CN108188406A - A kind of magnesium-base nanometer composite hydrogen-storing material and preparation method - Google Patents
A kind of magnesium-base nanometer composite hydrogen-storing material and preparation method Download PDFInfo
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- CN108188406A CN108188406A CN201711392302.8A CN201711392302A CN108188406A CN 108188406 A CN108188406 A CN 108188406A CN 201711392302 A CN201711392302 A CN 201711392302A CN 108188406 A CN108188406 A CN 108188406A
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/06—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars
- B22D11/0611—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars formed by a single casting wheel, e.g. for casting amorphous metal strips or wires
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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
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
- C22C32/0015—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
- C22C32/0031—Matrix based on refractory metals, W, Mo, Nb, Hf, Ta, Zr, Ti, V or alloys thereof
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
- C22C2026/002—Carbon nanotubes
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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
Abstract
A kind of magnesium-base nanometer composite hydrogen-storing material and preparation method, magnesium ingot is added in into atmosphere protection resistance furnace, it is warming up to 780~800 DEG C, it is allowed to be melted into liquid magnesium alloy, add in the nickel sheet pressed in advance, it is sufficiently stirred 10min, it is continuously heating to 880~900 DEG C, it stirs and keeps the temperature 20min, make the melt of even macroscopic property, the steel die of cast 200 DEG C of heating in advance, air-cooled acquisition as cast condition richness magnesium alloy, solution gets rid of band, richness Magnesium Alloy during sensing heating, using argon gas molten alloy liquid injection to the atwirl copper rollers of 45m/s, obtain tissue modulation richness magnesium alloy thin strip, think to shred alloy thin band, add in CNTs and Nb2O5High-energy ball milling 1h simultaneously obtains bulk modified nano combined rich magnesium hydrogen storing alloy powder, and the present invention not only maintains the large capacity hydrogen storage advantage of Mg base hydrogen bearing alloy, but also significantly improves activation characteristic and suction/put hydrogen thermodynamics characteristic.
Description
Technical field
The present invention relates to alloy material storing hydrogen technical field, more particularly to a kind of magnesium-base nanometer composite hydrogen-storing material and preparation
Method.
Background technology
The energy is the primary demand of daily life, is the motive power of human survival and social progress.Population gradually increase and
Heavy industry rapid development, causes energy demand constantly to rise.Traditional fossil energy is non-renewable and by exhaustive exploitation, forces full generation
Boundary is absorbed in the awkward situation of energy shortage and environmental pollution, develops and uses the regenerative resource of clean and effective and sustainable energy and upgrades
It is extremely urgent that current energy resource system is transformed.Hydrogen Energy has remarkable advantages such as " zero-emission, recyclable, high heating value, source are wide ", and
And Hydrogen Energy can be stored and be transported, and be expected to become new energy " driving " future life.It is the hydrogen producing technology of Cheap highly effective, safe and reliable
Hydrogen storage technology and economical rationality are to promote the three aspect problems that hydrogen energy source must pay close attention to hydrogen technology.Storage is stagnant with transportation development
Afterwards, become the bottleneck of hydrogen energy source popularization, it is the key that solve hydrogen storage to find a kind of reliable, efficient compression method.
At present, the high-pressure gaseous hydrogen storage mode not high compared to safety and energy storage density and excessive low temperature liquid hydrogen storage side of consuming energy
Formula, with the obvious advantage in a manner of the solid-state storage by metal hydride for medium, hydrogen-storage density is high, low energy consumption, safe and reliable, receives
Extensive concern, wherein magnesium metal become large capacity vehicle-mounted solid-state with the advantages that its hydrogen storage capability is high, density is small, rich reserves and store up
The ideal chose of hydrogen material.
