Hydrolysis hydrogen production materials and their preparation methods

Abstract

This application belongs to the technical field of hydrogen, and provides a hydrogen production material by hydrolysis and a preparation method thereof. The preparation method includes: heating and melting an alloy melt raw material containing aluminum, indium and tin to obtain an alloy melt; performing a first cooling treatment on the alloy melt, cooling the alloy melt to a transformation temperature, the transformation temperature ≥ 120 °C, and then performing a second cooling treatment to obtain a hydrogen production material by hydrolysis containing InSn4 and In3Sn; the cooling rate of the first cooling treatment is greater than that of the second cooling treatment, and the cooling rate of the second cooling treatment is 2 °C / s to 10 °C / s. The hydrogen production material by hydrolysis prepared in this application has the characteristics of low cost, fast hydrogen production rate and high efficiency.

Description

Technical Field

[0001] The present invention relates to the technical field of hydrogen, and particularly to a hydrogen production material by hydrolysis and a preparation method thereof. Background Art

[0002] At present, due to the urgent need for deep-sea exploration, underwater equipment urgently needs to improve the energy density of its own energy system to meet the requirements of long-distance and long-endurance use. At the same time, the hydrogen fuel cell system has become the best power system for underwater equipment because of its advantages such as high energy conversion efficiency, high energy storage density, pollution-free emissions, and low working noise. However, the enclosed scenario of underwater equipment creates more technical difficulties for the use of hydrogen fuel cells.

[0003] The aluminum hydrolysis hydrogen production technology has advantages such as high hydrogen storage density, mild hydrogen production conditions, high hydrogen purity, and environmentally friendly products, and has become one of the competitive hydrogen source technologies in underwater scenarios. However, due to its high reactivity, when aluminum is exposed to air, a dense oxide film will immediately form on its surface, preventing the aluminum hydrolysis reaction from proceeding. In traditional technologies, Al-Ga-In-Sn alloys are used to improve the reaction rate of aluminum hydrolysis hydrogen production, but usually the proportion of auxiliary metal addition is relatively large, accounting for 10% - 20% of the total mass of the alloy, which not only reduces the hydrogen storage density of the material, but also the prices of metals such as Ga and In are higher than that of aluminum, increasing the cost of the material.

[0004] Therefore, how to provide a hydrolysis hydrogen production material with low cost, high gas production efficiency and fast speed has become an urgent technical problem to be solved at present. Summary of the Invention

[0005] Based on this, the embodiments of the present application provide a hydrolysis hydrogen production material with low cost, high gas production efficiency and fast speed and a preparation method thereof.

[0006] In a first aspect, the present application provides a preparation method of a hydrolysis hydrogen production material, and the preparation method includes:

[0007] Heating and melting an alloy melt raw material containing aluminum, indium and tin to obtain an alloy melt;

[0008] Performing a first cooling treatment on the alloy melt, cooling the alloy melt to a transformation temperature, where the transformation temperature ≥ 120 °C, and then performing a second cooling treatment to obtain a hydrolysis hydrogen production material containing InSn4 and In3Sn;

[0009] The cooling rate of the first cooling treatment is greater than the cooling rate of the second cooling treatment, and the cooling rate of the second cooling treatment is 2 °C / s - 10 °C / s.

[0010] In some embodiments, the cooling rate of the first cooling treatment is 5 °C / s - 50 °C / s.

[0011] In some embodiments, the first cooling treatment includes at least two cooling stages, and during the first cooling treatment, the cooling rate of the cooling stages decreases step by step.

[0012] In some embodiments, the second cooling treatment includes at least two cooling stages, and during the second cooling treatment, the cooling rate of the cooling stages decreases step by step.

[0013] In some embodiments, the first cooling treatment and the second cooling treatment each independently include at least one of water cooling, oil cooling, air cooling, and rapid quenching.

[0014] In some embodiments, the heating and melting rate of temperature rise is 5 °C / min to 40 °C / min, the temperature is 700 °C to 1000 °C, and the heat preservation time is 1 h to 2 h.

[0015] In some embodiments, the mass proportion of aluminum in the alloy melt is 70% to 95%, the mass proportion of indium is 0.1% to 29.9%, and the mass proportion of tin is 0.1% to 29.9%.

[0016] In some embodiments, the mass ratio of indium to tin in the alloy melt is 30:1 to 1:30.

[0017] In some embodiments, the transformation temperature is 140 °C to 300 °C.

