CN111101041A - Magnesium-yttrium-zinc hydrogen storage magnesium alloy and preparation method thereof - Google Patents
Magnesium-yttrium-zinc hydrogen storage magnesium alloy and preparation method thereof Download PDFInfo
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- CN111101041A CN111101041A CN202010029969.7A CN202010029969A CN111101041A CN 111101041 A CN111101041 A CN 111101041A CN 202010029969 A CN202010029969 A CN 202010029969A CN 111101041 A CN111101041 A CN 111101041A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
- C22C23/06—Alloys based on magnesium with a rare earth metal as the next major constituent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/06—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of magnesium or alloys based thereon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/045—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by other means than ball or jet milling
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C2202/00—Physical properties
- C22C2202/04—Hydrogen absorbing
Abstract
The invention discloses a magnesium-yttrium-zinc hydrogen storage magnesium alloy and a preparation method thereof. The magnesium alloy consists of three elements of Mg, Y and Zn, and the chemical formula of the magnesium alloy can be expressed as MgY x2Zn x ,0.5≤xLess than or equal to 1, and provides a preparation method of the alloy and hydrogen storage performance of the alloy in an as-cast state, a homogenized state and an equal channel angular compression state (ECAP). The preparation process route is as follows: the method comprises the following steps of large furnace smelting, semi-continuous casting, homogenizing annealing and equal channel angular extrusion, so that three samples in different states are obtained, and a block sample is crushed into powder for hydrogen storage performance testing. The magnesium alloy has good hydrogen absorption and desorption dynamics, and samples in three different states are completely activated and then are at 360 DEG CThe hydrogen absorption amount can reach about 7wt%, the hydrogen absorption amount can reach about 5wt% at 280 ℃, and the hydrogen can be discharged to different degrees at 360 ℃, 320 ℃ and 280 ℃. The preparation method provided by the invention has a simple process, and can be used for large-scale preparation, and the prepared magnesium alloy has excellent hydrogen storage performance and good application prospect in the aspect of being used as a hydrogen fuel cell.
Description
Technical Field
The invention relates to a metal functional material, in particular to a magnesium-yttrium-zinc hydrogen storage magnesium alloy and a preparation method thereof.
Background
With environmental pollution and consumption of fossil fuels, energy issues have become a significant challenge for human beings. Although many new energy sources are currently used, such as nuclear energy, tidal energy, wind energy, etc., the distance to meet the human needs is far from enough, and a new energy source is urgently needed to replace fossil fuel. Hydrogen is an ideal fuel, has large heat per unit volume, and has no pollution after combustion. However, the storage of hydrogen is an obstacle to limiting the practical application of hydrogen fuel cells, where solid-state hydrogen storage dominates over gaseous and liquid-state hydrogen storage in terms of both safety and hydrogen storage capacity. In solid hydrogen storage, the magnesium-based hydrogen storage material has large hydrogen storage capacity (7.6wt%), rich magnesium resources and low cost. These two drawbacks have hindered the development and application of magnesium-based hydrogen storage materials due to their slow sorption and desorption kinetics and high thermodynamic stability. Many researchers have been working for decades to explore several methods for modifying magnesium-based hydrogen storage materials, such as adding catalysts, amorphization, nanocrystallization, alloying, etc. However, due to the inherent disadvantages and shortcomings of this method, it is difficult to put magnesium-based hydrogen storage materials into practical use.
Magnesium alloys containing LSPO phase are often used as structural materials, and few studies have been made on hydrogen storage properties so far. At present, some researchers have studied the hydrogen storage performance of Mg-Y-TM (TM is Cu, Ni, etc.) magnesium alloy, and found that decomposition occurs after hydrogenation of LPSO phase, and Y and H in LPSO phase combine to form YH x (x=2/3),YH x Is on the order of nanometers and is uniformly distributed in the magnesium matrix. Due to YH x With pinning action, in the course of multiple cycles YH x The size is hardly grown, and the growth of Mg grains in the circulation process can be inhibited. And the researchers showed YH by calculation2And Mg surface will be H2Provides additional energy in favor of H2Thereby promoting MgH2The nucleation of (2). In the process of hydrogen evolution, YH2Will be from MgH2H atoms are provided in the alloy, which is the 'hydrogen pump effect', so the alloy has the performance of absorbing and desorbing hydrogen for the magnesium alloyHas remarkable catalytic action.
