Solid-state hydrogen storage material, preparation method thereof, and hydrogen storage device using the same

Abstract

A solid hydrogen storage material, a preparation method thereof, and a hydrogen storage device using the same, belonging to the field of hydrogen storage and transportation. The solid hydrogen storage material can form a three-dimensional structure having two main surfaces facing each other, either alone or in combination; wherein the minimum circumscribed circle diameters of the two main surfaces are both between 6 and 25 cm; when combined to form a three-dimensional structure, the number of solid hydrogen storage materials is 2 to 5; the thickness of the three-dimensional structure is between 1 and 5 cm; one or more through holes are formed between the two main surfaces; and the three-dimensional structure can be accommodated inside a hydrogen storage device. The solid hydrogen storage material of the present invention can reduce the degree of wear between the material and the pallet during transportation and reduce the loss of hydrogen storage medium through shape and size design; the hydrogen release rate is fast, taking into account the hydrogen charging rate, which can improve operational efficiency; the hydrogen storage density is large, which is convenient and safe to transport, especially when a square cylinder is selected, the hydrogen storage density is the highest.

Description

Technical Field

[0001] The present invention relates to the field of hydrogen storage and transportation, and in particular to a solid hydrogen storage material, a preparation method thereof, and a hydrogen storage device using the same. Background Art

[0002] Solid-state hydrogen storage technology has been an important research direction in the hydrogen energy field in the past two years. It has significant advantages over traditional high-pressure gaseous hydrogen storage and low-temperature liquid hydrogen storage in terms of safety, economy, and hydrogen storage density. It has shown broad application potential, especially in the fields of automotive hydrogen energy, long-distance transportation, and large-scale energy storage.

[0003] Solid-state hydrogen storage technology stores hydrogen in solid materials through physical adsorption or chemical reaction. Compared with traditional high-pressure gaseous hydrogen storage and low-temperature liquid hydrogen storage methods, its significant advantages are reflected in the following aspects: (1) High hydrogen storage density: The hydrogen storage density of magnesium-based solid-state hydrogen storage materials can reach more than 6.4wt%, and the capacity of a single hydrogen storage tank is as high as 1 ton, which is much higher than traditional hydrogen storage methods. (2) High safety: The stability of solid-state hydrogen storage materials enables safe storage of hydrogen at room temperature and pressure, reducing the risks during transportation and use. (3) Good economy: It eliminates the complex compression or cryogenic process, reducing equipment costs and energy consumption. (4) Strong environmental adaptability: It has low requirements for ambient temperature and pressure and is suitable for a variety of application scenarios.

[0004] Because of these advantages, solid-state hydrogen storage technology has become a hot topic in current research, especially magnesium-based solid-state hydrogen storage technology, which has entered the commercial application stage and achieved breakthroughs in many fields. However, as a highly promising hydrogen storage and transportation solution, magnesium-based solid-state hydrogen storage technology has significant advantages in terms of safety, hydrogen storage density and normal temperature and pressure operation, but it has not yet become the main means of transporting hydrogen on vehicles. The main reasons include the following aspects: (1) On-vehicle gas storage equipment needs to fully consider the crash resistance and equipment safety of hydrogen storage materials. Compared with fixed hydrogen storage equipment, powder, small particles and other hydrogen storage materials cannot be used because they are easy to collide and crush, resulting in gas pipeline blockage and induce accidents, or hydrogen storage materials are lost due to airflow; (2) On-vehicle hydrogen storage equipment must also take into account the convenience of hydrogen charging and release. Magnesium-based solid-state hydrogen storage materials (such as MgH2) reach a temperature of 300℃ and a pressure of 1~5 MPa during hydrogen charging. When releasing hydrogen, it needs to reach a high temperature of more than 300℃. The hydrogen release temperature is high and the kinetics are slow, which requires the storage and transportation equipment to be able to withstand high temperature and high pressure. (3) On-board hydrogen storage equipment needs to fully improve its transportation capacity. If magnesium-based solid-state hydrogen storage technology is used, it is required to store as much hydrogen as possible per unit volume. This contradicts the above-mentioned point (1) because it is well known in the art that the smaller the particle volume of magnesium-based solid-state hydrogen storage material, the larger the surface area, the greater the hydrogen storage density and hydrogen release rate.

[0005] In summary, in order to better improve the efficiency and safety of on-board hydrogen transportation, there is an urgent need to develop a solid-state hydrogen storage material and equipment to at least partially solve the current defects and shortcomings. Summary of the Invention

[0006] In view of this, the main purpose of the present invention is to provide a solid hydrogen storage material, a preparation method thereof and a hydrogen storage device using the same, in order to at least partially solve the above technical problems.

