CN101259952A - Method for increasing aluminum-containing complex compound hydrogen-storing material circulation stability - Google Patents
Method for increasing aluminum-containing complex compound hydrogen-storing material circulation stability Download PDFInfo
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- CN101259952A CN101259952A CNA2008100358637A CN200810035863A CN101259952A CN 101259952 A CN101259952 A CN 101259952A CN A2008100358637 A CNA2008100358637 A CN A2008100358637A CN 200810035863 A CN200810035863 A CN 200810035863A CN 101259952 A CN101259952 A CN 101259952A
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Abstract
The invention belongs to the functional material technical field, in particular to a method for improving the circulatory stability of aluminiferous complex hydrogen storage materials. The method comprises the following steps that: aluminiferous complex hydrogen storage materials MA1H4(M represents Li, Na or K) are dissolved in a solvent, and the generated MA1H4 solution is loaded in a porous channel of a porous matrix by the infiltration technique, wherein the porous matrix is of porous materials such as meso-porous materials(SiO2), meso-porous materials(Al2O3), porous carbon, meso-porous carbon or zeolite; and the MA1H4 solution has the solution removed by drying, obtaining the nano sized MA1H4 which is filled in the porous channel of the porous matrix; the nano sized MA1H4 hydrogen storage materials are good in absorb-release hydrogen circulatory stability. The method is simple and low in cost, and high in commercial value for preparing hydrogen storage materials with high circulatory stability .
Description
Technical field
The invention belongs to technical field of function materials, be specially a kind of method that improves aluminum-containing complex compound hydrogen-storing material circulation stability.Prepared hydrogen storage material provides sources of hydrogen for fuel cell.
Background technology
Under and the dual-pressure that ecotope day by day worsens deficient day by day at fossil fuel resource, development has become global common recognition with hydrogen as the clean reproducible energy technology of energy carrier.Therefore, the new technology of energy that development and utilization is relevant with hydrogen is classified as the primary study content by many countries.The important achievement that some fields are obtained as fuel cell, electromobile etc., also develops to the direction of industrialization.Can predict, the world energy sources economic structure also will produce revolutionary variation thereupon, promptly change economy of energy form based on hydrogen into from the economy of energy form based on carbon, be called for short " hydrogen economy ".The introducing of hydrogen economic idea force industry member to the hydrogen storage amount of hydrogen storage material proposed up to 5-6.5wt% new demand ([1] Schlapbach L, Zuttel A, Nature, 2001,414:353).For realizing this goal, the research emphasis from this field in 1996 expands to NaAlH from traditional metal hydride
4Complex compound hydrogen storage material for representative.NaAlH
4Effective hydrogen storage amount can reach 5.6wt%.1997, German Max-Planck coal research reports such as Bogdanovic, complex metal hydride NaAlH
4In introduce molar fraction be 2% contain the Ti catalyzer after, can realize about 150 ℃ that reversible hydrogen adsorption and desorption reacts ([2] Bogdanovic B, Schwickardi M.J.Alloys Compd., 1997; 253-254:1).From the experimental result of having reported, contain the Ti catalyzer by interpolation and can improve NaAlH
4Hydrogen storage performance, but exist following two shortcomings to demand urgently overcoming.Shortcoming one is to add the NaAlH that contains the Ti catalyzer
4The reaction conditions of the higher hydrogen pressure of the hydrogen of suction again process need (greater than 10MPa).Shortcoming two is the NaAlH that prepare in this way
4Particle can be reunited after putting hydrogen, can generate by products such as Ti-Al simultaneously, causes effective hydrogen storage amount to put hydrogen circulation and carry out and reduce along with suction.For example, add the NaAlH that contains the Ti catalyzer
4Hydrogen desorption capacity promptly drops to about 70% of initial amount in 15 circulation backs of experience, far below the theoretical capacity of material.The performance that these two shortcomings have not only hindered the potential performance of material has also brought certain limitation to practical application.
