CN108588521A - A kind of high capacity Mg-Cu-Ni ternary hydrogen-storage alloys and preparation method thereof - Google Patents

A kind of high capacity Mg-Cu-Ni ternary hydrogen-storage alloys and preparation method thereof Download PDF

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CN108588521A
CN108588521A CN201810570859.4A CN201810570859A CN108588521A CN 108588521 A CN108588521 A CN 108588521A CN 201810570859 A CN201810570859 A CN 201810570859A CN 108588521 A CN108588521 A CN 108588521A
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hydrogen
alloy
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ternary
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高金良
尹奕
张羊换
李波
祁焱
李琦
李军
赵栋梁
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WEISHAN GANGYAN RARE EARTH MATERIALS Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C23/00—Alloys based on magnesium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04201—Reactant storage and supply, e.g. means for feeding, pipes
    • H01M8/04216—Reactant storage and supply, e.g. means for feeding, pipes characterised by the choice for a specific material, e.g. carbon, hydride, absorbent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C2202/00—Physical properties
    • C22C2202/04—Hydrogen absorbing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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Abstract

The present invention relates to a kind of fuel cell high capacity Mg Cu Ni ternary hydrogen-storage alloys and preparation method thereof, the hydrogen-storage alloy be include Mg85Cu5Ni10Alloy and catalyst nano Cr2O3Ultra-fine grain powder, wherein catalyst nano Cr2O3Mg is accounted for by mass percentage85 Cu 5Ni10The ratio of alloy is x%, x=0 ~ 8；The hydrogen-storage alloy has main phase Mg, the second phase Mg2Ni and Mg2Cu phases, and there is nano-amorphous structure.Cu, Ni in alloy of the present invention greatly reduce the bond energy between Mg H, the effective hydrogen storage performance for improving Mg base hydrogen storage material.The present invention passes through composition design, regulating microstructure and addition nanometer Cr2O3, the thermal stability of alloy hydride is reduced, the suction hydrogen release thermodynamics and kinetics performance of alloy is improved.Alloyed powder prepared by the present invention maintains higher hydrogen storage capacity and faster suction hydrogen desorption kinetics；Hydride hydrogen discharging temperature is substantially reduced, and the suction hydrogen release of Rapid reversible can be carried out at a temperature of 260 DEG C；Hydrogen release cyclical stability is inhaled to significantly improve.

Description

A kind of high capacity Mg-Cu-Ni ternary hydrogen-storage alloys and preparation method thereof
Technical field
The invention belongs to storage alloy material for hydrogen technical field, more particularly to a kind of fuel cell high capacity Mg-Cu-Ni three First hydrogen-storage alloy and preparation method thereof.
Background technology
Hydrogen is a kind of reproducible green energy resource.Hydrogen is not only resourceful, possesses high energy density and combustion heat value, and It is free from environmental pollution and since its combustion product is water, and can be applied to fuel cell.Therefore more and more to new energy demand Today's society, hydrogen storage is hydrogen and fuel cell technology in including fixed power source, portable power and storage transport applications Key technology.
The storage and transport of hydrogen are the most key important links in Hydrogen Energy application process.With traditional high pressure gas and Low temperature liquid storage hydrogen is compared, and it is reliable that metal hydride stores hydrogen more safety convenient.In metal hydride hydrogen storage material, magnesium-based storage Hydrogen material is due to its higher theoretical hydrogen storage capacity（7.6 wt.%）, it is resourceful, the advantages that having extended cycle life, it is considered as most The hydrogen storage material of application prospect.But since the metal hydride of magnesium has very high thermal stability, lead to the hydride needs of magnesium Hydrogen could be discharged under the high temperature conditions, and hydrogen discharging rate is very slow, this makes the practical application of Mg base hydrogen storage material by very big Limitation.Therefore, reducing the thermal stability of magnesium base hydrogen-storing alloy hydride and improving the dynamic performance of alloy hydrogen absorption and desorption becomes The most important thing.
