CN103789573B - A kind of Zr base Laves phase hydrogen storage alloy and preparation method thereof - Google Patents
A kind of Zr base Laves phase hydrogen storage alloy and preparation method thereof Download PDFInfo
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Abstract
A kind of Zr base Laves phase hydrogen storage alloy and preparation method thereof.In described Zr base Laves phase hydrogen storage alloy, the total content of the content of Zr to be the content of 30at.%, Ti be 3.33at.%, V and Al is 66.67at.%, and wherein the content of aluminium is 1.33-16.67at.%, and all the other are content of vanadium.Its chemical formula is Zr
0.9ti
0.1(V
1-xal
x)
2(x=0.02,0.05,0.10,0.15,0.25), and be prepared from by melting and vacuum annealing.The present invention is at AB
2type ZrV
2on alloy basis, use Ti element substitution A side Zr element respectively, substitute B side V element with Al, vacuum annealing makes alloy obtain more uniform Laves phase; Lowered the stability of alloy hydride by Al element, improving hydrogen storage alloy inhaling the lag-effect of putting in hydrogen process, improve the performance of alloy.The present invention also has simple for process, and efficiency is high, low for equipment requirements, the feature that cost is low.
Description
Technical field
The present invention relates to alloy material storing hydrogen technical field, be specifically related to a kind of ultralow equilibrium pressure AB
2type Zr-Ti-V-Al hydrogen storage alloy and preparation method thereof.
Background technology
Hydrogen storage material as a kind of novel functional materials and the energy, the features such as it has, and hydrogen-storage amount is large, energy consumption is low, environment compatibility is good, operating pressure is low, easy to use.LaNi is found since middle 1960s
5since the reversible hydrogen storage effect of the intermetallic compounds such as FeTi, hydrogen storage alloy and applied research thereof are developed rapidly.Oneself is widely used in storage and the transport of hydrogen in recent years, the separation that hydrogen coordination is tired, temperature and pressure sensor, the fields such as nickel-hydrogen chargeable cell.
Hydrogen isotope tritium and deuterium have a wide range of applications in nuclear energy field, but it is as radioactive hydrogen isotropic substance, in use must strictly control.Then, in actually operating, unavoidable generation contains tritium waste gas, directly can not discharge, need carry out tritium process.Hydrogen storage alloy is used for detritiation device, there is structure simple, economical convenient, safety coefficient is high, compares, do not produce the advantages such as secondary pollutant HTO with current main detritiation technique hydride process, zirconium base Laves phase hydrogen storage alloy is large with its hydrogen-storage amount, the advantages such as hydrogen absorption equilibrium pressure is low, easily-activated, existing own certain applications are in this field.Although zirconium base Laves phase hydrogen storage alloy suction hydrogen dynamic performance comparatively magnesium system and group of the lanthanides better, also need further improvement, and its hydride is too stable, not easily decomposes, inhales when putting hydrogen and there is obvious lag-effect.
In the preparation of Zr base Laves phase hydrogen storage alloy, alloying reduces the main path of its hydride Enthalpies of Formation.Alloying to a certain degree can improve the suction hydrogen desorption kinetics performance of Zr base Laves phase hydrogen storage alloy, and can inhale katalysis hydrogen discharge reaction temperature playing key.By adjusting in alloy ratio and the M-H bonding strength inhaling hydrogen and do not inhale protium, improving suction and putting hydrogen thermodynamics and kinetics performance, carrying heavy alloyed sucking/placing hydrogen amount.By adjusting the crystalline structure of alloy, control alloy hydrogen absorption and desorption plateau pressure and hysteretic properties.By changing surface composition and the structure of alloy, improving alloy conductive performance and electrocatalysis characteristic, and improving the resistance to corrosion of alloy, improve alloy cycle life.
Metal A l is proved the suction hydrogen desorption kinetics performance that effectively can improve Zr base alloy, adds the stability that Al element can reduce alloy hydride simultaneously.Adopt Al to substitute V, be expected to improve the suction hydrogen desorption kinetics of Zr base Laves phase hydrogen storage alloy and improve it and inhale the lag-effect of putting in hydrogen process.
