CN101153362A - High capacity vanadium hydrogen occluding alloy produced with intermediate alloy FeV80 - Google Patents
High capacity vanadium hydrogen occluding alloy produced with intermediate alloy FeV80 Download PDFInfo
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- CN101153362A CN101153362A CNA2007100500318A CN200710050031A CN101153362A CN 101153362 A CN101153362 A CN 101153362A CN A2007100500318 A CNA2007100500318 A CN A2007100500318A CN 200710050031 A CN200710050031 A CN 200710050031A CN 101153362 A CN101153362 A CN 101153362A
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Abstract
The present invention provides a high-capacity vanadium-base hydrogen-storage alloy prepared from a medium alloy FeV80, V content of which is 78-80 percent. The alloy provided by the present invention solves the puzzle of the high price of the vanadium alloy, and has good hydrogen discharging capacity, good activation efficacy and dynamic efficacy. The chemical formula of vanadium-base BBC melting type of the alloy is Ti(100-a-b-c-d-e-f-g) VaCrbFecAldREeMf, wherein, a is more than or equal to 15 and less than or equal to 60, b is more than or equal to 3 and less than or equal to 50, c is more than 0 and less than or equal to 20, d is more than 0 and less than or equal to 5, e is more than 0 and less than or equal to 5, f is more than 0 and less than or equal to 5, and a/c is less than or equal to 9, RE represents one of more that one of the thulium such as La, Ce, Pr, Nd, Sm, Gd, Dy, Tb, and Y, wherein, M represents one of or more than one of elements such as Zr, Mn, Co, Ni, C and Si. The preparation of the alloy includes the vacuum or inert atmosphere protection during the melting and thermal process, an electric arch furnace or a frequency induction melting furnace is adopted, and vacuum or high-purity argon protection is used during the melting process, wherein, the thermal treatment is heat preservation for 1 minute to 50 hours at 1000-1500 DEG C. The hydrogen absorption volume of the series alloy exceeds 3.6wt percent, and hydrogen discharging volume (below 373k, up to 0.1 atm) exceeds 2.2wt percent. The series alloy has simple preparation method, with wide applicable prospect on the storage and transportation of hydrogen, as well as on the fuel battery.
Description
Technical field
The present invention relates to a kind of V-Based Hydrogen Storage Alloy, this alloy is a raw material with FeV80 (V content the is 78-82wt%) master alloy of cheapness, have high suction and put hydrogen capacity and good activation performance, production method is simple, is with a wide range of applications at the storage and the aspects such as transportation and fuel cell of hydrogen.
Background technology
Along with being on the rise of oil crisis and environmental pollution, people are to having accelerated exploitation new, clean energy.In numerous new forms of energy (comprising Hydrogen Energy, sun power, nuclear energy, waterpower, wind energy etc.), Hydrogen Energy is subjected to especially paying attention to as one of most important renewable and clean energy resource in the future source of energy.Three big core technologies of Hydrogen Energy utilization comprise the storage of the producing of hydrogen, hydrogen and are the fuel cell of fuel with hydrogen.The storage of hydrogen is one of major obstacle of restriction hydrogen economy realization.Storage of hydrogen mainly contains 3 kinds of modes at present: low temperature liquid hydrogen storage hydrogen, high-pressure hydrogen storing and hydrogen storage material storage hydrogen.Adopt low temperature liquid hydrogen storage hydrogen, the energy that liquefaction of hydrogen (235 ℃) consumes is equivalent to 1/3rd of the hydrogen energy that is liquefied, and the safety problem that the vaporization of liquid hydrogen (particularly little storage tank) is brought also merits attention.Make this technology be not expected in the world.High-pressure hydrogen storing mode hydrogen-storage amount is less, in the use pressure drop very big, control is difficult, the energy of consumption is also more.Hydrogen storage material storage hydrogen is the most active hydrogen storage technologies of research and development at present.In numerous hydrogen storage materials, hydrogen storage alloy is to study the most sophisticated hydrogen storage material.
