Preparation method and application of five-element magnesium-based amorphous alloy hydrogen storage material

Abstract

The present invention discloses a preparation method and application method of a five-element magnesium-based amorphous hydrogen storage alloy, belonging to the field of hydrogen storage materials. The chemical formula of the five-element magnesium-based amorphous hydrogen storage alloy is Mg x Al y Ni z Co5RE w , wherein RE is one of Y, La and Ce, and 40≤x≤70, 5≤y≤10, 10≤z≤20, 10≤w≤20, and x+y+z+w=95. During the preparation, the present invention first obtains a five-element alloy ingot by arc melting and induction melting, then obtains an amorphous strip by melt rapid quenching, and finally obtains a powder sample by mechanical ball milling. Compared with the existing magnesium-based amorphous hydrogen storage materials, the hydrogen absorption and desorption kinetics of the present invention are significantly improved, and the hydrogen desorption temperature is reduced. In addition, the amorphous alloy proposed in the present invention can still maintain the amorphous structure well after hydrogen desorption. The preparation process of the present invention is mature and easy to operate, which is conducive to promotion and application, and can be used as a design reference for new high-capacity magnesium-based hydrogen storage alloys.

Description

Technical Field

[0001] The present invention belongs to the technical field of hydrogen storage materials, and particularly relates to a preparation method and application of a five-element magnesium-based amorphous alloy hydrogen storage material. Background Art

[0002] Energy is the cornerstone of human survival and development. The extensive use of traditional fossil energy has led to increasingly serious problems of resource depletion and environmental pollution. Hydrogen energy is considered to be an ideal energy source to replace traditional fossil energy due to its high combustion calorific value, wide range of sources, pollution-free products, and renewability. Hydrogen energy applications can be divided into three major links: production, storage and transportation, and application. Hydrogen energy storage and transportation plays an important role as a bridge connecting the two ends. According to the form of hydrogen, hydrogen storage methods can be divided into three types: solid hydrogen storage, liquid hydrogen storage, and gaseous hydrogen storage. Compared with liquid hydrogen storage and gaseous hydrogen storage, solid hydrogen storage has outstanding advantages such as high volume hydrogen storage density and good safety.

[0003] Among the many types of solid-state hydrogen storage materials, Mg-based hydrogen storage materials are considered to be an ideal type of hydrogen storage material due to their high mass hydrogen storage density, abundant magnesium resources, and low cost. However, due to the strong interaction between Mg-H bonds and the slow diffusion of H atoms in Mg, Mg-based hydrogen storage materials have disadvantages such as high hydrogen desorption temperature and slow hydrogen absorption and desorption rates near room temperature, which greatly limit their practical applications. To address the above shortcomings, researchers have adopted alloying, nano-sizing, catalysis and other means, but these methods generally have problems such as unsatisfactory improvement effects, complex processes, and excessively high costs. So far, no magnesium-based alloy can perfectly meet the needs of civilian hydrogen storage.

[0004] Due to their unique structural characteristics of short-range order and long-range disorder, amorphous alloys have two advantages over crystalline alloys in providing space for hydrogen atoms: one is that there are more of them; the other is that they are of richer types. A larger number of space for hydrogen atoms means that they can accommodate more hydrogen atoms and have a higher hydrogen storage capacity. A richer variety of space for hydrogen atoms means that the chemical environments in which hydrogen atoms are located are different. Among them, hydrogen atoms in certain spaces are in a higher energy state and have weaker binding forces with metal atoms, making it easier to detach, which is conducive to lowering the hydrogen desorption temperature. For the above reasons, there have been a lot of studies on the hydrogen storage properties of magnesium-based amorphous alloys. However, magnesium-based amorphous hydrogen storage alloys still have problems such as difficulty in low-temperature hydrogen desorption, low hydrogen absorption and desorption rates, and crystallization after hydrogen desorption, which require further exploration. Summary of the Invention

[0005] To address the challenges of magnesium-based hydrogen storage alloys in hydrogen absorption and desorption, one objective of the present invention is to provide a method for preparing a five-element magnesium-based amorphous alloy hydrogen storage material and its application. By leveraging the unique structural characteristics of amorphous alloys, a magnesium-based hydrogen storage material with excellent hydrogen absorption and desorption properties is obtained. Compared to existing amorphous alloy hydrogen storage materials, the five-element magnesium-based amorphous alloy of the present invention improves the hydrogen absorption and desorption rate, reduces the desorption temperature, and remains amorphous after desorption, while also possessing a high hydrogen storage capacity.

