Preparation method of magnesium-nickel-gadolinium block hydrogen storage material and product

Abstract

The invention relates to a preparation method of a magnesium-nickel-gadolinium block hydrogen storage material and a product, and belongs to the technical field of magnesium-based solid hydrogen storage materials. The material is prepared according to the following method: carrying out cold press molding on magnesium-nickel-gadolinium alloy powder with the particle size of less than 40 microns. The hydrogen storage capacity released by the magnesium-nickel-gadolinium block hydrogen storage material within 5 minutes at the temperature of 300 DEG C reaches up to 5.47 wt.%, meanwhile, the magnesium-nickel-gadolinium block hydrogen storage material has good structural stability, and the problem that an existing block magnesium-based hydrogen storage material is pulverized due to volume expansion and shrinkage caused by repeated hydrogen absorption and desorption can be effectively solved. The method is simple in process, easy to operate and low in cost, and has more economic benefits and scale benefits.

Description

Technical Field

[0001] The present invention belongs to the technical field of magnesium-based solid-state hydrogen storage materials, and relates to a preparation method and product of a magnesium-nickel-gadolinium bulk hydrogen storage material. Background Art

[0002] Hailed as the "ultimate energy source of the 21st century," hydrogen energy boasts high calorific value, light weight, and high gravimetric energy density (~33kWh / kg). It is also relatively abundant in nature, and its combustion produces only water, with no harmful emissions. This effectively addresses the greenhouse effect and environmental pollution, making it a highly suitable alternative to fossil fuels as a long-term energy source for the future. A complete hydrogen energy supply system consists of four key components: hydrogen production, storage, transportation, and application. Hydrogen storage significantly hinders its large-scale application in industrial production. Among various hydrogen storage technologies, solid-state hydrogen storage offers broad application prospects due to its high volumetric hydrogen storage density and superior safety.

[0003] Among the many solid-state hydrogen storage materials, magnesium-based hydrogen storage materials have the advantages of high theoretical volumetric hydrogen storage density (110 g / L), high theoretical mass hydrogen storage density (7.6 wt.%), abundant resources, and green environmental protection. They are considered to be one of the most promising solid-state hydrogen storage materials. The practical application of magnesium-based hydrogen storage materials usually requires filling them into solid-state hydrogen storage tanks in the form of blocks to ensure the stability of the internal structure of the tank. However, bulk magnesium-based hydrogen storage materials are very prone to pulverization due to volume expansion and contraction caused by repeated absorption and desorption of hydrogen, and their structural stability is destroyed. In addition, in order to ensure the structural stability of bulk magnesium-based hydrogen storage materials, some binders and curing agents will be applied to them, which causes a significant attenuation of hydrogen storage capacity, which is not conducive to practical application. Therefore, how to solve the problems of pulverization and capacity attenuation of bulk magnesium-based hydrogen storage materials is the key to promoting their practical application. Summary of the Invention

[0004] In view of this, one of the objects of the present invention is to provide a method for preparing a magnesium-nickel-gadolinium bulk hydrogen storage material; a second object is to provide a magnesium-nickel-gadolinium bulk hydrogen storage material.

[0005] In order to achieve the above object, the present invention provides the following technical solutions: 1. A method for preparing a magnesium-nickel-gadolinium bulk hydrogen storage material, comprising: cold-pressing magnesium-nickel-gadolinium alloy powder having a particle size of less than 40 μm.

[0006] Preferably, the magnesium-nickel-gadolinium alloy powder with a particle size of less than 40 μm is prepared by the following method: a magnesium-nickel-gadolinium alloy sheet with a length of 200-300 μm is ball-milled at a ball-to-material ratio of 10-30:1 at a speed of 100-300 rpm in forward and reverse intermittent ball milling for 8-12 hours.

[0007] Preferably, the forward and reverse intermittent ball milling is specifically: after each 5-15 minutes of ball milling, there is a 5-15 minute pause.

[0008] Preferably, the cold pressing forming is specifically: maintaining the pressure at a pressure of 0.25-0.75t for 90-150s.

[0009] 2. The magnesium nickel gadolinium bulk hydrogen storage material prepared by the above preparation method.