Summary of the invention
For overcoming the AB existed in prior art
2type Zr base Laves phase hydrogen storage alloy inhales the deficiency of hydrogen dynamic performance, and it is excessive that hydrogen hysteresis quality is put in suction, the present invention proposes a kind of Zr base Laves phase hydrogen storage alloy and preparation method thereof.
Zr-Ti-V-Al hydrogen storage alloy of the present invention by core level sponge Zr block, Ti plate and V crystal, by chemical formula Zr
0.9ti
0.1(V
0.75 ~ 0.98al
0.25 ~ 0.02)
2formulated; Described ratio is atomic ratio.
The purity of described core level sponge Zr block is 99.4%, and the purity of described Ti plate is 99.97%, and the purity of described V crystal is 99.5%.
The invention allows for a kind of method preparing Zr base Laves phase hydrogen storage alloy, material preparation method is specific as follows:
Step 1, melting.The hydrogen storage alloy raw material prepared is put into water jacketed copper crucible, adopts vacuum non-consumable arc-melting furnace to carry out melting, and overturn melting 4 times to ensure uniform composition.Obtain hydrogen storage alloy ingot.In melting, vacuum tightness is 6 × 10
-3pa, is filled with argon gas as protective atmosphere.
Step 2, vacuum annealing, melted hydrogen storage alloy ingot is used acetone respectively, the greasy dirt on surface is removed in dehydrated alcohol eccysis, then hydrogen storage alloy ingot is loaded silica tube, in advance at low temperatures by silica tube bakeout degassing, before sealing, repeatedly clean three times with high-purity Ar gas, then carry out vacuumizing process, when vacuum tightness reaches 10
-4during magnitude, complete the sealing of silica tube, packaged sample mouth as shown in Figure 1.Packaged hydrogen storage alloy ingot is put into chamber type electric resistance furnace, and heated under vacuum to 1273 is also incubated 168 hours.Insulation terminates rear furnace cooling with homogenizing annealing, obtains hydrogen storage alloy.
The present invention is at AB
2type ZrV
2on alloy basis, use Ti element substitution A side Zr element respectively, substitute B side V element with Al, advantage is specific as follows:
1, in prepared by hydrogen storage alloy, hydrogen storage alloy ingot is by non-consumable arc melting, carries out at water jacketed copper crucible, and because cooling rate is very fast, process of setting belongs to nonequilibrium freezing, and alloy reaction is incomplete, often there is Peritectic Reaction residual phase in cast alloy.And by homogenizing annealing process for a long time further, make the rich vanadium solid solution phase in alloy and α-Zr that solid solution reaction occur mutually further, alloy obtains more uniform Laves phase.
2, to prepare Zr-base hydrogenous alloy simple for process for the method, and efficiency is high, low for equipment requirements, and cost is low.
3, the interpolation of Al element adds the diffusion admittance of hydrogen atom, accelerates hydrogen molecule and resolves into hydrogen atom at alloy surface, therefore improve ZrV
2alloy hydrogen absorption and desorption dynamic performance.Al element can lower the stability of alloy hydride, and improve hydrogen storage alloy and inhaling the lag-effect of putting in hydrogen process, its performance is as Fig. 2 and Fig. 3.
4, alloy of the present invention is ultralow equilibrium pressure hydrogen storage alloy, and its equilibrium at room temperature pressure platform is lower than 10
-10pa, the advantages such as highest attainable vacuum ability is strong, to the operating mode such as separation and recovery of hydrogen and hydrogen isotope under ultralow equilibrium pressure condition, have very large application advantage.
