b indicates Comparative Example 41, and a characteristic line c indicates Comparative Example 42. Table 4 shows the theoretical hydrogen release rate (mass%) of each sample and the peak temperature (° C) of the hydrogen emission spectrum curve (hereinafter referred to as “hydrogen release peak temperature”).

[0150] From FIG. 12, the hydrogen release peak temperature of Example 41 was 209 ° C, which was lower than that of 239 ° C in Comparative Example 41 and 317 ° C in Comparative Example 42. It was confirmed that the temperature decreased. Also, as shown in Table 4, it was confirmed that the hydrogen release peak temperature in Example 42 47 was lower than that in Comparative Example 41.

[0151] Next, there is a mixture or a complex or a reaction product (mixture or the like) of a metal hydride and a metal amide compound, and these metal species are lithium (Li) and magnesium (Mg). The storage material will be described. As the hydrogen storage material, specifically, (1) a metal constituting the metal hydride is Li and a metal constituting the metal amide compound is Mg, (2) a metal constituting the metal hydride Is Li and the metal constituting the metal amide compound is Mg and Li, (3) the metal constituting the metal hydride is Mg, and the metal constituting the metal amide compound is Li, (4 ) The metal that constitutes the metal hydride is Mg, and the metal that constitutes the metal amide compound is Mg and Li. (5) The metal that constitutes the metal hydride is Mg and Li, and the metal amide compound Wherein the metal constituting Mg is Mg and / or Li.

[0152] A preferred example is that the metal hydride is lithium hydride (LiH) and the metal amide compound is magnesium amide (Mg (NH)) alone or a mixture thereof with lithium amide (LiNH)

2 2 2

[0153] In the case of a material using LiH and Mg (NH), each material is blended so as to be equivalent.

twenty two

In this case, the combination may be made as in the following equation (11). Further, in the case of a material using magnesium hydride (MgH) and LiNH, the combination is as shown in the following equation (12).

twenty two

I'll do it. According to these combinations, the theoretical hydrogen storage rate becomes 5.48% by mass. 2LiH + Mg (NH) ^ Li NH + MgNH + 2H †---(11)

2 2 2 2

MgH + 2LiNH ^ Li NH + MgNH + 2H † (12)

2 2 2 2 More preferably, in the case of a material using LiH and Mg (NH 2), one mole of Mg (N

twenty two

It is preferable that LiH be 1.5 mol or more and 4 mol or less with respect to H). Furthermore,

twenty two

More preferably, LiH is at least 2.5 mol and not more than 3.5 mol per mol of Mg (NH).

twenty two

That's right. For example, 1 mol of Mg (NH) per 2 · 67 mol of LiH (8LiH + 3Mg (NH)

2 2 2 2

) Is shown in the following equation (13). The theoretical hydrogen storage rate by the combination of the following equation (13) is 6.85% by mass, which is higher than that of the above equation (11).

8LiH + 3Mg (NH) ^ 4Li NH + Mg N + 8H † --- (13)

2 2 2 3 2 2

[0155] On the other hand, in the case of a material using MgH and LiNH, one mole of LiNH

Preferably, the mixing ratio of MgH is 0.5 mol or more and 2 mol or less.

2

The mixing ratio of MgH to 1 mol of LiNH should be 0.5 mol or more and 1 mol or less.

twenty two

More preferred. For example, they may be combined as in the following equation (14). The theoretical hydrogen storage rate according to the following equation (14) is 7.08% by mass, and the hydrogen storage rate is greatly improved from the case of the above equation (12).

3MgH + 4ΠΝΗ Mg N + 2Li NH + 6H † '' (14)

2 2 3 2 2 2

Here, in the reverse reaction of the above formula (1), that is, in the hydrogen releasing reaction, lithium nitride (Li

N), a hydrogen release rate of 9.3 mass% was confirmed, but this hydrogen release rate

Three

In order to obtain, it is necessary to decompose lithium imide (Li NH) to Li N. In this reaction,

twenty three

Although a high hydrogen release rate can be obtained, ΔΗ is as large as -148 kj / mol, so a high temperature is required and it is difficult to lower the hydrogen release temperature.

[0157] However, by combining Mg, which is more likely to be nitrided than Li, as in the above formulas (13) and (14), magnesium nitride (Mg N) and Li NH are generated, whereby the specific ratio is increased.

3 2 2

It has been found that the hydrogen release peak can be reduced at a low temperature while maintaining a relatively high hydrogen release rate.

That is, the above equation (13) is expressed by the following equations (15), (16) and (17):

It is thought to involve three stages of hydrogen release.

3Mg (NH) + 3LiH → 3MgNH + 3LiNH + 3H † --- (15)

2 2 2 2

3LiNH + 3LiH → 3Li NH + 3H † --- (16)

2 2 2

3MgNH + 2LiH → Mg N + Li NH + 2H †… (17)

3 2 2 2 [0159] In the above equation (13), the lowering of the hydrogen release peak temperature is due to the fact that Mg (NH) and LiH

twenty two

From the combination of LiNH and LiH, the release reaction (Eq. (15)) starts at a much lower temperature.

2

This is thought to be due to this. Further, the fact that the hydrogen storage material according to the present invention can maintain a relatively high hydrogen release rate despite the low hydrogen release peak temperature is based on the fact that the magnesium imide (MgNH) generated by the above formula (15) can Up to Mg N as in the formula

It is presumed that the reaction proceeds easily.

[0160] Such a mixture of a metal hydride and a metal amide compound is preferably nano-structured and organized by MeM treatment. This mechanical milling process can be performed by using a planetary ball mill or the like in the case of small-scale production, and in the case of mass production, various mixing / pulverization methods described later, for example, a roller mill, inner and outer cylinder rotation It can be carried out by using a mold mill, an attritor, an inner piece type mill, an airflow pulverizing type mill and the like.

[0161] In order to obtain a mixture or the like of a metal hydride and a metal amide compound, the mixing / crushing treatment of the metal hydride and the metal amide compound is performed using an inert gas (eg, argon (Ar), nitrogen (N)).

The test is performed under two atmospheres, a hydrogen atmosphere, or a mixed gas atmosphere of an inert gas and hydrogen. At this time, it is preferable that the atmospheric pressure (gas pressure) be equal to or higher than the atmospheric pressure. This increases the amount of hydrogen released from the mixture or the like after the mixing / crushing treatment.

[0162] It is preferable that a mixture of a metal hydride and a metal amide compound or the like contains a catalyst that enhances the ability to absorb and release hydrogen. Suitable catalysts are B, C, Mn, Fe, Co, Ni, Pt, Pd, Rh, Li, Na, Mg, K, Ir, Nd, Nb, La, Ca, V, Ti, Cr, Cu, Zn , Al, Si, Ru, Os, Mo, W, Ta, Zr, In, Hf, Ag, at least one metal or a compound or alloy thereof, or a hydrogen storage alloy.

[0163] The amount of such a catalyst carried is preferably 0.1% by mass or more and 20% by mass or less based on a mixture of a metal hydride and a metal amide. If the amount of supported catalyst is less than 0.1% by mass, the effect of accelerating the hydrogen generation reaction cannot be obtained. If the amount exceeds 20% by mass, the reaction between the reactants such as metal hydrides is adversely affected, and The rate of hydrogen release per mass will be reduced.

[0164] One of the following three methods is used as a method for causing a mixture of a metal hydride and a metal amide compound to carry a catalyst that enhances the ability to absorb and release hydrogen. That is, (a) A method in which a catalyst is added when mixing and pulverizing a metal hydride and a metal amide compound, thereby allowing the metal hydride and the metal amide compound to be supported on an object to be processed (that is, a metal hydride, a metal amide compound, a mixture thereof, or a reactant thereof); ) A method in which the catalyst is supported on the workpiece by mixing the catalyst with the workpiece obtained by mixing and pulverizing the metal hydride and the metal amide compound, (C) the metal hydride and the metal amide compound Before mixing and pulverizing, a method having a catalyst capable of absorbing and releasing hydrogen supported on at least one of a metal hydride and a metal amide compound by a mixing and pulverizing treatment or the like is used.

[0165] (Preparation of Mg (NH))

twenty two

Mg (NH) is a high-purity mill made of chrome Mg in a high-purity Ar glove box.

2 2 2

After being charged into a vessel (internal volume: 250 cm ³ ), the inside of the mill container is evacuated, and then a predetermined amount of ammonia gas (NH After introducing (g)), the mill container was sealed and then milled at room temperature and in an air atmosphere at a rotation speed of 250 rpm for a predetermined period of time to prepare. Mill vessel strength after milling The production of Mg (NH 丄) was confirmed by the amount of hydrogen in the reaction gas and XRD measurement.

twenty two

The raw materials used in the invention are as shown in Table 5.

MgH + 2NH (g) → Mg (NH) + 2H

2 3 2 2 2 Τ

[0166] [Table 5]

(Examples 51-57)

Table 66 shows the composition of the starting materials of Working Examples 5511-57. LiH, MgH, LiNH, Mg (

NH) force The selected raw material contains two types of metal elements as shown in Table 6.

twenty two

Titanium trichloride (TiCl) is the total of the metal components of the starting material so that it has the specified composition. It was weighed in a high-purity Ar glove box so as to have a molar amount of 1. Omol%, and was charged into a high-chromium steel mill container with a valve. Subsequently, after evacuation of the inside of the mill container, high-purity hydrogen was introduced into the mill container so that the inside of the mill container became IMPa, and room temperature was set using a planetary ball mill device (Fritsch, P5). Milling was performed at 250 rpm for 2 hours under an air atmosphere. After milling, the mill container was evacuated and filled with Ar, and then taken out in a high-purity Ar glove box.

[0168] [Table 6]

[0169] (Comparative Examples 51 and 52)

Table 6 shows the composition of the starting materials of Comparative Examples 51 and 52. In Comparative Example 51, LiH and LiNH were used, and in Comparative Example 52, the metal hydride and the metal amide compound contained one kind of metal.

2

MgH and Mg (NH 2) were each prepared so as to have a predetermined composition shown in Table 6, and TiCl

It was weighed in a high-purity Ar glove box and charged into a high-chromium steel valve-equipped mill vessel so that 2 2 2 3 was 1. Omol% of the total molar amount of the metal components of the starting material. Then, after evacuating the Minore container, high-purity hydrogen was introduced into the mill container so that the inside of the mill container became IMPa, and the planetary ball mill was used to rotate at 250 rpm at room temperature and in the atmosphere. Milled for 2 hours by number. After milling, the mill container was evacuated and filled with Ar, and then removed in a high-purity Ar glove box. [0170] (Sample evaluation)

The sample prepared as described above was placed in a TG-

Using a MASS device (thermogravimetry / mass spectrometer), the temperature was raised at a rate of 5 ° C / min, and the desorbed gas from each sample was sampled and analyzed.

[0171] (Result)

Fig. 13 shows the emission spectrum of desorbed hydrogen with increasing temperature by the TG-MASS device, that is, an explanatory diagram showing the relationship between temperature and hydrogen emission intensity. Note that the characteristic line a in FIG. 13 shows the example 51, the characteristic line b shows the example 52, the characteristic line c shows the comparative example 51, and the characteristic line d shows the comparative example 52, respectively. Table 6 also shows the peak temperature (° C) of the hydrogen emission spectrum curve of each sample (hereinafter referred to as “hydrogen emission peak temperature”).

[0172] As shown in Fig. 13, the hydrogen release peak temperature of Example 51 was 192 ° C, the peak hydrogen release temperature of Example 52 was 209 ° C, and the peak temperature of Comparative Example 51 was 239 ° C and that of Comparative Example 52 was 239 ° C. It was confirmed that the peak temperature of hydrogen release was lower than 317 ° C in this case. Further, as shown in Table 6, it was confirmed that in Examples 53-57, the hydrogen release peak temperature was lower than that in Comparative Example 51.

[0173] Further, in Examples 51-55, wherein the molar ratio between LiH and Mg (NH) was in the range of 1.5-4.

twenty two

The hydrogen release peak temperature is lower, and the molar ratio between LiH and Mg (NH) is 2.5- 3

twenty two

In Examples 51 and 53 in the range of 0.5, it was confirmed that the hydrogen release temperature was further lowered.

(Examples 58-62)

Table 7 shows the composition of the starting materials of Examples 58-62 described below. A given raw material selected from LiH, MgH, LiNH, and Mg (NH) is

2 2 2 2

TiCl is used as a starting material so that it has a predetermined composition containing the elemental elements.

Three

The solution was weighed in a high-purity Ar glove box so as to have a total molar amount of 1. Omol%, and charged into a high-chromium steel mill container with a valve. Subsequently, after evacuating the inside of the mill container, high-purity hydrogen was introduced into the mill container so that the inside of the mill container became IMPa, and the room temperature was adjusted using a planetary ball mill (Fritsch, P5). The milling treatment was performed at 250 rpm in an air atmosphere for 2 hours. After milling, the inside of the mill container was evacuated and filled with Ar. Later, it was taken out in a high purity Ar glove box

[0175] [Table 7]

[0176] From Table 7, it can be seen that in Examples 58-62 using MgH and LiNH, Comparative Example 51 and Comparative Example

twenty two

The hydrogen release peak temperature is lower than 52. Also, the molar ratio between MgH and LiNH is 0

twenty two

In Example 58-61 in the range of 5-2, the hydrogen release peak temperature was further lowered, and in Example 58-60 in which the molar ratio of MgH to LiNH was in the range of 0.5-1. You

twenty two

It was confirmed that the effect was remarkable.

[0177] Next, a method for producing a metal amide compound suitably used for the above-described hydrogen storage material will be described. Metal amide compounds react metal hydrides with ammonia (NH).

3 and manufacture. Metal hydrides include lithium hydride (LiH), sodium hydride (NaH), potassium hydride (KH), rubidium hydride (RbH), cesium hydride (CsH), magnesium hydride (MgH), Calcium hydride (CaH), beryllium hydride (BeH),

2 2 2 Strontium hydride (SrH), barium hydride (BaH), scandium hydride (ScH)

2 2 2

, Lanthanum hydride (LaH, LaH), titanium hydride (TiH), vanadium hydride (VH),

2 3 2 X Yttrium hydride (YH, YH), zirconium hydride (ZrH), neodymium hydride (N

3 2 2

dH, NdH) and the like. In addition, two or more types selected from these metal hydrides

3 2

Mixtures of metal hydrides are also suitably used.

[0178] The metal hydride preferably contains a hydride of an alkali metal or an alkaline earth metal. This is the hydrogen release of the metal amide compound obtained by the reaction. This is because the characteristics are good.

[0179] It is also preferable that the metal hydride is finely divided by predetermined mechanical grinding.

By the reaction of 3, a metal amide compound having good hydrogen releasing characteristics can be obtained. In the pulverization of metal hydrides alone or in the mixed pulverization of multiple types of metal hydrides, inorganic carriers, synthetic products, plant carriers, organic solvents, etc. should be added as grinding aids. This is effective for miniaturization.

[0180] For example, the reaction between LiH and NH is represented by the following formula (19). Also, the reaction between MgH and NH

The reaction is represented by the following formula (20), and the reaction between CaH and NH is represented by the following formula (21).

twenty three

LiH + NH → LiNH + H (19)

3 2 2

MgH + 2NH → Mg (NH) + 2H †… (20)

2 3 2 2 2

CaH + 2NH → Ca (NH) + 2H G-(21)

2 3 2 2 2

[0181] As NH, liquid ammonia (NH (liq)) is suitably used. In this case, of course

3 3

The reaction temperature is kept below the boiling point of NH (about -33 ° C). To increase reaction efficiency, N

Three

Preferably, H (liq) is sufficiently stirred.

Three

[0182] On the other hand, when ammonia gas (NH (g)) is used, for example, pentane, hexane,

Three

Metal hydrides are dispersed in various organic inert solvents such as saturated aliphatic hydrocarbons such as cyclohexane, aromatic hydrocarbons such as benzene and toluene, alkyl halides such as chloroform, and ethers. By stirring this solvent in NH (g),

Three

Is preferably performed. This allows the metal hydride to react evenly. These solvents may be used alone or in combination of two or more. After the reaction, the product can be isolated by evaporating the solvent.

[0183] As shown in the above formulas (19) and (21), NH reacts chemically with 1 mole of metal hydride.

Three

It is sufficient that the number of moles correspond to the equivalent amount, but excess NH is used to accelerate the progress of the reaction.

3 is preferred.

[0184] It is also preferable to mix a metal hydride with a simple metal or alloy that reacts with NH. This

Three

Examples of such simple metals or alloys include Li, Na, K, Be, Mg, Ca and the like. For example, the reaction between Li and NH is represented by the following formula (22).

Three

2Li + 2NH → 2LiNH + H †… (22)

3 2 2 [0185] By mixing a metal hydride and a simple substance or an alloy, the synthesized metal amide compound is destabilized, and the effect of lowering the decomposition temperature of the synthesized metal amide compound is obtained. It should be noted that these metal simple substances or metal alloys are combined with NH to form metal hydrides.

Three

It is preferable to perform the reaction in the absence of high temperature because high temperature and high pressure may be required (for example, in the case of metal Mg), which is difficult to operate practically and is not preferable in terms of energy efficiency. Not something.

[0186] The reaction of the metal amide compound described above may be any of a batch system, a semi-batch system, and a continuous system. By mixing the metal amide compound thus synthesized with a predetermined metal hydride, a hydrogen storage material having excellent hydrogen releasing characteristics can be obtained.

(Example 71)

In a high-purity argon (Ar) glove box, 10 g (0.24 mol) of CaH (Aldrich, purity: 95%) is charged into a 400 cm ³ stainless steel microreactor and sealed.

2

And then cool the microreactor to below the boiling point of NH with dry ice-methanol cryogen.

Three

About 10 g (about 0.60 mol) of NH (liq) supplied to the microreactor from the cylinder

Three

And stirred continuously for 5 hours.

[0188] Thereafter, the microreactor is returned to room temperature, and the pressure of the reaction gas containing NH (g) is measured.

Three

At the same time, a certain amount was sampled, and the composition was analyzed using a gas chromatograph (GC9A, TCD detector, column: Molecular Sieve 5A, manufactured by Shimadzu Corporation). As a result of measuring the amount of hydrogen in the sampled gas, the yield of Ca (NH) (solid) was 82%.

twenty two

It was. The resulting reaction product, Ca (NH), was placed in a high purity Ar glove box in a microreactor.

twenty two

It could be easily collected from actors.

(Example 72)

6 g (0.24 mol) of MgH (Aldrich, purity 9

2

5%) and reacted with NH (liq) under the same conditions as in Example 71 above. Sampling gas

Three

The yield of Mg (NH 2) was 72% by quantitative determination of the amount of hydrogen in the solution.

twenty two

(Example 73)

In a high-purity Ar glove box, 5 g (0.12 mol) of CaH and 1.6 g (0.24 mol) of metal Li were charged into a 400 cm ³ stainless steel microreactor, and sealed.

2 The reactor was cooled with dry ice-methanol cryogen, and about 10 g (about 0.60 mol) of NH (liq) was supplied from a bomb to the microreactor, and continuously stirred for 5 hours. Micro rear

Three

The container was returned to room temperature, the pressure of the generated gas was measured, and sampling was performed. As a result of analyzing the amount of hydrogen in the sampled reaction gas by gas chromatography, the yield of a mixture of Ca (NH 2) and LiNH (a solid equivalent to Ca Li (NH 2)) was 83%.

2 2 2 0.5 0.5 2 2

(Example 74)

In a high purity Ar glove box, 3.lg (0.12mol) MgH and 1.6g (0.24mol)

2

The metal Li was weighed and reacted with NH (liq) under the same conditions as in Example 73. Sampled

Three

As a result of analyzing the amount of hydrogen in the reaction gas, a mixture of Mg (NH) and LiNH (Mg

2 2 2 0

The yield of Li (NH 3) was 75%.

. 5 2 2

(Example 75)

In a high purity Ar glove box, weigh 2 g of CaH, and

2

It was put into a container (internal volume: 250 cm ³ ). Subsequently, after evacuation of the inside of the mill container, Ar was introduced into IMPa, and a milling treatment was performed for 30 minutes at room temperature and a revolution number of 250 rpm for 30 minutes using a planetary ball mill (Fritsch, P5). Was performed. Subsequently, after evacuation of the inside of the mill container, an Ar_10vol% NH mixed gas was introduced into the mill container so that the inside of the mill container became IMPa, and the same planetary ball mill device was used at room temperature and a revolution number of 250 rpm.

Three

After milling for 2 hours at m, the gas in the mill container after milling was sampled, and then the inside of the mill was evacuated. This reaction operation using the NH mixed gas was repeated five times.

Three

The yield was calculated by measuring the amount of hydrogen in the reaction gas collected from the inside of the mill after each milling, and the final yield of Ca (NH 3) was 83%.

twenty two

(Example 76)

2 g of MgH was weighed in a high-purity Ar glove box, and 1 M

2

After pulverization in Ar of Pa, 中で ~ 10νο1. /.反 10 hours (2 hours x 5 times) with mixed gas

Three

I responded. As a result of sampling the reaction gas and quantifying the amount of hydrogen in the gas, the final yield of Mg (N H) was 75%.

twenty two

(Example 77)

In a high purity Ar glove box, 1.5 g (0.036 mol) of CaH and 0.48 g (0.072 m

2 ol) were weighed and pulverized in Ar of IMPa in the same manner as in Example 75, and then reacted with an Ar-10vol% NH mixed gas for 10 hours (2 hours × 5 times). Reactant gas

Three

And the amount of hydrogen in the gas was quantified. As a result, the reactants Ca (NH) and LiNH

The final yield of the 22 mixture (solid equivalent to Ca Li (NH)) was 84%.

0.5 2

(Example 78)

In a high-purity Ar glove box, 1.32 g (0.051 mol) of MgH and 0.68 g (0.102 mol)

2

mol) of metallic Li was weighed and pulverized in Ar gas of IMPa in the same manner as in Example 75, and then reacted with Ar to 10 vol% NH mixed gas for 10 hours (2 hours X 5 times) . Reaction gas

Three

Was sampled and the amount of hydrogen in the gas was quantified. As a result, the reactants Mg (NH) and Li

twenty two

The final yield of the mixture of NH (solid equivalent to Mg Li (NH)) was 77%.

2 0.5 2 2

[0196] Next, various types of hydrogen storage materials capable of improving hydrogen release characteristics by setting a specific specific surface area will be described. This hydrogen storage material is roughly divided into two material systems. The first material system includes a material composed of a mixture or a composite or a reaction product (mixture or the like) of a metal hydride and a metal amide compound, which is finely divided by a predetermined mechanical pulverization treatment. Further, the second material system includes a material obtained by hydrogenating a material containing a metal imide compound. The material contained in the second material system is also preferably finely divided by a predetermined mechanical pulverizing process.

First, the first material system will be described. Lithium hydride (LiH), lithium amide (LiNH), LiH

2 each combination of magnesium amide (Mg (NH)), magnesium hydride (MgH) and LiNH

2 2 2 2 combination. These materials have different hydrogen release temperatures as the basic characteristics of the materials, and also have different values of the specific surface area for lowering the hydrogen release temperature.

[0198] As described in detail later, in the case of a combination of LiH and LiNH, the BET method is used.

2

When the specific surface area exceeds 15 m ² / g, the hydrogen release temperature decreases rapidly. Conversely, by setting the specific surface area to 15 m ² Zg or more, the hydrogen release temperature can be greatly reduced. From the viewpoint of further increasing the hydrogen release rate, the specific surface area is more preferably 30 m ² / g or more. Here, the hydrogen release rate must be 3% by mass (111 & 33%) or more. [0199] In the case of a combination of LiH and Mg (NH), the hydrogen release temperature is lowered to lower the temperature.

twenty two

The specific surface area by the BET method is 7.5 m ² / g or more. From the viewpoint of further increasing the hydrogen release rate, the specific surface area is preferably 15 m ² / g or more.

[0200] The hydrogen release reaction between LiH and Mg (NH) is represented by the following equations (23) and (24).

twenty two

The

2LiH + Mg (NH) ^ Li NH + MgNH + 2H… (23)

2 2 2 2

8LiH + 3Mg (NH) ^ 4Li NH + Mg N + 8H… (24)

2 2 2 3 2 2

[0201] Considering the above formulas (23) and (24), it is found that in the above formula (23), 1 mol of Mg (NH)

2 moles of LiH with respect to 2 2 is a chemical equivalent, and the theoretical hydrogen storage rate is 5.48% by mass. On the other hand, in the above equation (24), 2.67 moles of LiH are equivalent to 1 mole of Mg (NH) in a chemical equivalent.

twenty two

The theoretical hydrogen storage rate is 6.85% by mass. Therefore, the composition of Mg (NH) and LiH

twenty two

Changing the ratio changes the predominant reactions that occur, and also changes the hydrogen storage rate.

[0202] Here, the above equation (24) is divided into the following equations (25a) and (25b).

6LiH + 3Mg (NH) 3Li NH + 3MgNH + 6H… (25a)

2 2 2 2

3MgNH + 2LiH Li NH + Mg N + 2H… (25b)

2 3 2 2

Then, the above equation (25a) is three times the coefficient of each substance in the above equation (23), and is substantially the same as the above equation (23). The above equation (25b) is a reaction between the magnesium imide (MgNH) generated in the above equation (25a) and LiH.

[0203] That is, the above equation (24) is used to convert LiH to Mg (NH) in an attempt to cause the reaction of the above equation (23).

If the stoichiometric ratio is exceeded, a part of the generated MgNH will eventually react with the excessively added LiH, and the reaction will proceed to the point where magnesium nitride (MgN) is formed.

