Magnesium-based alloys, magnesium-based composites, methods of making, and hydrolytic hydrogen generation devices

Abstract

The application relates to a magnesium-based alloy, a magnesium-based composite material, a preparation method and a hydrogen production device by hydrolysis, wherein the magnesium-based alloy comprises Mg and a metal M, the metal M comprises at least one of Ca, In and a lanthanide element, the mass fraction of Mg in the magnesium-based alloy is 60% to 99.9%, and the mass fraction of the metal M in the magnesium-based alloy is 0.1% to 40%. The hydrogenation storage of hydrogen can be effectively carried out by adjusting the alloy composition, the hydrogen can be quickly released by hydrolysis, and the hydrogen production rate and the hydrogen production amount are improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of hydrogen production, in particular to a magnesium-based alloy, a magnesium-based composite material, a preparation method and a hydrolysis hydrogen production device. BACKGROUND

[0002] In the traditional hydrogen production technology, magnesium-based hydride (MgH2) has unique application advantages. It reacts completely with water and theoretically can release 1703 mL / g of hydrogen. If the weight of water is not taken into account, the weight hydrogen storage capacity of MgH2 hydrolysis can reach 15.2wt%, which has very practical value in some special scenarios. However, the hydrolysis product of MgH2 is Mg(OH)2 precipitate, which has a solubility of only 1.9 mg / L in water at 298K, and is very difficult to dissolve.

[0003] In order to break the passivation layer in the reaction and continue the reaction, additives or catalysts are added in the traditional technology to improve the hydrolysis performance of magnesium-based hydride, such as adding carbonaceous materials, oxides, acids or salts and other different media. These additives or catalysts can improve the hydrolysis performance of magnesium-based hydride to different degrees, but most of them show problems such as insufficient hydrolysis kinetics and serious decrease in hydrolysis capacity.

[0004] Therefore, it is urgent to develop a new material with high hydrolysis rate and high hydrogen production capacity. SUMMARY

[0005] Therefore, it is urgent to develop a new material with high hydrolysis rate and high hydrogen production capacity.

[0006] In a first aspect, the present application provides a magnesium-based alloy, which comprises Mg and a metal M, wherein the metal M comprises at least one of Ca, In and lanthanide elements.

[0007] The mass fraction of Mg in the magnesium-based alloy is 60% to 99.9%, and the mass fraction of the metal M in the magnesium-based alloy is 0.1% to 40%.

[0008] In some embodiments, the metal M in the magnesium-based alloy is Ca, In and lanthanide elements.

[0009] In some embodiments, the magnesium-based alloy comprises, in terms of mass percentage:

[0010] Mg, 60% to 90%; Ca, 4% to 20%; In, 2% to 10%; and lanthanide elements, 4% to 20%.

[0011] In some embodiments, the lanthanide elements comprise at least one of Ce, La, Pr and Nd.

[0012] In some embodiments, the particle size of the magnesium-based alloy is ≤ 300 mesh.

[0013] In a second aspect, the application provides a method for preparing a magnesium-based composite material, the method comprising:

[0014] The magnesium-based alloy of the first aspect is subjected to a hydrogenation treatment in a hydrogen atmosphere to obtain the magnesium-based composite material.

[0015] In some embodiments, the hydrogenation treatment step comprises heating and pressurizing the magnesium-based alloy in a hydrogen atmosphere.

[0016] In some embodiments, the heating temperature in the hydrogenation treatment step is 200-500°C.

[0017] In some embodiments, the hydrogen pressure in the hydrogenation treatment step is 1-10 MPa.

[0018] In some embodiments, the treatment time in the hydrogenation treatment step is ≥ 5 h.

[0019] In some embodiments, the magnesium-based alloy is prepared by metal smelting, and the smelting method of the magnesium-based alloy comprises:

[0020] The metal M material and Mg are mixed and heated to melt, and the alloy ingot is obtained after cooling. The alloy ingot is crushed to obtain the magnesium-based alloy.

[0021] In some embodiments, the temperature of the cooling medium during the cooling process is 18-22°C.

[0022] In a third aspect, the application provides a magnesium-based composite material prepared by the method for preparing a magnesium-based composite material of the second aspect.