Table 1Zr
0.9ti
0.1(V
1-xal
x)
2the thermodynamical coordinate of hydrogen storage alloy and room temperature extrapolation equilibrium pressure
Accompanying drawing explanation
Fig. 1 is the Zr-Ti-V-Al hydrogen storage alloy as cast condition sample after silica tube Vacuum Package;
Fig. 2 is Zr-Ti-V-Al hydrogen storage alloy annealed state sample SEM photo;
Wherein: (a) (b) (c) (d) (e) is respectively Zr
0.9ti
0.1(V
0.98al
0.02)
2, Zr
0.9ti
0.1(V
0.95al
0.05)
2, Zr
0.9ti
0.1(V
0.9al
0.1)
2, Zr
0.9ti
0.1(V
0.85al
0.15)
2, Zr
0.9ti
0.1(V
0.75al
0.25)
2sEM photo after alloy sample annealing;
Fig. 3 is Zr-Ti-V-Al hydrogen storage alloy as cast condition (a) and annealed state (b) X-ray diffractogram;
Fig. 4 is first suction hydrogen curve (a) and 773K Dynamic isotherms of hydrogen absorption (b) after the activation of Zr-Ti-V-Al hydrogen storage alloy;
Fig. 5 is Zr-Ti-V-Al hydrogen storage alloy P-C-T curve of hydrogen absorption;
Wherein: (a) (b) (c) (d) (e) is respectively Zr
0.9ti
0.1(V
0.98al
0.02)
2, Zr
0.9ti
0.1(V
0.95al
0.05)
2, Zr
0.9ti
0.1(V
0.9al
0.1)
2, Zr
0.9ti
0.1(V
0.85al
0.15)
2, Zr
0.9ti
0.1(V
0.75al
0.25)
2the P-C-T curve of alloy;
Fig. 6 is Van ' the tHoff regression straight line of Zr-Ti-V-Al alloy;
Wherein: (a) (b) (c) (d) (e) is respectively Zr
0.9ti
0.1(V
0.98al
0.02)
2, Zr
0.9ti
0.1(V
0.95al
0.05)
2, Zr
0.9ti
0.1(V
0.9al
0.1)
2, Zr
0.9ti
0.1(V
0.85al
0.15)
2, Zr
0.9ti
0.1(V
0.75al
0.25)
2van ' the tHoff regression straight line of alloy;
Fig. 7 is schema of the present invention.
Embodiment
Embodiment 1:
The present embodiment is a kind of Zr-Ti-V-Al hydrogen storage alloy, and described Zr-Ti-V-Al hydrogen storage alloy is core level sponge Zr block, the Ti plate of 99.97% and the V crystal of 99.5% of 99.4% by purity, by chemical formula Zr
0.9ti
0.1(V
0.98al
0.02)
2formulated, described ratio is atomic ratio.
The present embodiment also proposed a kind of method preparing described Zr-Ti-V-Al hydrogen storage alloy, and detailed process is:
Step 1, melting.Load weighted starting material are put into water jacketed copper crucible, according to a conventional method symmetrical measured starting material melting.In melting, be evacuated to 6 × 10
-3, carry out alloy melting at vacuum non-consumable arc-melting furnace during argon atmosphere protection is lower, even for ensureing the alloying constituent of the as cast condition hydrogen storage alloy ingot obtained, the hydrogen storage alloy ingot obtained is overturn remelting 4 times.
Step 2, Vacuum Package.By as cast condition hydrogen storage alloy ingot respectively with the greasy dirt on acetone, washes of absolute alcohol removing surface.Sample is loaded silica tube, by silica tube bakeout degassing at 150 ~ 200 DEG C, in the present embodiment, is 150 DEG C to silica tube storing temperature.Silica tube is repeatedly cleaned three times with high-purity Ar gas.Process is vacuumized, when vacuum tightness reaches 10 by diffusion pump
-4during Pa magnitude, silica tube is sealed.
Step 3, homogenizing annealing process.Chamber type electric resistance furnace put into by as cast condition hydrogen storage alloy ingot vacuum seal installed, and is heated to 1273K and is incubated 168 hours.Insulation terminates rear furnace cooling with homogenizing annealing, obtains hydrogen storage alloy ingot.
