CN105112724B - Laves-phase hydrogen storage alloy and preparation method thereof - Google Patents
Laves-phase hydrogen storage alloy and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of hydrogen storage materials and particularly relates to hydrogen storage alloy which is modified by aluminum, scandium and vanadium and has oxidation resistance and a large reversible hydrogen storage capacity. The general formula of the hydrogen storage alloy is (Ti1-yAly)1-xScx(Mn0.8V0.2)2, wherein 0.00≤y≤1.00, 0.00≤x≤0.20. The obtained hydrogen storage alloy is large in hydrogen storage capacity and liable to activation, thereby being more suitable for serving as a hydrogen source under the condition of the large-scale use of hydrogen.
Description
Technical field
The invention belongs to hydrogen storage material technical field, and in particular to the modified antioxidation of a kind of Jing aluminum, scandium, vanadium, height are reversible
The hydrogen-storage alloy of hydrogen storage amount.
Background technology
LaNi5And its improved serial hydrogen-storage alloy, although hydrogen storage amount only has 1.4wt%, activated and dynamic due to good
Mechanical property, has realized industrialization, is widely used.But this hydrogen storage amount is far below USDOE (DOE) regulation
The requirement of 6.5wt% hydrogen storage amounts, in order to reach the standard of DOE, many new hydrogen storage materials are also developed, such as AB2Type
Laves phase alloys, Mg based alloys and vanadio bcc alloys, its hydrogen storage amount is higher than LaNi5Alloy, but due to or to put hydrogen condition harsh,
Or the reasons such as difficulty are activated, limit its application in practice.
In the various hydrogen-storage alloys developed, Ti1-xZrxMnCr systems alloy has higher reversible hydrogen storage amount, good
Dynamicss, wherein, Ti0.68Zr0.32MnCr alloy compositions combination property is best, but this hydrogen-storage alloy exposes in atmosphere
When, surface can form one layer of dense oxide or hydroxide, cause its activation difficulty, and in addition Zr metals are heavier, relative to reduce
The hydrogen storage amount of alloy.And the Ti after Sc substitutes Zr1-xScxThe reversible hydrogen storage amount of MnCr systems alloy is compared with Ti1-xZrxMnCr systems close
Gold is increased substantially, wherein Ti0.78Sc0.22MnCr alloy compositions synthesis hydrogen storage performance is best, but than Ti0.68Zr0.32MnCr is closed
Golden its platform is deteriorated, and because the addition of Sc is more, increased the cost of alloy, and the antioxygenic property of alloy is not obtained
To remarkable improvement, it is caused to apply in practice.
The content of the invention
The present invention provides a kind of new Neale Lavis hydrogen storage alloy phase, and gained alloy synthesis hydrogen storage performance is good, is suitable as big
Hydrogen source under scale hydrogen condition.
Technical scheme：
The present invention provides a kind of Neale Lavis hydrogen storage alloy phase, and its formula is：(Ti1-yAly)1-xScx(Mn0.8V0.2)2, wherein,
0.00≤y≤1.00,0.00≤x≤0.20.
Preferably, in the hydrogen-storage alloy, x=0.1~0.2；Y=0~0.1.
Further, in the hydrogen-storage alloy, x=0.1, y=0,0.05 or 0.1；Preferably, x=0.1, y=0,0.05.
Further, in the hydrogen-storage alloy, x=0.15, y=0,0.05 or 0.1.
Further, in the hydrogen-storage alloy, x=0.2, y=0,0.05 or 0.1.
Further, the Neale Lavis hydrogen storage alloy phase is：Ti0.9Sc0.1(Mn0.8V0.2)2、Ti0.85Sc0.15
(Mn0.8V0.2)2、(Ti0.95Al0.05)0.85Sc0.15(Mn0.8V0.2)2Or (Ti0.95Al0.05)0.8Sc0.2(Mn0.8V0.2)2。
The preparation method of Neale Lavis hydrogen storage alloy phase of the present invention is：Each metal simple-substance is weighed according to formula proportioning, gold
The purity of category simple substance raw material more than 99%, melt by the then melting in non-consumable arc furnace or vacuum medium frequency induction furnace
Carry out under argon atmosphere for anti-oxidation during refining.
