Preparation method and application of flexible solid hydrogen storage bed body

Abstract

The invention relates to a preparation method of a flexible solid hydrogen storage bed body, which comprises the following steps: S1, mixing 74-90% by mass of hydrogen storage alloy powder and 3-16% by mass of carbon-based heat conduction material for 20-50 minutes in a mechanical stirring manner to obtain a dry powder mixture; s2, adding an organic silicon material with the mass fraction of 5-16%, and continuously mechanically stirring for 1-5 hours to obtain a non-dry powder mixture; and S3, carrying out vacuum drying on the non-dry powder mixture in the S2 at 60-100 DEG C for 8-20 hours, and naturally cooling to room temperature to obtain the required novel non-dry powdery hydrogen storage bed body. Through the synergistic effect of the hydrogen storage alloy, the expanded graphite and the double-liquid silica gel, the flexible solid hydrogen storage material is formed on the basis of optimizing the material ratio and the process sequence. The synergistic effect of the materials breaks through the defect that a traditional hydrogen storage bed body is too high in rigidity or in a loose powder state, and finally the hydrogen storage bed body has high hydrogen storage efficiency, stable cycle life and excellent safety performance.

Description

Technical Field

[0001] The present invention belongs to the technical field of hydrogen storage bottle filling, and relates to a preparation method and application of a flexible solid-state hydrogen storage bed. Background Art

[0002] With the growing global demand for clean energy, hydrogen energy has attracted significant attention due to its high efficiency, cleanliness, and sustainability. Solid-state hydrogen storage technology, with its advantages such as high hydrogen storage density and excellent safety, has become a research focus. Hydrogen storage alloys play a key role in this process and are widely used in hydrogen fuel cell vehicles, distributed energy storage, and other fields. However, in practical applications, the expansion of hydrogen storage bottles has become a key factor restricting the safety and stability of hydrogen storage systems, and requires in-depth research and resolution.

[0003] Hydrogen storage alloys store and release hydrogen through a reversible chemical reaction with hydrogen gas, a process accompanied by physical phenomena such as volume change, heat absorption and release. Although hydrogen storage bottles are made of high-strength materials to withstand pressure fluctuations, bottle expansion still occurs, disrupting the normal operation of the hydrogen storage system. The causes of bottle expansion are complex, with changes in the lattice structure of the hydrogen storage alloy during repeated cycles of hydrogen absorption and desorption being a key factor. Repeated insertion and extraction of hydrogen atoms imposes stress on the alloy lattice. Long-term accumulation leads to lattice distortion and increased defects, which in turn cause the alloy to expand. Different types of hydrogen storage alloys have different volume expansion characteristics due to differences in atomic structure and chemical properties. Furthermore, the volume expansion of hydrogen storage alloys during hydrogen absorption and desorption is uneven, leading to the generation of internal stresses. When the stress concentration exceeds the yield strength of the alloy, microcracks form within the alloy particles. These microcracks may further expand during desorption, ultimately causing the alloy particles to break up, a process known as pulverization. Furthermore, the irregular atomic arrangement and high energy at grain boundaries facilitate hydrogen atom aggregation at these boundaries, resulting in high grain boundary stresses and accelerating alloy pulverization. After the hydrogen storage alloy is pulverized, the powder will be refined, migrate, sink, and agglomerate, resulting in the concentration of powder at the bottom of the hydrogen storage bottle, causing local stress concentration, triggering elastic deformation and possibly evolving into plastic deformation. In severe cases, the bottle may rupture and fail, bringing product safety issues.

