Hydrogen storage material, method for producing same, and hydrogen container

WO2025057401A1PCT designated stage expired Publication Date: 2025-03-20JTEKT CORP
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Patent Information

Application Number
PCT/JP2023/033715
Authority / Receiving Office
WO · WO
Patent Type
Applications
Current Assignee / Owner
Filing Date
2023-09-15
Publication Date
2025-03-20

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Abstract

A hydrogen storage material (1) comprises: a porous metal body (2) having pores (21); and hydrogen storage alloy particles (3) that comprise a hydrogen storage alloy and are held in the pores (21) of the porous metal body (2). A portion of the surface of a hydrogen storage alloy particle (3) may be separated from the porous metal body (2). The hydrogen storage alloy particles (3) may be movably held in the pores (21) of the porous metal body (2). The porous metal body (2) may be a sintered material of a metal powder. The porous metal body (3) may have a three-dimensional network structure comprising columnar struts and a hub in which a plurality of struts are assembled.
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Description

Hydrogen storage material, its manufacturing method and hydrogen container

[0001] The present invention relates to a hydrogen storage material, a method for producing the same, and a hydrogen container.

[0002] In recent years, there has been concern about the environmental impact of using fossil fuels, and the use of hydrogen, which has a lower environmental impact, as an energy source is expected. To use hydrogen as an energy source, devices including a hydrogen storage material that can reversibly store and release hydrogen are sometimes used. For example, Patent Document 1 describes a hydrogen tank that stores hydrogen using a hydrogen storage material. Also, for example, Patent Document 2 describes a hydrogen pressure boosting system that uses a hydrogen storage material to boost the pressure of hydrogen.

[0003] JP 2007-309457 A JP 2019-19884 A

[0004] Powdered hydrogen storage alloys are often used as hydrogen storage materials in hydrogen tanks and hydrogen boosting systems. However, hydrogen storage alloys have the property of expanding when they absorb hydrogen and contracting when they release hydrogen. Furthermore, when powdered hydrogen storage alloys are filled into a container such as a hydrogen tank or hydrogen boosting system, the hydrogen storage alloy is densely packed in the lower part of the container, while a void is created in the upper part of the container. If hydrogen is absorbed into the hydrogen storage alloy in this unevenly distributed state within the container, the expansion of the hydrogen storage alloy may cause high stress on the container.

[0005] To mitigate the problems caused by the expansion of hydrogen storage alloys, a technique has been proposed in which resin is interposed between the particles of the hydrogen storage alloy, and the resin is deformed when the hydrogen storage alloy expands, thereby alleviating the stress on the container. However, because resin has a relatively high thermal resistance, interposing resin between the particles of the hydrogen storage alloy makes it difficult for the temperature of the hydrogen storage alloy to change. Therefore, in this case, there is a problem in that it becomes difficult to quickly absorb and release hydrogen into and from the hydrogen storage alloy.

[0006] The present invention has been made in consideration of such problems, and aims to provide a hydrogen storage material that undergoes little volume change upon absorbing hydrogen and has excellent thermal conductivity, a method for manufacturing the same, and a hydrogen container equipped with the hydrogen storage material.

[0007] One aspect of the present invention is a hydrogen storage material comprising: a metal porous body having pores; and hydrogen storage alloy particles made of a hydrogen storage alloy and held in the pores of the metal porous body.

[0008] The hydrogen storage alloy particles in the hydrogen storage material are held within the pores of the metal porous body. Therefore, even when hydrogen is absorbed into the hydrogen storage alloy particles, the hydrogen storage alloy particles can expand within the pores. This reduces the amount of change in volume of the hydrogen storage material when hydrogen is absorbed.

[0009] Furthermore, the metal porous body has high thermal conductivity, so that when the temperature of the hydrogen absorbing body is changed, the temperature of the hydrogen storage alloy particles held in the pores of the metal porous body can be quickly changed, thereby enabling hydrogen to be quickly absorbed into the hydrogen absorbing body and released from the hydrogen absorbing body.

[0010] As described above, according to the above-described embodiment, it is possible to provide a hydrogen absorbing material that undergoes little volume change upon absorbing hydrogen and has excellent thermal conductivity.

