CN114507798B - Magnesium-based hydrogen storage alloy block and preparation method thereof - Google Patents

Magnesium-based hydrogen storage alloy block and preparation method thereof Download PDF

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CN114507798B
CN114507798B CN202210150256.5A CN202210150256A CN114507798B CN 114507798 B CN114507798 B CN 114507798B CN 202210150256 A CN202210150256 A CN 202210150256A CN 114507798 B CN114507798 B CN 114507798B
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magnesium
alloy
rare earth
hydrogen storage
nickel
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CN114507798A (en
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韩胜利
郑开宏
张玉桧
徐静
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Institute of New Materials of Guangdong Academy of Sciences
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C31/00—Control devices, e.g. for regulating the pressing speed or temperature of metal; Measuring devices, e.g. for temperature of metal, combined with or specially adapted for use in connection with extrusion presses
    • 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
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/02—Compacting only
    • 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
    • B22F9/14—Making metallic powder or suspensions thereof using physical processes using electric discharge
    • 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
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/32—Hydrogen storage

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
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  • Battery Electrode And Active Subsutance (AREA)
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  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)

Abstract

The invention discloses a magnesium-based hydrogen storage alloy block and a preparation method thereof, belonging to the technical field of magnesium-based hydrogen storage materials. The method comprises the following steps: smelting and pouring the magnesium block, the magnesium-nickel intermediate alloy and the magnesium-rare earth intermediate alloy according to the mass ratio of magnesium element to nickel element to rare earth element of 50-90:10-20:1-10 to obtain an alloy ingot; then, hot extruding the alloy ingot into an alloy bar and processing the alloy bar into an alloy electrode; and then atomizing the alloy electrode to prepare powder to obtain magnesium-nickel-rare earth hydrogen storage alloy powder, and pressing and forming the magnesium-nickel-rare earth hydrogen storage alloy powder. The method is simple and easy to operate, and is suitable for batch preparation of the magnesium-based hydrogen storage alloy block. The magnesium-based hydrogen storage alloy block prepared by the method can achieve higher hydrogen absorption amount in a shorter time and at a lower pressure, and can be recycled for 2000 times of 1500-2000 times.

Description

Magnesium-based hydrogen storage alloy block and preparation method thereof
Technical Field
The invention relates to the technical field of magnesium-based hydrogen storage materials, in particular to a magnesium-based hydrogen storage alloy block and a preparation method thereof.
Background
The magnesium-based hydrogen storage material is a medium-temperature hydrogen storage material which has high safety, is convenient to store and transport, has the characteristics of low relative density and low cost, and is considered to be the hydrogen storage material with the most application and development values.
However, currently, magnesium-based hydrogen storage materials exist mainly in powder form, and the hydrogen absorption performance of bulk magnesium-based hydrogen storage materials under short-time and low-pressure conditions is not ideal.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
It is an object of the present invention to provide a process for producing a magnesium-based hydrogen storage alloy ingot which enables the production of a magnesium-based hydrogen storage alloy ingot which achieves a high hydrogen absorption capacity in a relatively short period of time and at a relatively low pressure.
The second purpose of the invention is to provide a magnesium-based hydrogen storage alloy block prepared by the preparation method.
The application can be realized as follows:
in a first aspect, the present application provides a method of making a magnesium-based hydrogen storage alloy mass comprising the steps of: smelting and pouring the magnesium block, the magnesium-nickel intermediate alloy and the magnesium-rare earth intermediate alloy according to the mass ratio of magnesium element to nickel element to rare earth element of 50-90:10-20:1-10 to obtain an alloy ingot; then, hot extruding the alloy ingot into an alloy bar and processing the alloy bar into an alloy electrode; and then atomizing the alloy electrode to prepare powder to obtain magnesium-nickel-rare earth hydrogen storage alloy powder, and pressing and molding the magnesium-nickel-rare earth hydrogen storage alloy powder.
