CN104357723A - Magnesium-based composite material having low-temperature dehydrogenation activity and preparation method of magnesium-based composite material - Google Patents

Magnesium-based composite material having low-temperature dehydrogenation activity and preparation method of magnesium-based composite material Download PDF

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CN104357723A
CN104357723A CN201410677464.6A CN201410677464A CN104357723A CN 104357723 A CN104357723 A CN 104357723A CN 201410677464 A CN201410677464 A CN 201410677464A CN 104357723 A CN104357723 A CN 104357723A
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composite material
temperature
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magnesium
mgh
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CN104357723B (en
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张耀
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Southeast University
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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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Hydrogen, Water And Hydrids (AREA)

Abstract

The invention provides a magnesium-based composite material having low-temperature dehydrogenation activity. The composite material is a Pd-doped xMgH2-TiH2 compound, wherein x is 1-8 and the mole fraction of the Pd dopant is 0.1-1%. The invention also provides a preparation method of the magnesium-based composite material having low-temperature dehydrogenation activity. The preparation method of the composite material is simple and low in cost; by adding Pd, the pathway for dehydrogenation reaction of the system is improved, the composite material has the advantages of suitable thermal stability high capacity and high dehydrogenation activity and has the characteristics of hydrogen release operating temperature suitable for an FC work, high hydrogen release rate and the like.