[0011] FIG. 1 is a partial cross-sectional view showing a main part of a hydrogen absorbing material in embodiment 1. FIG. 2 is a partial cross-sectional view showing a main part of a molded body of a mixture in the manufacturing method of a hydrogen absorbing material in embodiment 1. FIG. 3 is a partial cross-sectional view showing a main part of a hydrogen absorbing material in embodiment 2. FIG. 4 is a partial cross-sectional view showing a main part of a resin foam in the manufacturing method of a hydrogen absorbing material in embodiment 2. FIG. 5 is an SEM image of the surface of a hydrogen absorbing material in an experimental example. FIG. 6 is an enlarged SEM image of the opening of the pores in FIG. 5. FIG. 7 is a partial cross-sectional view showing a main part of a hydrogen container in embodiment 3.

[0012] (Embodiment 1) An embodiment of the hydrogen storage material will be described with reference to Figures 1 and 2. As shown in Figure 1, the hydrogen storage material 1 of this embodiment includes a metal porous body 2 having pores 21, and hydrogen storage alloy particles 3 made of a hydrogen storage alloy and held within the pores 21 of the metal porous body 2.

[0013] [Metal Porous Body 2] The metal porous body 2 is made of metal and has pores 21 that hold hydrogen storage alloy particles 3. As shown in Fig. 1 , the pores 21 of the metal porous body 2 may have a storage space 211 that stores the hydrogen storage alloy particles 3 and a connection space 212 that connects the storage space 211 to the outside of the metal porous body 2. For example, the metal porous body 2 of this embodiment is made of a sintered product of metal powder 22, and the voids between the metal particles 221 that make up the metal powder 22 form the connection space 212 of the pores 21. Furthermore, voids are formed around the hydrogen storage alloy particles 3 in the metal porous body 2, and the voids around the hydrogen storage alloy particles 3 form the storage space 211 of the pores 21.

[0014] Therefore, the hydrogen absorbing material 1 of this embodiment can guide hydrogen supplied from outside the metal porous material 2 to the hydrogen storage alloy particles 3 through the connecting spaces 212 and the storage spaces 211 of the pores 21, and store it in the hydrogen storage alloy particles 3. The hydrogen absorbing material 1 can also guide hydrogen released from the hydrogen storage alloy particles 3 to the outside of the metal porous material 2 through the storage spaces 211 and the connecting spaces 212 of the pores 21.

[0015] The average particle size of the metal particles 221 constituting the metal powder 22 can be appropriately set within the range of, for example, 0.1 μm or more and 20 μm or less.

[0016] When the metal porous body 2 is composed of a sintered product of metal powder 22, the average particle size of the metal particles 221 constituting the metal powder 22 is preferably smaller than the average particle size of the hydrogen storage alloy particles 3. In this case, the metal powder 22 can be sintered at a lower temperature during the manufacturing process of the hydrogen storage body 1. Therefore, the metal porous body 2 can be formed while suppressing deterioration of the hydrogen storage alloy particles 3 due to heating during sintering. From the viewpoint of more reliably achieving this effect, the average particle size of the metal particles 221 constituting the metal powder 22 is preferably ½ or less, more preferably ⅕ or less, and even more preferably ⅙ or less, of the average particle size of the hydrogen storage alloy particles 3.

[0017] The average particle diameters of the metal particles 221 and the hydrogen storage alloy particles 3 are median diameters (i.e., cumulative 50% particle diameters) determined based on a volumetric particle size distribution. The volumetric particle size distribution can be obtained using, for example, a laser diffraction / scattering particle size measuring device.

[0018] The pores 21 of the metal porous body 2 preferably have an interconnected pore structure, that is, a structure in which each pore 21 is connected to other pores 21. In this case, hydrogen can more easily flow throughout the entire hydrogen storage body 1, thereby increasing the amount of hydrogen that can be stored in the hydrogen storage body 1.

[0019] The metal constituting the metal porous body 2 may be any metal other than a hydrogen storage alloy, that is, any metal that cannot reversibly absorb and release hydrogen. More specifically, the metal constituting the metal porous body 2 may be iron, iron alloy, copper, copper alloy, aluminum, aluminum alloy, nickel, nickel alloy, or the like.

[0020] The metal constituting the metal porous body 2 preferably has a melting point lower than that of the hydrogen storage alloy. In this case, when the hydrogen storage material 1 is produced, the metal porous body 2 can be formed while suppressing deterioration of the hydrogen storage alloy particles 3 due to heating.