3 2

To do.

[0204] From these facts, if the mixing ratio of LiH to 1 mol of Mg (NH) is less than 2,

twenty two

At this time, the above equation (23) predominantly progresses because the Mg (NH) force is excessive with respect to SLiH.

twenty two

Run. Also, the mixing ratio of LiH to 1 mol of Mg (NH) is the stoichiometric ratio.

twenty two

Also in this case, the above equation (23) predominantly proceeds. Li, against Mg (NH)

twenty two

Even if the mixing ratio of H is adjusted to the above equation (23), the mixed state of MgNH and LiH is actually Depending on the (dispersion state), etc., the generated MgNH and LiH react with each other, and the reaction of the above formula (24) proceeds, and it is possible that some Mg (NH) may remain without reacting. Conceivable.

twenty two

[0205] On the other hand, when the mixing ratio of LiH to 1 mol of Mg (NH) is more than 2 and less than 2.67

twenty two

According to the above equation (23), LiH is excessive in relation to Mg (NH).

twenty two

Looking at it, there is a shortage of LiH relative to Mg (NH). In this case, the mixing ratio is close to 2

twenty two

In this case, the above equation (23) predominantly proceeds, and part of the generated MgNH is converted to MgN.

Equation (24) becomes dominant as the mixing ratio increases to 2.67. If the mixing ratio of LiH to 1 mol of Mg (NH) is 2.67 stoichiometric

twenty two

When the mixing ratio is greater than 2.67, equation (24) predominates.

[0206] Which of the above equation (23) and the above equation (24) is mainly used depends on, for example, the hydrogen storage rate and the cycle characteristics of the reaction for absorbing hydrogen again in the product after releasing hydrogen. In other words, the determination can be made in consideration of the equations (23) and (24), and the like. In addition, either LiH or Mg (NH)

twenty two

Thus, it is considered that the reaction probability of the other substance can be increased and hydrogen release can be promoted. However, if one substance is too much, there is a problem that the hydrogen storage rate with respect to the total amount is reduced.

[0207] Therefore, it is preferable to determine the amounts of LiH and Mg (NH 2) in consideration of the hydrogen storage rate, the utilization rate of the reactant, the cycle characteristics of the hydrogen absorption / desorption reaction, and the like. In particular

twenty two

The mixing ratio of LiH to 1 mol of Mg (NH) should be 1.5 mol or more and 4 mol or less.

twenty two

It is more preferable that the hydrogen storage rate be maintained higher than the other range by setting the molar ratio to 2.5 mol or more and 3.5 mol or less so that the above-mentioned formula (24) proceeds.

[0208] In the case of a combination of MgH and LiNH, in order to lower the hydrogen release temperature to a low temperature,

twenty two

The specific surface area by the BET method is 7.5 m ² Zg or more. From the viewpoint of further increasing the hydrogen release rate, the specific surface area is preferably 15 m ² / g or more.

[0209] The reaction between MgH and LiNH is represented by the following formulas (26) and (27).

twenty two

MgH + 2LiNH ^ Li NH + MgNH + 2H---(26)

2 2 2 2

3MgH + 4LiNH ^ Mg N + 2Li NH + 6H---(27)

2 2 3 2 2 2

[0210] Considering the above formulas (26) and (27), in the above formula (26), one mole of LiNH

2 Thus, 0.5 mole of MgH is a chemical equivalent, and the theoretical hydrogen storage rate is 5.48% by mass.

2 On the other hand, in the above formula (27), 0.75 mol of LiH is a chemical equivalent to 1 mol of LiNH,

2

The theoretical hydrogen storage rate is 7.08% by mass. Therefore, the composition ratio of MgH and LiNH changes.

twenty two

Changes dominantly change the reaction, and also change the hydrogen storage rate

[0211] In other words, in the case of the combination of MgH and LiNH, the combination of LiH and Mg (NH)

As in the case of the combination, it is preferable to determine the respective amounts of MgH and LiNH in consideration of the hydrogen storage rate, the utilization rate of the reactants, the vital properties of the hydrogen absorption / desorption reaction, and the like. Specifically

twenty two

It is preferable to use an excess of MgH, so that the mixing ratio of LiH to 1 mol of Mg (NH) is

2 2 2

It is preferable that the amount be 0.5 mol or more and 2 mol or less. Further, as the above equation (27) progresses, the hydrogen storage rate can be maintained higher than the other range by adjusting the amount to 0.5 mol or more and 1 mol or less.

Next, the second material system will be described. Materials obtained by hydrogenating a material containing a metal imide compound include materials obtained by hydrogenating lithium imide (Li NH), Mg N and Li NH

And a material obtained by hydrogenating a mixture of 232 and the like. Here, "hydrogenation of a substance" means that the substance changes into a state that has taken in hydrogen by reacting the substance with hydrogen. For example, hydrogenated Li NH can react Li NH with hydrogen.

twenty two

And its structure is not clear, but changes to LiNH or ammonia (NH)

twenty three

It is a material that reacts with hydrogen to capture hydrogen in some way, and when heated to a predetermined temperature, the captured hydrogen is released and returns to the original Li NH.

2

[0213] The hydrogenated Li NH has a specific surface determined by the BET method to lower the hydrogen release temperature.

2

The product should be 10m ² Zg or more. From the viewpoint of further increasing the hydrogen release rate, the specific surface area is preferably 15 m ² / g or more.

[0214] As Li NH, imidation by reacting lithium nitride (Li N) with hydrogen or Li

twenty three

Those synthesized by thermal decomposition of NH are preferably used. This is the same as LiH

2

When LiNH is synthesized by reacting with LiNH, this reaction must be a solid-phase reaction.

twenty two

In order to make LiH and LiNH contact homogeneously in a micro state, large mechanical energy

2

In this case, it is difficult to perform such treatment. Li NH with a large surface area can be synthesized and hydrogenation can be promoted.

2

It is.

[0215] Materials obtained by hydrogenating a mixture of MgN and LiNH have a low hydrogen release temperature.

3 2 2

Therefore, the specific surface area by the BET method is set to 5 m ² Zg or more. From the viewpoint of further increasing the hydrogen release rate, the specific surface area is preferably 10 m ² Zg or more.

[0216] The various hydrogen storage materials described above preferably further include a catalyst for enhancing the ability to absorb and release hydrogen. Examples of the catalyst include B, C, Mn, Fe, Co, Ni, Pt, Pd, Rh, Li, Na, Mg, K, Ir, Nd, Nb, La, Ca, V, Ti, Cr, Cu, Zn, Al, Si, Ru, 〇s, Mo, W, Ta, Zr, In, Hf, Ag One or more metals selected from the group consisting of a metal, a compound thereof, an alloy thereof, and a hydrogen storage alloy are preferably used.

[0217] As a method of supporting such a catalyst on the hydrogen storage material, a method of adding the raw material powder of various hydrogen storage materials to the raw material powder and pulverizing and mixing the raw material powder and then adding the raw material powder after the pulverization and mixing, and further mixing the raw material powder are used. Pulverization and mixing).

[0218] For example, a hydrogen storage material composed of a mixture of a metal hydride and a metal amide compound is prepared by simultaneously grinding and mixing a predetermined amount of a metal hydride powder, a metal amide compound powder, and a catalyst, or The hydride powder and the metal amide compound powder can be manufactured by pulverizing and mixing, adding a catalyst to the obtained object to be treated, and mixing. Then, the pulverizing and mixing conditions at that time are set so as to have a predetermined specific surface area after the pulverizing and mixing treatment.

[0219] Further, for example, a hydrogen storage material composed of hydrogenated Li NH is first combined with LiNH powder.

22 2 Mechanically pulverized and mixed with a catalyst that enhances the ability to absorb and release hydrogen, and then thermally decomposes the processed material obtained in the previous pulverization process to convert LiNH contained in this processed material into LiNH. Strange

It can be produced by hydrogenating the obtained Li NH 2.

2

[0220] Alternatively, the LiNH powder is first mechanically pulverized and then obtained by the previous pulverization process.

2

A catalyst to enhance hydrogen absorption / desorption is added to the obtained

2

The object to be treated supported on NH powder and then the catalyst is thermally decomposed and contained in the object to be treated.

2

The resulting LiNH may be converted to LiNH, and then the resulting LiNH may be hydrogenated.

2 2 2

In the manufacturing process of hydrogen storage material consisting of hydrogenated Li NH,

twenty two Is set so as to have a predetermined specific surface area after the pulverization treatment.

[0221] The material obtained by hydrogenating a mixture of MgN and LiNH is, for example, LiNH powder and MgN

It can be manufactured by pulverizing and mixing 3 2 2 2 3 2 and then performing imidation and hydrogenation. After pulverizing the LiNH powder, it is imidized and the resulting LiNH and MgH are powdered.

It can also be produced by a method involving crushing and mixing, followed by hydrogenation.

[0222] The mechanical pulverization of the hydrogen storage material belonging to each of the above-mentioned material systems may be performed, for example, by subjecting the raw material powder to a ball mill, a roller mill, an inner / outer cylinder rotary type mill, an attritor, an inner piece type mill, an airflow type mill, or the like. Can be performed using various known pulverizing means.

[0223] (Preparation of LiH + LiNH Sample)

2

LiH, LiNH and titanium trichloride (TiCl) (all manufactured by Aldrich, purity 95%)

twenty three

In a molar ratio of 1: 1: 0.02, and weighed in a high-purity argon (Ar) glove box so that the total amount thereof becomes 1.3 g, and a high-chromium steel mill container with a valve (250 cm ³ ). Subsequently, after evacuation of the inside of the mill container, high-purity Ar was introduced into the mill container so that the inside of the mill container became IMPa, and room temperature was reduced using a planetary ball mill (Fritsch, P5). Milling was performed at 60-250i "pm for 3-360 minutes to produce multiple samples with different specific surface areas. After evacuating the inside of the mill container and filling it with Ar, the mill container was placed in a high-purity Ar glove box. Opened and removed sample.

[0224] (Preparation of LiH + Mg (NH) based sample)

twenty two

(a) Preparation of Mg (NH)

twenty two

2 g of MgH (made by ADAMAX, 95% purity, MgH) in a high-purity Ar glove box

twenty two

After being charged into a high chrome steel mill container (internal volume: 250 cm ³ ), the inside of the mill container is evacuated, and then, in order to cause the reaction of the following formula (28), 1 mol of MgH 2 moles

2

After introducing ammonia gas (NH (g)) into the mill container as described above,

Three

This was sealed and then milled at room temperature and in an air atmosphere at a rotation speed of 250 rpm using a planetary ball mill for a predetermined time. After that, the amount of hydrogen in the reaction gas was measured from the mill container, and the XRD measurement of the pulverized product was performed to confirm the production of Mg (NH).

twenty two

I accepted.

MgH + 2NH (g) → Mg (NH) + 2H (g) ... (28)

2 3 2 2 2 [0225] (b) Mixed grinding of Mg (NH) and LiH

twenty two

The molar ratio of LiH and Mg (NH) produced as described above was 8: 3, and their total amount was 1

twenty two

It was weighed to 3 g in a high-purity Ar glove box and charged into a high-chromium steel mill container with a valve (250 cm ³ ). Subsequently, after evacuation of the inside of the mill container, high-purity Ar was introduced into the mill container so that the mill container internal pressure became SlMPa, and milling was performed using a planetary ball mill at room temperature and 250 rpm for 3 360 minutes. Then, several samples having different specific surface areas were prepared. Next, after the inside of the mill container was evacuated and filled with Ar, the mill container was opened in a high-purity Ar glove bot- tom, and a sample was taken out.

(Preparation of MgH + LiNH System Sample)

twenty two

MgH and LiNH are in a molar ratio of 3: 4, and high-purity Ar such that their total amount is 1.3 g.

twenty two

The sample was weighed in a glove box and placed in a high-chromium steel mill container with a valve (250 cm ³ ). Next, after evacuating the inside of the mill container, high-purity Ar was introduced into the mill container so that the inside of the mill container became IMPa, and the planetary ball mill was used at room temperature and 250i "pm for 3 to 360 minutes. After evacuating the inside of the mill container to fill it with Ar, the mill container was opened in a high-purity Ar glove box, and the samples were taken out. Was.

[0227] (Production of Li NH and its hydrogenation)

2

LiNH to TiCl at a molar ratio of 1: 0.01, and high purity so that their total amount is 1.3g

twenty three

The sample was weighed in an Ar glove box and placed in a high-chromium steel mill container with a valve (250 cm ³ ). Then, after evacuating the inside of the mill container, high-purity Ar was introduced into the mill container so that the inside of the mill container became IMPa, and the planetary ball mill was used at room temperature for 3 to 720 minutes at 250 rpm. Milling was performed to produce a plurality of samples having different specific surface areas. Subsequently, after the inside of the mill container was evacuated and filled with Ar, the mill container was opened in a high-purity Ar glove box, and each sample was transferred to a stainless steel reaction container (50 cm ³ ). The inside of the stainless steel container was evacuated and heat-treated at 350 ° C for 6 hours to thermally decompose LiNH.

2

Li NH was synthesized. Further treatment of the obtained Li NH in hydrogen at 3MPa, 180 ° C for 12 hours

twenty two

And hydrogenated.

[0228] (Preparation and hydrogenation of Mg N + Li NH system sample)

3 2 2 Li NH prepared as above and Mg N (Aldrich, purity 95%) in molar ratio

2 3 2

The ratio was set to 4: 1, and they were weighed in a high-purity Ar glove box so that the total amount thereof was 1.3 g, and was put into a high-chromium steel mill container with a valve (250 cm ³ ). Subsequently, after evacuating the inside of the mill container, high-purity Ar was introduced into the mill container so that the inside of the mill container became IMPa, and the planetary ball mill device was used at room temperature and 250 室温 ρπι for 3 360 minutes. Milling was performed to produce a plurality of samples with different specific surface areas. Next, after the inside of the mill container was evacuated and filled with Ar, the mill container was opened in a high-purity Ar glove box, and a sample was taken out. The sample after milling in a high-purity glove box was transferred to a stainless-steel reaction vessel (50 cm ³ ), evacuated, then introduced with high-purity hydrogen, and kept at 220 ° C, 3 MPa, and 12 hours for hydrogenation. Was.

[0229] (Method for measuring BET specific surface area)

The BET specific surface area of each sample prepared as described above was measured using a multipoint BET measurement (ASAP2400, manufactured by Micromeritics) with nitrogen gas.

[0230] (Measurement of DTA endothermic peak temperature due to hydrogen release)

10 mg of each sample prepared as described above was weighed, and the temperature was raised at a rate of 5 ° C / min. Using a TG / DTA apparatus (TG / DTA300, manufactured by Seiko Instruments Inc.) installed in high-purity Ar. The DTA curve was measured. Then, the endothermic peak temperature due to hydrogen release was measured from the obtained DTA curve, and the temperature was taken as the hydrogen release temperature.

[0231] (Measurement of hydrogen release amount)

From the TG / DTA apparatus, the mass reduction rate between 30 ° C and 250 ° C of the TG curve obtained from the TG / DTA measurement from room temperature to 400 ° C was determined from the TG curve, and this was defined as the hydrogen release rate.

[0232] (Test results of LiH + LiNH-based sample)

2

Figure 14 shows the DTA curves of four samples A to D selected from the prepared samples. Sample A was crushed at 250 rpm for 3 minutes, Sample B was crushed at 250 rpm for 10 minutes, Sample C was crushed at 250 rpm for 30 minutes, and Sample D was crushed at 250 rpm for 120 minutes. The specific surface areas of Samples A to D are 11.6 m ² Zg, 19.9 m ² / g, 34.8 m ² / g, and 40.5 m ² / g. As shown in Fig. 14, as the grinding time increases, grinding progresses. As the specific surface area increases, the hydrogen release temperature (the temperature of the valley position of the endothermic reaction indicated by the black dot in FIG. 14) shifts to a lower temperature side as the specific surface area increases. Sample A is outside the scope of the present invention, and Samples BD are within the scope of the present invention.

[0233] Fig. 15 shows a graph showing the relationship between the specific surface area of each sample, the hydrogen release temperature, and the hydrogen release rate. According to Fig. 15, the BET specific surface area of LiH + LiNH based hydrogen storage material is 1

2

Compared to the case of less than 15m ² Zg at 5m ² / g or more, it is confirmed that the temperature of hydrogen release drops sharply from around 320 ° C to 270 ° C or less, and the hydrogen release rate becomes 2% by mass or more. Was done. In addition, the hydrogen release temperature was 260 ° C or less when the BET specific surface area was 30 m ² Zg or more. It was confirmed that the temperature was further lowered and the hydrogen release rate exceeded 3% by mass.

[0234] (Test results of LiH + Mg (NH) based sample)

twenty two

Figure 16 shows a graph showing the relationship between the specific surface area of each sample and the hydrogen release temperature and hydrogen release rate. LiH + Mg (NH 2) based hydrogen storage material has a BET specific surface area of 7.5 m ²

twenty two

/ In the case of more than g 7. Compared to the case of less than 5 m ² / g, which a hydrogen release temperature exceeds the 230 ° C is confirmed to be low temperature below 230 ° C, also the hydrogen release rate 2 Mass% or more. Further, the hydrogen release temperature was 220 ° C. or less when the BET specific surface area was 15 m ² / g or more, and it was confirmed that the temperature was further lowered and the hydrogen release rate exceeded 3% by mass.

[0235] (Test results of MgH + ΠΝΗ-based samples)

twenty two

Figure 17 shows a graph showing the relationship between the specific surface area of each sample and the hydrogen release temperature and hydrogen release rate. In the case of MgH + ΠΝΗ-based samples, if the BET specific surface area is 7.5 m ² / g or more,

twenty two

In comparison with the case of less than 7.5 m ² / g, it was confirmed that the temperature at which the hydrogen release temperature exceeded 230 ° C decreased to 230 ° C or lower, and the hydrogen release rate also increased to 2% by mass. That's all. In addition, the hydrogen release temperature was 220 ° C or less when the BET specific surface area was 15 m ² Zg or more, and it was confirmed that the temperature was further lowered and the hydrogen release rate exceeded 3% by mass.

[0236] (Test results of hydrogenated Li NH)

2

Figure 18 shows a graph showing the relationship between the specific surface area of each sample and the hydrogen release temperature and hydrogen release rate. Hydrogenated Li NH has a BET specific surface area of 10m

In case of 2 ² Zg or more

Compared with the case of less than 10 m ² / g, it was confirmed that the temperature of hydrogen release decreased from around 300 ° C to 290 ° C or less, and the hydrogen release rate also became 2% by mass or more. The hydrogen release temperature is When the BET specific surface area was 15 m ² / g or more, the temperature was 280 ° C or less. It was confirmed that the temperature was further lowered and the hydrogen release rate exceeded 3% by mass.

[0237] (Test results of hydrogenated MgN + LiNH-based sample)

3 2 2

Figure 19 shows a graph showing the relationship between the specific surface area of each sample, the hydrogen release temperature and the hydrogen release rate. In hydrogen storage materials obtained by hydrogenating a crushed mixture of MgN and LiNH, the BE

3 2 2

It was confirmed that when the specific surface area was 5 m ² / g or more, the hydrogen release temperature exceeded 240 ° C compared to the case of less than 5 m ² / g, but the temperature dropped to 240 ° C or less. The release rate was 2% by mass or more. The hydrogen release temperature was 230 ° C or less when the BET specific surface area was 10 m ² Zg or more, and it was confirmed that the temperature was further lowered and the hydrogen release rate exceeded 3% by mass.

[0238] Next, various types of hydrogen storage materials that can enhance the hydrogen release characteristics by adding a catalyst having a nano-order size will be described. This hydrogen storage material is roughly divided into two material systems, and the first material system includes a mixture or a composite containing a metal hydride, a metal amide compound, and a catalyst that enhances the ability to absorb and release hydrogen. A hydrogen storage material having a compound or a reactant (such as a mixture) belongs to the second material system, and a hydrogenated hydrogen storage material containing a metal imide compound and a nanoparticle catalyst belongs to the second material system. Here, a catalyst composed of nanoparticles (hereinafter referred to as “nanoparticle catalyst”) is used. By loading the nanoparticle catalyst on the hydrogen storage material, the hydrogen release temperature can be lowered.

[0239] Generally, nanoparticles refer to particles having a particle size substantially smaller than the submicron order. However, the nanoparticle catalyst according to the present invention has a predetermined hydrogen storage according to this general definition. When added to a material, the peak temperature of the hydrogen release spectrum (hereinafter referred to as “hydrogen release temperature”) is higher than when a microparticle catalyst having the same composition as the nanoparticle catalyst is added to the hydrogen storage material at the same addition rate. It refers to one that shows the effect of lowering by 10 ° C or more. The term “microparticle catalyst” refers to particles having an average particle diameter of 0.5 111 or more and 30 111 or less, or particles in which 90% or more of the particles are in the range of 0.1 μm or more and 100 μm or less. or, the BET specific surface area is intended to refer to 1. 0 m ² Zg super 20 m ² Zg particles less than.

[0240] First, the first material force will be described. Any of lithium (Li), magnesium (Mg), and calcium (Ca) is preferably used as the metal species of the metal hydride and the metal amide compound. From the viewpoint of lowering the hydrogen release temperature, it is preferable to use two or more metal species of these metal hydrides and metal amide compounds.

[0241] Lithium hydride (LiH) and magnesium amide (Mg (N

H))). The hydrogen release reaction between LiH and Mg (NH) was described earlier.

2 2 2 2

As described above, it is expressed by the above equation (23) and the above equation (24). LiH and Mg (NH) amounts

As described above, 22 is preferably determined in consideration of the hydrogen storage rate, the utilization rate of the reactants, the cycle characteristics of the hydrogen absorption / desorption reaction, and the like. Specifically, for 1 mole of Mg (NH)

twenty two

It is preferable that the mixing ratio of LiH be 2 mol or more and 5 mol or less. Furthermore, as the above equation (24) progresses, by setting the mixing ratio of 2.5 mol or more to 3.5 mol or less, the hydrogen storage rate can be increased. Can be maintained higher than the other ranges.

[0242] Another preferred combination includes magnesium hydride (MgH 2) and lithium amide (Li

2

NH 3). The reaction between MgH and LiNH, as explained earlier,

2 2 2

, (26) and (27). MgH and LiNH are also stored in hydrogen.

twenty two

It is preferable to determine in consideration of the storage rate, the utilization rate of the reactants, the cycle characteristics of the hydrogen absorption / release reaction, and the like. Specifically, excess MgH is preferred for 1 mole of LiNH

It is preferable that the mixing ratio of MgH is 0.5 mol or more and 3 mol or less. Furthermore, even more

2

By setting the amount to 0.5 mol or more and 1 mol or less so that the above equation (27) proceeds, the hydrogen storage rate can be maintained higher than the other range.

[0243] The loading amount of the nanoparticle catalyst is preferably 0.1% by mass or more and 20% by mass or less based on the total amount of the mixture of the metal hydride and the metal amide compound. If the catalyst addition ratio is less than 0.1% by mass, the effect as a catalyst is not substantially obtained, and if it exceeds 20% by mass, the hydrogen absorption / desorption reaction is adversely inhibited, and the hydrogen release ratio with respect to the total amount decreases.

[02441] As a method for producing such a hydrogen storage material belonging to the first material system, any of the following four methods can be used. In the first production method, a nanoparticle catalyst is added to a metal hydride and a metal amide compound, and the mixture is placed under an inert gas atmosphere or a hydrogen atmosphere, or a mixed gas atmosphere of an inert gas and hydrogen (hereinafter, referred to as a mixed gas atmosphere). This is a method of mixing and miniaturizing by mechanical pulverization treatment.

[0245] In the second production method, a metal hydride and a metal amide compound are mixed under an inert gas atmosphere or the like. In this method, the particles are mixed and refined by mechanical pulverization, and a nanoparticle catalyst is added to the object to be treated thus obtained, so that the object to be treated carries the nanoparticle catalyst.

[0246] In the third production method, a nanoparticle catalyst is added to one or the other of the metal hydride and the metal amide compound, and the mixture is refined and mechanically pulverized under an inert gas atmosphere or the like, and thus, This is a method of mixing and pulverizing the obtained object and the other under an inert gas atmosphere or the like.

[0247] In the fourth production method, a nanoparticle catalyst is added to each of the metal hydride and the metal amide compound, and each of the metal hydride and the metal amide compound is subjected to mechanical pulverization treatment under an inert gas atmosphere or the like. This is a method of mixing and pulverizing, and mixing and pulverizing the objects to be processed thus obtained under an inert gas atmosphere or the like. In the latter stage of the mixing and pulverizing process, the pulverizing does not substantially occur, or the mixing and pulverizing process under the conditions may be performed.

[0248] Next, the second material system will be described. The hydrogen storage material belonging to the second material system includes a metal imide compound and a nanoparticle catalyst, and is hydrogenated. The definition of “hydrogenation of a substance” is as described above.

[0249] As a hydrogen storage material belonging to the second material system, hydrogenated lithium imide (LiN

2

H). According to the definition of hydrogenation, hydrogenated Li NH can be converted from Li NH to water.

It is obtained by reaction with 22 element, its structure is not clear, but LiNH and ammonia (

2

Reacts with hydrogen that does not change to NH 3) to take in some form of hydrogen and later

Three

When heated to a certain temperature, the captured hydrogen is released and returns to the original Li NH

2

[0250] In the hydrogenation of Li NH, Li NH is kept under a hydrogen atmosphere at a predetermined pressure and a predetermined temperature for a predetermined time.

twenty two

It can be done by holding. For the same reason as in the case of the first material system, the amount of the supported nanoparticle catalyst is preferably 0.1% by mass or more and 20% by mass or less of the total amount of the metal imide compound.