In an alternative embodiment, the rare earth comprises at least one of lanthanum, cerium, and yttrium.
In an alternative embodiment, the rare earth comprises at least one of yttrium and cerium.
In an alternative embodiment, the melting is performed at 680-720 ℃ for 1-3 h.
In an alternative embodiment, the smelting is carried out under stirring conditions.
In an alternative embodiment, the stirring speed is 200-1000 r/min.
In an alternative embodiment, the casting is performed at 650-700 ℃ for 5-30 min.
In an alternative embodiment, both melting and pouring are performed under a protective atmosphere;
in an alternative embodiment, the shielding gas is SF6And CO2The mixed gas of (2).
In an alternative embodiment, the process conditions for hot extrusion include: the hot extrusion temperature is 200-600 ℃, and the extrusion deformation ratio is 1-200: 1.
In an optional embodiment, before extrusion, the extrusion mold is preheated at a preheating temperature of 100-300 ℃, and the extrusion cylinder is preheated at a preheating temperature of 100-400 ℃.
In an optional embodiment, plasma rotating electrode powder-making equipment is adopted for atomizing powder-making, wherein in the atomizing powder-making process, the rotating speed of the electrode is 10000-30000r/min, the vacuum degree of a cavity is 10-1-10-3MPa, and the atomization time is 1-3 h.
In an alternative embodiment, the press forming process conditions include: the molding pressure is 200-2000MPa, and the pressure maintaining time is 1-100 s.
In a second aspect, the present application provides a magnesium-based hydrogen storage alloy ingot produced by the method of any one of the preceding embodiments.
In an optional embodiment, the magnesium-based hydrogen storage alloy block has the hydrogen absorption amount of 3-5wt% after being activated at the temperature of 300-350 ℃ and the pressure of 1-3MPa for 200-600 s.
The beneficial effect of this application includes:
by adding the magnesium-nickel intermediate alloy into the raw material mainly comprising the magnesium block according to the specific mass ratio of the magnesium element, the nickel element and the rare earth element, nickel contained in the magnesium-nickel intermediate alloy and magnesium in the raw material can form a solid solution, and the time for charging and discharging hydrogen is reduced; by adding the magnesium-rare earth intermediate alloy, the contained rare earth is not only beneficial to reducing the hydrogen charging and discharging time, but also beneficial to reducing the hydrogen charging and discharging temperature.
On the basis, the magnesium-based hydrogen storage alloy block has higher hydrogen absorption amount and higher cycle times in shorter time and lower pressure by combining a complete set of preparation process of smelting, pouring, hot extrusion, atomization powder making, electrode processing and compression molding.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The magnesium-based hydrogen storage alloy ingot provided by the present application and the method for preparing the same will be described in detail below.
The application provides a preparation method of a magnesium-based hydrogen storage alloy block, which comprises the following steps: smelting and pouring the magnesium block, the magnesium-nickel intermediate alloy and the magnesium-rare earth intermediate alloy according to the mass ratio of magnesium element to nickel element to rare earth element of 50-90:10-20:1-10 to obtain an alloy ingot; then, hot extruding the alloy ingot into an alloy bar and processing the alloy bar into an alloy electrode; and then atomizing the alloy electrode to prepare powder to obtain magnesium-nickel-rare earth hydrogen storage alloy powder, and pressing and forming the magnesium-nickel-rare earth hydrogen storage alloy powder.
By adding the magnesium-nickel intermediate alloy into the raw material, the nickel contained in the magnesium-nickel intermediate alloy and the magnesium in the raw material form a solid solution, the bonding force between the nickel element and the hydrogen is weaker, the formation enthalpy of hydride is lower, and the nickel has a catalytic action on hydrogen molecules, so that the hydrogen charging and discharging time can be shortened; by adding the magnesium-rare earth intermediate alloy into the raw materials, the addition of the rare earth element can change the crystal structure and hydride formation enthalpy of the magnesium-based hydrogen storage alloy, thereby not only being beneficial to reducing the hydrogen charging and discharging time, but also being beneficial to reducing the hydrogen charging and discharging temperature, and greatly improving the hydrogen storage performance of the alloy.