As shown in Figure 2, after homogenizing annealing process, in alloy structure, rich V sosoloid dentrite quantity obviously reduces.Before and after annealing shown in composition graphs 3, the X-ray diffractogram of alloy, can draw, when homogenizing annealing, and Zr
0.9ti
0.1(V
0.98al
0.02)
2alloy generation solid solution changes, and the dephasign quantity in alloy is able to obvious minimizing.After homogenizing annealing, alloy structure becomes more even.
Zr-Ti-V-Al hydrogen storage alloy ingot after annealing is cut into the thin slice of Φ 0.8mm × 1mm by machining, with acetone clean surface greasy dirt, then by sample surfaces polishing, washes of absolute alcohol, dry final vacuum encapsulation.
Test the Zr-Ti-V-Al hydrogen storage alloy thin slice after annealing hydrogen storage property, result is as shown in Figure 4 and Figure 5.Zr
0.9ti
0.1(V
0.98al
0.02)
2activation performance of hydrogen-storage alloy is better, through 723K vacuum activating after 1 hour when 303K inhales hydrogen first during incubation period compole short, hydrogen－sucking amount reaches 2.25wt.%; When 773K inhales hydrogen, can reach in 30 seconds and inhale hydrogen running balance, show as good dynamic performance; Suction hydrogen P-C-T test selection 673K, 723K, 773K and 823K tetra-temperature of alloy, put hydrogen P-C-T test selection 823K(as Fig. 5), alloy Hydrogen desorption isotherms and suction hydrogen curve co-insides, without putting hydrogen hysteresis phenomenon; Slope by thermodynamics fit line and the intercept in Y-axis (as Fig. 6) can determine the thermodynamical coordinate that absorption hydrogen reacts, and thermodynamical coordinate are substituted into Van ' tHoff equation, can try to achieve the hydrogen absorption equilibrium pressure of alloy under arbitrary temp.Zr is listed in table 1
0.9ti
0.1(V
0.98al
0.02)
2the room temperature hydrogen absorption equilibrium pressure value of alloy under different hydrogen－sucking amount, extrapolation equilibrium at room temperature forces down in 10
-12pa.
Embodiment 2
The present embodiment is a kind of Zr-Ti-V-Al hydrogen storage alloy, and described Zr-Ti-V-Al hydrogen storage alloy is core level sponge Zr block, the Ti plate of 99.97% and the V crystal of 99.5% of 99.4% by purity, by chemical formula Zr
0.9ti
0.1(V
0.95al
0.05)
2formulated, described ratio is atomic ratio.
The present embodiment also proposed a kind of method preparing described Zr-Ti-V-Al hydrogen storage alloy, and detailed process is:
Step 1, melting.Load weighted starting material are put into water jacketed copper crucible, according to a conventional method symmetrical measured starting material melting.In melting, be evacuated to 6 × 10
-3, carrying out alloy melting at vacuum non-consumable arc-melting furnace during argon atmosphere protection is lower, obtaining as cast condition hydrogen storage alloy ingot for ensureing that alloying constituent is even, by the hydrogen storage alloy ingot upset remelting that obtains 4 times.
Step 2, Vacuum Package.By as cast condition hydrogen storage alloy ingot respectively with the greasy dirt on acetone, washes of absolute alcohol removing surface.Sample is loaded silica tube, at low temperatures by silica tube bakeout degassing.Repeatedly clean silica tube three times with high-purity Ar gas, vacuumize process by diffusion pump, when vacuum tightness reaches 10
-4during Pa magnitude, silica tube is sealed.
Step 3, homogenizing annealing process.Chamber type electric resistance furnace put into by as cast condition hydrogen storage alloy ingot vacuum seal installed, and is heated to 1273K and is incubated 168 hours.Insulation terminates rear furnace cooling with homogenizing annealing, obtains hydrogen storage alloy ingot.
As shown in Figure 2, after homogenizing annealing process, in alloy structure, rich V sosoloid dentrite quantity obviously reduces.Before and after annealing shown in composition graphs 3, the X-ray diffractogram of alloy, can draw, when homogenizing annealing, and Zr
0.9ti
0.1(V
0.95al
0.05)
2alloy generation solid solution changes, and the dephasign quantity in alloy is able to obvious minimizing.After homogenizing annealing, alloy structure becomes more even.
