CN104357723B - A kind of can the magnesium base composite material and preparation method thereof of low-temperature dehydrogenation - Google Patents

A kind of can the magnesium base composite material and preparation method thereof of low-temperature dehydrogenation Download PDF

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CN104357723B
CN104357723B CN201410677464.6A CN201410677464A CN104357723B CN 104357723 B CN104357723 B CN 104357723B CN 201410677464 A CN201410677464 A CN 201410677464A CN 104357723 B CN104357723 B CN 104357723B
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dehydrogenation
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CN104357723A (en
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张耀
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Southeast University
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C23/00—Alloys based on magnesium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
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  • Hydrogen, Water And Hydrids (AREA)
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Abstract

The present invention provide a kind of can the magnesium base composite material of low-temperature dehydrogenation, this composite is the xMgH of Pd doping2‑TiH2Complex；Wherein, x is 1～8, and the molar fraction of alloy Pd is 0.1～1%.Additionally provide above-mentioned can the preparation method of magnesium base composite material of low-temperature dehydrogenation.This composite material and preparation method thereof is simple, cost is relatively low, by adding Pd, the dehydrogenation reaction approach of improved system, heat stability is suitable for, capacity is high, dehydrogenation activity is high, this material have be suitable to FC work put the characteristics such as hydrogen operating temperature, high hydrogen discharging rate.