Studies have shown that can significantly reduce the hydrogen release activation energy of magnesium-based metal hydride by adding transiting group metal elements, The suction hydrogen desorption kinetics of alloy can be significantly improved.In addition, the suction hydrogen desorption kinetics of alloy are non-to the microstructure of hydrogen storage material Often sensitive, the thermal stability of alloy hydride can be significantly reduced to Nano grade by reducing the crystallite dimension of alloy, and significantly be carried The suction hydrogen desorption kinetics performance of high alloy.Mechanical ball mill is to obtain the effective ways of Nanoalloy particle, and can easily add Add various auxiliary agents, especially high-energy ball milling, it is verified that the suction hydrogen desorption kinetics of magnesium base alloy can be significantly increased.
Invention content
The object of the present invention is to provide a kind of high power capacity and with the excellent fuel cell Mg- for inhaling hydrogen desorption kinetics performance Cu-Ni ternary hydrogen-storage alloys.
It is a further object to provide a kind of high power capacity and with the excellent fuel electricity for inhaling hydrogen desorption kinetics performance The Mg generated after the preparation method of pond Mg-Cu-Ni ternary hydrogen-storage alloys, magnesium and copper alloy2Cu phases are inhaling hydrogen release cycle In can easily detach hydrogen molecule, and quickly the hydrogen ion separated is combined with the magnesium ion adjoined, quickly forms hydrogen Compound, meanwhile, Cu and Ni can greatly weaken the bond energy between Mg-H, reduce the thermal stability of magnesium-based hydride, effectively change The hydrogen storage performance of kind Mg base hydrogen storage material.
To achieve the goals above, the present invention provides following technical solutions：
The present invention provides a kind of high capacity Mg-Cu-Ni ternary hydrogen-storage alloys, the hydrogen-storage alloy be include Mg85Cu5Ni10Alloy and Catalyst nano Cr2O3Ultra-fine nanocrystallines powder, wherein catalyst nano Cr2O3Mg is accounted for by mass percentage85Cu5Ni10 The ratio of alloy is x%, x=0 ~ 8；The hydrogen-storage alloy has main phase Mg phases, the second phase Mg2Ni and Mg2Cu phases, and have and receive Meter Jing-non crystalline structure.
Preferably, x=2 ~ 8.
The hydrogen-storage alloy powder is by as cast condition Mg85Cu5Ni10Catalyst nano Cr is added after broken, screening in alloy2O3 Ball milling obtains for 5 hours.
The suction hydrogen discharging temperature of the Mg-Cu-Ni ternarys hydrogen-storage alloy is 260 DEG C, and suction hydrogen initial hydrogen pressure is 2 MPa, is put Hydrogen is 1 × 10-4It is carried out under MPa pressure.
The Mg-Cu-Ni ternarys hydrogen-storage alloy has following hydrogen storage performance：
In the case where initial hydrogen pressure is 2 MPa and 260 DEG C, the hydrogen-sucking amount in 5 minutes is 4.584 ~ 5.158wt.%；
It is 1 × 10 in initial pressure-4 At MPa and 260 DEG C, the hydrogen desorption capacity in 30 minutes is 4.983 ~ 5.377wt.%；
Suction hydrogen rate after 50th cycle is 90.36 ~ 99.71%.
A kind of preparation method preparing high capacity Mg-Cu-Ni ternary hydrogen-storage alloys, this approach includes the following steps：
A, dispensing：It is chemical formula Mg by atomic ratio85Cu5Ni10Composition carry out dispensing, purity >=99.5% of raw material；
B, prepared by as cast condition master alloy：By the raw material prepared using conventional heating means melting, it is evacuated to 1 × 10-2 Pa~5 ×10-5Pa, it is 0.01MPa ~ 0.1MPa inert protective gas to be then charged with pressure, and the melting incipient stage, temperature is controlled 650 DEG C ± 10 DEG C, magnesium metal is made to melt, then heats up and control temperature at 1550 DEG C ± 10 DEG C, obtain the Mg of melting85Cu5Ni10Liquid State master alloy is kept for 1 ~ 5 minute in the molten state；Liquid master alloy is directly injected into Copper casting mould, with room temperature is furnace-cooled to, is obtained Obtain as cast condition mother alloy ingot；
C, ball-milling treatment：As cast condition mother alloy ingot prepared by step b is crushed and cross 200 mesh sieve, by the alloyed powder of sieving withx The catalyst nano Cr of wt.%2O3Nano particle is packed into stainless steel jar mill together,xFor Cr2O3Account for Mg85Cu5Ni10The matter of alloy Percentage is measured, andx= 0~8；High-purity argon gas, ratio of grinding media to material 40 are filled with after vacuumizing:1；Rotating speed：350 revs/min, ball milling 5 hours obtains Obtain the compound Mg-Cu-Ni ternarys hydrogen-storage alloy of high power capacity.