The pure magnesium that theoretical memory capacity is up to 7.6wt.% is that hydrogen-storage density is highest in current metal group material, because being more than
U.S. Department of Energy has received widespread attention the research and development index that vehicle-mounted hydrogen storage material is proposed with International Energy Agency.So
And surface passivated membrane leads to activation difficulty, MgH2Middle H mass transfers difficulty causes suction/hydrogen desorption kinetics slowly and Mg-H bonds are closed by force
Lead to the excessively high practical application for seriously limiting pure Mg systems of hydrogen discharging temperature.How large capacity hydrogen storage advantage is being kept
It improves simultaneously and inhales/put hydrogen thermokinetics, reduces hydrogen discharging temperature, improves activation characteristic and good modified effect is kept to become magnesium-based
The key of hydrogen bearing alloy research.
To improve magnesium-base hydrogen storage material performance, the main thought of people is at present：Its heat is improved by component system design
Mechanical property；Its dynamic performance is improved by preparation process.But often only stress to consider on one side or only consider into
Set up meter separately, and then improve thermodynamic property；Or only consider process optimization, improve dynamic performance, hydrogen storage material is activated
Characteristic and the concern of modified cyclical stability are less.But the storage and release of hydrogen are a complicated processes, to hydrogen storage material
Ingredient, internal organizational structure, surface property of material etc. have special requirement.It is big to be synthetically prepared hud typed magnesium-base hydrogen storage material
Amplitude improves the effective way of hydrogen storage property.
Invention content
In order to overcome the above-mentioned deficiencies of the prior art, the purpose of the present invention is to provide a kind of magnesium-base nano composite hydrogen-storage materials
Material and preparation method improve its activation characteristic on the basis of large capacity hydrogen storage is kept, accelerate to inhale hydrogen desorption kinetics, reduce hydride
System thermodynamic stability.
In order to achieve the above object, the technical solution adopted by the present invention is：
A kind of magnesium-base nanometer composite hydrogen-storing material, including Mg-Ni alloys and CNTs and Nb2O5Catalyst, Mg-Ni alloys：
CNTs：Nb2O5It is 8 by weight：1：In 1, Mg-Ni alloy, content of magnesium is 90~98at.%, remaining is nickel, Mg-Ni alloys and
CNTs and Nb2O5Catalyst is combined by the way of high-energy ball milling.
A kind of preparation method of magnesium-base nanometer composite hydrogen-storing material, includes the following steps；
Step 1, alloying ingredient：
The metal MAG block and nickel powder of purity >=99.8% are chosen, content of magnesium is 90~98at.%, remaining is nickel, by nickel powder
Precompressed is in blocks, added in magnesium metal, it is contemplated that scaling loss, magnesium add the scaling loss of 3~5wt.%, and nickel sheet is obtained by tabletting precompressed
, pressure 1.0MPa, dwell time 15s；
Step 2, alloy cast ingot is prepared：
The MAG block weighed up is put into the graphite crucible dried in advance, in SF6+CO2780 are heated under mixed atmosphere protection
~800 DEG C, pre-stamped nickel sheet is put into above-mentioned magnesium metal melting liquid, mechanical agitation 10min, obtain uniformly rich magnesium alloy
Alloy melt is continuously heating to 880~900 DEG C, and keep the temperature 20min, is mixed with mechanical agitation in melt insulating process, treats by melt
Casting is air-cooled to room temperature, obtains rich magnesium alloy ingot to being preheated in advance in 200 DEG C of steel die after nickel sheet all melts；
Step 3, interior tissue regulates and controls：
The rich magnesium alloy ingot that step 2 obtains is placed in bottom to be provided in the high purity quartz pipe of slit, it will by spun furnace
Above-mentioned alloy cast ingot sensing heating makes molten state richness magnesium alloy continuous from quartz ampoule slit to melting using inert gas argon gas
Injection to the copper roller surface rotated, the fast melt-quenching stove copper roller is rotated with the linear velocity of 45m/s, and it is thin to obtain hydrogen bearing alloy fast quenching
Band；
Step 4, surface catalysis：
Obtained alloy thin band is artificially divided into 1~2cm2Fragment, in alloy thin band fragment simultaneously add in CNTs
And Nb2O5And the high-energy ball milling 1h under high-purity argon gas protection, it realizes surface recombination catalytic modification, obtains the nano combined storage of Mg-Ni bases
Hydrogen alloyed powder.