[0018] In some embodiments, the alloy melt raw material further includes a doping metal, and the doping metal includes at least one of Ga, Zn, Cu, Hg, Na, Co, and Fe.

[0019] In some embodiments, the mass proportion of the doping metal in the alloy melt is 0% to 20%.

[0020] In a second aspect, the present application provides a hydrogen production material by hydrolysis, and the hydrogen production material by hydrolysis is prepared by the preparation method of the hydrogen production material by hydrolysis described in the first aspect, and the hydrogen production material by hydrolysis includes aluminum, InSn4, and In3Sn.

[0021] Compared with the traditional technology, the present application has at least the following beneficial effects:

[0022] In this application, by adopting cooling treatments with different cooling rates and controlling the cooling temperature, first performing a first cooling treatment on the alloy melt can refine the alloy grains, which is beneficial to increasing the surface area for reaction with water and improving the hydrogen production rate. Then, the alloy melt is subjected to a second cooling treatment at a cooling rate of 2°C / s to 10°C / s from the transformation temperature. At this transformation temperature and cooling rate, indium and tin have specific interactions and solid solubilities, and stable InSn4 and In3Sn can be formed through atomic rearrangement and phase transformation, reducing the segregation degree of the alloy components and making the alloy composition more uniform. During the hydrolysis hydrogen production process, In3Sn and InSn4 can change the surface tension of the low-melting-point metal, improving the hydrolysis rate, and having the characteristics of low cost, fast hydrogen production rate, and high efficiency. Description of the Drawings

[0023] Figure 1 It is a scanning electron microscope image of the hydrolysis hydrogen production material prepared in Example 1 of this application;

[0024] Figure 2 XRD diagrams of the hydrolysis hydrogen production materials prepared in Example 1 of this application and Comparative Examples 1-4;

[0025] Figure 3 It is a hydrogen production performance diagram of the hydrolysis hydrogen production materials prepared in Example 1 of this application and Comparative Examples 1-4. Detailed Embodiments

[0026] The following further elaborates on this application in combination with the embodiments and implementation manners. These embodiments and implementation manners are only used to illustrate this application and not to limit the scope of this application. The purpose of providing these embodiments and implementation manners is to make the understanding of the disclosed content of this application more thorough and comprehensive. It should also be understood that this application can be implemented in many different forms and is not limited to the embodiments and implementation manners described herein. Those skilled in the art can make various changes or modifications without departing from the connotation of this application, and the equivalent forms obtained also fall within the protection scope of this application. In addition, in the following description, a large number of specific details are given to provide a more thorough understanding of this application. It should be understood that this application can be implemented without one or more of these details.

[0027] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the technical field to which this application belongs. The terms used in the specification of this application herein are only for the purpose of describing specific embodiments and are not intended to limit this application.

[0028] In this application, "optionally", "optional", and "option" mean having or not having, that is, any one selected from two alternative options of "having" or "not having". If "optional" appears multiple times in a technical solution, without special instructions, and without contradictions or mutual restrictions, each "optional" is independent of each other.

[0029] In this application, in "the first aspect", "the second aspect", etc., the terms "first", "second", etc. are only for descriptive purposes and cannot be construed as indicating or implying relative importance or quantity, nor can they be construed as implicitly indicating the importance or quantity of the indicated technical features. Moreover, "first", "second", etc. only serve the purpose of non-exhaustive enumerative description and should be understood not to constitute a closed limitation on quantity.

[0030] In this application, for the technical features described in an open-ended manner, it includes a closed technical solution composed of the listed features, as well as an open technical solution including the listed features.

[0031] In this application, regarding numerical intervals (i.e., numerical ranges), unless otherwise specified, the distribution of the optional numerical values within this numerical interval is considered continuous and includes the two numerical endpoints of this numerical interval (i.e., the minimum value and the maximum value), as well as each numerical value between these two numerical endpoints. Unless otherwise specified, when the numerical interval only refers to the integers within this numerical interval, it includes the two endpoint integers of this numerical range, as well as each integer between the two endpoints, which is equivalent to directly listing each integer. When multiple numerical ranges are provided to describe features or characteristics, these numerical ranges can be combined. In other words, unless otherwise specified, the numerical ranges disclosed in this application should be understood to include any and all sub-ranges subsumed therein. The "numerical value" in this numerical interval can be any quantitative value, such as a number, a percentage, a ratio, etc. The "numerical interval" is allowed to broadly include quantitative intervals such as percentage intervals, ratio intervals, and ratio value intervals.

