CN105063425B - Improved Ti -based hydrogen storage alloy of vanadium iron and preparation method thereof - Google Patents
Improved Ti -based hydrogen storage alloy of vanadium iron and preparation method thereof Download PDFInfo
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- CN105063425B CN105063425B CN201510546789.5A CN201510546789A CN105063425B CN 105063425 B CN105063425 B CN 105063425B CN 201510546789 A CN201510546789 A CN 201510546789A CN 105063425 B CN105063425 B CN 105063425B
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Abstract
The present invention relates to a kind of high-performance and low-cost Ti -based hydrogen storage alloy modified through scandium, vanadium iron and preparation method thereof, belong to hydrogen-storage alloy field.The present invention provides a kind of improved Ti -based hydrogen storage alloy of vanadium iron, and its formula is：Ti0.95Sc0.05(Mn0.7‑xCr0.3Mx)2, wherein, M=FeV50 or FeV80；0≤x≤0.7.The reversible hydrogen storage amount of hydrogen-storage alloy of the present invention is higher than Ti1‑xZrxMnCr systems alloy and Ti1‑xScxMnCr systems alloy, and cost is less than both the above series alloy.This alloy can be applied in the separation of hydrogen, the isotopic separation of hydrogen and storage, catalyst and Ni-MH battery.
Description
Technical field
The present invention relates to a kind of high-performance and low-cost Ti -based hydrogen storage alloy modified through scandium, vanadium iron and its preparation side
Method, belongs to hydrogen-storage alloy field.
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 vanadium base bcc alloys, its hydrogen storage amount are 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 reversible hydrogen storage amount higher, good
Dynamics, wherein, Ti0.68Zr0.32MnCr alloy compositions combination property is best, but the exposure of this hydrogen-storage alloy is in atmosphere
When, surface can form one layer of dense oxide or hydroxide, cause its activation difficulty, and Zr metals are heavier in addition, 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 is directed to drawbacks described above, there is provided a kind of improved Ti -based hydrogen storage alloy of vanadium iron, the storage of gained hydrogen-storage alloy
Hydrogen amount is high, and is suitable as extensive hydrogen source under hydrogen condition.
Technical scheme：
The present invention provides a kind of improved Ti -based hydrogen storage alloy of vanadium iron, and its formula is：Ti0.95Sc0.05(Mn0.7- xCr0.3Mx)2, wherein, M=FeV50, FeV80 (content of V is 50wt% and 80wt%)；0≤x≤0.7.
Preferably, in the hydrogen-storage alloy, x=0,0.1,0.2,0.3,0.4,0.5,0.6,0.7
Further, the Ti -based hydrogen storage alloy is：Ti0.95Sc0.05(Mn0.4Cr0.3(FeV50)0.3)2、Ti0.95Sc0.05
(Mn0.3Cr0.3(FeV50)0.4)2、Ti0.95Sc0.05(Mn0.5Cr0.3(FeV80)0.2)2、Ti0.95Sc0.05(Mn0.4Cr0.3
(FeV80)0.3)2。
The preparation method of Ti -based hydrogen storage alloy of the present invention is：Each metal simple-substance, FeV50 are weighed according to chemical formula proportioning
Or FeV80, more than 99%, the purity of FeV50 or FeV80 is more than 98% for the purity of metal simple-substance raw material；Then non-
Melting in consumable vacuum arc furnace ignition or vacuum medium frequency induction furnace, for anti-oxidation is carried out under argon atmosphere during melting.
When further, using non-consumable arc furnace melting, to ensure that hydrogen-storage alloy composition is uniform, melting 3 need to be stood up
~5 (preferably 4) are secondary.