Magnesium in the chemical formula composition increases the scaling loss amount of 10% ratio in proportioning.
In the step b, heating means include electric arc melting and inducing melting.
In the step b, the inert protective gas is high-purity helium or the mixed gas of argon gas+helium, mixed gas The volume ratio of middle argon gas and helium is 1:1.
In the step c, shut down 1 hour within 1 hour per ball milling in mechanical milling process.
Compared with prior art, the beneficial effects of the present invention are：
In the present invention, the Mg that is generated after magnesium and copper alloy2Cu phases can easily detach hydrogen molecule in inhaling hydrogen release cycle, And quickly combined the hydrogen ion separated with the magnesium ion adjoined, hydride is quickly formed, meanwhile, Cu and Ni can be greatly The bond energy weakened between Mg-H, reduce the thermal stability of magnesium-based hydride, the effective storage hydrogen for improving Mg base hydrogen storage material Energy.The present invention devises novel Mg-Cu-Ni ternarys hydrogen-storage alloy, and magnesium-based hydride is reduced by the way that metallic copper and nickel is added Thermal stability obtains the alloy powder with ultra-fine grain (nanoscale) by ball-milling technology, improves the nanocrystalline of alloy And the Forming ability of amorphous, improve the suction hydrogen desorption kinetics of alloy.Moreover, by the way that catalyst nano Cr is added2O3Particle ball milling Afterwards, the particle size for reducing composite material makes the surface-active of alloying pellet be improved, and forms a large amount of crystal and lacks It falls into, increases the nucleation point and diffusion admittance of hydrogen, be conducive to the diffusion of hydrogen in the alloy, the hydrogen that further reduced alloy decomposes temperature The activation energy that material inhales hydrogen release is spent and can be reduced, the suction hydrogen desorption kinetics performance of alloy is made to be further enhanced.
Description of the drawings
Fig. 1 is microstructure morphology and electronic diffraction of the embodiment of the present invention 1 under high-resolution-ration transmission electric-lens (HRTEM) Ring；
Fig. 2 is microstructure morphology of the embodiment of the present invention 1 under scanning electron microscope (SEM)；
Fig. 3 is the XRD diffraction spectras of embodiment 1 ~ 5 and comparative example after ball-milling treatment；
Fig. 4 is microstructure morphology and electronic diffraction ring of the embodiment of the present invention 5 under high-resolution-ration transmission electric-lens (HRTEM)；
Fig. 5 is microstructure morphology of the embodiment of the present invention 5 under scanning electron microscope (SEM).
Fig. 6 is microstructure morphology of the comparative example under scanning electron microscope (SEM).
Specific implementation mode
With reference to embodiment, invention is further explained.
The present invention passes through the study found that metallic copper is added into Mg base hydrogen storage material can reduce magnesium base alloy hydride Thermal stability and improve its inhale hydrogen desorption kinetics performance.Meanwhile nickel is good active element, can be obviously improved magnesium-based conjunction The suction hydrogen release thermodynamics and kinetics performance of gold.In terms of technique preparation, ball-milling treatment can be obtained with ultra-fine grain（Nanometer Scale）Structure, be added suitable nanometer of Cr2O3Ball milling is carried out as catalyst and alloy, the ruler of alloying pellet can be reduced Very little, the alloy powder after ball milling possesses a large amount of crystal defect, nucleation point and diffusion admittance, is conducive to the expansion of hydrogen in the alloy It dissipates, further reduced the hydrogen decomposition temperature of alloy and reduces the activation energy that material inhales hydrogen release, keep the suction hydrogen release of alloy dynamic Mechanical property is further enhanced, highly beneficial for the suction hydrogen desorption kinetics performance for greatly improving and improving hydrogen storage material.