[0007] In order to achieve the above objectives, as a first aspect of the present invention, a hydrogen storage device is proposed, comprising:

[0008] a sealed housing with a cavity formed therein;

[0009] A plurality of limiting gas guide rods are arranged inside the cavity; a hydrogen delivery channel is formed inside the limiting gas guide rods, and a plurality of gas outlet holes are provided on the surface of the limiting gas guide rods, which can deliver hydrogen to the interior of the solid hydrogen storage material passing through the limiting gas guide rods, or output hydrogen from the interior of the solid hydrogen storage material;

[0010] A hydrogen input and output interface is provided on the sealed housing and is connected to the hydrogen delivery channel inside the limiting gas guide rod;

[0011] Solid-state hydrogen storage materials, either alone or in combination, constitute a three-dimensional structure having two main surfaces facing each other; wherein the minimum circumscribed circle diameters of the two main surfaces of the three-dimensional structure are both between 6 and 25 cm, and one or more through holes are formed between the two main surfaces of the three-dimensional structure; wherein each three-dimensional structure constituted by the solid-state hydrogen storage materials, either alone or in combination, is sequentially passed through a limiting gas guide rod, and its displacement in the radial direction of the limiting gas guide rod is limited by the limiting gas guide rod; any outermost end of the sequentially stacked three-dimensional structures abuts against the inner wall of the cavity through a buffer element, or each three-dimensional structure is connected through a buffer element; and a certain gap is formed between the side surfaces of each three-dimensional structure and the inner wall of the cavity.

[0012] As a second aspect of the present invention, a solid-state hydrogen storage material is also proposed, wherein:

[0013] The solid-state hydrogen storage materials can be individually or in combination to form a three-dimensional structure having two main surfaces facing each other; wherein the minimum circumscribed circle diameters of the two main surfaces of the three-dimensional structure are both in the range of 6 to 25 cm; when the three-dimensional structure is formed by combining the solid-state hydrogen storage materials, the number of the solid-state hydrogen storage materials is 2 to 5;

[0014] The thickness of the three-dimensional structure is in the range of 1 to 5 cm;

[0015] One or more through holes are formed between the two main surfaces of the three-dimensional structure;

[0016] The three-dimensional structure can be accommodated inside the hydrogen storage device as described above.

[0017] As a third aspect of the present invention, a method for preparing a solid hydrogen storage material is also proposed, comprising the following steps:

[0018] Forming solid hydrogen storage materials of suitable composition into a three-dimensional structure composed of the solid hydrogen storage materials described above, either alone or in combination, and forming one or more through holes on the main surface thereof, and dividing the three-dimensional structure into a corresponding number of blocks of solid hydrogen storage materials as needed; or

[0019] A three-dimensional structure composed of the above-mentioned solid hydrogen storage materials alone or in combination is prepared using a mold capable of forming one or more through holes on the main surface, and the three-dimensional structure is divided into a corresponding number of blocks of solid hydrogen storage materials as needed.

[0020] As a fourth aspect of the present invention, a hydrogen storage device is also proposed, which uses the solid-state hydrogen storage material as a hydrogen storage medium.

[0021] Based on the above technical solutions, it can be seen that the solid-state hydrogen storage material and the preparation method thereof of the present invention have at least one of the following beneficial effects compared with the prior art:

[0022] 1. The solid-state hydrogen storage material of the present invention is designed in shape and size, and matched with the corresponding tank limit gas guide rod design, so that the static friction coefficient between the solid-state hydrogen storage material and the pallet is high and the movable space is small. The relative displacement between the material and the pallet can be reduced during transportation, thereby reducing the degree of wear and tear, reducing the loss of hydrogen storage medium, and improving the durability of the material;

[0023] 2. The solid-state hydrogen storage material of the present invention has a fast hydrogen release rate and a good hydrogen filling rate through shape and size design, combined with the corresponding tank limit gas guide rod design, which can improve operating efficiency;

[0024] 3. The solid-state hydrogen storage material of the present invention is designed in shape and size, matched with the corresponding tank limit gas guide rod design and the integrated tank design, which facilitates transportation and hydrogen charging and release. It has a high hydrogen storage density, simple operation, a high number of repetitions, and ensures safe transportation. In particular, when a square cylinder is selected, the hydrogen storage density is maximized. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following briefly introduces the drawings required for use in the embodiments.

[0026] Figure 1 is a structural perspective view of a hydrogen storage device loaded with solid hydrogen storage material according to the present invention;

[0027] Figure 2 is a perspective view of a solid-state hydrogen storage material according to an embodiment of the present invention;

[0028] Figure 3 is a perspective view of a solid hydrogen storage material according to another embodiment of the present invention;

[0029] Figure 4 This is a perspective schematic diagram of an embodiment of a hydrogen storage device of the present invention in which a branch pipe is provided on a limiting gas guide rod;

[0030] Figure 5 is a schematic radial cross-sectional view of a three-part embodiment of the solid-state hydrogen storage material of the present invention;

[0031] Figure 6 It is a flow chart of the preparation method of the solid-state hydrogen storage material of the present invention.

