CN110387495A - A kind of antioxygen gas poisons Zr-V-Ni hydrogen storage material and preparation method thereof - Google Patents
A kind of antioxygen gas poisons Zr-V-Ni hydrogen storage material and preparation method thereof Download PDFInfo
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/02—Alloys based on vanadium, niobium, or tantalum
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
- C22F1/18—High-melting or refractory metals or alloys based thereon
Abstract
A kind of antioxygen gas poisons Zr-V-Ni hydrogen storage material and preparation method thereof, is Zr (V by chemical formula1‑xNix)2, wherein hydrogen-storage alloy raw material is put into crucible by x=0.02~0.25, carries out melting, then be put into resistance furnace after sealing, and heated under vacuum to 1173K-1473K simultaneously keeps the temperature 168 hours, cooling, obtains hydrogen-storage alloy.It by non-consumable electric arc melting, is carried out in water jacketed copper crucible, since cooling rate is very fast, process of setting belongs to nonequilibrium freezing, and alloy reaction not exclusively, often has peritectic reaction last phase in cast alloy.It is handled by vacuum homogenizing annealing, making the unreacted in alloy, completely richness V solid solution phase and α-Zr phase further occurrence solid solution reaction, alloy obtain more uniform Laves phase.This method preparation Zr- base hydrogen storage material is simple for process, high-efficient, low for equipment requirements, at low cost.
Description
Technical field
The present invention relates to storage alloy material for hydrogen technical fields, and in particular to a kind of antioxygen gas poisons Zr-V-Ni hydrogen storage material
And preparation method thereof.
Background technique
Hydrogen-storage alloy is divided by the main species of component: Rare Earth, titanium system, zirconium, four major class of magnesium system, by main group
It is divided at the atomic ratio of element: AB5Type, AB2Type, AB type, A2Type B, in addition can also by crystalline state and amorphous state, powder and film into
Row classification.Hydrogen-storage alloy essential characteristic: binary alloys (or intermetallic compound) substantially in 1970 before and after successive
It is found.These binary alloys can be divided into AB5(rare earth-based alloy such as forms LaNi to type5H6)、AB2(Laves's type is harmonious
Gold such as forms ZrV2H4.8), AB type (titanium alloy, such as formed TiFeH1.9) and A2(magnesium base alloy such as forms Mg to Type B2NiH4)。
Wherein A is hydride stabilizing element (fever type metal), and B is hydride unstability element (endothermic metal), A atom half
Diameter is greater than B atomic radius.Hydrogen is higher than the density of liquified hydrogen in metal and alloy, and hydrogen can be reversible under relatively mild conditions
Suction is put, and with the release and absorption of heat.Oil embargo and energy crisis has occurred along in the seventies, it is a large amount of to study
Persons have turned one's attention to the research that can be used for the metal hydride of energy storage and conversion.It has arrived in the 1980s, nickel-
Metal hydride (Ni-MH) rechargeable battery is successfully realized commercialization, has started the research heat of hydrogen bearing alloy in the world
Tide.In recent decades, worldwide numerous researchers and scientific research personnel expand extensive research to hydrogen bearing alloy, very much
Research achievement has been introduced into practical stage, for example, the storage and transport of hydrogen, the separation that hydrogen tires out with position, temperature and pressure
Sensor, the fields such as fuel cell all make great progress, and have been developed as the new branch of science of a gate pole richness vigor.
AB with C14, C15 structure Laves phase2Type Zr base intermetallic compound since its hydrogen storage capability is big, inhale by room temperature
Hydrogen balance is forced down, easily-activated, inhales the features such as hydrogen dynamics is fast, is met the storage in hydrogen and its isotope to a certain extent and is divided
From the application in, fields such as atmosphere purification, tritium recycling in nonevaporable getter (NEG), ultrahigh vacuum pump and nuclear industry.With
Scientific technological advance, the vacuum condition that many research and production fields need it is higher and higher.Such as Surface Science, semiconductor work
The vacuum degree that industry and high energy acclerator need reaches 10-8Pa or higher level.To reach vacuum environment horizontal in this way, do not have
Suitable material selection, surface treatment and air suction mode are difficult to realize.Due to Zr based alloy because having room temperature item
Of low equilibrium pressure under part, stable storing, small in size, pumping speed is big and can form stable compound with active gases at normal temperature, reaches
To pumping purpose, so being widely used in industry and scientific research field.Such as in electron-positron collider and synchrotron radiation light source
Storage rings in, electronics circles and generates synchrotron radiation light, synchrotron radiation light beat will be generated on vacuum box inner wall it is big
The gas desorption of amount.In order to keep electronics to have enough service life, it is desirable that the vacuum of storage rings reaches 10-8Pa or so, and storage rings
Vacuum box by structure and conductance due to being limited, it is impossible to the very more vacuum pump of installation.Pacify using along vacuum pipe side
Filling distributed nonevaporable getter and bringing the vacuum degree for obtaining and needing is a kind of extraordinary method, and Zr alloy oneself by conduct
Getter is applied to several big particle accelerator storage rings in the world.Although zirconium base Laves hydrogen storage alloy phase activity function,
The performances such as hydrogen-sucking amount, suction hydrogen dynamics are preferable compared with magnesium system and group of the lanthanides, but also need to be further improved, and its hydride is excessively steady
It is fixed, it is not easily decomposed, there are apparent hysteresis effects when inhaling hydrogen release.Meanwhile the foreign gas in hydrogen source is to alloy hydrogen storage property
Influence it is extremely obvious.Including N2、CO、CO2And O2Even if etc. the minimum Shi Douhui of foreign gases content cause include hydrogen-sucking amount, inhale
The sharp fall of the hydrogen bearing alloys important performance such as hydrogen dynamics and cyclical stability.