Description

A kind of can the magnesium base composite material and preparation method thereof of low-temperature dehydrogenation
Technical field
The invention belongs to battery material field, particularly to a kind of can the magnesium base composite material of low-temperature dehydrogenation, further relating to this can the preparation method of magnesium base composite material of low-temperature dehydrogenation.
Background technology
On the earth, fossil energy is the most exhausted, and ecological environment is continuous worsening, and finding reproducible clean energy resource has become the common recognition of the whole mankind.And hydrogen is as the energy carrier of high effect cleaning, it it is one of the energy substitution scheme of great potential quality.
The producing of hydrogen, store and application in terms of fuel cell constitutes three important steps that Hydrogen Energy recycles.And the storage as the hydrogen of intermediate link is faced with problems (hydrogen reversibility, capacity and cyclical stability, economy, safety etc. are put in dynamic performance, heat stability, suction) at present, become one of Main Bottleneck of restriction hydrogen cell automobile and the application of other aspects.In consideration of it, each developed country is all persistently being absorbed in the new material relevant to hydrogen storage, the research and development of new technique.
MgH2Because hydrogen storage capability is high, the earth resource of Mg is abundant and is paid close attention to widely.But MgH2And the higher (MgH of heat stability of compound system2Under vacuum condition, just start dehydrogenation close to 400 DEG C), inhale hydrogen desorption kinetics poor-performing, hinder the actual application of this system.For many years, people are devoted to reduce MgH always2And the heat stability of compound system, improve its dehydrogenation dynamic performance.Wherein, the dynamic performance of Mg-Ti-H composite hydrogen storage material system is more notable, and desorption temperature is also decreased significantly, can dehydrogenation at 150-200 DEG C, it is possible to reversible suction hydrogen under the temperature conditions of room temperature to 100 DEG C.This performance of Mg-Ti-H system shows preferably inhales hydrogen desorption kinetics characteristic, can use as the efficient hydrogen storage material of one, cause the extensive concern of people.However, the thermodynamic stability of Mg-Ti-H material is the highest, hydrogen discharging temperature is still above the operating temperature (～80 DEG C) of fuel cell (FC), and dynamic performance still also has the biggest room for promotion, the most distant apart from its actual application.
Conventional research shows, MgH2It is the hydrogen storage material of a kind of high power capacity (7.6wt.%), but there is high thermal stability (72kJ/mol H2), high desorption temperature temperature (～400 DEG C), the feature such as slower dehydrogenation dynamic performance.To this end, on its basis, generally by adding Nb2O5, TiH2Deng additive so that the dynamic performance of its dehydrogenation is significantly improved, desorption temperature also have decreased near 200 DEG C.But these additives are to MgH2Apparent activation energy weakened, but the macroscopic property of material intrinsic is not but had any change.Because the response path of material does not has any change, so the enthalpy change of dehydrogenation does not the most occur any change, heat stability the most substantially reduces.
Summary of the invention
Goal of the invention: in order to overcome above-mentioned the deficiencies in the prior art, it is an object of the invention to provide a kind of high power capacity, suitable heat stability, the MgH of high dehydrogenation activity2-TiH2-Pd composite hydrogen storage material and preparation method thereof.
Technical scheme: the present invention provide a kind of can the magnesium base composite material of low-temperature dehydrogenation, this composite is the xMgH of Pd doping2-TiH2Complex；Wherein, x is 1～8, and the molar fraction of alloy Pd is 0.1～1%.
Present invention also offers above-mentioned can the preparation method of magnesium base composite material of low-temperature dehydrogenation, it is characterised in that: comprise the following steps: under inert gas shielding, by MgH2、TiH2With Pd mixing, ball milling, to obtain final product.
Preferably Ball-milling Time is 1-20h, and ratio of grinding media to material is (80-100): 1, and ball mill revolution speed is 300-500rpm.
Beneficial effect: what the present invention provided can the magnesium base composite material preparation method of low-temperature dehydrogenation be simple, cost is relatively low, by adding Pd, the dehydrogenation reaction approach of improved system, heat stability is suitable for, capacity is high, dehydrogenation activity is high, this material have be suitable to FC work put the characteristics such as hydrogen operating temperature, high hydrogen discharging rate.
The present invention is by MgH2-TiH2Pd is introduced, with TiH in the middle of compound system2Improve the dynamic performance of composite together, make the path changing of reaction simultaneously, moderately reduce the thermodynamic stability of material system, serve the effect killed two birds with one stone.This is the Important Thought of the present invention, and the material system dehydrogenation initial temperature obtained based on this thought falls below 150 DEG C of effects, compares MgH2-TiH2Low 50 DEG C, the low-temperature dehydrogenation performance of this material has had and has been greatly improved.
Accompanying drawing explanation
Fig. 1 is MgH2-TiH2-Pd material mix grinding X-ray diffraction spectrogram after 5 hours；
Fig. 2 is MgH2-TiH2-Pd mix grinding test sample after 5 hours with temperature Hydrogen desorption isotherms；
Fig. 3 is MgH2-TiH2X-ray diffraction spectrogram after-Pd material mix grinding；
Fig. 4 is MgH2-TiH2-Pd material mix grinding X-ray diffraction spectrogram after 10 hours；
Fig. 5 is MgH2-TiH2-Pd mix grinding test sample after 10 hours with temperature Hydrogen desorption isotherms.
Detailed description of the invention
Below in conjunction with the accompanying drawings the present invention is made and further illustrating.
The hydrogen storage property test of inventive samples is carried out in Sievert type gas-solid reaction test equipment.Before putting hydrogen test, response system and the sample cell of equipment are all evacuated, and put hydrogen process and use temperature programmed control equipment to control programming rate, and sample temperature is risen to design temperature by room temperature.In experimentation, hydrogen pressure (can be converted into dehydrogenation capacity), program temperature and the thermocouple observed temperature of real-time automatic recording sample cell, provide the change curve of itself and temperature.
Before hydrogen test inhaled by sample, response system and the sample cell of equipment are first evacuated, and are then charged with the high-purity hydrogen (99.9999%) of certain pressure, use temperature programmed control equipment to control programming rate, and sample temperature is risen to design temperature by room temperature.In experimentation, hydrogen pressure (can be converted into hydrogen absorption capacity), program temperature and the thermocouple observed temperature of real-time automatic recording sample cell, provide the change curve of itself and temperature.
Embodiment 1
In the glove box of full argon, by the MgH of mol ratio 2:12-TiH2Mixing, the Pd adding molar fraction 0.5% is sufficiently mixed, and loads in the ball grinder with controlled valve, and after ball grinder forvacuum, ball milling mixing on planet gear type ball mill, ratio of grinding media to material is 90:1, and rotating speed is 400rpm, and Ball-milling Time is 5 hours.
Wherein, MgH2Purity is 95%, grain size is 300 mesh；TiH2Purity is 99.5%, and grain size is 200 mesh；Pd powder purity is 99.9%, and grain size is 300 mesh.
Fig. 1 is MgH2-TiH2-Pd material mix grinding X-ray diffraction spectrogram after 5 hours, shows MgH2And TiH2For both and reactionless generation during mechanical mixture, ball milling, Pd has a small amount of hydrogenation to generate PdH in mechanical milling process2。
The hydrogen storage property of test sample: in the glove box of full argon, the sample prepared by ball milling takes out after weighing, loads in the specific sample pond of Sievert type gas-solid reaction test equipment, sealed.Take out sample cell and be tightly connected with test equipment.Sample cell is first evacuated to vacuum, and the intensification Hydrogen desorption isotherms of re-test sample is (as in figure 2 it is shown, Fig. 2 is MgH2-TiH2-Pd mix grinding test sample after 5 hours with temperature Hydrogen desorption isotherms；).From Figure 2 it can be seen that MgH2-TiH2-Pd sample gets final product dehydrogenation when 150 DEG C, and its initial desorption temperature is well below pure MgH2The initial temperature (～300 DEG C) of phase.The termination temperature of dehydrogenation is at about 300 DEG C, not only well below pure MgH2The termination temperature of phase, but also less than MgH2-TiH2Termination temperature.Owing to sample easily reacts with oxygen and water, all of sample operation is all carried out in the glove box be filled with high-purity argon gas, and the oxygen of glove box and water content are below 1ppm concentration.
Fig. 3 is MgH2-TiH2X-ray diffraction spectrogram after-Pd material mix grinding, shows MgH in certain embodiments2And TiH2Both and reactionless generation.And Pd and MgH2Interact, have Mg-Pd mesophase to generate.
Embodiment 2
In the glove box of full argon, by the MgH of mol ratio 2:12-TiH2Mixing, the Pd adding molar fraction 3% is sufficiently mixed, and loads in the ball grinder with controlled valve, and after ball grinder forvacuum, ball milling mixing on planet gear type ball mill, ratio of grinding media to material is 90:1, and rotating speed is 400rpm, and Ball-milling Time is 10 hours.
Fig. 4 is MgH2-TiH2-Pd material mix grinding X-ray diffraction spectrogram after 10 hours, shows MgH2And TiH2For both and reactionless generation during mechanical mixture, ball milling, Pd has a small amount of hydrogenation to generate PdH in mechanical milling process2.The hydrogen storage property of test sample: in the glove box of full argon, the sample prepared by ball milling takes out after weighing, loads in the specific sample pond of Sievert type gas-solid reaction test equipment, sealed.Take out sample cell and be tightly connected with test equipment.First sample cell is evacuated to vacuum, re-test sample with temperature Hydrogen desorption isotherms (as it is shown in figure 5, Fig. 5 is MgH2-TiH2-Pd mix grinding test sample after 10 hours with temperature Hydrogen desorption isotherms).As seen from Figure 5, MgH2-TiH2-Pd sample gets final product dehydrogenation when 150 DEG C, and its initial desorption temperature is well below pure MgH2The initial temperature (～300 DEG C) of phase.The termination temperature of dehydrogenation is at about 300 DEG C, not only well below pure MgH2The termination temperature of phase, but also less than MgH2-TiH2Termination temperature.
Embodiment 3
In the glove box of full argon, by the MgH of mol ratio 2:12-TiH2Mixing, the Pd adding mol ratio 3% is sufficiently mixed, and loads in the ball grinder with controlled valve, and after ball grinder forvacuum, ball milling mixing on planet gear type ball mill, ratio of grinding media to material is 80:1, and rotating speed is 300rpm, and Ball-milling Time is 15 hours.
Embodiment 4
In the glove box of full argon, by the MgH of mol ratio 2:12-TiH2Mixing, the Pd adding molar fraction 3% is sufficiently mixed, and loads in the ball grinder with controlled valve, and after ball grinder forvacuum, ball milling mixing on planet gear type ball mill, ratio of grinding media to material is 100:1, and rotating speed is 500rpm, and Ball-milling Time is 20 hours.