[0251] Li NH is the reaction of lithium nitride (Li N) with hydrogen or the thermal decomposition of LiNH.

2 3 2

It is preferable to synthesize by the following. This is for the following reasons. That is, Li NH is Li

2

It can also be synthesized by mixing and reacting H and LiNH.

2

In order to make LiH and LiNH contact homogeneously in a micro state,

2 There is a problem that mechanical energy is required. On the other hand, thermal decomposition of Li NH

2

, The specific surface area of Li NH increases in the process, and hydrogenation proceeds easily.

2

There is a merit of becoming.

[0252] The second material system includes a metal imide compound, a metal nitride, and a nanoparticle catalyst, and also includes a hydrogenated hydrogen storage material. Specific examples include Li NH and magnesium nitride.

2

Including hydrogen (Mg N) and nanoparticle catalyst, and hydrogenated one. This material

3 2

In this case also, the supported amount of the nanoparticle catalyst is 0.1 mass of the total amount of Li NH and Mg N.

2 3 2

% To 20% by mass or less.

[0253] Examples of the nanoparticle catalyst contained in the various hydrogen storage materials described above include B, C, Mn, Fe, Co, Ni, Pt, Pd, Rh, Li, Na, Mg, K, Ir, Nd, and Nb. , La, Ca, V, Ti, Cr, Cu, Zn, Al, Si, Ru, 〇s, Mo, W, Ta, Zr, In, Hf, Ag Alternatively, a compound or an alloy thereof, or a hydrogen storage alloy is preferably used. As the form of the nanoparticle catalyst, nanometal particles, nanometal oxide particles, and nanometal chlorides are suitably used. More preferred examples of nanoparticle catalysts include TiO (

2-se type) nanoparticles and Ti nanoparticles.

[0254] As a method for producing such a hydrogen storage material belonging to the second material system, the following four methods are preferably used. The first production method is a method in which a nanoparticle catalyst is added to a metal imide compound, mixed and refined by a predetermined mechanical pulverization treatment in an inert gas atmosphere or the like, and then hydrogenated.

[0255] In the second production method, a metal nitride and a metal imide compound are mixed and refined by a predetermined mechanical pulverizing treatment under an inert gas atmosphere or the like, and the thus-obtained object is treated with a nanoparticle catalyst. This is a method in which a nanoparticle catalyst is supported on an object to be treated, followed by hydrogenation.

[0256] In the third production method, a nanoparticle catalyst is added to either the metal nitride or the metal imide compound, and the mixture is pulverized and pulverized by mechanical pulverization in an inert gas atmosphere or the like. This is a method in which the obtained object and the other are mixed and pulverized in an inert gas atmosphere or the like, and then hydrogenated.

[0257] In the fourth production method, a nanoparticle catalyst is added to each of a metal nitride and a metal imide compound. The metal nitride and the metal imide compound are mixed and refined by mechanical pulverization in an inert gas atmosphere or the like for each metal nitride and metal imide compound, and the objects to be treated thus obtained are mixed and pulverized in an inert gas atmosphere or the like. , Followed by hydrogenation. In the latter stage of the mixing and pulverizing treatment, substantially no pulverizing occurs, and the mixing and pulverizing treatment may be performed under conditions.

[0258] In the mechanical pulverization of the hydrogen storage material belonging to these material systems, the raw material powder is processed by, for example, a ball mill, a roller mill, an inner / outer cylinder rotary mill, an attritor, an inner piece mill, an airflow mill, or the like. Can be performed using various known pulverizing means. In such a mechanical pulverization treatment, addition of an inorganic carrier, a synthetic product carrier, a plant carrier, an organic solvent, or the like as a pulverization aid is effective in efficiently refining the raw material powder.

(Preparation of LiH + LiNH Samples (Examples 81 and 82, Comparative Examples 81 and 82))

2

As shown in Table 8, LiH and LiNH (both manufactured by Aldrich, purity 95%)

2

The medium was weighed in a high-purity argon (Ar) glove box such that the molar ratio was 1: 1: 0.02 and the total amount was 1.3 g. 250cm ³ ). Subsequently, after evacuation of the inside of the mill container, high-purity Ar was introduced into the mill container so that the inside of the mill container became IMPa, and room temperature was reduced using a planetary ball mill (Fritsch, P5). Milling treatment was performed at 250 rpm for 120 minutes. After the inside of the mill container was evacuated and filled with Ar, the mill container was opened in a high-purity Ar glove box, and a sample was taken out.

[0260] The TiO nanoparticles had a purity of 82.8% and a BET specific surface area of Millennium Chemicals.

2

Force 29.8m ² / g, TiO microparticles made by Aldrich, 99.9% purity and BET ratio

2

The surface area is 18m ² / g, the average particle size of the Ti nanoparticles is lnm, and the Ti microparticles have a purity of 99.9% and a particle size of 10-100 / im, manufactured by Rare Metals.

[0261] [Table 8] Mixing (molar ratio)

Catalyst,

Peak temperature

LiH LiNH ₂ヽ

Ti micro Ti0 ₂ nano Ti0 ₂ micro

Particles particles particles

Example 81 1 1 0.02 216 Comparative Example 81 1 1 0.02 247 Example 82 1 1 0.02 234

h- Comparative example 82 1 1 0.02 247

(Preparation of Li NH-based Samples (Examples 83 and 84, Comparative Examples 83 and 84))

As shown in Table 9, the raw material LiNH and the various catalysts were mixed at a molar ratio of 1: 0.01 so that the final molar ratio of LiNH and the various catalysts was 1: 0.02. It was weighed in a high-purity Ar glove box so as to have a weight of 1.3 g, and charged into a mill container (250 cm ³ ) made of high chromium steel with a valve. Subsequently, after evacuating the inside of the mill container, high-purity Ar was introduced into the mill container so that the mill container internal force became SlMPa, and milling was performed at room temperature and 250 rpm for 120 minutes using a planetary ball mill. went. Subsequently, after the inside of the mill container was evacuated and filled with Ar, the mill container was opened in a high-purity Ar glove box, and a sample was taken out and transferred to a stainless steel reaction container (50 cm ³ ). After evacuation of the reactor, LiNH was thermally decomposed by heat treatment at 350 ° C for 6 hours to synthesize LiNH supporting various catalysts. Further, the obtained Li NH was treated in hydrogen at 3 MPa and 180 ° C. for 12 hours to be hydrogenated.

[0263] [Table 9]

Mixing (molar ratio)

Catalyst Hydrogen release

Peak temperature

Li ₂ NH Ti0 ₂ micro

Particles

Example 83 1 0.02 243

Comparative Example 83 1 0.02 265

Example 84 1 0.02 258

Comparative Example 84 1 0.02 267

Ό-! Sub:

Subordinate

[0264] (Preparation of LiH + Mg (NH) based sample (Example 85 86, Comparative Examples 85 and 86))

twenty two

First, MgH (manufactured by ADAMAX, purity 95%) was reacted with ammonia to synthesize Mg (NH 2). Next, as shown in Table 10, Mg (NH) synthesized with LiH and various catalysts were used.

2

The mixture was weighed in a high-purity Ar glove box so as to have a molar ratio of 8: 3: 0.11 and a total amount of 1.3 g, and charged into a high-chromium steel mill container with a valve (250 cm ³ ). Subsequently, after evacuation of the inside of the mill container, high-purity Ar was introduced into the mill container so that the inside of the mill container became IMPa, and milling was performed at room temperature and 250 rpm for a predetermined time using a planetary ball mill. did. After the inside of the mill container was evacuated and filled with Ar, the mill container was opened in a high-purity Ar glove box, and a sample was taken out.

[Table 10]

Mixing (molar ratio)

Hydrogen release catalyst

Peak temperature

LiH Mg (NH ₂ ) ₂ Ti micro Ti0 ₂ nano Ti0 ₂ micro (° c) Particle Particle Particle

Example 85 8 3 0.11 190 Comparative Example 85 8 3 0.11 212 Example 86 8 3 0.11 197 Comparative Example 86 8 3 0.11 207 (Preparation of LiNH + MgH-based Samples (Examples 87 and 88, Comparative Examples 87 and 88))

twenty two

As shown in Table 11, LiNH, MgH and various catalysts were mixed at a molar ratio of 4: 3: 0

twenty two

It was weighed in a high-purity Ar glove box to a weighing of 1.3 g and placed in a mill container with a valve made of high chromium steel (250 cm ^d ). Then, after evacuating the inside of the mill container, high-purity Ar was introduced into the mill container so that the inside of the mill container became IMPa, and milled at room temperature and 250 rpm for a predetermined time using a planetary ball mill. . After the inside of the mill container was evacuated and filled with Ar, the mill container was opened in a high-purity Ar glove box, and a sample was taken out.

[0267] [Table 11]

[0268] (Preparation of Li NH + Mg N based sample (Examples 89 and 90, Comparative Examples 8 and 90))

2 3 2

As shown in Table 12, Li NH and Mg N synthesized by the above method (Aldrich, purity

2 3 2

(95%) in a high-purity Ar glove box with a molar ratio of 4: 1: 0.05 and a total amount of 1.3 g in a high-chromium steel mill with a valve. It was poured into a container (250 cm ³ ). Subsequently, after evacuating the inside of the mill container, high-purity Ar was introduced into the mill container so that the inside of the mill container became IMPa, and was milled at room temperature and 250 rpm for a predetermined time using a planetary ball mill. . After the inside of the mill container was evacuated and filled with Ar, the mill container was opened in a high-purity Ar glove box, and a sample was taken out. Further, the object to be treated was hydrogenated by treating it in hydrogen at 3 MPa and 220 ° C. for 12 hours.

[0269] [Table 12] Mixing (molar ratio)

Catalyst Hydrogen release Peak temperature

Li ₂ NH Mg ₃ N ₂ Ti micro Ti0 ₂ micro (.c) Particle Particle

Example 89 4 1 0.05 221 Comparative example 89 4 1 0.05 233 Example 90 4 1 0.05 225 Comparative example 90 4 1 0.05 236

[0270] (Sample evaluation)

The measurement of the BET specific surface area was performed by multipoint BET measurement (Micromeritics, ASAP2400) using nitrogen gas. Further, installed in a high purity Ar glow O in Bed Box TG-屮¹ ^

Using a MASS device (thermogravimetry / mass spectrometer), the temperature was raised at a rate of 5 ° C / min, and the hydrogen emission spectrum was measured. The peak temperature was defined as the hydrogen release temperature.

[0271] (Test results)

FIG. 20 is a graph showing the hydrogen release spectra of Example 81 and Comparative Example 81, and FIG. 21 is a graph showing the hydrogen release spectra of Example 82 and Comparative Example 82. Table 8 also shows the hydrogen release temperatures of Examples 81 and 82 and Comparative Examples 81 and 82. 20 and 21 and Table 8 show that the use of the nanoparticle catalyst narrows the temperature range in which the hydrogen release reaction occurs and shifts the hydrogen release temperature to a lower temperature. Thus, for example, when comparing Example 81 and Comparative Example 81 at 250 ° C., the total amount of hydrogen released up to 250 ° C. is greater in Example 81 than in Comparative Example 81. Ru same this and force ^s words also Comparative Example 82 Example 82.

[0272] The hydrogen release temperatures of Examples 83-90 and Comparative Examples 83-90 are also shown in Table 9 and Table 12. These surface forces also confirmed that the hydrogen release temperature shifted to the lower temperature side when the nanoparticle catalyst was used.

[0273] Next, a description will be given of a hydrogen storage material that releases two or more kinds of predetermined catalysts for releasing hydrogen by a reaction between a metal hydride and a metal amide and promoting the hydrogen release reaction. Do [0274] Fig. 22 is a flowchart showing a process for producing a hydrogen storage material having two or more types of catalysts supported thereon. As shown in FIG. 22, first, a metal hydride which is one of the components constituting the hydrogen storage material, a first catalyst for promoting the hydrogen release reaction of the hydrogen storage material, and A predetermined amount of each of the inorganic substance and the inorganic substance is weighed, and these are crushed and mixed under predetermined conditions (first step). The processing atmosphere in the first step is preferably a hydrogen atmosphere.

[0275] Subsequently, a metal amide, which is one of the components constituting the hydrogen storage material, and a second catalyst were added to the object to be treated obtained in the first step, and further, under predetermined conditions, Pulverize and mix (2nd step). The processing atmosphere in the second step is also preferably a hydrogen atmosphere. In the second step, the timing of adding the metal amide, which is one of the components constituting the hydrogen storage material, and the second catalyst to the object to be treated obtained in the first step may be shifted. . In other words, the object to be treated obtained in the first step may be first added with only the second catalyst, pulverized and mixed, and then metal amide may be added and further pulverized and mixed.

[0276] In the hydrogen storage material thus obtained, the easily crushable inorganic substance added in the first step is different from the first catalyst added in the first step and the second catalyst added in the second step. It functions as a separator for separating the catalyst. Thus, the direct contact between the first and second catalysts is suppressed, so that the direct interaction between them is suppressed. As a result, each catalyst effectively acts on the hydrogen release reaction in the hydrogen storage material, so that the hydrogen release rate can be increased, and the hydrogen release start temperature can be shifted to a lower temperature side.

[0277] In FIG. 22, in the first step, the first catalyst and the easily crushable inorganic substance are added to the metal hydride and crushed and mixed, and in the second step, the metal amide and the second catalyst are further added and crushed. The mixing is not limited to this. As shown in the flowchart of FIG. 23, the first catalyst and the easily crushable inorganic substance are added to the metal amide in the first step, and the mixture is crushed and mixed. And the second catalyst may be further added and pulverized and mixed.

[0278] When the third catalyst is further added, a predetermined amount of the easily crushable inorganic substance is added to the object to be treated in the second step, and the third catalyst is obtained in the second step as the third step. Object And milling and mixing. However, care must be taken in the amount of addition, as the easily crushable inorganic substance does not impair the function of the catalyst.

[0279] Next, another method for producing a hydrogen storage material carrying two or more types of catalysts will be described with reference to the flowchart shown in FIG. As shown in FIG. 24, a predetermined amount of each of the metal hydride, the first catalyst, and the easily crushable inorganic substance is weighed, and these are crushed and mixed under predetermined conditions. Further, the metal amide and the second catalyst are each weighed quantitatively, and they are pulverized and mixed under predetermined conditions. Preferably, these two treatments are both performed in a hydrogen atmosphere.

[0280] Next, the two workpieces obtained by the two independently performed pulverization / mixing processes are mixed together, and pulverized and mixed under predetermined conditions. The hydrogen storage material obtained by such a catalyst supporting method also has the same hydrogen storage characteristics and hydrogen release characteristics as the hydrogen storage material obtained by the catalyst supporting method shown in FIG.

[0281] In addition, when the metal amide and the second catalyst are pulverized and mixed, an easily pulverizable inorganic substance may be added. In addition, as shown in parentheses in the raw material column in FIG. 24, a metal amide, a first catalyst and a pulverizable inorganic substance were pulverized and mixed, and a metal hydride and a second catalyst were pulverized and mixed. The materials may be further ground and mixed.

[0282] In the method for supporting a catalyst on the hydrogen storage material and the hydrogen storage material obtained thereby, the main component of the metal hydride is preferably lithium hydride (LiH). In this case, lithium amide (LiNH 4) is preferable as the metal amide. However, limited to this

2

It does not need to include metal hydrides and metal amides. Examples of metal hydrides include sodium hydride (NaH) and magnesium hydride (MgH).

Group 2 amides include sodium amide (NaNH) and magnesium amide (Mg (NH)).

The hydrogen storage material may include two or more metal species.

[0283] As the easily crushable inorganic substance, sodium chloride (NaCl) or potassium chloride (KC1) is suitably used. Also, using magnesium chloride (MgCl) or calcium chloride (CaCl)

It is also preferable to use 22. Further, it is also preferable to use two or more selected from these. The preferable addition amount of such an easily crushable inorganic substance is determined experimentally, for example, appropriately according to the type and combination of the catalyst within a range where the hydrogen release reaction by the catalyst is improved. It is.

[0284] As the catalyst, B, C, Mn, Fe, Co, Ni, Pt, Pd, Rh, Li, Na, Mg, K, Ir, Nd, Nb, La, Ca, V, Ti, Cr, A metal selected from the group consisting of Cu, Zn, Al, Si, Ru, Os, Mo, W, Ta, Zr, In, Hf and Ag, or a compound or alloy thereof, or a hydrogen storage alloy is preferably used.

[0285] The amount of such a catalyst carried is preferably from 0.1% by mass to 20% by mass of the hydrogen storage material (total amount of metal hydride and metal amide). If the supported amount of the catalyst is 0.1% by mass or less, the effect is not exhibited. If the amount exceeds 20% by mass, the reaction between the metal hydride and the metal amide is inhibited, and the hydrogen release rate per mass is reduced. You will lose weight.

[0286] As a means for pulverizing and mixing various objects to be treated in the above-described method for supporting a catalyst on a hydrogen storage material, various known pulverizing means, for example, a ball mill, a roller mill, an inner and outer cylinder rotary mill, an attritor, an inner A piece mill, an air-flow crushing mill, or the like can be used.

[0287] (Sample preparation of Examples 91-93)

Table 13 shows the composition of each sample. The sample of Example 91 was weighed using the amounts shown in Table 13 of LiH (purity 95%), titanium trichloride (TiCl; purity 99 · 999%), and NaCl (purity 99.9%).

Three

Was ground in a hydrogen atmosphere for 2 hours using a planetary ball mill (Fritsch, P5 type), followed by chromium trichloride (CrCl; purity 99 · 999%) and LiNH (purity 95%).

3 2

) Was added, and the mixture was further pulverized in a hydrogen atmosphere for 2 hours. The sample of Example 92 uses KCl purity of 99.99%) instead of NaCl. The sample of Example 93 has a composition whose composition is the same as that of Example 91. First, LiNH and TiCl a

23, NCl was pulverized and mixed, and LiH and CrCl were added to the object to be treated and pulverized and mixed.

Three

It was.

[0288] A series of such grinding processes, high chromium steel mill vessel (volume: 250 cm ³⁾ and using a high-chrome steel balls of a predetermined amount, the sample was placed in a mill container, vacuum its internal After evacuation, hydrogen was introduced into the mill container so that the inside of the mill container became IMPa, and the operation was performed at 250 rpm at room temperature of 20 ° C for a predetermined time.

[0289] The sample after the pulverization and mixing treatment was used to minimize the effects of sample oxidation and moisture adsorption. Then, it was taken out in a glove box in an argon (Ar; purity: 99.995%) atmosphere, and transferred to a reaction vessel for a hydrogen storage treatment and a hydrogen release experiment described below in an Ar atmosphere.

[0290] (Sample preparation of Comparative Examples 91-93)

The sample of Comparative Example 91 was prepared using the amounts of LiH and TiCl shown in Table 13 (Example 91).

3-93) were weighed and crushed and mixed in a hydrogen atmosphere for 2 hours using a planetary ball mill as described above, and then added to CrCl and LiNH (as in Examples 91-93). Amount) and add water

3 2

It was produced by grinding and mixing in a raw atmosphere for 2 hours.

[0291] The sample of Comparative Example 92 contained the amounts of LiH and TiCl shown in Table 13.

3, CrCl (Example 91

3 Same as 93

) And crush them in a hydrogen atmosphere for 2 hours using a planetary ball mill as described above, then add LiNH (the same amount as in Examples 91-93) Atmosphere

2

It was prepared by pulverizing and mixing for 2 hours.

[0292] The sample of Comparative Example 93 was prepared using LiH, LiNH, and TiCl in the amounts shown in Table 13 (the same amounts as in Examples 91-93).

twenty three

) Were weighed and crushed under a hydrogen atmosphere for 4 hours using the same planetary ball mill. The operating conditions and the like of the planetary ball mill device in the preparation of these Comparative Examples 91-93 are the same as those in Examples 91-193, and the subsequent handling of the prepared samples is also the same as in Examples 91-193.

[0293] (Method of measuring hydrogen release amount)

The reaction containers in which the samples of Examples 91-93 and Comparative Examples 91-93 were respectively sealed and evacuated were heated in an electric furnace to a room temperature of 300 ° C at a rate of 5 ° C / min. At this time, the gas released at each temperature is collected in a gas sampling cylinder, the collected gas is cooled to 20 ° C, the released gas pressure is measured with a pressure gauge, and a gas chromatograph (manufactured by Shimadzu Corporation) is connected through a pipe. , GC9A, TCD detector, column: Molecular Sieve 5A), and the amount of hydrogen was measured. The value obtained by dividing the measured amount of hydrogen by the mass of the sample before heating was defined as the amount of released hydrogen.

[0294] [Table 13] Formulation (g)

Catalyst

LiNH ₂ LiH NaCI KCI

TiCI ₃ CrCI ₃ Example 91 0.9664 0.3346 (* 1) 0.312 0.13 0.13 Example 92 0.9664 0.3346 0.312 0.13 0.13 Example 93 0.9664 (* 2) 0.3346 0.312 0.13 0.13 Comparative example 91 0.9664 0.3346 0.13 0.13 Comparative example 92 0.9664 0.3346 0.13 0.13 Comparative Example 93 0.9664 0.3346 0.13

* 1: Mixed with NaCL TiCI ₃

* 2: Mixed with NaCU TiCI ₃

[0295] (Test results)

Figure 25 shows the relationship between the amount of released hydrogen and the processing temperature. Comparing Example 91 with Comparative Examples 91 and 92, it can be seen that Example 91 emits more hydrogen than Comparative Examples 91 and 92. Also, the rise of hydrogen release is steeper in Example 91 than in Comparative Examples 91 and 92. For this reason, in Example 91, the direct contact between the two catalysts was suppressed by NaCI, whereby the direct interaction between the two catalysts was suppressed, and the individual catalysts were allowed to react with the reaction system. It is considered that it worked effectively.

[0296] Further, comparing Example 91 with Comparative Example 93, it can be seen that Example 91 to which two types of catalysts are added has a larger hydrogen release amount than Comparative Example 93, and has a rising force of hydrogen release. It can be seen that has also become steep. This indicates that the use of the catalyst loading method according to the present invention can provide a hydrogen storage material having high hydrogen releasing ability.

[0297] When Example 91 and Example 92 were compared, they showed almost the same hydrogen release behavior. Therefore, NaCI and KC1 were substantially equivalent as separators for separating a plurality of catalysts. It was thought to have performance. In addition, when Example 91 and Example 93 are compared, they show almost the same hydrogen release behavior. Therefore, either metal hydride or metal amide may be used as the first raw material for pulverization. Was confirmed.

[0298] Note that LiH, TiCl, and NaCI were weighed, each having the same composition as in Examples 91 and 93, and pulverized in a hydrogen atmosphere using a planetary ball mill for 2 hours.

2 CrCl is weighed and powdered for 2 hours in a hydrogen atmosphere using a planetary ball mill.

Three

Crushed, mixed with each other, and then crushed in a hydrogen atmosphere using a planetary ball mill for 2 hours to produce a hydrogen storage material. As a result of the measurement, characteristics equivalent to those of Examples 91 and 93 were shown.

[0299] Next, an apparatus for producing a hydrogen storage material will be described. FIG. 26A shows a horizontal sectional view showing a schematic configuration of the first manufacturing apparatus, and FIG. 26A shows a vertical sectional view thereof. This hydrogen storage material manufacturing apparatus is of a high-speed centrifugal roller mill type, has a cylindrical crushing vessel 1, and a water cooling jacket 2 is provided around the vessel. The water cooling jacket 2 is provided with a cooling water inlet 3 and a cooling water outlet 4.

[0300] Inside the pulverizing container 1, three pulverizing rollers 5 are arranged along the inner wall of the pulverizing container 1 while the longitudinal direction of the rotation axis thereof coincides with the longitudinal direction of the pulverizing container 1. The crushing roller 5 has a spiral groove formed on the peripheral surface thereof, and has a rotating shaft 5 a along the longitudinal direction of the crushing container 1. Both ends of the plurality of grinding rollers 5 are rotatably attached to a pair of bearing assemblies 6. A rotating shaft 7 is provided so as to pass through the center of the pair of bearing assemblies 6 and the milling vessel 1. Then, the drive mechanism (not shown) rotates the bearing assembly 6 to revolve the three crushing rollers 5 integrally along the inner wall of the crushing vessel 1 and rotate each crushing roller 5 by the rotating shaft 5a. It is like that.

[0301] At one end face of the crushing container 1, a hydrogen inlet 8 for introducing hydrogen into the crushing container 1 and a raw material inlet 9 for introducing a hydrogen storage material are provided. A material discharge port 10 for discharging the hydrogen storage material obtained by pulverizing the hydrogen storage material from the pulverizing vessel 1 is provided on the other end face.

[0302] In the hydrogen storage material manufacturing apparatus configured as described above, first, hydrogen is introduced into the crushing container 1 from the hydrogen inlet 8, and the inside of the crushing container 1 is maintained at a predetermined pressure. In this state, the opening / closing mechanism (not shown) is opened to introduce a predetermined amount of the hydrogen storage material raw material into the pulverizing container 1 from the raw material inlet 9.