Hydrogen storage alloy mainly contains AB
5Type, AB
2Type, AB type, Mg base hydrogen bearing alloy (comprise A
2Type B) and vanadium base BCC solid solution hydrogen storage alloy.AB
5Type hydrogen storage alloy is (with LaNi
5Be representative), AB
2Type storage hydrogen is (with ZrMn
2, TiMn
2Be representative) and the equal not enough 2.0wt% of sucking/placing hydrogen amount of AB type hydrogen storage alloy (is representative with TiFe).Though the Mg base hydrogenous alloy has very high theoretical hydrogen-storage amount, reach as high as 7.6wt%, but need could realize down inhaling putting hydrogen in higher temperature (300～400 ℃), the suction hydrogen discharging temperature is too high, even after adopting technical finesses such as nano-structured, nano-catalytic and nano combinedization, the Mg hydrogen storage alloy at room temperature still can't be realized effectively inhaling putting hydrogen.Vanadium base BCC solid solution hydrogen storage alloy is inhaled hydrogen and can be reached very high hydrogen-storage amount (greater than 3.0wt%) under the room temperature, effective hydrogen desorption capacity has broad application prospects greater than 2.0wt% when putting hydrogen.But because the price of vanadium metal too high (price of pure metal surpasses 2,000,000/ton), too high cost restricts the application of this series alloy.
Nineteen ninety-five, [Kei Nomura, Etsuo Akiba, J.Alloys Comps, 231 (1995) 513-517] such as Kei Nomura have at first reported the Ti that adopts the preparation of FeV80 master alloy
40V
48.8Fe
11.2A
L3.5Alloy, this absorption hydrogen amount reaches 3.5wt%, but hydrogen desorption capacity only is 0.5wt%.Huang Taizhong etc. [Taizhong Huang, Zhu Wu, Baojia Xia, Jinzhou Chen, Xuebin Yu, Naixin Xu, Changwei Lu, Huimei Yu .Tech Adv Mater, 4 (2003) 491-494] report TiCr
1.2(V-Fe) 0.6 alloy, this absorption hydrogen amount is 3.2wt% only, hydrogen desorption capacity is 2.0wt% under the 333K.As seen, it is all lower to report that at present hydrogen capacity is put in the vanadium base BCC solid solution hydrogen storage alloy suction of adopting the preparation of FeV80 master alloy.
Summary of the invention
The object of the invention is to solve the expensive problem of V-Based Hydrogen Storage Alloy, and a kind of high capacity vanadium base BCC solid solution hydrogen storage alloy by the preparation of FeV80 master alloy is provided.
The present invention is a kind of high capacity vanadium base BCC solid solution hydrogen storage alloy by the preparation of FeV80 master alloy, it is characterized in that chemical formula is Ti (100-a-b-c-d-e-f-g) V
aCr
bFe
cAl
dRE
eM
f, 15≤a in the formula≤60,3≤b≤50,0＜c≤20,0＜d≤5,0＜e≤5,0＜f≤5, a/c≤9, RE represents rare-earth metals La, Ce, Pr, Nd, Sm, Gd, Dy, Tb, one or more among the Y, M represents Zr, Mn, Co, Ni, C, one or more among the Si.Alloy of the present invention can be by the preparation of arc melting or induction melting, and method is as follows: raw material be purity at 99.6% above elemental metals element, and V content is the FeV80 master alloy of 78-82wt%.Press the stoichiometric ratio batching of alloy, adopt electric arc furnace or medium-frequency induction furnace melting, fusion process adopts vacuum protection or high-purity argon gas protection; Be to guarantee the homogeneity of alloy, the alloy of the melting melting 3～5 times of need overturning in the vacuum arc fumace.The alloy of melting gained is at 1000 ℃～1500 ℃ insulation 1min～50h, and furnace cooling.The alloy of gained is removed after the oxide skin on surface, and Mechanical Crushing to 1 millimeter is got 3 grams and inhaled and put the hydrogen test.
Description of drawings
Fig. 1 is alloy V
29Ti
34Cr
24Fe
10Al
1.5Si
0.5Ce
1Inhale the kinetic curve of hydrogen under the room temperature (298K) first.
Fig. 2 is alloy V
37Ti
26Cr
24Fe
8Al
1.5Mn
2La
1.5The XRD diffracting spectrum.
