CN101623627B - Catalyst for improving hydrogen production kinetics performance of hydrogen storage material of Li-Mg-N-H system and using method thereof - Google Patents
Catalyst for improving hydrogen production kinetics performance of hydrogen storage material of Li-Mg-N-H system and using method thereof Download PDFInfo
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- CN101623627B CN101623627B CN2008101164925A CN200810116492A CN101623627B CN 101623627 B CN101623627 B CN 101623627B CN 2008101164925 A CN2008101164925 A CN 2008101164925A CN 200810116492 A CN200810116492 A CN 200810116492A CN 101623627 B CN101623627 B CN 101623627B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
Abstract
The invention relates to a catalyst (Ti-Cr-V)-Mn-R capable of improving the hydrogen production kinetics performance of a hydrogen storage material of a Li-Mg-N-H system, wherein R is Ce or Ce-enriched misch metal, and the alloy comprises the following components in percentage by weight: 20 to 30 percent of titanium element, 30 to 45 percent of vanadium element, 25 to 35 percent of chromium element, 5 to 15 percent of manganum element, and 1 to 5 percent of R. The catalyst is doped in the Li-Mg-N-H in certain proportion according to certain process to prepare a compound hydrogen storage material. By adopting the catalyst, the hydrogen production quantity of the compound hydrogen storage material of the Li-Mg-N-H within the first hour at a temperature of 200 DEG C is improved by over one time.
Description
Technical field
The present invention relates to the hydrogen storage material catalytic field, be specially a kind of catalyst that can improve Li-Mg-N-H system hydrogen storage material hydrogen desorption kinetics.
Background technology
The energy is the source of mankind's activity, and clean energy resource is the basis of human society realization sustainable development especially, and fossil fuel such as oil, coal is exhausted day by day because of undue exploitation in recent years, thereby has caused the deep energy crisis of human society.Hydrogen is a kind of fuel of cleaning, nontoxic, odorless; Burning produces pure water with oxygen.Therefore, its use is very little to the pollution of atmosphere, and from the angle of environmental protection, hydrogen is undoubtedly a kind of desirable fuel.In whole hydrogen energy system, storage hydrogen is the key link.Through the exploitation of 30 years of researches, hydrogen-storage alloy has been widely used in the storage and the fields such as transportation, hydrogen isotope separation, temperature and pressure sensor, hydrogenating organic compounds catalyst for reaction and Ni-MH battery of hydrogen.Yet, traditional hydrogen-storage alloy AB
5, AB
2, AB and A
2The hydrogen storage amount of Type B hydrogen-storage alloy all is no more than 2wt%.This some field (as fuel cell) of using for hydrogen-storage alloy is far from being enough.According to the estimation of USDOE (DOE), for Proton Exchange Membrane Fuel Cells (PEMFC) automobile of a standard, stroke 480km needs the about 358kg of hydrogen.This requires the hydrogen storage amount of hydrogen-storage alloy to surpass 6wt%, and volume ratio density surpasses 60kgm-3 (H
2).It is 5wt% that international energy association (IEA) also requires hydrogen storage amount, and hydrogen discharging temperature is lower than 423K, and cycle life is above 1000 times.World energy sources Network Dept. (WENET) is though requiring to 3wt% of reduction hydrogen storage amount requires hydrogen discharging temperature to be no more than 373K (this also is the requirement of hydrogen-storage alloy practicability) simultaneously, and cycle life is above 5000 times.Therefore, nearest 6 years, the research and development of hydrogen storage material turned to the research of high power capacity, long-life material, and wherein Metal-N-H series hydrogen storage material has very high hydrogen capacity.Li for example
3The theoretical maximum storage hydrogen quantity of N can reach 10.5wt%, and also between .5.5～8wt%, this system hydrogen storage material mainly comprises the theoretical hydrogen storage content of Li-Mg-N-H series hydrogen storage material: Mg (NH
2)
2+ LiH and LiNH
2+ MgH
2Two kinds of mixtures.This has attracted material science worker's interest strongly.Studies show that Li
2MgN
2H
2Hydrogen storage material 363K correspondence that to put hydrogen pressure be 0.1Mpa, this means that this material satisfies practical condition aspect the hydrogen thermodynamics putting, and has very high hydrogen content.But, itself have and inhale the hydrogen discharging temperature height, shortcoming such as hydrogen desorption kinetics is slow.So number of research projects is intended to solve the problems referred to above of Li-Mg-N-H system hydrogen storage material.