For reference, the content of the magnesium element may be 50, 55, 60, 65, 70, 75, 80, 85, or 90, etc., or may be any other value within a range of 50 to 90, in the same mass unit. The content of nickel element may be 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, etc., or may be any other value within the range of 10 to 20. The content of the rare earth element may be 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, etc., or may be any other value within the range of 1 to 10.
By controlling the mass ratio of magnesium, nickel and rare earth within the above range, the magnesium-based hydrogen storage alloy ingot can have a higher hydrogen absorption amount in a shorter time and at a lower pressure, and can have a higher cycle number. If the content of nickel is too high, the hydrogen charging and discharging temperature of the hydrogen storage alloy is easy to rise and the cost is increased; if the content of the rare earth element is too high, pulverization of the hydrogen storage alloy and reduction of the service life are likely to occur. It should be emphasized that, through research, the nickel and the rare earth in the application also play a certain synergistic effect.
The rare earth element in the present application may include at least one of lanthanum, cerium and yttrium, and in addition, may include other rare earth elements. In some preferred embodiments, the rare earth includes at least one of yttrium and cerium, and other rare earth elements may be selectively added as needed.
In the application, the smelting can be carried out for 1-3h under the conditions of 680-720 ℃. The process may be carried out, for example but not by way of limitation, in a well-type electric resistance furnace.
In some embodiments, the melting temperature may be 680 ℃, 685 ℃, 690 ℃, 695 ℃, 700 ℃, 705 ℃, 710 ℃, 715 ℃ or 720 ℃ or the like, or any other value within the range of 680 ℃ and 720 ℃. The smelting time can be 1h, 1.5h, 2h, 2.5h or 3h, and the like, and can also be any other value within the range of 1-3 h.
The vapor pressure of the magnesium alloy is low, so that the volatilization of the alloy is easily caused by overhigh melting temperature; the melting temperature is too low, so that the viscosity of the melt is increased, and the composition segregation is easily caused.
By smelting under the conditions, the smelted materials have lower viscosity, and are more beneficial to fully and uniformly mixing.
In a preferred embodiment, the melting is carried out under stirring conditions to enhance the degree of homogeneity of the ingredients. Illustratively, the stirring rotation speed can be 200-1000r/min, such as 200r/min, 300r/min, 400r/min, 500r/min, 600r/min, 700r/min, 800r/min, 900r/min, 1000r/min, etc., or can be any other value within the range of 200-1000 r/min.
The casting can be carried out for 5-30min under the conditions of 650-700 ℃. The process is also carried out in a well-type resistance furnace.
In some embodiments, the casting temperature can be 650 ℃, 655 ℃, 670 ℃, 675 ℃, 680 ℃, 685 ℃, 690 ℃, 695 ℃ or 700 ℃, etc., or any other value within the range of 650 ℃ to 700 ℃. The smelting time can be 5min, 10min, 15min, 20min, 25min or 30min, and the like, and can also be any other value within the range of 5-30 min.
It should be noted that, too high a pouring temperature tends to cause surface oxidation, and too low a pouring temperature tends to deteriorate the fluidity of the melt, resulting in generation of voids and bubbles in the ingot.
Preferably, the smelting and the pouring are carried out in a protective atmosphereAnd (6) a row. Illustratively, the shielding gas used may be SF6And CO2The mixed gas of (1). Under the protection of the mixed gas, not only can the magnesium be prevented from being oxidized, but also the magnesium can be prevented from being ignited.
And further, carrying out hot extrusion on the cast alloy ingot to obtain an alloy bar.
