CN111515405A - Preparation method of magnesium-based nano composite hydrogen storage material - Google Patents

Preparation method of magnesium-based nano composite hydrogen storage material Download PDF

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CN111515405A
CN111515405A CN202010482232.0A CN202010482232A CN111515405A CN 111515405 A CN111515405 A CN 111515405A CN 202010482232 A CN202010482232 A CN 202010482232A CN 111515405 A CN111515405 A CN 111515405A
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hydrogen
magnesium
hydrogen storage
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陈炎
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Shenzhen Yahuan Environmental Protection Technology Co ltd
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Abstract

The invention relates to a preparation method of a magnesium-based nano composite hydrogen storage material, belonging to the technical field of hydrogen storage materials. The method comprises the steps of taking a carbon nano tube grown in situ on the surface of a molecular sieve as a base material, taking rare earth lanthanum as a target material, sputtering a layer of lanthanum hydride film on the surface of the base material to be used as a filler of a hydrogen storage material, taking magnesium hydride as a raw material, and preparing the magnesium-based nano composite hydrogen storage material by mechanical ball milling; when hydrogen molecules contact with the material, the hydrogen molecules are adsorbed on the surface of the alloy, H-H bonds of the hydrogen molecules are dissociated into atomic hydrogen, the hydrogen atoms are diffused from the surface of the material to the inside, the hydrogen atoms are immersed into gaps between metal atoms and metal with a radius much larger than that of the hydrogen atoms to form a solid solution, the hydrogen dissolved in the metal is diffused to the inside, the diffusion has the activation energy converted from chemical adsorption to dissolution, and when the solid solution is saturated by the hydrogen, the excessive hydrogen atoms react with the solid solution to produce metal hydride, thereby achieving the purpose of storing the hydrogen.

Description

Preparation method of magnesium-based nano composite hydrogen storage material
Technical Field
The invention relates to a preparation method of a magnesium-based nano composite hydrogen storage material, belonging to the technical field of hydrogen storage materials.
Background
Among a plurality of new energy sources, hydrogen energy has the characteristics of abundant resources, extremely high energy density and mass ratio, environmental friendliness, good combustion performance, various storage forms, high potential economic benefits and the like, is called as ultimate clean energy of human beings, and is expected to become one of the most important new energy sources in the world energy stage in the future. The ideal hydrogen circulation relates to four links of hydrogen preparation, storage, transportation, application and the like. The following key problems exist in the development and application process of hydrogen energy: hydrogen production technology, hydrogen storage and transportation technology and hydrogen application.
The hydrogen energy system comprises the whole process from development to utilization, and is a complete industrial chain for economic operation of hydrogen energy. Including development of hydrogen energy, hydrogen production technology, hydrogen storage technology, hydrogen delivery technology, hydrogen utilization, and the like. When present in gaseous form, hydrogen has the characteristics of low density, flammability, explosiveness, and easy diffusion under normal conditions, thus causing great difficulty in storage and transportation. When hydrogen is used as a fuel, the technical requirements of large energy density (mainly mass hydrogen storage density and volume hydrogen storage density), low energy consumption and high safety are provided for the storage and transportation of hydrogen. The current technical problem of high-efficiency and safe hydrogen storage is not solved, so that the large-scale application of hydrogen energy in industrial production is limited.
The storage mode of hydrogen is divided into physical hydrogen storage and chemical hydrogen storage, the physical hydrogen storage mainly comprises high-pressure gaseous hydrogen storage, liquid hydrogen storage, active substance adsorption hydrogen storage and the like, and the chemical hydrogen storage method mainly comprises coordination hydride hydrogen storage, metal hydride hydrogen storage, chemical hydride (including inorganic matters and organic matters) hydrogen storage and the like.
High pressure gaseous hydrogen storage, which is currently the most widely used method of storing hydrogen in a steel container under pressure (about 15 MPa), is used. The method has the advantages of simplicity and convenience and high charging/discharging speed, but the energy density is generally lower, the high-pressure container is heavy, the mass of hydrogen only accounts for 1% -2% of the mass of the container, and a lot of extra hydrogen compression work is consumed in the hydrogen charging process. In addition, under high pressure conditions, safety is also an issue.