[0032] All the documents mentioned in this application are cited as references in this application, just as if each document is cited separately as a reference. Unless it conflicts with the inventive purpose and / or technical solution of this application, the cited documents related to this application are cited for their entire content and entire purpose. When this application involves cited documents, the definitions of relevant technical features, terms, nouns, phrases, etc. in the cited documents are also cited. When this application involves cited documents, the examples and preferred methods of the relevant technical features cited can also be incorporated as references into this application, but only to the extent that this application can be implemented. It should be understood that when the cited content conflicts with the description in this application, this application shall prevail or be amended adaptively according to the description in this application.

[0033] In the traditional technology, the alloy activation method is adopted to improve the hydrogen production effect of aluminum alloy. That is, aluminum is used as the base material, and some auxiliary metal elements are doped, such as Ga, In, Sn, Li, Bi, Mg, Ga, Co, etc. The alloy activation method can change the crystal phase structure of aluminum, and eutectic or intermetallic compounds will also be formed. When they encounter water, micro corrosion cells can be formed, thereby reducing the aluminum potential and achieving a relatively high hydrogen production effect by hydrolysis. However, the proportion of auxiliary metals added is relatively large, usually accounting for 10% - 20% of the total mass of the alloy. This not only reduces the hydrogen storage density of the material, but also the prices of metals such as Ga and In are higher than that of aluminum, increasing the cost of the material. Moreover, the gas production efficiency and gas production rate cannot meet the existing hydrogen production requirements. In this application, the stepwise cooling method is adopted, which not only realizes the grain refinement of aluminum alloy, but also forms In3Sn and InSn4 phases, effectively improving the hydrogen production rate and efficiency, and reducing the cost of the hydrogen production material by hydrolysis.

[0034] In the first aspect of this application, a preparation method of a hydrogen production material by hydrolysis is provided. The preparation method includes:

[0035] Heating and melting an alloy melt raw material containing aluminum, indium and tin to obtain an alloy melt;

[0036] Performing a first cooling treatment on the alloy melt, cooling the alloy melt to a transformation temperature, where the transformation temperature is greater than or equal to 120 °C, and then performing a second cooling treatment to obtain a hydrogen production material containing InSn4 and In3Sn;

[0037] The cooling rate of the first cooling treatment is greater than that of the second cooling treatment. The cooling rate of the second cooling treatment is 2 °C / s - 10 °C / s, for example, it can be 2 °C / s, 3 °C / s, 4 °C / s, 5 °C / s, 6 °C / s, 7 °C / s, 8 °C / s, 9 °C / s or 10 °C / s.

[0038] In this application, by adopting cooling treatments with different cooling rates and controlling the cooling temperature, first performing a first cooling treatment on the alloy melt can refine the alloy grains, which is beneficial to increasing the surface area for its reaction with water and improving the hydrogen production rate. Then, the alloy melt is subjected to a second cooling treatment at a cooling rate of 2 °C / s - 10 °C / s from the transformation temperature. At this transformation temperature and cooling rate, indium and tin have specific interactions and solid solubilities. Through atomic rearrangement and phase transformation, stable InSn4 and In3Sn can be formed, reducing the segregation degree of alloy components and making the alloy components more uniform. During the process of hydrogen production by hydrolysis, In3Sn and InSn4 can change the surface tension of low melting point metals, improve the hydrolysis rate, and have the characteristics of low cost, fast hydrogen production rate and high efficiency.

[0039] By selecting the cooling rate of the second cooling treatment as above, the present application can not only further refine the grains and reduce segregation, but also effectively ensure the complete and uniform phase transformation of InSn4 and In3Sn phases, which helps to achieve more stable hydrogen production performance by hydrolysis.

[0040] The present application controls the transformation temperature and cooling rate during the cooling process of the hydrogen production material by hydrolysis, thereby effectively ensuring the formation of stable In3Sn and InSn4 phases and an appropriate mass ratio of In3Sn and InSn4, and effectively improving the hydrogen production performance.

[0041] It can be understood that the hydrogen production material by hydrolysis in the present application refers to a material that can react with water to produce hydrogen.

[0042] In some embodiments, the cooling rate of the first cooling treatment is 5°C / s to 50°C / s, and for example, it can be 5°C / s, 7.5°C / s, 10°C / s, 15°C / s, 20°C / s, 25°C / s, 30°C / s, 35°C / s, 40°C / s, 45°C / s or 50°C / s. It can be optionally 5°C / s to 30°C / s.