[0004] Although the existing technologies have improved the hydrogen storage alloy bed to a certain extent, they still have many shortcomings. For example, CN115650157A uses a wet mixing method to prepare the hydrogen storage alloy bed (hydrogen storage alloy + thermal conductor + wetting agent + binder), but the bottle swelling phenomenon still exists during actual use; CN114440123A uses gel materials and thermal conductive materials to prepare hydrogen storage materials, but the preparation process is complicated and the actual performance remains to be verified. Although these existing technologies have their own characteristics, they still have limitations in solving the problems of hydrogen storage alloy pulverization and bottle swelling. There are problems such as reduced hydrogen storage efficiency, increased safety risks, shortened service life and increased costs. These are specifically reflected in the reduction of active surface area, complexity of hydrogen diffusion path, damage to the integrity of the bottle structure, risk of impurities and pollutants, accelerated degradation of alloy performance, accelerated fatigue of the bottle material, frequent replacement of parts, and increased maintenance and monitoring costs.

[0005] Specifically, (1) hydrogen storage efficiency is reduced:

[0006] Pulverization of hydrogen storage alloys reduces particle size, causing some surfaces to oxidize or form unfavorable compounds, significantly reducing the active surface area. For example, pulverization of LaNi5-based alloys reduces the active surface area by 30% to 50%, reducing hydrogen storage capacity. Furthermore, pulverization increases microcracks and small gaps, complicating hydrogen diffusion pathways. For example, pulverization of Mg-Ni-based alloys reduces the hydrogen diffusion coefficient by an order of magnitude, slowing hydrogen absorption and desorption, and impacting efficiency.

[0007] (2) Increased safety risks:

[0008] Pulverization causes bottle bulging, threatening the structural integrity of the bottle. The alloy's volumetric expansion exerts additional pressure on the bottle, leading to localized stress concentrations and accelerating material fatigue damage. For example, carbon fiber composite bottles exposed to prolonged additional pressure are susceptible to debonding, reducing their pressure resistance and increasing risk. Pulverization can also produce impurities such as metal dust, which, when carried by hydrogen, can clog components or trigger chemical reactions. For example, transition metal impurities can catalyze the reaction between hydrogen and oxygen, causing localized overheating and posing a significant safety hazard.

[0009] (3) Shortened service life:

[0010] Pulverization damages the alloy lattice, increases defects, and accelerates the degradation of hydrogen storage performance. Pressure fluctuations in the hydrogen absorption and desorption platforms lead to premature replacement of hydrogen storage bottles. Bottle expansion subjects the bottle material to additional fatigue loads, accelerating the fatigue process. For example, metal-lined hydrogen storage bottles exposed to long-term expansion pressure are prone to microcracks, leading to failure, significantly shortening service life and reducing system reliability and economic efficiency.

[0011] Given the significant impact of hydrogen storage alloy pulverization and bottle expansion problems on the development of solid-state hydrogen storage technology and the safe and stable operation of hydrogen energy systems, it is imperative to deeply explore their generation mechanism and seek effective solutions, which is of extremely important practical significance for promoting the widespread application of hydrogen energy technology.

[0012] In addition, on the one hand, there are differences in understanding among those skilled in the art; on the other hand, the inventor studied a large number of documents and patents when making the present invention, but due to space limitations, not all details and contents are listed in detail. However, this does not mean that the present invention does not have the characteristics of these prior arts. On the contrary, the present invention already has all the characteristics of the prior art, and the applicant reserves the right to add relevant prior art to the background art. Summary of the Invention

[0013] Based on the above technical problems, the present invention relates to a method for preparing a flexible solid-state hydrogen storage bed, which comprises the following steps:

[0014] S1: mixing 74-90% by mass of hydrogen storage alloy powder and 3-16% by mass of carbon-based thermal conductive material by mechanical stirring for 20-50 minutes to obtain a dry powder mixture;

[0015] S2: adding 5-16% by mass of an organosilicon material and continuously mechanically stirring for 1-5 hours to obtain a non-dry powder mixture;

[0016] S3: The non-dry powder mixture in S2 is vacuum dried at 60-100° C. for 8-20 hours, and after naturally cooling to room temperature, the desired novel non-dry powder hydrogen storage bed is obtained.