Zr-Ti-V-Al hydrogen storage alloy ingot after annealing is cut into the thin slice of Φ 0.8mm × 1mm by machining, with acetone clean surface greasy dirt, then by sample surfaces polishing, washes of absolute alcohol, dry final vacuum encapsulation.
Test the Zr-Ti-V-Al hydrogen storage alloy thin slice after annealing hydrogen storage property, result is as shown in Figure 4 and Figure 5.Zr
0.9ti
0.1(V
0.95al
0.05)
2activation performance of hydrogen-storage alloy is better, through 723K vacuum activating after 1 hour when 303K inhales hydrogen first during incubation period compole short, hydrogen－sucking amount reaches 2.19wt.%; When 773K inhales hydrogen, can reach in 30 seconds and inhale hydrogen running balance, show as good dynamic performance; Suction hydrogen P-C-T test selection 673K, 723K, 773K and 823K tetra-temperature of alloy, put hydrogen P-C-T test selection 823K(as Fig. 5), alloy Hydrogen desorption isotherms and suction hydrogen curve co-insides, without putting hydrogen hysteresis phenomenon; Slope by thermodynamics fit line and the intercept in Y-axis (as Fig. 6) can determine the thermodynamical coordinate that absorption hydrogen reacts, and thermodynamical coordinate are substituted into Van ' tHoff equation, can try to achieve the hydrogen absorption equilibrium pressure of alloy under arbitrary temp.Zr is listed in table 1
0.9ti
0.1(V
0.95al
0.05)
2the room temperature hydrogen absorption equilibrium pressure value of alloy under different hydrogen－sucking amount, extrapolation equilibrium at room temperature forces down in 10
-13pa.
Embodiment 3
The present embodiment is a kind of Zr-Ti-V-Al hydrogen storage alloy, and described Zr-Ti-V-Al hydrogen storage alloy is core level sponge Zr block, the Ti plate of 99.97% and the V crystal of 99.5% of 99.4% by purity, by chemical formula Zr
0.9ti
0.1(V
0.9al
0.1)
2formulated, described ratio is atomic ratio.
The present embodiment also proposed a kind of method preparing described Zr-Ti-V-Al hydrogen storage alloy, and detailed process is:
Step 1, melting.Load weighted starting material are put into water jacketed copper crucible, according to a conventional method symmetrical measured starting material melting.In melting, be evacuated to 6 × 10
-3, carrying out alloy melting at vacuum non-consumable arc-melting furnace during argon atmosphere protection is lower, obtaining as cast condition hydrogen storage alloy ingot for ensureing that alloying constituent is even, by the hydrogen storage alloy ingot upset remelting that obtains 4 times.
Step 2, Vacuum Package.By as cast condition hydrogen storage alloy ingot respectively with the greasy dirt on acetone, washes of absolute alcohol removing surface.Sample is loaded silica tube, at low temperatures by silica tube bakeout degassing.Repeatedly clean silica tube three times with high-purity Ar gas, vacuumize process by diffusion pump, when vacuum tightness reaches 10
-4during Pa magnitude, silica tube is sealed.
Step 3, homogenizing annealing process.Chamber type electric resistance furnace put into by as cast condition hydrogen storage alloy ingot vacuum seal installed, and is heated to 1273K and is incubated 168 hours.Insulation terminates rear furnace cooling with homogenizing annealing, obtains hydrogen storage alloy ingot.
As shown in Figure 2, after homogenizing annealing process, in alloy structure, rich V sosoloid dentrite quantity obviously reduces.Before and after annealing shown in composition graphs 3, the X-ray diffractogram of alloy, can draw, when homogenizing annealing, and Zr
0.9ti
0.1(V
0.9al
0.1)
2alloy generation solid solution changes, and the dephasign quantity in alloy is able to obvious minimizing.After homogenizing annealing, alloy structure becomes more even.