[0303] In this state, the opening and closing mechanism is closed to start the pulverization of the hydrogen storage material. During grinding, three grinding wheels attached to the bearing assembly 6 by a drive mechanism (not shown) While rotating the roller 5 in the direction of the arrow shown in FIG. 26A, it revolves along the inner wall of the milling vessel 1 in the direction opposite to the direction of rotation. At this time, cooling water is supplied to the water cooling jacket 2 to cool the milling vessel 1. By rotating and revolving the crushing roller 5 in this way, the hydrogen storage material 11 (see FIG. 26A) is mechanically crushed by a compressive force and a shearing force between the inner wall of the crushing container 1 and the crushing roller 5. .

[0304] In this case, the inside of the pulverizing vessel 1 was in a hydrogen atmosphere at a predetermined pressure, and the hydrogen storage material 11 was refined in the process of being pulverized by the mechanical pulverization under the hydrogen atmosphere. Hydrogen enters the hydrogen storage material, and is stored on the surface of the miniaturized hydrogen storage material and between the crystal grains. After the predetermined pulverization is completed, the obtained hydrogen storage material is discharged from the material discharge port 10.

[0305] Here, the hydrogen storage material includes not only the above-mentioned metal hydride and metal amide compound, but also carbonaceous materials such as graphite, amorphous carbon, activated carbon, carbon nanotube, and fullerene. Materials can be used. In this case, there are two types of hydrogen invasion, one with a carbon-hydrogen covalent bond and the other without a covalent bond. Of these, hydrogen mainly without a covalent bond can be reversibly extracted. Effective as stored hydrogen. Among the above carbonaceous materials, graphite is preferred because of its large hydrogen storage capacity. Since the graphite crystals have a layered structure, a large amount of hydrogen can be stored between the surfaces and between layers during the pulverization process in a hydrogen atmosphere.

[0306] In this production apparatus, when pulverizing the hydrogen storage material, the pulverizing roller 5 is rotated and revolved, and the hydrogen storage material is pulverized by the compressive force and the shearing force between the inner wall of the pulverizing container 1 and the pulverizing roller 5. Can be pulverized with high energy, and a hydrogen storage material having a high hydrogen storage capacity can be obtained. In addition, the crushing mechanism is sufficient for mass production where the amount of crushing is not restricted as in a planetary ball mill.

[0307] In the first production apparatus, a raw material introduction port (not shown) and a hydrogen storage material (not shown) capable of maintaining a hydrogen pressure equivalent to the hydrogen pressure in the crushing vessel 1 at a raw material inlet 9 and a material outlet 10 respectively. By attaching the material discharge mechanism, the hydrogen storage material can be continuously introduced into the crushing container 1 and the crushed hydrogen storage material can be continuously discharged from the crushing container 1. [0308] Further, by adding a metal component having a function of dissociating hydrogen molecules into hydrogen atoms during the mechanical pulverization of the hydrogen storage material, the hydrogen storage amount can be increased. For the addition of a metal component, for example, a metal component inlet is provided on the same end face as the raw material inlet 9 of the crushing vessel 1, and such a metal component is stored in the inlet, and the metal is held in a hydrogen atmosphere. What is necessary is just to provide an opening and closing mechanism that connects the component containers and opens and closes between the metal component container and the crushing container 1. Then, the hydrogen pressure in the crushing container 1 is measured, and the hydrogen pressure in the metal component container is set to the same value as the hydrogen pressure in the crushing container 1. Can be introduced within. Metal components having such a function include B, C, Mn, Fe, Co, Ni, Pt, Pd, Rh, Li, Na, Mg, K, Ir, Nd, Nb, La, Ca, V, Ti , Cr, Cu, Zn, Al, Si, Ru, 〇s, Mo, W, Ta, Zr, In, Hf, Ag, one or more metals or their compounds or their alloys, or Hydrogen storage alloys can be mentioned.

[0309] In the first manufacturing apparatus, the grinding container 1 itself is fixed, and the force of the grinding performed by the rotation and revolution of the grinding roller 5 In addition to this, the grinding container 1 may be rotated. . In this case, by setting the rotation direction of the crushing container 1 to be opposite to the revolving direction of the crushing roller 5, crushing can be performed with higher energy. Further, the crushing roller 5 may be configured to rotate only, and the crushing container 1 may be rotated. Further, the groove formed in the grinding roller 5 is not limited to a spiral shape, and may be another shape such as a circular groove.

[0310] FIG. 27 shows a schematic cross-sectional view of the second manufacturing apparatus. This hydrogen storage material manufacturing apparatus is of an inner and outer cylinder rotary mill type, and has an inner cylinder 22 and an outer cylinder 23 provided coaxially. It has a grinding vessel 21 in which an annular grinding chamber 24 is formed. A water cooling jacket 25 for the inner cylinder is provided inside the inner cylinder 22, and a water cooling jacket 26 for the outer cylinder is provided outside the outer cylinder 23. A cooling water supply pipe 25a and a cooling water discharge pipe 25b are connected to the water cooling jacket 25 for the inner cylinder, and a cooling water supply pipe 26a and a cooling water discharge pipe 26b are connected to the water cooling jacket 26 for the outer cylinder. .

[0311] The inner cylinder 22 of the pulverizing vessel 21 is provided with a plurality of stirring blades 27 extending vertically from the outer surface thereof, and the outer cylinder 23 is provided with a plurality of stirring blades 28 extending vertically from the inner surface thereof. Is provided. These stirring blades 27 and 28 stir the hydrogen storage material in the annular grinding chamber 24. I do.

[0312] On both sides of the inner cylinder 22, a rotating shaft 29 is fixed along the longitudinal direction, and a driving sprocket 30 is fixed to the rotating shaft 29. The rotating shaft 29 is rotated by a driving mechanism (not shown). The inner cylinder 22 is rotated via a shaft 29 in the direction of the arrow in the figure. The rotating shaft 29 is rotatably supported on the fixed base 31 via a bearing 32. On the other hand, the outer cylinder 23 is fixed to a fixed base 31, and a bearing 33 is provided between the outer cylinder 23 and the rotating shaft.

[0313] In the vicinity of one side end of the crushing container 21 at the upper part of the outer cylinder 23, a hydrogen inlet 34 for introducing hydrogen into the crushing container 21, that is, the annular crushing chamber 24, and a hydrogen storage material material are introduced. A mouth 35 is provided. A material for discharging the hydrogen storage material obtained by pulverizing the hydrogen storage material from the annular pulverizing chamber 24 in the pulverization container 21 is provided near the other side end of the pulverization container 21 below the outer cylinder 23. An outlet 36 is provided. A classifying plate 37 is disposed near the material discharge port 36 of the annular crushing chamber 24.

[0314] In the hydrogen storage material manufacturing apparatus configured as described above, first, a grinding ball 38 as a grinding medium is put into the annular grinding chamber 24 of the grinding vessel 21 as shown in FIG. Next, hydrogen is introduced into the annular crushing chamber 24 of the crushing vessel 21 from the hydrogen inlet 34 to maintain the inside of the annular crushing chamber 24 at a predetermined pressure. In this state, the opening / closing mechanism (not shown) is opened to introduce a predetermined amount of the hydrogen storage material raw material into the annular grinding chamber 24 from the raw material introduction port 35.

In this state, the opening / closing mechanism is closed to start pulverization of the hydrogen storage material. At the time of grinding, the inner cylinder 22 is rotated in the direction of the arrow through the driving sprocket 30 and the rotating shaft 29 by a driving mechanism (not shown). At this time, cooling water flows through the water cooling jackets 25 and 26 to cool the inner cylinder 22 and the outer cylinder 23.

[0316] By rotating the inner cylinder 22 in this way, as shown in Fig. 28, the grinding balls 38 flow by the stirring blades 27 and 28, and the energy of the grinding balls at that time causes the hydrogen storage material to be converted into a raw material. While mechanically pulverized, it moves toward the material discharge port 36 side as shown in FIG. 27, becomes a hydrogen storage material, and is discharged from the material discharge port 36 through the classification plate 37.

[0317] In this case, the inside of the annular crushing chamber 24 is in a hydrogen atmosphere at a predetermined pressure, and the hydrogen storage material is refined by the mechanical crushing process under the hydrogen atmosphere. Hydrogen enters the hydrogen storage material, and is stored on the surface and / or inside the miniaturized hydrogen storage material. Here, the term “inside” means between crystal grains, between layers, and in defects.

[0318] In the second production apparatus, during the pulverization of the hydrogen storage material, the relative rotation between the inner cylinder 22 and the outer cylinder 23 is caused to flow the pulverizing balls 38 as pulverization media. However, the hydrogen storage material can be pulverized with high energy and energy generated at that time, and a hydrogen storage material having a high hydrogen storage capacity can be obtained. In addition, the crushing mechanism is sufficiently compatible with mass production where the amount of crushing is not limited as in a planetary ball mill.

[0319] Also in this second production apparatus, a raw material introduction port (not shown) capable of maintaining a hydrogen pressure equivalent to the hydrogen pressure in the annular crushing chamber 24 at the raw material introduction port 35 and the material discharge port 36, respectively. And by installing a hydrogen storage material discharge mechanism, the hydrogen storage material raw material is continuously introduced into the annular grinding chamber 24, and the hydrogen storage material after grinding is continuously discharged from the annular grinding chamber 24. be able to.

[0320] When a metal component having a function of dissociating hydrogen molecules into hydrogen atoms is added during the mechanical pulverization of the hydrogen storage material, the first production equipment described above is basically used. It can be performed in the same way as the installation.

[0321] In the second manufacturing apparatus, only the outer cylinder 23 that rotates only the inner cylinder 22 may be rotated. Alternatively, both the inner cylinder 22 and the outer cylinder 23 may be rotated in opposite directions. In this case, the stirring power is increased, so that the hydrogen storage material can be ground with higher energy.

[0322] FIG. 29 is a perspective view showing the third manufacturing apparatus with a part cut away. This hydrogen storage material production apparatus is of the attritor type, has a cylindrical grinding vessel 41, and is arranged with its longitudinal direction vertical. The crushing container 41 is configured to be rotatable in the direction of the arrow by a drive mechanism (not shown), and a pair of end surface members 42 for closing both open ends thereof are fixedly provided. A water cooling jacket 43 is provided around the crushing container 41, and the water cooling jacket 43 is provided with a cooling water inlet 44 and a cooling water outlet 45.

[0323] At the center of the crushing container 41, a rotating shaft 46 is inserted along the longitudinal direction of the crushing container 41. The rotating shaft 46 has three impellers 47a, 47b, 4 7c is provided. These impellers 47a, 47b, 47c are arranged so that adjacent ones are orthogonal to each other. The rotating shaft 46 is configured to rotate in a direction opposite to the crushing container 41 indicated by an arrow by a drive mechanism (not shown), and accordingly, the impellers 47a, 47b, and 47c also rotate. Reference numeral 48 denotes a gas seal, and reference numeral 49 denotes a bearing.

[0324] The upper end member 42 is provided with a hydrogen inlet 50 for introducing hydrogen into the crushing vessel 41 and a raw material inlet 51 for introducing a hydrogen storage material. The lower end member 42 is provided with a material discharge port 52 for discharging a hydrogen storage material obtained by crushing a hydrogen storage material material from a crushing container 41.

[0325] In the hydrogen storage material manufacturing apparatus configured as described above, first, as shown in the figure, a pulverizing ball 53 serving as a pulverizing medium is filled in a pulverizing container 41, and then pulverized from a hydrogen inlet 50. Hydrogen is introduced into the container 41, and the inside of the crushing container 41 is maintained at a predetermined pressure. In this state, the opening / closing mechanism (not shown) is opened, and a predetermined amount of the hydrogen storage material is introduced into the crushing container 1 from the material introduction port 51.

In this state, the opening / closing mechanism is closed to start pulverization of the hydrogen storage material. During the pulverization, the driving mechanism (not shown) rotates the pulverizing container 41 in the direction of the arrow, and rotates the impellers 47a, 47b, 47c via the rotating shaft 46 in the direction opposite to the pulverizing container 41. At this time, cooling water is supplied to the water cooling jacket 43 to cool the crushing container 41.

[0327] By rotating the grinding container 41 and the impellers 47a, 47b, 47c in this manner, the grinding balls 53 flow, and the energy of the grinding balls 53 at that time causes the hydrogen storage material to be mechanically ground. Is done.

[0328] In this case, the inside of the pulverizing container 41 is in a hydrogen atmosphere at a predetermined pressure, and the hydrogen storage material is finely divided by the mechanical pulverization under the hydrogen atmosphere in this way, so that the reduced hydrogen Hydrogen enters the storage material and is stored between the surface of the micronized hydrogen storage material and the crystal grains. After the predetermined pulverization is completed in this way, the obtained hydrogen storage material is discharged from the material discharge port 52.

[0329] In the third manufacturing apparatus, when pulverizing the hydrogen storage material, the pulverizing container 41 is rotated and the impellers 47a, 47b, and 47c are rotated to pulverize the pulverizing balls 53 serving as a pulverizing medium. Hydrogen storage material can be crushed with high energy And a hydrogen storage material having a high hydrogen content. In addition, the crushing mechanism is sufficient for mass production where the crushing amount is not limited as in a planetary ball mill.

[0330] Also in this third manufacturing apparatus, the raw material introduction port 51 and the material discharge port 52 each have a hydrogen storage material raw material introduction mechanism (not shown) capable of maintaining a hydrogen pressure equivalent to the hydrogen pressure in the crushing vessel 41 and a hydrogen storage material. By attaching the storage material discharge mechanism, the hydrogen storage material raw material can be continuously introduced into the crushing container 41, and the crushed hydrogen storage material can be continuously discharged from the crushing container 41.

[0331] Further, when a metal component having a function of dissociating hydrogen molecules into hydrogen atoms is added during the mechanical pulverization of the hydrogen storage material, it is basically performed in the same manner as in the first production apparatus. I can.

FIG. 30 is a schematic sectional view of the fourth manufacturing apparatus. This manufacturing apparatus includes a cylindrical grinding vessel 61 having a bottom with a discharge port 61a formed at the bottom of the side wall for discharging a hydrogen storage material obtained by grinding a hydrogen storage material raw material to the outside, and a grinding vessel 61. And a housing 62 capable of holding the inside thereof in a predetermined gas atmosphere.

[0333] The housing 62 includes a lower container 62a and a lid 62b. The lower container 62a is fixed to a frame or the like (not shown) of the manufacturing apparatus, and the lid 62b is moved up and down by a lifting mechanism (not shown). It is free. By pressing the lid 62b against the lower container 62a with a predetermined force, the lower container 62a and the lid 62b are hermetically sealed, for example, via a copper seal ring (not shown). Note that, for example, the lower container 62a and the lid 62b may be externally tightened with a clamp or the like to hermetically seal their contact surfaces.

[0334] The lower container 62a and the lid 62b each have a jacket structure in which cooling water can be circulated internally. The lid 62b is provided with a hydrogen inlet 63a for introducing hydrogen therein and a material inlet 63b for introducing a hydrogen storage material into the pulverizing vessel 61 while maintaining the housing 62 in a hydrogen atmosphere. I have. The lower container 62a has a material outlet 63c for discharging a part of the hydrogen storage material discharged from the grinding container 61 through the outlet 61a, and a hydrogen outlet 63c discharged from the grinding container 61 through the outlet 61a. A circulation blade 63d for returning a part of the storage material into the grinding container 61 is provided. [0335] The grinding container 61 has a cylindrical curved surface (see Fig. 31 shown later), and the two inner pieces 65 held by the holding member 64 are provided between the cylindrical curved surface and the inner surface of the side wall of the grinding container 61. They are arranged so that there is a predetermined gap between them. The number of the inner pieces 65 is not limited to two, and may be one or three or more. The holding member 64 is attached to the lid 62b, and moves up and down together with the lid 62b.

[0336] The pulverizing container 61 is connected to a motor 67 via a pivot 66 that is disposed airtightly through the bottom surface of the lower container 62a. By driving the motor 67, it is possible to rotate the grinding container 61 so that the gap width between the grinding container 61 and the inner piece 65 does not substantially change. In addition, in a case where the holding member 64 is not fixed to the lid 62b but may be configured to penetrate the lid 62b to be rotatable, the crushing container 61 may be rotatable or non-rotatable.

[0337] In the manufacturing apparatus configured as described above, first, hydrogen is introduced into the housing 62 from the hydrogen inlet 63a, and the inside of the housing 62 is replaced with hydrogen. Preferably, the inside of the housing 62 is maintained at a predetermined positive pressure. I do. Then, the motor 67 is rotated at a predetermined number of revolutions, and preferably, after the number of revolutions becomes constant, a predetermined amount of the hydrogen storage material is fed into the pulverizing container 61 through the material introduction port 63b.

[0338] FIG. 31 is an explanatory diagram schematically showing a pulverization mode of the hydrogen storage material material charged into the pulverization container 61 when the pulverization container 61 is viewed from above. The hydrogen storage material fed into the housing 62 moves toward the side wall of the crushing vessel 61 due to the air current generated by the rotation of the crushing vessel 61 and the impact on the bottom wall of the crushing vessel 61, and the It is sandwiched between the side wall and the inner piece 65. At this time, a compressive force and a shear force act on the hydrogen storage material, and the hydrogen storage material is mechanically pulverized. The magnitudes of the compressive force and the shearing force can be changed by changing the number of revolutions of the crushing vessel 61, changing the amount of the hydrogen storage material fed at a time, and the like. In such an inner-piece type hydrogen storage material manufacturing apparatus, the hydrogen storage material raw material can be pulverized with high energy generated by rotating the pulverization container 61, so that a hydrogen storage material having a high hydrogen storage capacity can be produced. You can get S.

[0339] Since a discharge port 61a is provided at the lower part of the side wall of the crushing container 61, finely crushed water is provided. Element storage materials (including hydrogen storage material) are gradually discharged out of the crushing container 61 from the outlet 61a. The hydrogen storage material discharged from the crushing vessel 61 in this manner is sowed up by the interaction between the circulation blade 63d provided in the housing 62 and the airflow generated in the housing 62, returned to the crushing vessel 61, and further crushed. It is discharged to the outside of the housing 62 through the force to be processed or the material discharge port 63c, and collected in a collection container (not shown) or the like. When the hydrogen storage material is easily fixed to the inner surface of the side wall of the crushing container 61, a member for removing such a fixed material may be provided.

[0340] When the hydrogen storage material is no longer discharged from the material discharge port 63c, a predetermined amount of the hydrogen storage material is again charged into the pulverizing vessel 61 through the material inlet 63b, and the above-described processing is repeated. Can be.

[0341] The charging of the hydrogen storage material into the pulverizing vessel 61 may be performed in a batch process as described above, but is not limited to this. A hydrogen storage material introduction mechanism and a hydrogen storage material discharge mechanism (not shown) capable of maintaining a hydrogen pressure equivalent to the hydrogen pressure in the housing 62 are attached to the discharge port 63c. The hydrogen storage material may be continuously introduced into the pulverizing vessel 61 and the pulverized hydrogen storage material may be continuously discharged from the housing 62 so that the hydrogen storage material is present.

[0342] As described above, the fourth manufacturing apparatus can also sufficiently cope with mass production in which the restriction on the amount of pulverization is less than that of a planetary ball mill due to its pulverization mechanism. When a metal component having a function of dissociating hydrogen molecules into hydrogen atoms is added during the mechanical pulverization of the hydrogen storage material, it can be performed basically in the same manner as in the first production apparatus. .

FIG. 32 is a schematic sectional view of a fifth manufacturing apparatus. In this manufacturing apparatus, a jet nozzle 72 for injecting a predetermined processing gas containing hydrogen at a high pressure and a high-pressure processing gas injected from a jet nozzle 72 are introduced into the inside thereof. A crushing container 71 for crushing the raw material. The processing gas is preferably simple hydrogen, but may be a mixed gas of hydrogen and an inert gas (such as nitrogen or argon). When such a mixed gas is used, it is preferable to use a gas having a high hydrogen partial pressure so that the hydrogen and the hydrogen storage material are easily brought into contact with each other. [0344] The pulverizing container 71 has a substantially elliptical annular main body 71a and a branch 71b for charging a hydrogen storage material. The branch 71b was fed into the branch 71 from the material inlet 73 through which the hydrogen storage material could be introduced into the milling vessel 71 while maintaining the gas atmosphere in the milling vessel 71, and from the material inlet 73. A processing gas nozzle 75 for feeding the hydrogen storage material into the main body 71a is provided. The main body 71a of the pulverizing container 71 is provided with a material discharge port 74 for discharging a hydrogen storage material (that is, a material obtained by pulverizing the hydrogen storage material) and a collision plate 76.

[0345] In the air-flow crushing type manufacturing apparatus configured as described above, the processing gas is introduced from the jet nozzle 72 into the crushing vessel 71, and the inside of the crushing vessel 71 is set to an atmosphere containing hydrogen. The raw material introduction port 73 introduces the hydrogen storage material into the branch 71b of the pulverizing container 71 while introducing a certain amount of processing gas into the pulverizing container 71 from 75. As a result, the hydrogen storage material is sent to the main body 71a of the crushing container 71, and circulates in the main body 71a on the airflow of the high-pressure processing gas injected from the jet nozzle 72. At this time, the hydrogen storage material raw material riding on the gas flow of the processing gas is generated by the collision or grinding of the hydrogen storage material raw materials, the collision with the container wall of the main body 71a and the collision plate 76, and the gas flow of the high-pressure processing gas. It is pulverized mechanically by the applied shearing force or the like. The hydrogen storage material thus produced by being pulverized to a predetermined particle size is discharged from the material discharge port 74.

[0346] In such an airflow-pulverized type hydrogen storage material manufacturing apparatus, large energy is given to the hydrogen storage material raw material in order to flow the hydrogen storage material raw material by the high-pressure processing gas flowing in the pulverizing vessel 71. Since the raw material for hydrogen storage can be pulverized with high energy, a hydrogen storage material having a high hydrogen storage capacity can be obtained.

[0347] The charging of the hydrogen storage material into the pulverizing container 71 may be performed in a batch process as described above, but is not limited to this. The material discharge port 74 is equipped with a hydrogen storage material introduction mechanism (not shown) and a hydrogen storage material discharge mechanism (not shown) that can maintain the same gas pressure as the processing gas pressure in the crushing vessel 71. The raw material of the hydrogen storage material may be continuously introduced into the pulverizing vessel 71 so that a certain amount of the hydrogen storage material may be present, and the pulverized hydrogen storage material may be continuously discharged into the pulverizing vessel 71. [0348] The fifth manufacturing apparatus can sufficiently cope with mass production in which the amount of pulverization is not restricted by a planetary ball mill due to its pulverizing mechanism. In addition, when a metal component having a function of dissociating hydrogen molecules into hydrogen atoms is added during the mechanical pulverization of the hydrogen storage material, it is basically performed in the same manner as in the first production apparatus. it can.

[0349] Next, a description will be given of a hydrogen storage material manufactured using the above-described various manufacturing apparatuses. Here, the results using graphite as a hydrogen storage material (Examples 101 and 104 and Comparative Example 101) and the results using a mixture of lithium hydride and a metal amide compound (Examples 105 to 109 and Comparative Example 102) Will be described.

(Example 101)

In Example 101, a high-speed centrifugal roller mill type as shown in FIGS. 26A and 26B was basically used as an apparatus for producing a hydrogen storage material. However, not only the crushing roller but also the crushing container that rotates were used. The inner volume of the crushing vessel was 5 L, and the inner wall and rotor were made of zirconia. The container and the rotor can be rotated in the same or opposite directions, and in this example, they were used in the opposite direction. The rotation speed of the grinding container was 250 rpm, the rotation speed of the grinding roll was 2000 rpm, and the amount of the graphite powder was 50 g.

(Example 102)

In Example 102, an inner / outer cylinder rotary mill type as shown in FIG. 27 was basically used as an apparatus for producing a hydrogen storage material. However, the one that rotates not only the inner cylinder but also the outer cylinder was used. The inner and outer cylinders are installed horizontally, share a rotation axis, the outer diameter of the inner cylinder is φ152 mm, the inner diameter of the outer cylinder is φ254 mm, and the length of the annular crushing chamber between the inner and outer cylinders The height was 510 mm. The annular grinding chamber was filled with zirconia milling balls (diameter 10 mm) at an apparent filling rate of 80%. A plurality of plate-like stirring blades were arranged on the outer surface of the inner cylinder and the inner surface of the outer cylinder. The rotation directions of the inner and outer cylinders were reversed, the rotation speed of each was around 120 rpm, and the amount of graphite powder charged was 530 g.

(Example 103)

In Example 103, an apparatus of a lighter type as shown in FIG. 29 was basically used as an apparatus for producing a hydrogen storage material. The capacity of the crushing container was 5.4 L, and a crushing ball made of Zinoreconia having a diameter of 5 mm was used. The rotation directions of the impeller and the crushing vessel are opposite. The impeller rotation speed was 250 rpm, and the milling vessel was rotated at 60 i "pm. The amount of the graphite powder was 500 g.

(Example 104)

In Example 104, an inner piece type mill as shown in FIG. 30 was basically used as a hydrogen storage material manufacturing apparatus. The volume of the crushing container was 10 L, and two inner pieces were made of zirconium. While maintaining the inside of the housing in the hydrogen atmosphere of IMPa, the number of revolutions of the pulverizing container was set to 1500 i "pm, and the amount of the supplied graphite powder was set to 500 g.

[0354] (Comparative Example 101)

In Comparative Example 101, 2 g of graphite powder was placed in a mill container made of Zinoreconia having an internal volume of 250 cm ³ , and the inside of the mill container was evacuated, and then hydrogen was introduced into the mill container so that the inside of the mill container became IMPa. The mechanical pulverization was performed for a predetermined time at a room temperature of 20 ° C. and a number of revolutions of 250 rpm using a planetary ball mill (P5, manufactured by Fritsch). The crushed balls used were 60 zirconia balls (φ10 mm) having almost the same composition and hardness as the container. This mill vessel is equipped with a connection valve for introducing and evacuating hydrogen and a sample introduction valve for adding metals or their alloys having the function of dissociating hydrogen molecules into hydrogen atoms. Was.