As can be referenced, the process conditions for hot extrusion include: the hot extrusion temperature is 200-600 ℃, and the extrusion deformation ratio is 1-200: 1. Before extrusion, the extrusion die is preheated at the preheating temperature of 100-300 ℃, and the extrusion cylinder is preheated at the preheating temperature of 100-400 ℃.
In some embodiments, the temperature of the hot extrusion may be 200 ℃, 250 ℃, 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃ or 600 ℃, etc., and may be any other value within the range of 200 ℃ to 600 ℃.
The preheating temperature of the extrusion mold can be 100 ℃, 150 ℃, 200 ℃, 250 ℃ or 300 ℃ and the like, and can also be any other value within the range of 100 ℃ to 300 ℃.
The preheating temperature of the extrusion cylinder can be 100 ℃, 150 ℃, 200 ℃, 250 ℃, 300 ℃, 350 ℃ or 400 ℃ and the like, and can also be any other value within the range of 100 ℃ and 400 ℃.
The extrusion deformation ratio may be 1:1, 2:1, 5:1, 10:1, 20:1, 50:1, 100:1, 150:1, 200:1, or the like, or may be any other value within the range of 1 to 200: 1.
In the extrusion process, the extrusion deformation ratio can directly influence the density and strength of the alloy bar, and further influence the subsequent powder preparation quality.
It should be noted that, too high an extrusion temperature is likely to cause surface oxidation, which may further increase the oxygen content of the subsequently prepared powder; too low an extrusion temperature increases the rigidity of the extruded rod, which is not favorable for subsequent processing.
And further, processing the alloy bar into an alloy electrode according to a preset size, and then putting the alloy electrode into plasma rotating electrode powder-making equipment for atomizing and making powder.
In reference, during the atomization powder preparation process, the rotation speed of the electrode is 10000-30000r/min, and the cavity is in vacuumDegree of 10-1-10-3MPa, and the atomization time is 1-3 h.
In some embodiments, the rotation speed can be 10000r/min, 15000r/min, 20000r/min, 25000r/min, 30000r/min, etc., or any other value within the range of 10000-.
The vacuum degree of the cavity can be 10-1MPa、10-2MPa or 10-3MPa, etc., can be 10-1-10-3Any other value in the MPa range.
The atomization time can be 1h, 1.5h, 2h, 2.5h or 3h, and the like, and can also be any other value within the range of 1-3 h.
According to the atomization process, the alloy powder with the particle size of more than 0 and less than or equal to 1000 μm can be obtained, and the particle size of the atomized alloy powder is preferably 100-200 μm.
It should be noted that the particle size of the prepared powder is affected by the rotational speed of atomization powder preparation, the magnesium alloy is volatilized due to too high vacuum degree, and the oxygen content of the powder is increased due to too low vacuum degree.
Further, the alloy powder is press-molded.
As a reference, the process conditions of press forming include: the molding pressure is 200-2000MPa, and the dwell time is 1-100 s.
In some embodiments, the molding pressure may be 200MPa, 500MPa, 800MPa, 1000MPa, 1500MPa, 2000MPa, etc., or any other value within the range of 200MPa to 2000 MPa.
The dwell time may be 1s, 5s, 10s, 50s, 80s, 100s, etc., or may be any other value within the range of 1-100 s.
The magnesium-based hydrogen storage alloy block pressed under the pressing conditions has uniform components, higher density and good hydrogen absorption and cycle performance.
Accordingly, the present application also provides magnesium-based hydrogen storage alloy masses produced by the above-described production methods.
In reference, the hydrogen absorption amount of the obtained magnesium-based hydrogen storage alloy block is 3-5wt% (the hydrogen absorption amount accounts for 70-90% of the total hydrogen absorption amount) after the magnesium-based hydrogen storage alloy block is activated at the temperature of 300-350 ℃ and the pressure of 1-3 MPa; the cycle times of the magnesium-based hydrogen storage alloy block can reach 1500-2000 times.
