CN101597711B - Rare earth-magnesium-transition metal base hydrogen storage metal preparation method - Google Patents
Rare earth-magnesium-transition metal base hydrogen storage metal preparation method Download PDFInfo
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- CN101597711B CN101597711B CN2009100745206A CN200910074520A CN101597711B CN 101597711 B CN101597711 B CN 101597711B CN 2009100745206 A CN2009100745206 A CN 2009100745206A CN 200910074520 A CN200910074520 A CN 200910074520A CN 101597711 B CN101597711 B CN 101597711B
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Abstract
The invention relates to a rare earth-magnesium-transition metal base hydrogen storage metal with high hydrogen storage capacity and moderate hydrogen storage temperature and preparation method thereof. The metal is characterized in that the chemical formula thereof is REMgxMy, wherein x is more than 1 and less than 2, y is more than 1 and less than 3; RE is one or more than one of rare earth metals of La, Ce, Pr, Nd, cerium rich mish metal Mm and lanthanum rich mish metal M1; M is one or more than one of transition metals of Cu, Ni, Mn, Fe and Zn. The rare earth-magnesium-transition metal base hydrogen storage metal provided by the invention is also characterized in that the metal at least contains a multiphase structure of CeMg3 type LaMg3 phase and LaMg2Cu2 phase. The invention also provides a preparation method of the rare earth-magnesium-transition metal base hydrogen storage metal. The preparation method mainly includes that induction melting is adopted, Mg base master alloy is utilized to substitute magnesium and used as raw material, secondary charging is used for preparing the metal, and the metal is annealed. The hydrogen storage metal of the invention has the advantages that the hydrogen storage capacity at 200 DEG C is more than 3wt.% and the metal can be used as solid-state hydrogen storage material.
Description
Technical field
The present invention relates to the hydrogen storage material field, the preparation method of the big rare-earth and Mg-transition metal base hydrogen storage metal of the moderate and hydrogen-storage amount of a kind of hydrogen storage temperature is provided especially.
Background technology
Along with the scarcity of the environmental degradation and the energy, the friendly type energy of development environment has become the focus of various countries' research.At present, has high energy density owing to hydrogen and environment friendly becomes one of the most attractive energy form.But, how to realize that the safe and efficient storage of hydrogen and transportation are to solve one of key of Hydrogen Energy practical application at present.For this reason, people have researched and developed various dissimilar hydrogen storage materials.Metal and alloy hydride objects system have obtained fast development as hydrogen good storage and transporting material.Wherein, containing magnesium and rare earth is that density is low, hydrogen storage capability is big and cost is low that advantage is subjected to extensive concern owing to having for all kinds of rare-earth and Mg base hydrogen bearing alloy materials of basic material.But the ubiquitous problem of this class alloy is that when MAGNESIUM METAL content was higher, it is higher that the hydrogen temperature is put in the suction of alloy, generally is higher than 300 ℃, and speed for hydrogen absorbing and releasing is slow and cycle life is poor; And when MAGNESIUM METAL content was low, the hydrogen-storage amount of alloy was then lower, generally is lower than 3wt.%.Therefore, seek and develop the significant actual subject that the rare-earth and Mg base hydrogen bearing alloy material with store hydrogen structure and composition has become the hydrogen storage material area research.
The Chinese invention patent application number discloses a kind of hydrogen storage material that consists of La2-xMxMg17 of mechanical alloying method preparation for No. 03149652.0, and wherein M is selected from Cu, Al, Ni, Fe, Co, Mn, V, Cr, Zn and Sn etc., 0＜x＜2.
Chinese invention patent application number 200410012968.2 discloses the preparation method of a kind of RexMgyNi4-xAx hydrogen storage alloy and amorphous, Re=Ca, La, Ce, Pr, Nd, Y, mishmetal, A=Ti, Co, V, Zr, Nb, Mn, Mo, Cu, Al, Fe, wherein 0≤x≤2; 0≤y≤2; 0≤z≤1.