Summary of the invention
The method that the purpose of this invention is to provide a kind of simple to operate, raising aluminum-containing complex compound hydrogen-storing material circulation stability that cost is low.
The chemical molecular formula of material of the present invention is MAlH
4, M is alkali metal Li, Na or K.
The present invention adopts infiltration of solution wet method and dry technology with aluminum-containing complex compound hydrogen-storing material MAlH
4Be filled in the duct of porous matrix, make nano-scale MAlH
4, used here porous matrix is mesoporous SiO
2, mesoporous Al
2O
3, permeability material such as porous carbon, mesoporous carbon or zeolite, used solvent is to dissolve MAlH
4Organic solvent (as tetrahydrofuran (THF)).Prepared nano-scale MAlH
4The stable circulation performance is good, is more conducive to as the storage hydrogen carrier.
The method of the raising aluminum-containing complex compound hydrogen-storing material circulation stability that the present invention proposes, its concrete steps are as follows:
(1) under the protective atmosphere of room temperature and rare gas element, will contain aluminium complex metal hydride MAlH
4Be dissolved in fully in the solvent (as tetrahydrofuran (THF));
(2) MAlH that step (1) is obtained
4Drips of solution is added in the porous matrix, 40-50 ℃ of insulation infiltration 1-2 hour, so carries out repeatedly (as 3-6 time) dropping solution and insulation infiltration;
(3) infiltration that step (2) is obtained has MAlH
4Porous matrix under vacuum condition dry 24-48 hour, obtain to be filled in the nano-scale MAlH in the matrix duct
4
With the nano-scale MAlH that makes
4Carry out hydrogen storage property test, through inhale for 50 times put the hydrogen circulation after, still keep high hydrogen desorption capacity.
The present invention's implementation step more specifically is as follows:
(1) is equipped with MAlH
4Solution
Under the protective atmosphere of room temperature and inert nitrogen gas or argon gas, accurately weigh 1 gram conventional contain aluminium complex metal hydride MAlH
4Powder and 99 gram solvents are then with MAlH
4Powder joins in the solvent, is stirred well to dissolving fully, and the acquisition mass content is 1% MAlH
4Solution.
(2) MAlH
4Solution drips and is penetrated into porous matrix
The MAlH that step (1) is obtained
4Drips of solution is added on the porous matrix, 40-50 ℃ of insulation infiltration 1-2 hour, so repeatedly drips solution and insulation so that MAlH
4Enter in the duct.
(3) after step (2) is finished, under vacuum condition dry 24-48 hour, just can obtain to be filled into the nano-scale MAlH in the matrix duct
4High resolution transmission electron microscopy analysis revealed MAlH
4Particle be filled into well in the duct of porous matrix.
Be filled into nano-scale MAlH in the matrix duct with what step (3) made
4Carry out the hydrogen storage property test.The result shows nano-scale MAlH
4Is beneficial to and puts hydrogen at a lower temperature, and the stable circulation performance is improved, inhale through 50 times put the hydrogen circulation after, hydrogen desorption capacity still remains on 90% of theoretical capacity.
The porous matrix that the present invention selects for use has uniform sequential duct, and at nano-scale MAlH
4Preparation and suction are put in the hydrogen working cycle and can be kept Stability Analysis of Structures, channel diameter at 5-10nm for well.
The present invention passes through solution osmose process, MAlH in above-mentioned steps (2)
4Solution is filled in the nano pore of porous matrix.
The MAlH that the present invention obtains by vacuum-drying in above-mentioned steps (3)
4Granular size is subject to the duct size, and it is the MAlH of nano-scale
4Hydrogen storage material.
