Ni3InC for MgH2 hydrogen storage material 0.5 Process for catalyst preparation

Abstract

The application discloses a kind of Ni3InC for MgH2 hydrogen storage material 0.5 The application discloses a catalyst preparation method, (1) In(OH)3, Ni(OH)2, melamine are weighed at room temperature; the weighed In(OH)3, Ni(OH)2 and melamine are added to a crucible, and stirring is carried out with a glass rod; (2) the crucible in step (1) is placed in a tube furnace, and is heated to a certain temperature in a H2 atmosphere, and is naturally cooled to room temperature after heat preservation, to obtain black particles; (3) the sample obtained in step (2) is poured into a mortar for grinding, and Ni3InC 0.5 powder is obtained.The preparation method has the characteristics of low raw material cost, simple preparation process and obvious catalytic effect.

Description

Technical Field

[0001] This invention belongs to the field of hydrogen storage materials technology, and specifically relates to a Ni3InC material for MgH2 hydrogen storage. 0.5 Catalyst preparation method. Background Technology

[0002] With the fossil fuel crisis and environmental pollution becoming increasingly severe, hydrogen energy, due to its clean, efficient, and renewable characteristics, is considered an important component of the future energy system. In the hydrogen energy industry chain, safe, efficient, and economical hydrogen storage technology is one of the key bottlenecks restricting its large-scale application. Solid-state hydrogen storage materials have attracted much attention due to their high volumetric hydrogen storage density and good safety. Among them, magnesium-based hydrogen storage materials (MgH2) have become one of the most promising hydrogen storage materials due to their high theoretical hydrogen storage capacity (7.6 wt%), abundant resources, and low cost.

[0003] In recent years, nickel-based carbides (such as Ni3ZnC) have become increasingly popular. 0.7 Nickel-indium (Ni₃InC) has attracted widespread attention due to its significant effects in reducing the activation energy of MgH₂ dehydrogenation and increasing the hydrogen absorption and desorption rates. Furthermore, indium (In), a metal with a unique electronic structure, is increasingly being explored for its applications in catalysis. However, current research on nickel-indium composite carbides, especially non-stoichiometric Ni₃InC, remains limited. 0.5 Research on Ni-In-C ternary catalysts as hydrogen storage catalysts remains scarce. Existing catalyst systems mostly focus on single transition metals or common multi-metal combinations, and the synergistic catalytic mechanism, structural regulation, and systematic impact on the hydrogen storage performance of MgH2 have not been fully explored.

[0004] Ni3InC 0.5 With Ni3ZnC 0.7 While they share many similarities, hydrogen storage technology is more commonly used in batteries, photocatalysis, and other energy fields, but has never been applied to hydrogen storage, leaving a research gap.

[0005] Currently, regarding Ni3InC 0.5 The performance of catalytic MgH2 for hydrogen storage remains unknown. Currently reported Ni3InC... 0.5 Among the preparation methods, the liquid phase method (patent number: ZL202411642773.X) is widely used. Its raw materials are Ni and In ion hydrates. However, the preparation process of the liquid phase method is too complicated and the cost of its raw materials is too high. This invention has the characteristics of simple process and low cost, and it is the first time that this material has been applied to the field of hydrogen storage. Summary of the Invention

[0006] To overcome the above technical problems, the present invention aims to provide a Ni3InC material for MgH2 hydrogen storage. 0.5A catalyst preparation method is presented, which features low raw material cost, simple preparation process, and significant catalytic effect.

[0007] To achieve the above objectives, the technical solution adopted by the present invention is as follows: A Ni3InC 0.5 The catalytic MgH2 hydrogen storage material is mainly composed of micron-sized spherical particles, with a small number of spherical particles sintering and agglomerating to form a small amount of nanoparticles that modify the surface. The diameter of the spherical particles is 5-25 μm, and the surface is relatively smooth and uniformly distributed. The diameter of the nanoparticles is 10-40 nm. The surface of both types of particles is Ni3InC. 0.5 Mutually.

[0008] Micron-sized spherical particles possess excellent structural regularity and a high specific surface area, enabling them to uniformly expose catalytic active sites and promote the adsorption and dissociation of hydrogen molecules, thereby enhancing the kinetic performance of hydrogen storage reactions. Furthermore, the introduction of nanoparticles can form heterogeneous interfaces and crystal defects, serving as rapid channels for hydrogen diffusion and further enhancing the transport efficiency of hydrogen atoms in the bulk phase, achieving synergistic optimization of the hydrogen adsorption and desorption processes.