[0010] The beneficial effects of the present invention are as follows: the present invention provides a method for preparing a magnesium-nickel-gadolinium bulk hydrogen storage material and a product thereof. The magnesium-nickel-gadolinium bulk hydrogen storage material is prepared by cold pressing a magnesium-nickel-gadolinium alloy powder having a particle size of less than 40 μm as a raw material. The magnesium-nickel-gadolinium bulk hydrogen storage material has a hydrogen storage capacity of up to 5.47 wt.% released within 5 minutes at 300°C, and has good structural stability. It can effectively solve the problem of pulverization of current magnesium-based bulk hydrogen storage materials due to volume expansion and contraction caused by repeated absorption and desorption of hydrogen. The method has simple procedures, is easy to operate, has low cost, and is more economical and scale-effective.

[0011] Magnesium-based hydrogen storage materials store hydrogen by forming magnesium hydride through magnesium alloy and hydrogen. When magnesium hydride forms on the surface of magnesium-based hydrogen storage material particles, the diffusion rate of hydrogen in the magnesium hydride is slow, which makes hydrogenation inside the particles difficult. The larger the magnesium-based hydrogen storage material particles, the more difficult the internal hydrogenation will be, resulting in a low hydrogen storage capacity. Therefore, magnesium-nickel-gadolinium alloy powder with a particle size of less than 40μm is selected as the raw material to make hydrogenation inside the magnesium alloy particles easier, thereby effectively improving the hydrogen storage capacity of the material.

[0012] More importantly, the presence of gadolinium in magnesium-nickel-gadolinium bulk hydrogen storage materials enhances the grain strengthening of the alloy powder particles within the bulk hydrogen storage material, thereby increasing the strength of the alloy powder particles and making them highly resistant to deformation. This effectively suppresses stress concentration caused by hydrogen absorption and desorption, reducing cracking or pulverization caused by material brittleness. Furthermore, gadolinium exhibits strong stability under high-temperature conditions. In particular, during the absorption and desorption of hydrogen, the alloy powder particles within the strong bulk hydrogen storage material are subjected to significant stress due to thermal expansion and temperature changes. The addition of gadolinium effectively enhances their plasticity at high temperatures, making them less susceptible to breakage and reducing structural cracks caused by thermal expansion coefficient mismatch, thereby ensuring structural integrity under temperature fluctuations.

