CN109972010A - A kind of nano Mg base composite hydrogen storage material and preparation method - Google Patents
A kind of nano Mg base composite hydrogen storage material and preparation method Download PDFInfo
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- CN109972010A CN109972010A CN201910297922.6A CN201910297922A CN109972010A CN 109972010 A CN109972010 A CN 109972010A CN 201910297922 A CN201910297922 A CN 201910297922A CN 109972010 A CN109972010 A CN 109972010A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
- C22C23/06—Alloys based on magnesium with a rare earth metal as the next major constituent
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/383—Hydrogen absorbing alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/46—Alloys based on magnesium or aluminium
- H01M4/466—Magnesium based
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- 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
- Y02E60/10—Energy storage using batteries
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Abstract
The present invention is a kind of nano Mg base composite hydrogen storage material and preparation method thereof.Material main component is magnesium, while including mischmetal, carbonyl nickel powder and graphite multiple catalysts, to promote its low temperature hydrogen sucking function.The material has nanocrystalline structure, and crystallite dimension is 20-50 nanometers, and inhales hydrogen dynamic performance with excellent low temperature.In preparation method, pure magnesium and a certain amount of mischmetal are carried out by vacuum metling using vacuum induction melting method first, prepare the brittleness magnesium-rare earth ingot of magnesium rare earth doped element in situ；Then obtained alloy is mixed with carbonyl nickel powder, graphite powder, inertia Organic Grinding Aid, high capacity Mg-based composite hydrogen storage material is further prepared by mechanical ball mill method.The material preparation method overcomes the wall sticking phenomenon in Mg base hydrogen bearing alloy Mechanical Milling Process, improves material yield rate, and has obtained the excellent high capacity Mg-based composite hydrogen storage material of low temperature hydrogen sucking function.
Description
Technical field
The invention belongs to hydrogen storage material technical field, in particular to a kind of low temperature inhales the excellent high capacity of hydrogen dynamic performance
Magnesium-base hydrogen storage material and preparation method.
Background technique
Hydrogen Energy is considered as most development potentiality as a kind of clean and effective, rich reserves, sustainable ideal secondary energy sources
Energy and material, obtain worldwide extensive concern.During safe and efficient hydrogen storage technology is the key that hydrogen utilization
One of link.Metal hydride method hydrogen storage has many advantages, such as bulk density height, good reversibility, highly-safe, it is considered to be most
Has desired hydrogen storage material.The reversible hydrogen storage capacity of magnesium is up to 7.6wt.%, furthermore magnesium also have it is resourceful, cheap,
Advantages of environment protection, great application prospect.Although magnesium meets many Practical Conditions as hydrogen storage material, can't apply
In mobile hydrogen storage system, especially on-vehicle fuel hydrogen supply device.This is mainly due to pure magnesium hydrogen storage thermodynamic property is poor,
Hydrogenation and certain embodiments needs carry out under conditions of 300 DEG C or more.In addition, the suction hydrogen discharge reaction rate of pure magnesium is extremely slow,
It is unable to satisfy requirement.
Mechanical ball mill is one of the effective ways for improving mg-based material hydrogen storage property, the material grain obtained by ball grinding method
Diameter is obviously reduced, and surface-active increases.Shearing, grinding and squeezing action in mechanical milling process make material internal generate a large amount of lack
It falls into, even more so that the phase composition of material and crystal structure change, to influence the physics and chemical property of material.Patent
CN100358624 discloses one kind and prepares magnesium/graphite composite hydrogen storage material method using high-energy ball milling in a hydrogen atmosphere, obtains
The mg-based material crystallite dimension arrived be 70-100nm, although largely improving the hydrogen storage property of magnesium, reaction temperature according to
It is so very high.Patent CN102418018 also discloses a kind of magnesium/carbon load nickel hydrogen-bearing alloy powder preparation method, has at 100 DEG C
There are preferable suction hydrogen kinetic characteristics.But the material preparation flow is extremely complex, and production process has difficulties.