Further, using during non-consumable arc furnace melting, being to ensure that hydrogen-storage alloy composition is uniform, melting 4 need to be stood up
It is secondary.
Beneficial effects of the present invention：
The reversible hydrogen storage amount of hydrogen-storage alloy obtained by of the invention is high, and easily-activated, antioxidation, platform property is good, is suitable as big rule
Hydrogen source under mould hydrogen condition.The alloy can directly inhale hydrogen in room temperature, the pressure of 2MPa hydrogen, live without the need for high temperature or pre-press
Change.The addition of Sc greatly improves the hydrogen storage amount of alloy, and highest hydrogen storage amount is 2.3wt% under room temperature, 4MPa pressure, and highest can
Inverse hydrogen storage amount is 2.1wt%.The addition of V also significantly improves alloy surface, solves and cause hydrogenation difficulty due to oxidation
Problem.Meanwhile, the addition of Al improves the platform property and hysteresis quality of alloy.It is the hydrogen storage amount of alloy, reversible hydrogen storage amount, delayed
Property, the more unmodified Ti of platform pressure1-xZrxMnCr and Ti1-xScxMnCr systems alloy increased.This alloy is expected in hydrogen and its same
Position element is separated and is applied with storage, catalyst and Ni-MH battery.
Description of the drawings
Fig. 1 is (Ti1-yAly)1-xScx(Mn0.8V0.2)2The hydrogenation power that alloy block is depressed at room temperature with 2.0MPa hydrogen
Learn curve.
Fig. 2 is (Ti1-yAly)1-xScx(Mn0.8V0.2)2Alloy P-C-T curves at room temperature；Abscissa is hydrogen storage amount (H/
F.u.), vertical coordinate puts hydrogen balance pressure (KPa), wherein x=0.1, y=0,0.05,0.1 for suction.
Fig. 3 is (Ti1-yAly)1-xScx(Mn0.8V0.2)2Alloy P-C-T curves at room temperature；Abscissa is hydrogen storage amount (H/
F.u.), vertical coordinate puts hydrogen balance pressure (KPa) for suction；Wherein x=0.15, y=0,0.05,0.1.
Fig. 4 is (Ti1-yAly)1-xScx(Mn0.8V0.2)2Alloy P-C-T curves at room temperature；Abscissa is hydrogen storage amount (H/
F.u.), vertical coordinate puts hydrogen balance pressure (KPa) for suction；Wherein x=0.2, y=0,0.05,0.1.
Fig. 5 is (Ti1-yAly)1-xScx(Mn0.8V0.2)2Alloy at room temperature with atmospheric condition under XRD spectrum.
Fig. 6 is (Ti1-yAly)1-xScx(Mn0.8V0.2)2Alloy be flushed with hydrogen after XRD spectrum under room temperature and atmospheric condition.
Specific embodiment
The present invention provides a kind of Neale Lavis hydrogen storage alloy phase, and its chemical formula is：(Ti1-yAly)1-xScx(Mn0.8V0.2)2, its
In, 0.00≤y≤1.00,0.00≤x≤0.20.
Preferably, in the hydrogen-storage alloy, x=0.1~0.2；Y=0~0.1.
Further, in the hydrogen-storage alloy, x=0.1, y=0,0.05 or 0.1；Preferably, x=0.1, y=0,0.05.
Further, in the hydrogen-storage alloy, x=0.15, y=0,0.05 or 0.1.
Further, in the hydrogen-storage alloy, x=0.2, y=0,0.05 or 0.1.
Further, the Neale Lavis hydrogen storage alloy phase is：Ti0.9Sc0.1(Mn0.8V0.2)2、Ti0.85Sc0.15
(Mn0.8V0.2)2、(Ti0.95Al0.05)0.85Sc0.15(Mn0.8V0.2)2Or (Ti0.95Al0.05)0.8Sc0.2(Mn0.8V0.2)2。
The preparation method of Neale Lavis hydrogen storage alloy phase of the present invention is：Each metal simple-substance is weighed according to chemical formula proportioning,
The purity of metal simple-substance raw material more than 99%, the then melting in non-consumable arc furnace or vacuum medium frequency induction furnace,
Carry out under argon atmosphere for anti-oxidation during melting.