[0023] In a fourth aspect, the application provides the use of the magnesium-based composite material of the third aspect for hydrolysis to produce hydrogen.

[0024] In some embodiments, the temperature for the magnesium-based composite material to undergo hydrolysis to produce hydrogen is 20-80°C.

[0025] In some embodiments, the mass ratio of water to the magnesium-based composite material during the hydrolysis of the magnesium-based composite material is (80-120): 1.

[0026] In a fifth aspect, the application provides a device for hydrolysis to produce hydrogen, which uses the magnesium-based composite material of the third aspect.

[0027] The application has the following advantages:

[0028] The Mg element is used as the main body, and Ca, In or lanthanide elements are added to form a magnesium-based alloy, which can effectively store hydrogen by hydrogenation. Moreover, after hydrogenation treatment of the magnesium-based alloy, the metal elements can be hydrogenated to form metal hydride. In the process of hydrolysis to produce hydrogen, the metal hydride of Ca, In or lanthanide elements can be hydrolyzed, and then a heterogeneous interface is formed on the surface of the magnesium hydroxide passivation layer formed by Mg hydrolysis, which avoids the complete sealing and blocking of the hydrolysis reaction by the formed magnesium hydroxide passivation layer, and improves the hydrogen production rate and hydrogen production amount. In addition, the method of alloying the Mg element as the main body with Ca, In or lanthanide elements is simple, and the magnesium-based alloy is easy to process and carry. BRIEF DESCRIPTION OF DRAWINGS

[0029] Figure 1 The hydrogen production performance diagram of the magnesium-based composite material in Example 1-4, Example 8-9 and Comparative Example 1-2 in the present application is shown. DETAILED DESCRIPTION

[0030] In order to facilitate the understanding of the present application, the present application will be described more fully below with reference to the accompanying drawings. The preferred embodiments of the present application are shown in the drawings. However, the present application can be realized in many different forms and is not limited to the embodiments described herein. On the contrary, these embodiments are provided to make the disclosure of the present application more thorough and comprehensive.

[0031] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present application belongs. The terminology used in the description of the present application herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the present application. As used herein, the term "and / or" includes any and all combinations of one or more of the associated listed items.

[0032] The "range" disclosed in the present application is defined in the form of lower limit and upper limit, and a given range is defined by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundary of a particular range. The range defined in this way can include or not include the end value, and can be arbitrarily combined, i.e. any lower limit can be combined with any upper limit to form a range.

[0033] In the conventional technology, the research on hydrogen production by magnesium-based materials mainly improves the hydrolysis rate by adding additives or catalysts. In particular, the addition of catalysts requires a ball milling process to composite the additives / catalysts into the MgH2 matrix, and the ball milling process is difficult to adapt to the needs of industrialization due to the efficiency constraints. In addition, some improve the hydrolysis kinetics by improving the properties of the solution, such as adding citric acid. Although the hydrogen production rate of magnesium-based materials is significantly improved, it needs to carry more than 5 times the weight of the original material of citric acid. This undoubtedly increases the cost of the material, reduces the carrying space of the powder, and makes the system structure complex, especially in a specific environment, the hydrogen production is severely limited.

[0034] The present application is aimed at the problems existing in the above-mentioned conventional technology, and is committed to the method of alloying, by changing the alloy composition (M), so that the alloy forms different kinds of metal hydroxides (M(OH) x ) in the hydrolysis process, so that there is a heterogeneous interface, so that the hydroxide shell cannot be completely closed, there is a phase gap, and it can be separated from the phase gap, and promote the further hydrolysis reaction of the inner core MgH2.

[0035] The first aspect of the present application provides a magnesium-based alloy, which comprises Mg and a metal M, wherein the metal M comprises at least one of Ca, In and lanthanide elements;

[0036] The mass fraction of Mg in the magnesium-based alloy is 60% to 99.9%; and the mass fraction of the metal M in the magnesium-based alloy is 0.1% to 40%.