Chinese patent application number 01145250.1 and Chinese patent application 01131897.X disclose preparation method and the quenching process that a kind of novel rare-earth is a hydrogen-storage electrode, wherein molecular formula is Al-yByCx, 0.01≤y in the formula≤0.8,2.0≤x≤4.0, wherein A is a kind of, two or more composition among La, rich La mishmetal Ml, Ce, rich Ce mishmetal Mm, Pr, the Nd, B is a kind of, two or more composition among Mg, Ca, Be, Sr, the Ba, and C is a kind of, two or more composition in the elements such as Mn, Fe, Mo, Co, Al.
China Patent No. 200510033055.3 discloses a kind of REMg3 type hydrogen storage alloy and preparation method thereof, and the molecular formula of this alloy is RE1.2-xMg3Niy, and wherein RE is a mishmetal, 0≤x≤0.4,0≤y≤1.
The problem of mainly containing that the rare-earth and Mg of addressing in the above-mentioned document-Ni-based hydrogen storage alloy exists has:
(1) among the alloy La2-xMxMg17 since the too high alloying element or second high of Mg content with lacking catalytic activity mutually, thereby exist to inhale shortcomings such as hydrogen discharging temperature height and cycle life difference.In addition, adopting the method for mechanical ball milling to prepare alloy material exists complex process and is difficult for industrialized difficulty.
(2) contain the high elements of price such as Co, Mo, the cost of alloy height among the alloy RexMgyNi4-xAx.And the element that has environmental pollutions such as V, Zr.
(3) do not contain the high element of catalytic activity in the alloy A l-yByCx alloy, inhale and put the hydrogen difficulty.
(4) the RE1.2-xMg3Niy alloy is the LaMg3 type alloy of single structure, because Mg content is higher, has the problem that hydrogen discharging temperature is higher and the life-span is poor of inhaling.
(5) magnesium in alloy preparation very easily in volatilization loss, but all provide effective ways and the actual test composition deviation that makes sample of effectively controlling the magnesium loss in the melting among the embodiment of above-mentioned patent, exist actual composition to depart from alloy designs far away and form and the actual problem of unstable of forming.
Summary of the invention
The present invention relates to the hydrogen storage material field, the preparation method that a kind of hydrogen-storage amount is big and inhale euthermic rare-earth and Mg-transition metal base hydrogen storage metal is provided especially.
The invention provides a kind of preparation method who has at a lower temperature than the rare-earth and Mg-transition metal base hydrogen storage metal of high hydrogen storage, it is characterized in that: this alloy consist of REMgxMy, RE is one or more elements among La, Ce, Pr, the Nd, M is Cu, Ni, Mn, the Fe in the transition metal, one or more elements among the Zn, and 1≤x≤2,1≤y≤3.
The present invention also provides the preparation method of above-mentioned rare-earth and Mg-transition metal base hydrogen storage metal, it is characterized in that: at first prepare Mg-Ni or Mg-R master alloy that Mg content is 15-50%, wherein R is one or more elements among La, Ce, Pr, Nd, Cu, the Ni.The simple substance of other component in Mg-Ni or Mg-R master alloy and the hydrogen storage alloy as raw material, is formed by the atomic ratio of above-mentioned molten alloy and to be prepared burden.Except that Mg-Ni or Mg-R master alloy, other component simple substance are packed in the crucible of induction melting furnace.In the secondary charging device that the Mg-Ni or the Mg-R master alloy of weighing is put into induction melting furnace, vacuumize then,, charge into rare gas element when vacuum tightness reaches 10-2Pa when following, when furnace pressure reached 0.02-0.1MPa, heating was also regulated the power of smelting furnace raw material is all melted in the stove to making.Then, fast Mg-Ni in the secondary charging device or Mg-R master alloy are joined in the smelting pot, and continue heating and control smelting temperature between 500-650 ℃, be incubated 2-10 minute.At last the alloy water in the crucible is cast in rapidly in the mold of recirculated water refrigeration.Treat to come out of the stove after alloy is cooled to room temperature in the stove, and carry out anneal in argon gas atmosphere, annealing temperature is 350-450 ℃, is incubated 2-10 hour.