[0013] Other advantages, objects, and features of the present invention will be described in part in the following description and, in part, will be apparent to those skilled in the art upon examination of the following description or may be learned from practice of the present invention. The objects and other advantages of the present invention may be realized and obtained through the following description. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] In order to make the purpose, technical solutions and advantages of the present invention more clear, the present invention will be described in detail below with reference to the accompanying drawings, in which: Figure 1 1. The scanning electron microscope image and the corresponding particle size statistics of the magnesium-nickel-gadolinium alloy powder in Example 1; Figure 2 This is the appearance morphology of the magnesium nickel gadolinium bulk hydrogen storage material in Example 1; Figure 3 is the activation curve of the bulk magnesium-based hydrogen storage material prepared in Example 1 and Comparative Examples 1-4, wherein: Figure 3 (a) is the activation curve of the magnesium nickel gadolinium bulk hydrogen storage material prepared in Example 1; Figure 3 (b) is the activation curve of the magnesium nickel silicon bulk hydrogen storage material prepared in Comparative Example 1; Figure 3 (c) is the activation curve of the magnesium nickel yttrium silicon bulk hydrogen storage material prepared in Comparative Example 2; Figure 3 Middle (d) is the activation curve of the magnesium nickel yttrium neodymium bulk hydrogen storage material prepared in Comparative Example 3; Figure 3 (e) is the activation curve of the bulk magnesium-based hydrogen storage material containing a binder prepared in Comparative Example 4; Figure 4 The hydrogen release curves of the bulk magnesium-based hydrogen storage materials prepared in Example 1 and Comparative Examples 1-4 at 300°C, 280°C, and 260°C, respectively, wherein: Figure 4 (a) is the hydrogen desorption curve of the magnesium nickel gadolinium bulk hydrogen storage material prepared in Example 1 at 300°C, 280°C, and 260°C respectively; Figure 4 (b) is the hydrogen desorption curve of the magnesium nickel silicon bulk hydrogen storage material prepared in Comparative Example 1 at 300°C, 280°C, and 260°C respectively; Figure 4 (c) is the hydrogen desorption curve of the magnesium nickel yttrium silicon bulk hydrogen storage material prepared in Comparative Example 2 at 300°C, 280°C, and 260°C respectively; Figure 4 (d) is the hydrogen desorption curve of the magnesium nickel yttrium neodymium bulk hydrogen storage material prepared in Comparative Example 3 at 300°C, 280°C, and 260°C respectively; Figure 4 (e) is the hydrogen release curve of the bulk magnesium-based hydrogen storage material containing a binder prepared in Comparative Example 4 at 300°C, 280°C, and 260°C respectively; Figure 5 The morphology of the bulk magnesium-based hydrogen storage material prepared in Example 1 and Comparative Examples 1-4 after multiple cycles of hydrogen absorption and desorption is shown in FIG. Figure 5 (a) is the appearance morphology of the magnesium nickel gadolinium bulk hydrogen storage material prepared in Example 1 after multiple cycles of hydrogen absorption and desorption; Figure 5(b) is a morphology diagram of the magnesium nickel silicon bulk hydrogen storage material prepared in comparative example 1 after multiple cycles of hydrogen absorption and desorption; Figure 5 Middle (c) is the appearance morphology of the magnesium nickel yttrium silicon bulk hydrogen storage material prepared in Comparative Example 2 after multiple cycles of hydrogen absorption and desorption; Figure 5 Middle (d) is the appearance morphology of the magnesium nickel yttrium neodymium bulk hydrogen storage material prepared in Comparative Example 3 after multiple cycles of hydrogen absorption and desorption; Figure 5 (e) is a morphology diagram of the bulk magnesium-based hydrogen storage material containing a binder prepared in Comparative Example 4 after multiple cycles of hydrogen absorption and desorption. DETAILED DESCRIPTION

[0015] The following describes the embodiments of the present invention through specific examples. Those skilled in the art will readily understand the other advantages and benefits of the present invention from the disclosure herein. The present invention may also be implemented or applied through various other specific embodiments, and the details in this specification may be modified or altered based on different viewpoints and applications without departing from the spirit of the present invention.

[0016] Example 1 Preparation of magnesium nickel gadolinium bulk hydrogen storage material (1) Put the 200-300 μm-long magnesium-nickel-gadolinium alloy sheet and 304 stainless steel balls into a ball mill at a ball-to-material ratio of 20:1. Run the mill forward at 280 rpm for 10 min, rest for 10 min, and then reverse for 10 min and rest for 10 min. The effective milling time is 10 h to obtain magnesium-nickel-gadolinium alloy powder with a particle size range of 3-40 μm. (2) 75 mg of the magnesium-nickel-gadolinium alloy powder with a particle size range of 3 to 40 μm obtained in step (1) was placed in a compacting mold and maintained at a pressure of 0.5 t for 120 s to obtain a bulk magnesium-based hydrogen storage material.

[0017] The magnesium nickel gadolinium alloy powder in Example 1 was characterized by scanning electron microscopy. Figure 1 As shown, Figure 1 (a) is the SEM image, Figure 1 (b) is the particle size statistics diagram, Figure 1 It can be seen that the magnesium-nickel-gadolinium alloy powder after ball milling is irregular granular with an average particle size of 14.96 μm. After pressing and molding, the morphology of the obtained bulk magnesium-based hydrogen storage material is as follows Figure 2 As shown by Figure 2 It can be seen that the bulk magnesium-based hydrogen storage material exhibits obvious metallic luster and has no cracks on the surface.