In the preparation of Zr base Laves hydrogen storage alloy phase, alloying is to improve the main path of its hydrogen storage performance.To a certain degree
Alloying can improve suction hydrogen release heat/dynamics, antitoxinization performance of Zr base Laves hydrogen storage alloy phase, and can be put in suction
Crucial catalytic action is played in hydrogen reaction temperature.The ratio and M-H key of protium are not inhaled by adjusting suction hydrogen in alloy and
Intensity improves and inhales hydrogen release thermodynamics and kinetics performance, improves the sucking/placing hydrogen amount of alloy.By adjusting the crystal structure of alloy,
Control alloy hydrogen absorption and desorption plateau pressure and hysteretic properties.By changing the surface composition and structure of alloy, improve alloy conductive
Energy and electrocatalysis characteristic, and improve the resistance to corrosion of alloy, improve alloy cycle life.
In numerous elements, Ni race element has most positive facilitation to the dissociation of hydrogen molecule, and the addition of Ni element can
To drop low-alloyed initial suction hydrogen pressure and hydrogen release pressure, become easier to absorption hydrogen, the addition of Ni element can also change
Anti- disproportionation ability of the kind alloy in suction/hydrogen release circulation.V is substituted using Ni, is expected to improve AB2Type Zr base Laves phase hydrogen storage closes
Suction hydrogen release heat/dynamics of gold simultaneously improves its antitoxinization performance.
Summary of the invention
To overcome AB existing in the prior art2Type Zr base Laves hydrogen storage alloy phase inhales the deficiency of hydrogen dynamic performance, inhales
The excessive problem of hydrogen release hysteresis quality, the purpose of the present invention is to provide a kind of antioxygen gas to poison Zr-V-Ni hydrogen storage material and its system
Preparation Method.
To achieve the above object, the present invention adopts the following technical scheme that:
A kind of antioxygen gas poisons Zr-V-Ni hydrogen storage material, and chemical formula is Zr (V1-xNix)2, wherein x=0.02~0.25.
A further improvement of the present invention lies in that x=0.02,0.05,0.10,0.15 or 0.25.
A further improvement of the present invention lies in that Zr is the nuclear leve sponge Zr that purity is 99.4%.
A further improvement of the present invention lies in that Ti is the Ti plate that purity is 99.97%.
A further improvement of the present invention lies in that V is the dendrite V that purity is 99.5%.
A kind of preparation method of Zr base Laves hydrogen storage alloy phase, includes the following steps:
Step 1, melting: being Zr (V by chemical formula1-xNix)2, prepared hydrogen-storage alloy raw material is put into water jacketed copper crucible
It is interior, melting is carried out, hydrogen-storage alloy ingot casting is obtained；
Step 2, vacuum annealing: packaged hydrogen-storage alloy ingot casting is put into chamber type electric resistance furnace, heated under vacuum
To 1173K-1473K and 156-216 hours are kept the temperature, it is cooling, obtain hydrogen-storage alloy.
A further improvement of the present invention lies in that carrying out melting using vacuum non-consumable arc-melting furnace in step 1.
A further improvement of the present invention lies in that in melting, vacuum degree is 6 × 10 in step 1-3Pa is filled with argon gas as guarantor
Protect atmosphere.
A further improvement of the present invention lies in that hydrogen-storage alloy ingot casting is sealed by following procedure in step 2: will melt
After the hydrogen-storage alloy ingot casting cleaning refined, it is fitted into quartz ampoule, vacuumize process is carried out, when vacuum degree reaches 10-4It is complete when magnitude
At the sealing of quartz ampoule.
A further improvement of the present invention lies in that in step 2, it is cooling to use furnace cooling.
The present invention is in AB2Type ZrV2On the basis of alloy, with the side Ni element substitution B V element, compared with prior art, sheet
Invention has the advantages that
1, in terms of hydrogen-storage alloy preparation, alloy cast ingot is to be carried out by non-consumable electric arc melting in water jacketed copper crucible,
Since cooling rate is very fast, process of setting belongs to nonequilibrium freezing, and alloy reaction not exclusively, it is anti-often to have peritectoid in cast alloy
Answer last phase.It is handled by further vacuum homogenizing annealing, makes unreacted in alloy completely richness V solid solution phase and α-Zr
Phase further occurrence solid solution reaction, alloy obtain more uniform Laves phase.This method prepares Zr- base hydrogen storage material simple process
It is easy, it is high-efficient, it is low for equipment requirements, it is at low cost.