The CNTs and Nb added in the alloy thin band fragment2O5Weight ratio with alloy thin band fragment is 1：1：8.
The beneficial effects of the invention are as follows：
Bulk modified method provided by the present invention based on interior tissue regulation and control and surface catalysis, mainly passes through fast rapid hardening
Gu crystal grain thinning increases transmission process of the crystal boundary/phase boundary improvement hydrogen atom in material internal, while Dispersed precipitate limited second
Phase promotes self-catalysis efficiency, so as to improve the hydriding dehydriding of rich magnesium system.It is catalyzed by surface recombination, promotes H2Molecule table
Face adsorbs dissociation process and accelerates H atom surface penetration, improves activation characteristic, while nano combinedization can pass through the association of catalyst
Same-action reduces Mg-H bond energys, reduces system stability, improves rich magnesium system thermodynamic behaviour.The bulk modified method, not only
The large capacity hydrogen storage advantage of Mg base hydrogen bearing alloy is maintained, and significantly improves activation characteristic and suction/put hydrogen thermokinetics spy
Property.
Description of the drawings
Fig. 1 is as cast condition Mg-5at.%Ni richness magnesium alloy microstructures of the present invention.
Fig. 2 is rich magnesium alloy micro-structure after portion's tissue modulation of the present invention.
Fig. 3 is 250 DEG C of Mg5Ni richnesses magnesium alloy rear before modified of the invention, 2.5MPa isothermal Dynamic isotherms of hydrogen absorption.
Specific embodiment
The structural principle to the present invention and operation principle make narration in detail below in conjunction with the accompanying drawings.
Embodiment 1
The present invention is a kind of magnesium-base nanometer composite hydrogen-storing material, including Mg-Ni alloys and CNTs and Nb2O5Catalyst, Mg-
Ni alloys：CNTs：Nb2O5It is 8 by weight：1：In 1, Mg-Ni alloy, content of magnesium is 90~98at.%, remaining is nickel, Mg-
Ni alloys and CNTs and Nb2O5Catalyst is combined by the way of high-energy ball milling.Magnesium metal is 90at.% in the implementation case,
Nickel is 10at.%.
A kind of preparation method of magnesium-base nanometer composite hydrogen-storing material, including
Step 1, alloying ingredient：
The metal MAG block and nickel powder of purity >=99.8% are chosen, nickel powder precompressed is in blocks, added in magnesium metal, it is contemplated that
Scaling loss, magnesium adds the scaling loss of 3~5wt.%, and in the present embodiment, the scaling loss additive amount of magnesium is 5wt.%.Nickel sheet passes through tabletting precompressed
It obtains, pressure 1.0MPa, dwell time 15s；
Step 2, alloy cast ingot is prepared：
The MAG block weighed up is put into the graphite crucible dried in advance, in SF6+CO2780 are heated under mixed atmosphere protection
~800 DEG C, pre-stamped nickel sheet is put into above-mentioned magnesium metal melting liquid, mechanical agitation 10min, obtain uniformly rich magnesium alloy
Alloy melt is continuously heating to 880~900 DEG C, and keep the temperature 20min, is mixed with mechanical agitation in melt insulating process, treats by melt
Casting is air-cooled to room temperature, obtains rich magnesium alloy ingot to being preheated in advance in 200 DEG C of steel die after nickel sheet all melts；
Step 3, interior tissue regulates and controls：
The rich magnesium alloy ingot that step 2 obtains is placed in bottom to be provided in the high purity quartz pipe of slit, it will by spun furnace
Above-mentioned alloy cast ingot sensing heating makes molten state richness magnesium alloy continuous from quartz ampoule slit to melting using inert gas argon gas
Injection to the copper roller surface rotated, the fast melt-quenching stove copper roller is rotated with the linear velocity of 45m/s, and it is thin to obtain hydrogen bearing alloy fast quenching
Band；
Step 4, surface catalysis：
Obtained alloy thin band is artificially divided into 1~2cm2Fragment, in alloy thin band fragment simultaneously add in CNTs
And Nb2O5And the high-energy ball milling 1h under high-purity argon gas protection, it realizes surface recombination catalytic modification, obtains the nano combined storage of Mg-Ni bases
Hydrogen alloyed powder, the CNTs and Nb added in alloy thin band fragment2O5Weight ratio with alloy thin band fragment is 1：1：8.