[0017] Preferably, the preparation method comprises the following steps:

[0018] S1: 88% by mass of hydrogen storage alloy powder and 5% by mass of carbon-based thermal conductive material were mixed by mechanical stirring for 30 minutes to obtain a dry powder mixture;

[0019] S2: adding 7% by mass of organosilicon material and continuously stirring mechanically for 4.5 hours to obtain a non-dry powder mixture;

[0020] S3: The non-dry powder mixture in S2 is vacuum dried at 80° C. for 8 hours, and then naturally cooled to room temperature to obtain the desired new non-dry powder hydrogen storage bed.

[0021] According to a preferred embodiment, the hydrogen storage alloy powder is one or more of titanium AB2 type, titanium AB type, rare earth AB5 type, titanium vanadium solid solution BCC type and magnesium-based hydrogen storage alloy.

[0022] According to a preferred embodiment, the organosilicon material is selected from the following group:

[0023] Silicone oil; silicone gel; silicone rubber; silicone resin; silicone coupling agent.

[0024] Preferably, the silicone rubber is formed by crosslinking and vulcanizing at room temperature or under heating in the presence of a platinum catalyst using a vinyl-containing polyorganosiloxane as a base polymer and a Si-H bond-containing polyorganosiloxane as a crosslinking agent. The silicone rubber is an addition-type two-component silicone rubber.

[0025] According to a preferred embodiment, the viscosity of the organosilicon material is 500 to 2000 cst.

[0026] According to a preferred embodiment, the carbon-based thermally conductive material is carbon nanotubes, carbon fibers, graphene, graphite, amorphous carbon or activated carbon.

[0027] According to a preferred embodiment, the hydrogen storage alloy powder is TiMn2 alloy powder.

[0028] According to a preferred embodiment, 500 to 2000 cst of two-liquid silicone gel is used. Preferably, 500 cst of two-liquid silicone gel is used. Preferably, 1000 cst of two-liquid silicone gel is used. Preferably, 2000 cst of two-liquid silicone gel is used.

[0029] According to a preferred embodiment, 88-86% by mass of hydrogen storage alloy powder, 5% by mass of carbon-based thermal conductive material, and 7-9% by mass of organosilicon material are used. Preferably, 88% by mass of hydrogen storage alloy powder, 5% by mass of carbon-based thermal conductive material, and 7% by mass of organosilicon material are used. Preferably, 86% by mass of hydrogen storage alloy powder, 5% by mass of carbon-based thermal conductive material, and 9% by mass of organosilicon material are used.

[0030] Another aspect of the present invention relates to the use of a hydrogen storage bed prepared using the flexible solid-state hydrogen storage bed preparation method in the energy storage field. Preferably, the application includes renewable energy storage, portable power supply equipment, distributed energy systems, smart grids and load regulation, thermal management applications, or space exploration and aviation applications.

[0031] Another aspect of the present invention relates to a hydrogen storage device, part or all of which comprises a hydrogen storage bed prepared by the above-mentioned preparation method.

[0032] Beneficial effects of this technical solution:

[0033] The present invention forms a flexible solid-state hydrogen storage material through the synergistic effect of hydrogen storage alloy, expanded graphite and double-liquid silicone gel, on the basis of optimizing material ratio and process sequence. The hydrogen storage alloy serves as the core hydrogen storage medium. Its proportion control ensures the hydrogen storage capacity while optimizing the kinetics of the hydrogen absorption and desorption reaction by rationally distributing active sites, avoiding excessive addition resulting in over-dense particle accumulation and volume expansion stress accumulation; the expanded graphite, with its layered porous structure, acts as a heat-conducting network to accelerate heat transfer during the hydrogen absorption and desorption process, preventing local overheating, and promoting the diffusion and penetration of hydrogen through pore channels. At the same time, its composite with organic silicon materials enhances the mechanical support of the material, avoiding the performance degradation of traditional thermal conductive fillers due to loose structure. The layered porous structure of the expanded graphite powder not only constructs A highly efficient thermal conductivity path is established, ensuring rapid and uniform transfer of reaction heat. The interlamellar pores interlock with the hydrogen storage alloy particles, optimizing hydrogen diffusion and permeation channels while also enhancing the compressive resistance of the bed through mechanical reinforcement. The dual-liquid silicone gel, through a curing process, encapsulates the alloy particles and expanded graphite into a single, continuous, flexible colloidal network. This continuously cross-linked structure dynamically adjusts volume changes during hydrogen absorption and desorption, effectively suppressing deformation caused by cyclic expansion of the hydrogen storage device. Conventional liquid or uncured materials, lacking a stable bonding framework, struggle to maintain the structural integrity and stress dissipation of the bed. This network adaptively adjusts to changes in shape during the hydrogen absorption and desorption cycles, effectively buffering the volumetric expansion and contraction stresses of the alloy particles, thereby suppressing changes in the diameter of the hydrogen storage bottle and reducing material fatigue damage. Through optimized ratios and interfacial bonding, the three components complement each other functionally: the hydrogen storage alloy provides hydrogen storage capacity, the expanded graphite enhances thermal conductivity and diffusion, and the silicone gel ensures structural flexibility and stress buffering. The synergistic effect of the above materials breaks through the defects of traditional hydrogen storage beds that are too rigid or in a loose powder state, ultimately enabling the hydrogen storage bed to have high hydrogen storage efficiency, stable cycle life and excellent safety performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 It is a process flow chart of the present invention;

[0035] Figure 2 This is a comparison of the appearance of the bed before and after the hydrogen absorption and desorption cycle after the hydrogen storage bottle installed in Example 4 was used in the laboratory test for 5 days;

[0036] Figure 3 This is a comparison of the appearance of the bed before and after the hydrogen absorption and desorption cycle after the hydrogen storage bottle installed in Example 6 was used in the laboratory for 5 days;

[0037] Figure 4 Comparison of the appearance of the bottles of Example 9 and Example 1 before and after bottling for 5 days and hydrogen absorption and desorption cycles. The left picture shows the appearance of the bottle of Example 9, and the right picture shows the appearance of the bottle of Example 1.

[0038] Figure 5Graphs showing the hydrogen storage performance of Examples 1 to 9. DETAILED DESCRIPTION

[0039] In the description of the present invention, terms are used for descriptive purposes only and should not be understood to indicate or imply relative importance or implicitly indicate the number of technical features indicated. In the description of the present invention, "plurality" means two or more, unless otherwise specifically defined.

[0040] Among the silicone materials of the present invention, silicone gel, silicone rubber, and silicone resin are available in two-liquid form, while silicone oil and silicone coupling agent are generally not available in two-liquid form. Therefore, Liquid A and Liquid B generally refer to two-liquid silicone materials.

[0041] (1) Two-liquid silicone gel is usually composed of two components: a first component (liquid A) and a second component (liquid B). The first component is a base rubber containing a silicone polymer and a filler; the second component contains a curing agent such as a crosslinking agent and a catalyst. When used, they are mixed in a certain proportion and crosslinked and cured at room temperature or under heating conditions. The first component and the second component of the addition-type two-liquid silicone gel used in the embodiment of the present invention have a mixing ratio of 1:1. Preferably, the two-liquid silicone gel is Chongqing Si Ning silicone gel.

[0042] (2) Addition-type two-component silicone rubber is made of vinyl-containing polysiloxane as the base polymer and Si-H bond-containing polysiloxane as the crosslinking agent. It is cross-linked and vulcanized at room temperature or heated in the presence of a platinum catalyst.

[0043] The first component of silicone resin contains a silicone polymer (such as methyl silicone resin, phenyl silicone resin), fillers (such as silica, alumina), and additives (such as coupling agents, thixotropic agents), providing basic properties. The second component (curing agent) is a solution containing a crosslinker (such as hydrosilane, peroxide) and a catalyst (such as platinum catalyst, amine catalyst), which triggers the curing reaction.

[0044] Silicone oil is a low molecular weight polysiloxane.