Another unique advantage of mechanical ball mill is exactly almost can be compound by the progress of the material of any state, including physics
The biggish solid of nature difference and solid, solid and liquid and the materials such as solid and gas.But magnesium has certain modeling tough
Property, it can be adhered on abrading-ball and tank skin in Mechanical Milling Process, cause material composition uneven.Therefore, improve magnesium base alloy
Wall sticking phenomenon tool in material mechanical milling process has very important significance.
Summary of the invention
The purpose of the present invention is provide a kind of mechanical ball mill combination multiple catalysts association for deficiency existing for current techniques
With the high capacity Mg-based composite hydrogen storage material and preparation method of catalysis.The material is main suction hydrogen phase, the catalyst for including with magnesium
For mischmetal, carbonyl nickel powder and graphite, preparation process adjuvant is volatile inert organic solvents.The preparation method comprises the following steps: first
Pure magnesium and a certain amount of mischmetal are carried out by vacuum metling using vacuum induction melting method, it is rare earth doped in situ to prepare magnesium
The brittleness magnesium-rare earth ingot of element；Then obtained alloy and a certain proportion of carbonyl nickel powder, graphite powder, inertia is organic
Grinding aid mixing, further prepares composite material by mechanical ball mill method；Organic liquid is finally removed under vacuum conditions
Grinding aid obtains high capacity Mg-based composite hydrogen storage material.The material in Mechanical Milling Process is successfully overcome by the above method
Wall sticking phenomenon, and the Mg-based composite hydrogen storage material with nanocrystalline structure of multiphase concerted catalysis can be obtained, to substantially change
It has been apt to the suction hydrogen kinetic characteristics of magnesium-base hydrogen storage material.Composite hydrogen storage material provided by the invention can quickly inhale hydrogen at 100 DEG C,
Reach practical demand.
Technical solution of the present invention is as follows:
A kind of nano Mg base composite hydrogen storage material, the material main component are magnesium, and by mischmetal, carbonyl nickel powder and stone
Black multiple material concerted catalysis is made, and has nanocrystalline structure, and crystallite dimension is 20-50 nanometers；And there is excellent low temperature
Inhale hydrogen dynamic performance；Wherein, mischmetal accounts for the 10-15% of pure magnesia amount, and carbonyl nickel powder accounts for magnesium-rare earth gross mass 3-
10%, graphite accounts for magnesium-rare earth gross mass 3-5%.
It is specially in 100 DEG C and 3MPa hydrogen press strip that the superior low temperature of the Mg-based composite hydrogen storage material, which inhales hydrogen dynamic performance,
The hydrogen of 5-6.5wt% can be absorbed under part in 30 seconds.
The Mg-based composite hydrogen storage material preparation method includes following key step:
A, using magnesium and norium as raw material, brittleness magnesium-rare earth is prepared using vacuum induction melting method
Ingot；Wherein, smelting furnace back end vacuum is 2.0 × 10-2Pa, protective gas are the high-purity argon gas of 0.04-0.06MPa pressure, vacuum
Induction coil power when melting is 8-10kW, and melt holding time is 10-15 minutes；Ingot casting is poured into after melting；Institute
The quality for the mischmetal stated is the 10-15% of magnesium-rare earth mass fraction；
B, obtained magnesium-rare earth ingot casting machinery is broken for 100 mesh alloy powder below, then with carbonyl nickel
Powder, graphite powder and organic liquid grinding aid are uniformly mixed, and are ground 5-10 hours with planetary mechanical ball grinding machine；
Wherein, the quality of the carbonyl nickel powder is the 3-10% of magnesium-rare earth powder quality；The graphite powder
Quality is the 3-5% of magnesium-rare earth powder quality；The quality of the organic liquid grinding aid is magnesium-rare earth powder
The 50-100% of quality；
C, the mixing material after ball milling is dried in vacuo at room temperature, obtains Mg-based composite hydrogen storage material.
The mischmetal includes lanthanum, cerium, praseodymium, neodymium, samarium and other a small amount of rare earth elements and minimal amount of impurity member
Element, rare earth element total content are greater than 99.5%.