2, the process for accelerating hydrogen molecule and being dissociated into hydrogen atom of Ni element, lowers the stability of alloy hydride,
Improve suction/hydrogen release thermodynamics of alloy.The addition of Ni while the anti-disproportionation ability for improving alloy, alloy is in suction/hydrogen release process
In show good cyclical stability.Alloy when containing hydrogen is inhaled in a small amount of oxygen impurities gas, Ni element there are part compensation
Due to Zr element and V element be oxidized and the dissociation capability to hydrogen molecule lost, poison so as to improve alloy antioxygen gas
With power.
3, alloy of the present invention is ultralow balance pressure hydrogen-storage alloy, when Ni additive amount is not more than 0.10, equilibrium at room temperature pressure
Power platform is lower than 10-10The advantages that Pa, ultimate vacuum ability is strong, in the high particle accelerator storage rings of vacuum level requirements and surpasses
The operating conditions such as separation and recycling of hydrogen and hydrogen isotope under the conditions of low balance pressure have very big application advantage.
Detailed description of the invention
Fig. 1 is flow chart of the invention；
Fig. 2 is the SEM photograph after the annealing of Zr-V-Ni hydrogen-storage alloy sample；Wherein, (a) is Zr (V0.98Ni0.02)2, (b) it is
Zr(V0.95Ni0.05)2, (c) it is Zr (V0.9Ni0.1)2, (d) it is Zr (V0.85Ni0.15)2, (e) it is Zr (V0.75Ni0.25)2；
Fig. 3 is the X-ray diffractogram of Zr-V-Ni hydrogen-storage alloy；Wherein, (a) is as cast condition, (b) is annealed state.
Fig. 4 is Zr-V-Ni Hydrogen Storage Alloys kinetic curve；Wherein, (a) is Zr (V0.98Ni0.02)2The activation of alloy
Inhale hydrogen and 773K Dynamic isotherms of hydrogen absorption for the first time afterwards；It (b) is Zr (V0.9Ni0.1)2Hydrogen is inhaled after the activation of alloy for the first time and 773K inhales
Hydrogen kinetic curve；It (c) is Zr (V0.95Ni0.05)2Hydrogen and 773K Dynamic isotherms of hydrogen absorption are inhaled after the activation of alloy for the first time；(d) it is
Zr(V0.85Ni0.15)2Hydrogen and 773K Dynamic isotherms of hydrogen absorption are inhaled after the activation of alloy for the first time；It (e) is Zr (V0.75Ni0.25)2Alloy
Activation after inhale hydrogen and 773K Dynamic isotherms of hydrogen absorption for the first time；
Fig. 5 is Zr-V-Ni Hydrogen Storage Alloys P-C-T curve；Wherein: (a) being Zr (V0.98Ni0.02)2The P-C-T of alloy
Curve；It (b) is Zr (V0.95Ni0.05)2The P-C-T curve of alloy；It (c) is Zr (V0.9Ni0.1)2The P-C-T curve of alloy；(d) it is
Zr(V0.85Ni0.15)2The P-C-T curve of alloy；It (e) is Zr (V0.75Ni0.25)2The P-C-T curve of alloy；
Fig. 6 is Van ' the t Hoff regression straight line of Zr-V-Ni alloy；Wherein: (a) being Zr (V0.98Ni0.02)2Alloy
Van ' t Hoff regression straight line；It (b) is Zr (V0.95Ni0.05)2Van ' the t Hoff regression straight line of alloy；It (c) is Zr
(V0.9Ni0.1)2Van ' the t Hoff regression straight line of alloy；It (d) is Zr (V0.85Ni0.15)2Van ' the t Hoff of alloy returns straight
Line；It (e) is Zr (V0.75Ni0.25)2Van ' the t Hoff regression straight line of alloy；
Fig. 7 is Zr (V0.95Ni0.05)2Alloy contains 1vol.%O2O2/H2Hot activation curve in mixed gas；
Fig. 8 is Zr (V0.95Ni0.05)2Alloy contains 1vol.%O2O2/H2Hot activation curve in mixed gas；
Zr (V after activation when Fig. 9 is 308K0.95Ni0.05)2Suction hydrogen power of the alloy in different content oxygen after pre- exposure
Learn curve.
Specific embodiment
Present invention will now be described in detail with reference to the accompanying drawings..
A kind of antioxygen gas provided by the invention poisons Zr-V-Ni hydrogen storage material, and chemical formula is Zr (V1-xNix)2, wherein x=
0.02~0.25.Specifically, x=0.02,0.05,0.10,0.15 or 0.25.
In the present invention, Zr is the nuclear leve sponge Zr that purity is 99.4%.Ti is the Ti plate that purity is 99.97%.V is purity
For 99.5% dendrite V.