[0037] The present application takes Mg element as the main body, and cooperates with the addition of Ca, In or lanthanide elements to form an alloy. Among them, the Ca element can replace Mg to construct a Mg-Mg2Ca multi-phase alloy, and can form a MgH2-CaH2 composite material after hydrogenation, so as to form a heterogeneous interface after hydrolysis, and CaH2 can also produce hydrogen gas by reacting with water to make up for the problem of reduced hydrogen production caused by reduced magnesium content; the lanthanide element is easy to form a multi-phase alloy with Mg, and forms a rare earth hydride phase with a nanometer scale after hydrogenation, and is preferentially hydrolyzed to MgH2, and can release heat in the process of preferential hydrolysis, thereby promoting the local hydrolysis of MgH2 to improve the hydrolysis rate, and the lanthanide element is beneficial to the embrittlement of Mg alloy, and is convenient for processing and powdering. In addition, the lanthanide element and Ca are elements for refining the grains of magnesium alloy, which also helps to improve the subsequent hydrolysis performance. The In element can have a very high solid solubility in Mg, so as to form a large amount of Mg(In) interstitial solid solution, thereby reducing the chemical stability and increasing the strength of the alloy, reducing the plasticity and toughness, and facilitating subsequent processing.

[0038] In some embodiments, for example, the mass fraction of Mg in the magnesium-based alloy is 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, or 99.9%; and the mass fraction of metal M in the magnesium-based alloy is 0.1%, 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, or 40%.

[0039] The application controls the mass fraction of Mg in the magnesium-based alloy, ensures the hydrogen production while Mg is completely reacted, and if the mass fraction of Mg is low, there is a problem of low hydrogen production, and if the mass fraction of Mg is high, there is a problem of incomplete reaction of Mg.

[0040] In some embodiments, the metal M in the magnesium-based alloy is Ca, In, and a lanthanide element.

[0041] The application further adjusts the metal M to be a combination of Ca, In, and a lanthanide element, uses Ca element to play the role of Mg element, improves the hydrolysis speed and completeness, and at the same time makes up for the decrease in hydrogen production caused by the reduction of Mg, uses the lanthanide element to preferentially hydrolyze and release heat to improve the hydrolysis speed, and uses the In element to form a large amount of interstitial solid solution to reduce the chemical stability of the material, and in many ways to improve the hydrogen production and hydrogen production speed of the magnesium-based alloy.

[0042] In some embodiments, the magnesium-based alloy includes, in terms of mass percentage:

[0043] Mg, 60% to 90%; Ca, 4% to 20%; In, 2% to 10%; and a lanthanide element, 4% to 20%.

[0044] For example, the mass percentage of Ca in the magnesium-based alloy is 4%, 6%, 8%, 10%, 12%, 14%, 16%, 18%, or 20%; the mass percentage of In is 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, or 10%; and the mass percentage of the lanthanide element is 4%, 6%, 8%, 10%, 12%, 14%, 16%, 18%, or 20%.

[0045] In some embodiments, the lanthanide element includes at least one of Ce, La, Pr, and Nd. Taking Ce element as an example, the Ce element is easy to form CeMg 12 phase with Mg, and after hydrogenation, the original CeMg 2.72 phase has a nanoscale CeH phase, which preferentially hydrolyzes MgH2 and releases heat, promotes local hydrolysis of MgH2, and improves the speed, and is beneficial to the embrittlement of the Mg alloy, facilitating the subsequent powdering. In addition, Ce is an element for refining the grains of the magnesium alloy, which also helps to improve the subsequent hydrolysis performance.

[0046] In some embodiments, the magnesium-based alloy has a particle size of ≤ 300 mesh. The particle size of the magnesium-based alloy is further defined in the present application, so that the magnesium-based alloy has a higher specific surface area, can better perform hydrogen storage and hydrogenation treatment, and has a high specific surface area during hydrolysis, thereby increasing the hydrogen production rate.

[0047] The second aspect of the present application provides a preparation method of a magnesium-based composite material, the preparation method comprising:

[0048] The magnesium-based alloy of the first aspect is subjected to hydrogenation treatment under a hydrogen atmosphere to obtain the magnesium-based composite material.

[0049] In the magnesium-based alloy of the present application, the metals can react with hydrogen to form metal hydride for hydrogen storage, and can react with water to rapidly release hydrogen.

[0050] In some embodiments, the hydrogenation treatment step comprises heating and pressurizing the magnesium-based alloy under a hydrogen atmosphere.

