CN109972010B - Nano magnesium-based composite hydrogen storage material and preparation method thereof - Google Patents
Nano magnesium-based composite hydrogen storage material and preparation method thereof Download PDFInfo
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- C22C1/00—Making non-ferrous alloys
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/383—Hydrogen absorbing alloys
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Abstract
The invention relates to a nano magnesium-based composite hydrogen storage material and a preparation method thereof. The main component of the material is magnesium, and the material also comprises multiple catalysts of mixed rare earth, carbonyl nickel powder and graphite so as to improve the low-temperature hydrogen absorption performance of the material. The material has a nano-crystal structure, the grain size is 20-50 nanometers, and the material has excellent low-temperature hydrogen absorption dynamic performance. In the preparation method, firstly, pure magnesium and a certain amount of mixed rare earth are subjected to vacuum smelting by adopting a vacuum induction smelting method to prepare a brittle magnesium-rare earth alloy ingot with magnesium in-situ doped with rare earth elements; and then mixing the obtained alloy with carbonyl nickel powder, graphite powder and an inert organic grinding aid, and further preparing the high-capacity magnesium-based composite hydrogen storage material by a mechanical ball milling method. The preparation method of the material overcomes the wall adhesion phenomenon in the mechanical ball milling process of the magnesium-based hydrogen storage alloy, improves the recovery rate of the material, and obtains the high-capacity magnesium-based composite hydrogen storage material with excellent low-temperature hydrogen absorption performance.
Description
Technical Field
The invention belongs to the technical field of hydrogen storage materials, and particularly relates to a high-capacity magnesium-based hydrogen storage material with excellent low-temperature hydrogen absorption dynamic performance and a preparation method thereof.
Background
Hydrogen energy is regarded as the most potential energy source material for development as an ideal secondary energy source which is clean, efficient, abundant in reserves and sustainable, and has attracted wide attention worldwide. The safe and efficient hydrogen storage technology is one of the key links in the hydrogen energy utilization process. The metal hydride method has advantages of high volume density, good reversibility, high safety, etc., and is considered to be the most desirable hydrogen storage material. The reversible hydrogen storage capacity of magnesium is as high as 7.6 wt.%, and the magnesium also has the advantages of rich resources, low price, environmental protection and the like, thereby having great application prospect. Although magnesium as a hydrogen storage material meets many practical conditions, it has not been applicable to mobile hydrogen storage systems, particularly vehicle-mounted fuel cell hydrogen supply devices. This is mainly due to the poor thermodynamic properties of pure magnesium hydrogen storage, and the hydrogenation and dehydrogenation processes need to be carried out at temperatures above 300 ℃. In addition, the reaction rate of hydrogen absorption and desorption of pure magnesium is very slow and cannot meet the requirement.
Mechanical ball milling is one of effective methods for improving the hydrogen storage performance of the magnesium-based material, and the material obtained by the ball milling method has obviously reduced grain diameter and increased surface activity. The shearing, grinding and extrusion effects in the ball milling process cause a large number of defects in the material, even cause the phase composition and the crystal structure of the material to be changed, thereby influencing the physical and chemical properties of the material. Patent CN100358624 discloses a method for preparing magnesium/graphite composite hydrogen storage material by high energy ball milling in hydrogen atmosphere, the grain size of the obtained magnesium-based material is 70-100nm, although the hydrogen storage performance of magnesium is improved to a great extent, the reaction temperature is still very high. Patent CN102418018 also discloses a method for preparing magnesium/carbon-supported nickel hydrogen storage alloy powder, which has better hydrogen absorption dynamic characteristics at 100 ℃. However, the preparation process of the material is extremely complex, and the production process is difficult.
Another unique advantage of mechanical ball milling is that materials in almost any state can be compounded, including solids and solids, solids and liquids, and solids and gases, which have widely different physical properties. However, magnesium has certain plasticity and toughness, and can adhere to the grinding balls and the tank walls in the mechanical ball milling process, so that the material composition is not uniform. Therefore, the method has great significance for improving the wall adhesion phenomenon in the ball milling process of the magnesium-based alloy material.