The low-temperature liquid hydrogen storage is a hydrogen storage mode of storing hydrogen gas in a vacuum container after the hydrogen gas is liquefied, and the liquid hydrogen storage has higher volume density (70 kg/m)3) And the density is 845 times that of gaseous hydrogen, so the low-temperature liquefied hydrogen storage has the advantages of high volume density and small volume of a storage container. However, the liquefaction of hydrogen can be realized only by cooling to the ultralow temperature of 20K, and the energy consumed in the process accounts for 25 to 45 percent of the stored hydrogen energy. This greatly reduces the energy utilization. In addition, the liquid hydrogen storage vessel must use a special vessel for ultra-low temperature, and there is a relatively high requirement for the heat insulating property of the storage vessel, so that the hydrogen storage vessel has a complicated technology and the hydrogen storage cost is increased. At present, the liquid hydrogen storage technology is mainly applied to the field of aviation.
An excellent hydrogen storage alloy should have the following characteristics: (1) good thermodynamic properties are necessary. In addition to a high hydrogen storage capacity and a reversible hydrogen absorption amount, the hydrogen storage alloy should have a low dissociation temperature at 1 atmosphere and a small absolute value of change in enthalpy of hydrogen absorption and desorption reactions. (2) Excellent dynamic performance. This is determined by the material properties and the mechanism of hydrogen absorption and desorption at a specific temperature and pressure. (3) Stable cyclic usability. The hydrogen storage alloy has good poisoning resistance and pulverization resistance in the hydrogen absorption and desorption circulation process. (4) Easy to activate. The hydrogen storage material which is easy to activate can easily destroy the oxide layer on the surface. (5) The practicability is good. The hydrogen storage alloy systems which are relatively mature in research at present mainly comprise: rare earth lanthanum nickel series, titanium iron series, titanium zirconium series, vanadium-based solid solution, magnesium-based hydrogen storage alloy and the like.
Magnesium-based hydrogen storage alloy is recognized as one of the most promising hydrogen storage materials, but the thermodynamic and kinetic properties of hydrogen absorption and desorption are poor, and the practical application of the magnesium-based hydrogen storage alloy is seriously hindered. Most researchers believe that the main reason for the poor hydrogen absorption and desorption kinetics of pure magnesium is: (1) h2The adsorption dissociation/molecular recombination desorption rate on the magnesium surface is slow; (2) since magnesium is very active, it is easily oxidized in the alloySurface formation of dense MgO or Mg (OH)2The activation dissociation of hydrogen molecules on the surface of the alloy is hindered (the surface of the alloy can provide active sites for the dissociation of the hydrogen molecules); (3) hydrogen at MgH2Diffusion rates are relatively slow with Mg, especially at MgH2Diffusion in (2) is more difficult. At a higher temperature of 300 ℃, H-At MgH2Has a diffusivity of only 10-18m2And s. If the Mg particle size is large, MgH2Completely covering the surface of the Mg particles, the hydrogenation rate is slow and Mg will not be completely hydrogenated. At present, a great deal of research work is being carried out on how to improve the hydrogen absorption and desorption thermodynamic properties and kinetic properties of the magnesium-based hydrogen storage alloy. The method for effectively improving the hydrogen storage performance of the pure magnesium mainly comprises alloying or solid solution, nanocrystallization, catalyst doping and the like.
The reasons for improving the hydrogen storage performance of the Mg-based hydrogen storage alloy through nanocrystallization can be summarized as the following three points:
(1) the grain boundary density in the nanometer material is higher, and the grain boundary has higher energy and excess volume. The nano-grain boundaries can provide a fast channel for diffusion of hydrogen atoms, and the grain boundaries can become "traps" for trapping hydrogen when the hydrogen amount is low, and the diffusion coefficient of hydrogen in the nano-grain boundaries is much higher than that in a single crystal when the hydrogen amount is high. Thus, hydrogen is predominantly along Mg and MgH2Interface diffusion between them, or diffusion along grain boundaries and defects inside hydrides.
Due to the action of the surface effect, the nano particles have extremely high surface energy, so that the adsorption capacity and catalytic activity of the surfaces of the nano particles to hydrogen are obviously improved.