[0043] The present application controls the cooling rate of the first cooling treatment. While increasing the formation of crystal nuclei, it refines the grains, avoids over-large grains, can increase the contact area with water during the hydrogen production process by hydrolysis, and improves the hydrogen production performance.

[0044] In some embodiments, the first cooling treatment includes at least two cooling stages. During the first cooling treatment, the cooling rate of the cooling stage decreases step by step. It can be understood that the first cooling treatment in the present application can be divided into multiple cooling stages, and the cooling rates of each cooling stage can be different. For example, the first cooling treatment is divided into a first cooling stage and a second cooling stage. The cooling rate of the first cooling stage can be greater than or less than that of the second cooling stage.

[0045] In some embodiments, the second cooling treatment includes at least two cooling stages. During the second cooling treatment, the cooling rate of the cooling stage decreases step by step.

[0046] In some embodiments, the first cooling treatment and the second cooling treatment each independently include at least one of water cooling, oil cooling, air cooling, and rapid quenching.

[0047] In some embodiments, the heating rate for heating and melting is 5°C / min to 40°C / min, and for example, it can be 5°C / min, 8°C / min, 12°C / min, 16°C / min, 20°C / min, 24°C / min, 28°C / min, 32°C / min, 36°C / min or 40°C / min.

[0048] In some embodiments, the temperature for heating and melting is 700°C to 1000°C, and for example, it can be 700°C, 730°C, 760°C, 790°C, 820°C, 850°C, 880°C, 910°C, 940°C, 970°C or 1000°C.

[0049] In some embodiments, the holding time for heating and melting is 1 h to 2 h, and for example, it can be 1.0 h, 1.1 h, 1.2 h, 1.3 h, 1.4 h, 1.5 h, 1.6 h, 1.7 h, 1.8 h, 1.9 h or 2.0 h.

[0050] In some embodiments, the atmosphere for heating and melting is a protective atmosphere. It can be understood that the protective atmosphere refers to a gas that does not react with the raw materials, and can be reasonably selected according to the types of raw materials. For example, the gas used for the protective atmosphere can be nitrogen.

[0051] In some embodiments, the mass proportion of aluminum in the alloy melt is 70% to 95%, and for example, it can be 70%, 72%, 74%, 76%, 78%, 80%, 82%, 84%, 86%, 88%, 90%, 92%, 94% or 95%.

[0052] In some embodiments, the mass proportion of indium in the alloy melt is 0.1% to 29.9%, and for example, it can be 0.1%, 3%, 6%, 9%, 12%, 15%, 18%, 21%, 24%, 27% or 29.9%.

[0053] In some embodiments, the mass proportion of tin in the alloy melt is 0.1% to 29.9%, and for example, it can be 0.1%, 3%, 6%, 9%, 12%, 15%, 18%, 21%, 24%, 27% or 29.9%.

[0054] In some embodiments, the mass ratio of indium to tin in the alloy melt is 30:1 to 1:30.

[0055] This application controls the mass ratio of indium to tin, which can adjust the relative content of intermetallic compounds (In3Sn and InSn4) in the grain boundary phase (GBPs), and further affect the surface tension of GBPs. The change in surface tension is directly related to the diffusion rate of aluminum atoms and the dynamic process of hydrolysis reaction, thereby realizing the fine regulation of hydrogen release performance.

[0056] In some embodiments, the transition temperature is 140°C to 300°C, and for example, it can be 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, 240°C, 250°C, 260°C, 270°C, 280°C, 290°C or 300°C.

[0057] In some embodiments, the alloy melt raw material further includes a doped metal, and the doped metal includes at least one of Ga, Zn, Cu, Hg, Na, Co, and Fe. Preferably, it is Ga.

[0058] In some embodiments, the mass ratio of the doped metal in the alloy melt is 0% - 20%, and for example, it can be 0%, 2%, 4%, 6%, 8%, 10%, 12%, 14%, 16%, 18%, or 20%.

[0059] The second aspect of the present application provides a hydrogen production material by hydrolysis, which is prepared by the preparation method of the hydrogen production material by hydrolysis described in the first aspect, and the hydrogen production material by hydrolysis includes aluminum, InSn4, and In3Sn.