Beneficial effects of the present invention：
The alloy can directly inhale hydrogen in room temperature, the pressure of 2MPa hydrogen, be activated without high temperature or pre-press.Scandium it is a small amount of
Addition greatly improves the hydrogen storage amount of alloy, and the addition of chromium significantly improves the platform property of alloy.Compared to adding for high-purity V metals
Plus, two kinds of additions of different industrial alloys of FeV50 and FeV80 considerably reduce storage hydrogen on the basis of the hydrogen storage amount for improving alloy
The cost of alloy.The reversible hydrogen storage amount of alloy is higher than Ti1-xZrxMnCr systems alloy and Ti1-xScxMnCr systems alloy, and low cost
Two kinds of series alloys more than.This alloy can be obtained in the separation of hydrogen, the isotopic separation of hydrogen and storage, catalyst and Ni-MH battery
To application.
Specific embodiment
The present invention provides a kind of improved Ti -based hydrogen storage alloy of vanadium iron, and its formula is：Ti0.95Sc0.05(Mn0.7- xCr0.3Mx)2, wherein, (content of V is 50wt% and 80wt% for M=FeV50, FeV80.)；0≤x≤0.7.
Preferably, in the hydrogen-storage alloy, x=0,0.1,0.2,0.3,0.4,0.5,0.6,0.7
The preparation method of Ti -based hydrogen storage alloy of the present invention is：Each metal simple-substance, FeV50 are weighed according to chemical formula proportioning
Or FeV80, more than 99%, the purity of FeV50 or FeV80 is more than 98% for the purity of metal simple-substance raw material；Then non-
Melting in consumable vacuum arc furnace ignition or vacuum medium frequency induction furnace, for anti-oxidation is carried out under argon atmosphere during melting.
When further, using non-consumable arc furnace melting, to ensure that hydrogen-storage alloy composition is uniform, melting 4 need to be stood up
It is secondary.
The component of the modified hydrogen bearing alloy that the present invention is provided is designed as：Ti0.95Sc0.05(Mn0.7-xCr0.3Mx)2, its
In, M=FeV50, FeV80；0≤x≤0.7.The hydrogen storage performance of the alloy is more than Ti1-xZrxMnCr systems alloy and Ti1-xScxMnCr
It is alloy, a small amount of addition of scandium greatly improves the hydrogen storage amount of alloy, while the addition of scandium is seldom, compared to both the above alloy
Cost reduction, two kinds of industrial alloy prices of vanadium iron FeV50 and FeV80 are worked as with high-purity Cr metal phases, but due to the work of V element
With two kinds of additions of alloy improve the hydrogen storage amount of alloy on the premise of without cost of alloy is increased.Ti0.95Sc0.05
(Mn0.7-xCr0.3Mx)2System is expected to the hydrogen storage material as extensive hydrogen source, applies in terms of fuel, Ni-MH battery.
Sc can adjust the bonding force of metal and hydrogen as most light transition elements, play good catalytic action, and carry
Alloy hydrogen storage amount high.V element anti-oxidant and catalytic performance in itself, it can significantly improve alloy table in being added to alloy
Face, so as to improve the problem for causing hydrogenation difficult due to oxidation.Because high purity vanadium metal price is expensive, FeV50 and FeV80 two
Plant industrial alloy price to work as with high-purity Cr metal phases, the present invention substitutes High Purity Golds using two kinds of low-cost alloys of FeV50 and FeV80
Category V, on the premise of without cost is increased, the anti-oxidant and hydrogen storage amount of alloy has been held in raising.Therefore, the present invention devises one kind
Through the modified high-performance and low-cost Ti -based hydrogen storage alloy of scandium, vanadium iron.
Specific embodiment of the invention is further described with reference to embodiment, is not therefore limited the present invention
System is among described scope of embodiments.