The volume effect shortens the diffusion distance of hydrogen atoms and avoids long-range diffusion.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: aiming at the problem of poor hydrogen absorption and desorption dynamic performance of the existing hydrogen storage material, the preparation method of the magnesium-based nano composite hydrogen storage material is provided.
In order to solve the technical problems, the invention adopts the technical scheme that:
(1) uniformly mixing a molecular sieve and a ferrous sulfate solution with the mass fraction of 2%, standing for 1-2 days, taking out, naturally drying at room temperature to obtain a pretreated molecular sieve, placing the pretreated molecular sieve in a chemical vapor deposition furnace for deposition treatment to obtain a blank, performing heat treatment on the blank, and cooling to room temperature to obtain a base material;
(2) sputtering to form a film on the surface of the matrix to obtain the filler;
(3) mixing magnesium hydride and a filler, placing the mixture into a ball milling tank, and carrying out ball milling treatment according to a period to obtain a mixed material;
(4) and (3) placing the mixed material in a reaction tube, carrying out hydrogen absorption and desorption treatment, and cooling to room temperature to obtain the magnesium-based nano composite hydrogen storage material.
The mass ratio of the molecular sieve in the step (1) to the ferrous sulfate solution with the mass fraction of 2 percent is 1: 10.
The deposition treatment step in the step (1) is as follows: and (3) placing the pretreated molecular sieve in a chemical vapor deposition furnace, taking propylene as a carbon source, and depositing for 2-3 hours at the temperature of 900-920 ℃ in an argon atmosphere, wherein the gas flow is 6-12L/h.
The heat treatment step in the step (1) is as follows: and (3) placing the blank body at 2400-2500 ℃ for heat treatment for 1-2 h.
The sputtering film forming step in the step (2) is as follows: rare earth lanthanum is used as a target material, hydrogen is used as a reaction gas, argon is used as a sputtering gas, a film is formed on the surface of a substrate in a sputtering mode, the sputtering temperature is 200-300 ℃, the sputtering power is 60-200W, the deposition time is 10-20 s, and the distance between the target material and the substrate is 25-30 cm.
The ratio of the magnesium hydride to the filler in the step (3) is 1: 1 respectively.
The period of the step (3) is as follows: taking 60min as an operation period, operating for 50min in each period, and stopping for 10 min.
The ball milling treatment step in the step (3) is as follows: mixing magnesium hydride and a filler, placing the mixture into a ball milling tank, and ball milling for 40-42 h at the rotating speed of 250-300 r/min under the protection of argon, wherein the mass ratio of ball materials is 20: 1, the diameter of a small ball is 8-10 mm.
The hydrogen absorption and desorption treatment step in the step (4) is as follows: and (3) placing the mixed material in a reaction tube, and performing hydrogen absorption and desorption treatment for 3-4 hours at the temperature of 370-380 ℃.
Compared with other methods, the method has the beneficial technical effects that:
(1) the method comprises the steps of taking a carbon nano tube grown in situ on the surface of a molecular sieve as a base material, taking rare earth lanthanum as a target material, sputtering a layer of lanthanum hydride film on the surface of the base material to be used as a filler of a hydrogen storage material, taking magnesium hydride as a raw material, and preparing the magnesium-based nano composite hydrogen storage material by mechanical ball milling; when hydrogen molecules contact with the material, the hydrogen molecules are adsorbed on the surface of the alloy, H-H bonds of the hydrogen molecules are dissociated into atomic hydrogen, the hydrogen atoms are diffused from the surface of the material to the inside, the hydrogen atoms are immersed into interstitial spaces between metal atoms and metal with the radius much larger than that of the hydrogen atoms to form solid solution, the hydrogen dissolved in the metal is diffused to the