(Items Common to Examples 101—104 and Comparative Example 101)

(Pre- and post-treatment of sample and mechanical grinding)

Graphite powder (manufactured by Kishida Chemical Co., Ltd., synthetic graphite, average particle size: 36 μm) is placed in each of the above-mentioned pulverizing containers, and the inside of the pulverizing container (in the case of Example 104, the housing) is evacuated. Hydrogen was introduced into the milling vessel so as to obtain SlMPa. Milling was performed for a predetermined time at a room temperature of 20 ° C. using each manufacturing apparatus, and the graphite powder was mechanically pulverized. Note that "G17N" was used as hydrogen.

[0356] (Removal of Sample)

The sample after each milling was transferred under a hydrogen atmosphere into a container equipped with a valve attached to the discharge unit of each hydrogen storage material manufacturing device, and then the container was evacuated to high purity argon (Ar). Was introduced. Note that "Ar 26N" was used as Ar.

[0357] (Measurement of hydrogen release amount) The graphite in the evacuated heating vessel is heated in an electric furnace to room temperature-900 ° C at a heating rate of 10 ° C / min, the gas released from the graphite is cooled to 20 ° C, and the gas pressure is reduced. It was measured with a gas meter and collected in a gas cylinder. The released gas was introduced into a gas chromatograph (manufactured by Shimadzu Corporation, GC9A, TCD detector, column: Molecular Sieve 5A) through a pipe, and the amount of hydrogen was measured. The amount of hydrogen storage was determined by dividing the amount of hydrogen by the amount of graphite before heating.

[0358] (Measurement of average particle size)

The average particle size of the sample before and after milling was dispersed in ethanol and measured using LA-920 manufactured by HORIBA.

[Test results]

FIG. 33 shows the relationship between the milling time of each production apparatus and the average particle diameter of the obtained hydrogen storage material. FIG. 34 is an enlarged view of FIG. As shown in these figures, in the planetary ball mill of Comparative Example 101, an increase in the average particle size due to the mechanochemical phenomenon (agglomeration) is observed after the milling time of 30 hours. On the other hand, in the roller mill of Example 101, the inner and outer cylinder rotary type mill of Example 102, the attritor of Example 103, and the inner piece type mill of Example 104, because of the effect of the compressive force and the shear force, An increase in the average particle diameter was observed after 10 hours, which was shorter than that of the planetary ball mill of Comparative Example 101.

[0360] FIG. 35 shows the result of determining the amount of hydrogen released from the obtained hydrogen storage material. As shown in this figure, in the roller mills, inner and outer cylinder rotary mills, attritors and inner piece mills of Examples 101 to 104 in which the average particle diameter increase time was shorter than that of the planetary ball mill of Comparative Example 101, It was confirmed that the hydrogen storage capacity was higher than that of the ball mill, and that a higher hydrogen storage capacity could be obtained. In addition, although it is difficult to scale up planetary ball mills and cannot industrialize them, it was recognized that these devices can be industrialized and mass production of hydrogen storage goods becomes possible.

(Examples 105-109 and Comparative Example 102)

(Raw material preparation and crushing treatment (hydrogen storage treatment))

In a glove box with high purity Ar atmosphere, lithium amide (LiNH; pure

2 degrees 95. Sigma Aldrich) and lithium hydride (LiH; purity 95%, Sigma Al) So that the molar ratio is 1: 1 and chromium chloride (CrCl; Sigma) is used as a catalyst.

Three

• Aldrich) and 100 g of Li were weighed so that the total amount of Li was 0.05: 1 in atomic ratio. This raw material is transferred into a sealable raw material container, and each hydrogen storage material manufacturing device is maintained in a highly pure Ar atmosphere so that it is not exposed to air (Example 105; roller mill, Example 106; inner and outer cylinders). A rotary mill, Example 107; an attritor, Example 108; an inner piece mill, Example 109; an airflow mill, Comparative Example 102; a planetary ball mill). After performing pulverization and mixing for a predetermined time with a different processing time for each apparatus, the obtained hydrogen storage material was transferred to a certain sample container in a vacuum atmosphere so as not to be exposed to air.

[0362] (Measurement of hydrogen release amount)

The evacuated hydrogen storage material in the reaction vessel was heated in an electric furnace from room temperature to 250 ° C at a heating rate of 10 ° C / min, and kept at 250 ° C for 90 minutes. While maintaining the temperature at 250 ° C, the gas pressure was adjusted using a buffer container so that the released gas pressure was 2 OkPa or less, and the released gas was collected in a gas cylinder when a predetermined time had elapsed from the start of the maintenance at 250 ° C. The gas collected in this way was cooled to 20 ° C, the released gas pressure was measured with a pressure gauge, and the collected gas was passed through a pipe to a gas chromatograph (manufactured by Shimadzu Corporation, GC9A, TCD detector, column: Molecular Sieve 5A). And the amount of hydrogen was measured. The value obtained by dividing the measured amount of hydrogen by the mass of the hydrogen storage material before heating was defined as the hydrogen storage rate.

[0363] (Test results)

Figure 36 shows a graph showing the relationship between the retention time of the hydrogen storage material at 250 ° C and the hydrogen storage rate. In FIG. 36, the hydrogen storage rate is shown as a cumulative value. In addition, the hydrogen storage material power is the force with which hydrogen is released before it reaches 250 ° C. The amount of hydrogen is extremely small compared to the amount of hydrogen released from the start of holding at 250 ° C. Not calculated in rate. Fig. 36 The hydrogen storage material manufactured using a mass-producible manufacturing apparatus such as a roller mill, an inner and outer cylinder rotary mill, an attritor, an inner piece mill, and an air current mill of Example 105 109 is as follows. It was confirmed that the hydrogen storage rate was equal to or higher than the hydrogen storage material manufactured using the planetary ball mill of Comparative Example 102, which is difficult to mass-produce. Next, still another manufacturing apparatus will be described. FIG. 37 is a sectional view showing a schematic configuration of the sixth manufacturing apparatus 110. The manufacturing apparatus 110 introduces a cylindrical grinding vessel 111 for grinding a raw material for a hydrogen storage material (hereinafter referred to as “raw material”) therein, and a slurry composed of the raw material and a predetermined solvent into the grinding vessel 111. A slurry supply port 112, a first slurry discharge port 113a, a second slurry discharge port 113b for discharging the slurry in the grinding container 111, a grinding ball 114 filled in a predetermined amount in the grinding container 111, A stirrer 115 for rotating the crushing ball 114 in the crushing container 111, a circulation pump 116 for circulating the slurry in the crushing container 111, and a suction / exhaust port 117 for performing gas replacement in the crushing container 111. , Are provided.

[0365] The raw material is supplied to the grinding container 111 in the form of a slurry. The raw materials include carbonaceous materials such as graphite and carbon nanotubes, and inorganic hydrides (LiBH NaBH

Borohydrides such as 4 and aranates such as NaAlH Na A1H and Li A1H), gold

4 3 6 3 6

A mixture of a genus hydride (a hydride such as Li Be Na K Ca) and a metal amide compound (an amide compound such as Li Be Na K Ca), and a mixture of a metal hydride and a carbonaceous material are exemplified. For a material that requires a hydrogen storage treatment, hydrogen may be stored in the raw material, but it is preferable to further perform a hydrogen storage treatment on the powder obtained by the pulverization treatment.

[0366] It is also preferable to add a catalyst for promoting the hydrogen generation reaction to the raw materials. Such catalysts include B, C, Mn, Fe, Co, Ni, Pt, Pd, Rh, Li, Na, Mg, K, Ir, Nd, Nb, La, Ca, V, Ti, Cr, One or more metals selected from Cu, Zn, Al, Si, Ru, 〇s, Mo, W, Ta, Zr, In, Hf, Ag, their compounds or alloys, or hydrogen storage alloys Is mentioned.

[0367] Dichloropentafluoropropane was used as a solvent for preparing the slurry.

(Specific gravity 1.55, melting point _112 ° C, boiling point 54 ° C), n-xane (specific gravity 0.66, melting point-95.3 ° C, boiling point 68.7 ° C), pentane (specific gravity 0.63, melting point-129) 7 ° C, Boiling point 36.1 C), IPA (Isopyl pill alcohol: specific gravity 0.79, melting point—90 ° C, Boiling point 83 ° C), MEK (methyl ethyl ketone; Specific gravity 0.81, melting point— 83 ° C, boiling point 80 ° C), toluene (specific gravity 0.87, melting point-95 ° C, boiling point 111 ° C) and the like. Also, silicone oil can be used.

[0368] The cylindrical crushing container 111 is disposed with its longitudinal direction being horizontal. A slurry supply port 112 is provided on the end face side, a first slurry discharge section 113a is provided on an upper portion on the other end side, and a second slurry discharge port 113b is provided on a lower portion on the other end side. A valve 125 is provided in a pipe provided at the slurry supply port 112. In addition, a check valve 126 is provided in the pipe provided at the first slurry discharge port 113a so that air does not flow into the pulverizing container 111 from the first slurry discharge port 113a. .

[0369] In the production apparatus 110, as described later, a hydrogen storage material can be produced continuously. The first slurry discharge port 113a is used for slurry discharge during such a continuous process.

[0370] A switching valve 118 is attached to the pipe attached to the second slurry outlet 113b. By operating the switching valve 118, after a certain amount of slurry is introduced into the crushing container 111 and crushing treatment is performed for a predetermined time, the processed slurry can be collected. Further, by operating the switching valve 118, the slurry discharged from the second slurry discharge outlet 113b can be sent to the circulation pump 116.

[0371] The milling Benore 114 is a sealable ball inlet 1 provided at one end of the milling vessel 111.

Through 28, a predetermined amount is filled in the crushing container 111. As the milling balls 114, the components that will be mixed in the slurry due to wear during the milling are used as the hydrogen storage material.

Materials made of a material that does not adversely affect the release characteristics are preferably used, and for example, zirconia is preferable.

[0372] The stirring device 115 includes a pivot 121 disposed at one end of the crushing container 111 so as to coincide with the longitudinal direction of the crushing container 111, and a plurality of impellers 122 provided at predetermined intervals perpendicular to the longitudinal direction of the pivot 121. And a motor 123 for rotating the vehicle 121. When the pivot 121 is rotated by the motor 123, the grinding balls 114 are rotated by the impeller 122 in the grinding container 111, and the raw material in the slurry is ground by the collision and friction between the grinding balls 114 at this time.

The circulation pump 116 takes out the slurry at a constant flow rate from the second slurry discharge port 113 b through the switching valve 118 and sends the slurry to the slurry supply port 112. By performing the pulverizing process while circulating a part of the slurry in this manner, the raw material can be pulverized uniformly. [0374] A switching valve 119 is provided in a pipe provided at the intake / exhaust port 117. By operating the switching valve 119, the pressure inside the crushing vessel 111 can be reduced, and the inside of the crushing vessel 111 can be reduced. Is filled with a predetermined gas (for example, an inert gas such as nitrogen (N) or argon (Ar)).

2

You can do it. When the slurry is discharged from the second slurry discharge port 113b for recovery, the slurry can be easily discharged by supplying an inert gas into the crushing container 111.

Next, a description will be given of a manufacturing process of the hydrogen storage material in the batch processing by the manufacturing apparatus 110. First, in order to remove gas (air) in the crushing container 111, the pressure in the crushing container 111 is reduced through the suction / exhaust port 117 and the switching valve 119. In this state, a predetermined amount of slurry prepared in advance may be supplied into the grinding container 111 through the slurry supply port 112, or the slurry may be inertized into the grinding container 111 through the intake / exhaust port 117 and the switching valve 119. After supplying the gas, a certain amount of slurry may be supplied through the slurry supply port 112. In the latter case, the inert gas in the crushing vessel 111 is discharged from the first slurry discharge port 113a as the slurry is supplied into the crushing vessel 111.

[0376] Next, the stirring device 115 is driven, and the raw material is ground for a predetermined time. At this time, the circulation pump 116 is operated to circulate the slurry in the grinding container 111 at a constant flow rate. After the pulverization process for a predetermined time is completed, the slurry is recovered through a second slurry discharge port 113b into a container filled with, for example, nitrogen gas, a container reduced in vacuum, or the like so as not to come into contact with air. When the slurry is discharged from the crushing container 111, an inert gas is supplied into the crushing container 111 through the suction / exhaust port 117. As a result, the slurry can be discharged smoothly, and the preparation force for preparing the next batch process is prepared.

[0377] The slurry recovered in the container is heat-treated in an inert gas stream at a temperature equal to or higher than the boiling point of the solvent constituting the slurry and equal to or lower than the temperature at which the hydrogen storage material starts to release a substantial amount of hydrogen. As a result, the solvent evaporates from the slurry, and a dry hydrogen storage material is obtained. The solvent can be recovered by flowing the inert gas stream through the water-cooled trap, and the dried inert gas can be again subjected to the heat treatment of the slurry.

[0378] If such a heat treatment cannot be performed because the boiling point of the solvent used in the slurry is high, the slurry and the hydrogen storage material are separated using a filter or a centrifuge. After that, the hydrogen storage material is washed with a low-boiling solvent, and the low-boiling solvent is evaporated. Thereby, a dry hydrogen storage material can be obtained.

[0379] Next, an apparatus for producing a hydrogen storage material by continuous processing will be described. FIG. 38 is a cross-sectional view illustrating a schematic configuration of the manufacturing apparatus 130. This production apparatus 130 is prepared mainly by the production apparatus 110 described above, and further by a slurry preparation apparatus 131 for preparing a slurry composed of raw materials and a predetermined solvent, and a slurry preparation apparatus 131. A slurry supply pump 132 for continuously supplying the slurry through the slurry supply port 112 into the crushing vessel 111, and a slurry drying apparatus for heating the slurry discharged from the first slurry discharge port 113a to evaporate a solvent contained in the slurry. 133, and a filling container 134 for filling the hydrogen storage material dried by the slurry drying device 133.

[0380] The configuration of manufacturing apparatus 110 is as described above, and description thereof will not be repeated. As the slurry preparation device 131, for example, a mixer using a rotary blade is preferably used as long as the raw material and the predetermined solvent can be roughly and uniformly mixed. This is because the slurry is sufficiently stirred by the pulverizing process in the pulverizing vessel 111. The part of the container for preparing the slurry in the slurry preparation device 131 is maintained in an inert gas atmosphere so that the slurry does not come into contact with air. It is also preferable that the slurry preparation device 131 be configured to continuously add a fixed amount of raw materials and a solvent.

[0381] When the slurry in the grinding container 111 is filled with the slurry and the slurry is further supplied from the slurry preparation device 131 to the grinding container 111 by the slurry supply pump 132 at a constant flow rate, the slurry is supplied at a constant rate according to the supply pressure. An amount of the crushed slurry is discharged from the first slurry discharge port 113a.

[0382] As the slurry drying device 133, for example, the slurry discharged from the crushing container 111 through the first slurry discharge port 113a is dropped or sprayed into a zone heated and maintained at a predetermined temperature in an inert gas atmosphere. Accordingly, it is possible to use a structure that evaporates the solvent of the slurry and collects the dried hydrogen storage material.

[0383] The filling container 134 is maintained in an inert gas atmosphere, and collects the hydrogen storage material dried by the slurry drying device 133. The slurry drying device 133 and the filling container 134 are detachable by an unillustrated detachment mechanism so that air does not enter each. Yes, the transfer of the hydrogen storage material can be performed by transporting the filling container 134.

[0384] Next, a description will be given of a manufacturing process of the hydrogen storage material in the continuous processing by the manufacturing apparatus 130. First, a raw material and a solvent are charged into the slurry preparation device 131 to prepare a slurry. Further, as described above, after the pressure in the crushing container 111 is reduced in order to remove the gas (air) in the crushing container 111, an inert gas is supplied into the crushing container 111. Subsequently, the slurry supply pump 132 is operated to supply the slurry from the slurry preparation device 131 to the grinding container 111. For example, when a predetermined amount of slurry is supplied into the crushing container 111, the supply of the slurry is stopped once, and then the stirring device 115 is driven to start the crushing process of the raw material. At this time, the circulation pump 116 is operated to circulate the slurry in the crushing container 111 at a constant flow rate.

[0385] After a lapse of a predetermined time, the slurry is continuously supplied from the slurry preparation device 131 to the grinding container 111 at a constant flow rate. By the continuous supply of the slurry, the slurry is discharged from the grinding container 111 at a constant flow rate through the first slurry discharge outlet 113a to the slurry force slurry drying device 133 after the grinding process. In the slurry drying device 133, the solvent is evaporated from the slurry sent from the grinding container 111. The dried hydrogen storage material thus obtained is collected in the filling container 134.

[0386] When a predetermined amount of the hydrogen storage material is obtained, or when a predetermined amount of the slurry is supplied to the crushing container 111, the supply of the slurry to the crushing container 111 is stopped, and the stirring device 115 and the circulation pump 116 are turned off. Stop the operation. The slurry remaining in the milling vessel 111 is collected in a predetermined vessel through the second slurry discharge port 113b so that the slurry does not come into contact with air, and the time until the operation of the manufacturing apparatus 130 is resumed. If the interval is short, it is retained in the crushing container 111 as it is.

[0387] The method of recovering the hydrogen storage material in production apparatus 130 is not limited to the mode shown in FIG. FIG. 39 is a cross-sectional view showing a schematic configuration of another manufacturing apparatus 13 (Τ). In the manufacturing apparatus 13 (Τ), a method for handling the pulverized slurry discharged from the grinding container 111 is described above. Since this is different from the manufacturing apparatus 130 described above, this point will be described below. [0388] The manufacturing apparatus 130 'is provided with a slurry filling container 135 for collecting the slurry discharged from the pulverizing container 111 through the first slurry discharge port 113a. A heater 136 is provided inside the slurry filling container 135. Further, a gas discharge port 139 is provided at an upper portion of the slurry filling container 135, and an open / close valve 138 is attached to a pipe provided at the gas discharge port 139.

[0389] The slurry filling container 135 is detachable from a pipe connecting the crushing container 111 and the slurry filling container 135 by a detachment mechanism (not shown). The introduction of the slurry into the slurry filling container 135 can be performed while opening the opening / closing valve 138 and discharging the inert gas in the slurry filling container 135 so that air does not enter the slurry filling container 135.

[0390] The heater 136 is used to heat the slurry stored in the slurry filling container 135 and evaporate the solvent used for the slurry. The slurry filling container 135 has two openings, an opening provided for introducing the slurry and a gas outlet 139, so that it is provided for introducing the slurry when heating the stored slurry. By introducing an inert gas into the bottom of the slurry filling container 135 through the opening and discharging the gas through the gas outlet 139, the drying process can be promoted.

[0391] The heater 136 can also be used for heat treatment for releasing hydrogen from the hydrogen storage material. On the other hand, the release of hydrogen from the hydrogen storage material may be performed by disposing the slurry filling container 135 in a predetermined heating device 137 (for example, an electric furnace) and heating with calo. In addition, the slurry is collected in a slurry storage container where the heater 136 is not provided, and the entire slurry storage container is heated using a constant temperature drier or the like, so that the solvent of the slurry is evaporated, and the hydrogen storage material is removed. Can also be dried.

[0392] After the solvent evaporation treatment of the slurry is completed, since the dried hydrogen storage material is filled in the slurry filling container 135, the transfer of the hydrogen storage material can be performed by transporting the slurry filling container 135. it can.

[0393] (Example 111)

Add 3 L of IPA (isopropyl alcohol) as a solvent to a mixer (tank mixer) and adjust the solid content concentration to 60% with lithium hydride (LiH; purity 95%, Sigma-Aldrich). And Lithium amide (LiNH; 95% purity, Sigma-Aldrich) in a molar ratio of 1: 1.

2

Then, all of the salt was mixed with Sanshio Dani Titanium (TiCl; purity 99/999%, manufactured by Sigma-Aldrich).

Three

The mixture was weighed so as to be 1 mol% of the total volume, and mixed for 10 minutes to prepare a slurry.

[0394] Next, this slurry was put into a bead mill (product name: using ashizawane earthen star minole, bead diameter: 2 mm or less, bead material: zircon, bead filling amount: 80%, rotation speed: peripheral speed 10 mZ seconds) in an Ar atmosphere. Transfer and mix in bead mill for 60 minutes. The bead mill used in Example 111 was provided with a circulation tank mixer, and the slurry circulated between the bead mill and the circulation tank.

[0395] The crushed and mixed slurry was taken out of a container in an Ar atmosphere so as not to be exposed to the air, and was placed in an Ar gas stream (grade GAA (dew point:-88.8 ° C, O: 0.4 ppm), 90 Dry at ° C

2

It was. The solvent was recovered by flowing an Ar gas stream through a water-cooled trap. The dried hydrogen storage material was taken out in an Ar glove box, and the hydrogen release rate was measured based on the hydrogen release rate measurement method described later.

[0396] (Comparative Example 111)

LiH and LiNH are in a molar ratio of 1: 1 and TiCl is added so as to be 1 mol% of the total lithium amount.

twenty three

After weighing the mixture to a total volume of 50 g, place it in a 500 cm ³ high chrome steel mill container (with a vacuum exhaust valve and gas introduction valve), evacuate the mill container, and then evacuate the mill container. Ar (a2, 6N (dew point — 80 ° C, 〇: <0. lp)

2 pm). For the crushing and mixing, milling was carried out at a revolution number of 250 rpm for 60 minutes using a planetary ball mill (Fritsch, P5). In addition, 120 balls (Φ10 mm) made of Zirconia were used for the grinding balls.

[0397] (Measurement of hydrogen release amount)

In a high-purity Ar glove box, 500 mg of each of the samples of Example 111 and Comparative Example 111 was measured and transferred to a sample container. The hydrogen storage material in the evacuated sample container was heated in an electric furnace to room temperature-250 ° C at a heating rate of 10 ° C / min and kept at 250 ° C for 90 minutes. During the 250 ° C hold, the gas pressure was adjusted using a buffer container so that the released gas pressure was 20 kPa or less. The gas collected at each temperature and 250 ° C is cooled to 20 ° C, and this released gas is passed through a pipe to a gas chromatograph (Shimadzu Corporation, GC9A, TCD detector). Column: Molecular Sieve 5A), and the amount of hydrogen was measured. The amount of released hydrogen was a value obtained by dividing the amount of hydrogen by the mass of the hydrogen storage material before heating.

[0398] (Test results)

FIG. ₄₀ shows the relationship between the heating time and temperature of the hydrogen storage material and the hydrogen storage rate. In FIG. 40, the hydrogen storage rate is shown as a cumulative value, and the hydrogen storage material of Example 111 manufactured using the manufacturing apparatus 110 is the hydrogen storage material manufactured using the planetary mill of Comparative Example 111. It has been found that it has a higher hydrogen storage rate than the material.

[0399] In the various types of hydrogen storage materials described above, it is important that the hydrogen storage material precursor (that is, a hydrogen storage material by storing hydrogen) has a high hydrogen storage capacity. This also contributes to improving the cycle characteristics of the hydrogen-grade release reaction of the hydrogen storage material. Therefore, the hydrogen storage material precursor and its production method will be described next.

[0400] First, lithium imide (Li NH) will be described as an example of a hydrogen storage material precursor. L

2

i NH is a hydrogen storage material that reacts with hydrogen as shown in equation (29) below.

2

To a complex of lithium amide (LiNH 4) and lithium hydride (LiH). In this way

2

The resulting complex of LiNH and LiH releases hydrogen (H) by heating to a predetermined temperature.

2 2 changes to Li NH. In other words, the chemical reaction expressed by the following equation (29)

2

This is a so-called reversible disproportionation reaction in which the reaction proceeds reversibly, and such a reaction cycle is repeated.

LiNH + LiH Li NH + H… (29)

2 2 2

[0401] According to the above formula (29), in the synthesis of LiNH, LiNH and LiH are mixed, and

twenty two

This can be done by heating to a temperature. However, in the method of mixing solid materials, there is a limit to the fine composite of LiNH and LiH, and the mixing time for grinding is long.

2

There is a problem of hanging. Therefore, in the present invention, LiNH is converted into a reaction between LiNH and LiH.

twenty two

Synthesize without any response.

[0402] As a specific method for producing such LiNH, LiNH represented by the following formula (30) is used.

There is a method to thermally decompose 2 2.

2LiNH → Li NH + NH… (30)

2 2 3 [0403] Li NH synthesized by such a method has excellent composition and texture uniformity.

2

By reacting such LiNH and hydrogen, LiNH and LiH are uniformly finely divided.

22 2 A composite hydrogen storage material can be obtained.

[0404] Li NH synthesized in this manner has an occlusion of hydrogen.

It is preferable to support a catalyst that promotes 2Z release. The catalyst includes B, C, Mn, Fe, Co, Ni, Pt, Pd, Rh, Li, Na, Mg, K, Ir, Nd, Nb, La, Ca, V, Ti, Cr, Cu, Zn , Al, Si, Ru, 〇s, Mo, W

, Ta, Zr, In, Hf, Ag, one or more metals, their compounds or their alloys, or hydrogen storage alloys. Examples of compounds of these metals include halides such as chlorides, oxides, nitrides, and other compounds.