[0051] In some embodiments, the heating temperature in the hydrogenation treatment step is 200-500°C, for example, 200°C, 230°C, 260°C, 290°C, 320°C, 350°C, 380°C, 410°C, 440°C, 470°C, or 500°C.

[0052] In some embodiments, the hydrogen pressure in the hydrogenation treatment step is 1-10 MPa, for example, 1 MPa, 2 MPa, 3 MPa, 4 MPa, 5 MPa, 6 MPa, 7 MPa, 8 MPa, 9 MPa, or 10 MPa.

[0053] In some embodiments, the treatment time in the hydrogenation treatment step is ≥ 5 h, and optionally, the treatment time is 5-48 h, for example, 5 h, 10 h, 15 h, 20 h, 25 h, 30 h, 35 h, 40 h, 45 h, or 48 h.

[0054] The present application further regulates the temperature and pressure of the hydrogenation treatment to ensure that the metal elements in the magnesium-based alloy are converted into hydride, thereby completing hydrogenation and hydrogen storage.

[0055] Exemplarily, a preparation method of a magnesium-based composite material is provided, comprising:

[0056] A magnesium-based alloy with a particle size of ≤ 300 mesh is placed under a hydrogen pressure of 1-10 MPa and a temperature of 200-500°C for sufficient hydrogenation, and the hydrogenation time is ≥ 5 h, to obtain the magnesium-based composite material.

[0057] In some embodiments, the magnesium-based alloy is prepared by metal smelting, and the smelting method of the magnesium-based alloy comprises:

[0058] The metal M material and Mg are mixed and heated to melt, and the alloy ingot is obtained after cooling, and the alloy ingot is crushed to obtain the magnesium-based alloy.

[0059] It should be noted that in the process of smelting the magnesium-based alloy, the protective gas can not be introduced, for example, the smelting process is carried out in an air atmosphere.

[0060] In some embodiments, at least one of water cooling, oil cooling, air cooling and rapid quenching is used in the cooling process.

[0061] Optionally, the temperature of the cooling medium in the cooling process is 18-22℃, for example, 18.0℃, 18.5℃, 19.0℃, 19.5℃, 20.0℃, 20.5℃, 21.0℃, 21.5℃ or 22.0℃.

[0062] Optionally, the cooling time of the cooling process is 5-10s, and the temperature of the alloy ingot after cooling is 80-120℃. In the present application, the alloy is cooled by rapid cooling, the grain is refined, and the stress is eliminated, so as to facilitate the crushing process.

[0063] In some embodiments, the cooling method includes at least one of water cooling, oil cooling, air cooling and rapid quenching.

[0064] In some embodiments, the crushing method includes at least one of mechanical crushing, airflow crushing, gas atomization and ball milling.

[0065] Exemplarily, a preparation method of a magnesium-based alloy is provided, comprising:

[0066] Mg and metal M material are weighed according to the mass ratio, mixed and heated to melt, the molten metal liquid is cooled to form an alloy ingot, the temperature of the cooling medium is 18-22℃, and the temperature is cooled to 80-120℃ in 5-10s, and the alloy ingot is crushed to form a magnesium-based alloy with a particle size of ≤300 mesh.

[0067] The third aspect of the present application provides a magnesium-based composite material, which is prepared by the preparation method of the magnesium-based composite material according to the second aspect.

[0068] The fourth aspect of the present application provides an application of the magnesium-based composite material according to the third aspect, and the magnesium-based composite material is used for hydrolysis to produce hydrogen.

[0069] The magnesium-based composite material is obtained by hydrogenating a magnesium-based alloy, so that a closed magnesium hydroxide passivation layer is avoided during the hydrolysis process of the magnesium-based composite material, different types of metal hydroxides are formed during the hydrolysis process by matching the elements in the alloy, a heterogeneous interface exists in the magnesium-based composite material, so that the magnesium hydroxide shell layer cannot be completely closed, there is a phase gap, and then the hydrogen is separated from the phase gap, the hydrogen production rate and the hydrogen production amount during the hydrogen production process are improved.