[0032] In the above drawings, the meanings of the reference numerals are as follows:

[0033] 1- solid hydrogen storage material; 2- through hole; 3- limiting gas guide rod; 4- gas outlet; 5- buffer element; 6- cavity; 7- branch pipe. DETAILED DESCRIPTION

[0034] In order to make the objectives, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with specific embodiments and with reference to the accompanying drawings.

[0035] The terms used in the present invention are only for the purpose of describing specific embodiments and are not intended to limit the embodiments of the present invention. The singular forms "a", "an", "the" and "the" used in the embodiments of the present invention and the appended claims are also intended to include plural forms unless the context clearly indicates otherwise.

[0036] In this article, some terms have the following meanings:

[0037] The main surface refers to the most important surface among all surfaces of a three-dimensional structure, usually the surface with the largest area or the surface that best reflects the characteristics or functions of the three-dimensional structure.

[0038] Geometric diameter, usually refers to the maximum width of an irregular shape, that is, the maximum distance between any two points within the shape. For example, for a convex closed curve, the diameter can be defined by measuring the maximum distance between two points within the shape.

[0039] Minimal Circumscribed Circle Diameter: Find the smallest circle that can completely enclose the irregular shape and use the diameter of that circle to represent the diameter of the shape.

[0040] Aspect ratio, the ratio of height to the minimum circumscribed circle diameter of the surface in the direction perpendicular to the height, that is, the ratio of height to diameter.

[0041] In the present invention, for ease of description, the two opposing principal surfaces are disposed on the XY plane, and the maximum distance between the two principal surfaces, i.e., the thickness, is disposed in the Z-axis direction. Therefore, the two principal surfaces are referred to as the upper and lower surfaces, and the other surfaces surrounding the two principal surfaces are referred to as side surfaces.

[0042] At present, solid-state hydrogen storage technology is developing rapidly, and has excellent performance in both fixed hydrogen storage equipment and hydrogen production equipment. However, hydrogen storage equipment used for vehicle transportation is still mainly high-pressure gaseous or liquid hydrogen storage equipment. After careful analysis of the deficiencies of the existing technology and in-depth research through theoretical calculations, simulation experiments and experimental tests, the inventors found that by limiting the shape of solid-state hydrogen storage materials and combining them with specific hydrogen storage tank designs, it is possible to solve both the safety of hydrogen transportation and the problem of rapid hydrogen filling and release. Therefore, if Figure 1 As shown, the inventors have proposed a hydrogen storage device, such as a solid-state hydrogen storage cylinder or a solid-state hydrogen storage tank, comprising:

[0043] a sealed housing with a cavity 6 formed therein;

[0044] A plurality of limiting gas guide rods 3 are provided inside the cavity 6; a hydrogen delivery channel is formed inside the limiting gas guide rods 3, and a plurality of gas outlet holes 4 are provided on the surface thereof, which can deliver hydrogen to the interior of the solid hydrogen storage material 1 passing through the limiting gas guide rods 3;

[0045] The hydrogen input and output interface is provided on the sealed housing and is connected to the hydrogen delivery channel inside the limiting gas guide rod 3;

[0046] Solid-state hydrogen storage material 1, alone or in combination, constitutes a three-dimensional structure having two main surfaces opposite to each other; wherein the minimum circumscribed circle diameters of the two main surfaces of the three-dimensional structure are both between 6 and 25 cm, and one or more through holes 2 are formed between the two main surfaces of the three-dimensional structure; wherein each of the three-dimensional structures constituted by the solid-state hydrogen storage material 1 alone or in combination is sequentially penetrated on the limiting gas guide rod 3, and its displacement in the radial direction of the limiting gas guide rod 3 is limited by the limiting gas guide rod 3; any outermost end of the three-dimensional structure constituted by the solid-state hydrogen storage material 1 stacked in sequence, alone or in combination, abuts against the inner wall of the cavity 6 through the buffer element 5, or each three-dimensional structure is connected through the buffer element 5; a certain gap is formed between the side of the three-dimensional structure and the inner wall of the cavity 6.

[0047] Therefore, the limiting gas guide rod 3 can not only fix the solid hydrogen storage material 1 to prevent its radial and axial displacement, but also directly transport hydrogen to the interior of the solid hydrogen storage material 1 through the internal hydrogen transport channel, and export it from the interior, thereby increasing the rate of hydrogen charging and release.