For improving the hydrogen desorption kinetics of Li-Mg-N-H system hydrogen storage material, consider that from the catalyst angle of selecting the catalyst of having selected for use at present has: single wall, Duo Bi, active carbon and single wall, Ni, Fe, Co, Ti, TiO through modifying
2, VCl
3, TiCl
3Deng nano-powder.Yet above-mentioned catalyst also is not clearly to the effect that the Li-Mg-N-H hydrogen desorption kinetics improves, and the Preparation of catalysts cost is very high.
Summary of the invention
The object of the present invention is to provide a kind of cheap catalyst, utilize this catalyst can effectively improve Li-Mg-N-H system hydrogen storage material hydrogen desorption kinetics performance.
Another object of the present invention is to provide a kind of method of the Li-Mg-N-H of improvement system hydrogen storage material hydrogen desorption kinetics.
To achieve these goals, the present invention takes following technical scheme:
A kind of catalyst that improves Li-Mg-N-H system hydrogen storage material hydrogen desorption kinetics, this catalyst is (Ti-Cr-V)-Mn-R alloy, wherein R is Ce or rich Ce mishmetal, the composition of this alloy and content are: titanium elements is 20～30wt%, v element is 30～45wt%, the chromium element is 25～35wt%, and manganese element is 5～15wt%, and R is 1～5wt%.
The composition and the content of the mishmetal of rich Ce used in the present invention are as follows: Ce (50.57wt%), La (33.47wt%), Pr (4.64wt%), Nd (11.32wt%); But the present invention is not limited to have the mishmetal of mentioned component and the rich Ce of content, and in general, in cerium-rich mischmetal, the content of Ce is more than 40 weight %, and all the other are Nd, La and Pr rare earth element, and the present invention also can use this cerium-rich mischmetal.
Described (Ti-Cr-V)-Mn-R alloy is the alloyed powder of average grain diameter≤50 μ m.
Described alloyed powder is the powdery that the breaking method of employing hydrogenation treatment and/or Mechanical Crushing is made.
A kind of method of improving Li-Mg-N-H system hydrogen storage material hydrogen desorption kinetics, it is compound to utilize ball milling method and Li-Mg-N-H system material to carry out (Ti-Cr-V)-Mn-R alloy of the present invention, (Ti-Cr-V)-and the Mn-R alloy phase for the compositely proportional of Li-Mg-N-H system material is: 1～15mol%; The concrete technological parameter of ball milling is: ball material weight ratio 5～15: 1, charges into the protective atmosphere of 0.5～3Mpa at 5～30 hours ball milling time in jar.
Described protective atmosphere is one or more in hydrogen, argon gas, the helium.
In the present invention, (Ti-Cr-V)-the Mn-R alloy in titanium, chromium, vanadium be the matrix composition; And other composition is as the adding ingredient of alloy, and these elements play the effect that improves the hydrogen discharging performance of alloy own.
The invention has the beneficial effects as follows:
The catalyst that utilizes among the present invention to be set forth can make Li-Mg-N-H system hydrogen storage material hydrogen desorption kinetics be improved.
The specific embodiment
The material of employed abrading-ball all is the same with size in following embodiment 1-5.The material of abrading-ball and size and weight are as follows:
Material: the GCr15 that meets the GB308-2002 national standard;
Size: diameter is Φ 8mm;
Weight: 2g.