Magnesium has certain oxidation resistance after alloying, and researchers show that only a file is used for filing a block sample into powder, no additional treatment is needed, the hydrogen storage performance is still good, and the preparation process is simple and convenient. The method can be used for mass production, and provides a good idea for the practical application of the hydrogen fuel cell.
Disclosure of Invention
The invention aims to provide a magnesium-yttrium-zinc hydrogen storage magnesium alloy with good hydrogen storage performance and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
the magnesium-yttrium-zinc hydrogen storage magnesium alloy comprises MgY x2Zn x Wherein 0.5 is less than or equal tox≤1。
The preparation method of the magnesium-yttrium-zinc hydrogen storage magnesium alloy in three different states comprises the following steps:
(1) preparing materials: respectively weighing pure metal and alloy according to chemical composition components, cleaning the raw materials, and then baking and degassing;
(2) smelting: adopting a medium-frequency induction resistance furnace or a high-frequency induction resistance furnace;
(3) casting: rapidly solidifying by adopting a semi-continuous casting method to obtain a cast ingot;
(4) carrying out homogenization annealing on the cast ingot to obtain a homogenized spindle;
(5) carrying out equal channel angular extrusion treatment on the homogenizing spindle to obtain an equal channel angular extrusion spindle;
(6) and removing oxide layers on the surfaces of the block samples in the three states, and filing the block samples into powder by adopting a diamond file.
In the step (2), the smelting temperature is 650-720 ℃. Stirring once every 5-15 minutes, and standing for 40-1 hour after the alloy is completely melted; the atmosphere of the smelting is 99% CO2And 1% of SF6As a shielding gas.
In the step (3), the diameter of the ingot is phi 150-.
In the step (4), the ingot is mechanically processed, and the central part of the ingot is taken, wherein the diameter is phi 150 and phi 200mm, and the length is phi 100 and phi 150 mm; the homogenization annealing is carried out at 480-510 ℃ for 18-21 hours.
In the step (4), the homogenizing spindle is mechanically processed, and the central part of the homogenizing spindle is taken, and the size of the central part is 49 multiplied by 100 mm; carrying out 8-16 times of treatment at the temperature of 300-350 ℃, wherein the channel angle is 90-120 ℃.
In the step (6), the atmosphere for removing the powder from the bulk sample is under air or argon.
The use method of the magnesium-yttrium-zinc hydrogen storage magnesium alloy comprises the following steps: at H2Absorbing hydrogen for 3-4 hours under the conditions of pressure of 2.5-3.5MPa and temperature of 350-400 ℃, and dehydrogenating for 0.5-1 hour under the conditions of 350-400 ℃ and vacuum, and circulating for 3-5 times, wherein the activation process is carried out. The working temperature after activation is 250 ℃ or higher.
The invention has the advantages that:
the magnesium-yttrium-zinc hydrogen storage magnesium alloy has simple preparation process and can be used for mass industrial production; after activation, the catalyst has excellent hydrogen absorption and desorption kinetics and high theoretical hydrogen storage capacity (7.2 wt%); the hydrogen storage magnesium alloy has low cost because of low content of yttrium and low price of yttrium in rare earth system.
Drawings
FIG. 1 is an SEM image of three bulk morphologies in an example of the invention, (a) is an SEM image of an as-cast sample, and (b) is an enlarged area morphology of the box in (a); (c) is a SEM image of the homogenized sample, and (d) is the enlarged area morphology of the box in (c); (e) SEM images of samples in an equal channel angular pressing state (ECAP), and (f) is an enlarged area morphology of a box in (e).
Figure 2 is an XRD pattern of three blocks in an example of the invention.
FIG. 3 is an SEM image of three powders of an example of the invention, (a) is an SEM image of an as-cast sample, and (b) is an enlarged area topography of the box in (a); (c) is a SEM image of the homogenized sample, and (d) is the enlarged area morphology of the box in (c); (e) SEM images of samples in an equal channel angular pressing state (ECAP), and (f) is an enlarged area morphology of a box in (e).
FIG. 4 is an SEM image of three powders after activation in an example of the invention, (a) is an SEM image of an as-cast sample, and (b) is an enlarged area morphology of a box in (a); (c) is a SEM image of the homogenized sample, and (d) is the enlarged area morphology of the box in (c); (e) the (f) is the enlarged area morphology of the box in (e) in the equal channel angular extrusion state (ECAP).