[0021] [Hydrogen Storage Alloy Particles 3] The hydrogen storage alloy particles 3 are made of a hydrogen storage alloy and are held within the pores 21 of the metal porous body 2. It is preferable that a portion of the surface of the hydrogen storage alloy particles 3 is separated from the metal porous body 2. By providing a gap between the hydrogen storage alloy particles 3 and the metal porous body 2 in this manner, when the hydrogen storage alloy particles 3 absorb hydrogen, it is possible to more easily prevent the hydrogen storage alloy particles 3 from expanding beyond the pores 21 of the metal porous body 2 and deforming the metal porous body 2. Therefore, in this case, it is possible to more easily prevent the expansion of the hydrogen storage material 1 when hydrogen is absorbed.

[0022] The hydrogen storage alloy particles 3 may be fixed to the inner surface of the metal porous body 2, but are preferably held movably within the pores 21 of the metal porous body 2. In this case, too, when the hydrogen storage alloy particles 3 absorb hydrogen, it is possible to more easily prevent the hydrogen storage alloy particles 3 from expanding beyond the pores 21 of the metal porous body 2. Therefore, in this case, it is possible to more easily suppress the expansion of the hydrogen storage body 1 when hydrogen is absorbed.

[0023] There are no particular limitations on the composition of the hydrogen storage alloy that constitutes the hydrogen storage alloy particles 3. Examples of the hydrogen storage alloy that can be used to constitute the hydrogen storage alloy particles 3 include AB5-type rare earth alloys such as LaNi5 and mischmetal-nickel alloys, AB2-type Laves phase alloys such as MgZn2 and ZrNi2, AB-type titanium alloys such as TiFe and TiCo, A2B-type magnesium alloys such as Mg2Ni and Mg2Cu, and solid solution BCC alloys such as Ti-V alloys and Ti-Cr alloys.

[0024] The average particle size of the hydrogen storage alloy particles 3 can be appropriately set within the range of, for example, 1 μm or more and 200 μm or less.

[0025] [Method for manufacturing hydrogen storage material 1] In manufacturing the hydrogen storage material 1 of this embodiment, for example, a pore-forming material is attached to the surface of hydrogen storage alloy particles 3, and then the hydrogen storage alloy particles 3 are mixed with metal powder 22 to form the metal porous body 2 to produce a mixture, and the mixture is molded to produce the molded body 10 shown in Figure 2, and the molded body 10 is heated to remove the pore-forming material 213 and sinter the metal powder 22 to form the metal porous body 2.

[0026] In this way, by heating the hydrogen storage alloy particles 3, to which the pore-forming material 213 has been previously attached, together with the metal powder 22 and removing the pore-forming material 213, voids can be formed between the hydrogen storage alloy particles 3 and the metal porous body 2, while the hydrogen storage alloy particles 3 can be retained in the pores 21 of the metal porous body 2.

[0027] In the manufacturing method of this embodiment, first, a pore-forming material 213 is attached to the surface of the hydrogen storage alloy particles 3. As the pore-forming material 213, a substance that can be thermally decomposed at a temperature lower than the melting point of the hydrogen storage alloy particles 3 can be used. More specifically, as the pore-forming material 213, an organic polymer such as an acrylic resin, a styrene-based resin, or a urethane resin can be used. From the viewpoint of more reliably forming voids around the hydrogen storage alloy particles 3, it is preferable that the thermal decomposition temperature of the pore-forming material 213 be lower than the sintering temperature of the metal powder 22.

[0028] The form of the pore-forming material 213 is not particularly limited. For example, the pore-forming material 213 may be in the form of a film or particles. The pore-forming material 213 may also be adhered to the surface of the hydrogen storage alloy particles 3 via a pore-forming assistant made of an organic substance. As the pore-forming assistant, for example, an organic polymer having adhesive properties such as polyvinyl acetate can be used. The thermal decomposition temperature of the pore-forming assistant is preferably lower than the sintering temperature of the metal powder 22.

[0029] The amount of pore-forming material 213 attached is preferably 1 part by mass or more and 50 parts by mass or less per 100 parts by mass of hydrogen storage alloy particles 3, more preferably 3 parts by mass or more and 40 parts by mass or less, even more preferably 5 parts by mass or more and 30 parts by mass or less, and particularly preferably 7 parts by mass or more and 20 parts by mass or less.