The nano-scale MAlH that the present invention makes
4Do not adding under any catalyzer and the low hydrogen discharging temperature condition, hydrogen desorption capacity is 2.0wt% in 1 hour, and common MAlH
4Hydrogen desorption capacity is almost nil.After the hydrogen circulation is put in 50 suctions, nano-scale MAlH
4Hydrogen desorption capacity remain on 90% of theoretical capacity, and common MAlH
4Have only about 40%.These results show, aluminum-containing complex compound hydrogen-storing material is subject in the porous matrix duct, not only can improve the hydrogen discharging performance of hydrogen storage material, and it puts the Al that generates behind the hydrogen and MH and still is limited in the duct and can be agglomerated into large-size particle, and the stable circulation performance of hydrogen storage material is improved.
The present invention adopts infiltration of solution wet method and dry technology to make the nano-scale aluminum-containing complex compound MAlH of high cyclical stability
4, method is simple, and cost is low, is a kind of method for preparing the high-performance hydrogen-storage material of great commercial value.
The good aluminum-containing complex compound MAlH of stable circulation performance of the present invention's preparation
4Can be as the storage hydrogen carrier, for fuel cell provides hydrogen source in fuel cell.
Description of drawings
Fig. 1 is embodiment 1 sample NaAlH
4Be filled in mesoporous SiO
2High resolution transmission electron microscopy photo in the matrix duct.
Fig. 2 is embodiment 2 sample NaAlH
4Hydrogen desorption capacity under 150 ℃ of temperature with put the graphic representation of hydrogen time.Wherein curve (a) be the present invention prepare be filled in mesoporous SiO
2Nano-scale NaAlH in the matrix duct
4, curve (b) is common NaAlH
4
Fig. 3 is embodiment 3 sample NaAlH
4Hydrogen desorption capacity and the graphic representation of cycle index.Wherein curve (a) be the present invention prepare be filled in mesoporous SiO
2Nano-scale NaAlH in the matrix duct
4, curve (b) is common NaAlH
4
Embodiment
Embodiment 1
The good nano-scale NaAlH of preparation stable circulation performance
4, concrete steps are as follows:
(1) is equipped with NaAlH
4Solution
Under the protective atmosphere of room temperature and inert nitrogen gas or argon gas, accurately weigh 1 gram and contain aluminium complexing nano hydride NaAlH
4Powder and 99 gram tetrahydrofuran (THF)s are then with NaAlH
4Powder joins in the tetrahydrofuran (THF), is stirred well to dissolving fully, and the acquisition mass content is 1% NaAlH
4Solution.
(2) NaAlH
4Solution drips and is penetrated into mesoporous SiO
2
The NaAlH that will obtain by step (1)
4Drips of solution is added to the mesoporous SiO of channel diameter at 5-10nm
2Powder 40-50 ℃ of insulation infiltration 1-2 hour, carries out dripping for 3-6 time solution and insulation so that NaAlH
4Enter in the duct.
(3) will repeatedly permeate NaAlH will be arranged
4Sample under vacuum condition dry 24-48 hour, just can obtain to be filled in the nano-scale NaAlH in the porous matrix duct
4The high resolution transmission electron microscopy photo of sample as shown in Figure 1.
(4) further experiment proves, with the nano-scale NaAlH in the porous matrix duct of being filled in that makes
4Carry out hydrogen storage property test, sample has good cyclical stability, though through inhale for 50 times put the hydrogen circulation after, hydrogen desorption capacity still remains on 90% of theoretical capacity.
(5) the mesoporous SiO that selects for use of the present invention
2Have uniform sequential duct, channel diameter is at 5-10nm, and at NaAlH
4Suction is put in the hydrogen working cycle can keep Stability Analysis of Structures.Particle size also is limited in the 5-10nm.
As above-mentioned preparation method, use LiAlH
4Or KAlH
4Under the protective atmosphere of room temperature and inert nitrogen gas or argon gas, the outfit mass content is 1% solution, and solution repeatedly drips and insulation is penetrated into mesoporous SiO
2In the duct, under vacuum condition dry 24-48 hour, just can make and be filled into SiO
2The nano-scale LiAlH in duct
4Or KAlH
4, obtain the good LiAlH of stable circulation performance
4Or KAlH
4Hydrogen storage material.