The invention has the advantages that:
(1) during hydrogen storage material provided by the invention was formed, the content of MAGNESIUM METAL was moderate, and had equal with the LaMg2Cu2 mutually heterogeneous structure of LaMg3 of CeMg3 type, existed heterogeneous interaction.Thereby make alloy both have higher hydrogen-storage amount, hydrogen storage temperature is reduced.
(2) hydrogen storage alloy that provides among the present invention does not contain the metallic substance (V, Zr, Pd, Pb) of high metallic substance of cost (Mo, Co, Pt, Pd) and serious environment pollution, and alloy has with low cost and good environment friendly.
(3) alloy preparation method of the present invention is the induction melting method that industry is at present generally used, and has adopted with Mg base master alloy replacement Mg and made raw material and adopt the mode of secondary charging to add, and can effectively reduce and control the volatilization loss of MAGNESIUM METAL.The actual composition of the sample of the present invention preparation is formed with design and is coincide, and error can be controlled at ± and 0.5%.Realized the control alloy composition, it is simple and be easy to the characteristics of large-scale commercial production to have method.
Description of drawings
The XRD of Fig. 1 embodiment 1
The PCT curve of Fig. 2 embodiment 1
The suction hydrogen kinetic curve of Fig. 3 embodiment 1
The XRD of Fig. 4 embodiment 2
The XRD of Fig. 5 embodiment 3
The XRD of Fig. 6 embodiment 4
Embodiment
Embodiment 1:
LaMg2Cu1.5Ni0.5 prepares burden according to the alloy composition formula, and as raw material, it is raw material that other elements adopt metal simple-substance to Mg with the LaMg3 master alloy, and purity is all more than 99.9%.Use homemade 10Kg vacuum induction melting, be evacuated to 10-2Pa, charge into argon gas, regulate power and smelting temperature and make whole raw material fusings, adopt the secondary charging mode to add the Mg2Ni master alloy to pressure 0.06MPa.Insulation is 5 minutes about 500 ℃, after melting finishes melt metal is poured in the copper mold that has water coolant, to be cooledly comes out of the stove after 40 ℃.Then alloy cast ingot is carried out anneal under protection of inert gas, treatment temp is 350 ℃, is incubated 12 hours.Carry out ultimate analysis to carrying out inductively coupled plasma atomic emission (ICP) after the annealing, the results are shown in Table 1.Sample is carried out X-ray powder diffraction analysis (XRD), the results are shown in Figure 1.At the hydrogen sucking function of 200 ℃ of following applying pressures-composition-temperature measuring device (P-C-T) specimen, the PCT curve is seen Fig. 2, and hydrogen sees Table 1.In addition, in the time of 150 ℃, hydrogen pressure remains under the 3Mpa, measures the suction hydrogen kinetic curve of alloy, gets Fig. 3, and as seen, alloy is under 150 ℃, and the mass percent of inhaling hydrogen in 15 minutes reaches 3.3wt.%, accounts for 92% of maximum hydrogen.
Embodiment 2:
Chemical constitution formula is LaMg
2Fe
0.5Ni
1.5, wherein Mg is with MgNi
2Master alloy is as raw material, and other element material purities are with embodiment 1, and the melting method of alloy is with embodiment 1.Sample is come out of the stove the after annealing mode with embodiment 1, and annealing temperature is 400 ℃, and the time is 8 hours.The icp analysis result of alloy and the hydrogen of test see Table 1, and X ray diffracting spectrum is seen Fig. 4.
Embodiment 3:
Chemical constitution formula is LaMgNi
1.0Cu
1.0, batching and melting method are with embodiment 1.Annealing temperature is 430 ℃, and the annealing soaking time is 5 hours.The icp analysis result and the hydrogen of alloy see Table 1, and X ray diffracting spectrum is seen Fig. 5.
Embodiment 4:
Chemical constitution is LaMg
1.5Cu
1.25Ni
1.25, batching and melting method are with embodiment 2.Annealing temperature is 450 ℃, and the annealing soaking time is 2 hours.The icp analysis result and the hydrogen of alloy see Table 1, and X ray diffracting spectrum is seen Fig. 6.