[0045] Organic silicon coupling agents are generally also single components, used to improve the bonding performance of the interfaces of different materials, and are usually added directly to the system when used.

[0046] like Figure 1 As shown, the present invention adopts a specific ratio of hydrogen storage materials and process steps ( Figure 1A and 1B show this, significantly improving the hydrogen storage performance of the hydrogen storage bed. Specifically, during the preparation of the hydrogen storage material, by mixing the thermally conductive material with the hydrogen storage alloy in both solid and non-solid conditions, followed by vacuum drying within specific parameter constraints, the microstructure of the hydrogen storage material can be precisely controlled. This method not only overcomes the limitations of conventional hydrogen storage beds, which are often overly rigid or present in a loose powder state, but also optimizes the bed's internal microstructure, significantly improving its performance.

[0047] Specifically, strict control of the degree of dispersion, or parameters characterizing the degree of dispersion, during the mixing process ensures a uniform and stable bond between the thermally conductive material and the hydrogen storage alloy. Subsequently, a finely tuned vacuum drying step further consolidates this composite structure, resulting in a hydrogen storage bed that possesses both sufficient mechanical strength to maintain structural stability and appropriate flexibility and efficient hydrogen storage capacity. This approach, based on microscopic network adjustments, provides new ideas and technical paths for the development of a new generation of efficient and durable hydrogen storage materials.

[0048] Example 1

[0049] This embodiment relates to the preparation of a hydrogen storage material comprising 88% by mass of an alloy, 5% by mass of a thermal conductive material, and 7% by mass of a silicone gel.

[0050] The preparation method comprises the following steps:

[0051] 880 g of TiMn2 alloy powder (AB2 type), 50 g of expanded graphite powder, and 70 g of two-liquid silicone gel (500 cst) were weighed respectively;

[0052] First, TiMn2 alloy powder and expanded graphite powder were mixed by mechanical stirring for 30 minutes, and after thorough mixing, a dry powder mixture was obtained;

[0053] Then, 80 g of two-liquid silicone gel (35 g each of liquid A and liquid B) was added to the dry powder mixture, and mechanical stirring was continued for 4.5 h to obtain a non-dry powder mixture;

[0054] Finally, the non-dry powder mixture was vacuum dried at 100° C. for 8 h.

[0055] After naturally cooling to room temperature, the desired new non-dry powder hydrogen storage bed is obtained.

[0056] Example 2

[0057] This embodiment relates to the preparation of a hydrogen storage material comprising 86% by mass of an alloy, 5% by mass of a thermal conductive material, and 9% by mass of a silicone gel.

[0058] The preparation method comprises the following steps:

[0059] 860 g TiMn2 alloy powder (AB2 type), 50 g expanded graphite powder and 90 g two-liquid silicone gel (1500 cst) were weighed respectively;

[0060] First, TiMn2 alloy powder and expanded graphite powder were mixed by mechanical stirring for 20 minutes, and after thorough mixing, a dry powder mixture was obtained;

[0061] Then, 90 g of two-liquid silicone gel (45 g each of liquid A and liquid B) was added to the dry powder mixture, and mechanical stirring was continued for 4 h to obtain a non-dry powder mixture;

[0062] Finally, the non-dry powder mixture was vacuum dried at 80° C. for 12 h.

[0063] After naturally cooling to room temperature, the desired new non-dry powder hydrogen storage bed is obtained.

[0064] Example 3

[0065] This embodiment relates to the preparation of a hydrogen storage material comprising 74% by mass of an alloy, 16% by mass of a thermal conductive material, and 10% by mass of a silicone gel.

[0066] The preparation method comprises the following steps:

[0067] 740 g TiMn2 alloy powder (AB2 type), 160 g expanded graphite powder and 100 g two-liquid silicone gel (1000 cst) were weighed respectively;

[0068] First, TiMn2 alloy powder and expanded graphite powder were mixed by mechanical stirring for 30 minutes, and after thorough mixing, a dry powder mixture was obtained;

[0069] Then, 100 g of two-liquid silicone gel (50 g each of liquid A and liquid B) was added to the dry powder mixture, and mechanical stirring was continued for 1.5 h to obtain a non-dry powder mixture;

[0070] Finally, the non-dry powder mixture was vacuum dried at 80° C. for 12 h.

