CN100400690C - Hydrogen storage alloy Zr3V3O preparing method - Google Patents
Hydrogen storage alloy Zr3V3O preparing method Download PDFInfo
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- CN100400690C CN100400690C CNB2006100205596A CN200610020559A CN100400690C CN 100400690 C CN100400690 C CN 100400690C CN B2006100205596 A CNB2006100205596 A CN B2006100205596A CN 200610020559 A CN200610020559 A CN 200610020559A CN 100400690 C CN100400690 C CN 100400690C
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Abstract
The present invention relates to a preparation method of Zr3V3O hydrogen storage alloy, which comprises the following content: (1) material zirconium powder, metallic vanadium and V2O5 powder are evenly mixed in a definite stoichiometric proportion in a closed container which is filled with inert gas, after the material zirconium powder, the metallic vanadium and the V2O5 powder are evenly mixed, the material mixture is pressed into a compact column; (2) heat treatment is carried out for the material mixture column under an appropriate condition of heat treatment; (3) suitable technology is adopted to carry out electric arc melting under the protection of the inert gas; (4) uniform treatment for alloy ingots which are melted is carried out under a suitable condition of heat treatment. Thus, the Zr3V3O hydrogen storage alloy of an oxygen containing class, which has good hydrogen sucking and discharging performance at room temperature, is prepared. The preparation method of the present invention has the advantages of simple and convenient process, and mature technology.
Description
Technical field
The invention belongs to the hydrogen storage material preparation field, be specifically related to a kind of hydrogen-storage alloy Zr
3V
3The preparation method of O.
Background technology
From early seventies, people find TiFe, LaNi successively
5Since the hydrogen-storage alloy, hydrogen storage material has obtained developing rapidly as a kind of new-type functional material and energy and material.Before the eighties, people have carried out extensive studies to the hydrogen storage performance as compound between the metal simple-substance of hydrogen storage material such as U, Ti, V, Pd, Mg etc. and binary metal, for satisfying the demand of various practical applications, hydrogen storage material develops to the multicomponent alloy direction from simple substance, binary alloy.The hydrogen storage performance of intermetallic compound after deliberation must be more extensive in recent years.But the hydrogen storage performance of most of alloys all may cause owing to the introducing of oxygen poisoning, thereby has reduced their hydrogen storage capacity.Therefore all avoiding the pollution of oxygen as much as possible when preparation, use hydrogen-storage alloy, is unpractical but avoid the pollution of oxygen in actual applications fully.Point out the suitable ideal hydrogen storage material that Zr base or the basic low η phase alloy material that contains the O amount of Ti can be used as in CONF-820605-27 " the alloy hydride phase that the contains oxidation stability " report that Mendelson M.H. delivers in " the 4th world's hydrogen energy source progress meeting " that nineteen eighty-two California, USA Pa Sadina city holds, can regulate and control the stability of hydride and store hydrogen capacity by the oxygen level of regulating wherein.Its weak point is, though the employing arc melting is prepared oxygen containing hydrogen-storage alloy, and preparation technology's harshness, the product that obtains is impure, unstable properties.Therefore development can not cause owing to the introducing of oxygen poisoning, thereby the new oxygen class hydrogen storage material that contains that reduces hydrogen storage capacity becomes the task of top priority.
Summary of the invention
In order to overcome existing hydrogen-storage alloy since the introducing of oxygen cause poisoning, thereby reduce the deficiency of its hydrogen storage capacity, the invention provides a kind of hydrogen-storage alloy Zr
3V
3The preparation method of O.
The technical solution that the present invention adopts is: with zirconium powder, vanadium metal and V
2O
5Powder mixture is heat-treated, and carries out arc melting again and makes alloy pig, and then alloy pig is heat-treated, and obtains Zr
3V
3The O hydrogen-storage alloy.