[0070] In some embodiments, the temperature for the magnesium-based composite material to produce hydrogen by hydrolysis is 20-80℃, for example, 20℃, 25℃, 30℃, 35℃, 40℃, 45℃, 50℃, 55℃, 60℃, 65℃, 70℃, 75℃, or 80℃.

[0071] The temperature for the magnesium-based composite material to produce hydrogen by hydrolysis in the present application is 20-80℃, which is much lower than the hydrogen production temperature of MgH2 (more than 300℃), and the present application has the characteristics of high hydrogen production efficiency, mild conditions, and environmental friendliness.

[0072] In some embodiments, the mass ratio of water to the magnesium-based composite material during the hydrolysis process is (80-120):1, for example, 80:1, 85:1, 90:1, 95:1, 100:1, 105:1, 110:1, 115:1, or 120:1.

[0073] The fifth aspect of the present application provides a hydrogen production device by hydrolysis, which uses the magnesium-based composite material of the third aspect.

[0074] It should be noted that the structure and composition of the hydrogen production device by hydrolysis are not specifically required or specially limited in the present application. For example, the hydrogen production device by hydrolysis includes a hydrogen production shell, a drug storage cavity and a water storage cavity are arranged in the hydrogen production shell, the drug storage cavity is filled with the magnesium-based composite material, and the water storage cavity is filled with water. When hydrogen needs to be produced, the magnesium-based composite material in the drug storage cavity is contacted with water for hydrolysis to generate hydrogen for collection and use.

[0075] The following are specific embodiments.

[0076] Embodiment 1

[0077] (1) The mass ratio of the weighed metal materials is: Mg:Ca:Ce:In = a:b:c:d = 88:6:4:2, and a+b+c+d = 100. The weighed metal materials are mixed and melted, the melting process is carried out in an air atmosphere, a water-cooled copper roller rapid quenching cooling process is used during melting and pouring, the cooling water temperature is 20℃, rapid cooling is carried out for 10s, a magnesium-based alloy ingot with a temperature of 100℃ is obtained, and the cooled magnesium-based alloy ingot is subjected to mechanical pulverization treatment. The powder particle size of the magnesium-based alloy after the pulverization treatment is 200 mesh.

[0078] (2) Take 1 g of the magnesium-based alloy powder in step (1), place it under the condition of 3 MPa hydrogen pressure and 360°C temperature, and fully hydrogenate for 48 hours. After the hydrogenation is completed, the magnesium-based composite material is obtained.

[0079] Example 2

[0080] The magnesium-based composite material is prepared according to the method of Example 1, with the only difference being that in step (1), the mass ratio of metal materials in the preparation of the magnesium-based alloy is: Mg: Ca: Ce: In = a: b: c: d = 80: 15: 4: 1.

[0081] Example 3

[0082] The magnesium-based composite material is prepared according to the method of Example 1, with the only difference being that in step (1), the mass ratio of metal materials in the preparation of the magnesium-based alloy is: Mg: Ca: Ce: In = a: b: c: d = 70: 25: 4: 1.

[0083] Example 4

[0084] (1) Take the metal materials with a mass ratio of: Mg: Ca: Ce: In = a: b: c: d = 60: 20: 10: 10, and a + b + c + d = 100, mix the weighed metal materials, and melt them in an air atmosphere. The water-cooled copper roller rapid quenching cooling process is used during the pouring and casting process, with a cooling water temperature of 18°C and a cooling time of 8s to obtain a magnesium-based alloy ingot with a temperature of 80°C. The cooled magnesium-based alloy ingot is subjected to mechanical pulverization treatment, and the magnesium-based alloy powder after pulverization treatment has a particle size of 150 mesh;

[0085] (2) Take 1 g of the magnesium-based alloy powder in step (1), place it under the condition of 1 MPa hydrogen pressure and 500°C temperature, and fully hydrogenate for 24 hours. After the hydrogenation is completed, the magnesium-based composite material is obtained.

[0086] Example 5

[0087] The magnesium-based composite material is prepared according to the method of Example 1, with the only difference being that in step (1), the mass ratio of metal materials in the preparation of the magnesium-based alloy is: Mg: Ca = 88: 12.

[0088] Example 6

[0089] The magnesium-based composite material is prepared according to the method of Example 1, with the only difference being that in step (1), the mass ratio of metal materials in the preparation of the magnesium-based alloy is: Mg: Ce = 88: 12.