Embodiment 2
The present invention is a kind of magnesium-base nanometer composite hydrogen-storing material, including Mg-Ni alloys and CNTs and Nb2O5Catalyst, Mg-
Ni alloys：CNTs：Nb2O5It is 8 by weight：1：In 1, Mg-Ni alloy, content of magnesium is 90~98at.%, remaining is nickel, Mg-
Ni alloys and CNTs and Nb2O5Catalyst is combined by the way of high-energy ball milling.Magnesium metal is 95at.% in the implementation case,
Nickel is 5at.%.
A kind of preparation method of magnesium-base nanometer composite hydrogen-storing material, including
Step 1, alloying ingredient：
The metal MAG block and nickel powder of purity >=99.8% are chosen, nickel powder precompressed is in blocks, added in magnesium metal, it is contemplated that
Scaling loss, magnesium adds the scaling loss of 3~5wt.%, and in the present embodiment, the scaling loss additive amount of magnesium is 4wt.%.Nickel sheet passes through tabletting precompressed
It obtains, pressure 1.0MPa, dwell time 15s；
Step 2, alloy cast ingot is prepared：
The MAG block weighed up is put into the graphite crucible dried in advance, in SF6+CO2780 are heated under mixed atmosphere protection
~800 DEG C, pre-stamped nickel sheet is put into above-mentioned magnesium metal melting liquid, mechanical agitation 10min, obtain uniformly rich magnesium alloy
Alloy melt is continuously heating to 880~900 DEG C, and keep the temperature 20min, is mixed with mechanical agitation in melt insulating process, treats by melt
Casting is air-cooled to room temperature, obtains rich magnesium alloy ingot to being preheated in advance in 200 DEG C of steel die after nickel sheet all melts；
Step 3, interior tissue regulates and controls：
The rich magnesium alloy ingot that step 2 obtains is placed in bottom to be provided in the high purity quartz pipe of slit, it will by spun furnace
Above-mentioned alloy cast ingot sensing heating makes molten state richness magnesium alloy continuous from quartz ampoule slit to melting using inert gas argon gas
Injection to the copper roller surface rotated, the fast melt-quenching stove copper roller is rotated with the linear velocity of 45m/s, and it is thin to obtain hydrogen bearing alloy fast quenching
Band；
Step 4, surface catalysis：
Obtained alloy thin band is artificially divided into 1~2cm2Fragment, in alloy thin band fragment simultaneously add in CNTs
And Nb2O5And the high-energy ball milling 1h under high-purity argon gas protection, it realizes surface recombination catalytic modification, obtains the nano combined storage of Mg-Ni bases
Hydrogen alloyed powder, the CNTs and Nb added in alloy thin band fragment2O5Weight ratio with alloy thin band fragment is 1：1：8.
Embodiment 3
The present invention is a kind of magnesium-base nanometer composite hydrogen-storing material, including Mg-Ni alloys and CNTs and Nb2O5Catalyst, Mg-
Ni alloys：CNTs：Nb2O5It is 8 by weight：1：In 1, Mg-Ni alloy, content of magnesium is 90~98at.%, remaining is nickel, Mg-
Ni alloys and CNTs and Nb2O5Catalyst is combined by the way of high-energy ball milling.Magnesium metal is 98at.% in the implementation case,
Nickel is 2at.%.