[0048] in, Figure 1 The sealed housing is not shown in the figure. Its outermost shell has many elongated openings, forming a sandwich shell inside the sealed housing. A hydrogen transport channel is formed between the outermost shell and the sealed housing, thereby increasing the rate of hydrogen charging and release. When the outermost shell is not provided with elongated openings, it can also be used directly as a sealed housing. In this case, the gap formed by the side of the solid hydrogen storage material 1 and the inner wall of the cavity 6 can be used to form a hydrogen transport channel, thereby increasing the rate of hydrogen charging and release. It should be noted that the biggest difference from traditional solid-state hydrogen storage tanks is that the hydrogen storage device of the present invention emphasizes transportation. The tank body itself is not used as a reactor, so the tank body does not need to bear pressure, and the wall thickness can be greatly reduced, making transportation more convenient and safer. The sealed housing of the present invention does not require various heating elements to be installed inside, so the sealed housing can be made relatively thin, with a thickness of, for example, 0.5 to 2 mm. The material can be, for example, engineering plastics such as polycarbonate (PC) or polyetheretherketone, or aluminum or alloys, or iron or alloys.

[0049] Among them, the limiting gas guide rods 3 can be, for example, multiple rods arranged in parallel, so that the entire hydrogen storage device is a fat tank, that is, a solid-state hydrogen storage tank, or there can be only one rod located in the middle of the cavity 6, so that the entire hydrogen storage device is a slender long cylinder, that is, a solid-state hydrogen storage cylinder.

[0050] The outlet holes 4 on the limiting gas guide rod 3 are, for example, narrow holes, particularly elongated holes, to reduce the loss of effective hydrogen storage medium caused by crushed solid hydrogen storage material entering the hydrogen transport channel through the outlet holes. Preferably, the outlet holes 4 have a width / length ratio (e.g., the ratio of the minor axis to the major axis in the case of an elliptical or racetrack shape) of less than or equal to 1 / 3, more preferably less than 1 / 5.

[0051] Among them, the limiting gas guide rod 3 also includes, for example, several branch pipes 7 extending in the radial direction, and a through hole 2 or a blind hole is formed at the corresponding position of the solid hydrogen storage material 1 to accommodate the branch pipe 7, so that the hydrogen transported by the hydrogen transport channel can be better transported into the interior of the solid hydrogen storage material 1, ensuring the rate of hydrogen charging and release. When the limiting gas guide rod 3 includes a branch pipe 7, due to the lateral obstruction of the branch pipe 7, the three-dimensional structure formed by the solid hydrogen storage material 1 cannot be directly mounted on the limiting gas guide rod 3. At this time, the three-dimensional structure formed by the solid hydrogen storage material 1 can be divided into 2-5 parts, each of which is respectively passed through the corresponding branch pipe 7 of the limiting gas guide rod 3 in the radial direction, and the three-dimensional structure is formed after the positions are aligned. Preferably, the 2-5 portions of solid hydrogen storage material 1 are, for example, 2-5 portions divided by the through hole in the middle of the three-dimensional structure, and more preferably, evenly divided. In this case, each portion of the solid hydrogen storage material 1 is provided with one or more through holes 2 or blind holes in the direction of the limiting gas guide rod 3, which can be used to accommodate the branch pipe 7 extending into the interior of each portion of the solid hydrogen storage material 1, or simply form an internal air flow channel. In a preferred embodiment, as Figure 4 As shown, the limiting air guide rod 3 includes three branch pipes 7 with a radial angle of 120 degrees. The limiting air guide rod 3 is provided with a flat oval air outlet 4, and the branch pipes 7 are provided with a flat long strip air outlet 4.

[0052] Among them, the sealed shell is welded after being filled with the solid-state hydrogen storage material 1, thereby forming a disposable sealed device; or it can also be provided with an operating port for replacing the internal solid-state hydrogen storage material 1, which not only ensures its sealing requirements, but also enables the inner core to be replaced after it is recycled several times (generally more than 1000 to 1500 times), thereby extending the service life of the sealed shell.

[0053] The buffer element 5 is, for example, a spring or a deformable elastic material (such as metal foam, etc.), preferably a spring, because during the hydrogen release process, the entire hydrogen storage device needs to be heated to above 300°C, and the deformable elastic material is prone to aging and failure due to repeated heating.

[0054] The hydrogen storage device may be fixed or mobile, but is preferably mobile, particularly capable of cargo transportation, such as vehicle-mounted (e.g., by car or train), ship-mounted (e.g., by ship), or aircraft-mounted (e.g., by airplane). Thus, for example, it may be a vehicle-mounted hydrogen storage cylinder or tank, a ship-mounted hydrogen storage tank, etc. When the hydrogen storage device is a vehicle-mounted hydrogen storage cylinder or tank, these vehicle-mounted hydrogen storage cylinders or tanks can be loaded onto freight trucks or trains via specialized cargo racks, thereby enabling efficient batch transfer.

[0055] like Figure 2 、3 As shown, the present invention also proposes a solid hydrogen storage material 1, which has the following characteristics:

[0056] The solid hydrogen storage material 1 can be formed into a three-dimensional structure with two main surfaces facing each other, either alone or in combination. The two main surfaces include an upper surface and a lower surface, and the areas of the two surfaces can be the same or different, but both meet the diameter size requirements described below. Figure 2 As shown, it is the main surface of the square, such as Figure 3 As shown, the main surface is circular. The present invention does not specifically limit the surface other than the main surface. For example, it can be multiple side faces of a polygon, a completely arcuate side face of a cylinder, or an irregular shape. To facilitate processing and minimize damage to the container's inner wall, the side faces are preferably continuous or spliced ​​planes or curved surfaces, such as the arcuate face of an (elliptical) cylinder or the four rectangular faces of a cube.