The "number of cycles" described above means the number of cycles that have elapsed when the hydrogen absorption amount has decreased to 70% or less.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
This example provides a magnesium-based hydrogen storage alloy ingot, which is prepared by the following method:
according to Mg: ni: the component Y with the mass ratio of 80:10:10 is mixed with magnesium blocks, magnesium-nickel intermediate alloy and magnesium-rare earth intermediate alloy, and then the mixture is smelted for 2 hours in a well-type resistance furnace under the conditions of 720 ℃ and 500r/min and poured for 20 minutes under the condition of 690 ℃. The smelting and pouring processes are both in SF6And CO2Under the protection of the mixed gas.
And carrying out hot extrusion on the cast alloy ingot at 450 ℃, wherein the extrusion deformation ratio is 100:1, and obtaining the alloy bar. Before extrusion, the die is preheated at the preheating temperature of 200 ℃, and the extrusion cylinder is preheated at the preheating temperature of 250 ℃.
Processing the prepared alloy rod into an alloy electrode, putting the electrode into plasma rotating electrode powder-making equipment for atomizing and making powder, wherein the rotating speed of the electrode is 15000r/min, the vacuum degree of a cavity is 10-1MPa. To obtain the magnesium-nickel-rare earth hydrogen storage alloy powder.
And (3) performing compression molding on the alloy powder, wherein the molding pressure is 500MPa, and the pressure maintaining time is 10 seconds, so as to obtain the magnesium-nickel-rare earth hydrogen storage alloy block.
The magnesium-nickel-rare earth hydrogen storage alloy block prepared by the embodiment has uniform components and excellent comprehensive performance, and after activation at 350 ℃ and 3MPa, the hydrogen absorption amount of 500 seconds is 5wt%, which is 85% of the total hydrogen absorption amount. After 1600 cycles, the hydrogen absorption amount is reduced to below 70%.
Example 2
This example provides a magnesium-based hydrogen storage alloy ingot, which is prepared by the following method:
according to Mg: ni: y is 80:15:5 by mass, and is matched with magnesium blocks and magnesium nickelSmelting the intermediate alloy and the magnesium-rare earth intermediate alloy in a well type resistance furnace for 3h under the conditions of 710 ℃ and 200r/min, and pouring for 5min under the condition of 680 ℃. The smelting and pouring processes are both carried out in SF6And CO2Under the protection of the mixed gas.
And carrying out hot extrusion on the cast alloy ingot at 430 ℃, wherein the extrusion deformation ratio is 200:1, and obtaining the alloy bar. Before extrusion, the die is preheated at the preheating temperature of 100 ℃, and the extrusion cylinder is preheated at the preheating temperature of 100 ℃.
Processing the prepared alloy rod into an alloy electrode according to the required size, putting the electrode into plasma rotating electrode powder-making equipment for atomizing and making powder, wherein the rotating speed of the electrode is 20000 revolutions per minute, and the vacuum degree of a cavity is 10-2And (MPa) obtaining magnesium-nickel-rare earth hydrogen storage alloy powder.
And (3) performing compression molding on the alloy powder, wherein the molding pressure is 600MPa, and the pressure maintaining time is 15 seconds. Thus obtaining the magnesium-nickel-rare earth hydrogen storage alloy block.
The magnesium-nickel-rare earth hydrogen storage alloy block prepared by the embodiment has uniform components and excellent comprehensive performance, and the hydrogen absorption amount of 450 seconds is 4.5 wt% and reaches 80% of the total hydrogen absorption amount after activation at 300 ℃ and 2.5 MPa. After 1650 cycles, the hydrogen absorption rate is reduced to below 70%.
Example 3
This example provides a magnesium-based hydrogen storage alloy ingot, which is prepared by the following method:
according to Mg: ni: y is 77:20:3, magnesium blocks, magnesium-nickel intermediate alloy and magnesium-rare earth intermediate alloy are mixed, smelted for 1h in a well type resistance furnace at 700 ℃ and 1000r/min, and cast for 30min at 670 ℃. The smelting and pouring processes are both carried out in SF6And CO2Under the protection of the mixed gas.