Based on the atomicity percentage composition of each ingredient, the content of Zr is that the total content of 33.33at.%, V and Ni are
66.67at.%, wherein the content of Ni is 1.33-16.67at.%；
Referring to Fig. 1, a kind of preparation method of Zr base Laves hydrogen storage alloy phase as described above includes the following steps:
Step 1, melting: being Zr (V by chemical formula1-xNix)2, prepared hydrogen-storage alloy raw material is put into water jacketed copper crucible
It is interior, the vacuum degree of burner hearth is then evacuated to 6 × 10-3Pa is hereinafter, be re-filled with high-purity argon gas to 0.5 × 105Pa then begins to use
Vacuum non-consumable arc-melting furnace carries out melting, in order to improve the homogeneity of ingredients of material, applies electromagnetism in fusion process and stirs
It mixes, and overturns melting 3~4 times to guarantee that ingredient is uniform, obtain hydrogen-storage alloy ingot casting；In melting, vacuum degree is 6 × 10-3Pa fills
Enter argon gas as protective atmosphere.
Step 2, vacuum annealing: melted hydrogen-storage alloy ingot casting is used into acetone respectively, surface is gone in dehydrated alcohol washout
Then ingot casting is packed into quartz ampoule by greasy dirt, repeatedly clear with high-purity Ar gas before sealing in advance at low temperature by quartz ampoule bakeout degassing
It washes three times, vacuumize process is then carried out, when vacuum degree≤10-4) when, complete the sealing of quartz ampoule.Packaged storage hydrogen is closed
Golden ingot casting is put into chamber type electric resistance furnace, and heated under vacuum to 1173K-1473K simultaneously keeps the temperature 156-216 hours.Heat preservation terminates
Furnace cooling obtains hydrogen-storage alloy with homogenizing annealing afterwards.
The present invention has the advantage that
1, in terms of hydrogen-storage alloy preparation, alloy cast ingot is to be carried out by non-consumable electric arc melting in water jacketed copper crucible,
Since cooling rate is very fast, process of setting belongs to nonequilibrium freezing, and alloy reaction not exclusively, it is anti-often to have peritectoid in cast alloy
Answer last phase.It is handled by further vacuum homogenizing annealing, makes unreacted in alloy completely richness V solid solution phase and α-Zr
Phase further occurrence solid solution reaction, alloy obtain more uniform Laves phase.This method prepares Zr- base hydrogen storage material simple process
It is easy, it is high-efficient, it is low for equipment requirements, it is at low cost.
2, the process for accelerating hydrogen molecule and being dissociated into hydrogen atom of Ni element, lowers the stability of alloy hydride,
Improve suction/hydrogen release thermodynamics of alloy.The addition of Ni while the anti-disproportionation ability for improving alloy, alloy is in suction/hydrogen release process
In show good cyclical stability, performance such as Fig. 4, Fig. 5 and Fig. 6.When alloy inhales hydrogen in containing a small amount of oxygen impurities gas,
Ni element there are parts to compensate for due to the dissociation capability to hydrogen molecule that Zr element and V element are oxidized and are lost, thus
Improve that alloy antioxygen gas poisons with power, performance such as Fig. 7, Fig. 8 and Fig. 9.
3, alloy of the present invention is ultralow balance pressure hydrogen-storage alloy, when Ni additive amount is not more than 0.10, equilibrium at room temperature pressure
Power platform is lower than 10-10Pa, as shown in table 1, the advantages that ultimate vacuum ability is strong, in the high particle accelerator of vacuum level requirements
The operating conditions such as separation and recycling of hydrogen and hydrogen isotope under the conditions of storage rings and ultralow balance pressure have very big application advantage.
It is below specific embodiment.
Embodiment 1
The present embodiment is a kind of Zr-V-Ni Hydrogen storage materials of metal, and the Zr-V-Ni Hydrogen storage materials of metal is by purity
99.4% nuclear leve sponge Zr, 99.97% Ti plate and 99.5% dendrite V, by chemical formula Zr (V0.98Ni0.02)2Prepare and
At ratio described in chemical formula is atomic ratio.
Step 1, load weighted raw material are put into water jacketed copper crucible, are evacuated to 6 × 10-3, under argon atmosphere protection
In vacuum non-consumable arc-melting furnace carry out alloy melting.In fusion process, to guarantee that alloying component is uniform, by hydrogen-storage alloy
Ingot is overturn remelting 4 times；
Step 2, Vacuum Package.Acetone, washes of absolute alcohol is used to remove surface respectively on Zr-V-Ni hydrogen-storage alloy ingot casting
Then sample is packed into quartz ampoule by greasy dirt, repeatedly clear with high-purity Ar gas before sealing in advance at low temperature by quartz ampoule bakeout degassing
It washes three times, with diffusion pump vacuumize process, when vacuum degree reaches 10-4When Pa magnitude, the sealing of quartz ampoule is completed.
Step 3, homogenizing annealing is handled.The examination Zr-V-Ni hydrogen-storage alloy ingot casting that vacuum seal installs is put into box electricity yin
In furnace, it is heated to 1173K-1473K and keeps the temperature 156-216 hours.Furnace cooling is store after heat preservation with homogenizing annealing
Hydrogen alloy.As can be seen that richness V solid solution dendrite quantity significantly reduces in alloy structure after homogenizing annealing is handled, such as scheme
Shown in 2, the X-ray diffractogram of alloy before and after annealing in conjunction with Fig. 3, it can be deduced that, in homogenizing annealing, Zr (V0.98Ni0.02)2
Solid solution transformation occurs for alloy, and the miscellaneous phase quantity in alloy is drastically reduced.As can be seen that alloy structure becomes after homogenizing annealing
It obtains more uniform.