[0018] Example 2 Preparation of magnesium nickel gadolinium bulk hydrogen storage material (1) Put the 200-300 μm-long magnesium-nickel-gadolinium alloy sheet and 304 stainless steel balls into a ball mill at a ball-to-material ratio of 10:1. Run the mill forward at 100 rpm for 15 minutes, rest for 15 minutes, and then reverse for 15 minutes and rest for 15 minutes. The effective milling time is 12 hours to obtain magnesium-nickel-gadolinium alloy powder with a particle size range of 3-40 μm. (2) 75 mg of the magnesium-nickel-gadolinium alloy powder with a particle size range of 3 to 40 μm obtained in step (1) was placed in a compacting mold and maintained at a pressure of 0.25 t for 150 s to obtain a bulk magnesium-based hydrogen storage material.

[0019] Example 3 Preparation of magnesium nickel gadolinium bulk hydrogen storage material (1) Put the 200-300 μm-long magnesium-nickel-gadolinium alloy sheet and 304 stainless steel balls into a ball mill at a ball-to-material ratio of 30:1. The mill was run at a speed of 180 rpm for 5 min in the forward direction and 5 min in the reverse direction, with an effective milling time of 8 h to obtain magnesium-nickel-gadolinium alloy powder with a particle size range of 3-40 μm. (2) 75 mg of the magnesium-nickel-gadolinium alloy powder with a particle size range of 3 to 40 μm obtained in step (1) was placed in a compacting mold and maintained at a pressure of 0.75 t for 90 s to obtain a bulk magnesium-based hydrogen storage material.

[0020] Comparative Example 1 The magnesium-nickel-gadolinium alloy in Example 1 was replaced with a magnesium-nickel-silicon alloy to prepare a magnesium-nickel-silicon bulk hydrogen storage material.

[0021] Comparative Example 2 The magnesium-nickel-gadolinium alloy in Example 1 was replaced with a magnesium-nickel-yttrium-silicon alloy to prepare a magnesium-nickel-yttrium-silicon bulk hydrogen storage material.

[0022] Comparative Example 3 The magnesium-nickel-gadolinium alloy in Example 1 was replaced with a magnesium-nickel-yttrium-neodymium alloy to prepare a magnesium-nickel-yttrium-neodymium bulk hydrogen storage material.

[0023] Comparative Example 4 450 mg of the magnesium-nickel-gadolinium alloy powder having a particle size range of 3 to 40 μm in Example 1 was mixed with 50 mg of the polyvinyl alcohol binder powder. During the mixing process, an n-heptane organic solution was added to uniformly mix the two. The mixture was then placed in a briquetting mold and maintained at a pressure of 0.5 t for 120 seconds to produce a briquette. The briquette was then placed in a vacuum drying oven and dried at 60° C. for 12 hours to remove the n-heptane organic solution.

[0024] The bulk magnesium-based hydrogen storage materials prepared in Example 1 and Comparative Examples 1-4 were activated five times at 350°C, with hydrogen absorption for 1.5 hours (40 bar) and hydrogen release for 15 minutes (0.01 bar). Figure 3 As shown by Figure 3 As shown in (a), the magnesium nickel gadolinium bulk hydrogen storage material prepared in Example 1 can absorb hydrogen after the initial activation, and the subsequent four activations can achieve the optimal activation effect, with a final hydrogen storage capacity of 5.71wt.%; Figure 3 As shown in (b), the magnesium nickel silicon bulk hydrogen storage material prepared in comparative example 1 can absorb hydrogen after the initial activation, and the subsequent four activations can achieve the optimal activation effect, with a final hydrogen storage capacity of 4.69wt.%; Figure 3 As shown in (c), the magnesium nickel yttrium silicon bulk hydrogen storage material prepared in comparative example 2 can absorb hydrogen after the first activation, and the subsequent four activations can achieve the optimal activation effect, with a final hydrogen storage capacity of 4.99wt.%; Figure 3 As shown in (d), the magnesium nickel yttrium neodymium bulk hydrogen storage material prepared in comparative example 3 can absorb hydrogen after the initial activation, and the subsequent four activations can achieve the optimal activation effect, with a final hydrogen storage capacity of 5.32wt.%; Figure 3 As shown in (e), the bulk magnesium-based hydrogen storage material containing a binder prepared in Comparative Example 4 can absorb hydrogen after the initial activation, and the subsequent four activations can achieve the optimal activation effect, with a final hydrogen storage capacity of 4.70 wt.%.