[0071] After naturally cooling to room temperature, the desired new non-dry powder hydrogen storage bed is obtained.

[0072] Example 4

[0073] This embodiment relates to the preparation of a hydrogen storage material comprising 80% by mass of an alloy, 4% by mass of a thermal conductive material, and 16% by mass of a silicone gel.

[0074] The preparation method comprises the following steps:

[0075] 800 g TiMn2 alloy powder (AB2 type), 40 g expanded graphite powder and 160 g two-liquid silicone gel (2000 cst) were weighed respectively;

[0076] TiMn2 alloy powder and expanded graphite powder were first mixed by mechanical stirring for 40 minutes to obtain a dry powder mixture after thorough mixing;

[0077] Then, 160 g of two-liquid silicone gel (80 g each of liquid A and liquid B) was added to the dry powder mixture, and mechanical stirring was continued for 2 h to obtain a non-dry powder mixture;

[0078] Finally, the non-dry powder mixture was vacuum dried at 60° C. for 20 h.

[0079] After naturally cooling to room temperature, the desired new non-dry powder hydrogen storage bed is obtained.

[0080] Example 5

[0081] This embodiment relates to the preparation of a hydrogen storage material comprising 74% by mass of an alloy, 21% by mass of a thermal conductive material, and 5% by mass of silicone oil.

[0082] The preparation method comprises the following steps:

[0083] 740 g TiMn2 alloy powder (AB2 type), 210 g carbon fiber and 50 g silicone oil (1000 cst) were weighed respectively;

[0084] First, TiMn2 alloy powder and carbon fiber are mixed by mechanical stirring for 30 minutes, and after thorough mixing, a dry powder mixture is obtained;

[0085] Then, 50 g of silicone oil was added to the dry powder mixture, and mechanical stirring was continued for 1.5 h to obtain a non-dry powder mixture;

[0086] Finally, the non-dry powder mixture was vacuum dried at 80° C. for 12 h.

[0087] After naturally cooling to room temperature, the desired new non-dry powder hydrogen storage bed is obtained.

[0088] Example 6

[0089] This embodiment relates to the preparation of a hydrogen storage material containing 78% by mass of alloy, 6% by mass of thermal conductive material, and 16% by mass of silicone oil.

[0090] The preparation method comprises the following steps:

[0091] Weigh 780 g of TiMn2 alloy powder (AB2 type), 60 g of expanded graphite powder, and 160 g of silicone oil (1000 cst) respectively;

[0092] First, TiMn2 alloy powder and expanded graphite powder were mixed by mechanical stirring for 50 minutes to obtain a dry powder mixture after thorough mixing;

[0093] Then, 160 g of silicone oil was added to the dry powder mixture, and mechanical stirring was continued for 2 h to obtain a non-dry powder mixture;

[0094] Finally, the non-dry powder mixture was vacuum dried at 60° C. for 16 h.

[0095] After naturally cooling to room temperature, the desired new non-dry powder hydrogen storage bed is obtained.

[0096] Example 7

[0097] This embodiment relates to the preparation of a hydrogen storage material comprising 74% by mass of an alloy, 16% by mass of a thermal conductive material, and 10% by mass of a silicone gel.

[0098] The preparation method comprises the following steps:

[0099] 740 g TiMn2 alloy powder (AB2 type), 160 g expanded graphite powder and 100 g two-liquid silicone gel (1000 cst) were weighed respectively;

[0100] First, 100g of two-liquid silicone gel (50g each of liquid A and liquid B) and TiMn2 alloy powder were mechanically stirred for 30min and thoroughly mixed to obtain a non-dry powder mixture;

[0101] Expanded graphite powder was then added to the non-dry powder mixture, and the mixture was stirred for 1.5 hours by mechanical stirring to fully mix the mixture, and then vacuum dried at 80° C. for 12 hours.