Fig. 3 is alloy V
29Ti
31Cr
31Fe
6Al
1.5Si
0.5Ce
1Put hydrogen PCT curve under the alloy 298K.
Fig. 4 is alloy V
33.5Ti
29Cr
25Fe
7Ni
2Al
2Si
0.5Ce
1Put hydrogen PCT curve under the alloy 298K.
Embodiment
The invention will be further described below by the specific embodiment description, but the present invention only limits to fact Example absolutely not:
Embodiment:
Embodiment 1: the composition of alloy is V
29Ti
34Cr
24Fe
10Al
1.5Si
0.5Ce
1, electric arc melt back 5 times is adopted down in argon shield, and then 1300 ℃ of following vacuum annealings 0.5 hour, the gained alloy is crushed in air about 1mm, gets 3 grams and does to inhale and put the hydrogen test.The container that alloy is housed vacuumize with mechanical pump under the room temperature (25 ℃) 30min (minute) after, charge into the hydrogen of 3MPa, alloy begins to inhale rapidly hydrogen through 0.2min after incubation period, hydrogen reaches 3.68wt% behind the 5min, substantially reach and inhale the saturated (see figure 1) of hydrogen, the hydrogen desorption capacity of 100 ℃ of following alloys reaches 2.2wt%.
Embodiment 2: the composition of alloy is V
37Ti
26Cr
24Fe
8Al
1.5Mn
2La
1.5, electric arc melt back 5 times is adopted in argon shield down, then 1400 ℃ of following vacuum annealings 2 hours.The gained alloy is broken in air, and particle diameter is that the powder about 1mm is used for inhaling and puts the hydrogen test, and particle diameter is that the powder of 75 μ m is used for the X-ray diffraction test.The container that alloy is housed vacuumize with mechanical pump under the room temperature (25 ℃) 30min (minute) after, charge into the hydrogen of 3MPa, can directly inhale hydrogen under the alloy room temperature, maximum hydrogen reaches 3.65wt%, 100 ℃ of hydrogen desorption capacities reach 2.5wt%.This alloy has BCC phase structure (see figure 2), and lattice parameter reaches 0.3037nm.
Embodiment 3: the composition of alloy is V
29Ti
31Cr
31Fe
6Al
1.5Si
0.5Ce
1, electric arc melt back 5 times is adopted in argon shield down, then 1400 ℃ of following vacuum annealings 0.5 hour.Alloy is crushed to 1～5mm in air, get 3 grams and do to inhale and put the hydrogen test.The container that alloy is housed vacuumize with mechanical pump under the room temperature (25 ℃) 30min (minute) after, charge into the hydrogen of 3MPa, alloy at room temperature can directly be inhaled hydrogen, hydrogen reaches 3.76wt% behind the 5min, hydrogen desorption capacity reaches the 2.35wt% (see figure 3) under the 298K, and 100 ℃ of following hydrogen desorption capacities reach 2.56wt%.
Embodiment 4: the composition of alloy is V
33.5Ti
29Cr
25Fe
7Ni
2Al
2Si
0.5Ce
1, electric arc melt back 5 times is adopted in argon shield down, then 1400 ℃ of following vacuum annealings 0.5 hour.Alloy is crushed in air about 1～5mm, gets 3 grams and does to inhale and put the hydrogen test.The container that alloy is housed is after vacuumizing 30min with mechanical pump under the room temperature (25 ℃), charge into the hydrogen of 3MPa, alloy is direct hydrogen at room temperature, and maximum hydrogen reaches 3.72wt%, hydrogen desorption capacity reaches the 2.23wt% (see figure 4) under the room temperature, and 100 ℃ of following hydrogen desorption capacities reach 2.48wt%.