[0006] In order to achieve the above object, the present invention adopts the following technical solutions:

[0007] A five-element magnesium-based amorphous hydrogen storage alloy, the chemical formula of which is Mg x Al y Ni z Co5RE w , wherein RE is one of Y, La and Ce, and 40≤x≤70, 5≤y≤10, 10≤z≤20, 10≤w≤20, and satisfies x+y+z+w=95.

[0008] The main phase of the five-element magnesium-based amorphous hydrogen storage alloy is an amorphous phase, and may contain a small amount of Al1Ni1 crystal phase.

[0009] Another object of the present invention is to provide a method for preparing a five-element magnesium-based amorphous hydrogen storage alloy, comprising the following steps:

[0010] S1: Selecting 99.9% pure Mg, Al, Ni, Co, and RE elemental metals as smelting raw materials, firstly obtaining an Al-Ni-Co-RE quaternary intermediate ingot by arc melting, and then induction melting the Al-Ni-Co-RE quaternary intermediate ingot together with Mg to obtain a Mg-Al-Ni-Co-RE quinary alloy ingot;

[0011] S2: The Mg-Al-Ni-Co-RE five-element alloy ingot obtained in step S1 is placed in a belt-spinning furnace, and Mg is obtained by a melting and rapid quenching method. x Al y Ni z Co5RE w amorphous strips;

[0012] S3: Mg obtained in step S2 x Al y Ni z Co5RE w The amorphous strips are placed in a ball mill, followed by metal grinding balls of a certain mass. The ball mill is then sealed in an argon atmosphere glove box and finally placed in a planetary ball mill for ball milling under certain operating parameters.

[0013] S4: After the ball milling is completed, take out the ball mill jar and put it into an argon atmosphere glove box, disassemble the ball mill jar and take out the powder obtained after ball milling to obtain the five-element magnesium-based amorphous hydrogen storage alloy.

[0014] Preferably, as a preferred embodiment, the Mg in step S2 x Al y Ni z Co5RE w The amorphous component specifically includes Mg 45 Al 10 Ni 20 Co5La 20 Mg 50 Al5Ni 20 Co5La 20 Mg 55 Al5Ni 20 Co5La 15 and Mg 60 Al5Ni 20 Co5La 10 .

[0015] Preferably, as a preferred embodiment, during the melting and rapid quenching in step S2, the linear speed of the copper roller is 40 m / s.

[0016] Preferably, as a preferred embodiment, the mass of the grinding balls used in step S3 is about the same as that of Mg x Al y Ni z Co5RE w The ratio of amorphous ribbon mass is 100:1.

[0017] Preferably, as a preferred embodiment, the rotation speed of the planetary ball mill during ball milling in step S3 is 200 rpm, the ball milling is performed for 30 minutes, and the mill is stopped for 30 minutes, and the total rotation time of the ball mill is 4 hours.

[0018] The third object of the present invention is to provide an application of a five-element magnesium-based amorphous hydrogen storage alloy in solid-state hydrogen storage materials.

[0019] Compared with the prior art, the advantages and beneficial technical effects of the present invention are:

[0020] (1) The preparation process of the present invention is mature and the operation is simple and convenient, which is conducive to promotion to large-scale production.

[0021] (2) The amorphous strips of the present invention are formed into powder during the ball milling process, which greatly improves the surface activity while maintaining the amorphous structure.

[0022] (3) Mg with the best performance 60 Al5Ni20 Co5La 10 The amorphous alloy has a hydrogen absorption capacity of more than 3.0 wt.% within 1.5 hours at 150° C. and a hydrogen release capacity of more than 1.0 wt.% at 225° C., which is superior to other magnesium-based amorphous alloys in hydrogen absorption and desorption properties.

[0023] (4) The amorphous alloy of the present invention has good thermal stability and can basically maintain the amorphous structure after hydrogen release. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 The XRD diffraction patterns of the magnesium-based amorphous ribbons of Examples 1-4 of the present invention are shown.

[0025] Figure 2 The XRD diffraction patterns of the powders obtained after ball milling of the amorphous strips of Examples 1-4 of the present invention are shown.

[0026] Figure 3 The hydrogen absorption kinetic curves of the powders obtained after ball milling of the amorphous strips of Examples 1-4 of the present invention at 150° C. and 4.5 MPa-H 2 are shown.

[0027] Figure 4 The temperature-dependent hydrogen release kinetic curves of the powders obtained after ball milling of the amorphous strips of Examples 1-4 of the present invention are shown.