[0057] The two main surfaces of the three-dimensional structure formed by the solid hydrogen storage material 1 alone or in combination have a minimum circumscribed circle diameter, for example, in the range of 6 to 25 cm; the purpose of setting the minimum circumscribed circle diameter is to limit the size of the solid hydrogen storage material 1. If it is too small, it is easy for them to collide with each other and crush each other, causing powder to block the gas pipeline, or cause the effective hydrogen storage medium to be lost as the airflow overflows; if it is too large, it may increase the risk of accidents, because the vehicle container may become a bomb when encountering a violent collision. The larger the hydrogen storage volume, the higher the risk of flash explosion and violent combustion and explosion. After careful calculation, it was determined that the minimum circumscribed circle diameter of 6 to 25 cm is the best effect. Preferably, the two main surfaces of the solid hydrogen storage material 1 have a minimum circumscribed circle diameter of, for example, 6 to 20 cm, and more preferably 8 to 15 cm.

[0058] The thickness of the three-dimensional structure formed by the solid-state hydrogen storage material 1, either alone or in combination, is, for example, 1 to 5 cm; this is also obtained through careful calculation and simulation experiments. Preferably, the thickness of the three-dimensional structure formed by the solid-state hydrogen storage material 1, either alone or in combination, is, for example, 1.5 to 4.5 cm, and more preferably 2 to 4 cm. In some cases, the three-dimensional structure formed by the solid-state hydrogen storage material 1, either alone or in combination, is formed by compressing or stacking multiple sheets of material with a thickness of less than 1 cm. This design can meet the requirements of the present invention when used less frequently. However, during repeated hydrogen charging and release, the expansion of the different sheets may be asynchronous, leading to delamination and peeling. This can exacerbate the collision of the different layers during transportation and make them more susceptible to breakage. Therefore, while this design meets the basic requirements, it is not the optimal choice. In other words, in general, the solid-state hydrogen storage material 1 of the present invention includes the use of multiple sheets of material with a thickness of less than 1 cm, compressed or stacked. However, in applications where service life is important, the solid-state hydrogen storage material 1 of the present invention preferably does not include this configuration, requiring the thickness of a single sheet to be within the range of 1 to 5 cm.

[0059] One or more through-holes 2 are formed between the two main surfaces of the three-dimensional structure formed by the solid hydrogen storage material 1, either alone or in combination. The through-holes 2 can be used to pass through the limiting gas guide rods 3 for limiting position, or can serve as airflow channels to allow hydrogen gas to directly reach the interior of the solid hydrogen storage material, reducing the hydrogen penetration distance and increasing the hydrogen charging and release rate.

[0060] Among them, the shape of at least one of the two main surfaces of the three-dimensional structure composed of the solid-state hydrogen storage material 1 alone or in combination conforms to axial symmetry, rotational symmetry or central symmetry. The shapes of the upper and lower surfaces can be completely consistent or slightly different, but it must be ensured that the three-dimensional structure can be easily accommodated in the cavity of the hydrogen storage device.

[0061] The aspect ratio of the three-dimensional structure of the solid hydrogen storage material 1 alone or in combination is, for example, in the range of 0.04 to 0.33, thereby ensuring the density uniformity of the solid hydrogen storage material 1 .

[0062] Among them, when a three-dimensional structure is formed by combining multiple portions of solid hydrogen storage materials, each solid hydrogen storage material is provided with one or more through holes 2 or blind holes on the side facing the limiting gas guide rod 3 with the air outlet 4, part of which can accommodate the branch pipe 7 radially extending from the limiting gas guide rod 3, and part of which can simply serve as a hydrogen gas flow channel. Due to the lateral obstruction of the branch pipe 7, the three-dimensional structure formed by the solid hydrogen storage material 1 cannot be directly mounted on the limiting gas guide rod 3. At this time, the three-dimensional structure formed by the solid hydrogen storage material 1 can be divided into 2-5 parts, and each part is respectively passed through the branch pipe 7 of the limiting gas guide rod 3 in the radial direction, and the three-dimensional structure is formed after the positions are aligned. Preferably, the 2-5 parts of solid hydrogen storage material 1 are, for example, 2-5 parts cut by the through hole in the middle position of the three-dimensional structure, and more preferably, they are evenly divided. In a preferred embodiment, as Figure 5 As shown, Figure 5 It is a radial cross-sectional schematic diagram of a three-part embodiment of the solid-state hydrogen storage material 1 of the present invention. The three parts of the solid-state hydrogen storage material 1 constitute the three-dimensional structure, and the three parts are evenly divided through the center point. A blind hole is provided on the side of each part of the solid-state hydrogen storage material 1 facing the limiting gas guide rod 3 with the air outlet 4, which can accommodate the branch pipe 7 (gray part) radially extending from the limiting gas guide rod 3.