Zr-Ti-V-Al hydrogen storage alloy ingot after annealing is cut into the thin slice of Φ 0.8mm × 1mm by machining, with acetone clean surface greasy dirt, then by sample surfaces polishing, washes of absolute alcohol, dry final vacuum encapsulation.
Test the Zr-Ti-V-Al hydrogen storage alloy thin slice after annealing hydrogen storage property, result is as shown in Figure 4 and Figure 5.Zr
0.9ti
0.1(V
0.9al
0.1)
2activation performance of hydrogen-storage alloy is better, through 723K vacuum activating after 1 hour when 303K inhales hydrogen first during incubation period compole short, hydrogen－sucking amount reaches 2.10wt.%; When 773K inhales hydrogen, can reach in 30 seconds and inhale hydrogen running balance, show as good dynamic performance; Suction hydrogen P-C-T test selection 673K, 723K, 773K and 823K tetra-temperature of alloy, put hydrogen P-C-T test selection 823K(as Fig. 5), alloy Hydrogen desorption isotherms and suction hydrogen curve co-insides, without putting hydrogen hysteresis phenomenon; Slope by thermodynamics fit line and the intercept in Y-axis (as Fig. 6) can determine the thermodynamical coordinate that absorption hydrogen reacts, and thermodynamical coordinate are substituted into Van ' tHoff equation, can try to achieve the hydrogen absorption equilibrium pressure of alloy under arbitrary temp.Zr is listed in table 1
0.9ti
0.1(V
0.9al
0.1)
2the room temperature hydrogen absorption equilibrium pressure value of alloy under different hydrogen－sucking amount, extrapolation equilibrium at room temperature forces down in 10
-9pa.
Embodiment 4
The present embodiment is a kind of Zr-Ti-V-Al hydrogen storage alloy, and described Zr-Ti-V-Al hydrogen storage alloy is core level sponge Zr block, the Ti plate of 99.97% and the V crystal of 99.5% of 99.4% by purity, by chemical formula Zr
0.9ti
0.1(V
0.85al
0.15)
2formulated, described ratio is atomic ratio.
The present embodiment also proposed a kind of method preparing described Zr-Ti-V-Al hydrogen storage alloy, and detailed process is:
Step 1, melting.Load weighted starting material are put into water jacketed copper crucible, according to a conventional method symmetrical measured starting material melting.In melting, be evacuated to 6 × 10
-3, carrying out alloy melting at vacuum non-consumable arc-melting furnace during argon atmosphere protection is lower, obtaining as cast condition hydrogen storage alloy ingot for ensureing that alloying constituent is even, by the hydrogen storage alloy ingot upset remelting that obtains 4 times.
Step 2, Vacuum Package.By as cast condition hydrogen storage alloy ingot respectively with the greasy dirt on acetone, washes of absolute alcohol removing surface.Sample is loaded silica tube, at low temperatures by silica tube bakeout degassing.Repeatedly clean silica tube three times with high-purity Ar gas, vacuumize process by diffusion pump, when vacuum tightness reaches 10
-4during Pa magnitude, silica tube is sealed.
Step 3, homogenizing annealing process.Chamber type electric resistance furnace put into by as cast condition hydrogen storage alloy ingot vacuum seal installed, and is heated to 1273K and is incubated 168 hours.Insulation terminates rear furnace cooling with homogenizing annealing, obtains hydrogen storage alloy ingot.
As shown in Figure 2, after homogenizing annealing process, in alloy structure, rich V sosoloid dentrite quantity obviously reduces.Before and after annealing shown in composition graphs 3, the X-ray diffractogram of alloy, can draw, when homogenizing annealing, and Zr
0.9ti
0.1(V
0.85al
0.15)
2alloy generation solid solution changes, and the dephasign quantity in alloy is able to obvious minimizing.After homogenizing annealing, alloy structure becomes more even.
Zr-Ti-V-Al hydrogen storage alloy ingot after annealing is cut into the thin slice of Φ 0.8mm × 1mm by machining, with acetone clean surface greasy dirt, then by sample surfaces polishing, washes of absolute alcohol, dry final vacuum encapsulation.