[0009] A MgH2 hydrogen storage material using Ni3InC 0.5 The method for preparing the catalyst includes the following steps; (1) Weigh In(OH)3, Ni(OH)2 and melamine at room temperature; add the weighed In(OH)3, Ni(OH)2 and melamine to a crucible and stir with a glass rod; (2) Place the crucible from step (1) into a tube furnace, heat it to a certain temperature in an H2 atmosphere, keep it at that temperature for a certain time, and then cool it naturally to room temperature to obtain black particles. (3) The sample obtained in step (2) was poured into a mortar and ground to obtain Ni3InC. 0.5 powder; In step (1), the mass of In(OH)3 is 0.8-1.2g, the mass of Ni(OH)2 is 1.4-2.0g, and the mass of melamine is 3-8g. Controlling the molar ratio of nickel (Ni) to indium (In) to be (3.1-2.9):(0.9-1.1) ensures the formation of Ni3InC with a specific chemical composition in subsequent reactions. 0.5 Precursor. During the synthesis process, melamine serves as a carbon source, helping to provide a homogeneous reaction environment for subsequent coordination reactions.

[0010] In step (1), the crucible has a volume of 5-10 ml and the stirring time is 3-10 min. A large-capacity crucible can provide the space required for the reaction, and sufficient stirring time can ensure that the phases are mixed evenly.

[0011] In step (2), the heating rate is 3-8℃ / min, the temperature is raised to 923-1000K, and the holding time is 4-5h.

[0012] In step (3), the Ni3InC obtained by grinding 0.5 The powder particle size ranges from 5 to 25 μm.

[0013] Ni3InC 0.5 Catalytic MgH2 hydrogen storage materials are applied in the field of hydrogen storage.

[0014] The beneficial effects of the present invention.

[0015] The most significant feature of this invention is that it is the first time that Ni3InC has been prepared using a solid-state method. 0.5 The catalytic performance of this catalyst for MgH2 hydrogen storage was tested. Combined with kinetic performance analysis, it was found that it exhibited good catalytic effect within a MgH2 mass ratio ranging from 2.5 wt% to 7.5 wt%. At 573 K, the hydrogen release of all three samples exceeded 6 wt% within 1200 s, and all showed good kinetic performance. At a low temperature of 423 K, the samples in this range all achieved a hydrogen absorption of 4.2 wt% within 600 s, indicating that the catalyst has good catalytic effect. The catalytic performance was optimal at a mass ratio of 7.5 wt% (i.e., a catalyst-to-MgH2 mass ratio of approximately 2.9-3.1:36.8-37.2). This invention incorporates Ni3InC. 0.5 The catalyst exhibits significantly improved performance compared to pure MgH2: The optimal embodiment (MgH2 - 7.5 wt% Ni3InC) shows a substantial improvement. 0.5 Taking this as an example, in terms of hydrogen absorption, at 473 K, the composite material can rapidly absorb 6.78 wt% H2 within 120 s. In terms of hydrogen release, at 673 K, the composite material can release 6.8 wt% of hydrogen within 150 s, and when the temperature is lowered to 573 K, it can release 5.8 wt% of H2 within 900 s. Under the same conditions, this represents a significant improvement compared to pure MgH2. Furthermore, after 20 cycles, the hydrogen absorption and release rates of the catalyst remain above 99%. Attached Figure Description

[0016] Figure 1 The Ni3InC obtained in Example 1 0.5 X-ray diffraction pattern of the material.

[0017] Figure 2 The Ni3InC obtained in Example 1 0.5 Scanning electron microscope image of the material.

[0018] Figure 3The MgH2-7.5 wt% Ni3InC in Example 2 0.5 X-ray diffraction pattern of the composite material.

[0019] Figure 4 The MgH2-7.5 wt% Ni3InC in Examples 2, 3, and 4 0.5 kinetic properties of composite materials.

[0020] Figure 5 The MgH2-7.5 wt% Ni3InC in Example 2 0.5 Performance graph of the composite material after 20 cycles. Detailed Implementation

[0021] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. Example

[0022] (1) Weigh 1g In(OH)3, 1.68g Ni(OH)2 and 5g melamine at room temperature.

[0023] (2) Place the weighed sample into a 5 ml crucible and stir with a glass rod for more than 5 minutes.

[0024] (3) Place the crucible in a tube furnace and heat it to 973 K at a heating rate of 5℃ / min in an H2 atmosphere. Calcine for 4 hours and cool to room temperature to obtain black granules.

[0025] (4) Pour the black particles obtained in step (3) into a mortar and grind them. Finally, Ni3InC can be obtained. 0.5 Black powder.