Zr-V-Ni hydrogen-storage alloy ingot casting after annealing is cut into the thin slice of Φ 0.8mm × 1mm by machining, with third
Ketone clean the surface greasy dirt, then by sample surfaces polishing, washes of absolute alcohol, dry rear Vacuum Package.
The hydrogen storage property of Zr-V-Ni hydrogen-storage alloy thin slice after testing annealing, as a result as shown in Figure 4 and Figure 5.Zr
(V0.98Ni0.02)2Hydrogen-storage alloy activity function is preferable, after 723K vacuum activating 1 hour when the incubation period when 303K inhales hydrogen for the first time
Between it is extremely short, hydrogen-sucking amount reaches 2.25wt.%；When 773K inhales hydrogen, it can reach in 30 seconds and inhale hydrogen dynamic equilibrium, show as preferably
Dynamic performance；Suction hydrogen P-C-T test selection tetra- temperature of 673K, 723K, 773K and 823K of alloy, hydrogen release P-C-T are surveyed
Examination selection 823K (such as Fig. 5), alloy Hydrogen desorption isotherms and suction hydrogen curve co-insides, no hydrogen release hysteresis；Pass through thermodynamics fit line
Slope and intercept (such as Fig. 6) in Y-axis, can determine the thermodynamic parameter of absorption hydrogen reaction, thermodynamic parameter is substituted into
Van ' t Hoff equation, can acquire the hydrogen absorption equilibrium pressure of alloy at ambient temperature.Zr (V is listed in table 10.98Ni0.02)2
Room temperature hydrogen absorption equilibrium pressure value of the alloy under different hydrogen-sucking amounts, extrapolation equilibrium at room temperature are forced down in 10-12Pa。
Embodiment 2
The present embodiment is a kind of Zr-V-Ni Hydrogen storage materials of metal, and the Zr-V-Ni Hydrogen storage materials of metal is by purity
99.4% nuclear leve sponge Zr, 99.97% Ti plate and 99.5% dendrite V, by chemical formula Zr (V0.95Ni0.05)2Prepare and
At the ratio is atomic ratio.
Step 1, load weighted raw material are put into water jacketed copper crucible, are evacuated to 6 × 10-3, under argon atmosphere protection
In vacuum non-consumable arc-melting furnace carry out alloy melting.In fusion process, to guarantee that alloying component is uniform, by hydrogen-storage alloy
Ingot is overturn remelting 4 times；
Step 2, Vacuum Package.Acetone, washes of absolute alcohol is used to remove surface respectively on Zr-V-Ni hydrogen-storage alloy ingot casting
Then sample is packed into quartz ampoule by greasy dirt, repeatedly clear with high-purity Ar gas before sealing in advance at low temperature by quartz ampoule bakeout degassing
It washes three times, with diffusion pump vacuumize process, when vacuum degree reaches 10-4When Pa magnitude, the sealing of quartz ampoule is completed.
Step 3, homogenizing annealing is handled.The examination Zr-V-Ni hydrogen-storage alloy ingot casting that vacuum seal installs is put into box electricity yin
In furnace, it is heated to 1173K-1473K and keeps the temperature 168 hours.Furnace cooling is obtained storage hydrogen and is closed after heat preservation with homogenizing annealing
Gold.As can be seen that richness V solid solution dendrite quantity significantly reduces in alloy structure, such as Fig. 2 institute after homogenizing annealing is handled
Show, the X-ray diffractogram of alloy before and after annealing in conjunction with Fig. 3, it can be deduced that, in homogenizing annealing, Zr (V0.95Ni0.05)2Alloy
Solid solution transformation occurs, the miscellaneous phase quantity in alloy is drastically reduced.As can be seen that alloy structure becomes more after homogenizing annealing
Add uniformly.
Zr-V-Ni hydrogen-storage alloy ingot casting after annealing is cut into the thin slice of Φ 0.8mm × 1mm by machining, with third
Ketone clean the surface greasy dirt, then by sample surfaces polishing, washes of absolute alcohol, dry rear Vacuum Package.