Hydrogen-storage alloy Zr of the present invention
3V
3The preparation method of O may further comprise the steps: (1) is in being full of the encloses container of rare gas element, with raw material zirconium powder, vanadium metal and V
2O
5The stoichiometric ratio Zr of powder: V: V
2O
5=15: (12.6～14.2): the ratio of (0.4～1.2) is carried out uniform mixing, is pressed into cylinder closely behind the mixing; (2) be 800K～1000K in temperature, vacuum tightness is 10
-3Pa～10
-5Under the Pa condition, the raw mix cylinder is heat-treated, heat treatment time is 4h～8h; (3) under protection of inert gas, carry out arc melting; (4) in temperature 1250K～1450K, vacuum tightness 10
-3Pa～10
-5Under the Pa condition, the alloy pig after the melting is carried out homogenization handle, the treatment time is 20h～200h, makes the hydrogen-storage alloy Zr that at room temperature has good hydrogen storage property
3V
3O.
The protection of inert gas atmosphere of arc melting adopts argon gas in the step (3), stands up melting 3～5 times.
The thermal treatment of raw mix cylinder helps V
2O
5Uniform distribution in raw mix.
Melting helps preventing the loss of oxygen in the raw material under argon shield, stands up melting and can guarantee that alloying constituent is even for 3～5 times.
The alloy that heat-treat condition when high temperature is long is beneficial to the homogeneous pure phase generates, and reduces the dephasign in the alloy.
Adopt the present invention, what can obtain that purity height, thing all have good hydrogen storage performance mutually in the lump contains oxygen Zr
3V
3The O alloy, the preparation method is easy, technical maturity, reaction conditions gentleness.
Description of drawings
Fig. 1 is the XRD spectra of ingot casting in the embodiments of the invention 1 (1);
Fig. 2 is the XRD spectra of ingot casting in the embodiments of the invention 1 (2);
Fig. 3 is the XRD spectra of ingot casting in the embodiments of the invention 1 (3);
Fig. 4 is the XRD spectra of ingot casting in the embodiments of the invention 4 (3);
Fig. 5 is hydrogen-storage alloy Zr under the room temperature condition of effect example 1 of the present invention
3V
3The suction deuterium curve of O.
The invention will be further described below in conjunction with the drawings and specific embodiments.
Embodiment
Hydrogen-storage alloy Zr of the present invention
3V
3The preparation method of O may further comprise the steps: (1) is in being full of the encloses container of rare gas element, with raw material zirconium powder, vanadium metal and V
2O
5Powder is by stoichiometric ratio Zr: V: V
2O
5=15: (12.6～14.2): (0.4～1.2) carries out uniform mixing, is pressed into cylinder closely behind the mixing; (2) be 10 in vacuum tightness
-3Pa～10
-5In the environment of Pa the raw mix cylinder is heated to 800K～1000K, thermal treatment 4h～8h; (3) under argon shield, the raw mix after the thermal treatment is carried out arc melting, stand up melting 3～5 times; (4) be 10 in vacuum tightness
-3Pa～10
-5In the environment of Pa the alloy pig after the melting is heated to 1250K～1450K, 20h～200h is handled in homogenization, and what obtain at room temperature to have good hydrogen storage property contains oxygen class Zr
3V
3The O hydrogen-storage alloy.
Embodiment 1: the contrast experiment
Under different raw material ratio, adopt the arc melting preparation to contain oxygen class hydrogen-storage alloy Zr
3V
3O compares experiment.
(1) stoichiometric ratio is Zr: V: V
2O
5=15: 14.2: 0.4
In being full of the encloses container of argon gas, with raw material zirconium powder, vanadium metal and V
2O
5Powder is by stoichiometric ratio Zr: V: V
2O
5=15: carrying out uniform mixing at 14.2: 0.4, be pressed into cylinder closely behind the mixing, is 10 in vacuum tightness
-5In the environment of Pa the raw mix cylinder is heated to 950K, thermal treatment 5h carries out arc melting to the raw mix after the thermal treatment then under argon shield, stands up melting 5 times, and XRD analysis is carried out in the ingot casting sampling that obtains.