[0090] Example 7

[0091] Magnesium-based composite materials were prepared according to the method of Example 1, except that in step (1), the mass ratio of metal materials in the magnesium-based alloy preparation process was Mg:In ​​= 88:12.

[0092] Example 8

[0093] Magnesium-based composite materials were prepared according to the method of Example 1, except that in step (1), the mass ratio of metal materials in the magnesium-based alloy preparation process was Mg:Ca:Ce=88:6:6.

[0094] Example 9

[0095] Magnesium-based composite materials were prepared according to the method of Example 1, except that in step (1), the mass ratio of metal materials in the magnesium-based alloy preparation process was Mg:Ca:In=88:6:6.

[0096] Example 10

[0097] Magnesium-based composite materials were prepared according to the method of Example 1, except that in step (1), the mass ratio of metal materials in the magnesium-based alloy preparation process was Mg:Ce:In=88:6:6.

[0098] Comparative Example 1

[0099] Take 1g of Mg powder with a particle size of 200 mesh, place it under a hydrogen pressure of 3MPa and a temperature of 360℃, and carry out full hydrogenation for 48 hours to obtain MgH2 material.

[0100] Comparative Example 2

[0101] Magnesium-based composite materials were prepared according to the method of Example 1, except that in step (1), the mass ratio of metal materials in the magnesium-based alloy preparation process was: Mg:Ca:Ce:In=52:24:16:8.

[0102] Test case

[0103] Take 0.2g of the magnesium-based composite material from the above examples and comparative examples, add it to a two-necked glass bottle, place the two-necked flask in an 80°C constant temperature aqueous solution (heated in a constant temperature water bath), and seal it;

[0104] 20 mL of deionized water was heated to the same temperature as in a constant-temperature water bath and then added to a two-necked glass bottle through a constant-pressure separatory funnel. The water contacted the magnesium-based composite material for hydrolysis. The generated hydrogen gas was drawn out through a delivery tube and entered a gas washing bottle. An equal volume of water was discharged from the gas washing bottle and entered a graduated cylinder. The volume of gas produced and the time were recorded based on the volume of water discharged from the graduated cylinder. The hydrogen production results for 2 min and 5 min are shown in Table 1. The hydrogen production performance graphs for Examples 1-4, Examples 8-9, and Comparative Examples 1-2 are shown below. Figure 1 As shown.

[0105] Table 1

[0106]

[0107]

[0108] From the above table, it can be seen that:

[0109] (1) By comparing Example 1 with Examples 6-10, and combining Figure 1 It can be seen that the present application further adjusts the metal M to be a combination of Ca, In and lanthanide elements, uses Ca element to improve reaction completeness, thereby improving hydrogen production, uses lanthanide elements to preferentially release heat during hydrolysis to improve hydrogen production speed, and uses In element to form a large amount of interstitial solid solution, thereby reducing material chemical stability and improving hydrogen production and hydrogen production speed of the magnesium-based alloy in multiple ways.

[0110] (2) By comparing Example 1 with Comparative Examples 1-2, and combining Figure 1 It can be seen that the present application controls the mass fraction of Mg in the magnesium-based alloy, ensures hydrogen production while Mg is completely reacted, if the mass fraction of Mg is low, there is a problem of low hydrogen production, and if the mass fraction of Mg is high, there is a problem of incomplete reaction of Mg.

[0111] From the above examples and comparative examples, the present application uses Mg element as the main body, and cooperates with the addition of Ca, In or lanthanide elements to form an alloy. Among them, Ca element is used to replace Mg to construct Mg-Mg2Ca multi-phase alloy, and after hydrogenation, MgH2-CaH2 composite material can be formed, so as to utilize the formation of a heterogeneous interface after hydrolysis, and CaH2 also reacts with water to produce considerable hydrogen, so as to make up for the problem of reduced hydrogen production caused by reduced magnesium content; lanthanide elements are easy to form multi-phase alloys with Mg, and after hydrogenation, they form rare earth hydride phases with nanometer scale, which preferentially hydrolyze MgH2 and can release heat, thereby promoting local MgH2 hydrolysis to improve hydrolysis speed, and lanthanide elements are beneficial to the embrittlement of Mg alloy, which is convenient for processing and powdering. In addition, lanthanide elements and Ca are elements for refining the grains of magnesium alloy, which also help to improve the subsequent hydrolysis performance. In element has a very high solid solubility in Mg, so as to form a large amount of Mg(In) interstitial solid solution, thereby reducing its chemical stability, increasing alloy strength, reducing its plasticity and toughness, and facilitating subsequent processing.