Disclosure of Invention
The invention aims to provide a high-capacity magnesium-based composite hydrogen storage material combining mechanical ball milling and multiple catalysts for concerted catalysis and a preparation method thereof aiming at the defects in the prior art. The material takes magnesium as a main hydrogen absorption phase, comprises catalysts of mixed rare earth, carbonyl nickel powder and graphite, and auxiliary agents in the preparation process are volatile inert organic solvents. The preparation method comprises the following steps: firstly, carrying out vacuum smelting on pure magnesium and a certain amount of mixed rare earth by adopting a vacuum induction smelting method to prepare a brittle magnesium-rare earth alloy ingot with magnesium in situ doped with rare earth elements; then mixing the obtained alloy with carbonyl nickel powder, graphite powder and an inert organic grinding aid in a certain proportion, and further preparing a composite material by a mechanical ball milling method; and finally, removing the organic liquid grinding aid under the vacuum condition to obtain the high-capacity magnesium-based composite hydrogen storage material. The method successfully overcomes the phenomenon of material wall adhesion in the mechanical ball milling process, and can obtain the magnesium-based composite hydrogen storage material with a multiphase concerted catalysis and a nanocrystal structure, thereby greatly improving the hydrogen absorption kinetic properties of the magnesium-based hydrogen storage material. The composite hydrogen storage material provided by the invention can rapidly absorb hydrogen at 100 ℃, thereby meeting the practical requirement.
The technical scheme of the invention is as follows:
a nanometer magnesium-based composite hydrogen storage material is prepared by taking magnesium as a main component, performing concerted catalysis on multiple materials including mixed rare earth, nickel carbonyl powder and graphite, and has a nanometer crystal structure, wherein the grain size is 20-50 nanometers; and has excellent low-temperature hydrogen absorption dynamic performance; wherein, the mixed rare earth accounts for 10-15% of the mass of the pure magnesium, the carbonyl nickel powder accounts for 3-10% of the total mass of the magnesium and the rare earth, and the graphite accounts for 3-5% of the total mass of the magnesium and the rare earth.
The magnesium-based composite hydrogen storage material has excellent low-temperature hydrogen absorption dynamic performance, and can absorb 5-6.5wt% of hydrogen within 30 seconds under the conditions of 100 ℃ and 3MPa of hydrogen pressure.
The preparation method of the magnesium-based composite hydrogen storage material comprises the following main steps:
a. preparing a brittle magnesium-rare earth alloy ingot by using magnesium and mixed rare earth metal as raw materials and adopting a vacuum induction melting method; wherein the back bottom vacuum of the smelting furnace is 2.0 multiplied by 10-2Pa, the protective gas is high-purity argon with the pressure of 0.04-0.06MPa, the power of an induction coil during vacuum melting is 8-10kW, and the heat preservation time of a melt is 10-15 minutes; casting into cast ingots after smelting is finished; the mixed rare earth is magnesium in mass-10-15% of the mass fraction of rare earth alloy;
b. mechanically crushing the obtained magnesium-rare earth alloy ingot into alloy powder with the granularity of less than 100 meshes, uniformly mixing the alloy powder with carbonyl nickel powder, graphite powder and an organic liquid grinding aid, and grinding for 5-10 hours by using a planetary mechanical ball mill;
wherein, the mass of the carbonyl nickel powder is 3-10% of that of the magnesium-rare earth alloy powder; the mass of the graphite powder is 3-5% of that of the magnesium-rare earth alloy powder; the mass of the organic liquid grinding aid is 50-100% of that of the magnesium-rare earth alloy powder;
c. and (4) drying the ball-milled mixed material at room temperature in vacuum to obtain the magnesium-based composite hydrogen storage material.
The mixed rare earth contains lanthanum, cerium, praseodymium, neodymium, samarium, other small amount of rare earth elements and a very small amount of impurity elements, and the total content of the rare earth elements is more than 99.5 percent.
The nickel carbonyl powder is superfine nickel powder obtained by reducing nickel carbonyl, and the particle size range is 0.5-1 micron.
The organic liquid grinding aid can be one or more of ethanol, cyclohexane, hexane, n-heptane, benzene, toluene and tetrahydrofuran.
The purity of the high-purity argon gas is 99.999 Vol.%.
The preparation method of the magnesium-based composite hydrogen storage material basically does not have the phenomenon of wall adhesion of the material in the mechanical ball milling process.