[0063] The specific material composition of the solid-state hydrogen storage material 1 is not limited and can be various existing magnesium elements or magnesium alloy materials with excellent performance, or other aluminum-based or rare earth solid-state hydrogen storage materials. Preferably, the magnesium content is required to be greater than 50% to ensure that magnesium is the primary element for hydrogen storage. Examples of magnesium-based hydrogen storage materials include pure magnesium, transition metal-doped magnesium-based materials, Mg-Ni alloys, and Mg-Ni-RE alloys.

[0064] Wherein, the two main surfaces of the three-dimensional structure composed of the solid hydrogen storage material 1 alone or in combination are, for example, planes, or have concave-convex or wavy structures on the plane, so as to facilitate the upper and lower engagement and positioning and reduce left and right shaking. When the three-dimensional structures composed of the solid hydrogen storage material 1 alone or in combination are stacked on each other, any outermost end is in contact with the inner wall of the cavity 6 through the buffer element 5, rather than each three-dimensional structure being connected through the buffer element, the three-dimensional structure is also required to be able to be stacked up and down. Therefore, when the lower surface of a three-dimensional structure is wavy, the upper surface of the three-dimensional structure stacked below it needs to be a matching wavy shape. Whether the lower surface of the three-dimensional structure stacked below it is wavy is not limited, as long as it matches the shape of the upper surface of the corresponding next three-dimensional structure.

[0065] Among them, the one or more through holes 2 include at least one main hole, the minimum circumscribed circle diameter is between 0.5 and 5 cm, or relative to the total area of ​​the main surface, the area of ​​the at least one main hole accounts for 1% to 25% of the total area of ​​the main surface, and can be passed through the limiting air guide rod 3 with the air outlet 4.

[0066] Among them, the solid-state hydrogen storage material 1 is a vehicle-mounted solid-state hydrogen storage material, which complies with relevant transportation regulations.

[0067] like Figure 6 As shown, the present invention also proposes a method for preparing the solid hydrogen storage material 1 as described above, comprising the following steps:

[0068] Method 1: solid hydrogen storage materials 1 of suitable composition are formed into a three-dimensional structure consisting of the solid hydrogen storage materials 1 described above, either individually or in combination, and one or more through holes 2 are formed on the main surface thereof. The three-dimensional structure is then divided into a corresponding number of blocks of solid hydrogen storage materials 1 as needed;

[0069] Alternatively, method 2: using a mold capable of forming one or more through holes 2 on the main surface to prepare a three-dimensional structure composed of solid hydrogen storage materials 1 alone or in combination, and dividing the three-dimensional structure into a corresponding number of blocks of solid hydrogen storage materials 1 as needed.

[0070] The present invention also provides a hydrogen storage device, such as a hydrogen storage tank, which uses the solid-state hydrogen storage material as a hydrogen storage medium.

[0071] The present invention will be further described below through specific examples. It should be noted that the following examples are merely illustrative and are not intended to limit the present invention. Based on the embodiments of the present invention shown below, all other embodiments obtained by those of ordinary skill in the art without creative work are within the scope of protection of the embodiments of the present invention.

[0072] Specific experimental methods

[0073] 1. The degree of collision wear and powderization of various shapes and sizes

[0074] Coefficient of friction: The ratio of the friction between two surfaces to the perpendicular force acting on one surface. The taller and larger the diameter of the magnesium cake (ingot), the greater the coefficient of friction, the less likely it is to slide, and the fewer collisions it will experience. Refer to "Test Method for Coefficient of Friction of Thin Plates and Strips of Metallic Materials," standard number YB / T4286-2012.

[0075] Solid-state hydrogen storage materials expand during hydrogen absorption, generating expansion stress within the material. This in turn can cause cracks to initiate, leading to material breakage or even pulverization. Collisions during transportation can cause crack propagation, exacerbating breakage and pulverization. The extent of material breakage and pulverization can be measured using weighing methods.

[0076] 2. Hydrogen charging and releasing rate

[0077] The hydrogen charge and release rate can be measured using a Sieverts device to measure the amount of hydrogen released per unit mass of material per unit time. The testing process can be referenced in the national standard "Rare Earth Hydrogen Storage Alloys for Solid-State Hydrogen Storage," GB / T 44754-2024. For larger materials, the charge and release rate is related to heat and mass transfer.

[0078] 3. Radial thermal resistance and axial thermal resistance

[0079] Axial thermal resistance , where is the heat transfer distance, is the thermal conductivity, The larger the magnesium cake, the longer the heat transfer distance, the greater the thermal resistance, and the slower the heat transfer. This can be tested using an interface material thermal conductivity and thermal resistance meter.