[0025] The bulk magnesium-based hydrogen storage materials prepared in Example 1 and Comparative Examples 1-4 were subjected to isothermal hydrogen release performance tests at 300°C, 280°C, and 260°C, respectively. The results are as follows: Figure 4 As shown by Figure 4 As shown in (a), the magnesium nickel gadolinium bulk hydrogen storage material prepared in Example 1 can release 5.47 wt.%, 5.35 wt.% and 5.17 wt.% of hydrogen within 5 min, 10 min and 20 min at 300 ° C, 280 ° C and 260 ° C, respectively, showing excellent hydrogen release kinetics; Figure 4 As shown in (b), the Mg-Ni-Si bulk hydrogen storage material prepared in Comparative Example 1 can release 4.46 wt.%, 4.42 wt.% and 4.21 wt.% of hydrogen within 5 min, 10 min and 20 min respectively at 300 ° C, 280 ° C and 260 ° C, showing certain hydrogen release kinetics; Figure 4 As shown in (c), the magnesium nickel yttrium silicon bulk hydrogen storage material prepared in Comparative Example 2 can release 5.16wt.%, 4.86wt.% and 4.50wt.% of hydrogen within 3min, 5min and 8min at 300℃, 280℃ and 260℃, respectively, showing good hydrogen release kinetics. Figure 4As shown in (d), the Mg-Ni-YN bulk hydrogen storage material prepared in Comparative Example 3 can release 4.86 wt.%, 4.68 wt.% and 4.46 wt.% of hydrogen within 5 min, 10 min and 20 min at 300 ° C, 280 ° C and 260 ° C, respectively, showing certain hydrogen release kinetics; Figure 4 As shown in (e), the bulk magnesium-based hydrogen storage material containing a binder prepared in Comparative Example 4 can release 4.68 wt.%, 4.90 wt.% and 4.98 wt.% of hydrogen within 5 min, 10 min and 20 min at 300 °C, 280 °C and 260 °C, respectively, showing certain hydrogen release kinetics.

[0026] The appearance of the bulk magnesium-based hydrogen storage materials prepared in Example 1 and Comparative Examples 1-4 after multiple cycles of hydrogen absorption and desorption was observed. Figure 5 As shown by Figure 5 As can be seen from (a), the magnesium-nickel-gadolinium bulk hydrogen storage material prepared in Example 1 exhibits good structural stability after multiple cycles of hydrogen absorption and desorption, and it still maintains the initial structure after pressing, without powder shedding. The magnesium-nickel-silicon bulk hydrogen storage material, magnesium-nickel-yttrium-silicon bulk hydrogen storage material, magnesium-nickel-yttrium-neodymium bulk hydrogen storage material and bulk magnesium-based hydrogen storage material containing a binder prepared in Comparative Examples 1-4 all show damage to their initial structures after multiple cycles of hydrogen absorption and desorption, and do not have good structural stability.

[0027] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not limiting. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present invention can be modified or replaced by equivalents without departing from the purpose and scope of the technical solutions, which should all be included in the scope of the claims of the present invention.

Claims

1. A method for preparing a magnesium nickel gadolinium bulk hydrogen storage material, characterized in that: The method comprises the following steps: cold-pressing magnesium-nickel-gadolinium alloy powder having a particle size of less than 40 μm into a mold.

2. The preparation method according to claim 1, wherein The magnesium-nickel-gadolinium alloy powder with a particle size of less than 40 μm is prepared by the following method: a magnesium-nickel-gadolinium alloy sheet with a length of 200-300 μm is ball-milled at a ball-to-material ratio of 10-30:1 at a speed of 100-300 rpm in forward and reverse intermittent milling for 8-12 hours.

3. The preparation method according to claim 2, wherein The intermittent ball milling in the forward and reverse directions is specifically as follows: after each ball milling for 5 to 15 minutes, pause for 5 to 15 minutes.

4. The preparation method according to any one of claims 1 to 3, characterized in that The cold pressing process is specifically as follows: maintaining the pressure for 90-150 seconds at a pressure of 0.25-0.75 t.

5. A magnesium nickel gadolinium bulk hydrogen storage material prepared by the preparation method according to any one of claims 1 to 4.

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