CN102225748B - Synthesis method for novel M-N-H hydrogen storage material - Google Patents
Synthesis method for novel M-N-H hydrogen storage material Download PDFInfo
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- CN102225748B CN102225748B CN 201110089159 CN201110089159A CN102225748B CN 102225748 B CN102225748 B CN 102225748B CN 201110089159 CN201110089159 CN 201110089159 CN 201110089159 A CN201110089159 A CN 201110089159A CN 102225748 B CN102225748 B CN 102225748B
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Abstract
The invention relates to a synthesis method for a novel M-N-H (Mg(NH2)2-LiH) hydrogen storage material, which mainly comprises three steps of: 1. carrying out high-energy ball milling on a metal hydride and high-purity ammonia at a certain pressure; 2. carrying out heat treatment on the ball-mill product in a high-purity ammonia atmosphere to obtain a high-purity metal amino compound; and 3. ball-milling the amino compound with the hydride at a certain ratio in a high-purity argon atmosphere to obtain the M-N-H hydrogen storage material. According to the synthesis method provided by the invention, a Mg(NH2)2-LiH reversible hydrogen storage material can be directly prepared, and has the advantages of difficulty in loss of hydrogen storage capacity, low hydrogen pressure and temperature during activation and no need for activation even when the ball milling time is long.
Description
Technical field: the present invention relates to a kind of synthetic method of hydrogen storage material, especially a kind of synthetic method of the M-N-H class hydrogen storage material that forms with amides and hydride belongs to material science.
Background technology: Greenhouse effect and environmental pollution that fossil oil causes are on the rise, and force clean energy to become the study hotspot of whole world development and utilization, and wherein representative have renewable energy sources such as wind energy, tidal energy, sun power, Geothermal energy.Yet these renewable energy systems are owing to the intermittence of operation and often remote regional, and therefore cleaning, safety, efficient easily energy carrier become the gordian technique of these clean energies utilizations.The electricity conduct up to now clear energy sources carrier of most convenient is widely used in each area, the whole world, although the fossil oil of the usefulness of sometimes generating electricity not is clear energy sources such as coal, oil and natural gas.Hydrogen is another kind of clear energy sources carrier, the product of hydrogen behind burning or catalyzed oxidation is liquid water or water vapor, so hydrogen is as energy carrier, with respect to other carrier such as gasoline, ethane and methyl alcohol, have that the source is abundant, lightweight, energy density is high, environmental protection, storing mode and utilize the characteristics such as various informative, therefore hydrogen the most effectively replenishes as this clear energy sources carrier of electric energy, can satisfy nearly all energy requirement, thereby form a permanent system that solves energy problem.Hydrogen Technology comprises hydrogen manufacturing, storage (fortune) hydrogen and uses hydrogen, and wherein hydrogen storage technology becomes the key factor of Hydrogen Energy industrialization safely and efficiently.The hydrogen storage mode has three kinds, and namely gaseous state high-pressure hydrogen storing, cryogenic high pressure liquid storage hydrogen and solid-state hydrogen storage material are stored up hydrogen, and wherein the most rising is solid-state hydrogen storage material.M-N-H system, good reversibility large owing to its hydrogen-storage amount and dynamic performance receive much concern soon in the solid-state hydrogen storage material, this system generally is made of Lithamide and lithium hydride or magnesium hydride, yet the amides of alkali and alkaline earth metal ions is expensive and only have Lithamide commercially available on market, therefore cheaply effectively synthesis of high purity metal amino compound become one of industrialized restraining factors of this system.
Summary of the invention: for above problem, the invention provides the method that a kind of low cost simple to operate, easy to implement is synthesized the M-N-H hydrogen storage material.
For achieving the above object, the technical solution used in the present invention is: a kind of synthetic method of novel M-N-H hydrogen storage material, synthesize the M-N-H hydrogen storage material with metal hydride as raw material, mainly divided for three steps carried out: one, with metal hydride high-energy ball milling in high-purity ammon; Two, thereby the thermal treatment under high-purity ammon atmosphere of ball milling product is obtained the metal amino compound; Three, ball milling under high-purity argon gas atmosphere obtains the M-N-H hydrogen storage material with metal amino compound and hydride.