The invention has the substantive characteristics that:
the invention uses the mixed rare earth in the preparation of the high-capacity magnesium-based hydrogen storage material, not only improves the ball milling efficiency and overcomes the wall adhesion phenomenon by smelting the mixed rare earth and magnesium to form brittle alloy, but also plays a role in nano-phase catalysis in the hydrogen absorption and desorption process and improves the low-temperature hydrogen absorption performance of the material.
The invention has the beneficial effects that:
1) the brittle magnesium-rare earth alloy is used as a raw material for mechanical ball milling, and graphite powder is added in the ball milling process, so that the ball milling efficiency is improved, the wall sticking effect in the ball milling process is overcome, and the recovery rate of a sample is basically higher than 90 percent and can reach 99 percent at most; 2) the synergistic catalytic action of the rare earth element, the graphite and the carbonyl nickel powder greatly improves the reversible hydrogen storage property of the magnesium, so that the material can rapidly absorb hydrogen at 100 ℃, the performance of the material is superior to that of the existing published literature, and the material has good application prospect in the aspect of a metal hydride hydrogen storage system for a fuel cell automobile.
Drawings
FIG. 1 is an SEM micrograph of a hydrogen storage material obtained in example 1 of the present invention.
FIG. 2 is an SEM micrograph of a hydrogen storage material obtained in example 3 of the present invention.
FIG. 3 is a TEM micrograph of the hydrogen storage material obtained in example 4 of the present invention after hydrogen absorption.
FIG. 4 is an SEM micrograph of a hydrogen storage material obtained in example 5 of the present invention.
FIG. 5 is a graph showing hydrogen absorption kinetics at different temperatures of the hydrogen storage material obtained in example 1 of the present invention.
FIG. 6 is a graph showing hydrogen absorption kinetics at different temperatures of the hydrogen storage material obtained in example 2 of the present invention.
FIG. 7 is a graph showing hydrogen absorption kinetics at different temperatures of the hydrogen storage material obtained in example 3 of the present invention.
FIG. 8 is a graph showing hydrogen absorption kinetics at different temperatures of the hydrogen storage material obtained in example 4 of the present invention.
FIG. 9 is a graph showing hydrogen absorption kinetics at different temperatures of the hydrogen storage material obtained in example 5 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples.
The nickel carbonyl powder is a known material, and refers to ultrafine nickel powder obtained by reducing nickel carbonyl, and the particle size range of the nickel carbonyl powder used in the embodiment of the invention is 0.5-1 micron.
The mixed rare earth is a known material, is a rare earth metal mixture obtained by purifying and smelting natural rare earth ores in nature, and comprises lanthanum, cerium, praseodymium, neodymium, samarium and other rare earth elements and impurity elements with a small amount, wherein the total content of the rare earth elements is more than 99.5 percent, and the proportion of each rare earth element is slightly different with the production place and the batch, but the use effect of the invention is not influenced; the following examples relate to mischmetal from Baotou rare earth research institute (CAS: 62379-61-7), but the present invention is not limited thereto.
Example 1
1kg of pure magnesium ingot (the purity is more than 99 percent) and 0.15kg of mixed rare earth metal (15 weight percent) are put into a magnesia crucible of a vacuum induction melting furnace and vacuumized to 2.0 multiplied by 10-2Below Pa, then high purity argon (purity 99.999 Vol.%) is fed at a pressure of 0.04-0.06 MPa. Adjusting the power of the medium-frequency induction coil to 8-10kW, heating the metal raw materials, and continuing to keep the temperature for 10-15 minutes after all metal blocks are completely melted to homogenize the components of the alloy. And after the smelting is finished, casting the alloy melt into a circular cast ingot with the diameter of 30mm in a cast iron mould, and cooling to room temperature to obtain the magnesium-rare earth alloy ingot. Mechanically crushing an alloy ingot, sieving the crushed alloy ingot by a standard sieve of 100 meshes, putting 5g of magnesium-rare earth alloy powder, 0.25g (5 wt%) of nickel carbonyl powder, 0.15g (3 wt%) of graphite powder and 5g (100 wt%) of organic liquid grinding aid tetrahydrofuran into a 300ml stainless steel vacuum ball-milling tank, putting an agate grinding ball, vacuumizing, and filling high-purity argon of 0.15MPa as protective gas. The ball-material ratio adopted in the embodiment of the invention is 20:1, the rotating speed of the ball mill is 350r/min, and the ball milling time is 10 hours. And (3) placing the ball-milled material in a vacuum drying oven, and performing vacuum drying at room temperature for more than 2 hours to obtain the magnesium-based hydrogen storage material. The degree of wall sticking of the material is measured in terms of sample recovery, i.e. the mass of the recovered solid sample as a percentage of the mass of the input solid raw material. The recovery rate can reflect the wall sticking phenomenon of the material in the ball milling process, and the lower the recovery rate of the sample is, the more remarkable the wall sticking effect of the material in the ball milling process is, and the more adverse to the preparation of the material is. The material recovery in this example was about 88%.