[0060] The embodiments of the present invention will be described in detail below in conjunction with the examples. It should be understood that these examples are only used to illustrate the present invention and not to limit the scope of the present invention. For the experimental methods without specific conditions in the following examples, the guidance given in the present invention is preferably referred to, and it can also be carried out according to the experimental manuals or conventional conditions in the art, or according to the conditions recommended by the manufacturers, or referring to the experimental methods known in the art.

[0061] Example 1

[0062] Weigh the mass ratio of aluminum: gallium: indium: tin = a:b:c:d = 94:4.1:0.8:1.1, and a + b + c + d = 100; under the protection of a nitrogen atmosphere, heat from room temperature to 800°C at a rate of 10°C / min uniformly and keep it warm for 1 h to obtain an alloy melt;

[0063] During melting and forming, first perform a first cooling treatment on the alloy melt. The first cooling treatment uses water cooling, and the cooling rate is 5.7°C / s to cool the alloy melt to 280°C; then perform a second cooling treatment, and the second cooling treatment includes a first cooling stage and a second cooling stage in sequence. The first cooling stage uses air cooling to cool the alloy melt to 100°C at a cooling rate of 2.7°C / s; the second cooling stage uses air cooling to cool the alloy melt to room temperature at a cooling rate of 2.5°C / s to prepare a hydrogen production material by hydrolysis containing In3Sn and InSn4 phases. The scanning electron microscope image is as Figure 1 shown.

[0064] Example 2

[0065] Weigh the mass ratio of aluminum: gallium: indium: tin = a:b:c:d = 70:5:10:15, and a + b + c + d = 100; under the protection of a nitrogen atmosphere, heat from room temperature to 900°C at a rate of 20°C / min uniformly and keep it warm for 1.5 h to obtain an alloy melt;

[0066] During smelting and forming, first perform a first cooling treatment on the alloy melt. The first cooling treatment uses water cooling with a cooling rate of 5.7 °C / s to cool the alloy melt to a transformation temperature of 140 °C. Then perform a second cooling treatment. The second cooling treatment uses air cooling to cool the alloy melt to room temperature at a cooling rate of 2.7 °C / s ° / min, and a hydrogen production material by hydrolysis containing In3Sn and InSn4 phases is prepared.

[0067] Example 3

[0068] Weigh the mass ratio of aluminum: gallium: indium: tin = a:b:c:d = 95:0:2.5:2.5, and a + b + c + d = 100; under the protection of a nitrogen atmosphere, uniformly heat from room temperature to 1000 °C at a rate of 15 °C / min and hold for 2 h to obtain an alloy melt;

[0069] During smelting and forming, first perform a first cooling treatment on the alloy melt. The first cooling treatment uses water cooling with a cooling rate of 7.5 °C / s to cool the alloy melt to 200 °C. Then perform a second cooling treatment. The second cooling treatment uses air cooling to cool the alloy melt to room temperature at a cooling rate of 5 °C / s, and a hydrogen production material by hydrolysis containing In3Sn and InSn4 phases is prepared.

[0070] Example 4

[0071] Prepare the hydrogen production material by hydrolysis according to the method of Example 2, the only difference being that the cooling rate of the first cooling treatment is 55 °C / s.

[0072] Example 5

[0073] Prepare the hydrogen production material by hydrolysis according to the method of Example 2, the only difference being that the cooling rate of the first cooling treatment is 40 °C / s.

[0074] Example 6

[0075] Prepare the hydrogen production material by hydrolysis according to the method of Example 2, the only difference being that the cooling rate of the first cooling treatment is 4 °C / s.

[0076] Example 7

[0077] Prepare the hydrogen production material by hydrolysis according to the method of Example 2, the only difference being that the transformation temperature is 130 °C.

[0078] Example 8

[0079] Prepare the hydrogen production material by hydrolysis according to the method of Example 2, the only difference being that the transformation temperature is 400 °C.

[0080] Example 9 The hydrolytic hydrogen production material was prepared according to the method of Example 2, with the only difference being that the mass ratio of aluminum: gallium: indium: tin was weighed as a:b:c:d = 70:5:0.5:24.5, and a + b + c + d = 100; among them, the mass ratio of indium to tin was 1:49.

[0081] Example 10

[0082] The hydrolytic hydrogen production material was prepared according to the method of Example 2, with the only difference being that the mass ratio of aluminum: gallium: indium: tin was weighed as a:b:c:d = 70:5:24.4:0.6, and a + b + c + d = 100; among them, the mass ratio of indium to tin was 40.7:1.