Characteristics of the present invention: the M-N-H hydrogen storage material is by LiNH usually
2-MgH
2Consist of, system becomes Mg (NH after hydrogen is inhaled in dehydrogenation
2)
2-LiH reversible hydrogen storage material is because LiNH
2Higher and its degradation production NH of heat decomposition temperature
3With MgH
2Therefore the speed of reaction is slower, generally needs under the comparatively high temps (110bar) activation under vacuum or the high hydrogen pressure, when activating under so easy loss the part hydrogen-storage amount, particularly vacuum.Using the present invention can be first by MgH
2Synthesis of high purity Mg (NH
2)
2Thereby, obtain Mg (NH with the direct ball milling of LiH
2)
2-LiH reversible hydrogen storage material.The present invention has hydrogen-storage amount hydrogen pressure and temperature is lower and even the advantage that need not activate when being difficult for loss, activation when Ball-milling Time is longer.
Embodiment:
As the method that raw material synthesizes the M-N-H hydrogen storage material, mainly divided for three steps carried out: one, with metal hydride high-energy ball milling in high-purity ammon (purity is more than 99.999%): the MgH that takes by weighing the 0.5-2g quality with metal hydride
2In ball grinder, Stainless Steel Ball and MgH in the tank
2Mass ratio be 10-50: 1, be evacuated to less than the ammonia that is filled with 0.3-0.7MPa behind the 5Pa, repeatedly vacuumize and fill ammonia at least three times with air in the emptying ball grinder, then the rotating speed ball milling that turns with 200-500 of ball mill is 4-20 hour; Two, with the ball milling product at high-purity ammonia (purity is more than 99.999%) thus thermal treatment obtains the metal amino compound under the atmosphere: the product behind the ball milling is put into the ammonia that is filled with 0.1-0.5MPa after heating tank is evacuated to less than 5Pa, repeatedly vacuumize and fill ammonia at least three times with air in the emptying heating tank, then after 200-300 ℃ of lower thermal treatment 2-10 hour, obtain Mg (NH
2)
2Three, ball milling under high-purity argon gas (purity is more than 99.999%) atmosphere obtains the M-N-H hydrogen storage material with amides and hydride: go on foot the Mg (NH that makes with above two
2)
2With LiH take mol ratio as 1: after the ratio of 2.0-2.2 takes by weighing, with the mass ratio of Stainless Steel Ball still be 1: 10-50 places and carries out ball milling in the ball grinder, and the rotating speed of ball mill is that 200-500 turns, and obtains Mg (NH after ball milling 10-30 hour
2)
2-LiH reversible hydrogen storage material.
Embodiment 1
Take above implementation method to prepare Mg (NH
2)
2-LiH reversible hydrogen storage material: the MgH that at first takes by weighing 1g
2In ball grinder, Stainless Steel Ball and MgH in the tank
2Mass ratio be 20: 1, be evacuated to less than the 99.999% high-purity ammonia that is filled with 0.5MPa behind the 5Pa, repeatedly vacuumize and fill ammonia at least three times with air in the emptying ball grinder, then ball mill was with 400 rotating speed ball millings that turn 8 hours; Then the product behind the ball milling is put into heating tank and be evacuated to less than the 99.999% high-purity ammonia that is filled with 0.3MPa behind the 5Pa, repeatedly vacuumize and fill ammonia at least three times with air in the emptying heating tank, then obtain Mg (NH after 3 hours 300 ℃ of lower thermal treatments
2)
2Mg (the NH that at last above two steps is made
2)
2After taking by weighing take mol ratio as 1: 2.2 ratio with LiH, still be to place that 99.999% high-purity argon gas carries out ball milling in the ball grinder at 1: 20 with the mass ratio of Stainless Steel Ball, the rotating speed of ball mill is 400 to turn, and ball milling obtains Mg (NH after 24 hours
2)
2-LiH reversible hydrogen storage material.Behind the lower activation of 100bar hydrogen pressure, 240 ℃ 24h, adopt PCT pro2000 pressure-composition-temperature measuring device to test Mg (NH
2)
2The hydrogen storage property of-LiH system comprises the mensuration of inhaling hydrogen and dehydrogenation kinetics and dehydrogenation p-c-T curve.The p-c-T test result shows that the reversible hydrogen storage capacity of this system is not less than 4.5wt% at 200-240 ℃, 180 ℃ hydrogen-storage amount is reduced to about 3.6wt%, only having system's hydrogen pressure to be low to moderate 0.6bar in the time of 150 ℃ just has hydrogen to emit, and hydrogen-storage amount is low to moderate 0.6wt%, illustrate that the initial hydrogen discharging temperature of this system is about about 150 ℃, the suction hydrogen desorption kinetics of each temperature has further been verified the result of p-c-T test hydrogen-storage amount, and speed for hydrogen absorbing and releasing is all very fast.