inside, the diffusion has the activation energy converted from chemical adsorption to dissolution, and when the solid solution is saturated by the hydrogen, the excessive hydrogen atoms react with the solid solution to produce metal hydride, thereby achieving the purpose of storing the hydrogen; the metal hydride stores hydrogen, and the hydrogen is stored in the material in an atomic state and undergoes the processes of diffusion, phase change, chemical combination and the like when being released again; the processes are restricted by thermal effect and speed, are not easy to explode, have strong safety, and can be used as a hydrogen storage material and an energy working material;
(2) the carbon nano tube grows on the surface of the molecular sieve in situ, hydrogen is stored by utilizing the adsorption effect of the molecular sieve and the carbon nano tube on hydrogen molecules, and the molecular sieve and the carbon nano tube have larger hydrogen storage capacity, relatively lighter weight and convenient carrying; the reason why the prepared magnesium-based nano composite hydrogen storage material has excellent activation performance and kinetic performance is that: hydrogen atoms are easy to diffuse on a large number of nanometer crystal boundaries; the nanocrystalline has extremely high specific surface area, so that hydrogen atoms can easily permeate into the hydrogen storage material; the nano hydrogen storage material avoids hydrogen atoms from diffusing for a long distance through the hydride layer, and the diffusion of the hydrogen atoms in the hydride layer is the most main factor for controlling the dynamic performance, so the magnesium-based nano composite hydrogen storage material has better hydrogen absorption and desorption performance;
(3) the invention takes rare earth lanthanum as a target material, and a layer of lanthanum hydride film is sputtered on the surface of a substrate, wherein the rare earth is a rare earth systemHaving CaCu5The hexagonal structure, the rare earth alloy has the advantages of high hydrogen storage speed, easy activation, difficult poisoning and the like; magnesium hydride is the one with the largest available hydrogen storage amount in all hydrogen storage alloy systems, is an ionic hydride, has a tetragonal crystal rutile type structure, and has 2 Mg atoms in a unit cell; one at the vertex and the other at the center, 2 of the 4H atoms in the cell being on the cell surface and the other 2 being in the cell.
Detailed Description
Uniformly mixing a molecular sieve and a ferrous sulfate solution with the mass fraction of 2% according to the mass ratio of 1: 10, standing for 1-2 days, taking out, naturally drying at room temperature to obtain a pretreated molecular sieve, placing the pretreated molecular sieve in a chemical vapor deposition furnace, depositing for 2-3 hours at the temperature of 900-920 ℃ in an argon atmosphere by taking propylene as a carbon source and the gas flow rate of 6-12L/h to obtain a blank, placing the blank at the temperature of 2400-2500 ℃ for heat treatment for 1-2 hours, and cooling to room temperature to obtain a base material; taking rare earth lanthanum as a target material, hydrogen as a reaction gas and argon as a sputtering gas, and sputtering the rare earth lanthanum on the surface of a substrate to form a film, wherein the sputtering temperature is 200-300 ℃, the sputtering power is 60-200W, the deposition time is 10-20 s, and the distance between the target material and the substrate is 25-30 cm, so as to obtain the filler; mixing magnesium hydride and a filler according to the mass ratio of 1: 1, placing the mixture into a ball milling tank, under the protection of argon, ball milling for 40-42 h at the rotating speed of 250-300 r/min with the ball material mass ratio of 20: 1 and the diameter of a small ball of 8-10 mm, taking 60min as an operation period, operating for 50min in each period, and stopping for 10min to obtain a mixed material; and (3) placing the mixed material in a reaction tube, carrying out hydrogen absorption and desorption treatment for 3-4 h at the temperature of 370-380 ℃, and cooling to room temperature to obtain the magnesium-based nano composite hydrogen storage material.