[0112] The magnesium-based alloy in the application can effectively store hydrogen and release it quickly. Further, by adjusting the alloy composition and hydrogenation treatment, a magnesium-based composite hydrogen storage system is constructed, which can quickly react with water, improve the reaction rate and hydrogen production rate, and the hydrogen production amount can reach 1550 mL / g, the average hydrogen production rate reaches 4.8 mL / s, and the hydrogen production rate can reach 13.6 mL / s within 100, which meets the needs of application under normal conditions.

[0113] The technical features of the above-described embodiments can be combined in any manner. In order to make the description concise, all possible combinations of the technical features in the above-described embodiments are not described, but as long as the combinations of the technical features do not exist, they should be considered as the scope of the description.

[0114] The above-described embodiments only express several embodiments of the application, which are described in detail and in detail, but should not be construed as limiting the scope of the patent. It should be pointed out that for ordinary skilled in the art, without departing from the concept of the application, a number of modifications and improvements can be made, which are within the scope of the application. Therefore, the scope of protection of the patent of the application should be subject to the appended claims.

Claims

1. A magnesium-based alloy, characterized by, The magnesium-based alloy comprises Mg and a metal M, wherein the metal M is Ca, In and a lanthanide element; The magnesium-based alloy comprises, by mass percentage, Mg 60-90%, Ca 4-20%, In 2-10%, and a lanthanide element 4-20%. The magnesium-based alloy comprises Mg2Ca phase and Mg(In) interstitial solid solution.

2. The magnesium-based alloy of claim 1, wherein The magnesium-based alloy satisfies at least one of the following conditions: (1) the lanthanide element comprises at least one of Ce, La, Pr and Nd; (2) the particle size of the magnesium-based alloy is ≤300 mesh.

3. A method of producing a magnesium-based composite material, characterized by, The preparation method comprises: The magnesium-based alloy of claim 1 or 2 is subjected to hydrogenation treatment under a hydrogen atmosphere to obtain the magnesium-based composite material.

4. The production method according to claim 3, wherein The hydrogenation treatment step comprises heating and pressurizing the magnesium-based alloy under a hydrogen atmosphere.

5. The production method according to claim 4, wherein The hydrogenation treatment satisfies at least one of the following conditions: (1) the heating temperature in the hydrogenation treatment step is 200-500°C; (2) the hydrogen pressure in the hydrogenation treatment step is 1-10 MPa; (3) the treatment time in the hydrogenation treatment step is ≥5 h.

6. The production method according to claim 3, wherein The magnesium-based alloy is prepared by metal smelting, and the smelting method of the magnesium-based alloy comprises: The metal M material and Mg are mixed and then heated and melted, and the alloy ingot is obtained after cooling, which is crushed to obtain the magnesium-based alloy.

7. The production method according to claim 6, wherein During the cooling process, the temperature of the cooling medium is 18-22°C.

8. A magnesium-based composite material, characterized by, The magnesium-based composite material is prepared by the preparation method of the magnesium-based composite material according to any one of claims 3-7.

9. Use of the magnesium-based composite material according to claim 8, characterized in that, The magnesium-based composite material is used for hydrolysis to produce hydrogen.

10. Use of a magnesium-based composite material according to claim 9, characterized in that, The magnesium-based composite material satisfies at least one of the following conditions during the hydrolysis to produce hydrogen: (1) the temperature for the magnesium-based composite material to produce hydrogen by hydrolysis is 20-80°C; (2) the mass ratio of water to the magnesium-based composite material during the hydrolysis is (80-120):

1.

11. A device for hydrogen production by hydrolysis, characterized in that it comprises: The hydrolysis device for producing hydrogen uses the magnesium-based composite material of claim 8.

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