CN104709873A - Novel Mg-Li-Al-Ti hydrogen storage material and preparing method thereof - Google Patents
Novel Mg-Li-Al-Ti hydrogen storage material and preparing method thereof Download PDFInfo
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- CN104709873A CN104709873A CN201510109564.3A CN201510109564A CN104709873A CN 104709873 A CN104709873 A CN 104709873A CN 201510109564 A CN201510109564 A CN 201510109564A CN 104709873 A CN104709873 A CN 104709873A
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Abstract
The invention relates to a novel Mg-Li-Al-Ti hydrogen storage material using metal and metal hallide as catalysts and a preparing method of the novel Mg-Li-Al-Ti hydrogen storage material. The main components of the hydrogen storage material are mMgH2, Li3AlH6, x% of Al/AlCl3 and y% of Ti/TiF3 (wherein x and y refer to mass percentages that the substances occupy the total mass, x is larger than 5 and smaller than 20, y is large than 5 and smaller than 15, and m is larger than 2 and smaller than 5). The preparing method comprises the following steps: filling hydride Li3AlH6 of MgH2 and Li-Al and a certain quantity of Al/AlCl3, Ti/TiF3 and the like into a stainless steel tank, and ball-milling under the condition of inert gas for 1-6 hours in a mode of mechanical ball-milling to obtain the Mg-Li-Al-Ti hydrogen storage material. The Mg-Li-Al-Ti hydrogen storage material has the advantages that an Al3Ti catalyst can be generated in situ under the condition of mechanical mixing through adding x% of Al/AlCl3 and y% of Ti/TiF3; 2, the hydrogen absorbing temperature is low, the initial hydrogen release temperature can be lowered to 58 DEG C, 5.6wt% of hydrogen gas can be released at 250 DEG C, and the total dehydrogenation quantity reaches 7.2wt% when the temperature is raised to 400 DEG C; 3, the hydrogen absorbing speed is high, the invertibility is great, and the hydrogen storage material with excellent performance can be used for storing and transporting hydrogen; 4, the raw materials are easy to acquire, and the cost is low.
Description
Technical field
The present invention relates to hydrogen storage material, specifically a kind of novel Mg-Li-Al-Ti hydrogen storage material and preparation method thereof.
Background technology
Along with the series of problems that limited consumption and the environmental pollution of oil bring, finding a kind of clean green energy resource becomes the problem received much concern, and Hydrogen Energy receives much concern as clean secondary energy.The transport of hydrogen manufacturing, Chu Qing and hydrogen is the subject matter of restriction Hydrogen Energy development, and hydrogen storage technology is that hydrogen utilization moves towards practical and key, particularly hydrogen storage material of mass-producing research and development are important steps of hydrogen storage technology development.Magnesium-base hydrogen storage material is due to advantages such as hydrogen-storage amount is large, cost is low, aboundresources, be considered to one of the most promising hydrogen storage material, but too high hydrogen discharging temperature (>350 DEG C) and inhale hydrogen desorption kinetics slowly and become restriction it moves towards the biggest obstacle of practical application, and additive is considered to a kind of effective approach improving the hydrogen storage property of magnesium.