The carbonyl nickel powder refers to the extra-fine nickel powder obtained by reducing carbonyl nickel, and particle size range is 0.5-1 microns.
The organic liquid grinding aid, can be ethyl alcohol, hexamethylene, hexane, normal heptane, benzene, toluene, in tetrahydrofuran
One or more.
The purity of the high-purity argon gas is 99.999Vol.%.
The viscous wall of material is substantially not present in the Mg-based composite hydrogen storage material preparation method in Mechanical Milling Process
Phenomenon.
Substantive distinguishing features of the invention are as follows:
The present invention has used mischmetal in the preparation of high capacity magnesium-base hydrogen storage material, not only through by itself and Smelting magnesium
After form brittle alloy, improve grinding efficiency and overcome wall sticking phenomenon, more important is play a nanometer phase during inhaling hydrogen release
Catalytic action improves the low temperature hydrogen sucking function of material.
The beneficial effects of the present invention are:
1) mechanical ball mill is carried out by raw material of brittleness magnesium-rare earth, and adds graphite powder in mechanical milling process, improved
Grinding efficiency, overcomes the viscous wall effect in mechanical milling process to reach as high as 99% so that sample recovery rate is substantially higher than 90%；
2) the concerted catalysis effect of rare earth element, graphite, carbonyl nickel powder greatly improves the reversible hydrogen storage characteristic of magnesium, so that material exists
Hydrogen is quickly inhaled under the conditions of 100 DEG C, performance is better than existing open source literature data, in fuel cell car hydride hydrogen-storing system
System aspect shows good application prospect.
Detailed description of the invention
Fig. 1 is the hydrogen storage material SEM microscopic appearance figure that embodiment 1 of the present invention obtains.
Fig. 2 is the hydrogen storage material SEM microscopic appearance figure that embodiment 3 of the present invention obtains.
Fig. 3 is that the hydrogen storage material that embodiment 4 of the present invention obtains inhales the TEM microscopic appearance figure after hydrogen.
Fig. 4 is the hydrogen storage material SEM microscopic appearance figure that embodiment 5 of the present invention obtains.
Fig. 5 is the Dynamic isotherms of hydrogen absorption of the obtained hydrogen storage material of embodiment 1 of the present invention at different temperatures.
Fig. 6 is the Dynamic isotherms of hydrogen absorption of the obtained hydrogen storage material of embodiment 2 of the present invention at different temperatures.
Fig. 7 is the Dynamic isotherms of hydrogen absorption of the obtained hydrogen storage material of embodiment 3 of the present invention at different temperatures.
Fig. 8 is the Dynamic isotherms of hydrogen absorption of the obtained hydrogen storage material of embodiment 4 of the present invention at different temperatures.
Fig. 9 is the Dynamic isotherms of hydrogen absorption of the obtained hydrogen storage material of embodiment 5 of the present invention at different temperatures.
Specific embodiment
Below with reference to embodiment, the present invention is further described in detail.
The carbonyl nickel powder is well known materials, refers to the extra-fine nickel powder obtained by reducing carbonyl nickel, and the present invention is implemented
Carbonyl nickel powder particle size range used in example is 0.5-1 microns.
The mischmetal is well known materials, refer to the natural Rare Earth Mine in nature is purified, smelt after obtained rare earth
Metal mixture includes lanthanum, cerium, praseodymium, neodymium, samarium and other a small amount of rare earth elements and impurity element, rare earth element total content
Greater than 99.5%, each rare earth element ratio is slightly different with the place of production and batch, but does not influence using effect of the present invention；Following reality
It applies the norium that example is related to and is purchased from Baotou tombar thite institute (CAS:62379-61-7), however, the present invention is not limited thereto.