[0083] Comparative Example 1

[0084] The hydrolytic hydrogen production material was prepared according to the method of Example 1, with the only difference being that during melting and forming, first, the temperature of the alloy melt was cooled to 100 °C at a cooling rate of 2.7 °C / s by air cooling, and then it was cooled to room temperature at a cooling rate of 1.4 °C / s by air cooling.

[0085] Comparative Example 2

[0086] The hydrolytic hydrogen production material was prepared according to the method of Example 1, with the only difference being that during melting and forming, first, the temperature of the alloy melt was cooled to 100 °C at a cooling rate of 5.7 °C / s by water cooling, and then it was cooled to room temperature at a cooling rate of 1.4 °C / s by air cooling.

[0087] Comparative Example 3

[0088] The hydrolytic hydrogen production material was prepared according to the method of Example 1, with the only difference being that during melting and forming, the temperature of the alloy melt was directly cooled to room temperature at a cooling rate of 5.7 °C / s by water cooling.

[0089] Comparative Example 4

[0090] The hydrolytic hydrogen production material was prepared according to the method of Example 1, with the only difference being that during melting and forming, the temperature of the alloy melt was directly cooled to room temperature at a cooling rate of 1.4 °C / s by air cooling.

[0091] Comparative Example 5

[0092] The hydrolytic hydrogen production material was prepared according to the method of Example 2, with the only difference being that first, the alloy melt was cooled to 140 °C at a cooling rate of 2.7 °C / s, and then it was cooled to room temperature at a cooling rate of 5.7 °C / s.

[0093] Comparative Example 6

[0094] The hydrolytic hydrogen production material was prepared according to the method of Example 2, with the only difference being that the cooling rate of the second cooling treatment was 15 °C / s.

[0095] Comparative Example 7

[0096] The hydrolytic hydrogen production material was prepared according to the method of Example 2, except that the temperature after the first cooling treatment was 100 °C.

[0097] The hydrolytic hydrogen production materials prepared in the above Example 1 and Comparative Examples 1-4 were subjected to XRD detection, and the test results are as Figure 2 shown.

[0098] The hydrolytic hydrogen production materials prepared in the above examples and comparative examples were subjected to performance tests. The test methods included:

[0099] Take 0.2 g of the hydrolytic hydrogen production material and put it into a flask. Heat it in a water bath to 80 °C. Inject deionized water into the flask, and use the water displacement method to collect the produced hydrogen until no more hydrogen is produced, to obtain the fastest hydrogen production rate and hydrogen production rate. The test results are shown in Table 1, and the hydrogen production performance diagrams of Example 1 and Comparative Examples 1-4 as Figure 3 shown were plotted.

[0100] Table 1

[0101]

[0102] It can be seen from the above table that

[0103] (1) Comparing Example 2 with Examples 4-6, it can be seen that by controlling the cooling rate of the first cooling treatment in the present application, while increasing the formation of crystal nuclei, the grain size is prevented from being too large, thereby refining the grains, increasing the contact area with water during the hydrolytic hydrogen production process, and improving the hydrogen production performance.

[0104] (2) Comparing Example 2 with Examples 7-8, it can be seen that by controlling the transformation temperature in the present application, the phase transformation of InSn4 and In3Sn phases is effectively ensured to be complete and stable, and the hydrolytic hydrogen production effect is improved.

[0105] (3) Comparing Example 2 with Examples 9-10, it can be seen that by controlling the mass ratio of indium and tin in the present application, the relative content of intermetallic compounds (In3Sn and InSn4) in the grain boundary phase (GBPs) can be adjusted, and then the surface tension of GBPs is affected. The change in surface tension is directly related to the diffusion rate of aluminum atoms and the dynamic process of the hydrolysis reaction, thereby realizing the fine regulation of the hydrogen release performance.

[0106] (4) Comparing Example 1 with Comparative Examples 1-4, and comparing Example 2 with Comparative Examples 5-7, and combining Figure 1 and Figure 2 , it can be seen that as Figure 1As shown in the figure, the hydrolytic hydrogen production material prepared in Example 1 of the present application forms low-melting-point metal spheres, which increases the surface tension of the low-melting-point metal, making it easier for aluminum atoms to migrate from the interior of the metal to the metal surface and participate in the reaction, thus facilitating hydrolytic hydrogen production. In addition, by Figure 2 It can be seen that the hydrolytic hydrogen production material prepared in Example 1 of the present application contains In3Sn and InSn4, while the hydrolytic hydrogen production material prepared in the comparative example only contains In3Sn or InSn4, and the fastest hydrogen production rate is significantly lower than that of the present application. By controlling the cooling rate of the second cooling treatment in the present application, not only can the grains be further refined and segregation be reduced, but also the phase transformation of the InSn4 and In3Sn phases can be effectively ensured to be complete and have good stability, improving the hydrolytic hydrogen production effect.