[0102] After naturally cooling to room temperature, the desired new non-dry powder hydrogen storage bed is obtained.

[0103] Example 8

[0104] This embodiment relates to the preparation of a hydrogen storage material comprising 74% by mass of an alloy, 21% by mass of a thermal conductive material, and 5% by mass of a silicone gel.

[0105] The preparation method comprises the following steps:

[0106] 740 g TiMn2 alloy powder (AB2 type), 210 g carbon fiber and 50 g two-liquid silicone gel (1000 cst) were weighed respectively;

[0107] First, two-liquid silicone gel (25g each of liquid A and liquid B) and TiMn2 alloy powder were mechanically stirred for 30 minutes and fully mixed to obtain a non-dry powder mixture;

[0108] Then, carbon fiber was added to the non-dry powder mixture, and the mixture was stirred for 1.5 hours by mechanical stirring to fully mix the mixture, and then vacuum dried at 80°C for 12 hours;

[0109] After naturally cooling to room temperature, the desired new non-dry powder hydrogen storage bed is obtained.

[0110] Example 9

[0111] This embodiment relates to the preparation of a hydrogen storage material comprising 88% by mass of an alloy, 5% by mass of a thermal conductive material, and 7% by mass of pure water.

[0112] The preparation method comprises the following steps:

[0113] Weigh 880g TiMn2 alloy powder (AB2 type), 50g expanded graphite powder and 70g pure water respectively;

[0114] First, TiMn2 alloy powder and expanded graphite powder were mixed by mechanical stirring for 30 minutes, and after thorough mixing, a dry powder mixture was obtained;

[0115] Then, 70 g of pure water was added to the dry powder mixture, and mechanical stirring was continued for 3 h to obtain a non-dry powder mixture;

[0116] Finally, the non-dry powder mixture was vacuum dried at 100° C. for 8 h.

[0117] After naturally cooling to room temperature, the moisture is completely dried, so the hydrogen storage bed obtained in this comparative example is a dry powder state.

[0118] In order to compare the two process technology routes of the present invention, the four kinds of hydrogen storage beds obtained by the four technical solutions of Example 3, Example 5, Example 7 and Example 8 were loaded into four hydrogen storage bottles (0.39L) and numbered respectively as hydrogen storage bottle 01#, hydrogen storage bottle 02#, hydrogen storage bottle 03# and hydrogen storage bottle 04#, and the four hydrogen storage bottles were subjected to a 5-day hydrogen absorption and desorption cycle test. The diameter of the hydrogen storage bottle was measured with a caliper, and the measurement results were compared with the original design dimensions. Generally speaking, if the change in diameter exceeds a certain range, it means that the hydrogen storage bottle has undergone abnormal expansion (the original circumference of the hydrogen storage bottle body is ~190mm). The test performance data and measurement results are shown in Tables 1 and Figure 4 The data in Table 1 are the increase in the outer bottle diameter at the bottom of the bottle (about 25mm from the bottom) after 5 days of hydrogen absorption and desorption testing in the laboratory. Figure 2 and Figure 3It can be seen that after using the organosilicon material, the hydrogen storage bed of the present invention presents a distinct "thin mud" shape, with certain wettability and flexibility, and is not in the dry powder state of the traditional powder hydrogen storage bed. The results show that the scheme of the present invention can effectively fix the hydrogen storage alloy powder, provide a buffer space for the expansion of the alloy powder, and slow down the powder loss problem; secondly, after 5 days of hydrogen absorption and desorption testing, the new non-dry powder bed of the present invention has no obvious difference in appearance compared with the one before hydrogen absorption, indicating that it has good stability. Figure 4 As shown in FIG, compared with Example 1, the outer bottle body of Example 9 is significantly expanded. Figure 5 It can be seen that the hydrogen storage capacity of the hydrogen storage bottle prepared in Example 1 is 1.634wt%; the hydrogen storage capacity of the hydrogen storage bottle prepared in Example 2 is 1.623wt%; the hydrogen storage capacity of the hydrogen storage bottle prepared in Example 3 is 1.561wt%; the hydrogen storage capacity of the hydrogen storage bottle prepared in Example 4 is 1.582wt%; the hydrogen storage capacity of the hydrogen storage bottle prepared in Example 5 is 1.54wt%; the hydrogen storage capacity of the hydrogen storage bottle prepared in Example 6 is 1.581wt%; the hydrogen storage capacity of the hydrogen storage bottle prepared in Example 7 is 1.536wt%; the hydrogen storage capacity of the hydrogen storage bottle prepared in Example 8 is 1.518wt%; and the hydrogen storage capacity of the hydrogen storage bottle prepared in Example 9 is 1.619wt%.