A kind of preparation method of magnesium-base nanometer composite hydrogen-storing material, including
Step 1, alloying ingredient：
The metal MAG block and nickel powder of purity >=99.8% are chosen, nickel powder precompressed is in blocks, added in magnesium metal, it is contemplated that
Scaling loss, magnesium adds the scaling loss of 3~5wt.%, and in the present embodiment, the scaling loss additive amount of magnesium is 3wt.%.Nickel sheet passes through tabletting precompressed
It obtains, pressure 1.0MPa, dwell time 15s；
Step 2, alloy cast ingot is prepared：
The MAG block weighed up is put into the graphite crucible dried in advance, in SF6+CO2780 are heated under mixed atmosphere protection
~800 DEG C, pre-stamped nickel sheet is put into above-mentioned magnesium metal melting liquid, mechanical agitation 10min, obtain uniformly rich magnesium alloy
Alloy melt is continuously heating to 880~900 DEG C, and keep the temperature 20min, is mixed with mechanical agitation in melt insulating process, treats by melt
Casting is air-cooled to room temperature, obtains rich magnesium alloy ingot to being preheated in advance in 200 DEG C of steel die after nickel sheet all melts；
Step 3, interior tissue regulates and controls：
The rich magnesium alloy ingot that step 2 obtains is placed in bottom to be provided in the high purity quartz pipe of slit, it will by spun furnace
Above-mentioned alloy cast ingot sensing heating makes molten state richness magnesium alloy continuous from quartz ampoule slit to melting using inert gas argon gas
Injection to the copper roller surface rotated, the fast melt-quenching stove copper roller is rotated with the linear velocity of 45m/s, and it is thin to obtain hydrogen bearing alloy fast quenching
Band；
Step 4, surface catalysis：
Obtained alloy thin band is artificially divided into 1~2cm2Fragment, in alloy thin band fragment simultaneously add in CNTs
And Nb2O5And the high-energy ball milling 1h under high-purity argon gas protection, it realizes surface recombination catalytic modification, obtains the nano combined storage of Mg-Ni bases
Hydrogen alloyed powder, the CNTs and Nb added in alloy thin band fragment2O5Weight ratio with alloy thin band fragment is 1：1：8.
Embodiment
Magnesium ingot is added in into atmosphere protection resistance furnace, is warming up to 780~800 DEG C, is allowed to be melted into liquid magnesium alloy, is added in pre-
The nickel sheet pressed, is sufficiently stirred 10min, is continuously heating to 880~900 DEG C, stirs and keeps the temperature 20min, makes macroscopical equal
The melt of even property pours into a mould the steel die of 200 DEG C of heating in advance, air-cooled acquisition as cast condition richness magnesium alloy.Solution gets rid of band, and sensing adds
Re Shifu Magnesium Alloys using argon gas molten alloy liquid injection to the atwirl copper rollers of 45m/s, obtain tissue modulation
Rich magnesium alloy thin strip.Think to shred alloy thin band, add in CNTs and Nb2O5High-energy ball milling 1h simultaneously, obtains bulk modified nanometer and answers
Close rich magnesium hydrogen storing alloy powder.
Fig. 1 obtains as cast condition richness magnesium alloy microstructures shape appearance figure for founding, and as can be seen, as-cast structure is coarse, expands
It is few to dissipate channel, it is difficult to be rapidly saturated inhaling hydrogen in short-term, plays Mg base hydrogen bearing alloy large capacity advantage.Entirety proposed by the invention changes
Property work well, as shown in Fig. 2, interior tissue regulation and control after, body Mg the second phases of base Mg2Ni is obtained for notable refinement, whole
Nanosizing is realized, compare cast alloy, and the microstructure after regulation and control is more conducive to hydrogen storage.Nano combined hydrogen storage after whole regulation and control
The suction hydrogen effect of alloyed powder is as shown in Figure 3.It can be seen that bulk modified Mg2The initial hydrogen-absorption speed of Ni richness magnesium alloys and final suction
Hydrogen capacity significantly improves, 1.5min can Rapid inhalation to 6.0wt.% or so.Unmodified Mg5Ni alloys 60min air-breathings are not
Sufficient 1wt.%.
1st, prepared by master alloy：Compared with coverture Protection Code, inert atmosphere protection method efficiently solves evaporation and the oxygen of magnesium
Change problem adds in nickel powder is tabletted in magnesium molten metal, increases the contact area of metallic nickel and magnesium, by diffusion reaction,
Nickel is made to realize alloying rapidly at the temperature (890 DEG C) far below its fusing point (1455 DEG C), so as to reduce alloying element, especially
It is the oxidation, volatilization and burning of Mg, Mg-Ni alloy ingredient prepared by melting is accurate, and even tissue, phase composition is reasonable, as a result sees
Fig. 1.