Figure 5 is an XRD pattern after activation of three powders in the examples of the invention.
FIG. 6 is TEM images of three activated samples (a), (d), and (g) in the invention example, as-cast, homogenized, and equal channel angular Extruded (ECAP), respectively; HRTEM images (b), (e) and (h) are respectively in an as-cast state, a homogenized state and an equal channel angular extrusion state (ECAP); SAED patterns (c), (f) and (i) are respectively in an as-cast state, a homogenized state and an equal channel angular compression state (ECAP).
FIG. 7 is a graph showing hydrogen absorption and desorption curves of three powders at different temperatures in the example of the present invention, wherein (a) and (b) are as-cast hydrogen absorption and desorption curves; (c) and (d) is a homogenized hydrogen absorption and desorption curve; (e) and (f) is the hydrogen absorption and desorption curve of the equal channel angular compression state (ECAP).
Detailed Description
The following detailed description of specific embodiments of the present invention is provided in connection with the accompanying drawings and examples.
Firstly, according to the chemical composition MgY x2Zn x Preparing the materials, wherein the content of the materials is more than or equal to 0.5xLess than or equal to 1. Cleaning the above materials, drying, removing oxide layer, and oven drying. And smelting by adopting a medium-frequency induction resistance furnace or a high-frequency induction resistance furnace, stirring and standing in the second process, and then rapidly cooling by adopting a semi-continuous casting method to obtain the ingot. Taking the core area of the ingot for homogenization annealing treatment, preserving the heat for 18-21 hours at 480-510 ℃, and cooling along with the furnace. And then mechanically processing the homogenized spindle, removing the center area of the spindle to obtain a rectangular spindle with the size of 49 multiplied by 100mm, and performing Equal Channel Angular Pressing (ECAP) treatment, wherein the pressing temperature is 300 and 350 ℃, and the pressing pass is 8-16, so as to obtain a sample in an equal channel angular pressing state. Powder is withdrawn from the three block samples and sieved by a sieve with 150-300 meshes, thus obtaining the magnesium-yttrium-zinc hydrogen storage magnesium alloy in different states. MaterialWhen in use, the activating is needed: h at 350-400 ℃ and 2.5-3.5MPa2And respectively carrying out hydrogen absorption and hydrogen desorption processes under vacuum conditions, and circulating for 3-5 times. Then the hydrogen content can be in the range of 2-3MPa2The hydrogen absorption and desorption reaction is carried out under the pressure and at the temperature of more than 250 ℃.
Example (b):
the raw material adopts Mg (99.9%), Zn (99.9%) and master alloy Mg-30% Y (wt%), uses a medium frequency induction resistance furnace and CO at 99%2And 1% of SF6Smelting under the protective gas. When the temperature reaches 676 ℃, the alloy is completely melted, stirred once every 10 minutes in the secondary process, and finally kept stand for 1 hour. And (3) rapidly solidifying by adopting a semi-continuous casting method to obtain an ingot with the size of phi 150mm and the length of 500 mm. Taking the core area of the ingot, wherein the size is phi 150mm, and the length is 150 mm. The ingot is held at 510 ℃ for 20 hours for homogenization annealing treatment and is cooled along with the furnace. And then taking the core area of the homogenizing spindle, wherein the size is 49 multiplied by 100mm, performing equal channel angular extrusion treatment, wherein the extrusion temperature is 300 ℃, the extrusion pass is 13 passes, and the angle between each channel is 90 degrees. The above results in an as-cast, homogenized and equal channel angular Extruded (ECAP) spindle, each of which has a morphology as shown in fig. 1 and a phase as shown in fig. 1 and 2. The oxide layer on the surface of the three kinds of ingots was removed first, and then the powder was removed from the three kinds of bulk samples under an air atmosphere and sieved with a 200-mesh sieve, and the morphology of the final powder was as shown in fig. 3. Three kinds of powder are respectively in H at 400 ℃ and 3MPa2Hydrogen is absorbed for 3.5 hours under pressure, dehydrogenation is carried out for 1 hour under the vacuum condition at 400 ℃, the two reactions are circulated for three times to be an activation process, and the shape and the phase composition of the powder after three states of activation are respectively shown in a figure 4, a figure 5 and a figure 6. And the hydrogen absorption and desorption curves at different temperatures are tested, as shown in figure 7, the hydrogen absorption amount can reach about 7wt% at 360 ℃, and the hydrogen desorption rate is very high; the hydrogen absorption at 280 deg.c may also reach around 5wt%, but the hydrogen release rate at this temperature is relatively slow.