Claims (8)
1. the synthetic method of a M-N-H hydrogen storage material is synthesized the M-N-H hydrogen storage material with metal hydride as raw material, mainly divides for three steps carried out: one, with metal hydride high-energy ball milling in ammonia; Two, thereby the thermal treatment under ammonia atmosphere of ball milling product is obtained the metal amino compound, concrete operations are as follows: thus the ball milling product is obtained the metal amino compound in thermal treatment under the ammonia atmosphere: the product behind the ball milling is put into the ammonia that is filled with 0.1-0.5MPa after heating tank is evacuated to less than 5Pa, repeatedly vacuumize and fill ammonia at least three times with air in the emptying heating tank, then after 200-300 ℃ of lower thermal treatment 2-10 hour, obtain Mg (NH
2)
2Three, ball milling under argon gas atmosphere obtains the M-N-H hydrogen storage material with metal amino compound and hydride.
2. the synthetic method of a kind of M-N-H hydrogen storage material as claimed in claim 1 is characterized in that, the concrete operations of step 1 are as follows: the MgH that takes by weighing the 0.5-2g quality
2In ball grinder, Stainless Steel Ball and MgH in the tank
2Mass ratio be 10-50:1, be evacuated to less than the ammonia that is filled with 0.3-0.7MPa behind the 5Pa, repeatedly vacuumize and fill ammonia at least three times with air in the emptying ball grinder, then the rotating speed ball milling that turns with 200-500 of ball mill is 4-20 hour.
3. the synthetic method of a kind of M-N-H hydrogen storage material as claimed in claim 1 is characterized in that, the concrete operations of step 3 are as follows: ball milling under argon gas atmosphere obtains the M-N-H hydrogen storage material with amides and hydride: go on foot the Mg (NH that makes with above two
2)
2After taking by weighing with the ratio of LiH take mol ratio as 1:2.0-2.2, still carry out ball milling in the ball grinder for 1:10-50 places with the mass ratio of Stainless Steel Ball, the rotating speed of ball mill is that 200-500 turns, and obtains Mg (NH after ball milling 10-30 hour
2)
2-LiH reversible hydrogen storage material.
4. such as the synthetic method of each described a kind of M-N-H hydrogen storage material of claim 1-3, it is characterized in that described ammonia is that purity is at the high-purity ammon more than 99.999%.
5. such as the synthetic method of each described a kind of M-N-H hydrogen storage material of claim 1-3, it is characterized in that described ammonia is that purity is at the high-purity ammonia more than 99.999%.
6. such as the synthetic method of each described a kind of M-N-H hydrogen storage material of claim 1-3, it is characterized in that described argon gas is that purity is at the high-purity argon gas more than 99.999%.