[0107] Through the above examples and comparative examples, in the present application, by adopting cooling treatments with different cooling rates and controlling the cooling temperature, first performing the first cooling treatment on the alloy melt can refine the alloy grains, which is beneficial to increasing the surface area for reaction with water and improving the hydrogen production rate; then performing the second cooling treatment on the alloy melt at a cooling rate of 2 °C / s to 10 °C / s from the transformation temperature. At this transformation temperature and cooling rate, indium and tin have specific interactions and solid solubilities, and stable InSn4 and In3Sn can be formed through atomic rearrangement and phase transformation, reducing the degree of segregation of the alloy components and making the alloy components more uniform. During the process of hydrolytic hydrogen production, In3Sn and InSn4 can change the surface tension of the low-melting-point metal, increasing the hydrolysis rate, and having the characteristics of low cost, fast hydrogen production rate, and high efficiency.

[0108] The technical features of the above embodiments can be combined arbitrarily. For the sake of brevity of description, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, it should be considered as the scope described in this specification.

[0109] The above embodiments only represent several implementation manners of the present invention, and their descriptions are relatively specific and detailed, but they should not be construed as limiting the scope of the invention patent. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can still be made, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the invention patent should be subject to the appended claims.

Claims

1. A preparation method of a hydrogen production material by hydrolysis, characterized in that, The preparation method includes: Heating and melting an alloy melt raw material containing aluminum, indium, and tin to obtain an alloy melt, wherein the mass ratio of aluminum in the alloy melt is 82% - 95%, the mass ratio of indium is 0.1% - 15%, and the mass ratio of tin is 0.1% - 15%; Performing a first cooling treatment on the alloy melt, cooling the alloy melt to a transformation temperature, the transformation temperature being 140°C - 300°C, and then performing a second cooling treatment to obtain a hydrogen production material by hydrolysis containing InSn4 and In3Sn, and the hydrogen production material by hydrolysis contains a metal sphere structure; The cooling rate of the first cooling treatment is greater than that of the second cooling treatment, the cooling rate of the first cooling treatment is 5°C / s - 50°C / s, and the cooling rate of the second cooling treatment is 2°C / s - 10°C / s.

2. The preparation method of the hydrogen production material by hydrolysis according to claim 1, characterized in that, The preparation method satisfies at least one of the following conditions: (1) The first cooling treatment includes at least two cooling stages, and during the first cooling treatment, the cooling rate of the cooling stage decreases step by step; (2) The second cooling treatment includes at least two cooling stages, and during the second cooling treatment, the cooling rate of the cooling stage decreases step by step.

3. The preparation method of the hydrogen production material by hydrolysis according to claim 1, characterized in that, The first cooling treatment and the second cooling treatment each independently include at least one of water cooling, oil cooling, air cooling, and rapid quenching.

4. The preparation method of the hydrogen production material by hydrolysis according to claim 1, characterized in that, The heating rate for heating and melting is 5°C / min - 40°C / min, the temperature is 700°C - 1000°C, and the holding time is 1h - 2h.

5. The preparation method of the hydrogen production material by hydrolysis according to claim 1, characterized in that, The mass ratio of indium to tin in the alloy melt is 30:1 - 1:

30.

6. The preparation method of the hydrogen production material by hydrolysis according to any one of claims 1-5, characterized in that, The alloy melt raw material further includes a doped metal, and the doped metal includes at least one of Ga, Zn, Cu, Hg, Na, Co, and Fe.

7. The preparation method of the hydrogen production material by hydrolysis according to claim 6, characterized in that, The mass ratio of the doped metal in the alloy melt is 0% - 20%.

8. A hydrogen production material by hydrolysis, characterized in that, The hydrogen production material by hydrolysis is prepared by the preparation method of the hydrogen production material by hydrolysis according to any one of claims 1 - 7, and the hydrogen production material by hydrolysis includes aluminum, InSn4, and In3Sn.

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