Example 1
Uniformly mixing a molecular sieve and a ferrous sulfate solution with the mass fraction of 2%, standing for 1 day, taking out, naturally drying at room temperature to obtain a pretreated molecular sieve, placing the pretreated molecular sieve in a chemical vapor deposition furnace for deposition treatment to obtain a blank, performing heat treatment on the blank, and cooling to room temperature to obtain a base material; sputtering to form a film on the surface of the matrix to obtain the filler; mixing magnesium hydride and a filler, placing the mixture into a ball milling tank, and carrying out ball milling treatment according to a period to obtain a mixed material; and (3) placing the mixed material in a reaction tube, carrying out hydrogen absorption and desorption treatment, and cooling to room temperature to obtain the magnesium-based nano composite hydrogen storage material. The mass ratio of the molecular sieve to the ferrous sulfate solution with the mass fraction of 2 percent is 1: 10. The deposition treatment steps are as follows: and (3) placing the pretreated molecular sieve in a chemical vapor deposition furnace, taking propylene as a carbon source, and depositing for 2 hours at 900 ℃ in an argon atmosphere, wherein the gas flow is 6L/h. The heat treatment step is as follows: and (3) placing the blank body at the temperature of 2400 ℃ for heat treatment for 1 h. The sputtering film-forming step is as follows: rare earth lanthanum is used as a target material, hydrogen is used as a reaction gas, argon is used as a sputtering gas, a film is formed on the surface of a substrate in a sputtering mode, the sputtering temperature is 200 ℃, the sputtering power is 60W, the deposition time is 10s, and the distance between the target material and the substrate is 25 cm. The ratio between magnesium hydride and filler is 1: 1, respectively. The period is as follows: taking 60min as an operation period, operating for 50min in each period, and stopping for 10 min. The ball milling treatment steps are as follows: mixing magnesium hydride and a filler, placing the mixture into a ball milling tank, and ball milling for 40 hours at the rotating speed of 250r/min under the protection of argon, wherein the mass ratio of ball materials is 20: 1, the diameter of a small ball is 8 mm. The hydrogen absorption and desorption treatment steps are as follows: the mixed material is placed in a reaction tube and is subjected to hydrogen absorption and desorption treatment for 3 hours at the temperature of 370 ℃.
Example 2
Uniformly mixing a molecular sieve and a ferrous sulfate solution with the mass fraction of 2%, standing for 1 day, taking out, naturally drying at room temperature to obtain a pretreated molecular sieve, placing the pretreated molecular sieve in a chemical vapor deposition furnace for deposition treatment to obtain a blank, performing heat treatment on the blank, and cooling to room temperature to obtain a base material; sputtering to form a film on the surface of the matrix to obtain the filler; mixing magnesium hydride and a filler, placing the mixture into a ball milling tank, and carrying out ball milling treatment according to a period to obtain a mixed material; and (3) placing the mixed material in a reaction tube, carrying out hydrogen absorption and desorption treatment, and cooling to room temperature to obtain the magnesium-based nano composite hydrogen storage material. The mass ratio of the molecular sieve to the ferrous sulfate solution with the mass fraction of 2 percent is 1: 10. The deposition treatment steps are as follows: and (3) placing the pretreated molecular sieve in a chemical vapor deposition furnace, taking propylene as a carbon source, and depositing for 2 hours at the temperature of 910 ℃ under the argon atmosphere, wherein the gas flow is 9L/h. The heat treatment step is as follows: and (3) placing the blank at 2450 ℃ for heat treatment for 1 h. The sputtering film-forming step is as follows: rare earth lanthanum is used as a target material, hydrogen is used as a reaction gas, argon is used as a sputtering gas, a film is formed on the surface of a substrate in a sputtering mode, the sputtering temperature is 250 ℃, the sputtering power is 130W, the deposition time is 15s, and the distance between the target material and the substrate is 28 cm. The ratio between magnesium hydride and filler is 1: 1, respectively. The period is as follows: taking 60min as an operation period, operating for 50min in each period, and stopping for 10 min. The ball milling treatment steps are as follows: magnesium hydride and filler are mixed and placed in a ball milling tank, under the protection of argon, the mass ratio of ball materials is 20: 1, the diameter of a small ball is 9mm, and ball milling is carried out for 41 hours at the rotating speed of 275 r/min. The hydrogen absorption and desorption treatment steps are as follows: placing the mixed material in a reaction tube, and performing hydrogen absorption and desorption treatment for 3h at the temperature of 375 ℃.