And carrying out hot extrusion on the cast alloy ingot at 400 ℃, wherein the extrusion deformation ratio is 1:1, and thus obtaining the alloy bar. Before extrusion, the die is preheated at the preheating temperature of 300 ℃, and the extrusion cylinder is preheated at the preheating temperature of 400 ℃.
The prepared alloy rod is processed into an alloy electrode according to the required sizeThe electrode is put into plasma rotating electrode powder-making equipment to make atomized powder, the rotating speed of the electrode is 25000r/min, the vacuum degree of the cavity is 10-3And (MPa) obtaining the magnesium-nickel-rare earth hydrogen storage alloy powder.
And (3) performing compression molding on the alloy powder, wherein the molding pressure is 800MPa, and the pressure maintaining time is 20 seconds, so as to obtain the magnesium-nickel-rare earth hydrogen storage alloy block.
The magnesium-nickel-rare earth hydrogen storage alloy block prepared by the embodiment has uniform components and excellent comprehensive performance, and the hydrogen absorption amount of 400 seconds after activation at 250 ℃ and 2.0MPa is 4.0 wt% and reaches 75% of the total hydrogen absorption amount. After 1680 times of circulation, the hydrogen absorption amount is reduced to below 70%.
Example 4
This example differs from example 1 in that: in the raw materials, the rare earth elements contain Y and La at the same time, and the mass ratio of Mg to Ni to Y to La is 80:10:5: 5.
The magnesium-nickel-rare earth hydrogen storage alloy block prepared by the embodiment has uniform components and excellent comprehensive performance, and after activation at 350 ℃ and 3MPa, the hydrogen absorption amount of 500 seconds is 4.0 wt% and reaches 80% of the total hydrogen absorption amount. After 1600 cycles, the hydrogen absorption amount is reduced to below 70%.
Example 5
This example differs from example 1 in that: in the raw materials, the rare earth elements simultaneously contain Y and Ce, and the mass ratio of Mg to Ni to Y to Ce is 80:10:5: 5.
The magnesium-nickel-rare earth hydrogen storage alloy block prepared by the embodiment has uniform components and excellent comprehensive performance, and after activation at 350 ℃ and 3MPa, the hydrogen absorption amount of 500 seconds is 4.5 wt%, which is 85% of the total hydrogen absorption amount. After 1800 cycles, the hydrogen absorption amount is reduced to below 70%.
Comparative example 1
This comparative example differs from example 1 in that: the raw materials do not contain magnesium rare earth intermediate alloy, and the amount of the partial raw materials is supplemented by magnesium nickel intermediate alloy.
The magnesium-nickel-rare earth hydrogen storage alloy block prepared by the comparative example has uniform components and excellent comprehensive performance, and the hydrogen absorption amount of 500 seconds after activation at 350 ℃ and 3MPa is 2.0 wt% and reaches 70% of the total hydrogen absorption amount. After 500 cycles, the hydrogen absorption amount is reduced to below 70%.
Comparative example 2
This comparative example differs from example 1 in that: the raw materials do not contain magnesium-nickel intermediate alloy, and the amount of the raw materials is supplemented by magnesium-rare earth intermediate alloy.
The magnesium-nickel-rare earth hydrogen storage alloy block prepared by the comparative example has uniform components and excellent comprehensive performance, and after activation at 350 ℃ and 3MPa, the hydrogen absorption amount of 500 seconds is 2.5 wt% and reaches 65% of the total hydrogen absorption amount. After 800 cycles, the hydrogen absorption amount is reduced to below 70%.
Comparative example 3
This comparative example differs from example 1 in that: in the raw materials, the mass ratio of the magnesium element, the nickel element and the rare earth element is 60:25: 15.