[0028] Figure 5 The XRD diffraction patterns of the powders obtained after ball milling of the amorphous strips of Examples 1-4 of the present invention after hydrogen release are shown. DETAILED DESCRIPTION

[0029] In order to make the purpose and advantages of the present invention more clearly understood, the present invention is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0030] 1. Example 1

[0031] A five-element magnesium-based amorphous hydrogen storage alloy, the chemical formula of which is Mg 45 Al 10 Ni 20 Co5La 20 The preparation method of the five-element magnesium-based amorphous alloy hydrogen storage material comprises the following steps:

[0032] S1: Select Mg, Al, Ni, Co, and La elemental metals with a purity of 99.9% as smelting raw materials, first prepare Al by vacuum arc melting. 10 Ni 20 Co5La 20 The quaternary intermediate ingot is then melted together with Mg by vacuum induction melting to obtain Mg45 Al 10 Ni 20 Co5La 20 Five-element alloy ingot;

[0033] S2: The five-element alloy ingot obtained in S1 is spun off by melting and rapid quenching to obtain Mg 45 Al 10 Ni 20 Co5La 20 The linear speed of the copper roller during the spinning of the amorphous alloy strip is 40 m / s. The XRD diffraction pattern of the amorphous strip is as follows: Figure 1 As shown;

[0034] S3: The amorphous ribbon obtained in S2 was crushed into powder by planetary ball milling. 45 Al 10 Ni 20 Co5La 20 The amorphous strips were added to a planetary ball mill, followed by 100 g of grinding balls to a ball-to-material ratio of 100:1. The mill was then sealed in an argon atmosphere glove box. The ball mill was then mounted on a ball mill with the speed set to 200 rpm. The mill was milled for half an hour, followed by a half-hour cooling cycle, for a total of 4 hours.

[0035] S4: After the ball milling is completed, the powder is taken out of the can in an argon atmosphere glove box to obtain the five-element magnesium-based hydrogen storage alloy powder.

[0036] The XRD diffraction pattern of the obtained five-element magnesium-based hydrogen storage alloy powder is as follows: Figure 2 As shown, after ball milling, Mg 45 Al 10 Ni 20 Co5La 20 The main phase remains amorphous, while a small amount of Al1Ni1 crystal phase exists. Figure 3 The hydrogen absorption kinetics curve is shown in Figure 2. At 150°C and 4.5MPa-H2, Mg 45 Al 10 Ni 20 Co5La 20 The hydrogen absorption of the sample can reach about 2.3wt.% within 2.5 hours. Figure 4 (a) is Mg 45 Al 10 Ni 20 Co5La 20 The temperature-dependent hydrogen desorption kinetic curve shows that at a temperature of 250°C, the final hydrogen desorption amount exceeds 0.5 wt.%. The XRD diffraction pattern of the sample after hydrogen desorption at 250°C is shown in FIG. Figure 5 As shown, it can be seen that the sample still maintains the main phase as an amorphous phase and no obvious crystallization occurs.

[0037] 2. Example 2

[0038] A five-element magnesium-based amorphous hydrogen storage alloy, the chemical formula of which is Mg 50 Al5Ni 20 Co5La 20 The preparation method of the five-element magnesium-based amorphous alloy hydrogen storage material comprises the following steps:

[0039] S1: Select Mg, Al, Ni, Co, and La elemental metals with a purity of 99.9% as smelting raw materials, and first prepare Al5Ni by vacuum arc melting. 20 Co5La 20 The quaternary intermediate ingot is then melted together with Mg by vacuum induction melting to obtain Mg 50 Al5Ni 20 Co5La 20 Five-element alloy ingot;

[0040] S2: The five-element alloy ingot obtained in S1 is spun off by melting and rapid quenching to obtain Mg 50 Al5Ni 20 Co5La 20 The linear speed of the copper roller during the spinning of the amorphous alloy strip is 40 m / s. The XRD diffraction pattern of the amorphous strip is as follows: Figure 1 As shown;

[0041] S3: The amorphous ribbon obtained in S2 was crushed into powder by planetary ball milling. 50 Al5Ni 20 Co5La 20 The amorphous strips were added to a planetary ball mill, followed by 100 g of grinding balls to a ball-to-material ratio of 100:1. The mill was then sealed in an argon atmosphere glove box. The ball mill was then mounted on a ball mill with the speed set to 200 rpm. The mill was milled for half an hour, followed by a half-hour cooling cycle, for a total of 4 hours.