[0405] As a method for supporting the catalyst on LiNH, the catalyst is added to the synthesis atmosphere of LiNH beforehand.

twenty two

Exposing the synthesized Li NH to the catalyst reagent atmosphere (liquid or vapor) on the surface

2

Method of adsorbing catalyst, method of adding and mixing catalyst fine powder to synthesized Li NH

2

And the like. The loading amount of such a catalyst is not less than 0.1% by mass and not more than 20% by mass of Li NH.

2

It is preferred to be below. If the supported amount of the catalyst is 0.1% by mass or less, the effect is not exhibited. If the amount exceeds 20% by mass, the reaction between the reactants such as Li NH is adversely affected, and

2

This will reduce the rate of hydrogen release.

[0406] The metal imide compound is not limited to Li NH, but may be another metal imide compound, for example,

2

For example, sodium imide (Na NH), magnesium imide (MgNH), calcium imide (CaN

2

H). These various metal imide compounds may be used alone or as a mixture containing two or more kinds. The production method of Na NH is described above.

2

According to the formula (30). The method for producing MgNH is represented by the following equation (31), and the method for producing CaNH conforms to the equation (31).

Mg (NH) → MgNH + NH---(31)

2 2 3

(Sample Preparation of Examples 121 to 123)

Starting materials include LiNH (purity 95%), LiH (purity 95%), Sanshio Titanium (TiCl),

23 3 Chromium trichloride (CrCl 2) (both manufactured by Sigma-Aldrich) was used. In addition, this

Three

These raw materials were also used in Comparative Examples 121 and 123. [0408] LiNH as a starting material was subjected to heat treatment at 450 ° C in vacuo to produce LiNH.

twenty two

This Li NH is pulverized using a planetary ball mill (Fritsch, P5 type).

2

Thus, the sample of Example 121 was produced. This crushing process is performed by mixing Li NH powder lg and a predetermined amount.

2

The high chrome steel balls of the above were put into a high chrome steel mill container (volume: 250 cm ³ ), and the inside of the mill container was evacuated. Then, argon (Ar) was introduced into the mill container so that the inside of the mill container became IMPa. Grade: Hi 2) was introduced, and the reaction was carried out at 250i "pm for 15 minutes at room temperature of 20 ° C. The sample of Example 122 had a composition in which Li NH and TiCl were mixed at a mass ratio of 100: 5. Example 123

twenty three

Has a composition in which Li NH, TiCl, and CrCl are blended at a mass ratio of 100: 4: 1. Fruit

2 3 3

The samples of Examples 122 and 123 were also prepared by pulverization and mixing using a planetary ball mill in the same manner as in Example 121. The sample after the grinding and mixing treatment was taken out in a glove box in an Ar (purity 99.995%) atmosphere in order to minimize the effects of oxidation and moisture adsorption, and then subjected to hydrogen absorption treatment and Ar atmosphere described later. Was transferred to a reaction vessel for the hydrogen release experiment. Table 1 shows the manufacturing conditions of Examples 121 to 123.

[0409] (Sample preparation method for Comparative Examples 121 to 123)

The total lg was weighed so that LiNH and LiH became equimolar, and this was weighed in Example 121-1.

2

The same planetary ball mill as used in the preparation of No. 23 was used, and the mixture was ground and mixed. At that time, the atmosphere in the mill container was adjusted by evacuating the inside of the mill container and then introducing hydrogen (purity 99.995%) into the mill container so that the inside of the mill container became IMPa. Comparative Example 121 did not contain a catalyst, and the pulverization / mixing treatment time was 120 minutes. Comparative Example 122 is LiNH and Li

2

The total amount of H and TiCl are blended so that the mass ratio is 100: 5.

Three

The interval was 120 minutes. Comparative Example 123 had the same composition as Comparative Example 122. The milling and mixing treatment time was 15 minutes. The sample after the pulverization and mixing process was taken out of the glove box in an Ar (purity 99.995%) atmosphere to minimize the effects of oxidation and moisture adsorption. Transferred to reaction vessel for experiment. Table 14 shows the production conditions of Comparative Examples 121 and 123.

[0410] [Table 14] Mixing (mass ratio)

Mixing time Catalyst

LiNH ₂ Li ₂ NH LiH (min)

TiCI ₃ CrCI ₃

Example 121 100 15 Example 122 100 5 15 Example 123 100 4 1 15 Comparative example 121 74.28 25.72 120 Comparative example 122 74.28 25.72 5 120 Comparative example 123 74.28 25.72 5 15

(Examples 121-123 hydrogen storage treatment)

After evacuation of the inside of the reaction vessel, the inside of the reaction vessel was set to a hydrogen atmosphere of 3 MPa, and this reaction vessel was kept at 180 ° C for 8 hours, whereby the hydrogen absorbing treatment of Examples 121 to 123, that is, LiNH and LiH Was converted to a hydrogen storage material consisting of And then the reaction

2

The inside of the container was evacuated.

[0412] (Measurement of hydrogen release amount in Examples 121-123 and Comparative Example 121 123)

The hydrogen storage material prepared from Examples 121-123 and the samples of Comparative Examples 121-123 were respectively sealed, and the reaction vessel evacuated and evacuated was heated in an electric furnace from room temperature to 250 ° C. at a heating rate of 5 ° C./min. Heated and held at 250 ° C for 90 minutes. While maintaining the temperature at 250 ° C, the gas pressure was adjusted using a buffer container so that the pressure of the gas released from the reaction container was 20 kPa or less. The gas released at each temperature and 250 ° C is stored in a gas sampling cylinder, the collected gas is cooled to 20 ° C, the released gas pressure is measured with a pressure gauge, and a gas chromatograph (manufactured by Shimadzu Corporation) is connected through a pipe. , GC9A, TCD detector, column: Molecular Sieve 5A), and the amount of hydrogen was measured. The amount of released hydrogen was calculated by dividing the measured amount of hydrogen by the mass of the sample before heating.

[0413] FIGS. 41 and 42 show the relationship between the amount of released hydrogen and the processing temperature and time. When Example 121 containing no catalyst is compared with Comparative Example 121, as shown in FIG. 41, it can be seen that Example 121 emits more hydrogen than Comparative Example 121. In addition, since the rising gradient of hydrogen release was steeper in Example 121 than in Comparative Example 121, the hydrogen release in Example 121 was steeper. It turns out that the speed is fast. This fact indicates that LiNH and LiH produced using LiNH obtained by thermal decomposition of LiNH are better than the complex of LiNH and LiH obtained by solid mixing.

It was confirmed that the complex with 222 had better hydrogen release characteristics. Further, while the pulverization time was 15 minutes in Example 121, the pulverization / mixing process was performed according to the sample preparation method of Example 121 since the pulverization / mixing process was performed in Comparative Example 121 for 120 minutes. Ability to reduce time S

As shown in FIG. 42, comparing Example 122 and Comparative Example 122, which have the same composition, shows that Example 122 emits more hydrogen than Comparative Example 122. In addition, the onset of hydrogen release is earlier in Example 122 than in Comparative Example 122. This indicates that hydrogen release is started at a lower temperature in Example 122 than in Comparative Example 122. In other words, the complex of LiNH and LiH produced using LiNH obtained by thermal decomposition of LiNH releases hydrogen.

twenty two

It can be seen that the output characteristics are good. The better hydrogen release characteristics in Examples 122 and 123 than in Example 121 may be due to the effect of the catalyst. The slight difference in the hydrogen release characteristics between Example 122 and Example 123 is considered to be due to the difference in the composition of the catalyst. As can be seen from a comparison between Comparative Example 122 and Comparative Example 123, in the method of pulverizing and mixing the solid materials, the length of the pulverizing and mixing treatment time has a great influence on the hydrogen release characteristics.

[0415] Next, a filling container for filling (storing) the powder-type hydrogen storage material, a method of releasing hydrogen from the hydrogen storage material filled in the filling container, and a hydrogen storage material precursor after releasing hydrogen A method for storing hydrogen in the gas will be described. That is, the “filled container” here refers to one having a function of absorbing and releasing hydrogen from the filled hydrogen storage material, rather than merely filling the hydrogen storage material.

FIG. 43 is a sectional view showing a schematic structure of the filling container 201. The filling container 201 includes a tank 203, an internal circulation pipe 204, a safety knob 205, a heater 206, an external circulation pipe 207, and a finoleta 208. The hydrogen storage material 202 is stored in the tank 203. Is filled.

[0417] The tank 203 stores the hydrogen storage material 202 and has an airtight structure except for an opening through which hydrogen flows. The tank 203 is not particularly limited as long as it is a material and a shape that can withstand a pressure of about several MPa at the time of storing hydrogen in the hydrogen storage material 202. Is selected from materials and shapes that can withstand pressures up to lOMPa. As a result, the strength is sufficient and safety can be maintained even when the pressure of hydrogen is released due to rapid release. In FIG. 43, a cylindrical shape having rounded edges is shown as the tank 203. However, when the tank 203 is mounted on an automobile, it may be shaped, for example, in accordance with a rear seat to eliminate unnecessary space.

[0418] The tank 203 is provided with a safety vanoleb 205 set to open at a predetermined pressure (pressure less than the pressure resistance of the tank 203). Such a safety valve 205 is not always necessary, but is preferably provided from the viewpoint of safety. The tank 203 may be provided with an entrance / exit mechanism such as an openable / closable entrance / exit through which the hydrogen storage material 202 can be taken in and out. In this case, a mechanism that can force the hydrogen storage material 202 into and out of the tank 203 in the form of a cartridge may be used.

[0419] The internal flow pipe 204 is a member that forms a flow path for sending hydrogen into the hydrogen storage material 202 and discharging the hydrogen released from the hydrogen storage material 202 to the outside of the tank 203. The internal flow pipe 204 is a flow pipe formed in a cylindrical shape by a porous pipe wall through which hydrogen is permeable. One end of the pipe communicates with the outside of the tank 203 through the opening of the tank 203, and the other end is closed. Have been. Thus, the internal flow pipe 204 is inserted through the hydrogen storage material 202. Since hydrogen uniformly penetrates from the entire wall of the inserted internal flow tube 204, hydrogen can be efficiently absorbed or released.

[0420] The heater 206 as a calorie heating means is provided outside the tank 203 by an electric heating method so that the hydrogen storage material 202 can be indirectly heated to a temperature of 80 ° C or more via the tank 203. It is. Note that the heater 206 may be provided so as to directly heat the hydrogen storage material 202. Preferably, the heater 206 is capable of heating up to 250 ° C. A power supply (not shown) is connected to the heater 206. In addition, a control system (not shown) for feeding back the amount of released hydrogen is provided in the power supply. As a result, it is possible to control the amount of hydrogen release.

[0421] Since the heater 206 is provided in the filling container 201, when the hydrogen storage material 202 is heated by the heater 206, the function of storing or releasing hydrogen of the hydrogen storage material 202 is activated. Therefore, it is possible to quickly store and release hydrogen. [0422] The external circulation pipe 207 is made of a material that does not allow hydrogen to pass therethrough. A filter 208 having a function of preventing a reactive gas other than hydrogen, such as oxygen or water vapor, from entering the outer circulation pipe 207 is provided. Thereby, the hydrogen storage material is prevented from deteriorating by reacting with oxygen, water vapor, or the like, and its storage performance can be maintained.

[0423] As a material of the filter 208, for example, a hydrogen permeable substance such as a palladium alloy (Au: 5%, Ag: 20%, Pd: 70%) is suitable. The filter 208 may be provided inside the internal circulation pipe 204. Further, instead of the filter 208, a force for forming a film of a hydrogen permeable substance on the inner or outer surface of the internal flow pipe 204 or a hydrogen permeable substance may be used as a material of the pipe wall of the internal flow pipe 204. In some cases, such a filter 208 need not be provided.

[0424] Examples of the hydrogen storage material 202 include lithium amide (LiNH4) and lithium hydride (LiH),

2

Or lithium imide (Li NH). In this case, mix appropriate amount of LiNH and LiH,

twenty two

A hydrogen storage material can be prepared by mixing and pulverizing mechanochemically by milling in an atmosphere of hydrogen or an inert gas and adding an appropriate amount of a catalyst material described later. However, it is not necessarily limited to this method.

[0425] Other hydrogen storage materials may be used as long as the function of absorbing or releasing hydrogen is activated at 80 ° C or higher. For example, non-lithium metal amides and metal amide compounds, metal hydrides, arylate materials such as NaAlH, and carbon nanotubes

Four

Any carbon-based material may be used. The hydrogen storage material 202 has a form of, for example, a powder, a granule, or a molded body.

[0426] The hydrogen storage material 202 preferably contains a catalyst component that promotes the storage and release of hydrogen. The catalyst components include B, C, Mn, Fe, Co, Ni, Pt, Pd, Rh, Li, Na, Mg, K, Ir, Nd, Nb, La, Ca, V, Ti, Cr, Cu, Zn , Al, Si, Ru, 〇s, Mo, W, Ta, Zr, In, Hf, Ag, one or more metals or their compounds or alloys, or hydrogen storage alloys. Can be

[0427] Next, the hydrogen absorption / desorption operation using the filling container 201 will be described using a case where a material containing LiNH and LiH as main components is used as the hydrogen storage material 202 as an example. Hydrogen storage material

2

When using a lithium-based storage material as the main material for 202, adjust the temperature of the hydrogen storage material 202 to 100 250 ° C in order to efficiently absorb and release hydrogen. Is preferred.

[0428] That is, when hydrogen is to be stored in the hydrogen storage material 202, the hydrogen storage material 202 is first heated by the heater 206, and the temperature at which the hydrogen storage material 202 sufficiently exhibits a hydrogen storage function, for example, 120 ° C Keep at C. Hydrogen is pumped at a predetermined pressure by a compressor (not shown) connected to the external circulation pipe 207, and is stored in the hydrogen storage material 202 through the internal circulation pipe 204. At the time of this occlusion treatment, a reaction represented by the following formula (32) occurs in the hydrogen storage material 202.

Li NH + H → LiNH + LiH---(32)

2 2 2

On the other hand, when hydrogen is released from the filling container 201, first, the hydrogen storage material 202 is heated by the heater 206, and is maintained at a temperature at which a sufficient hydrogen releasing function is exhibited, for example, 200 ° C. The heating releases hydrogen from the hydrogen storage material 202, and the hydrogen is sent to the external circulation pipe 207 through the internal circulation pipe 204. Upon release, the hydrogen storage material 202 undergoes a reaction represented by the following formula (33).

LiNH + LiH → Li NH + H… (33)

2 2 2

[0430] As described above, in the filling container 201, by heating the hydrogen storage material 202, not only the hydrogen release treatment but also the occlusion treatment can be performed in an extremely short time. Further, since the lithium-based material has a larger hydrogen storage amount per unit weight than a hydrogen storage alloy or the like, the hydrogen storage amount per mass of the filling container 201 can be increased. By virtue of these features, the filling container 201 can be used for hydrogen supply devices mounted on fuel cell vehicles, etc., buffer tanks for stationary fuel cells, and storage systems for hydrogen stations. It can be applied to all hydrogen storage devices in the hydrogen energy society.

[0431] Next, the second filling container will be described. FIG. 44 is a cross-sectional view showing a schematic structure of the second filling container 201a. In the above-described filling container 201, the heater 206 is provided outside the tank 203. However, the second filling container 201a has a structure in which the heater 210 is provided inside the tank 203, and the other parts are The same as the filling container 201. For this reason, the description of the overlapping part is omitted.

[0432] The heater 210 is an electrothermal type, and its function is the same as that of the heater 206. Of tank 203 By providing the heater 210 in the section, the temperature of the hydrogen storage material 202 can be easily controlled, and the efficiency of hydrogen storage and release can be increased. Heater fins may be provided around heater 210 to improve its thermal conductivity. In the filling container 201a, a power source (not shown) is connected to the heater 210. Due to the need to control the amount of released hydrogen, this power supply is equipped with a control system (not shown) that feeds back the amount of released hydrogen.

Next, the third filling container will be described. FIG. 45 is a cross-sectional view showing a schematic structure of the third filling container 201b. The filling container 201 has a structure in which a heater 206 is provided outside the tank 203. However, the filling container 201b uses a heating medium (not shown) having a boiling point of at least 100 ° C. instead of the heater 206. It has a structure including a circulation pipe 220 for circulating between the outside and the inside of the vessel, a heater 221 for heating the heat medium, and a circulation pump 222 for pumping the heat medium into the circulation pipe 220.

[0434] The heater 221 is of an electrothermal type, and a power supply (not shown) is connected to the heater 221 as an external system. Due to the need to control the amount of hydrogen released, the power supply is equipped with a control system (not shown) that feeds back the amount of hydrogen released. Thereby, the hydrogen storage material 202 can be efficiently heated, and the storage and release of hydrogen can be performed in a short time. When this heating means is used, the temperature of the heat medium is kept below the boiling point. Further, the circulation pipe 220 may be provided with heat transfer fins around the circulation pipe 220 in order to improve thermal conductivity.

Next, the fourth filling container will be described. FIG. 46 is a sectional view showing a schematic structure of the fourth filling container 201c. The filling container 201 has a cylindrical internal circulation pipe 204, but this filling container 210c has a structure in which a spiral internal circulation pipe 230 is provided instead. In this case, the surface area of the internal circulation pipe 230 can be increased, and the efficiency with which the hydrogen storage material absorbs or releases hydrogen can be increased.

[0436] These filling containers 201 and the like can be mounted on a fuel cell vehicle as a moving body. As a result, it is possible to realize a light-weight, long-distance fuel-cell vehicle that can run with one refueling. FIG. 47 is an explanatory diagram showing a schematic configuration of an automobile 240 on which the filling container 201 is mounted.

[0437] Since the temperature of the filling container 201 increases, it is preferable to cover the periphery with a heat insulating material. Filling When an access mechanism that allows the hydrogen storage material 202 to be put in and out of the tank 203 of the filling container 201 is provided, a mechanism that allows the filling container 201 to be loaded and unloaded while mounted on the automobile 240 may be used, or the filling container 201 may be removed and removed. It is good also as a mechanism which puts in and out at the place of.

[0438] The external circulation pipe 207 of the filling container 201 is branched into an external circulation pipe 207a for storing hydrogen and an external circulation pipe 207b for releasing hydrogen. The external circulation pipe 207a for storing hydrogen and the external circulation pipe 207b for releasing hydrogen are provided with a lid or a valve (not shown) capable of closing the respective pipes. An external circulation pipe 207b for releasing hydrogen is disposed so as to straddle a rear shaft 251 connected to the rear tire 250, and is connected to the fuel cell 260.

[0439] On the opposite side of the filling container 201, an oxygen suction pipe 261 is provided so as to be connected to the compressor 262. On the opposite side of the oxygen suction pipe 261, a pressure feeding pipe 263 is provided so as to connect the fuel cell 260 and the compressor 262. The fuel cell 260 is provided with a water discharge pipe 264.

[0440] The fuel cell 260 is connected to a conductor 270 that conducts the generated power, and the other end of the conductor 270 is connected to the battery 271. The lead 272 is connected to the battery 271, and the other end is connected to the motor 280. A front shaft 282 that transmits the power of the motor 280 to the front tire 281 is rotatably attached to the motor 280. In FIG. 47, for the sake of simplicity, the front shaft 282 is shown as being directly attached to the motor 280. Force Actually, the power of the motor 280 is applied to the front tire 281 using a pulley or a clutch mechanism. Convey power.

[0441] Next, the operation of the automobile 240 will be described. First, when refilling the automobile 240 with hydrogen, the filling vessel 201 is heated to an optimum temperature at a hydrogen station or the like provided with a hydrogen replenishment system, and the external circulation pipe is moved in the direction of arrow A shown in FIG. Pump hydrogen from 207a. At this time, the external circulation pipe 207b is closed. In this way, hydrogen is stored in the hydrogen storage material (that is, the hydrogen storage material precursor) in the filling container 201.

[0442] When driving the automobile 240, first, with the external circulation pipe 207a closed, the hydrogen storage material inside is heated to an optimum temperature by the heating means of the filling container 201 and discharged from the filling container 201. The supplied hydrogen is sent to the fuel cell 260 through the external flow pipe 207b. On the other hand, The presser 262 is started, and oxygen (air) is fed from the oxygen suction pipe 261 to the fuel cell 260 through the pressure feed pipe 263 in the direction of arrow B shown in FIG. By operating the fuel cell 260 in this manner, the obtained electric power is stored in the battery 271. At this time, the water generated by the reaction is discharged from the water discharge pipe 264 to the outside. The motor 280 is driven by the electric power stored in the battery 271 to rotate the front shaft 282 and the front tire 281. In this way, the vehicle 240 is driven.

[0443] The moving body on which the filling container 201 and the like are mounted is not limited to a fuel cell vehicle, but may be a hydrogen engine vehicle. The moving object is not limited to an automobile, but may be a vehicle such as a motorcycle, a ship, and an airplane.

[0444] Next, the fourth filling container will be described. FIG. 48 is a perspective view showing a schematic structure of the fourth filling container 301. The filling container 301 has a substantially cylindrical shape and is filled with hydrogen in a horizontal state (a state in which a bottom surface is a side surface).

[0445] The filling container 301 is a high-temperature, high-pressure container that can withstand the conditions of a temperature of 200 ° C and a pressure of 5 MPa. For this reason, stainless steel, an aluminum alloy, or the like is preferably used for the filling container 301. The dimensions and volume of the filling container 301 are not particularly limited, and are designed according to the purpose. For example, when applied to a fuel cell vehicle, the volume is preferably about 100L.

[0446] The interior of the filling container 301 is partitioned by a floor plate 304, and the lower space is used as a hydrogen introduction line 303, while the upper space is used to fill a hydrogen storage material precursor 310, The partition 302 further divides the room into three independent rooms (hereinafter referred to as “material filling room”). The material filling chamber is not limited to three chambers, but is preferably two to four chambers. Further, the same material as the filling container 301 is suitably used for the partition wall 302.

[0447] Floor plate 304 is made of a porous metal sintered body such as aluminum or stainless steel. The porous metal sintered body has a three-dimensionally formed communication hole having a diameter of, for example, 0.5 to 2 zm. Through this communication hole, the material filling chamber and the hydrogen introduction line 303 communicate with each other. are doing. In FIG. 43, the surface exposed portion of the communication hole (hereinafter, referred to as “ejection port”) is schematically indicated by reference numeral 305. Examples of the porous metal sintered body include a sintered metal filter element manufactured by Micro Filter Corporation. [0448] As described later, in the filling container 301, hydrogen is supplied to the material filling chamber by blowing hydrogen from the hydrogen introduction line 303 into the material filling chamber through the communication hole of the floor plate 304. For this reason, the thickness of the floorboard 304 is preferably 5-30 mm. If the thickness is less than 5 mm, sufficient strength to withstand the pressure will not be obtained, and if the thickness is more than 30 mm, the pressure loss against hydrogen injection will increase. The diameter of the communication hole may be in the range of several zm to several tens zm. The volume of the hydrogen introduction line 303 can be about 1Z5 of the total volume of the filling container 301. At the end (side surface) of the hydrogen introduction line 303, a hydrogen introduction port 306 for introducing hydrogen from outside is provided.

[0449] The material filling chamber at the top of the filling container 301 is filled with the hydrogen storage material precursor 310. The filling amount of the hydrogen storage material precursor 310 is preferably set such that the hydrogen storage material precursor 310 can be sufficiently scattered into the air of each material filling chamber by blowing by blowing hydrogen from the floor plate 304 of the material filling chamber. The remaining volume that is preferably set to about 1Z4 1Z2 of the volume is the space 311.

[0450] A hydrogen discharge port 307 for releasing hydrogen is provided on the ceiling surface of each material filling chamber. In order to prevent the hydrogen transport pipe connected to the hydrogen outlet 307 from being clogged by the scattered hydrogen storage material precursor 310, the hydrogen outlet 307 is provided with a clogging prevention filter 308. The clogging prevention filter 308 is made of a porous metal sintered body such as aluminum or stainless steel similar to the floor plate 304, and substantially separates hydrogen from the scattered fine powder of the hydrogen storage material precursor 310. In addition, a powder filling port 309 for taking in and out the hydrogen storage material precursor 310 is provided on the ceiling surface. The size and shape of the powder filling port 309 are not particularly limited.

[0451] A suitable example of the hydrogen storage material precursor 310 is lithium imide (Li NH). This Li

2

NH is produced by the reaction of lithium amide (LiNH) and lithium hydride (LiH)

twenty two

It is. Other examples of the hydrogen storage material precursor 310 include Li NH, other than lithium.

2

Examples thereof include a mixture of a metal imide compound having a potassium metal or an alkaline earth metal, a metal-based hydrogen storage material such as a hydrogen storage alloy, and a graphite-based hydrogen storage material such as nanographite.

Next, the hydrogen storage material precursor 310 filled in each material filling chamber of the filling container 301 Hydrogen filling method using Li NH as hydrogen storage material precursor 310

2

Will be described. The hydrogen to be charged is introduced from a hydrogen inlet 306 to a hydrogen inlet line 303. This hydrogen is a high-pressure gas of a predetermined pressure. This hydrogen is ejected from an ejection port 305 provided in the floor plate 304 to scatter the hydrogen storage material precursor 310 filled in each material filling chamber into the space 311 of each material filling chamber.

[0453] At this time, each material charging chamber is adjusted so that the temperature is between room temperature and 180 ° C, the pressure is 0.1 lMPa, preferably the temperature is 120 to 150 ° C, and the pressure is 0.2 to 0.3MPa. The temperature of the material filling chamber can be adjusted, for example, by covering the filling container 301 with a jacket through which a heat medium adjusted to a predetermined temperature flows. The pressurization of the material filling chamber is performed by adjusting the pressure of hydrogen to be introduced at the hydrogen introduction line 303, and the pressure of hydrogen introduced to the hydrogen introduction line 303 is made higher than the holding pressure of the material filling chamber. For example, in order to hold each material filling chamber at 0.2-0.3 MPa, high-pressure hydrogen of about 0.4 MPa may be used.