Test the Zr-Ti-V-Al hydrogen storage alloy thin slice after annealing hydrogen storage property, result is as shown in Figure 4 and Figure 5.Zr
0.9ti
0.1(V
0.85al
0.15)
2activation performance of hydrogen-storage alloy is better, through 723K vacuum activating after 1 hour when 303K inhales hydrogen first during incubation period compole short, hydrogen－sucking amount reaches 2.01wt.%; When 773K inhales hydrogen, can reach in 30 seconds and inhale hydrogen running balance, show as good dynamic performance; Suction hydrogen P-C-T test selection 673K, 723K, 773K and 823K tetra-temperature of alloy, put hydrogen P-C-T test selection 823K(as Fig. 5), alloy Hydrogen desorption isotherms and suction hydrogen curve co-insides, without putting hydrogen hysteresis phenomenon; Slope by thermodynamics fit line and the intercept in Y-axis (as Fig. 6) can determine the thermodynamical coordinate that absorption hydrogen reacts, and thermodynamical coordinate are substituted into Van ' tHoff equation, can try to achieve the hydrogen absorption equilibrium pressure of alloy under arbitrary temp.Zr is listed in table 1
0.9ti
0.1(V
0.85al
0.15)
2the room temperature hydrogen absorption equilibrium pressure value of alloy under different hydrogen－sucking amount, extrapolation equilibrium at room temperature forces down in 10
-10pa.。
Embodiment 5
The present embodiment is a kind of Zr-Ti-V-Al hydrogen storage alloy, and described Zr-Ti-V-Al hydrogen storage alloy is core level sponge Zr block, the Ti plate of 99.97% and the V crystal of 99.5% of 99.4% by purity, by chemical formula Zr
0.9ti
0.1(V
0.25al
0.75)
2formulated, described ratio is atomic ratio.
The present embodiment also proposed a kind of method preparing described Zr-Ti-V-Al hydrogen storage alloy, and detailed process is:
Step 1, melting.Load weighted starting material are put into water jacketed copper crucible, according to a conventional method symmetrical measured starting material melting.In melting, be evacuated to 6 × 10
-3, carrying out alloy melting at vacuum non-consumable arc-melting furnace during argon atmosphere protection is lower, obtaining as cast condition hydrogen storage alloy ingot for ensureing that alloying constituent is even, by the hydrogen storage alloy ingot upset remelting that obtains 4 times.
Step 2, Vacuum Package.By as cast condition hydrogen storage alloy ingot respectively with the greasy dirt on acetone, washes of absolute alcohol removing surface.Sample is loaded silica tube, at low temperatures by silica tube bakeout degassing.Repeatedly clean silica tube three times with high-purity Ar gas, vacuumize process by diffusion pump, when vacuum tightness reaches 10
-4during Pa magnitude, silica tube is sealed.
Step 3, homogenizing annealing process.Chamber type electric resistance furnace put into by as cast condition hydrogen storage alloy ingot vacuum seal installed, and is heated to 1273K and is incubated 168 hours.Insulation terminates rear furnace cooling with homogenizing annealing, obtains hydrogen storage alloy ingot.
As shown in Figure 2, after homogenizing annealing process, in alloy structure, rich V sosoloid dentrite quantity obviously reduces.Before and after annealing shown in composition graphs 3, the X-ray diffractogram of alloy, can draw, when homogenizing annealing, and Zr
0.9ti
0.1(V
0.25al
0.75)
2alloy generation solid solution changes, and the dephasign quantity in alloy is able to obvious minimizing.After homogenizing annealing, alloy structure becomes more even.
Zr-Ti-V-Al hydrogen storage alloy ingot after annealing is cut into the thin slice of Φ 0.8mm × 1mm by machining, with acetone clean surface greasy dirt, then by sample surfaces polishing, washes of absolute alcohol, dry final vacuum encapsulation.