[0030] By setting the amount of the pore-forming material 213 to be preferably 1 part by mass or more, more preferably 3 parts by mass or more, even more preferably 5 parts by mass or more, and particularly preferably 7 parts by mass or more per 100 parts by mass of the hydrogen storage alloy particles 3, it is possible to appropriately widen the voids formed around the hydrogen storage alloy particles 3. Furthermore, by setting the amount of the pore-forming material 213 to be preferably 50 parts by mass or less, more preferably 40 parts by mass or less, even more preferably 30 parts by mass or less, and particularly preferably 20 parts by mass or less per 100 parts by mass of the hydrogen storage alloy particles 3, it is possible to increase the amount of hydrogen storage alloy particles 3 held in the hydrogen storage material 1 and increase the amount of hydrogen that can be storable by the hydrogen storage material 1. Furthermore, in this case, it is possible to easily prevent the volume ratio of pores in the metal porous body 2 from becoming excessively high. As a result, it is possible to more easily prevent a decrease in the strength of the metal porous body 2.

[0031] Next, the hydrogen storage alloy particles 3 with the pore-forming material 213 attached thereto are mixed with the metal powder 22 that will become the metal porous body 2 to prepare a mixture. The content of the hydrogen storage alloy particles 3 in the mixture is preferably 40% by mass or more and 90% by mass or less, more preferably 45% by mass or more and 85% by mass or less, even more preferably 50% by mass or more and 80% by mass or less, and particularly preferably 55% by mass or more and 75% by mass or less, based on the total mass of the hydrogen storage alloy particles 3 and the metal powder 22.

[0032] By setting the content of hydrogen storage alloy particles 3 in the mixture to preferably 40 mass% or more, more preferably 45 mass% or more, even more preferably 50 mass% or more, and particularly preferably 55 mass% or more, relative to the total mass of the hydrogen storage alloy particles 3 and the mass of the metal powder 22, the amount of hydrogen storage alloy particles 3 held in the hydrogen storage material 1 can be increased, and the amount of hydrogen that can be absorbed by the hydrogen storage material 1 can be increased.

[0033] Furthermore, by setting the content of the hydrogen storage alloy particles 3 in the mixture to preferably 90 mass % or less, more preferably 85 mass % or less, even more preferably 80 mass % or less, and particularly preferably 75 mass % or less, based on the total mass of the hydrogen storage alloy particles 3 and the metal powder 22, it is possible to easily prevent the volume ratio of pores in the metal porous body 2 from becoming excessively high. As a result, it is possible to more easily prevent a decrease in the strength of the metal porous body 2.

[0034] If necessary, a liquid dispersion medium may be added to the mixture to disperse the hydrogen storage alloy particles 3 and the metal powder 22. By dispersing the hydrogen storage alloy particles 3 and the metal powder 22 in the liquid dispersion medium and liquefying the mixture, the mixture can be more easily formed into a desired shape. As a result, a hydrogen storage material 1 having the desired shape can be obtained.

[0035] As the liquid dispersion medium, for example, a liquid organic polymer such as polyalkylene oxide or polyvinyl alcohol, or a solution containing such an organic polymer, can be used.

[0036] After preparing the mixture, the mixture is molded into a desired shape to obtain a molded body 10. The molded body 10 thus obtained has a structure in which hydrogen storage alloy particles 3, to which pore-forming material 213 is attached, are embedded in metal powder 22, as shown in Fig. 2. The method for molding the mixture is not particularly limited, and an appropriate method may be selected from known methods such as press molding, injection molding, powder rolling, and gelation freezing, depending on the properties of the mixture.

[0037] The compact 10 thus obtained is heated at a temperature higher than the thermal decomposition temperature of the pore-forming material 213 and the sintering temperature of the metal powder 22, but lower than the melting point of the hydrogen storage alloy particles 3. When the compact 10 is heated at such a temperature, the pore-forming material 213 attached to the periphery of the hydrogen storage alloy particles 3 disappears due to thermal decomposition, and voids are formed around the hydrogen storage alloy particles 3. In addition, the metal powder 22 present around the hydrogen storage alloy particles 3 is integrated to form a metal porous body 2. Therefore, by heating the compact 10 at the aforementioned temperature, a hydrogen storage body 1 can be obtained.

[0038] 1 , the hydrogen storage alloy particles 3 in the hydrogen storage material 1 of this embodiment are held within the pores 21 of the metal porous body 2. Therefore, even when hydrogen is absorbed into the hydrogen storage alloy particles 3, the hydrogen storage alloy particles 3 can expand within the pores 21. Therefore, the hydrogen storage material 1 can reduce the amount of change in volume when hydrogen is absorbed.