Embodiment 1
The pure magnesium ingot (purity is greater than 99%) of 1kg and the norium of 0.15kg (15wt%) are put into vacuum induction
In the Magnesia crucible of smelting furnace, it is evacuated to 2.0 × 10-2Pa is hereinafter, be then charged with the high-purity argon gas of 0.04-0.06MPa pressure
(purity 99.999Vol.%).Medium frequency induction coil power is adjusted to 8-10kW, heating raw metal is complete to all metal blocks
After running down, continues heat preservation 10-15 minutes, homogenize alloying component.By alloy melt in cast iron die after melting
The circular ingot that diameter is 30mm is poured into, magnesium-rare earth ingot is obtained after being cooled to room temperature.Mistake after alloy pig is mechanically pulverized
Then 100 the polished standard screens take magnesium-rare earth powder 5g, carbonyl nickel powder 0.25g (5wt%), graphite powder 0.15g
(3wt%), organic liquid grinding aid tetrahydrofuran 5g (100wt%) are placed in the stainless-steel vacuum ball grinder of 300ml, are then put
Enter agate abrading-ball, the high-purity argon gas of 0.15MPa is filled with after vacuumizing as protective gas.The ball material used in the embodiment of the present invention
Than for 20:1, drum's speed of rotation 350r/min, Ball-milling Time 10 hours.Material after ball milling is placed in a vacuum drying oven,
Be dried in vacuo 2 hours at room temperature or more, obtain magnesium-base hydrogen storage material.The viscous wall degree of material is measured with sample recovery rate, i.e.,
Withdraw the quality of solid sample and the percentage of investment solid raw material quality.The size of the rate of recovery can reflect material in ball milling
Wall sticking phenomenon in the process, sample recovery rate is lower, shows that viscous wall effect of the material in mechanical milling process is more significant, is more unfavorable for
Material preparation.Material yield rate is about 88% in the present embodiment.
The microstructure of composite material is observed with SEM, bulky grain made of discovery material is reunited by little particle forms,
Big partial size is 10-50 microns, as shown in Fig. 1.The carbonyl nickel powder and graphite of addition are dispersed under mechanical ball mill effect
Inside material matrix, composite material is formed.5 activation are carried out to material at 300 DEG C with Sieverts equipment and inhale hydrogen release processing,
Dynamic performance tests material isothermal after stablizing inhales hydrogen curve, initial hydrogen pressure 3MPa, test temperature is respectively 300,
200,100 DEG C, as a result as shown in Fig. 5.It can be seen that material is by saturation hydrogen-sucking amount after five minutes at 300 DEG C
5.9wt%.The suction hydrogen dynamic performance that temperature greatly improves material instead is reduced, material is in 30 seconds under the conditions of 100 DEG C
Hydrogen-sucking amount can reach 5.7wt%, show fabulous low temperature and inhale hydrogen kinetic characteristics.
Embodiment 2
The other steps of material preparation method in the present embodiment are same as Example 1, the difference is that Ball-milling Time is 5
Hour, the carbonyl nickel powder in mechanical milling process is 0.5g (10wt%), and graphite powder is 0.25g (5wt%), and grinding aid is ethyl alcohol, is helped
Grinding agent additive amount is 2.5g (50wt%).
Material after ball milling does not find that apparent wall sticking phenomenon, material yield rate are about 94%.The composite material is inhaled through 5 times
Dynamic isotherms of hydrogen absorption after hydrogen release activation is as shown in Fig. 6.It can be seen that material is at 300 DEG C by saturation after five minutes
Hydrogen-sucking amount is about 5.2wt%, slightly below embodiment 1.Material equally has at 100 DEG C inhales hydrogen kinetic characteristics well,
Hydrogen-sucking amount in 30 seconds can reach 5wt% or more.
Embodiment 3
The other steps of material preparation method in the present embodiment are same as Example 1, the difference is that alloy melting mistake
Rare earth additive amount is 0.1kg (10wt%) in journey, and the carbonyl nickel powder quality in mechanical milling process is 0.15g (3wt%), graphite silty
Amount is 0.05g (1wt%), and grinding aid is normal heptane.