[0454] In order to promote the scattering of the hydrogen storage material precursor 310, the wall surface, the partition wall 302, and the floor plate 304 of the filling container 301 may be appropriately lightly vibrated, ultrasonic vibration may be applied, or the filling container 301 may be used. Auxiliary means such as shaking or rotating itself may be added.

[0455] The hydrogen filling time is appropriately set depending on the hydrogen pressure and the holding temperature of the material filling chamber.

. In the case of Li NH, under the above temperature and pressure conditions, to fill Li NH with hydrogen 10

twenty two

It is preferable to keep each particle of Li NH in hydrogen for about a minute. So, for example,

2

Each particle of the hydrogen storage material precursor 310 is kept in hydrogen for a total of about 30 minutes. In the meantime, hydrogen is charged into the hydrogen storage material precursor 310. The blowing of hydrogen into the hydrogen introduction line 303 may be continuous or intermittent.

[0456] According to the above-described hydrogen filling method using the filling container 301, when the hydrogen storage material precursor 310 is LiNH, the hydrogen filling amount is 45 mass%, and the conventional method (that is, the material filling method)

2

In charge filling chamber one filled container is brought into contact with hydrogen while keeping deposited hydrogen storage material precursor, higher than the 2 3MAS _S% in the case of performing hydrogen method of filling).

[0457] The hydrogen storage material precursor 310 filled with hydrogen (that is, the hydrogen storage material) may be taken out from the powder filling port 309 and put into another filling container, or may be used as the filling container 301, for example, as a fuel. Installed in a battery-powered vehicle and used to release hydrogen from the hydrogen outlet 307 Oh good.

[0458] In the former case, for example, a large-sized filling container 301 is provided in a hydrogen supply station, where the hydrogen storage material precursor is filled with hydrogen to produce a hydrogen storage material. The hydrogen storage material thus produced is put into a small container that can be mounted on a fuel cell vehicle, and mounted on the fuel cell vehicle. For example, such small containers are of a cartridge type that can be easily attached to and detached from automobiles, and are replaced together at the hydrogen supply station.

[0459] On the other hand, in the latter case, a small-sized filling container 301 is mounted on a fuel cell vehicle.

Fuel cell vehicles receive hydrogen at hydrogen storage stations where hydrogen is stored. The hydrogen supply station is the same as a gas station. By connecting a hydrogen supply hose from the hydrogen supply station to the hydrogen inlet 306, the hydrogen filling method is used to fill each material filling chamber of the filling container 301 with the above-described hydrogen filling method. A certain hydrogen storage material precursor 310 is filled with hydrogen. In this case, the filling container (and the hydrogen storage material) mounted on the fuel cell vehicle receives only the supply of hydrogen at the hydrogen supply station while it is mounted on the vehicle.

[0460] Next, a gas purification device for purifying hydrogen released from the above-described filling container 201 and the like and hydrogen supplied to the filling container 201 and the like will be described. This gas purification device generally includes a hydrogen gas containing ammonia (NH (g)) and / or water (steam; H 0 (g)).

3 2

(H) or their inertness with helium (He), neon (Ne), argon (Ar), nitrogen (N)

It has a structure in which a filter made of alkali metal hydride and / or alkaline earth metal hydride is installed in the flow path of one or more gas mixtures selected from 22 gases

[0461] As the alkali metal hydride or alkaline earth metal hydride, lithium hydride (LiH), magnesium hydride (MgH), calcium hydride (CaH), or a mixture thereof

twenty two

Is preferably used.

[0462] For example, if a filter made of LiH is installed, H 2 O (g) is removed by the reaction of the following equation (34).

2

The resulting hydroxide is considered to generate H by the reaction of the following formula (35).

2

Is called. This reaction proceeds at a high reaction rate even with a very small amount of H 2 O (g).

2 _C is suitable for the removal of HO (g) present in trace amounts in

LiH + H〇 → Li〇H + H

twenty two

LiH + Li〇H → Li Ο + Η---(35)

twenty two

[0463] When passing through the filter, the impurity ΝΗ (g), as shown by the following equation (36),

Three

Reacts with LiH in the filter component to form 11 with lithium amide (LiNH). In other words, NH (g)

2 2 3 Removed to prevent flow into the fuel cell and prevent fuel cell poisoning by NH (g)

Three

There is. Since this reaction proceeds sufficiently even at room temperature of about 20 ° C., for example, the reaction can be sufficiently promoted by the residual heat of the filling container 201 or the like. The reactant LiNH is replaced with LiH.

2

It can remain in the filter in the form of being replaced and be prevented from being discharged out of the filter. Similar effects are observed when other alkali metal hydrides or alkaline earth metal hydrides are used in place of LiH, and particularly good effects are obtained with CaH and MgH.

twenty two

LiH + NH (g) → LiNH + H

3 2 2

[0464] Further, LiNH or the like generated by removing NH (g) is re-formed by the reaction of the following formula (37) and the like.

3 2

May generate NH (g). To prevent this, the filter temperature should be 70 ° C

Three

It is desirable to keep below. Lithium oxide (Li〇) is a stable substance, and filters

2

Other gases will not be released if kept below ° C.

2LiNH → Li NH + NH---(37)

2 2 3

[0465] When LiH is converted to LiNH, the reaction with NH (g) is unlikely to occur.

twenty three

It is desirable to replace it with new LiH as appropriate. As one of the methods, there is a method of installing a filter in a flow path in a state where it can be replaced at a predetermined cycle. For example, the filter can be replaced by a rotating method such as a revolver or a detachable method of inserting and removing the filter.

[0466] An inert gas such as He is inert with lithium hydride, and selectively removes H〇 (g),

2

There is a merit of not causing other impurity components. Thus, the flow of H 2 O (g) to the fuel cell

2

This has the effect of preventing fuel cell poisoning and preventing poisoning of the fuel cell. By using such a gas purification device, the life of the fuel cell and the hydrogen storage material can be extended.

[0467] Alkali metal hydride and alkaline earth metal hydride filled in the filter include B, C, Mn, Fe, Co, Ni, Pt, Pd, Rh, Li, Na, Mg, K, Ir, Nd, Nb, La , Ca, V, Ti, Cr, Cu, Zn, Al, Si, Ru, Os, Mo, W, Ta, Zr, In, Hf, Ag Alternatively, it is preferable to add an alloy thereof.

[0468] The amount of the supported catalyst is preferably from 0.1% by mass to 20% by mass of the alkali metal hydride and / or the alkaline earth metal hydride. By supporting such a catalyst on an alkali metal hydride or the like, the absorption of NH (g) and the like is promoted, and the fuel cell

Three

Poison can be prevented.

[0469] As a filter, granular LiH, CaH, Mg with a diameter of 3 mm or less

2

Those filled with H are preferably used. If the diameter is more than 3 mm, the contact area with gas is not

2

Will be enough. If the packing ratio of LiH, etc. to the column is less than 60%, sufficient purification cannot be realized when the gas flow rate is high, but sufficient effect can be obtained when the gas flow rate is low. The packing ratio of granular solids such as LiH in the column refers to the volume occupying the column volume including the excluded volume.

[0470] In order to promote the reaction with H 2 O (g) and NH (g), a molecular filter was used as the filter.

twenty three

LiH, CaH, MgH, etc. were immersed, mixed, adhered, and supported on at least one (carrier) selected from sieves, activated carbon, activated alumina, silica gel, and clay mineral with a large surface area

twenty two

Those are also preferably used. Among the clay minerals, it is particularly preferable to use halloysite-based clay minerals (atapalgite, sepiolite). These carriers can be used alone or in H 2 O (g)

It is particularly preferably used because its adsorption performance of 2 and NH (g) is recognized. LiH on carrier

Three

The supporting treatment such as the above can be performed, for example, by dispersing LiH in a predetermined liquid, immersing the solution in a carrier, and drying. The column may be packed by mixing the carrier and the granular LiH described above.

[0471] Examples of the hydrogen storage material filled in a filling container used in combination with such a gas purification device include those containing a metal hydride and a metal amide compound. In this case, the metal imide compound as the hydrogen storage material precursor is preferably synthesized at first without undergoing a reaction between the metal hydride and the metal amide. A metal imide compound generated by thermal decomposition of is preferably used.

According to such a gas purification device, it is possible to prevent poisoning of the fuel cell by NH (g).

Three Not only is it possible, but also in the compressed storage of hydrogen using a high-pressure cylinder and the cooling and storage of liquid hydrogen, H 液体 (g) is mixed in during processing and handling, which poisons the fuel cell.

2

Can solve the problem. The gas purifier is suitably provided in a hydrogen generator for stationary fuel cells and a hydrogen generator for fuel cell vehicles, and the hydrogen generator and the gas purifier can be integrally designed. Thereby, the performance of the gas purification device can be further improved.

[0473] Next, the gas purification apparatus will be described in more detail. Water that may generate NH (g)

Three

When combined with a container filled with Li NH

2

Will be explained.

[0474] Fig. 49 shows an example of a configuration in which a gas purifier 402 is combined with a filling container 201. The gas purification device 402 includes a plurality of cylindrical filters 421 rotatably arranged around a pivot 411, and a connecting member 423 holding the filter 421 and connected to the pivot 411. The filter 421 is filled with a predetermined amount of, for example, molecular sieves 412 and LiH granules 413. At both ends of the filter 421, a scattering prevention member 422 made of a porous material is attached so that the internal molecular sieves 412 and the like are not scattered.

[0475] More specifically, the filter 421 is filled with a mixture of LiH granules 413 and molecular sieves 412 prepared to a particle size of 30 mesh in a column of 0.6 cm in diameter and 300 cm in length. I have. Such a long column is used in a fixed diameter and in a wound state.

[0476] The external circulation pipe 207 of the filling container 201 and one end of one filter 421 can be air-tightly connected. Further, the filter 421 and a gas pipe 425 branched to a gas introduction pipe 404 and a gas discharge pipe 403 held by a frame or the like (not shown) can be air-tightly connected. By rotating the connecting member 432 about the pivot 411, the filter 421 can be replaced with another one.

[0477] LiNH filled in the filling container 201 reacts with H as shown in the following formula (38).

2 2 changes into a composite of the hydrogen storage materials LiNH and LiH. Thus obtained

2

The complex of LiNH and LiH releases H by heating to a predetermined temperature,

It changes to 2 2 2. In other words, the chemical reaction expressed by the following equation (38) can be performed between different substances. This is a so-called reversible disproportionation reaction that proceeds in reverse, and such a reaction cycle is repeated.

Li NH10H LiNH10 LiH〜 (38)

2 2 2

According to the above formula (38), in the synthesis of Li NH, LiNH is mixed with LiH, and

twenty two

2

There is a problem of hanging. Therefore, LiNH is synthesized without going through the reaction between LiNH and LiH.

twenty two

Is preferred. The specific production method is LiNH as shown in the following formula (39).

2 is a method of thermal decomposition.

2LiNH → Li NH10 NH (g)… (39)

2 2 3

[0479] Li NH synthesized by such a method has excellent composition and structure uniformity.

2

By reacting such LiNH and hydrogen, LiNH and LiH are uniformly finely divided.

twenty two

A composite hydrogen storage material can be obtained.

[0480] The LiNH synthesized in this manner carries a catalyst that promotes the storage / release of hydrogen.

2

It is preferable to let. The catalyst includes B, C, Mn, Fe, Co, Ni, Pt, Pd, Rh, Li, Na, Mg, K, Ir, Nd, Nb, La, Ca, V, Ti, Cr, Cu, Zn , Al, Si, Ru, Os, Mo, W, Ta, Zr, In, Hf, Ag, one or more metals or their compounds or alloys, or hydrogen storage alloys . Examples of compounds of these metals include halides such as chlorides, oxides, nitrides, and other compounds.

[0481] As a method of supporting the catalyst on Li NH, the catalyst is added to the synthesis atmosphere of Li NH.

twenty two

2

It is preferred to be below. If the supported amount of the catalyst is less than 0.1% by mass, the effect is not exhibited. If the amount exceeds 20% by mass, the reaction between the reactants such as LiNH is hindered.

2

The hydrogen release rate is reduced.

[0482] Li NH absorbs H and is converted to a complex of LiNH and LiH, but NH (

2 2 2 3 g), and the NH (g) poisons the fuel cell when introduced directly into the fuel cell.

Three

Battery life. If Li NH contains moisture, Li NH and H〇 (g)

NH (g) generated by the reaction with 222 may be introduced into the fuel cell and poison it

Three

. Further, when moisture is absorbed by LiNH or a complex of LiNH and LiH, these hydrogen absorption

twenty two

May reduce storage / release capacity.

[0483] As shown in Fig. 49, by attaching a gas purification device 402 to the filling container 201, H O (g) and NH (g) can be added to the molecular sieves 412 and the LiH granules 413 filled in the filter 421.

2 3 can be absorbed, and at this time, by keeping the filter 421 at room temperature (for example, 20 ° C), it is possible to suppress the progress of the reaction that releases H NH (g) and NH (g). Can be.

twenty three

[0484] When LiH granules 413 become Li NH, the reaction with NH (g) becomes difficult to occur.

twenty three

It is also preferable that 1 is automatically replaced by rotating the connecting member 423 to another filter filled with new LiH granules 413 every predetermined time (for example, 180 minutes). Filter 421 contains CaH instead of LiH granules 413, etc.

2, May be filled with MgH.

2

[0485] Hereinafter, the results of evaluating the characteristics of the filter 421 by keeping the configuration of the filter 421 constant and changing the hydrogen storage material and gas type for generating the gas to be supplied to the filter 421 will be described.

[0486] (Hydrogen generation source 1-3)

Table 15 shows the fabrication conditions for the hydrogen sources 13. LiNH (95% pure, Sigma Aldrich

2

Li NH) was prepared by heat-treating (Tsuchi Corporation) at 450 ° C in a vacuum. This Li N

twenty two

H was pulverized using a planetary ball mill (Fritsch, P5 type) to prepare a sample of the hydrogen generation source 1. This milling process is performed by combining lg Li NH powder with a predetermined amount of high

2

The chrome steel balls are placed in a high chrome steel mill container (volume: 250 ml), and after evacuating the inside of the mill container, Ar is placed in the mill container so that the inside of the mill container becomes IMPa (grade: Hi 2). , And the reaction was performed at 250 rpm at room temperature of 20 ° C. for 15 minutes.

[0487] The sample of hydrogen source 2 was prepared LiNH and titanium trichloride (TiCl, Sigma-Aldrich).

twenty three

And 100% by mass in a mass ratio.

2

TiCl and Sanshio-Dani Chromium (CrCl, manufactured by Sigma-Aldrich) are 100: 4: 1 in mass ratio.

3 3

Has a formulated composition. Hydrogen sources 2 and 3 are also planetary-type It is prepared by a pulverizing and mixing process using a nore mill device. The sample after pulverization and mixing was taken out of a glove box with an Ar (purity of 99.995%) atmosphere to minimize the effects of oxidation and moisture adsorption. Transferred to a reaction vessel for hydrogen release experiments at

[0488] After evacuation of the inside of the reaction vessel, the inside of the reaction vessel was set to a hydrogen atmosphere of 3MPa, and the reaction vessel was held at 180 ° C for 8 hours, so that the hydrogen absorbing treatment of the hydrogen source 13 was performed. Mari Conversion treatment to a hydrogen storage material consisting of LiNH and LiH was performed. And then the reaction

2

The inside of the container was evacuated.

[0489] [Table 15]

[0490] (Hydrogen generation source 4-7)

Hydrogen generation source 4 uses 10vol% of H in a cylinder instead of hydrogen storage material.

2, NH (g) to lv

3 ol%, H〇 (g) lvol. / ₀ , hydrogen mixed gas containing 88vol% Ar, filling pressure 2at

2

What was filled with m was used as a hydrogen generator. The hydrogen source 57 was obtained by replacing Ar in the hydrogen source 4 with He, Ne, and N of the same volume.

2

[0491] (Production of filter of Example 1)

A mixture of 12 cm ^{3 of} LiH (purity 95%, manufactured by Sigma's Aldrich) with a particle size of 30 mesh and 5 cm ³ of molecular sieves (manufactured by Wako Pure Chemical Industries, Ltd.) with a diameter of 30 mesh has a diameter of 6 mm. A 300 cm long stainless steel column (GL Science) was packed to form a filter. A plurality of such filters were manufactured. Temperature control was unnecessary because the filter was maintained at around 20 ° C near room temperature in the test environment. H

In order to maintain the removal performance of O (g) and NH (g), use the gas purifier 402 shown in Fig. 49. The filter is automatically replaced every 180 minutes with new LiH granules.

[0492] (Evaluation of filter performance)

The gas generated by heating the hydrogen generation source 113 and the gas discharged from the cylinder of the hydrogen generation source 417 are connected by connecting the hydrogen generation source 117 described above to the filter manufactured as described above. The performance of the filter was evaluated by analyzing the composition of the gas supplied to the filter and passing through the filter.

[0493] Specifically, the hydrogen storage materials of the hydrogen generating sources 13 to 13 were respectively sealed, and the evacuated reaction vessel was heated in an electric furnace to room temperature-250 ° C at a heating rate of 5 ° CZ for 5 minutes. And kept at 250 ° C for 90 minutes. Here, while maintaining the temperature at 250 ° C, the gas pressure was adjusted using a buffer container so that the gas pressure released from the reaction vessel was 20 kPa or less, and the gas released at each temperature and 250 ° C was sampled. The collected gas is stored in a cylinder, the collected gas is cooled to 20 ° C, the released gas pressure is measured with a pressure gauge, and the gas is connected to a gas chromatograph (Shimadzu Corporation, GC9A, TCD detector, column: Molecular Sieve 5A) through piping. And the amount of H was measured. Hydrogen release

2

The amount was the value obtained by dividing the measured amount of H by the mass of the hydrogen storage material before heating. Ma

2

In addition, the amount of NH (g) in the sampling gas is measured by FIA (flow injection analysis).

Three

did. In addition, the measurement of H〇 (g) amount in the sampling gas is based on Karl Fischer

2

This was performed using a minute meter.

[0494] (Comparative Example 131)

Comparative Example 131 has a configuration in which the above-described filter is not provided in the hydrogen generation source corresponding to the hydrogen generation sources 17. In this case, the gas released from each hydrogen source was directly sampled, and the H amount, NH (g) amount, and H 2 O (g) amount were measured.

2 3 2

[0495] Table 16 shows that NH (g) in the sampling gas when the gas released from the hydrogen generation source 17 was passed through the filter (Example 131) and when it was not passed through the filter (Comparative Example 131). Indicate quantity

Three

. Regarding the amount of H〇 (g), the detection limit of the Karl Fischer method is about 5 ppm.

2

Therefore, when the filter of Example 131 was used, all the gases released from the hydrogen generating source 117 were released from the hydrogen generating source 113 when the filter of Comparative Example 131 was used. Each of the gases was below the detection limit. However, the comparative example 131 When a filter was used, 5000 ppm of H〇 (g) was measured for the gas released from the hydrogen source 417. As can be seen by comparing Example 131 and Comparative Example 131, hydrogen generation

2

When the source is the same, the amount of NH (g) is significantly reduced in Example 131 as compared with Comparative Example 131.

Three

Re, it was confirmed that.

[0496] [Table 16]

(Examples 132, 133)

Instead of the molecular sieves filled in the filter of Example 1, a filter using activated alumina of the same mesh (manufactured by Sumitomo Chemical Co., Ltd.) and sepiolite clay mineral of the same mesh (Sepiolite from Turkey manufactured by Taiheiyo Cement Corporation) was used. As a result of purifying the gas released from each of the above hydrogen generation sources, when activated alumina was used (Example 132), the amount of NH (g) was 50 ppm, and sepiolite clay mineral was used. In case (Example 131), N

Three

It was confirmed that the H (g) amount was about lppm or less.

Three

(Example 134)

Furthermore, the TiCl powder was added to the LiH filled in the filter of Example 131 in an amount of 3% by weight of LiH. A filter (Example 134) was prepared by filling a column with a mixture of a considerable amount and the same test was performed. As a result, both the NH (g) and HO (g) amounts were suppressed below the detection limit.

3 2

It was confirmed that.

[0499] The embodiments described above are intended only to clarify the technical contents of the present invention, and the present invention should not be construed as being limited to such specific examples only. Various modifications can be made within the spirit and scope of the present invention.

Industrial applicability

[0500] The present invention can be suitably used for a fuel cell that generates power using hydrogen and oxygen as fuel. Specifically, it can be used in a wide range of technical fields as a power source for automobiles, home power generation, vending machines, mobile phones, cordless home appliances such as laptop computers, or as a power source for autonomous robots and micromachines. It is possible.

Claims

The scope of the claims

[1] A hydrogen storage material containing at least a nanostructured 'organized lithium imide compound precursor complex,

The lithium imide compound precursor composite was nano-structured by treating a mixture obtained by adding a fine powder of lithium hydride as a starting material to a fine powder of lithium hydride in a predetermined ratio by a predetermined compounding method. A hydrogen storage material.

[2] The lithium imide compound precursor complex is used as a catalyst for enhancing the ability to absorb and release hydrogen, as B, C, Mn, Fe, Co, Ni, Pt, Pd, Rh, Li, Na, Mg, K, Ir, Nd. , Nb, La, Ca, V, Ti, Cr, Cu, Zn, Al, Si, Ru, 〇s, Mo, W, Ta, Zr, In, Hf, Ag A mixture of the finely divided lithium hydride, the finely divided lithium amide, and the catalyst, further comprising at least one of an inert gas, a hydrogen gas, and a nitrogen gas; 2. The hydrogen storage material according to claim 1, wherein the hydrogen storage material is obtained by a mechanical milling process in which a predetermined grinding medium is repeatedly subjected to microscopic collision in a mixed atmosphere.

[3] A mixture of finely powdered lithium amide and finely powdered lithium hydride in a predetermined ratio is treated by a predetermined complexing method to form a nanostructured and organized lithium imide compound precursor composite. Method for producing the obtained hydrogen storage material.

[4] B, C, Mn, Fe, Co, Ni, Pt, Pd, Rh, Li, Na, Mg, K, Ir, Nd, Nb, La, Ca, One or more metals selected from the group consisting of V, Ti, Cr, Cu, Zn, Al, Si, Ru, Os, Mo, W, Ta, Zr, In, Hf, and Ag. Alternatively, a compound is added, and as the complexing method, microscopic collision with a predetermined grinding medium is performed in an atmosphere of an inert gas, a hydrogen gas, a nitrogen gas, or a mixed atmosphere thereof. 4. The method for producing a hydrogen storage material according to claim 3, wherein the mechanical milling process is repeated.

[5] A hydrogen storage material that contains metal hydrides and ammonia and generates hydrogen by the reaction between them.

[6] The hydrogen storage material according to [5], wherein the metal hydride is refined by a predetermined mechanical milling treatment.

7. The hydrogen storage material according to claim 5, wherein the metal hydride carries a catalyst that promotes a hydrogen generation reaction between the metal hydride and ammonia.

[8] The catalyst comprises B, C, Mn, Fe, Co, Ni, Pt, Pd, Rh, Li, Na, Mg, K, Ir, Nd, Nb, La, Ca, V, Ti, Cr, One or more metals selected from Cu, Zn, Al, Si, Ru, Os, Mo, W, Ta, Zr, In, Hf, Ag forces, or their compounds or alloys, or hydrogen storage 8. The hydrogen storage material according to claim 7, which is an alloy.

[9] The hydrogen storage material according to claim 7, wherein the supported amount of the catalyst is 0.1% by mass or more and 20% by mass or less of the metal hydride.

[10] A hydrogen generation method in which hydrogen is generated by reacting a metal hydride with ammonia.

11. The hydrogen generation method according to claim 10, wherein a metal hydride carrying a predetermined catalyst is used.

[12] A hydrogen storage material having a mixture, a complex, or a reactant of a metal hydride and a metal amide compound, wherein at least two of these metal species are used.

13. The hydrogen storage material according to claim 12, further comprising a catalyst that enhances the ability to absorb and release hydrogen.

[14] The catalyst includes B, C, Mn, Fe, Co, Ni, Pt, Pd, Rh, Li, Na, Mg, K, Ir, Nd, Nb, La, Ca, V, Ti, Cr, One or more metals selected from the group consisting of Cu, Zn, Al, Si, Ru, Os, Mo, W, Ta, Zr, In, Hf, and Ag or their compounds or alloys, or hydrogen storage alloys 14. The hydrogen storage material according to claim 13.

15. The hydrogen storage material according to claim 13, wherein the supported amount of the catalyst is 0.1% by mass or more and 20% by mass or less of the mixture, the complex, or the reaction product of the metal hydride and the metal amide compound.

16. The hydrogen storage material according to claim 12, wherein the metal hydride is lithium hydride, and the metal amide compound contains at least magnesium amide, calcium amide alone or a mixture thereof.

17. The hydrogen storage material according to claim 12, wherein the mixture, the composite, or the reactant is nanostructured and organized by a mechanical milling process.

[18] A metal hydride, a metal amide compound, and a catalyst for enhancing the ability to absorb and release hydrogen are mixed with an inert gas atmosphere. A step of mixing the catalyst so as to be supported on the metal hydride and the metal amide compound under an atmosphere or a hydrogen gas atmosphere or a mixed gas atmosphere of an inert gas and a hydrogen gas,

A method for producing a hydrogen storage material, wherein the metal hydride and the metal amide compound have two or more metal components.