The microstructure of the composite material was observed by SEM and the material was found to be composed of large particles of 10-50 microns size agglomerated from small particles, as shown in FIG. 1. The added nickel carbonyl powder and graphite are uniformly dispersed in the material matrix under the action of mechanical ball milling to form the composite material. The material is subjected to 5 times of activation hydrogen absorption and desorption treatments at 300 ℃ by using Sieverts equipment, and after the dynamic performance is stable, the isothermal hydrogen absorption curve of the material is tested, the initial hydrogen pressure is 3MPa, and the test temperatures are respectively 300 ℃, 200 ℃ and 100 ℃, and the result is shown in figure 5. It can be seen that the saturated hydrogen absorption of the material after 5 minutes at 300 ℃ was 5.9 wt%. The temperature is reduced, the hydrogen absorption dynamic performance of the material is greatly improved, the hydrogen absorption amount of the material in 30 seconds can reach 5.7 wt% under the condition of 100 ℃, and the material shows excellent low-temperature hydrogen absorption dynamic characteristics.
Example 2
The other steps of the material preparation method in this example are the same as those in example 1, except that the ball milling time is 5 hours, the carbonyl nickel powder in the ball milling process is 0.5g (10 wt%), the graphite powder is 0.25g (5 wt%), the grinding aid is ethanol, and the addition amount of the grinding aid is 2.5g (50 wt%).
No obvious wall sticking phenomenon is found in the ball-milled material, and the material recovery rate is about 94%. The hydrogen absorption kinetic curve of the composite material after 5 times of hydrogen absorption and desorption activation is shown in figure 6. It can be seen that the saturated hydrogen uptake of the material after 5 minutes at 300 ℃ is about 5.2 wt%, which is slightly lower than that of example 1. The material has good hydrogen absorption dynamic property at 100 ℃, and the hydrogen absorption amount in 30 seconds can reach more than 5 wt%.
Example 3
The other steps of the material preparation method in the embodiment are the same as those of the embodiment 1, except that the addition amount of the rare earth in the alloy smelting process is 0.1kg (10 wt%), the mass of the nickel carbonyl powder in the ball milling process is 0.15g (3 wt%), the mass of the graphite powder is 0.05g (1 wt%), and the grinding aid is n-heptane.
The material after ball milling has obvious wall sticking phenomenon, and the recovery rate of the sample is about 68 percent. The SEM microstructure of the composite material of the embodiment is shown in figure 2, and the material is also formed by clustering fine particles, and the particle size of large particles is 10-70 microns. The hydrogen absorption kinetic curve of the material after 5 times of hydrogen absorption and desorption activation is shown in the attached figure 7. It can be seen that the saturated hydrogen absorption amount of the material after 5 minutes at 300 ℃ is about 6.3 wt%, but the hydrogen absorption kinetic performance of the material at 100 ℃ is not obviously improved, and the hydrogen absorption rate is far lower than that of the material in examples 1 and 2, because the content of graphite powder in the embodiment is low, the material components after ball milling are not uniform enough, the carbonyl nickel powder is not uniformly dispersed in the alloy, and the catalytic effect is limited.
Example 4
The other steps of the material preparation method in the embodiment are the same as those of the embodiment 1, except that the addition amount of the rare earth is 0.1kg (10 wt%) and the grinding aid is cyclohexane in the alloy smelting process.