[0080] Radial thermal resistance Where r2 is the outer diameter of the magnesium cake, r1 is the inner diameter of the magnesium cake, and L is the length of the magnesium cake.

[0081] 4. Gas pressure drop between main surfaces per unit area

[0082] The gas pressure drop per unit area between the main surfaces represents the ease with which gas diffuses within the material. The greater the distance between the two main surfaces of the magnesium cake, the greater the gas pressure drop, indicating that it is more difficult for gas to penetrate the material. This can be measured using a permeability tester.

[0083] 5. Hydrogen storage density per unit volume

[0084] The volumetric hydrogen storage density is related to the magnesium cake's manufacturing process. Assuming the magnesium cake is compacted using a briquetting machine, the higher the compaction pressure, the greater the volumetric hydrogen storage density. The volumetric hydrogen storage density can be determined by measuring the hydrogen storage capacity using a Sieverts apparatus and then dividing it by the volume.

[0085] 6. Density uniformity

[0086] Uniform block density leads to more uniform block performance. The smaller the block height, the smaller the density variation; the larger the block diameter, the smaller the density variation. To ensure uniform density, the block's height-to-diameter ratio should be reduced. The density of a compact can be determined by cutting the block axially, measuring the hardness distribution along the cross-section, and then converting the hardness value into density using a standard curve.

[0087] Specific experimental steps

[0088] Example 1

[0089] The magnesium-based solid hydrogen storage material is a square cylinder with a square main surface, a minimum circumscribed circle diameter of 6 cm, and a thickness of 1 cm. A through hole with a diameter of 1 cm is formed in the center of the main surface.

[0090] Examples 2-14

[0091] The specific solution is the same as that in Example 1, except that the parameters shown in Table 1 below are different, and the solid-state hydrogen storage material in Examples 1-12 is magnesium-nickel alloy, while the solid-state hydrogen storage material in Examples 13 and 14 is magnesium-rare earth alloy.

[0092] The specific experimental data (partially using simulation data) of the above embodiments 1-14 are also shown in Table 1 below.

[0093] Table 1 Specific parameter settings and experimental (simulation) results of Examples 1-14

[0094]

[0095] Comparative Examples 1-10

[0096] The specific solution is the same as Example 1, except that the parameters shown in Table 2 below are different, and the solid hydrogen storage material in Comparative Examples 1-9 uses magnesium-nickel alloy, and the solid hydrogen storage material in Comparative Example 10 uses magnesium-rare earth alloy.

[0097] The specific experimental data (partially using simulation data) of the above comparative examples 1-10 are also shown in Table 2 below.

[0098] Table 2 Specific parameter settings and experimental (simulation) results of comparative examples 1-10

[0099]

[0100] The above comparative study reveals that while traditional powdered solid-state hydrogen storage materials offer high hydrogen charging and discharging efficiency, they are prone to shifting after pulverization, leading to safety hazards and loss of effective storage medium. They also violate transportation regulations. Solid-state hydrogen storage materials with minimum circumscribed diameters less than 5 cm and greater than 30 cm, or without through-hole structures, are inferior to the shapes and sizes designed in the present invention in terms of hydrogen charging and release rates and frictional stability (safety). Further experimental research also demonstrates that by limiting the numerical ranges of diameter and thickness, and by coordinating the placement of through-holes in the limiting gas guide rod, regardless of the specific material of the hydrogen storage medium, the charging and release rates and storage density can be further improved while ensuring safety, achieving a balance between safe transportation and high charging and release rates. Further adjustments to the proportion of the main surface occupied by the through-holes and the shape and distribution of the outlet holes on the limiting gas guide rod of the hydrogen storage device can achieve even better technical results.

[0101] In the description of the present invention, the description with reference to the terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In the present invention, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art can combine and combine different embodiments or examples described in the present invention and features of different embodiments or examples without contradiction.

[0102] Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be understood to indicate or imply relative importance or implicitly specify the number of the technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one of such features. In the description of the embodiments of the present invention, "plurality" means at least two, for example, two, three, etc., unless otherwise specifically defined.