The hydrogen storage property of Zr-V-Ni hydrogen-storage alloy thin slice after testing annealing, as a result as shown in Figure 4 and Figure 5.Zr
(V0.95Ni0.05)2Hydrogen-storage alloy activity function is preferable, after 723K vacuum activating 1 hour when the incubation period when 303K inhales hydrogen for the first time
Between it is extremely short, hydrogen-sucking amount reaches 2.19wt.%；When 773K inhales hydrogen, it can reach in 30 seconds and inhale hydrogen dynamic equilibrium, show as preferably
Dynamic performance；Suction hydrogen P-C-T test selection tetra- temperature of 673K, 723K, 773K and 823K of alloy, hydrogen release P-C-T are surveyed
Examination selection 823K (such as Fig. 5), alloy Hydrogen desorption isotherms and suction hydrogen curve co-insides, no hydrogen release hysteresis；Pass through thermodynamics fit line
Slope and Y-axis intercept (such as Fig. 6) can determine absorption hydrogen reaction thermodynamic parameter, thermodynamic parameter is substituted into
Van ' t Hoff equation, can acquire the hydrogen absorption equilibrium pressure of alloy at ambient temperature.Zr (V is listed in table 10.95Ni0.05)2
Room temperature hydrogen absorption equilibrium pressure value of the alloy under different hydrogen-sucking amounts, extrapolation equilibrium at room temperature are forced down in 10-13Pa。
Referring to Fig. 7, Fig. 8 and Fig. 9, alloy when containing hydrogen is inhaled in a small amount of oxygen impurities gas, Ni element there are part compensation
Due to Zr element and V element be oxidized and the dissociation capability to hydrogen molecule lost, poison so as to improve alloy antioxygen gas
With power.
Embodiment 3
The present embodiment is a kind of Zr-V-Ni Hydrogen storage materials of metal, and the Zr-V-Ni Hydrogen storage materials of metal is by purity
99.4% nuclear leve sponge Zr, 99.97% Ti plate and 99.5% dendrite V, by chemical formula Zr (V0.9Ni0.1)2It is formulated,
The ratio is atomic ratio.
Step 1, load weighted raw material are put into water jacketed copper crucible, are evacuated to 6 × 10-3, under argon atmosphere protection
In vacuum non-consumable arc-melting furnace carry out alloy melting.In fusion process, to guarantee that alloying component is uniform, by hydrogen-storage alloy
Ingot is overturn remelting 4 times；
Step 2, Vacuum Package.Acetone, washes of absolute alcohol is used to remove surface respectively on Zr-V-Ni hydrogen-storage alloy ingot casting
Then sample is packed into quartz ampoule by greasy dirt, repeatedly clear with high-purity Ar gas before sealing in advance at low temperature by quartz ampoule bakeout degassing
It washes three times, with diffusion pump vacuumize process, when vacuum degree reaches 10-4When Pa magnitude, the sealing of quartz ampoule is completed.
Step 3, homogenizing annealing is handled.The examination Zr-V-Ni hydrogen-storage alloy ingot casting that vacuum seal installs is put into box electricity yin
In furnace, it is heated to 1273K and keeps the temperature 168 hours.Furnace cooling obtains hydrogen-storage alloy with homogenizing annealing after heat preservation.It can
To find out, after homogenizing annealing is handled, richness V solid solution dendrite quantity is significantly reduced in alloy structure, as shown in Fig. 2, knot
Close the X-ray diffractogram of Fig. 3 annealing front and back alloy, it can be deduced that, in homogenizing annealing, Zr (V0.9Ni0.1)2Alloy occurs solid
Molten transformation, the miscellaneous phase quantity in alloy are drastically reduced.As can be seen that alloy structure becomes more after homogenizing annealing
It is even.
Zr-V-Ni hydrogen-storage alloy ingot casting after annealing is cut into the thin slice of Φ 0.8mm × 1mm by machining, with third
Ketone clean the surface greasy dirt, then by sample surfaces polishing, washes of absolute alcohol, dry rear Vacuum Package.
The hydrogen storage property of Zr-V-Ni hydrogen-storage alloy thin slice after testing annealing, as a result as shown in Figure 4 and Figure 5.Zr
(V0.9Ni0.1)2Hydrogen-storage alloy activity function is preferable, after 723K vacuum activating 1 hour when the incubation period when 303K inhales hydrogen for the first time
Between it is extremely short, hydrogen-sucking amount reaches 2.10wt.%；When 773K inhales hydrogen, it can reach in 30 seconds and inhale hydrogen dynamic equilibrium, show as preferably
Dynamic performance；Suction hydrogen P-C-T test selection tetra- temperature of 673K, 723K, 773K and 823K of alloy, hydrogen release P-C-T are surveyed
Examination selection 823K (such as Fig. 5), alloy Hydrogen desorption isotherms and suction hydrogen curve co-insides, no hydrogen release hysteresis；Pass through thermodynamics fit line
Slope and Y-axis intercept (such as Fig. 6) can determine absorption hydrogen reaction thermodynamic parameter, thermodynamic parameter is substituted into
Van ' t Hoff equation, can acquire the hydrogen absorption equilibrium pressure of alloy at ambient temperature.Zr (V is listed in table 10.9Ni0.1)2It closes
Room temperature hydrogen absorption equilibrium pressure value of the gold under different hydrogen-sucking amounts, extrapolation equilibrium at room temperature are forced down in 10-9Pa。
Embodiment 4
The present embodiment is a kind of Zr-V-Ni Hydrogen storage materials of metal, and the Zr-V-Ni Hydrogen storage materials of metal is by purity
99.4% nuclear leve sponge Zr, 99.97% Ti plate and 99.5% dendrite V, by chemical formula Zr (V0.85Ni0.15)2Prepare and
At the ratio is atomic ratio.