[0039] Furthermore, the metal porous body 2 of this embodiment has high thermal conductivity. Therefore, when the temperature of the hydrogen absorbing body 1 is changed, the temperature of the hydrogen storage alloy particles 3 held in the pores of the metal porous body 2 can be quickly changed. This allows hydrogen to be quickly absorbed into the hydrogen absorbing body 1 and released from the hydrogen absorbing body 1.

[0040] Therefore, the hydrogen absorbing material 1 of this embodiment undergoes little volume change due to hydrogen absorption and has excellent thermal conductivity.

[0041] (Embodiment 2) In this embodiment, another example of a hydrogen storage material will be described. Note that, among the symbols used in this embodiment and subsequent embodiments, the same symbols as those used in the previous embodiments represent the same components as those in the previous embodiments, unless otherwise specified.

[0042] As shown in Fig. 3 as an example, the porous metal body 202 in the hydrogen absorbing body 102 of this embodiment has a three-dimensional network structure including columnar struts 23 and a hub 24 where a plurality of struts 23 are gathered together, and the voids around the struts 23 and the hub 24 form pores 21. The pores 21 in the porous metal body 202 are interconnected in portions not shown in Fig. 3. In other words, the porous metal body 202 has a continuous pore structure.

[0043] The hydrogen storage alloy particles 3 are held in the three-dimensional network structure of the metal porous body 202. Voids are formed between the metal porous body 202 and the hydrogen storage alloy particles 3, and the voids around the hydrogen storage alloy particles 3 in the pores 21 form storage spaces 211. The portions of the pores 21 excluding the storage spaces 211 form connection spaces 212.

[0044] To produce the hydrogen storage material 102 of this embodiment, a pore-forming material 213 is attached to the surface of the hydrogen storage alloy particles 3; then, as shown in Figure 4, a resin foam 4 containing the hydrogen storage alloy particles 3 and having an open pore structure is produced; a metal film that will become the metal porous material 202 is formed on the surface of the cell walls 42 of the resin foam 4; and then, by heating the resin foam 4, the pore-forming material 213 and the cell walls 42 are removed, thereby forming the metal porous material 202.

[0045] In the manufacturing method of this embodiment, first, a pore-forming material 213 is attached to the surface of the hydrogen storage alloy particle 3. The configuration of the hydrogen storage alloy particle 3, the configuration of the pore-forming material 213, and the amount of the pore-forming material 213 attached used in the manufacturing method of this embodiment are the same as those of the hydrogen storage alloy particle 3 and the pore-forming material 213 in the first embodiment.

[0046] Next, the hydrogen storage alloy particles 3 with the pore-forming material 213 attached thereto are mixed with an expandable resin, and the expandable resin is then expanded to produce a resin foam 4 containing the hydrogen storage alloy particles 3. The cells 41 of the resin foam 4 obtained in this manner have an open pore structure, i.e., a structure in which multiple cells are interconnected. Furthermore, the cell walls 42 of the resin foam 4 have a three-dimensional network structure having columnar struts 421 and hubs 422 where multiple struts 421 are aggregated, as shown in FIG. 4 . The hydrogen storage alloy particles 3 are held within the cell walls 42 of the resin foam 4.

[0047] There are no particular limitations on the foamable resin used to produce the resin foam 4, and any known foamable resin capable of forming an open pore structure can be used. For example, the resin constituting the resin foam 4 may be polyurethane, polyethylene, polystyrene, etc. Furthermore, there are no particular limitations on the method for foaming the foamable resin, and any known foaming method can be used.

[0048] It is preferable that the content of hydrogen storage alloy particles 3 in the resin foam 4 is, for example, in the range of 1 volume % or more and 55 volume % or less relative to the apparent volume of the resin foam 4, i.e., the volume of the resin foam 4 including the volume of the air bubbles 41.

[0049] By setting the content of hydrogen storage alloy particles 3 in the resin foam 4 to preferably 10 volume % or more, more preferably 20 volume % or more, and even more preferably 30 volume % or more of the apparent volume of the resin foam 4, the amount of hydrogen storage alloy particles 3 held in the hydrogen storage material 102 can be increased, and the amount of hydrogen that can be absorbed by the hydrogen storage material 102 can be increased.