Embodiment 1
The concrete composition of catalyst is: when setting the alloying component total amount as 100wt%, titanium is 20wt%, and v element is 45wt%, and the chromium element is 25wt%, and manganese element is 5wt%, and Ce elements is 5wt%.According to said ratio, preparation TiV
2.11Cr
1.2Mn
0.21Ce
0.09Alloy.With a certain amount of this alloy, by hydrogenation and two kinds of crumbling methods of ball milling alloy is carried out thinning processing, the alloy average grain diameter that obtains is 40 μ m.At last, to 2LiNH
2+ MgH
2Add with respect to this 2LiNH in the hydrogen storage material
2+ MgH
2The 4mol% catalyst of hydrogen storage material, by ball mill mixing, technological parameter is: ball milling time 5h, ball material weight ratio 10: 1 charge into the hydrogen shield gas of certain pressure (0.5Mpa) in ball grinder.Test result shows that this catalyst can make 2LiNH
2+ MgH
2The hydrogen desorption capacity that began 1 hour promotes 1.5 times.
Embodiment 2
The concrete composition of catalyst is: when setting the alloying component total amount as 100wt%, titanium is 30wt%, and v element is 30wt%, and the chromium element is 30wt%, and manganese element is 5wt%, and Ce elements is 5wt%.According to said ratio, preparation TiV
0.94Cr
0.92Mn
0.15Ce
0.06Alloy is put the hydrogen thinning processing by repeatedly inhaling, and the alloy average grain diameter that obtains is 50 μ m.To Mg (NH
2)
2Add with respect to this Mg (NH in the+2LiH system hydrogen storage material
2)
2This catalyst of the 8mol% of+2LiH hydrogen storage material, by ball mill mixing, technological parameter is: ball milling time 10h, ball material weight ratio 10: 1 charge into hydrogen (1Mpa) in ball grinder.Test result shows that this catalyst can make Mg (NH
2)
2+ 2LiH hydrogen storage material is under 200 ℃ of conditions, and the hydrogen desorption capacity that began 1 hour promotes 1.4 times.
Embodiment 3
The concrete composition of catalyst is: when setting the alloying component total amount as 100wt%, titanium is 20wt%, and v element is 34wt%, and the chromium element is 30wt%, and manganese element is 15wt%, and Ce elements is 1wt%.According to said ratio, preparation TiV
1.6Cr
1.4Mn
0.65Ce
0.02Alloy, and this alloy repeatedly inhaled put hydrogen and handle, making alloy refinement, the alloy average grain diameter that obtains is 50 μ m.To 3Mg (NH
2)
2Add with respect to this 3Mg (NH in the+8LiH system
2)
2This catalyst of the 10mol% of+8LiH hydrogen storage material, by ball mill mixing, technological parameter is: ball milling time 15h, ball material weight ratio 15: 1 charge into the helium (1.5Mpa) of certain pressure in the ball grinder.Test result shows that this catalyst can make 3Mg (NH
2)
2+ 8LiH hydrogen storage material is under 200 ℃ of conditions, and the hydrogen desorption capacity that began 1 hour promotes 1.2 times.
Embodiment 4
The concrete composition of catalyst is: when setting the alloying component total amount as 100wt%, titanium is 25wt%, and v element is 40wt%, and the chromium element is wt25%, and manganese element is 8wt%, and Ce elements is 2wt%.According to said ratio, preparation TiV
1.5Cr
0.92Mn
0.28Ce
0.03Alloy carries out thinning processing by ball milling to alloy, and the alloy average grain diameter that obtains is 30 μ m.。To 3Mg (NH
2)
2Add with respect to this 3Mg (NH in the+12LiH system
2)
2This catalyst of the 4mol% of+12LiH hydrogen storage material, by ball mill mixing, technological parameter is: ball milling time 30h, ball material weight ratio 20: 1 charge into the argon gas of (2Mpa) in the ball grinder.Test result shows that this catalyst can make 3Mg (NH
2)
2+ 12LiH hydrogen storage material is under 200 ℃ of conditions, and the hydrogen desorption capacity that began 1 hour promotes 1.1 times.