No obvious wall sticking phenomenon is found in the ball-milled material, and the material recovery rate is about 93%. The TEM microstructure of the material of the embodiment after 5 times of hydrogen activation and desorption cycles is shown in figure 3, and the material is seen to be composed of 20-50 nm crystal grains and is integrally represented as a nanocrystalline structure. The hydrogen absorption kinetic curve of the material after 5 times of hydrogen absorption and desorption activation is shown in the attached figure 8. It can be seen that the saturated hydrogen absorption of the material after 5 minutes at 300 c is about 6.1 wt%. The magnesium-based composite material obtained by the embodiment has excellent hydrogen absorption dynamic performance at 100 ℃, and the hydrogen absorption amount can reach more than 6 wt% within 30 seconds.
Example 5
The other steps of the material preparation method in the embodiment are the same as those of the embodiment 1, except that the addition amount of the rare earth is 0.1kg (10 wt%) in the alloy smelting process, the mass of the graphite powder is 0.5g (10 wt%), and the grinding aid is cyclohexane.
The material after ball milling has no wall sticking phenomenon at all, and the recovery rate of the material is 99 percent. The SEM microstructure of the composite material of this example is shown in FIG. 4, and it can be seen that the material is composed of coarse particles with graphite powder distributed between the alloy particles. The over-lubrication effect produced by the higher graphite powder content causes the ball milling efficiency to drop sharply, and the added nickel hardly enters the interior of the alloy. The hydrogen absorption kinetic curve of the composite material after 5 times of hydrogen absorption and desorption activation is shown in figure 9. It can be seen that the saturated hydrogen absorption of the material after 10 minutes at 300 c is about 5.6 wt%. The mg-based composite material in this example has poor kinetic properties at a lower temperature, and the hydrogen absorption amount after 10 minutes at 100 c is only 2.8 wt%. Therefore, the hydrogen absorption dynamic characteristics of the material are not improved due to the higher addition amount of the graphite.
According to the invention, the alloy smelting is carried out by selecting the mixed rare earth element and magnesium, on one hand, the magnesium and the rare earth element form an intermetallic compound after vacuum induction smelting, the brittleness of the magnesium-based alloy is improved, and the crushing efficiency and the wall adhesion phenomenon of the material in the ball milling process can be improved; on the other hand, the rare earth element in the composite material is in-situ precipitated into a secondary phase of the nanometer rare earth hydride in the hydrogenation process, and the secondary phase can be used as a catalyst to improve the hydrogen storage performance of magnesium. Small amounts of rare earth elements do not cause the alloy to form brittle phases, and too much rare earth elements can reduce the reversible hydrogen storage capacity of the material. Through a plurality of experiments, the alloying of 10-15 wt% of the mixed rare earth and the magnesium has the optimal comprehensive performance. The lubricating effect of the graphite can improve the wall adhesion phenomenon in the ball milling process, improve the contact effect of the carbonyl nickel powder and the alloy matrix, promote the dispersion effect of the nickel in the alloy matrix and further improve the catalytic efficiency of the nickel in the hydrogen absorption and desorption reaction process of the material. However, excessive graphite produces excessive lubrication during ball milling, for example, the graphite content in example 5 is 10 wt%, which reduces the ball milling efficiency and is not favorable for increasing the hydrogen absorption rate and reversible hydrogen storage capacity of the material. By comparing the results of the above examples, it is believed that the material formulation provided in example 4 has the best overall hydrogen absorption properties.
The invention is not the best known technology.
Claims (6)
1. A nanometer magnesium-based composite hydrogen storage material is characterized in that the main component of the material is magnesium, the material comprises multiple catalysts of mixed rare earth, carbonyl nickel powder and graphite, the material has a nanocrystal structure, the grain size of the material is 20-50 nanometers, and the material has excellent low-temperature hydrogen absorption dynamic performance; wherein, the mixed rare earth accounts for 10-15% of the pure magnesium, the carbonyl nickel powder accounts for 3-10% of the total mass of the magnesium-rare earth, and the graphite accounts for 3-5% of the total mass of the magnesium-rare earth;
the preparation method of the magnesium-based composite hydrogen storage material comprises the following main steps:
a. magnesium and mixed rare earth metal are used as raw materials, and vacuum induction melting is adoptedPreparing a brittle magnesium-rare earth alloy ingot by a smelting method; wherein the back bottom vacuum of the smelting furnace is 2.0 multiplied by 10−2Pa, the protective gas is high-purity argon with the pressure of 0.04-0.06MPa, the power of an induction coil during vacuum melting is 8-10kW, and the heat preservation time of a melt is 10-15 minutes; casting into cast ingots after smelting is finished; the mass of the mixed rare earth is 10-15% of the mass fraction of the magnesium-rare earth alloy;
b. mechanically crushing the magnesium-rare earth alloy ingot into alloy powder with the granularity of less than 100 meshes, uniformly mixing the alloy powder with carbonyl nickel powder, graphite powder and an organic liquid grinding aid, and grinding for 5-10 hours by using a planetary mechanical ball mill;
wherein, the mass of the carbonyl nickel powder is 3-10% of that of the magnesium-rare earth alloy powder; the mass of the graphite powder is 3-5% of that of the magnesium-rare earth alloy powder; the mass of the organic liquid grinding aid is 50-100% of that of the magnesium-rare earth alloy powder;
c. and (3) drying the mixed material subjected to mechanical ball milling in vacuum at room temperature to obtain the magnesium-based composite hydrogen storage material.