Step 1, load weighted raw material are put into water jacketed copper crucible, are evacuated to 6 × 10-3, under argon atmosphere protection
In vacuum non-consumable arc-melting furnace carry out alloy melting.In fusion process, to guarantee that alloying component is uniform, by hydrogen-storage alloy
Ingot is overturn remelting 4 times；
Step 2, Vacuum Package.Acetone, washes of absolute alcohol is used to remove surface respectively on Zr-V-Ni hydrogen-storage alloy ingot casting
Then sample is packed into quartz ampoule by greasy dirt, repeatedly clear with high-purity Ar gas before sealing in advance at low temperature by quartz ampoule bakeout degassing
It washes three times, with diffusion pump vacuumize process, when vacuum degree reaches 10-4When Pa magnitude, the sealing of quartz ampoule is completed.
Step 3, homogenizing annealing is handled.The examination Zr-V-Ni hydrogen-storage alloy ingot casting that vacuum seal installs is put into box electricity yin
In furnace, it is heated to 1173K-1473K and keeps the temperature 168 hours.Furnace cooling is obtained storage hydrogen and is closed after heat preservation with homogenizing annealing
Gold.As can be seen that richness V solid solution dendrite quantity significantly reduces in alloy structure, such as Fig. 2 institute after homogenizing annealing is handled
Show, the X-ray diffractogram of alloy before and after annealing in conjunction with Fig. 3, it can be deduced that, in homogenizing annealing, Zr (V0.85Ni0.15)2Alloy
Solid solution transformation occurs, the miscellaneous phase quantity in alloy is drastically reduced.As can be seen that alloy structure becomes more after homogenizing annealing
Add uniformly.
Zr-V-Ni hydrogen-storage alloy ingot casting after annealing is cut into the thin slice of Φ 0.8mm × 1mm by machining, with third
Ketone clean the surface greasy dirt, then by sample surfaces polishing, washes of absolute alcohol, dry rear Vacuum Package.
The hydrogen storage property of Zr-V-Ni hydrogen-storage alloy thin slice after testing annealing, as a result as shown in Figure 4 and Figure 5.Zr
(V0.85Ni0.15)2Hydrogen-storage alloy activity function is preferable, after 723K vacuum activating 1 hour when the incubation period when 303K inhales hydrogen for the first time
Between it is extremely short, hydrogen-sucking amount reaches 2.01wt.%；When 773K inhales hydrogen, it can reach in 30 seconds and inhale hydrogen dynamic equilibrium, show as preferably
Dynamic performance；Suction hydrogen P-C-T test selection tetra- temperature of 673K, 723K, 773K and 823K of alloy, hydrogen release P-C-T are surveyed
Examination selection 823K (such as Fig. 5), alloy Hydrogen desorption isotherms and suction hydrogen curve co-insides, no hydrogen release hysteresis；Pass through thermodynamics fit line
Slope and Y-axis intercept (such as Fig. 6) can determine absorption hydrogen reaction thermodynamic parameter, thermodynamic parameter is substituted into
Van ' t Hoff equation, can acquire the hydrogen absorption equilibrium pressure of alloy at ambient temperature.Zr (V is listed in table 10.85Ni0.15)2
Room temperature hydrogen absorption equilibrium pressure value of the alloy under different hydrogen-sucking amounts, extrapolation equilibrium at room temperature are forced down in 10-10Pa。。
Embodiment 5
The present embodiment is a kind of Zr-V-Ni Hydrogen storage materials of metal, and the Zr-V-Ni Hydrogen storage materials of metal is by purity
99.4% nuclear leve sponge Zr, 99.97% Ti plate and 99.5% dendrite V, by chemical formula Zr (V0.75Ni0.25)2Prepare and
At the ratio is atomic ratio.
Step 1, load weighted raw material are put into water jacketed copper crucible, are evacuated to 6 × 10-3, under argon atmosphere protection
In vacuum non-consumable arc-melting furnace carry out alloy melting.In fusion process, to guarantee that alloying component is uniform, by hydrogen-storage alloy
Ingot is overturn remelting 4 times；
Step 2, Vacuum Package.Acetone, washes of absolute alcohol is used to remove surface respectively on Zr-V-Ni hydrogen-storage alloy ingot casting
Then sample is packed into quartz ampoule by greasy dirt, repeatedly clear with high-purity Ar gas before sealing in advance at low temperature by quartz ampoule bakeout degassing
It washes three times, with diffusion pump vacuumize process, when vacuum degree reaches 10-4When Pa magnitude, the sealing of quartz ampoule is completed.
Step 3, homogenizing annealing is handled.The examination Zr-V-Ni hydrogen-storage alloy ingot casting that vacuum seal installs is put into box electricity yin
In furnace, it is heated to 1173K-1473K and keeps the temperature 168 hours.Furnace cooling is obtained storage hydrogen and is closed after heat preservation with homogenizing annealing
Gold.As can be seen that richness V solid solution dendrite quantity significantly reduces in alloy structure, such as Fig. 2 institute after homogenizing annealing is handled
Show, the X-ray diffractogram of alloy before and after annealing in conjunction with Fig. 3, it can be deduced that, in homogenizing annealing, Zr (V0.75Ni0.25)2Alloy
Solid solution transformation occurs, the miscellaneous phase quantity in alloy is drastically reduced.As can be seen that alloy structure becomes more after homogenizing annealing
Add uniformly.