Claims (2)

1. one kind can the magnesium base composite material of low-temperature dehydrogenation, it is characterised in that: this composite is Pd doping xMgH2-TiH2Complex；Wherein, x is 1～8, and the molar fraction of alloy Pd is 0.1～1%.
2. according to claim 1 can the preparation method of magnesium base composite material of low-temperature dehydrogenation, it is special Levy and be: comprise the following steps: under inert gas shielding, by MgH2、TiH2With Pd mixing, ball milling, Obtain；Ball-milling Time is 1-20h, and ratio of grinding media to material is (80-100): 1, and ball mill revolution speed is 300-500rpm.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1351184A (en) * 2000-10-26 2002-05-29 中国科学院金属研究所 Process for preparing hydrogen-bearing Mg-base composition
CN103526141A (en) * 2013-09-05 2014-01-22 华南理工大学 Magnesium-based hydrogen storage material and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060194695A1 (en) * 2004-08-27 2006-08-31 Westinghouse Savannah River Co., Llc Destabilized and catalyzed borohydrided for reversible hydrogen storage

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1351184A (en) * 2000-10-26 2002-05-29 中国科学院金属研究所 Process for preparing hydrogen-bearing Mg-base composition
CN103526141A (en) * 2013-09-05 2014-01-22 华南理工大学 Magnesium-based hydrogen storage material and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
synthesis of fcc Mg-Ti-H alloy by high energy ball milling:Structure and electrochemical hydrogen storage properties;Steeve Rousselot,et al.;《Journal of Power Sources》;20100121;第195卷;4370-4374 *

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