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 a kind of can the magnesium base composite material of low-temperature dehydrogenation, also relating to this can the preparation method of magnesium base composite material of low-temperature dehydrogenation.
Background technology
On the earth, fossil energy is day by day exhausted, and ecotope is continuous worsening, finds the common recognition that reproducible clean energy has become the universe.And hydrogen is as the energy carrier of high effect cleaning, it is one of energy substitution scheme having potential quality.
The producing of hydrogen, to store and application in fuel cell constitutes three important steps of Hydrogen Energy recycle.And be faced with problems (dynamic performance, thermostability, suction put reversible hydrogen, capacity and cyclical stability, economy, security etc.) at present as the storage of the hydrogen of middle-chain, become one of Main Bottleneck of restriction hydrogen cell automobile and the application of other aspects.Given this, each developed country is all continuing to be absorbed in the novel material relevant to storage hydrogen, the research and development of new technology.
MgH 2because hydrogen storage capability is high, the earth resources of Mg is abundant and paid close attention to widely.But MgH 2and the higher (MgH of the thermostability of compound system 2under vacuum condition, just start dehydrogenation close to 400 DEG C), inhale hydrogen desorption kinetics poor-performing, hinder the practical application of this system.For many years, people are devoted to reduce MgH always 2and the thermostability of compound system, improve its dehydrogenation dynamic performance.Wherein, the dynamic performance of Mg-Ti-H composite hydrogen storage material system is comparatively remarkable, and desorption temperature is also decreased significantly, can dehydrogenation at 150-200 DEG C, and can under the temperature condition of room temperature to 100 DEG C reversible suction hydrogen.This performance of Mg-Ti-H system shows inhales hydrogen desorption kinetics characteristic preferably, can use, cause the extensive concern of people as the efficient hydrogen storage material of one.However, the thermodynamic stability of Mg-Ti-H material is still higher, hydrogen discharging temperature is still higher than the working temperature (~ 80 DEG C) of fuel cell (FC), and dynamic performance still also has very large room for promotion, also distant apart from its practical application.
Research in the past shows, MgH 2be the hydrogen storage material of a kind of heavy body (7.6wt.%), but there is high thermal stability (72kJ/mol H 2), the feature such as high desorption temperature temperature (~ 400 DEG C), slower dehydrogenation dynamic performance.For this reason, on its basis, usually by adding Nb 2o 5, TiH 2deng additive, the dynamic performance of its dehydrogenation is significantly improved, and desorption temperature also have decreased near 200 DEG C.But these additives are just to MgH 2apparent activation energy weaken, but to the thermodynamic property of material intrinsic but without any change.Because the response path of material is without any change, so the enthalpy change of dehydrogenation just any change does not occur yet, thermostability does not also substantially reduce.
Summary of the invention
Goal of the invention: in order to overcome above-mentioned the deficiencies in the prior art, the object of the present invention is to provide the MgH of a kind of heavy body, suitable thermostability, high dehydrogenation activity 2-TiH 2-Pd composite hydrogen storage material and preparation method thereof.
Technical scheme: provided by the invention a kind of can the magnesium base composite material of low-temperature dehydrogenation, this matrix material is the xMgH of Pd doping 2-TiH 2mixture; Wherein, x is 1 ~ 8, and the molar fraction of hotchpotch 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 characterized in that: comprise the following steps: under protection of inert gas, by MgH 2, TiH 2mix with Pd, ball milling, to obtain final product.
Preferred 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: provided by the invention can the magnesium base composite material preparation method of low-temperature dehydrogenation simple, cost is lower, by adding Pd, the dehydrogenation reaction approach of improved system, thermostability be applicable to, capacity is high, dehydrogenation activity is high, this material have be suitable for FC work put the characteristics such as hydrogen working temperature, high hydrogen discharging rate.
The present invention passes through at MgH 2-TiH 2pd is introduced, with TiH in the middle of compound system 2improve the dynamic performance of matrix material together, make the path changing reacted simultaneously, moderately reduce the thermodynamic stability of material system, serve the effect killed two birds with one stone.This is Important Thought of the present invention, and the material system dehydrogenation starting temperature obtained based on this thought has dropped to 150 DEG C of effects, compares MgH 2-TiH 2low 50 DEG C, the low-temperature dehydrogenation performance of this material has had and has significantly improved.
Accompanying drawing explanation
Fig. 1 is MgH 2-TiH 2the X-ray diffraction spectrogram of-Pd material mix grinding after 5 hours;
Fig. 2 is MgH 2-TiH 2the test sample of-Pd mix grinding after 5 hours with warm Hydrogen desorption isotherms;
Fig. 3 is MgH 2-TiH 2x-ray diffraction spectrogram after-Pd material mix grinding;
Fig. 4 is MgH 2-TiH 2the X-ray diffraction spectrogram of-Pd material mix grinding after 10 hours;
Fig. 5 is MgH 2-TiH 2the test sample of-Pd mix grinding after 10 hours with warm Hydrogen desorption isotherms.
Embodiment
Below in conjunction with accompanying drawing the present invention 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, reactive system and the sample pool of equipment are all evacuated, and put hydrogen process service routine temperature controlling instruments and control heat-up rate, sample temperature rises to design temperature by room temperature.The hydrogen pressure (can be converted into dehydrogenation capacity) of real-time automatic recording sample pool, program temperature and thermopair observed temperature in experimentation, provide the change curve of itself and temperature.
Before hydrogen test inhaled by sample, reactive system and the sample pool of equipment are first evacuated, and are then filled with the high-purity hydrogen (99.9999%) of certain pressure, and service routine temperature controlling instruments controls heat-up rate, and sample temperature rises to design temperature by room temperature.The hydrogen pressure (can be converted into hydrogen absorption capacity) of real-time automatic recording sample pool, program temperature and thermopair observed temperature in experimentation, provide the change curve of itself and temperature.
Embodiment 1
In the glove box being full of argon gas, by the MgH of mol ratio 2:1 2-TiH 2mixing, then the Pd adding molar fraction 0.5% fully mixes, and loads in the ball grinder with opening-closing valve, 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, MgH 2purity is 95%, grain size is 300 orders; TiH 2purity is 99.5%, and grain size is 200 orders; Pd powder purity is 99.9%, and grain size is 300 orders.
Fig. 1 is MgH 2-TiH 2the X-ray diffraction curve of-Pd sample, shows MgH 2and TiH 2for mechanically mixing, both and reactionless generation during ball milling, Pd has a small amount of hydrogenation to generate PdH in mechanical milling process 2.
The hydrogen storage property of test sample: in the glove box being full of argon gas, after the sample prepared by ball milling takes out and weighs, loads in the specific sample pond of Sievert type gas-solid reaction test equipment, is sealed.Take out sample pool and be tightly connected with testing apparatus.First sample pool is evacuated to vacuum, then tests the intensification Hydrogen desorption isotherms (as shown in Figure 2) of sample.As seen from Figure 2, MgH 2-TiH 2-Pd sample gets final product dehydrogenation 150 DEG C time, and its initial desorption temperature is well below pure MgH 2the starting temperature (~ 300 DEG C) of phase.The termination temperature of dehydrogenation at about 300 DEG C, not only well below pure MgH 2the termination temperature of phase, but also lower than MgH 2-TiH 2termination temperature.Because sample is easy and oxygen G&W reacts, all sample operation are all carried out in the glove box being filled with high-purity argon gas, and the oxygen of glove box and water-content are all lower than 1ppm concentration.
Fig. 3 is the X-ray diffraction curve of dehydrogenation sample, shows MgH in certain embodiments 2and TiH 2both and reactionless generation.And Pd and MgH 2interact, have Mg-Pd mesophase spherule to generate.
Embodiment 2
In the glove box being full of argon gas, by the MgH of mol ratio 2:1 2-TiH 2mixing, then the Pd adding molar fraction 3% fully mixes, and loads in the ball grinder with opening-closing valve, 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 the X-ray diffraction curve of sample, shows MgH 2and TiH 2for mechanically mixing, both and reactionless generation during ball milling, Pd has a small amount of hydrogenation to generate PdH in mechanical milling process 2.
The hydrogen storage property of test sample: in the glove box being full of argon gas, after the sample prepared by ball milling takes out and weighs, loads in the specific sample pond of Sievert type gas-solid reaction test equipment, is sealed.Take out sample pool and be tightly connected with testing apparatus.First sample pool is evacuated to vacuum, then test sample with warm Hydrogen desorption isotherms (as shown in Figure 5).As seen from Figure 5, MgH 2-TiH 2-Pd sample gets final product dehydrogenation 150 DEG C time, and its initial desorption temperature is well below pure MgH 2the starting temperature (~ 300 DEG C) of phase.The termination temperature of dehydrogenation at about 300 DEG C, not only well below pure MgH 2the termination temperature of phase, but also lower than MgH 2-TiH 2termination temperature.
Embodiment 3
In the glove box being full of argon gas, by the MgH of mol ratio 2:1 2-TiH 2mixing, then the Pd adding mol ratio 3% fully mixes, and loads in the ball grinder with opening-closing valve, 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 being full of argon gas, by the MgH of mol ratio 2:1 2-TiH 2mixing, then the Pd adding molar fraction 3% fully mixes, and loads in the ball grinder with opening-closing valve, 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 (3)