Test the Zr-Ti-V-Al hydrogen storage alloy thin slice after annealing hydrogen storage property, result is as shown in Figure 4 and Figure 5.Zr
0.9ti
0.1(V
0.25al
0.75)
2activation performance of hydrogen-storage alloy is better, through 723K vacuum activating after 1 hour when 303K inhales hydrogen first during incubation period compole short, hydrogen－sucking amount reaches 1.98wt.%; When 773K inhales hydrogen, can reach in 30 seconds and inhale hydrogen running balance, show as good dynamic performance; Suction hydrogen P-C-T test selection 673K, 723K, 773K and 823K tetra-temperature of alloy, put hydrogen P-C-T test selection 823K(as Fig. 5), alloy Hydrogen desorption isotherms and suction hydrogen curve co-insides, without putting hydrogen hysteresis phenomenon; Slope by thermodynamics fit line and the intercept in Y-axis (as Fig. 6) can determine the thermodynamical coordinate that absorption hydrogen reacts, and thermodynamical coordinate are substituted into Van ' tHoff equation, can try to achieve the hydrogen absorption equilibrium pressure of alloy under arbitrary temp.Zr is listed in table 1
0.9ti
0.1(V
0.25al
0.75)
2the room temperature hydrogen absorption equilibrium pressure value of alloy under different hydrogen－sucking amount, extrapolation equilibrium at room temperature forces down in 10
-10pa.
Claims (3)
1. a Zr base Laves phase hydrogen storage alloy, is characterized in that, described Zr-Ti-V-Al hydrogen storage alloy by core level sponge Zr block, Ti plate and V crystal, by chemical formula Zr
0.9ti
0.1(V
0.75 ~ 0.98al
0.25 ~ 0.02)
2formulated; In described chemical formula, element ratio is atomic ratio.
2. a kind of Zr base Laves phase hydrogen storage alloy as claimed in claim 1, it is characterized in that, the purity of described core level sponge Zr block is 99.4%, and the purity of described Ti plate is 99.97%, and the purity of described V crystal is 99.5%.
3. prepare a method for Zr base Laves phase hydrogen storage alloy described in claim 1, it is characterized in that, detailed process is:
Step 1, melting; Load weighted starting material are put into water jacketed copper crucible, according to a conventional method symmetrical measured starting material melting; In melting, be evacuated to 6 × 10
-3, during argon atmosphere protection is lower, carry out alloy melting at vacuum non-consumable arc-melting furnace; In melting, the hydrogen storage alloy ingot obtained is overturn remelting 4 times;
Step 2, Vacuum Package; By the greasy dirt on as cast condition hydrogen storage alloy ingot cleaning removing surface; Sample is loaded silica tube, by silica tube bakeout degassing at 150 ~ 200 DEG C; Process is vacuumized, when vacuum tightness reaches 10 by diffusion pump
-4during Pa magnitude, silica tube is sealed;
Step 3, homogenizing annealing process; Chamber type electric resistance furnace put into by as cast condition hydrogen storage alloy ingot vacuum seal installed, and is heated to 1273K and is incubated 168 hours; Insulation terminates rear furnace cooling with homogenizing annealing, obtains hydrogen storage alloy ingot.
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| CN201410027987.6A CN103789573B (en) | 2014-01-22 | 2014-01-22 | A kind of Zr base Laves phase hydrogen storage alloy and preparation method thereof |
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| CN108411182A (en) * | 2018-04-13 | 2018-08-17 | 江苏理工学院 | A kind of Zr-Ti-Cr-V complex phases hydrogen bearing alloy and preparation method thereof |
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| CN110042304A (en) * | 2019-04-22 | 2019-07-23 | 宁夏大学 | A kind of high-pressure metal hydride composite hydrogen occluding tank high platform pressure hydrogen bearing alloy |
| CN111118378A (en) * | 2019-12-31 | 2020-05-08 | 西安西工大超晶科技发展有限责任公司 | High-entropy alloy for nuclear and preparation method thereof |
| CN112779439A (en) * | 2021-01-28 | 2021-05-11 | 桂林电子科技大学 | Hydrogen storage material doped with V and capable of improving performance of ZrCo hydrogen storage alloy and preparation method of hydrogen storage material |
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