As above-mentioned preparation method, use NaAlH
4, LiAlH
4Or KAlH
4Can be filled into mesoporous Al by the solution infiltration technology equally
2O
3, in the permeability material ducts such as porous carbon, mesoporous carbon or zeolite, obtain the NaAlH of good cycling stability
4, LiAlH
4Or KAlH
4Hydrogen storage material
Embodiment 2
With NaAlH
4Be example, Fig. 2 has compared 150 ℃ of uniform temps and transferred hydrogen 1 hour, hydrogen desorption capacity with put the curve of hydrogen time.As can be seen from the figure, under the condition of not adding any catalyzer, under lower hydrogen discharging temperature condition, common NaAlH
4Sample is put hydrogen hardly, and the present invention preparation be filled in mesoporous SiO
2Nano-scale NaAlH in the matrix duct
4There is the hydrogen of 2.0wt% to emit.
With NaAlH
4Be example, Fig. 3 has compared to inhale under the same conditions puts hydrogen circulation, the curve of sample hydrogen desorption capacity and cycle index, and as can be seen from the figure, under the condition of not adding any catalyzer, the present invention makes is filled in mesoporous SiO
2Nano-scale NaAlH in the matrix duct
4, have extraordinary cyclical stability, wherein after the hydrogen circulation was put in 50 suctions of experience, hydrogen desorption capacity remained on 90% of theoretical capacity, and conventional NaAlH
4Have only about 40%.
Claims (3)
1, a kind of method that improves aluminum-containing complex compound hydrogen-storing material circulation stability is characterized in that concrete steps are as follows:
(1) under the protective atmosphere of room temperature and rare gas element, will contain aluminium complex metal hydride MAlH
4Be dissolved in the solvent fully;
What (2) step (1) is obtained contains aluminium complex metal hydride MAlH
4Drips of solution is added in the porous matrix, 40-50 ℃ of insulation infiltration 1-2 hour, so repeatedly drips solution and insulation infiltration;
(3) infiltration that step (2) is obtained has the aluminium of containing complex metal hydride MAlH
4Porous matrix under vacuum condition dry 24-48 hour, obtain to be filled in the nano-scale MAlH in the porous matrix duct
4
The above-mentioned aluminium complex metal hydride chemical molecular formula MAlH that contains
4In, M is alkali metal Li, Na or K.
2, method according to claim 1, the material that it is characterized in that described porous matrix is mesoporous SiO
2, mesoporous Al
2O
3, porous carbon, mesoporous carbon or zeolite.
3, method according to claim 1, the channel diameter that it is characterized in that described porous matrix is 5-10nm.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103183314A (en) * | 2011-12-31 | 2013-07-03 | 北京有色金属研究总院 | Composite hydrogen storage material with foamed structure and preparation method thereof |
| CN105060245A (en) * | 2015-07-28 | 2015-11-18 | 安徽工业大学 | Lithium aluminum hydride based composite hydrogen storage material and preparation method thereof |
| CN114870650A (en) * | 2022-05-16 | 2022-08-09 | 南京工业大学 | Zinc-based MOF (Metal-organic framework) membrane material with interpenetrating composite structure as well as preparation method and application thereof |
-
2008
- 2008-04-10 CN CNA2008100358637A patent/CN101259952A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103183314A (en) * | 2011-12-31 | 2013-07-03 | 北京有色金属研究总院 | Composite hydrogen storage material with foamed structure and preparation method thereof |
| CN105060245A (en) * | 2015-07-28 | 2015-11-18 | 安徽工业大学 | Lithium aluminum hydride based composite hydrogen storage material and preparation method thereof |
| CN114870650A (en) * | 2022-05-16 | 2022-08-09 | 南京工业大学 | Zinc-based MOF (Metal-organic framework) membrane material with interpenetrating composite structure as well as preparation method and application thereof |
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Open date: 20080910 |