2010100608075.x(Beijing Non-Ferrous Metal Research General Academy is applied for a patent, meter Jing etc. in China) transition metal such as Bi, Sb, In, Ge, Sn are added in Li-Mg system by the ratio x=3wt% ~ 30wt% of total mass and carries out mechanical ball milling, catalysis MgH
2hydrogen storage property, can dehydrogenase 13 .5wt% 180 DEG C of first times, but it is unsatisfactory to inhale hydrogen kinetics.In addition, Chinese patent 201120338160.3(Nankai University, Wang Yijing, Yuan Huatang etc.) transition metal boride is added MgH by certainweight per-cent
2after powder Homogeneous phase mixing, carry out mechanical ball milling modification, at 300 DEG C of first time dehydrogenase 35 .5wt%, complete dehydrogenation time needs 1000s.The patent No. be 201310259727.7 applicants will add MgH to containing iron sulfide
2grinding is carried out in argon atmospher, only can dehydrogenase 34 wt% at 350 DEG C.Document (I.E. Malka, M. Pisarek, T.Czujko, J.Bystrzycki. International Journal of Hydrogen Energy. 36 (2011) 12909-12917) then proposes at MgH
2the a series of transition metal halide of middle interpolation, the alloy hydrogen absorption and desorption speed obtained by ball milling has had raising, but desorption temperature improvement is not obvious.Document (I.E, Rohit R. Shahi, Anand P. Tiwari, M.A. Shaz, O.N. Srivastava. International Journal of Hydrogen Energy. 38 (2013) 2778-2784) passes through at MgH
2the alloys such as middle interpolation Ti, Fe, Ni improve desorption temperature, and initial desorption temperature is reduced to 280 DEG C, being heated to 420 DEG C of total amount of dehydrogenation is 5.2wt%.Document (I.E, Hayao Imamura, Yoshiyuki Hashimoto, Takanori Aoki, Tomoki Ushijima and Yoshihisa Sakata. Materials Transactions, 55 (2014) 572-576) is to MgH
2middle interpolation Al, and carry out nanometer process, initial dehydrogenated temperature is reduced to 473K, but inhaling hydrogen dynamic performance is not very significantly improved.Add these transition metal or metal halide can effectively improve hydrogen discharging performance and hydrogen discharging temperature as catalyzer.But the circulation dynamics performance of hydrogen storage material and desorption temperature is higher is not still very significantly improved, hydrogen uptake condition requires high, and hydrogen－sucking amount is few, the time longly remains a large problem to be solved.In addition, the catalytic performance of catalyzer is unstable also very large on the impact of desorption temperature.
Summary of the invention
The object of the invention is will provide a kind of novel Mg-Li-Al-Ti hydrogen storage material and preparation method thereof, the method in-situ preparation catalyst A l
3ti, efficient catalytic MgH
2hydrogen storage material carries out can the preparation method of inverse put hydrogen.Consisting of of the hydrogen storage material invented: MgH
2, Li
3alH
6, Al/AlCl
3and Ti/TiF
3.This material can inhale under relatively mild condition put hydrogen (250 DEG C, 3Mpa inhales hydrogen; 0.1Mpa puts hydrogen), reversible hydrogen storage capacity reaches 3.5wt%.
For achieving the above object, the present invention adopts following technical scheme:
A kind of novel Mg-Li-Al-Ti hydrogen storage material, its composition general formula is: mMgH
2+ Li
3alH
6+ x% Al/AlCl
3+ y% Ti/TiF
3, 2 < m < 5,5 < x < 20,5 < y < 15 and 10 < x+y < 20;
A preparation method for novel Mg-Li-Al-Ti hydrogen storage material, comprises the steps:
(1) by LiH and LiAlH
4put into ball grinder by the mol ratio of 1 ~ 3:1, under the protection of rare gas element, carry out mechanically mixing, Ball-milling Time is 5 ~ 10 hours, and rotating speed is 150 ~ 300rpm, and ratio of grinding media to material is 200:1, obtained Li
3alH
6;
(2) by MgH
2with Li
3alH
6be (2 ~ 5) with mol ratio: the ratio of 1 puts into ball grinder, then by x% Al/AlCl
3+ y% Ti/TiF
3the mixture of (5 < x < 20,5 < y < 15) puts into ball grinder; ratio of grinding media to material is 100 ~ 300:1; ball milling 1 ~ 6 h under the protection of rare gas element, rotating speed is 50 ~ 300 rpm.
The novel Mg-Li-Al-Ti hydrogen storage material of the one that the present invention adopts ball milled to prepare, not only maintains MgH
2high capacity hydrogen storage performance, and generated in-situ catalyzer obviously can improve MgH
2the dynamic performance of hydrogen storage material, significantly reduces its reversible hydrogen uptake condition simultaneously.Material of the present invention is for efficient, the safety in transportation and storage, particularly MgH of hydrogen
2hydrogen storage material has great importance in pragmatize application.