2. The nano magnesium-based composite hydrogen storage material as claimed in claim 1, wherein the magnesium-based composite hydrogen storage material has excellent low temperature hydrogen absorption kinetics of 5-6.5wt% hydrogen absorption within 30 seconds at 100 ℃ and 3MPa hydrogen pressure.
3. The nano magnesium-based composite hydrogen storage material of claim 1, wherein the mixed rare earth comprises lanthanum, cerium, praseodymium, neodymium, samarium and other minor rare earth elements and a very small amount of impurity elements, and the total content of the rare earth elements is more than 99.5%.
4. The magnesium-based composite hydrogen storage material as claimed in claim 1, wherein in the preparation method, the particle size of said nickel carbonyl powder is in the range of 0.5-1 μm.
5. The Mg-based composite hydrogen storage material as claimed in claim 4, wherein in the preparation method, the organic liquid grinding aid is one or more of ethanol, hexane, n-heptane, benzene, toluene and tetrahydrofuran.
6. The magnesium-based composite hydrogen storage material as claimed in claim 4, wherein in the preparation method, the purity of the high purity argon gas is 99.999 Vol.%.
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| 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 |
| CN112961996B (en) * | 2021-02-01 | 2022-05-03 | 中国科学院江西稀土研究院 | Rare earth hydrogen storage alloy and preparation method and application thereof |
| CN113104811A (en) * | 2021-03-25 | 2021-07-13 | 太原科技大学 | Transition metal-N/C composite magnesium-based hydrogen storage material and preparation method thereof |
| CN114411028B (en) * | 2022-01-21 | 2022-09-20 | 徐州工程学院 | Trace nickel composite layered magnesium composite material and preparation method and application thereof |
| CN114507798B (en) * | 2022-02-18 | 2022-07-15 | 广东省科学院新材料研究所 | Magnesium-based hydrogen storage alloy block and preparation method thereof |
| CN115595482A (en) * | 2022-10-25 | 2023-01-13 | 云南电网有限责任公司电力科学研究院（Cn） | Magnesium-based hydrogen storage material and preparation method thereof |
| TWI838186B (en) * | 2023-03-24 | 2024-04-01 | 純萃材料股份有限公司 | Gas storage structure and gas storage device |
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| CN102277508A (en) * | 2011-08-09 | 2011-12-14 | 安泰科技股份有限公司 | Preparation method of magnesium-based hydrogen storage alloy |
| CN103952647A (en) * | 2011-08-09 | 2014-07-30 | 安泰科技股份有限公司 | Magnesium base hydrogen storage nanometer.amorphous alloy preparation method |
| CN103317128A (en) * | 2013-05-27 | 2013-09-25 | 西北工业大学 | Mg-Ni-La based composite hydrogen-storage alloy powder and preparation process thereof |
| CN105274395A (en) * | 2014-07-24 | 2016-01-27 | 北京有色金属研究总院 | La-Mg-Ni hydrogen storage material |
| CN105063457A (en) * | 2015-09-02 | 2015-11-18 | 微山钢研稀土材料有限公司 | Nano-graphite compounded high-capacity RE-Mg-Ni-based hydrogen storage material and preparation method thereof |
| CN105316501A (en) * | 2015-11-12 | 2016-02-10 | 国网智能电网研究院 | Rare earth-magnesium-based hydrogen storage alloy and preparation method thereof |
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