[0050] The content of the hydrogen storage alloy particles 3 in the resin foam 4 can be adjusted by the mixing ratio of the expandable resin to the hydrogen storage alloy particles 3 and the expansion ratio of the expandable resin.

[0051] After obtaining a resin foam 4 containing hydrogen storage alloy particles 3 and having an open pore structure as described above, a metal film is formed on the surfaces of the cell walls 42 of the resin foam 4. While the method for forming the metal film on the surfaces of the cell walls 42 is not particularly limited, from the viewpoint of forming a metal film evenly over the entire resin foam 4, it is preferable to form the metal film on the surfaces of the cell walls 42 by a plating method. The metal constituting the metal film may be any metal other than a hydrogen storage alloy, i.e., any metal that cannot reversibly absorb and release hydrogen and that can be used to form a metal film by a plating method. Examples of metals that can be used to form the metal film include iron alloys, copper, copper alloys, chromium, chromium alloys, nickel, and nickel alloys.

[0052] The molded body is then heated at a temperature higher than the thermal decomposition temperature of the pore-forming material 213 and the thermal decomposition temperature of the cell walls 42 in the resin foam 4 (i.e., the thermal decomposition temperature of the resin that constitutes the resin foam 4), but lower than the melting point of the hydrogen storage alloy particles 3. When the molded body is heated at such a temperature, the pore-forming material 213 attached to the periphery of the hydrogen storage alloy particles 3 disappears due to thermal decomposition, and voids are formed around the hydrogen storage alloy particles 3. Furthermore, the cell walls 42 in the resin foam 4 disappear due to thermal decomposition, leaving behind metal films, and a metal porous body 202 is formed that has a three-dimensional network structure that reflects the shape of the cell walls 42 in the resin foam 4.

[0053] As described above, a hydrogen storage material 102 having the above-described structure can also be obtained by heating a resin foam 4 containing hydrogen storage alloy particles 3 and removing the pore-forming material 213 and the cell walls 42 of the resin foam 4.

[0054] (Experimental Example) In this example, an example is described in which a hydrogen storage material in embodiment 1 was produced using hydrogen storage alloy particles made of LaNi5 and having a particle diameter of 100 μm and metal powder made of stainless steel and having an average particle diameter of 3 μm.

[0055] In this example, polyvinyl acetate was dissolved in acetone to prepare a 5% by mass solution of the pore-forming aid. Next, 50 parts by mass of the pore-forming aid solution was added to 100 parts by mass of the hydrogen storage alloy particles, and the mixture was thoroughly mixed and dried to adhere the pore-forming aid to the surfaces of the hydrogen storage alloy particles.

[0056] Next, a pore-forming agent was added to the hydrogen storage alloy particles and thoroughly mixed to adhere the pore-forming agent to the surfaces of the hydrogen storage alloy particles. The pore-forming agent used was spherical resin particles made of polymethyl methacrylate and having an average particle size of 10 μm ("Ganzpearl (registered trademark) GM-1001" manufactured by Aica Kogyo Co., Ltd.). The amount of pore-forming agent added was 10 parts by mass per 100 parts by mass of the hydrogen storage alloy particles before the pore-forming aid was attached.

[0057] Separately from the preparation of the hydrogen storage alloy particles, polyvinyl alcohol was dissolved in distilled water to prepare a dispersion medium with a polyvinyl alcohol concentration of 10 mass %.

[0058] The hydrogen storage alloy particles thus obtained were mixed with a metal powder and a dispersion medium to prepare a slurry mixture. The amount of metal powder in the mixture was 66 parts by mass per 100 parts by mass of the hydrogen storage alloy particles before the pore-forming material was attached. The amount of binder solution in the mixture was 59 parts by mass per 100 parts by mass of the hydrogen storage alloy particles before the pore-forming material was attached.

[0059] The mixture obtained as described above was poured into a rectangular parallelepiped mold having a length of 50 mm, a width of 10 mm, and a thickness of 5 mm, and then cooled to a temperature of -18°C or lower. This caused the mixture in the container to gel, resulting in a molded body. This molded body was dried to remove the distilled water, and then heated at 500°C for 2 hours in an inert gas atmosphere to thermally decompose the pore-forming material, pore-forming aid, and polyvinyl alcohol in the molded body. The molded body was then heated at 750°C for 3 hours to sinter the metal powder and form a metal porous body. In this manner, a hydrogen storage body was obtained.