[0119] Table 1

[0120]

[0121] From the above results, it can be seen that Example 1 has the best expansion inhibition effect, and the hydrogen storage capacity of Examples 1 to 9 is not much different, indicating that the technical effect achieved under this limitation (1≤thermal conductive material ratio≤20%; thermal conductive material is limited to expanded graphite; thermal conductive material needs to be mixed with hydrogen storage alloy first and then silicon material is added) is relatively good.

[0122] It should be noted that the above-described specific embodiments are illustrative only. Those skilled in the art may devise various solutions based on the disclosure of the present invention, and such solutions fall within the scope of the present invention and are intended to be protected by the present invention. Those skilled in the art should understand that the present description and its accompanying drawings are intended to be illustrative only and are not intended to limit the scope of the claims. The scope of protection of the present invention is defined by the claims and their equivalents.

Claims

1. A method for preparing a flexible solid-state hydrogen storage bed, characterized in that: The following steps are involved: S1: mixing 74-90% by mass of hydrogen storage alloy powder and 3-16% by mass of carbon-based thermal conductive material by mechanical stirring for 20-50 minutes to obtain a dry powder mixture; S2: adding 5-16% by mass of an organosilicon material and continuously mechanically stirring for 1-5 hours to obtain a non-dry powder mixture; S3: The non-dry powder mixture in S2 is vacuum dried at 60-100° C. for 8-20 hours, and after naturally cooling to room temperature, the desired novel non-dry powder hydrogen storage bed is obtained.

2. The preparation method according to claim 1, characterized in that The hydrogen storage alloy powder is one or more of titanium AB2 type, titanium AB type, rare earth AB5 type, titanium-vanadium solid solution BCC type and magnesium-based hydrogen storage alloy.

3. The preparation method according to claim 1, characterized in that The organosilicon material is selected from the following group: Silicone oil; Silicone gel; Silicone rubber; Silicone resin; Silicone coupling agent.

4. The preparation method according to claim 1, characterized in that The viscosity of the organic silicon material is 500 to 2000 cst.

5. The preparation method according to claim 1, characterized in that The carbon-based thermal conductive material is carbon nanotube, carbon fiber, graphene, graphite, amorphous carbon or activated carbon.

6. The preparation method according to claim 1, characterized in that The hydrogen storage alloy powder is TiMn2 alloy powder.

7. The preparation method according to claim 1, characterized in that Use 500-2000cst two-component silicone gel.

8. The preparation method according to claim 1, characterized in that The method uses 88-86% by mass of hydrogen storage alloy powder, 5% by mass of carbon-based thermal conductive material and 7-9% by mass of organic silicon material.

9. Application of a hydrogen storage bed in the field of energy storage, characterized in that: The hydrogen storage bed is prepared by using the flexible solid-state hydrogen storage bed preparation method according to any one of claims 1 to 8.

10. A hydrogen storage device, characterized in that: Part or all of the hydrogen storage structure of the hydrogen storage device is composed of a hydrogen storage bed prepared by the preparation method according to any one of claims 1 to 8.

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