Further, using during non-consumable arc furnace melting, being to ensure that hydrogen-storage alloy composition is uniform, melting 4 need to be stood up
It is secondary.
The present invention is attempted by Ti1-xZrxMnCr and Ti1-xScxZr is substituted with Sc in MnCr systems alloy, Al substitutes Ti, uses
V substitutes Cr, improves the reversible hydrogen storage amount of alloy, significantly improves activation condition and platform property so as to be more suitable for
On a large scale with the hydrogen source under hydrogen condition.
Sc can adjust the bonding force of metal and hydrogen as most light transition elements, play good catalytic action.Simultaneously
Sc atomic weighies are far below Zr atomic weighies, and Sc substitutes Zr and can significantly improve alloy hydrogen storage amount.The antioxidation and catalytic of V element itself
Can, it is added in alloy can significantly improve alloy surface, carry heavy alloyed antioxygenic property.A small amount of Al substitutes Ti can be substantially
Improve the platform gradient and hysteresis quality of alloy, and in the electrodes Al can significantly reduce the corrosion of electrode, make the circulation longevity of alloy
Life increases.Therefore, the present invention devises a kind of new component hydrogen-storage alloy, improves hydrogen storage amount, activity function, the antioxidation of alloy
Performance and platform hysteretic properties.The design of components of modified hydrogen-storage alloy that the present invention is provided is：(Ti1-yAly)1-xScx
(Mn0.8V0.2)2, wherein, 0.00≤y≤1.00,0.00≤x≤0.20.
The specific embodiment of the present invention is further described with reference to embodiment, not therefore by present invention limit
System is among described scope of embodiments.
Embodiment
The synthesis of Ti-Al-Sc-Mn-V alloys：Using commercial metal element ti, Sc, Al, V block and Mn lamellar bodies as starting
Material, elemental purity is not less than 99%, according to nominal composition (Ti1-yAly)1-xScx(Mn0.8V0.2)2Carry out dispensing (alloy into
Atomize percentage ratio, at.%), wherein, the concrete atomic percent of each element is as shown in table 1, in high-purity Ar after dispensing
(99.999%) melt back (will enter at high temperature while hot for 4 times during alloy pig upset remelting in the magnetic control arc stove of atmosphere protection
OK, in order to avoid fragmentation), make the alloy pig that weight is about 30 grams.
Alloy pig is broken and removes one piece about 0.8 gram or so the sample for having unsalted surface, be put into homemade Sieverts types
In the sample room of hydrogenation plant, mechanical pump evacuation is filled with the hydrogen of 2.0MPa in hydrogenation plant after 40 minutes, does first adding
Hydrogen kinetic test, to investigate activation and the dynamic performance of alloy, is as a result shown in Fig. 1.It can be seen that, the alloy is in room temperature, 2MPa hydrogen
Pressure can directly inhale hydrogen, without the need for high temperature or pre-press activation.
By 0.8 gram or so of similar sample, in being put into the sample room of homemade Sieverts types hydrogenation dress, mechanical pumping is true
After empty 40 minutes, alloy is flushed with hydrogen at a temperature of 293K, when hydrogen content reaches saturation in the hydride that absorption hydrogen is formed
And till equilibrating to 4.0MPa, then carry out dehydrogenation.Reduction system hydrogen pressure makes alloy hydride put hydrogen, reaches in system relatively low
423K is warmed to sample room after balance pressure (1.0KPa), the complete dehydrogenation of alloy is made, a charge and discharge hydrogen circulation is completed.Carry out 4 times
The circulation of above-mentioned charge and discharge hydrogen ensures that alloy is activated completely, carry out at a temperature of 293K, in the range of the hydrogen pressure of 0.1kPa~4MPa pressure-
Component-temperature (P-C-T) is tested, and surveys the P-C-T curves of alloy, wherein, x=0.1 in alloy type, y=0,0.05,0.1 as
Shown in Fig. 2；X=0.15 in alloy type, y=0,0.05,0.1 it is as shown in Figure 3；X=0.2, y=0,0.05,0.1 in alloy type
It is as shown in Figure 4.