2nd, the interior tissue regulation and control of as cast condition Mg-Ni alloys：Melt belt-rejecting technology method is selected, is added using spun furnace sensing
Heat, the cast alloy fusing being placed in high purity quartz pipe, melt is sprayed, be injected in the smooth copper of rotation using argon pressure
Rod surface, the quenching effect generated by rotation copper rod realize quick solidification, and refining alloy tissue increases crystal boundary/phase boundary diffusion
Channel prepares crystalline state nanometer richness magnesium alloy, and the results are shown in Figure 3.The high-energy ball milling method that compares is prepared for amorphous/nanocrystalline
(1397659 2003.02.19 of CN), this method preparation efficiency is high, and the alloy purity of preparation is high, because high-energy-milling is imitated
Rate is low (1644737 2005.07.27 of CN), if Ball-milling Time is too long or abrading-ball selects not at that time, milling material may be dirty
Dye.
3rd, preparation process of the invention is simple, efficient, and only getting rid of band method by inert atmosphere protection method and melt can prepare
The nano combined hydrogen bearing alloy of a large amount of Mg-Ni richness magnesium.Used smelting equipment is common crucible electrical resistance furnace, and protection gas is SF6+
CO2, avoid the drawbacks of flux protective covering method easily introduces solid inclusion, it is ensured that melted alloying component accuracy.Soon
Rapid hardening promotes a small amount of Mg admittedly2Ni phase nanosizings, and more disperse is uniformly distributed, and improves " self-catalysis " efficiency of system, is improved
It inhales and puts hydrogen thermodynamics characteristic.
4th, the present invention is different from the independent addition manner of Conventional catalytic, has selected while has added CNTs and Nb2O5Two kinds of catalysis
The composite catalyzing mode of agent.The study found that the CNTs with special tubular structure can remarkably promote the diffusion of H atom；Nb2O5
Addition can dramatically speed up H2Molecule is in the absorption dissociation process of material surface.CNTs and Nb2O5After compound addition, pass through collaboration
Hydrogen thermodynamics characteristic is put in catalysis, the suction that can significantly improve rich magnesium alloy.It is the verification present invention as a result, to obtained Mg-
The nano combined hydrogen storing alloy powders of Ni carry out dynamics and inhale hydrogen test, and the results are shown in Figure 3.
To retain magnesium base alloy large capacity hydrogen storage advantage, this patent proposes one for microalloying Mg-Ni-La ternary alloy three-partalloys
Kind of the bulk modified method based on internal regulation and control and surface modification, with keep high hydrogen storage capability under the premise of significantly improve its work
Change, thermokinetics and cycle characteristics, meet application request.
Claims (3)
1. a kind of magnesium-base nanometer composite hydrogen-storing material, which is characterized in that including Mg-Ni alloys and CNTs and Nb2O5Catalyst, Mg-
Ni alloys：CNTs：Nb2O5It is 8 by weight：1：In 1, Mg-Ni alloy, content of magnesium is 90~98at.%, remaining is nickel, Mg-
Ni alloys and CNTs and Nb2O5Catalyst is combined by the way of high-energy ball milling.