(2) stoichiometric ratio is Zr: V: V
2O
5=15: 13.4: 0.8
In being full of the encloses container of argon gas, with raw material zirconium powder, vanadium metal and V
2O
5Powder is by stoichiometric ratio Zr: V: V
2O
5=15: carrying out uniform mixing at 13.4: 0.8, be pressed into cylinder closely behind the mixing, is 10 in vacuum tightness
-5In the environment of Pa the raw mix cylinder is heated to 970K, thermal treatment 4h carries out arc melting to the raw mix after the thermal treatment then under argon shield, stands up melting 5 times, and XRD analysis is carried out in the ingot casting sampling that obtains.
(3) stoichiometric ratio is Zr: V: V
2O
5=15: 13.0: 1.0
In being full of the encloses container of argon gas, with raw material zirconium powder, vanadium metal and V
2O
5Powder is by stoichiometric ratio Zr: V: V
2O
5=15: carrying out uniform mixing at 13: 1.0, be pressed into cylinder closely behind the mixing, is 10 in vacuum tightness
-4In the environment of Pa the raw mix cylinder is heated to 970K, thermal treatment 6h carries out arc melting to the raw mix after the thermal treatment then under argon shield, stands up melting 3 times, and XRD analysis is carried out in the ingot casting sampling that obtains.
Fig. 1 is the ingot casting sample XRD spectra that obtains among the embodiment 1 (1), and Fig. 2 is the ingot casting sample XRD spectra that obtains among the embodiment 1 (2), and Fig. 3 is the ingot casting sample XRD spectra that obtains among the embodiment 1 (3).Table 1 is the experimental result contrast table of embodiment 1 different material than following arc melting.
Table 1 embodiment 1 different material is than the experimental result comparison sheet of following arc melting
As can be seen from Table 1: the employing stoichiometric ratio is Zr: V: V
2O
5=15: 14.2: 0.4 raw material carries out arc melting, does not occur Zirconium oxide in the product, but obtained contain oxygen hydrogen-storage alloy Zr
3V
3The phase abundance of O only is 53%, and more dephasign ZrV is arranged
2Generate with the zirconium based solid solution; The employing stoichiometric ratio is Zr: V: V
2O
5=15: 13.4: 0.8 raw material carries out arc melting, does not also occur Zirconium oxide, dephasign ZrV in the product
2Reduce with the content of zirconium based solid solution, contain oxygen hydrogen-storage alloy Zr
3V
3The phase abundance of O is increased to 67%; The employing stoichiometric ratio is Zr: V: V
2O
5=15: 13: 1.0 raw material carries out arc melting, though there is Zirconium oxide to occur in the product, the total content of dephasign further reduces, and contains oxygen hydrogen-storage alloy Zr
3V
3The phase abundance of O further is increased to 70%.Experimental result shows that adopting stoichiometric ratio is Zr: V: V
2O
5=15: 13: 1.0 raw material carries out the total content that arc melting can reduce dephasign, improves required product Zr
3V
3The phase abundance of O.
Embodiment 2: the contrast experiment
Select different thermal treatment process to compare experiment to the raw mix cylinder.
In being full of the encloses container of argon gas, with raw material zirconium powder, vanadium metal and V
2O
5Powder is by stoichiometric ratio Zr: V: V
2O
5=15: carry out uniform mixing at 13: 1.0; be pressed into cylinder closely behind the mixing; under the condition of different vacuum tightness environment and different heat treatment temperature, the raw mix cylinder is heat-treated certain hour; under argon shield, the raw mix after the thermal treatment is carried out arc melting then; stand up melting 3 times, to ingot casting sampling carrying out XRD analysis and the oxygen analysis that obtains.
Select the thermal treatment process of raw mix cylinder to be respectively: (1) vacuum tightness: 10
-3Pa, temperature: 970K, time: 4h; (2) vacuum tightness: 10
-4Pa, temperature: 970K, time: 4h; (3) vacuum tightness: 10
-5Pa, temperature: 970K, time: 7h; (4) vacuum tightness: 10
-5Pa, temperature: 910K, time: 8h; (5) vacuum tightness: 10
-5Pa, temperature: 1000K, time: 6h; (6) vacuum tightness: 10
-5Pa, temperature: 970K, time: 4h carries out six experiments.