(Ti1-yAly)1-xScx(Mn0.8V0.2)2It is that alloy is shown in Table 1 with the Performance comparision of existing alloy.As can be seen that this
Bright hydrogen-storage alloy puts hydrogen platform gradient coefficient ratio LaNi except suction5Beyond platform is big, the more existing several alloys of remaining performance have
Improved, especially activity function and reversible hydrogen storage amount are more superior.
The hydrogen-storage alloy Performance comparision of table 1
After alloy is crushed, the mesh of Jing 200 sieves, and carries out phase composition measure to alloy with X-ray diffractometer (XRD), as a result such as
Fig. 5 and Fig. 6.XRD test results are proved：The introducing of Sc, V and a small amount of Al elements, does not change alloy phase composition, remains
C14Laves phases.
(Ti1-yAly)1-xScx(Mn0.8V0.2)2It is that XRD result of the alloy under the conditions of atmosphere at room temperature is shown in Fig. 5, it can be seen that
Alloy is AB2The side's Laves phases of type six, Laves phases are topology Mi Dui phases, with high symmetry, big ligancy and high-bulk-density
The features such as, close heap alloy lattice parameter c is 1.633 with a ideal ratios, and (Ti1-yAly)1-xScx(Mn0.8V0.2)2It is alloy c/a
It is worth for 1.64, closely ideal value.Fig. 6 is (Ti1-yAly)1-xScx(Mn0.8V0.2)2It is in room temperature and air after alloy is flushed with hydrogen
Under the conditions of test XRD spectrum, it can be seen that, although in atmosphere alloy hydride surface can it is a certain degree of be oxidized, hinder
Hinder the release of hydrogen in hydride lattice, but having part hydrogen can discharge, and also hydride stability is lower, and hydrogen release is put
It is more.Therefore for the (Ti existed with single Laves phases1-yAly)1-xScx(Mn0.8V0.2)2It is different for alloy
The hydride of Laves phase lattice paprmeters correspond to different hydrogen contents.This alloy is relatively easy point under atmospheric condition and room temperature
Solution, therefore alloy has very high reversible hydrogen storage amount.On the other hand, to the research table of Ti-Zr series Laves hydrogen storage alloy phases
Bright, element A proportioning change within the specific limits in alloy can improve hydrogen storage performance, and in B element Cr and Mn optimum ratio
Also 1 is deviateed to a certain extent, wherein Al, Sc, Mn element proportioning composition in design alloy changes within the specific limits.
As shown in table 1, (Ti1-yAly)1-xScx(Mn0.8V0.2)2It is the hydrogen storage performance of alloy more than Ti1-xZrxMnCr and Jing
Cross the Ti of Sc optimizations1-xScxMnCr alloys, are expected to the hydrogen storage material as extensive hydrogen source, apply in fuel, Ni-MH battery side
Face.
Claims (7)
1. Neale Lavis hydrogen storage alloy phase, it is characterised in that its formula is：(Ti1-yAly)1-xScx(Mn0.8V0.2)2, wherein, 0.00
＜ y≤1.00,0.00 ＜ x≤0.20.
2. Neale Lavis hydrogen storage alloy phase according to claim 1, it is characterised in that the x in the hydrogen-storage alloy, in formula
=0.1, y=0.05 or 0.1.
3. Neale Lavis hydrogen storage alloy phase according to claim 1, it is characterised in that the x in the hydrogen-storage alloy, in formula
=0.15, y=0.05 or 0.1.
4. Neale Lavis hydrogen storage alloy phase according to claim 1, it is characterised in that the x in the hydrogen-storage alloy, in formula
=0.2, y=0.05 or 0.1.
5. the preparation method of the Neale Lavis hydrogen storage alloy phase described in any one of Claims 1 to 4, it is characterised in that according to described
Formula proportioning weighs each metal simple-substance, the purity of metal simple-substance raw material more than 99%, then in non-consumable arc furnace
Or melting in vacuum medium frequency induction furnace, carry out under argon atmosphere during melting.
6. the preparation method of Neale Lavis hydrogen storage alloy phase according to claim 5, it is characterised in that using non-consumable vacuum
During arc melting, melting 3~5 times need to be stood up.
7. the preparation method of Neale Lavis hydrogen storage alloy phase according to claim 6, it is characterised in that melting 4 times need to be stood up.
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