[0026] For the synthesized Ni3InC 0.5 The material was characterized by X-ray diffraction, and the results are as follows: Figure 1 As shown, diffraction peaks appear at 2θ = 23.51°, 33.5°, 41.34°, 48.1°, 70.42°, and 85.02°, which can be indexed to the standard card Ni3InC. 0.5 PDF#28-0468, and the absence of other impurities, proves the successful preparation of pure-phase Ni3InC. 0.5 Sample. Subsequently, Ni3InC... 0.5 Morphological characterization was performed, such as Figure 2As shown, under low-magnification scanning electron microscopy, the particles are mainly micron-sized spherical particles with surface modification of nanoparticles. Upon magnification, the spherical particles are found to be approximately 5-25 μm in size, with relatively smooth surfaces and uniform distribution. Example

[0027] Synthesis of MgH2-7.5 wt% Ni3InC 0.5 The specific steps for composite materials are as follows: (1) Weigh 1g In(OH)3, 1.68g Ni(OH)2 and 5g melamine at room temperature.

[0028] (2) Place the weighed sample into a 5 ml crucible and stir with a glass rod for more than 5 minutes.

[0029] (3) Place the crucible in a tube furnace and heat it to 973 K at a heating rate of 5℃ / min in an H2 atmosphere. Calcine for 4 hours and cool to room temperature to obtain black granules.

[0030] (4) Pour the black particles obtained in step (3) into a mortar and grind them. Finally, Ni3InC can be obtained. 0.5 Black powder.

[0031] (5) Take 0.15g of the sample obtained in step (4) and 1.85g of MgH2 powder and put it into a ball mill jar. The ball-to-material ratio is 60:1. Mill at 500rpm for 10h to finally obtain MgH2-7.5 wt% Ni3InC. 0.5 Composite materials were used for hydrogen absorption and desorption kinetics testing.

[0032] Phase analysis was performed on it using an X-ray diffractometer (ShimadzuXRD-7000), such as... Figure 3 As shown, it can be observed that no phase change occurred between the catalyst and MgH2 during the ball milling process.

[0033] Utilization of hydrogen storage equipment for MgH2-7.5 wt% Ni3InC 0.5 The composite material underwent hydrogen absorption / desorption kinetics and cycling performance testing, and the results are as follows: Figure 4 c,f indicates MgH2-7.5 wt% Ni3InC 0.5 Regarding hydrogen absorption, the sample, at 473 K, showed MgH₂-7.5 wt% Ni₃InC 0.5 The composite material can rapidly absorb 5.9 wt% H2 within 120 s. Regarding hydrogen release, at 673 K, it can absorb MgH2-7.5 wt% Ni3InC. 0.5The composite material can release 6.8 wt% hydrogen within 150 s, and when the temperature is reduced to 573 K, it can release 5.8 wt% H2 within 900 s. Under the same conditions, this represents a significant improvement compared to pure MgH2. Figure 5 As shown, the catalyst can still maintain a hydrogen absorption and desorption capacity of over 99% after 20 cycles. Example

[0034] Synthesis of MgH2-5 wt% Ni3InC 0.5 The specific steps for composite materials are as follows: (1) Weigh 1g In(OH)3, 1.68g Ni(OH)2 and 5g melamine at room temperature.

[0035] (2) Place the weighed sample into a 5 ml crucible and stir with a glass rod for more than 5 minutes.

[0036] (3) Place the crucible in a tube furnace and heat it to 973 K at a heating rate of 5℃ / min in an H2 atmosphere. Calcine for 4 hours and cool to room temperature to obtain black granules.

[0037] (4) Pour the black particles obtained in step (3) into a mortar and grind them. Finally, Ni3InC can be obtained. 0.5 Black powder.

[0038] (5) Take 0.1g of the sample obtained in step (4) and 1.9g of MgH2 powder and put it into a ball mill jar. The ball-to-material ratio is 60:1. Ball mill at 500rpm for 10h to finally obtain MgH2-5 wt% Ni3InC. 0.5 Composite materials were used for hydrogen absorption and desorption kinetics testing.