The present invention makees hydrogen-storage alloy ingredient involved in the present invention and preparation method by the following examples further Explanation.
A kind of fuel cell high capacity Mg-Cu-Ni ternary hydrogen-storage alloys of the present invention, Components Chemical formula are： Mg85Cu5Ni10 + x wt.%( Cr2O3), whereinxFor Cr2O3The mass percent of shared alloy, andx= 0~8；The Mg- Cu-Ni ternary hydrogen-storage alloys have main phase Mg phases, the second phase Mg2Ni and Mg2Cu phases, and there is nanocrystalline and amorphous structure.
The suction hydrogen discharging temperature of the Mg-Cu-Ni ternarys hydrogen-storage alloy is 260 DEG C, and suction hydrogen initial hydrogen pressure is 2 MPa, is put Hydrogen is 1 × 10-4It is carried out under MPa pressure.
The preparation method of fuel cell high capacity Mg-Cu-Ni ternary hydrogen-storage alloys of the present invention includes the following steps：
A, dispensing：Mg is formed by chemical formula85Cu5Ni10Carry out dispensing, wherein the magnesium in the chemical formula composition increases in proportioning Add the scaling loss amount of 10% ratio, purity >=99.5% of raw material；
B, prepared by as cast condition master alloy：The raw material prepared is placed in magnesia crucible, outside demagging, all material is added in no particular order Magnesium is finally placed on top by crucible.Using conventional heating means, including electric arc melting, inducing melting or other heating Method is evacuated to 1 × 10-2 Pa~5×10-5Pa, it is 0.01MPa ~ 0.1MPa inert protective gas to be then charged with pressure, lazy Property protective gas be high-purity helium；The heating power that melting starts is adjusted to about 5 kW, and temperature is controlled at 650 DEG C or so, makes gold Belonging to magnesium fusing, heating power is then increased to 25 kW, temperature is controlled at about 1550 DEG C, it is ensured that raw metal is completely melt, Obtain the Mg of melting85Cu5Ni10Liquid master alloy is kept for 1 ~ 5 minute in the molten state；Liquid master alloy is directly injected into copper In mold, with room temperature is furnace-cooled to, as cast condition mother alloy ingot is obtained.
C, ball-milling treatment：By the above-mentioned steps b alloy cast ingot Mechanical Crushings prepared and 200 mesh sieve is crossed, by the alloy of sieving Powder withxThe catalyst nano Cr of wt.%2O3It is packed into stainless steel jar mill together,xFor Cr2O3The quality percentage of shared hydrogen-storage alloy Than, andx= 0~8；High-purity argon gas, ratio of grinding media to material 40 are filled with after vacuumizing:1；Rotating speed：350 revs/min, in comprehensive planetary high energy Ball milling 5 hours in ball mill obtain high capacity Mg-Cu-Ni ternary hydrogen-storage alloys.
It is shut down 1 hour within 1 hour per ball milling in mechanical milling process, to prevent ball grinder temperature excessively high.
The structure that ball-milled powder is tested with XRD observes ball with high-resolution-ration transmission electric-lens (HRTEM) and scanning electron microscope (SEM) The pattern and microstructure of alloying pellet after mill, are used in combination selective electron diffraction (SEAD) to determine the crystalline state of ball milling alloy.With it is complete from The gaseous state hydrogen storage capacity and suction hydrogen desorption kinetics of dynamic Sieverts equipment beta alloy powder.It is 260 DEG C to inhale hydrogen discharging temperature, is inhaled Hydrogen initial hydrogen pressure is 2 MPa, and hydrogen release is 1 × 10-4 It is carried out under MPa pressure.