7. the synthetic method of a kind of M-N-H hydrogen storage material as claimed in claim 1 is characterized in that, its concrete operation step is: one, with metal hydride high-energy ball milling in high-purity ammon: the MgH that takes by weighing the 0.5-2g quality
2In ball grinder, Stainless Steel Ball and MgH in the tank
2Mass ratio be 10-50:1, be evacuated to less than the ammonia that is filled with 0.3-0.7MPa behind the 5Pa, repeatedly vacuumize and fill ammonia at least three times with air in the emptying ball grinder, then the rotating speed ball milling that turns with 200-500 of ball mill is 4-20 hour; Two, thereby the ball milling product is obtained the metal amino compound in thermal treatment under high-purity ammonia atmosphere: the product behind the ball milling is put into the ammonia that is filled with 0.1-0.5MPa after heating tank is evacuated to less than 5Pa, repeatedly vacuumize and fill ammonia at least three times with air in the emptying heating tank, then after 200-300 ℃ of lower thermal treatment 2-10 hour, obtain Mg (NH
2)
2Three, ball milling under high-purity argon gas atmosphere obtains the M-N-H hydrogen storage material with amides and hydride: go on foot the Mg (NH that makes with above two
2)
2After taking by weighing with the ratio of LiH take mol ratio as 1:2.0-2.2, still carry out ball milling in the ball grinder for 1:10-50 places with the mass ratio of Stainless Steel Ball, the rotating speed of ball mill is that 200-500 turns, and obtains Mg (NH after ball milling 10-30 hour
2)
2-LiH reversible hydrogen storage material.
8. the synthetic method of a kind of M-N-H hydrogen storage material as claimed in claim 1 is characterized in that, its concrete operation step is: the MgH that at first takes by weighing 1g
2In ball grinder, Stainless Steel Ball and MgH in the tank
2Mass ratio be 20:1, be evacuated to less than the 99.999% high-purity ammonia that is filled with 0.5MPa behind the 5Pa, repeatedly vacuumize and fill ammonia at least three times with air in the emptying ball grinder, then ball mill was with 400 rotating speed ball millings that turn 8 hours; Then the product behind the ball milling is put into heating tank and be evacuated to less than the 99.999% high-purity ammonia that is filled with 0.3MPa behind the 5Pa, repeatedly vacuumize and fill ammonia at least three times with air in the emptying heating tank, then obtain Mg (NH after 3 hours 300 ℃ of lower thermal treatments
2)
2Mg (the NH that at last above two steps is made
2)
2After taking by weighing with the ratio of LiH take mol ratio as 1:2.2, still 99.999% high-purity argon gas carries out ball milling in the ball grinder for 1:20 places with the mass ratio of Stainless Steel Ball, and the rotating speed of ball mill is 400 to turn, and ball milling obtains Mg (NH after 24 hours
2)
2-LiH reversible hydrogen storage material.
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| CN103832983A (en) * | 2012-11-22 | 2014-06-04 | 中国科学院大连化学物理研究所 | Synthesis method of amino metal compounds |
| CN103880752B (en) * | 2012-12-21 | 2016-06-01 | 中国科学院大连化学物理研究所 | The preparation of nitrogen heterocyclic metal-salt or its heterogeneous ring compound title complex |
| CN104710440B (en) * | 2013-12-11 | 2017-06-23 | 中国科学院大连化学物理研究所 | Containing the secondary amine metallo-organic compound of β H and its preparation and application |
| CN112110427A (en) * | 2020-08-20 | 2020-12-22 | 浙江工业大学 | Synthesis method of lithium potassium amino fluoride |
| CN112079339B (en) * | 2020-08-20 | 2021-11-02 | 浙江工业大学 | Method for synthesizing lithium amide |
| CN112079331B (en) * | 2020-08-20 | 2022-06-03 | 浙江工业大学 | Synthesis method of metal-nitrogen-hydrogen system hydrogen storage material |
| CN112265958B (en) * | 2020-10-29 | 2022-06-24 | 中国计量大学 | Composite hydrogen storage material and preparation method thereof |
| CN112758890A (en) * | 2021-02-20 | 2021-05-07 | 烟台大学 | Preparation method of amino metal solid hydrogen storage material and solid hydrogen storage material |
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| CN1876561A (en) * | 2005-06-10 | 2006-12-13 | 中国科学院金属研究所 | Li-Mg-N-H hydrogen storage material and process for preparing same |
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| CN1876561A (en) * | 2005-06-10 | 2006-12-13 | 中国科学院金属研究所 | Li-Mg-N-H hydrogen storage material and process for preparing same |
Non-Patent Citations (1)
| Title |
|---|
| 刘述丽 等.Li-N-H储氢材料的高能球磨制备工艺研究.《沈阳师范大学学报（自然科学版）》.2011,第29卷(第1期),第87页实验方法. * |
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