Claims (2)
1. a vanadium fundamental mode hydrogen-storage alloy as the preparation of vanadium source, is characterized in that chemical formula is Ti (100-a-b-c-d-e-f-g) V by the FeV80 master alloy
aCr
bFe
cAl
dRE
eM
f, 15≤a in the formula≤60,3≤b≤50,0＜c≤20,0＜d≤5,0＜e≤5,0＜f≤5, a/c≤9, RE represents rare-earth metals La, Ce, Pr, Nd, Sm, Gd, Dy, Tb, among the Y one or several, M represents Zr, Mn, Co, Ni, C, one or more among the Si.Alloy adopts arc melting or induction melting, and fusion process adopts vacuum or argon gas atmosphere protection.Melting postheat treatment process is: at 1000 ℃～1500 ℃ insulation 1min～50h, and furnace cooling.
2. according to right 1 described vanadium-based alloys, it is characterized in that alloy forms single BCC phase or BCC comprises rich rare earth phase two phase structure mutually.
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|---|---|---|---|
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108913972A (en) * | 2018-07-04 | 2018-11-30 | 南通志乐新材料有限公司 | A kind of iron-based complex phase environmental protection hydrogen storage material |
| CN111636022A (en) * | 2020-05-19 | 2020-09-08 | 有研工程技术研究院有限公司 | Long-life high-capacity vanadium-based hydrogen storage alloy and hydrogenation powder preparation method thereof |
| CN113502424A (en) * | 2021-07-07 | 2021-10-15 | 中国科学院江西稀土研究院 | Low-temperature activated vanadium-based hydrogen storage alloy and preparation method and application thereof |
| CN114427045A (en) * | 2021-12-10 | 2022-05-03 | 厚普清洁能源股份有限公司 | High-uniformity vanadium-titanium-based hydrogen storage alloy and preparation method thereof |
| CN114502756A (en) * | 2019-08-05 | 2022-05-13 | 新南创新私人有限公司 | Method for preparing hydrogen storage alloy |
| CN115612903A (en) * | 2022-12-12 | 2023-01-17 | 四川大学 | High-vanadium solid solution type hydrogen storage alloy and preparation method thereof |
| CN114502756B (en) * | 2019-08-05 | 2024-04-19 | 新南创新私人有限公司 | Method for preparing hydrogen storage alloy |
-
2007
- 2007-09-17 CN CNA2007100500318A patent/CN101153362A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108913972A (en) * | 2018-07-04 | 2018-11-30 | 南通志乐新材料有限公司 | A kind of iron-based complex phase environmental protection hydrogen storage material |
| CN108913972B (en) * | 2018-07-04 | 2019-10-01 | 南理工泰兴智能制造研究院有限公司 | A kind of vanadium base complex phase environmental protection hydrogen storage material |
| WO2020006842A1 (en) * | 2018-07-04 | 2020-01-09 | 黄倩 | Iron-based complex phase environmentally-friendly hydrogen storage material |
| CN114502756A (en) * | 2019-08-05 | 2022-05-13 | 新南创新私人有限公司 | Method for preparing hydrogen storage alloy |
| CN114502756B (en) * | 2019-08-05 | 2024-04-19 | 新南创新私人有限公司 | Method for preparing hydrogen storage alloy |
| CN111636022A (en) * | 2020-05-19 | 2020-09-08 | 有研工程技术研究院有限公司 | Long-life high-capacity vanadium-based hydrogen storage alloy and hydrogenation powder preparation method thereof |
| CN111636022B (en) * | 2020-05-19 | 2021-12-03 | 有研工程技术研究院有限公司 | Long-life high-capacity vanadium-based hydrogen storage alloy and hydrogenation powder preparation method thereof |
| CN113502424A (en) * | 2021-07-07 | 2021-10-15 | 中国科学院江西稀土研究院 | Low-temperature activated vanadium-based hydrogen storage alloy and preparation method and application thereof |
| CN114427045A (en) * | 2021-12-10 | 2022-05-03 | 厚普清洁能源股份有限公司 | High-uniformity vanadium-titanium-based hydrogen storage alloy and preparation method thereof |
| CN115612903A (en) * | 2022-12-12 | 2023-01-17 | 四川大学 | High-vanadium solid solution type hydrogen storage alloy and preparation method thereof |
| CN115612903B (en) * | 2022-12-12 | 2023-03-17 | 四川大学 | High-vanadium solid solution type hydrogen storage alloy and preparation method thereof |
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