The chemical composition of the specific embodiment of the invention and comparative example（Atomic ratio）Selection is as follows：
Embodiment 1: Mg85Cu5Ni10(5 h of ball milling)
Embodiment 2: Mg85Cu5Ni10 + 2 wt.% (Cr2O3) (5 h of ball milling)
Embodiment 3: Mg85Cu5Ni10 + 4 wt.% (Cr2O3) (5 h of ball milling)
Embodiment 4: Mg85Cu5Ni10 + 6 wt.% (Cr2O3) (5 h of ball milling)
Embodiment 5: Mg85Cu5Ni10 + 8 wt.% (Cr2O3) (5 h of ball milling)
Comparative example: Mg85Cu5Ni10 (as cast condition)
Embodiment 1
By chemical formula Mg85Cu5Ni10, choose reguline metal magnesium, metallic copper and metallic nickel.These metal purity >=99.5%, by change Dose ratio is learned to weigh.The capacity of the magnesia crucible of smelting equipment is 2 kilograms, and alloy material gross weight is calculated with 2 kilograms.Weigh metal 1530.013 grams of magnesium（To prevent the volatilization of magnesium, add the magnesium into 10wt.%）, 213.917 grams of metallic copper, metallic nickel 395.161 Gram, it is placed in the magnesia crucible of intermediate frequency furnace, vacuum degree 1 × 10 is evacuated to after covering bell-2 Pa or more is re-filled with Pressure is 0.04MPa helium as protective gas.The heating power that melting starts is adjusted to about 5 kW, and temperature is controlled at 650 DEG C Left and right, makes magnesium metal melt, and heating power is then increased to 25 kW, and temperature is controlled at about 1550 DEG C, keeps all metals molten Change.It keeps after five minutes, liquid alloy directly being poured into Copper casting mould under melting condition, cooling about 30 under helium protective atmosphere It comes out of the stove after minute, obtains the cylindric mother alloy ingot of 30 mm of diameter.
By as cast condition Mg85Cu5Ni10Alloy mechanical is crushed and crosses 200 mesh sieve, weighs 100 grams of loadings of alloy powder after sieving In stainless steel jar mill, vacuumizes and sealed after being filled with high-purity argon gas.Ball milling 5 is small in comprehensive planetary high-energy ball mill When.Ratio of grinding media to material 40:1, rotating speed is 350 revs/min.In mechanical milling process, shut down 1 hour within 1 hour per ball milling.
XRD test results show that the hydrogen storage material has nanocrystalline and amorphous structure, as a result see Fig. 3, and electricity is transmitted with high-resolution Mirror (HRTEM) and scanning electron microscope (SEM) observe the microscopic appearance of ball milling state alloy, as depicted in figs. 1 and 2.It is surveyed with full-automatic The gaseous state hydrogen sucting discharging hydrogen capacity and dynamics of the hydrogen storage material are tried, the results are shown in Table 1.
Embodiment 2
Alloying component is：Mg85Cu5Ni10 + 2 wt.% (Cr2O3), weigh 1530.013 grams of magnesium metal（To prevent waving for magnesium Hair, adds the magnesium into 10wt.%）, 213.917 grams of metallic copper, 395.161 grams of metallic nickel.Casting is smelted according to the method for embodiment 1 Then state master alloy carries out Mechanical Crushing and ball-milling treatment, except that the Cr used2O3Additive amount be 2 wt.%, ball milling Time is 5 hours.XRD test results show that alloy has nanocrystalline and amorphous structure, as a result see Fig. 3；Test the gas of alloy State hydrogen sucting discharging hydrogen capacity and dynamics, the results are shown in Table 1.
Embodiment 3
Alloying component is：Mg85Cu5Ni10 + 4 wt.% (Cr2O3), weigh 1530.013 grams of magnesium metal（To prevent waving for magnesium Hair, adds the magnesium into 10wt.%）, 213.917 grams of metallic copper, 395.161 grams of metallic nickel.As cast condition is smelted according to the method for example 1 Then master alloy carries out Mechanical Crushing and ball-milling treatment, except that the Cr used2O3Additive amount be 4wt.%, when ball milling Between be 5 hours.XRD test results show that alloy has nanocrystalline and amorphous structure, as a result see Fig. 3；Test the gaseous state of alloy Hydrogen sucting discharging hydrogen capacity and dynamics, the results are shown in Table 1.