Embodiment 5
The concrete composition of catalyst is: when setting each composition total amount of alloy as 100wt%, titanium is 20wt%, and v element is 45wt%, and the chromium element is 25wt%, and manganese element is 8wt%, and rich Ce mixed rare-earth elements is 2wt%.According to said ratio, preparation TiV
2.1Cr
1.3Mn
0.35Mm
0.03Alloy, wherein, Mm is rich Ce mixed rare-earth elements.With a certain amount of this alloy, put hydrogen and ball milling carries out thinning processing to alloy by repeatedly inhaling, the alloy average grain diameter that obtains is 25 μ m.To 2LiNH
2+ MgH
2Add with respect to this 2LiNH in the system
2+ MgH
2This catalyst of the 4mol% of hydrogen storage material, by ball mill mixing, technological parameter is: ball milling time 5h, ball material weight ratio 20: 1 charge into the hydrogen of 3Mpa in ball grinder.Test result shows that this catalyst can make 2LiNH
2+ MgH
2Hydrogen storage material is under 200 ℃ of conditions, and the hydrogen desorption capacity that began 1 hour promotes 1.5 times.
Claims (5)
1. improve the catalyst of Li-Mg-N-H system hydrogen storage material hydrogen desorption kinetics, it is characterized in that: this catalyst is (Ti-Cr-V)-Mn-R alloy, wherein R is Ce or rich Ce mishmetal, and the composition of this alloy and content are: titanium elements is 20～30wt%, and v element is 30～45wt%, the chromium element is 25～35wt%, manganese element is 5～15wt%, and R is 1～5wt%, in cerium-rich mischmetal, the content of Ce is more than 40 weight %, and all the other are Nd, La and Pr rare earth element.
2. the catalyst that improves Li-Mg-N-H system hydrogen storage material hydrogen desorption kinetics according to claim 1 is characterized in that: described (Ti-Cr-V)-Mn-R alloy is the alloyed powder of average grain diameter≤50 μ m.
3. the catalyst that improves Li-Mg-N-H system hydrogen storage material hydrogen desorption kinetics according to claim 2 is characterized in that: described alloyed powder is the powdery that the breaking method of employing hydrogenation treatment and/or Mechanical Crushing is made.
4. method of improving Li-Mg-N-H system hydrogen storage material hydrogen desorption kinetics, it is characterized in that: it is compound to utilize ball milling method and Li-Mg-N-H system material to carry out claim 1 or 2 described (Ti-Cr-V)-Mn-R alloy, (Ti-Cr-V)-and the Mn-R alloy phase for the compositely proportional of Li-Mg-N-H system material is: 1～15mol%; The concrete technological parameter of ball milling is: ball material weight ratio 5～15: 1, charges into the protective atmosphere of 0.5～3MPa at 5～30 hours ball milling time in jar.
5. the method for improving Li-Mg-N-H system hydrogen storage material hydrogen desorption kinetics according to claim 4 is characterized in that: described protective atmosphere is one or more in hydrogen, argon gas, the helium.
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| CN101623627B true CN101623627B (en) | 2011-08-17 |
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| CN102556971A (en) * | 2010-12-16 | 2012-07-11 | 北京有色金属研究总院 | Li-Mg-based composite hydrogen storage material and preparation method thereof |
| CN105084310B (en) * | 2014-05-07 | 2017-09-01 | 安泰科技股份有限公司 | LiMgN/LiH hydrogen storage materials of doping and preparation method thereof |
| CN105039815B (en) * | 2015-08-20 | 2017-03-22 | 广西大学 | Preparation method of Mg-Li solid solution hydrogen storage material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1316537A (en) * | 2001-03-23 | 2001-10-10 | 天津南开戈德集团有限公司 | Mg-base hydrogen-bearing alloy material and its preparing process and application |
| WO2005014871A1 (en) * | 2003-08-08 | 2005-02-17 | Mitsui Mining & Smelting Co., Ltd. | LOW Co HYDROGEN OCCLUSION ALLOY |
| CN1752252A (en) * | 2005-10-26 | 2006-03-29 | 南京工业大学 | Nano Mg base composite material, preparing process and use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1316537A (en) * | 2001-03-23 | 2001-10-10 | 天津南开戈德集团有限公司 | Mg-base hydrogen-bearing alloy material and its preparing process and application |
| WO2005014871A1 (en) * | 2003-08-08 | 2005-02-17 | Mitsui Mining & Smelting Co., Ltd. | LOW Co HYDROGEN OCCLUSION ALLOY |
| CN1752252A (en) * | 2005-10-26 | 2006-03-29 | 南京工业大学 | Nano Mg base composite material, preparing process and use thereof |
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