[0060] 5 and 6 show examples of SEM images of the surface of a hydrogen storage material 103 obtained by observing the surface of the hydrogen storage material using a scanning electron microscope. As shown in Fig. 5, the hydrogen storage material 103 has a metal porous body 2 with a large number of pores 21, and it can be seen that the pores 21 are open on the surface of the metal porous body 2. It can also be seen that the metal porous body 2 contains hydrogen storage alloy particles 3, which are shown in a lighter color tone than the metal powder 22 that constitutes the metal porous body 2.

[0061] 6, it can be seen that hydrogen storage alloy particles 3 are held in the pores 21, with voids being formed between the hydrogen storage alloy particles 3 and the metal porous body 2. Furthermore, it can be seen that the metal porous body 2 is made of a sintered body of metal powder 22, and that voids are also formed between the metal particles that make up the metal powder 22.

[0062] As described above, the method of this example made it possible to obtain a hydrogen storage body comprising a metal porous body having pores and hydrogen storage alloy particles made of a hydrogen storage alloy and held within the pores of the metal porous body.

[0063] (Embodiment 3) In this embodiment, an example of the use of the hydrogen absorbing material 1 will be described. The hydrogen absorbing material 1 may be applied to hydrogen-related equipment configured to be able to reversibly absorb and release hydrogen. For example, the hydrogen absorbing material 1 of this embodiment is used in a hydrogen container 5 configured to be able to reversibly absorb and release hydrogen, as shown in FIG. 7.

[0064] The hydrogen container 5 has a container body 51 with a storage space 511 for storing hydrogen gas, a hydrogen storage material 1 arranged in the storage space 511, and a temperature adjustment means 52 configured to change the temperature of the hydrogen storage material 1.

[0065] The container body 51 of the hydrogen container 5 is configured to be able to retain hydrogen supplied from outside the hydrogen container 5 and hydrogen released from the hydrogen absorbing material 1 in the storage space 511. The container body 51 has at least one hydrogen port 53 configured to connect the outside of the hydrogen container 5 to the storage space 511. The hydrogen port 53 is configured to connect the external space to the storage space 511, thereby allowing hydrogen to be supplied from outside the hydrogen container 5 to the storage space 511 and / or hydrogen to be released from the hydrogen container 5 to the outside. The number of hydrogen ports 53 provided on the container body 51 may be one or two or more. For example, as shown in FIG. 7 , the container body 51 of this embodiment has one hydrogen port 53, and is configured so that the hydrogen port 53 can be used both to supply hydrogen from outside the hydrogen container 5 to the storage space 511 and to release hydrogen from the hydrogen container 5 to the outside.

[0066] The shape of the container body 51 is not particularly limited, and various shapes such as a cylindrical shape, a spherical shape, a box shape, etc. For example, the container body 51 of this embodiment has a cylindrical shape as shown in FIG.

[0067] The volume of the container body 51 is 300 m 3 The pressure fluctuation when releasing hydrogen from the hydrogen container 5 tends to increase as the volume of the container body 51 decreases. 3 By setting the volume of the vessel body 51 to 300 m or less, the effect of suppressing the pressure fluctuation during hydrogen release can be more effectively achieved. 3 By adopting the following configuration, the hydrogen container 5 can be easily made smaller, and restrictions on installation location can be reduced.

[0068] The maximum value of the internal pressure of the container body 51 is preferably 1 MPa (G) or less in terms of gauge pressure. 3 In addition to keeping the maximum internal pressure of the container body 51 at 1 MPa (G) or less, the safety of the container body 51 can be improved and maintenance of the container body 51 can be made easier.

[0069] The hydrogen absorbing material 1 is provided in the storage space 511 of the container body 51. The number, shape, arrangement, etc. of the hydrogen absorbing materials 1 provided in the container body 51 are not particularly limited, and can be set appropriately depending on the desired maximum hydrogen storage amount, the pressure when releasing hydrogen from the hydrogen container 5, etc.