Embodiment 1
Synthesis Ti-Sc-Mn-FeV-Cr alloys：Using commercial metal element ti, Sc, Cr, Mn, FeV50, FeV80 as starting
Material, metal purity is：Purity >=98% of Ti >=99%, Sc >=99%, Cr >=99%, Mn >=99%, FeV50 and FeV80,
According to Ti0.95Sc0.05(Mn0.4Cr0.3(FeV50)0.3)2Alloy formula (alloying component is atomic percent (at.%)) weighs each
The metal of component respective quality, 4 times (alloy pigs of melt back in the magnetic control arc stove of high-purity Ar (99.999%) atmosphere protection
To be carried out at high temperature while hot during upset remelting, in order to avoid fragmentation), it is made the alloy pig that weight is about 30 grams.
0.8 gram or so of similar sample is 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 untill equilibrating to 4.0MPa, then carry out dehydrogenation.Reduction system hydrogen pressure makes alloy hydride put hydrogen, is reached in system relatively low
423K is warmed to sample room after balance pressure (1.0KPa), makes the complete dehydrogenation of alloy, complete a charge and discharge hydrogen circulation.Carry out 4 times
Above-mentioned charge and discharge hydrogen circulation ensures that alloy is activated completely, and alloy is surveyed at a temperature of 293K, in the range of the hydrogen pressure of 0.1kPa~4MPa
P-C-T curves, the reversible hydrogen storage amount and hydrogen sucting platform pressure of test gained hydrogen-storage alloy, as a result as shown in table 1.
The reversible hydrogen storage amount and hydrogen sucting platform pressure of the hydrogen-storage alloy of table 1
| Alloy | Reversible hydrogen storage amount (wt.%) | Hydrogen sucting platform pressure (MPa) |
| Embodiment 1 | 2.14 | 320.5 |
| Embodiment 2 | 2.12 | 300.4 |
| Embodiment 3 | 2.19 | 312.3 |
| 1.90 | 296.4 | |
| 2.07 | 268.7 |
Embodiment 2-3
Preparation method etc. is same as Example 1, and simply alloy proportion is different from embodiment, embodiment 2 and embodiment 3
Alloy formula is respectively Ti0.95Sc0.05(Mn0.3Cr0.3(FeV50)0.4)2、Ti0.95Sc0.05(Mn0.4Cr0.3(FeV80)0.3)2。
Claims (5)
1. the improved Ti -based hydrogen storage alloy of vanadium iron, it is characterised in that its formula is：Ti0.95Sc0.05(Mn0.7-xCr0.3Mx)2,
Wherein, M=FeV50 or FeV80；0<x≤0.7.
2. the improved Ti -based hydrogen storage alloy of vanadium iron according to claim 1, it is characterised in that the hydrogen-storage alloy
In, x=0.1,0.2,0.3,0.4,0.5,0.6 or 0.7.
3. the preparation method of the improved Ti -based hydrogen storage alloy of vanadium iron described in claim 1 or 2, it is characterised in that according to institute
State formula proportioning and weigh FeV50 or FeV80, and each metal simple-substance, the purity of metal simple-substance is in more than 99wt%, FeV50
Or the purity of FeV80 is in more than 98wt%；Then the melting in non-consumable arc furnace or vacuum medium frequency induction furnace, during melting
For anti-oxidation is carried out under argon atmosphere.
4. the preparation method of the improved Ti -based hydrogen storage alloy of vanadium iron according to claim 3, it is characterised in that using non-
During consumable vacuum arc furnace melting, to ensure that hydrogen-storage alloy composition is uniform, melting 3~5 times need to be stood up.
5. the preparation method of the improved Ti -based hydrogen storage alloy of vanadium iron according to claim 4, it is characterised in that need to stand up
Melting 4 times.
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| CN1570176A (en) * | 2004-05-14 | 2005-01-26 | 中国科学院上海微系统与信息技术研究所 | Manganese ,vanadium ,iron simultaneously modified titanium chrome based oxygen storage alloy and its preparation method |
| CN101624674A (en) * | 2008-07-08 | 2010-01-13 | 北京有色金属研究总院 | Solid solution hydrogen storage alloy taking low-cost ferrovanadium as raw material |
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