2. a kind of preparation method of magnesium-base nanometer composite hydrogen-storing material, which is characterized in that include the following steps；
Step 1, alloying ingredient：
The metal MAG block and nickel powder of purity >=99.8% are chosen, content of magnesium is 90~98at.%, remaining is nickel, by nickel powder precompressed
In flakes, added in magnesium metal, it is contemplated that scaling loss, magnesium add the scaling loss of 3~5wt.%, and nickel sheet is obtained by tabletting precompressed, press
Power is 1.0MPa, dwell time 15s；
Step 2, alloy cast ingot is prepared：
The MAG block weighed up is put into the graphite crucible dried in advance, in SF6+CO2780~800 are heated under mixed atmosphere protection
DEG C, pre-stamped nickel sheet is put into above-mentioned magnesium metal melting liquid, mechanical agitation 10min, obtains uniformly rich magnesium alloy fused mass,
Alloy melt is continuously heating to 880~900 DEG C, and keep the temperature 20min, mechanical agitation is mixed in melt insulating process, treats nickel sheet
All casting to being preheated in advance in 200 DEG C of steel die, is air-cooled to room temperature, obtains rich magnesium alloy ingot after fusing；
Step 3, interior tissue regulates and controls：
The rich magnesium alloy ingot that step 2 obtains is placed in bottom to be provided in the high purity quartz pipe of slit, it will be above-mentioned by spun furnace
Alloy cast ingot sensing heating makes molten state richness magnesium alloy continuously be sprayed from quartz ampoule slit to melting using inert gas argon gas
To the copper roller surface of rotation, the fast melt-quenching stove copper roller is rotated with the linear velocity of 45m/s, obtains hydrogen bearing alloy fast quenching thin strap；
Step 4, surface catalysis：
Obtained alloy thin band is artificially divided into 1~2cm2Fragment, in alloy thin band fragment simultaneously add in CNTs and
Nb2O5And the high-energy ball milling 1h under high-purity argon gas protection, it realizes surface recombination catalytic modification, obtains the nano combined hydrogen storage of Mg-Ni bases
Alloyed powder.
3. the preparation method of a kind of magnesium-base nanometer composite hydrogen-storing material according to claim 2, which is characterized in that described
The CNTs and Nb added in alloy thin band fragment2O5Weight ratio with alloy thin band fragment is 1：1：8.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109898002A (en) * | 2019-04-30 | 2019-06-18 | 三桥惠(佛山)新材料有限公司 | A kind of Mg base hydrogen bearing alloy and preparation method thereof |
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| CN110327936A (en) * | 2019-07-08 | 2019-10-15 | 陕西科技大学 | A kind of EG-SnO2The nano combined catalyzing hydrolysis of@Mg-Ni produces hydrogen material and preparation method thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109898002A (en) * | 2019-04-30 | 2019-06-18 | 三桥惠(佛山)新材料有限公司 | A kind of Mg base hydrogen bearing alloy and preparation method thereof |
| CN109898002B (en) * | 2019-04-30 | 2020-10-27 | 三桥惠(佛山)新材料有限公司 | Magnesium-based hydrogen storage alloy and preparation method thereof |
| CN110282602A (en) * | 2019-07-08 | 2019-09-27 | 陕西科技大学 | A kind of MoS2The nano combined rich magnesium hydrolysis of-EG concerted catalysis produces hydrogen material and preparation method thereof |
| CN110327936A (en) * | 2019-07-08 | 2019-10-15 | 陕西科技大学 | A kind of EG-SnO2The nano combined catalyzing hydrolysis of@Mg-Ni produces hydrogen material and preparation method thereof |
| CN110282602B (en) * | 2019-07-08 | 2022-12-09 | 陕西榆镁广技术开发有限公司 | MoS 2 -EG synergistic catalytic nano composite magnesium-rich hydrolysis hydrogen production material and preparation method thereof |
| CN110327936B (en) * | 2019-07-08 | 2022-12-23 | 陕西榆镁广技术开发有限公司 | EG-SnO 2 @ Mg-Ni nano composite catalytic hydrolysis hydrogen production material and preparation method thereof |
| CN112225174A (en) * | 2020-10-16 | 2021-01-15 | 南京工程学院 | Oxidation-resistant magnesium-based composite hydrogen storage material and preparation method thereof |
| CN113695536A (en) * | 2021-08-24 | 2021-11-26 | 上海交通大学 | Preparation method of hydrogen storage magnesium alloy |
| CN113789462A (en) * | 2021-08-24 | 2021-12-14 | 上海交通大学 | Hydrogen storage magnesium alloy and preparation method thereof |
| CN113695536B (en) * | 2021-08-24 | 2022-05-27 | 上海交通大学 | Preparation method of hydrogen storage magnesium alloy |
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