Embodiment 4
Alloying component is：Mg85Cu5Ni10 + 6 wt.% (Cr2O3), weigh 1530.013 grams of magnesium metal（To prevent waving for magnesium Hair, adds the magnesium into 10wt.%）, 213.917 grams of metallic copper, 395.161 grams of metallic nickel.As cast condition is smelted according to the method for example 1 Then master alloy carries out Mechanical Crushing and ball-milling treatment, except that the Cr used2O3Additive amount be 6 wt.%, when ball milling Between be 5 hours.XRD test results show that alloy has nanocrystalline and amorphous structure, as a result see Fig. 3；Test the gaseous state of alloy Hydrogen sucting discharging hydrogen capacity and dynamics, the results are shown in Table 1.
Embodiment 5
Alloying component is：Mg85Cu5Ni10 + 8 wt.% (Cr2O3), weigh 1530.013 grams of magnesium metal（To prevent waving for magnesium Hair, adds the magnesium into 10wt.%）, 213.917 grams of metallic copper, 395.161 grams of metallic nickel.As cast condition is smelted according to the method for example 1 Then master alloy carries out Mechanical Crushing and ball-milling treatment, except that the Cr used2O3Additive amount be 8 wt.%, when ball milling Between be 5 hours.XRD test results show that alloy has nanocrystalline and amorphous structure, as a result see Fig. 2；Use high-resolution-ration transmission electric-lens (HRTEM) and scanning electron microscope (SEM) observes the microscopic appearance of ball milling state alloy, as shown in Figure 4 and Figure 5.Test alloy Gaseous state hydrogen sucting discharging hydrogen capacity and dynamics, the results are shown in Table 1.
Comparative example
Alloying component is：Mg85Cu5Ni10, weigh 1530.013 grams of magnesium metal（To prevent the volatilization of magnesium, add into 10wt.%'s Magnesium）, 213.917 grams of metallic copper, 395.161 grams of metallic nickel.As cast condition master alloy is smelted according to the method for example 1, then carries out machine Tool break process, except that comparative example is without addition catalyst and ball-milling treatment.XRD test results show that alloy does not have There is nanocrystalline and amorphous structure, as a result sees Fig. 3；Its SEM is shown in Fig. 6.The gaseous state hydrogen sucting discharging hydrogen capacity and dynamics of alloy are tested, The results are shown in Table 1.
The hydrogen storage capacity and cyclical stability of the hydrogen-storage alloy of 1 heterogeneity alloy powder of table
C max (wt.%) Ca 5 (wt%) Cd 30 (wt%) S 50 (%)
Embodiment 1 5.422 5.158 5.377 92.45
Embodiment 2 5.342 5.001 5.205 99.71
Embodiment 3 5.224 4.835 5.185 99.52
Embodiment 4 5.115 4.863 5.002 99.29
Embodiment 5 5.071 4.721 4.983 99.15
Comparative example 5.572 4.584 5.341 90.36
C max- saturation the hydrogen-sucking amount (wt.%) in the case where initial hydrogen pressure is 2 MPa and 260 DEG C；
Ca 5—In the case where initial hydrogen pressure is 2 MPa and 260 DEG C, the hydrogen-sucking amount (wt.%) in 5 minutes；
Cd 30—It is 1 × 10 in initial pressure-4 At MPa and 260 DEG C, the hydrogen desorption capacity (wt.%) in 30 minutes；
S 50 = C 50/C max × 100%, whereinC maxIt is the saturation hydrogen-sucking amount of alloy,C 50Hydrogen-sucking amount after 50th cycle.
Table 1 the result shows that, ball milling alloy powder have higher suction hydrogen release capacity and excellent dynamic performance.With state Inside and outside studied similar alloy compares, and hydrogen storage performance of the alloy of the present invention under low-temperature condition is significantly improved, and Alloy has good suction hydrogen release cyclical stability.
Although the present invention is described its preferred embodiment, it is clear that those skilled in the art can take other realities Mode is applied, such as changes the technical parameters such as alloying component, catalyst charge, Ball-milling Time, ratio of grinding media to material or rotating speed, is not being departed from In the range of design philosophy of the present invention, various changes and modifications can be carried out, these variations belong to the protection of the present invention.

Claims (9)

1. a kind of high capacity Mg-Cu-Ni ternary hydrogen-storage alloys, it is characterised in that：The hydrogen-storage alloy be include Mg85 Cu 5Ni10It closes Gold and catalyst nano Cr2O3Ultra-fine grain powder, wherein catalyst nano Cr2O3Mg is accounted for by mass percentage85Cu5Ni10The ratio of alloy is x%, x=0 ~ 8；Hydrogen-storage alloy tool the main phase Mg, the second phase Mg2Ni and Mg2Cu phases, and have and receive Meter Jing-non crystalline structure.