Table 1 embodiment 1-4 ultimate analysis and hydrogen
Claims (3)
1. the preparation method of a rare-earth and Mg-transition metal base hydrogen storage metal is characterized in that: this alloy consist of REMg
xM
y, RE is more than one elements among rare-earth metal La, Ce, Pr, Nd, cerium-rich mischmetal metal M m, the lanthanum rich norium M1; M is (Cu+Ni) or (Fe+Ni) in the transition metal, and 1≤x≤2,1≤y≤3, adopt protection of inert gas in vacuum induction furnace, to prepare alloy, use the master alloy of Mg-R, wherein R is more than one elements among La, Ce, Pr, Nd, the Fe, replaces magnesium as raw material, and adopts the mode of secondary charging to join in the smelting pot; Alloy needs anneal behind the smelting and pouring, and treatment process is to be incubated 2-10 hour down in 350-450 ℃ in inert gas atmosphere.
2. the preparation method of a kind of rare-earth and Mg-transition metal base hydrogen storage metal according to claim 1, it is characterized in that: this alloy has higher gas-solid hydrogen-storage amount at a lower temperature, hydrogen-storage amount under 200 ℃ is higher than 3wt.%, can be used as solid-state hydrogen storage material.
3. the preparation method of a kind of rare-earth and Mg-transition metal base hydrogen storage metal according to claim 1, it is characterized in that: this alloy contains CeMg at least
3The LaMg of type
3Phase and LaMg
2Cu
2The heterogeneous structure of phase.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102191416B (en) * | 2011-04-26 | 2012-11-28 | 燕山大学 | Magnesium-based hydrogen storage alloy composite material and preparation method thereof |
| CN102586660B (en) * | 2012-02-27 | 2013-06-05 | 燕山大学 | Magnesium-based hydrogen storage alloy composite material with added metal sulfide |
| CN103540960B (en) * | 2013-09-30 | 2016-08-17 | 赣南师范学院 | A kind of preparation method of the Ni-based hydrogen bearing alloy of rare earth magnesium |
| CN104131315B (en) * | 2014-08-20 | 2017-11-07 | 赣南师范大学 | A kind of Ni-based hydrogen bearing alloy electrolysis eutectoid alloy method of rare earth magnesium |
| CN105063447B (en) * | 2015-08-17 | 2017-04-19 | 安泰科技股份有限公司 | High-capacity Mg-Ni-Cu-La hydrogen storage alloy and preparing method thereof |
| CN105238956B (en) * | 2015-10-22 | 2017-01-25 | 燕山大学 | Preparation method and hydrogen storage application of 3R type super stacking single-phase Sm-Mg-Ni alloy |
| CN105514402B (en) * | 2016-01-27 | 2018-01-23 | 燕山大学 | A kind of PuNi3The preparation method of the single-phase neodymium-magnesium-nickel alloy electrode material of type |
| CN108220739A (en) * | 2016-12-22 | 2018-06-29 | 北京有色金属研究总院 | A kind of Y-Fe bases rare earth hydrogen storage material and preparation method thereof |
| CN107201457B (en) * | 2017-06-30 | 2018-12-28 | 燕山大学 | A kind of preparation method of Gd2Co7 type Nd-Mg-Ni system single-phase alloy |
Citations (1)
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| CN1563453A (en) * | 2004-04-01 | 2005-01-12 | 桂林电子工业学院 | rEXmGYnI4-zAz alloy of storing hydrogen and uncrystallized preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1563453A (en) * | 2004-04-01 | 2005-01-12 | 桂林电子工业学院 | rEXmGYnI4-zAz alloy of storing hydrogen and uncrystallized preparation method |
Non-Patent Citations (3)
| Title |
|---|
| K.Kadir.Hydrogen behavior in th La-Mg-Cu system.《Journal of Alloys and Compounds》.1999,(第289期),66-70. * |
| 韩树民 等.Ni/MH电极负极用高容量稀土-镁-镍基储氢合金.《西安交通大学学报》.2008,第42卷(第3期),377-380. |
| 韩树民等.Ni/MH电极负极用高容量稀土-镁-镍基储氢合金.《西安交通大学学报》.2008,第42卷(第3期),377-380. * |
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