After XRD result shows arc melting: more Zirconium oxide (ZrO is arranged among the embodiment 2 (1)
2) generate, its phase abundance is 30%, and Zr
3V
3The phase abundance of O is 58%; Then have the protoxide of a certain amount of zirconium to generate among the embodiment 2 (2), its phase abundance is 13%, and Zr
3V
3The phase abundance of O is 63%; Among the embodiment 2 (3) content of Zirconium oxides seldom, its phase abundance is 6%, and Zr
3V
3The phase abundance of O is 73%, and this shows that the vacuum tightness in the thermal treatment process of raw mix cylinder will directly influence the productive rate of product and the content of oxide compound dephasign.Zr among the embodiment 2 (4)
3V
3O output is less, and its phase abundance is 42%, and the ingot structure structure has obvious segregation, but the oxygen level of ingot casting is 3.6%, with the Zr of Design Theory
3V
3The oxygen level unanimity of O; Zr among the embodiment 2 (5)
3V
3The phase abundance of O is 67%, the ingot structure even structure, but the oxygen level of ingot casting is 3.0%, less than the Zr of Design Theory
3V
3The oxygen level of O, this shows that the thermal treatment temp of raw mix cylinder will finally influence phase homogeneity, the Zr of the ingot casting of arc melting acquisition
3V
3The output of O phase.The result of embodiment 2 (6) is more consistent with embodiment 2 (3), but its phase homogeneity is relatively poor, Zr
3V
3The phase abundance of O phase is lower slightly.
Embodiment 3: repeated experiments
Carry out repeated experiments according to processing condition among the embodiment 1 (3), investigate the repeatability of this technology.
(1) ingot casting that arc melting among the embodiment 3 is obtained carries out XRD analysis.
The result shows, Ti
2The Zr of Ni type η phase
3V
3O is a principal phase; Contain a small amount of V based solid solution and Zr based solid solution, the two content is suitable substantially, contains the intermetallic compound ZrV of the Laves phase of trace simultaneously
2And Zirconium oxide.As seen, by in raw material, adding V
2O
5Powder, utilization arc melting method can be prepared Ti under certain process conditions
2The Zr of Ni type η phase
3V
3O is the alloy cast ingot of principal phase.
(2) ingot casting that arc melting among the embodiment 3 is obtained carries out determination of oxygen content.
The ingot casting sample is cut into sheet with wire cutting machine, behind the sample cleaning-drying, measures its oxygen level (worst error is 1%), detect and carry out according to the GB/T14265-93 standard with TC-436 oxygen apparatus for nitrogen examination.
Table 2 is the Zr that embodiment 3 arc meltings obtain
3V
3The determination of oxygen content result of O ingot casting.
The Zr that table 2 embodiment 3 arc meltings obtain
3V
3The determination of oxygen content result of O ingot casting
Arc melting obtains Zr as can be known from Table 2
3V
3The oxygen level of O ingot casting should be about 3.7% (weight percent m/m), with the Zr of Design Theory
3V
3The oxygen level 3.61% of O (weight percent m/m) is relatively more consistent.Therefore, in the scope of error permission, by in raw material, adding V
2O
5Powder, utilization arc melting method can be prepared the ingot casting sample that oxygen level reaches the requirement of expection alloy set component under suitable process conditions.
Embodiment 4: the contrast experiment
Select the Zr of different thermal treatment process to preparing according to processing condition among the embodiment 1 (3)
3V
3The O ingot casting compares experiment, and the product that obtains is carried out XRD analysis.
(1) vacuum tightness: 10
-5Pa, temperature: 1423K, time: 24h, furnace cooling;
(2) vacuum tightness: 10
-5Pa, temperature: 1423K, time: 120h, furnace cooling;
(3) vacuum tightness: 10
-5Pa, 1423K constant temperature 96h+1273K constant temperature 96h, furnace cooling;
(4) vacuum tightness: 10
-4Pa, 1423K constant temperature 96h+1273K constant temperature 96h, furnace cooling;
Table 3 is the experimental result contrast table of embodiment 4 different heat treatment technologies.