2. high capacity Mg-Cu-Ni ternary hydrogen-storage alloys according to claim 1, it is characterised in that：The hydrogen-storage alloy powder It is by as cast condition Mg85Cu5Ni10Catalyst nano Cr is added after broken, screening in alloy2O3Ball milling obtains for 5 hours.
3. high capacity Mg-Cu-Ni ternary hydrogen-storage alloys according to claim 1, it is characterised in that：The Mg-Cu-Ni tri- The suction hydrogen discharging temperature of first hydrogen-storage alloy is 260 DEG C, and suction hydrogen initial hydrogen pressure is 2 MPa, and hydrogen release is 1 × 10-4Under MPa pressure into Row.
4. high capacity Mg-Cu-Ni ternary hydrogen-storage alloys according to claim 1, it is characterised in that：The Mg-Cu-Ni tri- First hydrogen-storage alloy has following hydrogen storage performance：
In the case where initial hydrogen pressure is 2 MPa and 260 DEG C, the hydrogen-sucking amount in 5 minutes is 4.584 ~ 5.158wt.%；
It is 1 × 10 in initial pressure-4 At MPa and 260 DEG C, the hydrogen desorption capacity in 30 minutes is 4.983 ~ 5.377wt.%；
Suction hydrogen rate after 50th cycle is 90.36 ~ 99.71%.
5. a kind of preparation method preparing high capacity Mg-Cu-Ni ternary hydrogen-storage alloys described in claim 1, it is characterised in that： This approach includes the following steps：
A, dispensing：It is chemical formula Mg by atomic ratio85Cu5Ni10Composition carry out dispensing, purity >=99.5% of raw material；
B, prepared by as cast condition master alloy：By the raw material prepared using conventional heating means melting, it is evacuated to 1 × 10-2 Pa~5× 10-5Pa, it is 0.01MPa ~ 0.1MPa inert protective gas to be then charged with pressure, and the melting incipient stage, temperature is controlled at 650 DEG C ± 10 DEG C, magnesium metal is made to melt, then heats up and control temperature at 1550 DEG C ± 10 DEG C, obtain the Mg of melting85Cu5Ni10Liquid Master alloy is kept for 1 ~ 5 minute in the molten state；Liquid master alloy is directly injected into Copper casting mould, with room temperature is furnace-cooled to, is obtained As cast condition mother alloy ingot；
C, ball-milling treatment：As cast condition mother alloy ingot prepared by step b is crushed and cross 200 mesh sieve, by the alloyed powder of sieving withx The catalyst nano Cr of wt.%2O3It is packed into stainless steel jar mill together,xFor Cr2O3Account for Mg85Cu5Ni10The mass percent of alloy, Andx= 0~8；High-purity argon gas, ratio of grinding media to material 40 are filled with after vacuumizing:1；Rotating speed：350 revs/min, ball milling 5 hours obtains high power capacity Compound Mg-Cu-Ni ternarys hydrogen-storage alloy.
6. the preparation method of high capacity Mg-Cu-Ni ternary hydrogen-storage alloys according to claim 5, it is characterised in that：It is described Magnesium in chemical formula composition increases the volatile quantity of 10wt.% ratios in proportioning.
7. the preparation method of high capacity Mg-Cu-Ni ternary hydrogen-storage alloys according to claim 5, it is characterised in that：It is described In step b, heating means include electric arc melting and inducing melting.
8. the preparation method of high capacity Mg-Cu-Ni ternary hydrogen-storage alloys according to claim 5, it is characterised in that：It is described In step b, the inert protective gas is the mixed gas of high-purity helium or argon gas+helium, argon gas and helium in mixed gas Volume ratio be 1:1.
9. the preparation method of high capacity Mg-Cu-Ni ternary hydrogen-storage alloys according to claim 5, it is characterised in that：It is described In step c, shut down 1 hour within 1 hour per ball milling in mechanical milling process.
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