[19] A hydrogen storage material produced by the method for producing a hydrogen storage material according to claim 18.

[20] a step of mixing the metal hydride and the metal amide compound under an inert gas atmosphere, a hydrogen gas atmosphere, or a mixed gas atmosphere of an inert gas and a hydrogen gas; A step of supporting a catalyst for enhancing the ability to absorb and release hydrogen on the object to be treated;

Has,

[21] A hydrogen storage material produced by the method for producing a hydrogen storage material according to claim 20.

[22] a step of supporting at least one of a metal hydride and a metal amide compound with a catalyst that enhances the ability to absorb and release hydrogen;

A metal hydride and a metal amide compound each carrying the catalyst, or a metal hydride carrying the catalyst and a metal amide compound carrying the catalyst; or the catalyst carries a metal hydride and a metal amide compound. Mixing the metal amide compound and the metal hydride on which the catalyst is not supported under an inert gas atmosphere, a hydrogen gas atmosphere, or a mixed gas atmosphere of an inert gas and a hydrogen gas,

Has,

Storage material.

[23] A hydrogen storage material produced by the method for producing a hydrogen storage material according to claim 22.

[24] A hydrogen storage material that has a mixture, complex, or reaction product of a metal hydride and a metal amide compound, and has two kinds of metal species, lithium and magnesium.

25. The hydrogen storage material according to claim 24, wherein the metal hydride is lithium hydride, and the metal amide compound is magnesium amide.

26. The hydrogen storage material according to claim 25, wherein a mixing ratio of lithium hydride is 1.5 mol or more and 4 mol or less with respect to 1 mol of magnesium amide.

27. The hydrogen storage material according to claim 24, wherein the metal hydride is magnesium hydride, and the metal amide compound is lithium amide.

28. The hydrogen storage material according to claim 27, wherein a mixing ratio of the magnesium hydride to 1 mol of the lithium amide is 0.5 mol or more and 2 mol or less.

29. The hydrogen storage material according to claim 24, further comprising a catalyst that enhances the ability to absorb and release hydrogen.

[30] The catalyst comprises B, C, Mn, Fe, Co, Ni, Pt, Pd, Rh, Li, Na, Mg, K, Ir, Nd, Nb, La, Ca, V, Ti, Cr, One or more metals selected from the group consisting of Cu, Zn, Al, Si, Ru, Os, Mo, W, Ta, Zr, In, Hf and Ag forces, or their compounds or alloys, or hydrogen storage alloys 30. The hydrogen storage material according to claim 29, wherein

31. The hydrogen storage material according to claim 29, wherein the supported amount of the catalyst is 0.1% by mass or more and 20% by mass or less of the mixture, the complex, or the reaction product of the metal hydride and the metal amide compound.

[32] A method for producing a hydrogen storage material that includes a metal hydride and a metal amide compound, and generates hydrogen by a reaction between the two,

A method for producing a hydrogen storage material, comprising: reacting a metal hydride with ammonia to synthesize a metal amide compound; and mixing the metal hydride with the metal amide compound obtained in the synthesis step.

33. The method for producing a hydrogen storage material according to claim 32, wherein a predetermined elemental metal or an alloy is further added to the metal hydride to react with the ammonia.

[34] A hydrogen storage material obtained by pulverizing a mixture, complex, or reaction product of lithium hydride and lithium amide by a predetermined mechanical pulverization process,

Hydrogen storage material whose specific surface area by BET method is 15m ² Zg or more.

35. The hydrogen storage material according to claim 34, further comprising a catalyst that enhances the ability to absorb and release hydrogen.

[36] The catalyst includes B, C, Mn, Fe, Co, Ni, Pt, Pd, Rh, Li, Na, Mg, K, Ir, Nd, Nb, La, Ca, V, Ti, Cr, One or more metals selected from the group consisting of Cu, Zn, Al, Si, Ru, Os, Mo, W, Ta, Zr, In, Hf, and Ag or their compounds or alloys, or hydrogen storage alloys 36. The hydrogen storage material according to claim 35.

[37] A hydrogen storage material obtained by refining a mixture, complex, or reaction product of lithium hydride and magnesium amide by a predetermined mechanical pulverization treatment,

Hydrogen storage material with a specific surface area of 7.5 m ² Zg or more by BET method.

38. The hydrogen storage material according to claim 37, further comprising a catalyst that enhances the ability to absorb and release hydrogen.

[39] The catalyst includes B, C, Mn, Fe, Co, Ni, Pt, Pd, Rh, Li, Na, Mg, K, Ir, Nd, Nb, La, Ca, V, Ti, Cr, One or more metals selected from Cu, Zn, Al, Si, Ru, Os, Mo, W, Ta, Zr, In, Hf and Ag forces, or their compounds or alloys, or hydrogen storage alloys 39. The hydrogen storage material according to claim 38, wherein

[40] A hydrogen storage material obtained by refining a mixture, complex, or reaction product of magnesium hydride and lithium amide by a predetermined mechanical pulverization treatment,

Hydrogen storage material whose specific surface area by BET method is 7.5 m ² / g or more.

41. The hydrogen storage material according to claim 40, further comprising a catalyst that enhances the ability to absorb and release hydrogen.

[42] The catalyst includes B, C, Mn, Fe, Co, Ni, Pt, Pd, Rh, Li, Na, Mg, K, Ir, Nd, Nb, La, Ca, V, Ti, Cr, One or more metals selected from the group consisting of Cu, Zn, Al, Si, Ru, Os, Mo, W, Ta, Zr, In, Hf, and Ag or their compounds or alloys, or hydrogen storage alloys 42. The hydrogen storage material according to claim 41.

[43] A hydrogen storage material having hydrogenated lithium imide,

Hydrogen storage material whose specific surface area by BET method is 10m ² Zg or more.

44. The hydrogen storage material according to claim 43, further comprising a catalyst that enhances the ability to absorb and release hydrogen.

[45] The catalyst includes B, C, Mn, Fe, Co, Ni, Pt, Pd, Rh, Li, Na, Mg, K, Ir, Nd, Nb, La, Ca, V, Ti, Cr, One or more metals selected from Cu, Zn, Al, Si, Ru, Os, Mo, W, Ta, Zr, In, Hf, and Ag forces, or compounds or alloys thereof, or hydrogen storage alloys The hydrogen storage material according to claim 44, wherein the hydrogen storage material is:

[46] Hydrogenate a mixture or complex or reactant of Πquinomide Hydrogen storage material,

Hydrogen storage material whose specific surface area by BET method is 5m ² / g or more.

47. The hydrogen storage material according to claim 46, further comprising a catalyst that enhances the ability to absorb and release hydrogen.

[48] The catalyst includes B, C, Mn, Fe, Co, Ni, Pt, Pd, Rh, Li, Na, Mg, K, Ir, Nd, Nb, La, Ca, V, Ti, Cr, One or more metals selected from Cu, Zn, Al, Si, Ru, Os, Mo, W, Ta, Zr, In, Hf, and Ag forces, or compounds or alloys thereof, or hydrogen storage alloys 48. The hydrogen storage material according to claim 47, wherein

[49] A hydrogen storage material having a mixture, a complex, or a reactant containing a metal hydride, a metal amide compound, and a catalyst for enhancing the ability to absorb and release hydrogen,

The catalyst is a hydrogen storage material comprising nanoparticles.

[50] The metal species comprising the metal hydride and the metal amide compound, such as potassium and magnesium

50. The hydrogen storage material according to claim 49, wherein the amount of calcium is less than the amount of calcium.

51. The hydrogen storage material according to claim 49, wherein the metal hydride is lithium hydride, and the metal amide compound is magnesium amide.

[52] The catalyst includes B, C, Mn, Fe, Co, Ni, Pt, Pd, Rh, Li, Na, Mg, K, Ir, Nd, Nb, La, Ca, V, Ti, Cr, One or more metals selected from Cu, Zn, Al, Si, Ru, Os, Mo, W, Ta, Zr, In, Hf and Ag forces, or their compounds or alloys, or hydrogen storage alloys 50. The hydrogen storage material according to claim 49, wherein

53. The hydrogen storage material according to claim 49, wherein the catalyst is selected from nano metal particles, nano metal oxide particles, and nano metal chlorides.

[54] A hydrogenated hydrogen storage material containing a metal imide compound and a catalyst for enhancing the ability to absorb and release hydrogen, and

The catalyst is a hydrogen storage material comprising nanoparticles.

[55] The metal imide compound is lithium imide, further comprising magnesium nitride.

54. The hydrogen storage material according to 54.

[56] The catalyst includes B, C, Mn, Fe, Co, Ni, Pt, Pd, Rh, Li, Na, Mg, K, Ir, Nd, Nb, La, Ca, V, Ti, Cr, One or more metals selected from Cu, Zn, Al, Si, Ru, Os, Mo, W, Ta, Zr, In, Hf, Ag forces, or compounds or alloys thereof, or The hydrogen storage material according to claim 54, which is a hydrogen storage alloy.

57. The hydrogen storage material according to claim 54, wherein the catalyst is nano metal particles, nano metal oxide particles, or nano metal chloride.

[58] A method for producing a hydrogen storage material comprising two or more types of catalysts which release hydrogen by a reaction between a metal hydride and a metal amide compound and promote the hydrogen release reaction, comprising: a metal hydride and a metal amide compound Adding one kind of catalyst and a predetermined easily crushable inorganic substance to one of the two, and crushing and mixing;

Pulverizing and mixing by adding one of the remaining metal hydride and the metal amide compound to the object to be treated obtained in the pulverizing and mixing step, and another type of catalyst that promotes a hydrogen releasing reaction; ,

A method for producing a hydrogen storage material having:

[59] A method for producing a hydrogen storage material comprising two or more types of catalysts that release hydrogen by the reaction between a metal hydride and a metal amide compound and promote the hydrogen release reaction, comprising: Adding one kind of catalyst and a predetermined easily crushable inorganic substance to one of the two, followed by crushing and mixing,

A step of adding another catalyst to one of the remaining metal hydride and the metal amide compound and pulverizing and mixing,

A method of pulverizing and mixing the objects to be processed obtained by the two mixing steps, and a method of producing a hydrogen storage material.

[60] A cylindrical grinding vessel for grinding the hydrogen storage material therein,

A hydrogen gas introduction unit that introduces hydrogen gas into the pulverization container so that the inside of the pulverization container can be maintained in a hydrogen atmosphere;

A hydrogen storage material introduction unit capable of introducing a hydrogen storage material into the grinding container while maintaining the hydrogen gas atmosphere in the grinding container;

A hydrogen storage material discharge section for discharging the hydrogen storage material in the pulverizing container; and a plurality of pulverizing rollers arranged along the inner wall of the pulverizing container, with a longitudinal direction of a rotating shaft coinciding with a longitudinal direction of the pulverizing container. When,

Relative rotational movement between the crushing container and the plurality of crushing rollers; A drive mechanism for causing a number of grinding rollers to rotate,

With

Making the inside of the pulverizing container a hydrogen atmosphere, introducing a hydrogen storage material into the pulverizing container, mechanically pulverizing the hydrogen storage material by a compressive force and a shearing force between an inner wall of the pulverizing container and the pulverizing roller. For producing hydrogen storage material.

[61] A grinding container having an inner cylinder and an outer cylinder provided coaxially, and an annular grinding chamber being formed between the inner cylinder and the outer cylinder;

A hydrogen gas introduction unit for introducing hydrogen gas into the annular grinding chamber so that the annular grinding chamber can be maintained in a hydrogen atmosphere;

A hydrogen storage material source introduction unit capable of introducing a hydrogen storage material into the annular grinding chamber while maintaining a hydrogen gas atmosphere in the annular grinding chamber;

A hydrogen storage material discharge unit that discharges the hydrogen storage material in the annular crushing chamber, and a drive mechanism that causes a relative rotational movement between the inner cylinder and the outer cylinder,

By making the annular grinding chamber a hydrogen atmosphere, a hydrogen storage material and a grinding medium are introduced into the annular grinding chamber, and a relative rotation between the inner cylinder and the outer cylinder is caused to occur, so that a hydrogen storage material is produced. Hydrogen storage material production equipment

[62] A rotatable cylindrical grinding vessel for grinding the hydrogen storage material therein,

A hydrogen storage material discharge unit that discharges the hydrogen storage material in the pulverization container; and an impeller provided in the pulverization container with a longitudinal direction of a rotating shaft coinciding with a longitudinal direction of the pulverization container.

A drive mechanism for rotating the crushing container and the impeller in directions opposite to each other, By setting the inside of the pulverizing container to a hydrogen atmosphere, filling the raw material for hydrogen storage material and the pulverizing medium into the pulverizing container, and rotating the pulverizing container and the impeller in directions opposite to each other, the hydrogen storage material raw material is obtained. Hydrogen storage material manufacturing equipment that mechanically pulverizes the hydrogen storage material.

[63] A bottomed cylindrical pulverizing container having a hydrogen storage material discharge port at the lower side wall for pulverizing the hydrogen storage material material therein and discharging the pulverized hydrogen storage material to the outside, A housing capable of accommodating the container and maintaining the inside at a predetermined gas atmosphere;

One or more inner pieces having a cylindrical curved surface and arranged so as to form a predetermined gap between the curved surface and the inner surface of the side wall of the crushing container;

A holding member for holding the inner piece,

A container rotating mechanism that rotates the crushing container and / or the holding member so that a gap width between the crushing container and the inner piece does not substantially change,

A housing for introducing a hydrogen gas into the housing, a hydrogen storage material introduction unit for introducing a hydrogen storage material into the pulverization container while maintaining the inside of the housing in a hydrogen gas atmosphere; A hydrogen storage material discharge portion for discharging a part of the hydrogen storage material discharged through the hydrogen storage material discharge port from the inside to the outside, and a hydrogen storage material discharge portion discharged from the grinding container through the hydrogen storage material discharge port. A hydrogen storage material circulating unit for returning a part of the hydrogen storage material to the grinding container,

A hydrogen atmosphere is introduced into the housing to introduce a hydrogen storage material into the pulverizing container, and the hydrogen storage material is mechanically converted by a compressive force and a shearing force between a side wall of the pulverizing container and the inner piece. Manufacture of hydrogen storage material that is crushed to produce hydrogen storage material

[64] a jet nozzle for injecting a predetermined processing gas containing hydrogen at a high pressure,

A high-pressure processing gas injected from the jet nozzle is introduced into the inside thereof, and a pulverizing container having a predetermined shape for pulverizing the hydrogen storage material by an air current of the high-pressure processing gas; Hydrogen storage material raw material in the grinding container A hydrogen storage material introduction unit capable of introducing

A hydrogen storage material discharge unit that discharges the hydrogen storage material in the grinding container,

The inside of the pulverizing container is set to an atmosphere containing hydrogen gas, and a hydrogen storage material is introduced into the pulverization container. The collision or polishing of the hydrogen storage material is carried by the high-pressure processing gas injected from the jet nozzle. An apparatus for producing a hydrogen storage material for producing a hydrogen storage material by mechanically pulverizing a hydrogen storage material raw material by crushing or shearing force given from an air flow of the high-pressure processing gas.

[65] A hydrogen storage material is introduced into the pulverizing container while the inside of the cylindrical pulverizing container is kept in a hydrogen atmosphere. The hydrogen storage material is mechanically pulverized by a compressive force and a shear force generated between the inner wall of the pulverizing container and the pulverizing roller due to relative rotational movement between the pulverizing rollers and rotation of the plurality of pulverizing rollers. A method for producing a hydrogen storage material for producing a material.

[66] A hydrogen storage material obtained by the production method according to claim 65.

[67] In a grinding vessel having an inner cylinder and an outer cylinder provided coaxially, while the annular grinding chamber formed between the inner cylinder and the outer cylinder is in a hydrogen atmosphere, a grinding medium and hydrogen are introduced into the annular grinding chamber. A method for producing a hydrogen storage material, comprising: introducing a storage material and causing relative rotation between the inner cylinder and the outer cylinder to mechanically pulverize the hydrogen storage material to produce a hydrogen storage material.

[68] A hydrogen storage material obtained by the production method according to claim 67.

[69] A grinding medium and a hydrogen storage material are filled in the grinding container while the inside of the cylindrical grinding container is kept in a hydrogen atmosphere, and the impeller provided in the grinding container and the inside of the grinding container are opposed to each other. A method for producing a hydrogen storage material in which a hydrogen storage material is mechanically pulverized by rotating in a direction to produce a hydrogen storage material.

[70] A hydrogen storage material obtained by the production method according to claim 69.

[71] A hydrogen storage material was introduced into the pulverizing container while the inside of the pulverized cylindrical pulverizing container was set to a hydrogen atmosphere, and the inner curved piece of the inner piece having a cylindrical curved surface provided in the pulverizing container was removed. In order to prevent the gap width with the side wall of the crushing container from substantially changing, The hydrogen storage material is mechanically pulverized by a force for rotating one piece or a compressive force and a shearing force generated between the inner piece and the side wall of the pulverization container by rotating the pulverization container. A method for producing a hydrogen storage material for producing a material.

[72] A hydrogen storage material obtained by the production method according to claim 71.

[73] By injecting a predetermined processing gas containing hydrogen into the pulverizing container at a high pressure and introducing a hydrogen storage material material into the pulverizing container so as to ride on the gas flow of the processing gas generated in the pulverizing container, A method for producing a hydrogen storage material, wherein the hydrogen storage material is produced by mechanically pulverizing the hydrogen storage material by collision or grinding of the hydrogen storage material on the gas stream or by shearing force applied from the gas stream.

[74] A hydrogen storage material obtained by the production method according to claim 73.

[75] a cylindrical grinding container for grinding the hydrogen storage material therein;

A slurry supply unit for introducing a slurry composed of a hydrogen storage material and a predetermined solvent into the pulverizing vessel;

A slurry discharging unit for discharging the slurry in the grinding container,

A grinding ball filled in a predetermined amount in the grinding container,

A stirrer that spins the crushing ball in the crushing container,

An apparatus for producing a hydrogen storage material comprising:

[76] a slurry preparation apparatus for preparing the slurry,

A slurry supply mechanism for continuously supplying the slurry prepared in the slurry preparation device into the pulverizing container through the slurry supply unit,

A slurry drying device for heating the slurry discharged from the slurry discharge portion to evaporate a solvent contained in the slurry to produce a continuously dried hydrogen storage material,

A hydrogen storage material filling container for filling the hydrogen storage material dried by the slurry drying device;

The apparatus for producing a hydrogen storage material according to claim 75, further comprising:

[77] A grinding container, which is maintained in a liquid-tight manner, is filled with grinding balls, a slurry containing a hydrogen storage material and a solvent, and the impeller provided in the grinding container is rotated. A method for producing a hydrogen storage material, wherein the hydrogen storage material is mechanically pulverized by collision of the pulverized balls to produce a hydrogen storage material.

[78] The power of the crushing container The heated slurry is evaporated to evaporate the solvent contained in the slurry, thereby continuously drying the hydrogen storage material. The dried hydrogen storage material is filled in a predetermined filling container. 78. The method for producing a hydrogen storage material according to claim 77, wherein the hydrogen storage material is charged.

[79] A hydrogen storage material precursor having a metal imide compound which changes to a hydrogen storage material containing a metal hydride and a metal amide compound simultaneously by reacting with hydrogen, wherein the metal imide compound is a metal hydride A hydrogen storage material precursor synthesized without undergoing a reaction between the hydrogen storage material and the metal amide compound.

80. The precursor of the hydrogen storage material according to claim 79, wherein the metal imide compound includes one or more of lithium imide, sodium imide, magnesium imide, and carbimide.

[81] The hydrogen storage material precursor according to [79], wherein the metal imide compound supports a predetermined catalyst.

[82] The catalyst includes B, C, Mn, Fe, Co, Ni, Pt, Pd, Rh, Li, Na, Mg, K, Ir, Nd, Nb, La, Ca, V, Ti, Cr, One or more metals selected from Cu, Zn, Al, Si, Ru, Os, Mo, W, Ta, Zr, In, Hf and Ag forces, their compounds or alloys, or hydrogen storage alloys 83. The hydrogen storage material precursor according to claim 81, wherein

83. The hydrogen storage material precursor according to claim 81, wherein an amount of the catalyst carried is 0.1% by mass or more and 20% by mass or less of the metal imide compound.

[84] A hydrogen storage material precursor that reversibly changes into a hydrogen storage material capable of releasing hydrogen by reacting with hydrogen,

A hydrogen storage material having a metal imide compound generated by thermal decomposition of a metal amide compound.

[85] The precursor of the hydrogen storage material according to [84], wherein the metal imide compound includes one or more of lithium imide, sodium imide, magnesium imide, and calcium imide.

86. The hydrogen storage according to claim 84, wherein the metal imide compound supports a predetermined catalyst. Material precursor.

[87] The catalyst comprises B, C, Mn, Fe, Co, Ni, Pt, Pd, Rh, Li, Na, Mg, K, Ir, Nd, Nb, La, Ca, V, Ti, Cr, One or more metals selected from Cu, Zn, Al, Si, Ru, Os, Mo, W, Ta, Zr, In, Hf and Ag forces, their compounds or alloys, or hydrogen storage alloys 89. The hydrogen storage material precursor according to claim 86, wherein

88. The hydrogen storage material precursor according to claim 86, wherein the supported amount of the catalyst is 0.1% by mass or more and 20% by mass or less of the metal imide compound.

[89] A method for producing a hydrogen storage material precursor having a metal imide compound which reversibly changes to a hydrogen storage material capable of releasing hydrogen by reacting with hydrogen,

A method for producing a hydrogen storage material precursor, wherein the metal amide compound is obtained by thermally decomposing a metal amide compound.

[90] The method for producing a hydrogen storage material precursor according to [89], wherein the metal amide compound is mainly composed of lithium amide.

[91] The method for producing a hydrogen storage material precursor according to [89], wherein a predetermined catalyst is supported on the metal imide compound.

[92] The catalyst comprises B, C, Mn, Fe, Co, Ni, Pt, Pd, Rh, Li, Na, Mg, K, Ir, Nd, Nb, La, Ca, V, Ti, Cr, One or more metals selected from Cu, Zn, Al, Si, Ru, Os, Mo, W, Ta, Zr, In, Hf and Ag forces, their compounds or alloys, or hydrogen storage alloys 92. The method for producing a hydrogen storage material precursor according to claim 91, wherein

93. The method for producing a hydrogen storage material precursor according to claim 91, wherein the supported amount of the catalyst is 0.1% by mass or more and 20% by mass or less of the metal imide compound.

[94] A solid hydrogen storage material containing a hydrogen storage material that activates the function of storing or releasing hydrogen at a temperature of 80 ° C. or higher and a catalyst that enhances the storage and release of hydrogen of the hydrogen storage material is filled A hydrogen storage material-filled container for

A container for enclosing the hydrogen storage material,

A flow path forming member communicating with the outside and forming a flow path of hydrogen gas inside the container;

Heating means for heating the hydrogen storage material to a temperature of 80 ° C. or higher; A hydrogen storage material-filled container comprising:

95. The hydrogen storage material according to claim 94, wherein the hydrogen storage material is any of lithium imide, a combination of lithium amide and lithium hydride, or a combination of lithium imide, lithium amide and lithium hydride. Hydrogen storage material filled container.

[96] A moving object equipped with the hydrogen storage material-filled container according to [94].

[97] a plurality of independent storage chambers filled with a powdered hydrogen storage material,

Openings provided on each floor of the plurality of storage rooms,

A hydrogen gas introduction line that communicates with the plurality of storage chambers through the opening,

In a state where the hydrogen storage material occludes hydrogen gas, the hydrogen gas is introduced from the outside through the hydrogen gas introduction line, and is ejected from the opening into the plurality of storage chambers. A hydrogen storage material-filled container that scatters a storage material in each storage chamber to bring the hydrogen storage material into contact with the hydrogen gas, and cause the hydrogen storage material to absorb the hydrogen gas.

[98] In a state where the hydrogen storage material does not absorb hydrogen, lithium imide produced by the reaction of a metal amide compound having an alkali metal or an alkaline earth metal as a component with lithium hydride, or an alkali metal other than lithium 100. The hydrogen storage material-filled container according to claim 97, wherein the container is a mixture of a metal imide compound having an alkaline earth metal as a component and lithium imide.

[99] Alkali metal water is passed through a flow path of hydrogen gas containing ammonia and / or water vapor, or a mixed gas of the hydrogen gas and one or more selected from He, Ne, Ar, and N forces.

2

A gas purification apparatus, wherein a filter containing a hydride and / or an alkaline earth metal hydride is installed.

100. The method according to claim 99, wherein the alkali metal hydride and / or alkaline earth metal hydride is any of lithium hydride, magnesium hydride, and calcium hydride.

[101] The filter may include one or more selected from molecular sieves, activated alumina, and sepiolite viscous mineral, and may include lithium hydride, magnesium hydride, or calcium hydride. The gas purification apparatus according to claim 99, wherein one or more selected from the group are supported.

[102] The apparatus further comprises a filling container filled with a hydrogen storage material having a metal hydride and a metal amide compound,

100. The gas purification apparatus according to claim 99, wherein the hydrogen gas containing ammonia and / or water vapor is sent to the filling container through the filter, and is discharged from the filling container through the filter.

[103] The gas purification device according to claim 99, wherein the filter is installed in a hydrogen generator for stationary fuel cells and a hydrogen generator for fuel cell vehicles.