Accompanying drawing explanation
Fig. 1,2,3 is mMgH
2+ Li
3alH
6+ x%Al/AlCl
3+ y%Ti/TiF
3the temperature programming Hydrogen desorption isotherms (laboratory apparatus: the TG-DSC synchronous solving of French Setaram instrument company) of material;
Fig. 4 is the XRD curve (laboratory apparatus: X ' the Pert MPD PRO diffractometer that Dutch PANalytical company produces, Co palladium) after ball milling;
Fig. 5 is mMgH
2+ Li
3alH
6+ x%Al/AlCl
3+ y%Ti/TiF
3, mMgH
2+ Li
3alH
6the dynamic performance curve (laboratory apparatus: the PCTpro instrument of French Setaram instrument company carries out) of system.
Embodiment
embodiment 1:
A preparation method for novel Mg-Li-Al-Ti hydrogen storage material, comprises the steps:
Step 1, gets 0.8855g LiH and 2.1149gLiAlH
4, put into the ball grinder being placed with 24 steel balls, utilize mechanical attrition method to mix, under inert gas conditions, rotating speed is 270rpm, and Ball-milling Time is 8h.Take out in glove box after ball milling terminates, obtain Li
3alH
6;
Step 2, by each composition sampling in table 1, put into the ball grinder that 24 steel balls are housed respectively, utilize mechanical attrition method Homogeneous phase mixing, under inert gas conditions, rotating speed is 270rpm, Ball-milling Time 2h, obtains sample a(66.2wt.% MgH
2-33.8wt.% Li
3alH
6), b(58.8 wt.% MgH
2-27.2 wt.% Li
3alH
6-8 wt.% AlCl
3-6 wt.% Ti) and c(53 wt.% MgH
2-27 wt.% Li
3alH
6-14 wt.% AlCl
3-6 wt.% Ti).
The composition of table 1 three kinds of samples
Product test: a, b, c tri-kinds of samples are carried out temperature programmed control dehydrogenation experiment respectively, and temperature rise rate is 10 DEG C/min, and carrier gas is Ar.(see figure 1) can be found out, non-doped with Al Cl from Hydrogen desorption isotherms
3with the sample a of Ti, its initial desorption temperature is 175 DEG C, and when being heated to 400 DEG C, total amount of dehydrogenation is 5.5wt.%; As interpolation AlCl
3after Ti, the initial desorption temperature of system is reduced to 100 DEG C (see sample b and c).And for system total amount of dehydrogenation when 400 DEG C, Ti amount is constant, it is along with AlCl
3when amount is increased to 14wt.% from 8wt.%, its total amount of dehydrogenation first reduces to 5.2wt.%, is then increased to 6.5wt.%.
embodiment 2
By the composition of sample c, when other conditions are constant, (h), the compound system of preparation three kinds of different Ball-milling Times, investigates Ball-milling Time to the impact of this system H2-producing capacity for 1 h, 4 h and 5 only to change Ball-milling Time.
As can be seen from the Hydrogen desorption isotherms of Fig. 2, the initial desorption temperature of ball milling 1 h and 5 h is at about 100 DEG C, and when Ball-milling Time is 4 h, its initial desorption temperature is reduced to about 58 DEG C, reduces nearly 40 DEG C than the initial desorption temperature of the compound system of 1 h and 5 h; And total amount of dehydrogenation (being heated to 400 DEG C) during ball milling 4 h is maximum, can reach 7.2wt.%.This result shows, the long or too short amount of dehydrogenation that all can make of Ball-milling Time reduces.
embodiment 3
By the composition of sample c, Ball-milling Time is 4 h, when other conditions are constant, only change ratio of grinding media to material in ball milling condition [100:1(sample I), 200:1(sample II), 250:1(sample III)], investigate ratio of grinding media to material to the impact of this system H2-producing capacity.