Zr-V-Ni hydrogen-storage alloy ingot casting after annealing is cut into the thin slice of Φ 0.8mm × 1mm by machining, with third
Ketone clean the surface greasy dirt, then by sample surfaces polishing, washes of absolute alcohol, dry rear Vacuum Package.
The hydrogen storage property of Zr-V-Ni hydrogen-storage alloy thin slice after testing annealing, as a result as shown in Figure 4 and Figure 5.Zr
(V0.75Ni0.25)2Hydrogen-storage alloy activity function is preferable, after 723K vacuum activating 1 hour when the incubation period when 303K inhales hydrogen for the first time
Between it is extremely short, hydrogen-sucking amount reaches 1.98wt.%；When 773K inhales hydrogen, it can reach in 30 seconds and inhale hydrogen dynamic equilibrium, show as preferably
Dynamic performance；Suction hydrogen P-C-T test selection tetra- temperature of 673K, 723K, 773K and 823K of alloy, hydrogen release P-C-T are surveyed
Examination selection 823K (such as Fig. 5), alloy Hydrogen desorption isotherms and suction hydrogen curve co-insides, no hydrogen release hysteresis；Pass through thermodynamics fit line
Slope and Y-axis intercept (such as Fig. 6) can determine absorption hydrogen reaction thermodynamic parameter, thermodynamic parameter is substituted into
Van ' t Hoff equation, can acquire the hydrogen absorption equilibrium pressure of alloy at ambient temperature.Zr (V is listed in table 10.75Ni0.25)2
Room temperature hydrogen absorption equilibrium pressure value of the alloy under different hydrogen-sucking amounts, extrapolation equilibrium at room temperature are forced down in 10-10Pa。
1 Zr (V of table1-xNix)2Thermodynamic parameter and room temperature the extrapolation balance pressure of hydrogen-storage alloy
Alloy of the present invention is ultralow balance pressure hydrogen-storage alloy, when Ni additive amount is not more than 0.10, equilibrium at room temperature pressure
Platform is lower than 10-10Pa, as shown in table 1, the advantages that ultimate vacuum ability is strong, in the high particle accelerator storage of vacuum level requirements
The operating conditions such as separation and recycling of hydrogen and hydrogen isotope under the conditions of ring and ultralow balance pressure are deposited, there is very big application advantage.
Claims (10)
1. a kind of antioxygen gas poisons Zr-V-Ni hydrogen storage material, which is characterized in that chemical formula is Zr (V1-xNix)2, wherein x=
0.02~0.25.
2. a kind of antioxygen gas according to claim 1 poisons Zr-V-Ni hydrogen storage material, which is characterized in that x=0.02,
0.05,0.10,0.15 or 0.25.
3. a kind of antioxygen gas according to claim 1 poisons Zr-V-Ni hydrogen storage material, which is characterized in that Zr is that purity is
99.4% nuclear leve sponge Zr.
4. a kind of antioxygen gas according to claim 1 poisons Zr-V-Ni hydrogen storage material, which is characterized in that Ti is that purity is
99.97% Ti plate.
5. a kind of antioxygen gas according to claim 1 poisons Zr-V-Ni hydrogen storage material, which is characterized in that V is that purity is
99.5% dendrite V.
6. a kind of preparation method of the Zr base Laves hydrogen storage alloy phase as described in any one of claim 1-5, feature exist
In including the following steps:
Step 1, melting: being Zr (V by chemical formula1-xNix)2, prepared hydrogen-storage alloy raw material is put into water jacketed copper crucible, into
Row melting obtains hydrogen-storage alloy ingot casting；
Step 2, vacuum annealing: packaged hydrogen-storage alloy ingot casting is put into chamber type electric resistance furnace, heated under vacuum is extremely
1173K-1473K simultaneously keeps the temperature 156-216 hours, cooling, obtains hydrogen-storage alloy.
7. the preparation method of Zr base Laves hydrogen storage alloy phase according to claim 5, which is characterized in that in step 1, adopt
Melting is carried out with vacuum non-consumable arc-melting furnace.
8. the preparation method of Zr base Laves hydrogen storage alloy phase according to claim 5, which is characterized in that in step 1, melt
In refining, vacuum degree is 6 × 10-3Pa is filled with argon gas as protective atmosphere.
9. the preparation method of Zr base Laves hydrogen storage alloy phase according to claim 5, which is characterized in that in step 2, storage
Hydrogen alloy cast ingot is sealed by following procedure: after melted hydrogen-storage alloy ingot casting is cleaned, being fitted into quartz ampoule, is carried out
Vacuumize process, when vacuum degree reaches 10-4When magnitude, the sealing of quartz ampoule is completed.
10. the preparation method of Zr base Laves hydrogen storage alloy phase according to claim 5, which is characterized in that cold in step 2
But furnace cooling is used.
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