[0042] S4: After the ball milling is completed, the powder is taken out of the can in an argon atmosphere glove box to obtain the five-element magnesium-based hydrogen storage alloy powder.

[0043] The XRD diffraction pattern of the obtained five-element magnesium-based hydrogen storage alloy powder is as follows: Figure 2 As shown, after ball milling, Mg 50 Al5Ni 20 Co5La 20 The main phase remains amorphous, while a small amount of Al1Ni1 crystal phase exists. Figure 3 The hydrogen absorption kinetics curve is shown in Figure 2. At 150°C and 4.5MPa-H2, Mg 50 Al5Ni 20 Co5La 20The sample can absorb hydrogen up to about 2.6 wt.% within 1 hour. Figure 4 (b) is Mg 50 Al5Ni 20 Co5La 20 The temperature-dependent hydrogen desorption kinetic curve shows that at a temperature of 250°C, the final hydrogen desorption amount is close to 0.9wt.%. The XRD diffraction pattern of the sample after hydrogen desorption at 250°C is shown in the figure. Figure 5 As shown, it can be seen that the sample still maintains the main phase as an amorphous phase and no obvious crystallization occurs.

[0044] 3. Example 3

[0045] A five-element magnesium-based amorphous hydrogen storage alloy, the chemical formula of which is Mg 55 Al5Ni 20 Co5La 15 The preparation method of the five-element magnesium-based amorphous alloy hydrogen storage material comprises the following steps:

[0046] S1: Select Mg, Al, Ni, Co, and La elemental metals with a purity of 99.9% as smelting raw materials, and first prepare Al5Ni by vacuum arc melting. 20 Co5La 15 The quaternary intermediate ingot is then melted together with Mg by vacuum induction melting to obtain Mg 55 Al5Ni 20 Co5La 15 Five-element alloy ingot;

[0047] S2: The five-element alloy ingot obtained in S1 is spun off by melting and rapid quenching to obtain Mg 55 Al5Ni 20 Co5La 15 The linear speed of the copper roller during the spinning of the amorphous alloy strip is 40 m / s. The XRD diffraction pattern of the amorphous strip is as follows: Figure 1 As shown;

[0048] S3: The amorphous ribbon obtained in S2 was crushed into powder by planetary ball milling. 55 Al5Ni 20 Co5La 15 The amorphous strips were added to a planetary ball mill, followed by 100 g of grinding balls to a ball-to-material ratio of 100:1. The mill was then sealed in an argon atmosphere glove box. The ball mill was then mounted on a ball mill with the speed set to 200 rpm. The mill was milled for half an hour, followed by a half-hour cooling cycle, for a total of 4 hours.

[0049] S4: After the ball milling is completed, the powder is taken out of the can in an argon atmosphere glove box to obtain the five-element magnesium-based hydrogen storage alloy powder.

[0050] The XRD diffraction pattern of the obtained five-element magnesium-based hydrogen storage alloy powder is as follows: Figure 2 As shown, after ball milling, Mg 55 Al5Ni 20 Co5La 15 The main phase remains amorphous, while a small amount of Al1Ni1 crystal phase exists. Figure 3 The hydrogen absorption kinetics curve is shown in Figure 2. At 150°C and 4.5MPa-H2, Mg 55 Al5Ni 20 Co5La 15 The hydrogen absorption of the sample can reach about 2.7wt.% within 3 hours. Figure 4 (c) is Mg 55 Al5Ni 20 Co5La 15 The temperature-dependent hydrogen desorption kinetic curve shows that at a temperature of 250°C, the final amount of hydrogen desorption is about 0.25 wt.%. The XRD diffraction pattern of the sample after hydrogen desorption at 250°C is shown in FIG. Figure 5 As shown, it can be seen that the sample still maintains the main phase as an amorphous phase and no obvious crystallization occurs.

[0051] 4. Example 4

[0052] A five-element magnesium-based amorphous hydrogen storage alloy, the chemical formula of which is Mg 60 Al5Ni 20 Co5La 10 The preparation method of the five-element magnesium-based amorphous alloy hydrogen storage material comprises the following steps:

[0053] S1: Select Mg, Al, Ni, Co, and La elemental metals with a purity of 99.9% as smelting raw materials, and first prepare Al5Ni by vacuum arc melting. 20 Co5La 10 The quaternary intermediate ingot is then melted together with Mg by vacuum induction melting to obtain Mg 60 Al5Ni 20 Co5La 10 Five-element alloy ingot;