As can be seen from the Hydrogen desorption isotherms of Fig. 3, the increase of ratio of grinding media to material for initial desorption temperature impact little (the initial desorption temperature of sample I, II, III is all at about 58 DEG C), but has impact for total amount of dehydrogenation of 400 DEG C.As seen from the figure, when ratio of grinding media to material is 100:1, total amount of dehydrogenation is 5.2wt.%; When increasing ratio of grinding media to material to 200:1, total amount of dehydrogenation is increased to 7.2wt.%; When continuing to increase ratio of grinding media to material to 250:1, total amount of dehydrogenation slightly reduces (being only 6.3wt.%), but still total amount of dehydrogenation when being 100:1 higher than ratio of grinding media to material.This is because the increase of ball material, the energy of ball milling system can be improved, be conducive to material and fully mix, but energy is too high, and to make in tank local temperature increase too fast, causes Li
3alH
6decomposed (due to Li
3alH
6unstable to heat).
embodiment 4
In order to study the H_2-producing mechanism of this system, choosing sample II and carrying out before ball milling and XRD composition analysis (see figure 4) after ball milling.
In JADE6.0 software, analysis is carried out to XRD diffractogram known, after ball milling, occurred cenotype Al and Al
3the peak of Ti.This is attributed to part Li in mechanical milling process
3alH
6with AlCl
3generate Al, according to document (Ares Fernandez J R, Aguey-Zinsou F, Elsaesser M, et a. Int J Hydrogen Energy, 2007,32 (8): 1033) report that Al has good heat conduction function, can infer, the increase of Al amount can improve the thermal conduction of this compound system, and then improves its dehydrogenation.In addition, ball milling Ti, AlCl
3with Li
3alH
6al can be generated
3ti(is shown in Fig. 4), according to document (Hendrik W. Brinks, Martin Sulic, Craig M. Jensen, and Bj rn C. Hauback.
j. Phys. Chem. B 2006, 110,2740-2745) known, in certain embodiments, Al
3ti can serve as core center and weaken Mg-H key, thus promotes dehydrogenation, reduces desorption temperature.And in hydrogen abstraction reaction, Al
3ti can catalysis H
2division and the restructuring of H, simultaneously for nucleation and diffusion provide condition.
embodiment 5
By the same method, control ratio of grinding media to material 200:1 and Ball-milling Time 4 h, obtained sample N(66.2wt.%MgH
2-33.8wt.%Li
3alH
6) and sample n:(53 wt.%MgH
2-27 wt.%Li
3alH
6-14wt.%AlCl
3-6wt.%Ti), investigate AlCl
3with Ti to MgH
2-Li
3alH
6system inhales the impact of hydrogen desorption kinetics performance.
1. and 2. in Fig. 5 is the dehydrogenation kinetic curve of sample N and sample n, and its experiment condition is 250 DEG C, 0.1MPa.Result of study shows, AlCl
3the dehydrogenation dynamic performance of this system significantly can be improved with Ti.Can find out from figure, non-doped with Al Cl
3with the sample of Ti in 8000s first time amount of dehydrogenation be 5.2wt.%; And the sample after doping can reach 5.3 wt.% in about 500s first time amount of dehydrogenation, shorten 7500s than the complete dehydrogenation time of non-doped samples, and amount of dehydrogenation is increased to 5.6wt.% in 3000s.2nd dehydrogenation, non-doped with Al Cl
3obviously extend with the dehydrogenation time of the sample of Ti, and amount of dehydrogenation is reduced to 2.7 wt.% (as shown in Fig. 5 2.); But the amount of dehydrogenation of the 3rd time remains unchanged substantially; And doped with Al Cl
3after Ti, the dehydrogenation time of system slightly increases, but still can be able to complete in 1000s (as shown in Fig. 5 1.); Although its 2nd amount of dehydrogenation decreased than first time, be only about 3.5 wt%, the amount of dehydrogenation after 5 circulations still can reach 3.3wt.% (as shown in Fig. 5 2.), and this shows doped with Al Cl
3mgH can be made with after Ti
2-Li
3alH
6the dehydrogenation dynamic performance of system is stablized.