Material after ball milling has more apparent wall sticking phenomenon, and sample recovery rate is about 68%.The embodiment composite material
SEM microstructure is as shown in Fig. 2, and material is equally formed by fine particle cluster, and bulky grain partial size is 10-70 microns.Material
Dynamic isotherms of hydrogen absorption after 5 times are inhaled hydrogen release activation is as shown in Fig. 7.It can be seen that material is at 300 DEG C by after five minutes
Saturation hydrogen-sucking amount be about 6.3wt%, but at 100 DEG C material inhale hydrogen dynamic performance be not obviously improved, inhale hydrogen
Rate is far below embodiment 1 and embodiment 2, this is because graphite powder content is lower in the present embodiment, the material composition after ball milling
Not enough uniformly, carbonyl nickel powder not can be uniformly dispersed in inside alloy, and catalytic action is limited.
Embodiment 4
The other steps of material preparation method in the present embodiment are same as Example 1, the difference is that alloy melting mistake
Rare earth additive amount is 0.1kg (10wt%) in journey, and grinding aid is hexamethylene.
Material after ball milling does not find that apparent wall sticking phenomenon, material yield rate are about 93%.The embodiment material is through 5 times
It is as shown in Fig. 3 that the TEM microstructure after hydrogen release recycles is inhaled in activation, it can be seen that material is made of 20-50 nanometers of crystal grain, whole
Body shows as nanocrystalline structure.Dynamic isotherms of hydrogen absorption of the material after 5 times are inhaled hydrogen release activation is as shown in Fig. 8.It can be seen that
Material is about 6.1wt% by saturation hydrogen-sucking amount after five minutes at 300 DEG C.The magnesium-based that the embodiment obtains at 100 DEG C is multiple
Condensation material equally has excellent suction hydrogen dynamic performance, and the hydrogen-sucking amount in 30 seconds can reach 6wt% or more.
Embodiment 5
The other steps of material preparation method in the present embodiment are same as Example 1, the difference is that alloy melting mistake
Rare earth additive amount is 0.1kg (10wt%) in journey, and graphite powder quality is 0.5g (10wt%), and grinding aid is hexamethylene.
Material absolutely not wall sticking phenomenon after ball milling, material yield rate 99%.Embodiment composite material SEM is microcosmic
Structure is as shown in Fig. 4, it can be seen that material is made of coarse particle, and graphite powder is distributed between alloying pellet.Higher stone
The over-lubrication effect that ink powder content generates causes grinding efficiency sharply to decline, and the nickel of addition is almost without entering inside alloy.
Dynamic isotherms of hydrogen absorption of the composite material after 5 times are inhaled hydrogen release activation is as shown in Fig. 9.It can be seen that material is at 300 DEG C
It is about 5.6wt% by saturation hydrogen-sucking amount after ten minutes.Magnesium-based composite material at lower temperature in the embodiment has
Very poor dynamic performance is also only 2.8wt% through hydrogen-sucking amount after ten minutes at 100 DEG C.It can be seen that higher graphite addition
Amount is unfavorable for promoting the suction hydrogen kinetic characteristics of material.
The present invention chooses mixed rare-earth elements and magnesium carries out alloy melting, on the one hand, magnesium and rare earth element pass through vacuum sense
Intermetallic compound is formed after answering melting, improves the brittleness of magnesium base alloy, it is broken in mechanical milling process that material can be improved
Efficiency and wall sticking phenomenon；On the other hand, nano rare earth hydrogenation is precipitated in the rare earth element in composite material in situ in hydrogenation process
Object secondary phase can be used as catalyst to improve the hydrogen storage property of magnesium.A small amount of rare earth element can not make alloy form brittlement phase, mistake
More rare earth elements can reduce the reversible hydrogen storage capacity of material.It is found through many experiments, the mischmetal and magnesium of 10-15wt% closes
Aurification has optimal comprehensive performance.The lubricating action of graphite can not only improve the wall sticking phenomenon in mechanical milling process, but also can mention
Contact effect of the carbonyl nickel powder with alloy substrate is risen, peptizaiton of the nickel in alloy substrate is promoted, and then improves nickel in material
Inhale the catalytic efficiency during hydrogen discharge reaction.But excessive graphite generates excessive lubricating action in mechanical milling process, such as on
Stating in embodiment 5 content of graphite is 10wt%, instead grinding efficiency is declined, and is unfavorable for promoting the hydrogen-absorption speed of material and can
Inverse hydrogen storage capability.By comparing above-described embodiment result, it is believed that the material mixture ratio that embodiment 4 provides has optimal comprehensive suction hydrogen
Performance.