Example 3
Uniformly mixing a molecular sieve and a ferrous sulfate solution with the mass fraction of 2%, standing for 2 days, taking out, naturally drying at room temperature to obtain a pretreated molecular sieve, placing the pretreated molecular sieve in a chemical vapor deposition furnace for deposition treatment to obtain a blank, performing heat treatment on the blank, and cooling to room temperature to obtain a base material; sputtering to form a film on the surface of the matrix to obtain the filler; mixing magnesium hydride and a filler, placing the mixture into a ball milling tank, and carrying out ball milling treatment according to a period to obtain a mixed material; and (3) placing the mixed material in a reaction tube, carrying out hydrogen absorption and desorption treatment, and cooling to room temperature to obtain the magnesium-based nano composite hydrogen storage material. The mass ratio of the molecular sieve to the ferrous sulfate solution with the mass fraction of 2 percent is 1: 10. The deposition treatment steps are as follows: and (3) placing the pretreated molecular sieve in a chemical vapor deposition furnace, taking propylene as a carbon source, and depositing for 3 hours at the temperature of 920 ℃ under the argon atmosphere, wherein the gas flow is 12L/h. The heat treatment step is as follows: and (3) placing the blank body at the temperature of 2500 ℃ for heat treatment for 2 h. The sputtering film-forming step is as follows: rare earth lanthanum is used as a target material, hydrogen is used as a reaction gas, argon is used as a sputtering gas, a film is formed on the surface of a substrate in a sputtering mode, the sputtering temperature is 300 ℃, the sputtering power is 200W, the deposition time is 20s, and the distance between the target material and the substrate is 30 cm. The ratio between magnesium hydride and filler is 1: 1, respectively. The period is as follows: taking 60min as an operation period, operating for 50min in each period, and stopping for 10 min. The ball milling treatment steps are as follows: mixing magnesium hydride and a filler, placing the mixture into a ball milling tank, and ball milling for 42 hours at the rotating speed of 300r/min under the protection of argon, wherein the mass ratio of ball materials is 20: 1, the diameter of a small ball is 10 mm. The hydrogen absorption and desorption treatment steps are as follows: placing the mixed material in a reaction tube, and performing hydrogen absorption and desorption treatment for 4 hours at the temperature of 380 ℃.
Comparative example: a magnesium-based nano-composite hydrogen storage material produced by Dongguan company.
The magnesium-based nano-composite hydrogen storage material prepared in the examples and the comparative examples is detected as follows:
hydrogen desorption activation energy is another important index for measuring hydrogen storage alloys. Under the condition of different temperature rising speeds, the DSC curve of the hydrogenated nano Mg has only one narrow symmetrical endothermic peak, which shows that the hydrogen releasing process is completed in one step and is formed by MgH2→ Mg. The heating rate is 3 ℃/min, the heating rate is 5 ℃/min, and the DSC curve peak temperature of 10 ℃/min is 332.7 ℃, 340.8 ℃ and 352.9 ℃. From the DSC curve with a temperature rise rate of 3 ℃/min, the initial hydrogen desorption temperature of the nano Mg after hydrogenation is 311.1 ℃. Study of MgH2Influence of particle size on its Hydrogen evolving Properties, commercial MgH2The initial hydrogen release temperature of the ball mill is higher than 400 ℃, and after the ball mill is used for 100 hours, the initial hydrogen release temperature is reduced to 340 ℃. Carbon gel supported nano MgH prepared by nano confinement method2The initial hydrogen evolution temperature under the same conditions was 358.7 ℃. MgH prepared by ball milling method2And carbon gel loaded nano MgH by nano confinement method2Compared with the prior art, the hydrogenated nano Mg has better hydrogen releasing performance.
The particle size of the hydrogen storage material prepared by the invention is reduced in the ball milling process, and GNS can stably exist before and after hydrogen absorption and desorption cycles. The reduction of the grain size of the material in the ball milling process can promote the hydrogen absorption and desorption dynamic performance of the material, GNS with high surface area and porosity is broken in the ball milling process and is uniformly distributed in the hydrogen storage material in a disordered and irregular shape, the agglomeration of the particles of the material in the hydrogen absorption and desorption process can be prevented, and in addition, a large number of defect vacancies and active site pairs promote H2Plays an important role in dissociation and diffusion. Therefore, the composite hydrogen storage material prepared by the invention has excellent hydrogen absorption and desorption propertiesCan be used for stabilizing the hydrogen absorption and desorption circulation.