1. can the magnesium base composite material of low-temperature dehydrogenation, it is characterized in that: this matrix material is the xMgH of Pd doping 2-TiH 2mixture; Wherein, x is 1 ~ 8, and the molar fraction of hotchpotch Pd is 0.1 ~ 1%.
2. can the preparation method of magnesium base composite material of low-temperature dehydrogenation, it is characterized in that: comprise the following steps: under protection of inert gas, by MgH 2, TiH 2mix with Pd, ball milling, to obtain final product.
3. according to claim 2 a kind of can the preparation method of magnesium base composite material of low-temperature dehydrogenation, it is characterized in that: Ball-milling Time is 1-20h, ratio of grinding media to material is (80-100): 1, and ball mill revolution speed is 300-500rpm.
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Citations (3)

* 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
US20060194695A1 (en) * 2004-08-27 2006-08-31 Westinghouse Savannah River Co., Llc Destabilized and catalyzed borohydrided for reversible hydrogen storage
CN103526141A (en) * 2013-09-05 2014-01-22 华南理工大学 Magnesium-based hydrogen storage material and preparation method thereof

Patent Citations (3)

* 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
US20060194695A1 (en) * 2004-08-27 2006-08-31 Westinghouse Savannah River Co., Llc Destabilized and catalyzed borohydrided for reversible hydrogen storage
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
STEEVE ROUSSELOT,ET AL.: "synthesis of fcc Mg-Ti-H alloy by high energy ball milling:Structure and electrochemical hydrogen storage properties", 《JOURNAL OF POWER SOURCES》 *

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