The experimental result comparison sheet of table 3 embodiment 4 different heat treatment technologies
As can be seen from Table 1: among the embodiment 4 (1) 10
-5Pa can homogenization ingot casting sample under the heat-treat condition of 1423K; In embodiment 4 (2), further prolong heat treatment time, η-phase Zr
3V
3O content rises thereupon, but homogenization speed is very slow; At embodiment 4 (4) though in reduced homogenization speed, eliminated ZrV
2Dephasign; Among the embodiment 4 (3) 10
-5Pa, process 96h thermal treatment under the condition of 1423K is again 10
-5Pa, through 96h thermal treatment, energy is the homogenizing sample further, its Zr under the condition of 1273K
3V
3O content can satisfy the requirement of use greater than 90%.
Fig. 4 is the Zr after the homogenization thermal treatment in embodiment 4 (3) experiments
3V
3The XRD spectra of O alloy pig.Among Fig. 4, the value of diffraction angle (2 θ) is that the diffraction peak of 29.11 °, 31.90 °, 36.02 °, 38.24 °, 41.80 °, 44.41 °, 47.29 °, 49.51 °, 53.62 °, 56.53 °, 58.03 °, 60.73 °, 62.95 °, 64.90 °, 66.34 °, 68.95 °, 70.24 °, 72.82 °, 76.54 °, 77.92 °, 79.99 ° and 81.79 ° is Ti
2The Zr of Ni type η phase
3V
3The characteristic peak of O, the characteristic peak of dephasign disappears substantially.As seen, the Zr of arc melting acquisition
3V
3The O ingot casting can obtain the Ti of enough homogeneous after homogenization thermal treatment
2The Zr of Ni type η phase
3V
3The O alloy.
Effect example 1: effect experiment
Zr after the selection homogenization thermal treatment
3V
3The O alloy is inhaled the experiment of deuterium effect.Sample is packed in the sample chamber, handle through the degassing, vacuum tightness reaches 10
-2Put into several kPas deuterium gas behind the Pa, measure it and inhale the deuterium curve.
Fig. 5 is the Zr after the homogenization thermal treatment in 1 experiment of effect example
3V
3The initial suction deuterium curve of O alloy pig sample, sample size is 0.7642g, initial deuterated is pressed and is 1840Pa.As shown in Figure 5, material is active very good to deuterium gas, at room temperature, induce and can activate without deuterium, and suction deuterium speed is very fast, in the 30s deuterium gas is almost exhausted.
Claims (3)
1. hydrogen-storage alloy Zr
3V
3The preparation method of O is characterized in that may further comprise the steps: (1) is in being full of the encloses container of rare gas element, with raw material zirconium powder, vanadium metal and V
2O
5Powder is by stoichiometric ratio Zr: V: V
2O
5=15: (12.6～14.2): (0.4～1.2) carries out uniform mixing, is pressed into cylinder closely behind the mixing; (2) be 10 in vacuum tightness
3Pa～10
5In the environment of Pa, the raw mix cylinder is heated to 800K～1000K, thermal treatment 4h～8h; (3) under protection of inert gas, the raw mix after the thermal treatment is carried out arc melting; (4) be 10 in vacuum tightness
3Pa～10
5In the environment of Pa, the alloy pig after the melting is heated to 1250K～1450K, 20h～200h is handled in homogenization, obtains hydrogen-storage alloy Zr
3V
3O.
2. hydrogen-storage alloy Zr according to claim 1
3V
3The preparation method of O is characterized in that: raw material zirconium powder, vanadium metal and V in the step (1)
2O
5Powder is by stoichiometric ratio Zr: V: V
2O
5=15: (13.0～13.8): the mixed of (0.6～1.0) is even.
3. hydrogen-storage alloy Zr according to claim 1
3V
3The preparation method of O is characterized in that: raw material zirconium powder, vanadium metal and V in the step (1)
2O
5Powder is by stoichiometric ratio Zr: V: V
2O
5=15: 13.0: 1.0 mixed is even.
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