[0103] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A hydrogen storage device, characterized in that: include: A sealed housing having a cavity formed therein; wherein the thickness x of the sealed housing satisfies 0.5 mm ≤ x < 2 mm, and the sealed housing is made of engineering plastic, or a single substance or alloy of aluminum, or a single substance or alloy of iron; A limiting gas guide rod is disposed within the cavity; a hydrogen delivery channel is formed within the limiting gas guide rod, and a plurality of gas outlet holes are provided on the surface thereof, capable of delivering hydrogen to the interior of the solid hydrogen storage material passing through the limiting gas guide rod, or outputting hydrogen from the interior of the solid hydrogen storage material; the limiting gas guide rod is also provided with a plurality of branch pipes extending in the radial direction; A hydrogen input and output interface is provided on the sealed housing and is connected to the hydrogen delivery channel inside the limiting gas guide rod; Solid-state hydrogen storage materials are combined to form a three-dimensional structure with two main surfaces facing each other. The number of solid-state hydrogen storage materials is 2 to 5. Each combined solid-state hydrogen storage material is a segmented body of the three-dimensional structure through a through hole in the middle position, and each combined solid-state hydrogen storage material is provided with one or more through holes or blind holes on the side facing the limiting gas guide rod with the air outlet, for accommodating the branch pipe; wherein the minimum circumscribed circle diameters of the two main surfaces of the three-dimensional structure are both between 6 and 25 cm, and one or more through holes are formed between the two main surfaces of the three-dimensional structure; wherein each three-dimensional structure formed by the combination of solid-state hydrogen storage materials is sequentially passed through the limiting gas guide rod, and its displacement in the radial direction of the limiting gas guide rod is limited by the limiting gas guide rod; any outermost end of the three-dimensional structures stacked in sequence abuts against the inner wall of the cavity through a buffer element, or each three-dimensional structure is connected through a buffer element; and a certain gap is formed between the side of each three-dimensional structure and the inner wall of the cavity.

2. The hydrogen storage device according to claim 1, characterized in that The limiting air guide rod is located in the middle of the cavity; and / or The sealed shell is provided with an operating port for replacing the three-dimensional structure composed of the internal solid hydrogen storage material combination.

3. The hydrogen storage device according to claim 1, characterized in that The hydrogen storage device is a vehicle-mounted, ship-mounted or aircraft-mounted hydrogen storage device.

4. A solid-state hydrogen storage material, characterized in that: The solid-state hydrogen storage materials can be combined to form a three-dimensional structure having two main surfaces facing each other. The number of the solid-state hydrogen storage materials is 2 to 5. Each combined solid-state hydrogen storage material is a segmented body of the three-dimensional structure through a through hole in the middle position, and each combined solid-state hydrogen storage material is provided with one or more through holes or blind holes on the side facing the limiting gas guide rod with the gas outlet. The minimum circumscribed circle diameter of the two main surfaces of the three-dimensional structure is both between 6 and 25 cm. The thickness of the three-dimensional structure is in the range of 1 to 5 cm; One or more through holes are formed between the two main surfaces of the three-dimensional structure; The three-dimensional structure can be accommodated inside the hydrogen storage device according to any one of claims 1 to 3.

5. The solid-state hydrogen storage material according to claim 4, characterized in that The shape of at least one of the two main surfaces of the three-dimensional structure conforms to axial symmetry, rotational symmetry or central symmetry; and / or The magnesium content of the solid-state hydrogen storage material is greater than 50%; and / or The minimum circumscribed circle diameters of the two main surfaces of the three-dimensional structure are both within the range of 6 to 20 cm; and / or The thickness of the three-dimensional structure is in the range of 1.5 to 4.5 cm.

6. The solid-state hydrogen storage material according to claim 5, characterized in that The shapes of the two main surfaces of the three-dimensional structure are selected from a regular polygon, a racetrack, a circle or an ellipse; and / or The material of the solid-state hydrogen storage material is selected from pure magnesium, magnesium-aluminum alloy, magnesium-rare earth alloy, magnesium-transition metal alloy, magnesium-transition metal-rare earth alloy; and / or The minimum circumscribed circle diameters of the two main surfaces of the three-dimensional structure are both within the range of 8 to 15 cm; and / or The thickness of the three-dimensional structure is in the range of 2 to 4 cm.

7. The solid-state hydrogen storage material according to claim 4, characterized in that The two main surfaces of the three-dimensional structure are planes; or, the two main surfaces of the three-dimensional structure have concave-convex or wavy structures.

8. The solid-state hydrogen storage material according to claim 4, characterized in that The one or more through holes include at least one main hole, the area of ​​the at least one main hole accounts for 1% to 25% of the total area of ​​the main surface, and the at least one main hole can be provided on a limiting air guide rod with an air outlet; and / or The aspect ratio of the three-dimensional structure is in the range of 0.04 to 0.

33.

9. A method for preparing a solid hydrogen storage material, characterized in that: The steps include: Forming the solid hydrogen storage material of the selected components into a three-dimensional structure composed of the solid hydrogen storage material combination according to any one of claims 4 to 8, forming one or more through holes on the main surface thereof, and dividing the three-dimensional structure into a corresponding number of blocks of solid hydrogen storage material as needed; or A three-dimensional structure composed of the solid hydrogen storage material combination as described in any one of claims 4 to 8 is prepared using a mold capable of forming one or more through holes on the main surface, and the three-dimensional structure is divided into a corresponding number of blocks of solid hydrogen storage material as needed.

10. A hydrogen storage device using the solid hydrogen storage material according to any one of claims 4 to 8 as a hydrogen storage medium.

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