Meanwhile, 250 DEG C, under 3MPa condition, to sample N and sample n carry out inhaling hydrogen dynamic experiment (see in Fig. 5 3. and 4.).From in Fig. 5 3., it is 10000s that the first time of non-doped samples inhales the hydrogen time completely, and total hydrogen－sucking amount is only 3wt.%; And add 14 wt.%AlCl
3with (i.e. sample n) after 6wt.%Ti, sample n can reach 3.1wt.% at the 1st hydrogen－sucking amount of 500s, and when the suction hydrogen time is 1000 s, hydrogen－sucking amount is increased to 3.5wt.%, and suction hydrogen reaches balance.Inhale hydrogen 2nd time, the hydrogen－sucking amount of non-doped samples is reduced to 2.8 wt.%, substantially remains unchanged for the 3rd time; And doped with Al Cl
3with the 2nd hydrogen－sucking amount of sample after Ti at about 3.3 wt%, hydrogen-absorption speed be obviously better than unadulterated sample (see in Fig. 5 3.).After 4 circulations, the hydrogen－sucking amount of sample n still can reach 3.2wt.%(as 4. shown in Fig. 5).Visible, AlCl
3obviously MgH can be improved with Ti
2-Li
3alH
6the suction hydrogen dynamic performance of system.
The foregoing is only preferred embodiment of the present invention, be not used for limiting practical range of the present invention, so the equivalent change of all feature raw materials according to scope of the present invention, characterization step and improvement, all should be included within claim of the present invention.
Claims (2)
1. a novel Mg-Li-Al-Ti hydrogen storage material, is characterized in that: its composition general formula is: mMgH
2+ Li
3alH
6+ x% Al/AlCl
3+ y%Ti/TiF
3; Wherein 5 < x < 20,5 < y < 15,2 < m < 5.
2. a preparation method for novel Mg-Li-Al-Ti hydrogen storage material, is characterized in that: comprise the steps:
(1) by LiH and LiAlH
4put into ball grinder by the mol ratio of 1 ~ 3:1, under the protection of rare gas element, carry out mechanically mixing, Ball-milling Time is 5 ~ 10 hours, and rotating speed is 150 ~ 300rpm, and ratio of grinding media to material is 200:1, obtained Li
3alH
6;
(2) by MgH
2with Li
3alH
6be (2 ~ 5) with mol ratio: the ratio of 1 puts into ball grinder, then by x% Al/AlCl
3+ y% Ti/TiF
3the mixture of (5 < x < 20,5 < y < 15) puts into ball grinder; ratio of grinding media to material is 100 ~ 300:1; ball milling 1 ~ 6 h under the protection of rare gas element; rotating speed is 50 ~ 300 rpm, obtained Mg-Li-Al-Ti hydrogen storage material.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105565266A (en) * | 2015-12-15 | 2016-05-11 | 湖北航天化学技术研究所 | Endothermic hydrogen-loaded fuel for hypersonic aircraft |
| CN106477521A (en) * | 2016-09-30 | 2017-03-08 | 桂林电子科技大学 | One kind is based on LiBH4Hydrogen storage material and preparation method thereof |
-
2015
- 2015-03-13 CN CN201510109564.3A patent/CN104709873A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105565266A (en) * | 2015-12-15 | 2016-05-11 | 湖北航天化学技术研究所 | Endothermic hydrogen-loaded fuel for hypersonic aircraft |
| CN105565266B (en) * | 2015-12-15 | 2018-01-30 | 湖北航天化学技术研究所 | A kind of hypersonic aircraft carries hydrogen fuel with heat absorbing type |
| CN106477521A (en) * | 2016-09-30 | 2017-03-08 | 桂林电子科技大学 | One kind is based on LiBH4Hydrogen storage material and preparation method thereof |
| CN106477521B (en) * | 2016-09-30 | 2019-01-18 | 桂林电子科技大学 | One kind being based on LiBH4Hydrogen storage material and preparation method thereof |
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