[0054] S2: The five-element alloy ingot obtained in S1 is spun off by melting and rapid quenching to obtain Mg 60 Al5Ni 20 Co5La 10 The linear speed of the copper roller during the spinning of the amorphous alloy strip is 40 m / s. The XRD diffraction pattern of the amorphous strip is as follows: Figure 1 As shown;

[0055] S3: The amorphous ribbon obtained in S2 was crushed into powder by planetary ball milling. 60 Al5Ni 20 Co5La10 The amorphous strips were added to a planetary ball mill, followed by 100 g of grinding balls to a ball-to-material ratio of 100:1. The mill was then sealed in an argon atmosphere glove box. The ball mill was then mounted on a ball mill with the speed set to 200 rpm. The mill was milled for half an hour, followed by a half-hour cooling cycle, for a total of 4 hours.

[0056] S4: After the ball milling is completed, the powder is taken out of the can in an argon atmosphere glove box to obtain the five-element magnesium-based hydrogen storage alloy powder.

[0057] The XRD diffraction pattern of the obtained five-element magnesium-based hydrogen storage alloy powder is as follows: Figure 2 As shown, after ball milling, Mg 60 Al5Ni 20 Co5La 10 The main phase remains amorphous, while a small amount of Al1Ni1 crystal phase exists. Figure 3 The hydrogen absorption kinetics curve is shown in Figure 2. At 150°C and 4.5MPa-H2, Mg 60 Al5Ni 20 Co5La 10 The hydrogen absorption of the sample can reach about 3.0wt.% within 1.5 hours. Figure 4 (a) is Mg 60 Al5Ni 20 Co5La 10 The temperature-dependent hydrogen desorption kinetic curve shows that at a temperature of 250°C, the final hydrogen desorption amount exceeds 1.0 wt.%. The XRD diffraction pattern of the sample after hydrogen desorption at 225°C is shown in FIG. Figure 5 As shown, it can be seen that the sample has a certain degree of crystallization at this time, and Al2La1 crystal phase exists.

[0058] All the above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be considered as equivalent replacement methods and are included in the scope of protection of the present invention.

Claims

1. A five-element magnesium-based amorphous hydrogen storage alloy, characterized in that: The chemical formula of the five-element magnesium-based amorphous alloy is Mg x Al y Ni z Co5RE w , where RE is one of Y, La, and Ce, and 40 x 70,5 y 10, 10 z 20, 10 w 20, and satisfying x + y + z + w = ​​95; the main phase of the five-element magnesium-based amorphous hydrogen storage alloy is an amorphous phase, containing a small amount of Al1Ni1 crystal phase.

2. The method for preparing a five-element magnesium-based amorphous hydrogen storage alloy according to claim 1, characterized in that: The steps include: S1: Selecting 99.9% pure Mg, Al, Ni, Co, and RE elemental metals as smelting raw materials, first preparing an Al-Ni-Co-RE quaternary intermediate ingot by arc melting, and then induction melting the Al-Ni-Co-RE quaternary intermediate ingot with Mg to obtain a Mg-Al-Ni-Co-RE quinary alloy ingot; S2: The Mg-Al-Ni-Co-RE five-element alloy ingot obtained in step S1 is placed in a belt-spinning furnace, and Mg is obtained by a melting and rapid quenching method. x Al y Ni z Co5RE w amorphous strips; S3: Mg obtained in step S2 x Al y Ni z Co5RE w The amorphous strips were placed in a ball mill, followed by metal grinding balls, which were then sealed in an argon atmosphere glove box and finally placed in a planetary ball mill for ball milling. S4: After the ball milling is completed, the ball mill jar is taken out and placed in an argon atmosphere glove box, and the ball mill jar is opened to take out the powder obtained after the ball milling to obtain the five-element magnesium-based amorphous hydrogen storage alloy; Wherein, in step S3, the metal grinding balls and Mg x Al y Ni z Co5RE w The mass ratio of the amorphous strip is 50:1 to 200:1; the rotation speed of the planetary ball mill is set to 100 to 300 rpm during ball milling, the ball milling is performed for 20 to 40 minutes, and the mill is stopped for 20 to 40 minutes, for a total ball milling time of 3 to 5 hours.

3. The method for preparing a five-element magnesium-based amorphous hydrogen storage alloy according to claim 2, characterized in that: During the melt quenching in step S2, the linear speed of the copper roller is 30 to 60 m / s.

4. Application of the five-element magnesium-based amorphous alloy as claimed in claim 1 in hydrogen storage materials, characterized in that: The five-element magnesium-based amorphous alloy is used as a solid-state hydrogen storage material.

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