Unaccomplished matter of the present invention is well-known technique.
Claims (7)
1. a kind of nano Mg base composite hydrogen storage material, it is characterized in that the material main component is magnesium, it include mischmetal, carbonyl nickel
Powder and graphite multiple catalysts have nanocrystalline structure, and material grains are inhaled having a size of 20-50 nanometers with excellent low temperature
Hydrogen dynamic performance；Wherein, mischmetal accounts for the 10-15% of pure magnesia amount, and carbonyl nickel powder accounts for magnesium-rare earth gross mass 3-10%,
Graphite accounts for magnesium-rare earth gross mass 3-5%.
2. nano Mg base composite hydrogen storage material as described in claim 1, it is characterized in that the Mg-based composite hydrogen storage material is excellent
It is the hydrogen that can absorb 5-6.5wt% in 30 seconds under the conditions of 100 DEG C and 3MPa hydrogen pressure that different low temperature, which inhales hydrogen dynamic performance,.
3. nano Mg base composite hydrogen storage material as described in claim 1, it is characterized in that the mischmetal include lanthanum, cerium, praseodymium,
Neodymium, samarium and other a small amount of rare earth elements and minimal amount of impurity element, rare earth element total content are greater than 99.5%.
4. Mg-based composite hydrogen storage material preparation method as described in claim 1, it is characterized in that this method includes following main step
It is rapid:
A, using magnesium and norium as raw material, brittleness magnesium-rare earth ingot is prepared using vacuum induction melting method；Its
In, smelting furnace back end vacuum is 2.0 × 10−2Pa, protective gas is the high-purity argon gas of 0.04-0.06MPa pressure, when vacuum melting
Induction coil power be 8-10kW, melt holding time be 10-15 minutes；Ingot casting is poured into after melting；Described is mixed
Close the 10-15% that rare earth quality is magnesium-rare earth mass fraction；
B, magnesium-rare earth ingot casting machinery is broken for 100 mesh alloy powder below, then with carbonyl nickel powder, graphite powder with
And organic liquid grinding aid is uniformly mixed, and is ground 5-10 hours with planetary mechanical ball grinding machine；
Wherein, the quality of the carbonyl nickel powder is the 3-10% of magnesium-rare earth powder quality；The quality of the graphite powder
For the 3-5% of magnesium-rare earth powder quality；The quality of the organic liquid grinding aid is magnesium-rare earth powder quality
50-100%；
C, the mixing material after mechanical ball mill is dried in vacuo at room temperature, obtains Mg-based composite hydrogen storage material.
5. Mg-based composite hydrogen storage material preparation method as claimed in claim 4, it is characterized in that the granularity of the carbonyl nickel powder
Range is 0.5-1 microns.
6. Mg-based composite hydrogen storage material preparation method as claimed in claim 4, it is characterized in that the organic liquid grinding aid
For one or more of ethyl alcohol, hexamethylene, hexane, normal heptane, benzene, toluene, tetrahydrofuran.
7. Mg-based composite hydrogen storage material preparation method as claimed in claim 4, it is characterized in that the purity of the high-purity argon gas
For 99.999Vol.%.
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| 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 |
| CN112921188A (en) * | 2019-12-05 | 2021-06-08 | 本田技研工业株式会社 | Magnesium powder anodes and electrochemical cells comprising such anodes |
| CN112961996A (en) * | 2021-02-01 | 2021-06-15 | 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 |
| CN114411028A (en) * | 2022-01-21 | 2022-04-29 | 徐州工程学院 | Trace nickel composite layered magnesium composite material and preparation method and application thereof |
| CN114507798A (en) * | 2022-02-18 | 2022-05-17 | 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 |
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