The magnesium-nickel-rare earth hydrogen storage alloy block prepared by the comparative example has uniform components and excellent comprehensive performance, and after activation at 350 ℃ and 3MPa, the hydrogen absorption amount of 500 seconds is 2.8 wt% and reaches 60% of the total hydrogen absorption amount. After 1000 cycles, the hydrogen absorption amount is reduced to below 70%.
Comparative example 4
This comparative example differs from example 1 in that: the melting temperature is 750 ℃.
The magnesium-nickel-rare earth hydrogen storage alloy block prepared by the comparative example has uniform components and excellent comprehensive performance, and after activation at 350 ℃ and 3MPa, the hydrogen absorption amount of 500 seconds is 4.0 wt% and reaches 80% of the total hydrogen absorption amount. After 1000 cycles, the hydrogen absorption amount is reduced to below 70%.
Comparative example 5
This comparative example differs from example 1 in that: the hot extrusion temperature was 650 ℃.
The magnesium-nickel-rare earth hydrogen storage alloy block prepared by the comparative example has uniform components and excellent comprehensive performance, and the hydrogen absorption amount of 500 seconds after activation at 350 ℃ and 3MPa is 3.9 wt% and reaches 75% of the total hydrogen absorption amount. After 1000 cycles, the hydrogen absorption amount is reduced to below 70%.
Comparative example 6
This comparative example differs from example 1 in that: the crush ratio was 250: 1.
The magnesium-nickel-rare earth hydrogen storage alloy block prepared by the comparative example has uniform components and excellent comprehensive performance, and after activation at 350 ℃ and 3MPa, the hydrogen absorption amount of 500 seconds is 4.1 wt%, which reaches 82% of the total hydrogen absorption amount. After 900 cycles, the hydrogen absorption amount is reduced to below 70%.
Comparative example 7
This comparative example differs from example 1 in that: the electrode rotation speed was 8000 r/min.
The magnesium-nickel-rare earth hydrogen storage alloy block prepared by the comparative example has uniform components and excellent comprehensive performance, and the hydrogen absorption amount of 500 seconds is 3.5 wt% and reaches 60% of the total hydrogen absorption amount after activation at 350 ℃ and 3 MPa. After 1000 cycles, the hydrogen absorption amount is reduced to below 70%.
Comparative example 8
The comparative example differs from example 1 in that: the electrode rotation speed was 32000 r/min.
The magnesium-nickel-rare earth hydrogen storage alloy block prepared by the comparative example has uniform components and excellent comprehensive performance, and after activation at 350 ℃ and 3MPa, the hydrogen absorption amount of 500 seconds is 5.0 wt% and reaches 80% of the total hydrogen absorption amount. After 1200 cycles, the hydrogen absorption amount is reduced to below 70%.
Comparative example 9
The comparative example differs from example 1 in that: the vacuum degree of the cavity is 10-4MPa。
The magnesium-nickel-rare earth hydrogen storage alloy block prepared by the comparative example has uniform components and excellent comprehensive performance, and after activation at 350 ℃ and 3MPa, the hydrogen absorption amount of 500 seconds is 4.8 wt% and reaches 80% of the total hydrogen absorption amount. After 1200 cycles, the hydrogen absorption amount is reduced to below 70%.
Comparative example 10
The comparative example differs from example 1 in that: the molding pressure was 2500 MPa.
The magnesium-nickel-rare earth hydrogen storage alloy block prepared by the comparative example has uniform components and excellent comprehensive performance, and the hydrogen absorption amount of 500 seconds is 3.0 wt% and reaches 60% of the total hydrogen absorption amount after activation at 350 ℃ and 3 MPa. After 1000 cycles, the hydrogen absorption amount is reduced to below 70%.