[0039] Utilization of hydrogen storage equipment for MgH2-5 wt% Ni3InC 0.5 The hydrogen absorption and desorption kinetics of the composite material were tested. The results are as follows: Figure 4 As shown in b and e, under conditions of 473 K, MgH2-7.5 wt% Ni3InC 0.5 The composite material can rapidly absorb 5.8 wt% H2 within 120 s. Regarding hydrogen release, at 673 K, it can absorb MgH2-7.5 wt% Ni3InC. 0.5 The composite material can release 7.0 wt% hydrogen within 160 s, and when the temperature is reduced to 573 K, it can release 6.2 wt% H2 within 900 s. Under the same conditions, it shows a significant improvement compared to pure MgH2. Example

[0040] Synthesis of MgH2-2.5 wt% Ni3InC0.5 The specific steps for composite materials are as follows: (1) Weigh 1g In(OH)3, 1.68g Ni(OH)2 and 5g melamine at room temperature.

[0041] (2) Place the weighed sample into a 5 ml crucible and stir with a glass rod for more than 5 minutes.

[0042] (3) Place the crucible in a tube furnace and heat it to 973 K at a heating rate of 5℃ / min in an H2 atmosphere. Calcine for 4 hours and cool to room temperature to obtain black granules.

[0043] (4) Pour the black particles obtained in step (3) into a mortar and grind them. Finally, Ni3InC can be obtained. 0.5 Black powder.

[0044] (5) Take 0.05g of the sample obtained in step (4) and 1.95g of MgH2 powder and put it into a ball mill jar. The ball-to-material ratio is 60:1. Ball mill at 500rpm for 10h to finally obtain MgH2-2.5 wt% Ni3InC. 0.5 Composite materials were used for hydrogen absorption and desorption kinetics testing.

[0045] Using hydrogen storage equipment to process MgH2-2.5 wt% Ni3InC 0.5 The hydrogen absorption and desorption kinetics of the composite material were tested. The results are as follows: Figure 4 As shown in a and d, under conditions of 473 K, MgH2-7.5 wt% Ni3InC 0.5 The composite material can rapidly absorb 5.5 wt% H2 within 100 s. Regarding hydrogen release, at 673 K, it can absorb MgH2-7.5 wt% Ni3InC. 0.5 The composite material can release 6.9 wt% of hydrogen within 130 s, and when the temperature is reduced to 573 K, it can release 6.1 wt% of H2 within 900 s. Under the same conditions, it shows a significant improvement compared to pure MgH2.

[0046] In summary, the above are merely embodiments of the present invention and are not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A Ni3InC 0.5 Catalytic MgH2 hydrogen storage material, characterized in that, The particles are mainly micron-sized spherical particles, with a small number of sintered and agglomerated to form a small amount of nanoparticles that modify the surface. The diameter of the spherical particles is 5-25 μm, and the surface is relatively smooth and uniformly distributed. The diameter of the nanoparticles is 10-40 nm. The surface of both types of particles is Ni3InC. 0.5 Mutually.

2. The Ni3InC material for MgH2 hydrogen storage as described in claim 1 0.5 A method for preparing a catalyst, characterized in that, Includes the following steps; (1) Weigh In(OH)3, Ni(OH)2 and melamine at room temperature; add the weighed In(OH)3, Ni(OH)2 and melamine to a crucible and stir with a glass rod; (2) Place the crucible from step (1) into a tube furnace, heat it to a certain temperature in an H2 atmosphere, keep it at that temperature, and then let it cool naturally to room temperature to obtain black particles. (3) The sample obtained in step (2) was poured into a mortar and ground to obtain Ni3InC. 0.5 powder.

3. The Ni3InC for MgH2 hydrogen storage material according to claim 2 0.5 A method for preparing a catalyst, characterized in that, In step (1), the mass of In(OH)3 is 0.8-1.2g, the mass of Ni(OH)2 is 1.4-2.0g, and the mass of melamine is 3-8g. The molar ratio of nickel (Ni) to indium (In) is controlled at (3.1-2.9):(0.9-1.1).

4. The Ni3InC for MgH2 hydrogen storage material according to claim 2 0.5 A method for preparing a catalyst, characterized in that, In step (1), the volume of the crucible is 5-10 ml, and the stirring time is 3-10 min.

5. The Ni3InC material for MgH2 hydrogen storage as described in claim 2 0.5 A method for preparing a catalyst, characterized in that, In step (2), the heating rate is 3-8℃ / min, the temperature is raised to 923-1000K, and the holding time is 4-5h.

6. The Ni3InC for MgH2 hydrogen storage material according to claim 2 0.5 A method for preparing a catalyst, characterized in that, In step (3), the Ni3InC obtained by grinding 0.5 The powder particle size ranges from 5 to 25 μm.

7. Ni3InC prepared by the method according to any one of claims 1-6 0.5 The application of powder is characterized by, Ni3InC 0.5 Powdered catalytic MgH2 hydrogen storage material is applied in the field of hydrogen storage.

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