[0070] The temperature adjustment means 52 changes the temperature of the hydrogen absorbing body 1, thereby releasing hydrogen absorbed in the hydrogen absorbing body 1 from the hydrogen absorbing body 1 to the storage space 511, or absorbing hydrogen in the storage space 511 into the hydrogen absorbing body 1. The method by which the temperature adjustment means 52 changes the temperature of the hydrogen absorbing body 1 is not particularly limited and various embodiments are possible. For example, the temperature adjustment means 52 in this embodiment is configured to change the temperature of the hydrogen absorbing body 1 by heating or cooling the entire container body 51. Therefore, for example, by increasing the temperature of the hydrogen absorbing body 1 with the temperature adjustment means 52, hydrogen can be released from the hydrogen absorbing body 1 to the storage space 511. Also, for example, by lowering the temperature of the hydrogen absorbing body 1, hydrogen in the storage space 511 can be absorbed into the hydrogen absorbing body 1.

[0071] As described above, the hydrogen storage alloy particles 3 in the hydrogen storage material 1 are held within the pores 21 of the metal porous body 2. Therefore, the hydrogen storage material 1 can reduce the amount of change in volume when hydrogen is absorbed. Therefore, by applying the hydrogen storage material 1 to the hydrogen container 5 as in this embodiment, the load applied to the container body 51 when hydrogen is absorbed into the hydrogen storage material 1 can be more easily reduced, making it less likely that distortion will occur in the container body 51. Furthermore, in this case, hydrogen can be stored more efficiently in the hydrogen container 5.

[0072] The hydrogen absorbing material 1 used in the hydrogen container 5 preferably has hydrogen storage alloy particles made of a TiFe-based hydrogen storage alloy. Because TiFe-based hydrogen storage alloys are easy to handle, applying hydrogen storage alloy particles made of a TiFe-based hydrogen storage alloy to the hydrogen absorbing material 1 of the hydrogen container 5 can further improve the safety of the hydrogen container 5. In addition, because TiFe-based hydrogen storage alloys are relatively inexpensive among hydrogen storage alloys, further cost reductions in the hydrogen container 5 can be expected.

[0073] The TiFe-based alloys described above include TiFe binary alloys and TiFe-based multi-component alloys in which part of the Ti and / or Fe in the TiFe binary alloy is replaced with another element. The TiFe-based alloy may be, for example, a TiFeMn ternary alloy in which part of the Fe in the TiFe binary alloy is replaced with Mn. The TiFe-based alloy may also be a multi-component alloy obtained by further adding another metal element to the TiFeMn ternary alloy.

[0074] The above describes aspects of the hydrogen storage material and its manufacturing method based on embodiments and experimental examples, but the specific aspects of the hydrogen storage material and its manufacturing method according to the present invention are not limited to the above embodiments and experimental examples, and the configuration can be changed as appropriate within the scope that does not deviate from the gist of the present invention.

Claims

1. A hydrogen storage body comprising: a metal porous body having pores; and hydrogen storage alloy particles made of a hydrogen storage alloy and held within the pores of the metal porous body.

2. The hydrogen storage material according to claim 1, wherein a portion of the surface of said hydrogen storage alloy particles is separated from said metal porous body.

3. The hydrogen storage material according to claim 1, wherein the hydrogen storage alloy particles are movably held within the pores of the metal porous body.

4. The hydrogen storage material according to any one of claims 1 to 3, wherein the metal porous body is a sintered product of metal powder.

5. A hydrogen storage material according to any one of claims 1 to 3, wherein the metal porous body has a three-dimensional mesh structure consisting of columnar struts and hubs formed by assembling a plurality of the struts.

6. A method for producing a hydrogen storage body as described in claim 4, comprising the steps of: attaching a pore-forming material to the surface of the hydrogen storage alloy particles; then mixing the hydrogen storage alloy particles with a metal powder that will become the metal porous body to produce a mixture; molding the mixture to produce a compact; and heating the compact to remove the pore-forming material and sinter the metal powder to form the metal porous body.

7. A method for producing a hydrogen storage body as described in claim 5, comprising the steps of: attaching a pore-forming material to the surface of the hydrogen storage alloy particles; then producing a resin foam containing the hydrogen storage alloy particles and having an open pore structure; forming a metal film that will become the metal porous body on the surface of the cell walls of the resin foam; and then heating the resin foam to remove the pore-forming material and the cell walls to form the metal porous body.

8. A hydrogen container comprising the hydrogen storage material according to any one of claims 1 to 3.

9. A hydrogen container according to claim 8, wherein said hydrogen storage alloy particles in said hydrogen storage body are composed of a TiFe-based hydrogen storage alloy.

Citation Information

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