In summary, the magnesium-based hydrogen storage alloy block provided by the application has the advantages of simple preparation method and easy operation, and is suitable for batch preparation of the magnesium-based hydrogen storage alloy block. The magnesium-based hydrogen storage alloy block prepared by the method can achieve higher hydrogen absorption amount in a shorter time and at a lower pressure, and can be recycled for 2000 times of 1500-.
The present invention has been described in terms of the preferred embodiment, and it is not intended to be limited to the embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (6)

1. A method for preparing a magnesium-based hydrogen storage alloy block is characterized by comprising the following steps: smelting and pouring the magnesium block, the magnesium-nickel intermediate alloy and the magnesium-rare earth intermediate alloy according to the mass ratio of magnesium element to nickel element to rare earth element of 50-90:10-20:1-10 to obtain an alloy ingot; then, hot extruding the alloy ingot into an alloy bar and processing the alloy bar into an alloy electrode; then atomizing the alloy electrode to prepare powder to obtain magnesium-nickel-rare earth hydrogen storage alloy powder, and pressing and molding the magnesium-nickel-rare earth hydrogen storage alloy powder;
the smelting is carried out for 1-3h under the conditions of 680-720 ℃; smelting is carried out under the condition of stirring; the stirring speed is 200-1000 r/min;
the pouring is carried out for 5-30min at the temperature of 650-700 ℃;
the hot extrusion process conditions include: the hot extrusion temperature is 200-600 ℃, and the extrusion deformation ratio is 1-200: 1;
before extrusion, preheating an extrusion die at the preheating temperature of 100-300 ℃, and preheating an extrusion cylinder at the preheating temperature of 100-400 ℃;
atomizing powder preparation by adopting plasma rotating electrode powder preparation equipment, wherein in the atomizing powder preparation process, the rotating speed of the electrode is 10000-30000r/min, and the vacuum degree of a cavity is 10-1-10-3MPa, and the atomization time is 1-3 h;
the process conditions of the press forming comprise: the molding pressure is 200-2000MPa, and the pressure maintaining time is 1-100 s;
the magnesium-based hydrogen storage alloy block has the hydrogen absorption amount of 3-5wt% in 200-600s after being activated at the temperature of 350 ℃ and the pressure of 1-3 MPa.
2. The method of claim 1, wherein the rare earth includes at least one of lanthanum, cerium, and yttrium.
3. The method of claim 2, wherein the rare earth comprises at least one of yttrium and cerium.
4. The method of claim 1, wherein the melting and the pouring are both performed in a protective atmosphere.
5. The method of claim 4, wherein the shielding gas is SF6And CO2The mixed gas of (1).
6. A magnesium-based hydrogen absorbing alloy mass produced by the production method according to any one of claims 1 to 5.
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Citations (3)

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Publication number Priority date Publication date Assignee Title
CN1502712A (en) * 2002-11-26 2004-06-09 有研稀土新材料股份有限公司 Hydrogen storage alloy and process for preparing quick cooling thick band thereof
CN101260492A (en) * 2008-04-29 2008-09-10 安泰科技股份有限公司 Magnesium-base nano hydrogen-storage material and preparing method thereof
CN109972010A (en) * 2019-04-15 2019-07-05 河北工业大学 A kind of nano Mg base composite hydrogen storage material and preparation method

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EP2096691B1 (en) * 2007-12-27 2012-02-08 Sanyo Electric Co., Ltd. Hydrogen storage alloy and alkaline storage battery employing hydrogen storage alloy as negative electrode active material

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Publication number Priority date Publication date Assignee Title
CN1502712A (en) * 2002-11-26 2004-06-09 有研稀土新材料股份有限公司 Hydrogen storage alloy and process for preparing quick cooling thick band thereof
CN101260492A (en) * 2008-04-29 2008-09-10 安泰科技股份有限公司 Magnesium-base nano hydrogen-storage material and preparing method thereof
CN109972010A (en) * 2019-04-15 2019-07-05 河北工业大学 A kind of nano Mg base composite hydrogen storage material and preparation method

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