Claims (9)

1. A method for preparing magnesium-based nano composite hydrogen storage material is characterized by comprising the following specific preparation steps:
(1) uniformly mixing a molecular sieve and a ferrous sulfate solution with the mass fraction of 2%, standing for 1-2 days, taking out, naturally drying at room temperature to obtain a pretreated molecular sieve, placing the pretreated molecular sieve in a chemical vapor deposition furnace for deposition treatment to obtain a blank, performing heat treatment on the blank, and cooling to room temperature to obtain a base material;
(2) sputtering to form a film on the surface of the matrix to obtain the filler;
(3) mixing magnesium hydride and a filler, placing the mixture into a ball milling tank, and carrying out ball milling treatment according to a period to obtain a mixed material;
(4) and (3) placing the mixed material in a reaction tube, carrying out hydrogen absorption and desorption treatment, and cooling to room temperature to obtain the magnesium-based nano composite hydrogen storage material.
2. The method of claim 1, wherein the magnesium-based nanocomposite hydrogen storage material comprises: the mass ratio of the molecular sieve in the step (1) to the ferrous sulfate solution with the mass fraction of 2 percent is 1: 10.
3. The method of claim 1, wherein the magnesium-based nanocomposite hydrogen storage material comprises: the deposition treatment step in the step (1) is as follows: and (3) placing the pretreated molecular sieve in a chemical vapor deposition furnace, taking propylene as a carbon source, and depositing for 2-3 hours at the temperature of 900-920 ℃ in an argon atmosphere, wherein the gas flow is 6-12L/h.
4. The method of claim 1, wherein the magnesium-based nanocomposite hydrogen storage material comprises: the heat treatment step in the step (1) is as follows: and (3) placing the blank body at 2400-2500 ℃ for heat treatment for 1-2 h.
5. The method of claim 1, wherein the magnesium-based nanocomposite hydrogen storage material comprises: the sputtering film forming step in the step (2) is as follows: rare earth lanthanum is used as a target material, hydrogen is used as a reaction gas, argon is used as a sputtering gas, a film is formed on the surface of a substrate in a sputtering mode, the sputtering temperature is 200-300 ℃, the sputtering power is 60-200W, the deposition time is 10-20 s, and the distance between the target material and the substrate is 25-30 cm.
6. The method of claim 1, wherein the magnesium-based nanocomposite hydrogen storage material comprises: the ratio of the magnesium hydride to the filler in the step (3) is 1: 1 respectively.
7. The method of claim 1, wherein the magnesium-based nanocomposite hydrogen storage material comprises: the period of the step (3) is as follows: taking 60min as an operation period, operating for 50min in each period, and stopping for 10 min.
8. The method of claim 1, wherein the magnesium-based nanocomposite hydrogen storage material comprises: the ball milling treatment step in the step (3) is as follows: mixing magnesium hydride and a filler, placing the mixture into a ball milling tank, and ball milling for 40-42 h at the rotating speed of 250-300 r/min under the protection of argon, wherein the mass ratio of ball materials is 20: 1, the diameter of a small ball is 8-10 mm.
9. The method of claim 1, wherein the magnesium-based nanocomposite hydrogen storage material comprises: the hydrogen absorption and desorption treatment step in the step (4) is as follows: and (3) placing the mixed material in a reaction tube, and performing hydrogen absorption and desorption treatment for 3-4 hours at the temperature of 370-380 ℃.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112609102A (en) * 2020-12-09 2021-04-06 浙江大学 Preparation method of magnesium-based hydrogen storage material coated by rare earth oxide and nano nickel-boron
CN114952203A (en) * 2022-06-28 2022-08-30 重庆大学 Magnesium-based alloy-molecular sieve composite hydrogen storage material and preparation method thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112609102A (en) * 2020-12-09 2021-04-06 浙江大学 Preparation method of magnesium-based hydrogen storage material coated by rare earth oxide and nano nickel-boron
CN112609102B (en) * 2020-12-09 2021-09-10 浙江大学 Preparation method of magnesium-based hydrogen storage material coated by rare earth oxide and nano nickel-boron
CN114952203A (en) * 2022-06-28 2022-08-30 重庆大学 Magnesium-based alloy-molecular sieve composite hydrogen storage material and preparation method thereof
CN114952203B (en) * 2022-06-28 2024-02-20 重庆大学 Magnesium-based alloy-molecular sieve composite hydrogen storage material and preparation method thereof

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