Claims (6)
1. A magnesium-yttrium-zinc hydrogen storage magnesium alloy is characterized in that: the hydrogen storage magnesium alloy consists of three elements of Mg, Y and Zn, and the chemical formula of the hydrogen storage magnesium alloy can be expressedIs MgY x2Zn x ，0.5≤xLess than or equal to 1; the hydrogen storage magnesium alloy takes LPSO phase and Mg phase as main components, and LPSO phase in alloy in different states can be distributed in Mg matrix in different structures. In the casting state, the LPSO phase structure is 18R, the shape is blocky, and the LPSO phase structure is mainly distributed in crystal boundaries and crystals; after homogenization treatment, the LPSO phase structure is changed from 18R to 14H, the metastable LPSO phase in the crystal is changed into lamellar 14H, the blocky 14H phase is mainly distributed in the crystal and among the crystal, and the lamellar 14H phase is distributed in the crystal; when the equal channel angular extrusion state is adopted, the grain size is greatly reduced, even dynamic recrystallization is generated, some blocky 14H phases are broken, and the lamellar 14H phases are kinked.
2. A method of making the magnesium-yttrium-zinc hydrogen storage magnesium alloy of claim 1, wherein: the method comprises the following steps:
(1) under the protection atmosphere, pure Mg (99.9wt%), pure Zn (99.9wt%) and intermediate alloy Mg-30% Y (wt%) are smelted, and then the as-cast MgY is obtained by a semi-continuous casting method x2Zn x The ingot blank has the diameter phi of 150 plus 200mm and the length phi of 500 plus 800 mm.
(2) The as-cast MgY obtained in the step (1) is used x2Zn x And the spindle is mechanically cut, the central part is taken, the diameter is phi 150 plus 200mm, and the length is phi 100 plus 150 mm. The central spindle is then incubated at 480 ℃ and 520 ℃ for 18-25 hours.
(3) Mechanically cutting the homogenized spindle in the step (2), taking the core part with the size of 49 multiplied by 100mm, and performing equal channel angular extrusion treatment at the extrusion temperature of 300 and 350 ℃, the extrusion pass is 8 to 16, and the channel angle is 90 to 120 degrees.
(4) Removing the oxide film on the surfaces of the ingots in the casting state, the homogenization state and the equal channel angle extrusion state obtained in the steps (1), (2) and (3), then filing the powders from the surfaces of the three ingots by a file, and sieving the powders by a sieve with 300 meshes of 150 meshes, thereby obtaining the magnesium-yttrium-zinc hydrogen storage magnesium alloy powder for testing the hydrogen storage performance.
3. Preparation of a magnesium-yttrium-zinc reservoir according to claim 2The method for preparing the hydrogen magnesium alloy is characterized by comprising the following steps: 99% of CO is used in the smelting in the step (1)2And 1% of SF6As a shielding gas.
4. The method of preparing a magnesium-yttrium-zinc hydrogen storage magnesium alloy of claim 2, wherein: the smelting temperature in the step (1) is 650-720 ℃.
5. The method of preparing a magnesium-yttrium-zinc hydrogen storage magnesium alloy of claim 2, wherein: and (3) cooling in the step (2) in a furnace cooling mode.
6. The method of preparing a magnesium-yttrium-zinc hydrogen storage magnesium alloy of claim 2, wherein: the environment for powder mixing in the step (4) is in air or argon atmosphere.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112624038A (en) * | 2020-12-18 | 2021-04-09 | 长沙理工大学 | Method for regulating and controlling hydrogen storage performance of Mg-Y-Zn magnesium alloy |
| CN114229797A (en) * | 2022-01-17 | 2022-03-25 | 重庆大学 | Method for preparing hydrogen based on hydrolysis of Mg-Ni-Y alloy containing LPSO second phase |
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| CN114229797B (en) * | 2022-01-17 | 2024-01-12 | 重庆大学 | Method for producing hydrogen based on hydrolysis of Mg-Ni-Y alloy containing LPSO second phase |
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Application publication date: 20200505 |