CN102167284B - Light-metal composite hydrogen storage material and preparation method thereof - Google Patents
Light-metal composite hydrogen storage material and preparation method thereof Download PDFInfo
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- CN102167284B CN102167284B CN2011100700734A CN201110070073A CN102167284B CN 102167284 B CN102167284 B CN 102167284B CN 2011100700734 A CN2011100700734 A CN 2011100700734A CN 201110070073 A CN201110070073 A CN 201110070073A CN 102167284 B CN102167284 B CN 102167284B
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Abstract
The invention discloses a light-metal composite hydrogen storage material and a preparation method thereof, relating to the technical field of hydrogen storage materials. The light-metal composite hydrogen storage material comprises Li1-xNaxCaAlH6 (x is not less than 0 and not more than 1) metal hydride and a fluoride catalyst. The preparation method of the composite hydrogen storage material comprises the following steps of: with LiH, NaH and Al as raw materials, preparing Li1-xNaxCaAlH6 intermediate hydride in an organic solvent by adopting a reaction ball-milling method; carrying out high-energy ball-milling on the Li1-xNaxCaAlH6 and CaCl2 under an argon atmosphere to prepare Li1-xNaxCaAlH6 metal hydride; and directly doping the fluoride catalyst to the Li1-xNaxCaAlH6 metal hydride in the ball-milling process carried out under a hydrogen atmosphere to prepare the composite hydrogen storage material. The metal composite hydrogen storage material provided by the invention is high in hydrogen storage capacity and rapid in hydrogen release characteristic, and can be synthesized at room temperature with high yield. The preparation method of the light-metal composite hydrogen storage material is simple to operate, safe, reliable and beneficial to scale production.
Description
Technical field
The present invention relates to the hydrogen storage material technical field, related in particular to a kind of light metal composite hydrogen-storage material preparation method for material.
Background technology
Fossil energy peter out and use causes serious problem of environmental pollution to make Hydrogen Energy cause the concern that People more and more is many; Along with the fast development with the hydrogen field such as the continuous progress of hydrogen producing technology and fuel cell; The Hydrogen Energy field obtains high speed development in recent years, is still bottleneck (M.G. Schultz, the T. Diehl that the mass-producing of restriction Hydrogen Energy is quoted but lack safe, reliable, efficient storage hydrogen gordian technique at present; G.P. Brasseur; W. Zittel. Science, 2003,302 (5645): 624 – 627.).In the existing hydrogen storage technology, through chemical reaction or physical adsorption the solid-state hydrogen storage technology of hydrogen storage in material being had advantages such as the volume hydrogen-storage density is high, security is good, is a kind of up-and-coming storage hydrogen mode.Therefore, researching and developing various novel high-capacity hydrogen storage material system is the most important things that solve above-mentioned bottleneck problem.Wherein, the coordination aluminum hydride that contains basic metal and earth alkali metal is (like NaAlH
4, Na
3AlH
6And Li
3AlH
6) have development prospect preferably, inhale shortcoming (J. Yang, A. Sudik such as hydrogen desorption kinetics is slow, storage hydrogen over-all properties is relatively poor but all exist to some extent; C. Wolvertonb; D. J. Siegel. Chem. Soc. Rev., 2010,39:656 – 675.).
At present, the preparation method of hydrogen storage material mainly includes powder sintering, alloy melting method, solid phase diffusion method, vapour deposition process, chemical synthesis etc.But, adopt the prepared hydrogen storage material of aforesaid method all to exist material to inhale to some extent and put shortcomings such as hydrogen activation difficulty, severe reaction conditions.Therefore, development novel hydrogen storage material system and to optimize its preparation method be to accelerate hydrogen storage material mass-producing key in application.
Summary of the invention
The invention provides a kind of employing Li
1-xNa
xCaAlH
6It is AB that the light metal composite hydrogen storage material that metal hydride and fluoride catalysts are formed substitutes present rare earth
5The type hydrogen storage material, storage hydrogen dynamic performance is good, and hydrogen storage material is with low cost, good and environment amenable light metal composite hydrogen storage material of reaction efficiency and preparation method thereof.
In order to solve the problems of the technologies described above, the present invention is able to solve through following technical proposals:
Light metal composite hydrogen storage material, metal composite hydrogen storage material comprise metal hydride and the fluoride catalysts that accounts for this metal hydride total amount 0 ~ 5 mol%, and said metal hydride is Li
1-xNa
xCaAlH
6, 0≤x≤1 wherein.
As preferably, described fluoride catalysts is TiF
3, LaF
3, CeF
3, NbF
5, FeF
3, CoF
2And NiF
2In any.
Implement the preparation method of above-mentioned light metal composite hydrogen storage material, may further comprise the steps:
(1) under protection of inert gas atmosphere, with LiH, NaH and Al powder raw material according to Li
3-xNa
xAlH
6The proportion relation uniform mixing of (0≤x≤1) places the ball grinder of ball mill with mixed powder again and sealing vacuumizes to ball grinder; Utilize syringe to injecting organic solvent in the ball grinder subsequently, charge into behind the hydrogen of 1-5MPa pressure ball milling 10-20h on ball mill again, can obtain Li at last
3-xNa
xAlH
6Middle hydrogenate;
(2) at synthetic Li
3-xNa
xAlH
6Ball grinder in further add the CaCl of equimolar amount
2Powder carries out ball milling 10h, can pass through Li
+And Ca
2+Ionic replacement(metathesis)reaction and prepare Li
1-xNa
xCaAlH
6Metal hydride and LiCl by product filter, distill and purify the ball-milling reaction product subsequently, remove the LiCl by product and organic solvent is reclaimed, and can obtain highly purified Li
1-xNa
xCaAlH
6Metal hydride;
(3) with the Li that is obtained
1-xNa
xCaAlH
6Metal hydride mixes 1 ~ 5h with the fluoride catalysts that accounts for said metal hydride total amount 0 ~ 5 mol% mechanical ball milling under the nitrogen atmosphere of 1 ~ 10MPa pressure, finally obtains the light metal composite hydrogen storage material.
As preferably, the ball-to-powder weight ratio in the described mechanical milling process is 20 ~ 40:1, and drum's speed of rotation is 300 ~ 480rpm.
As preferably, the used organic solvent of described building-up process is any in THF and the ether.
The present invention has significant technique effect owing to adopted above technical scheme:
Compared with prior art, light metal composite hydrogen storage material of the present invention passes through at Li
3-xNa
xAlH
60.98,0.93 and 1.00) and the Li of formation (Li, Na and Ca three's electronegativity is respectively: with high Ca than Li and Na to introduce electronegativity in the complex hydrides
1-xNa
xCaAlH
6Metal hydride can further reduce the thermostability of hydrogenate, and then effectively reduces the hydrogen discharging temperature of this hydrogen storage material; Li
1-xNa
xCaAlH
6Utilize the Na element that the Li element is carried out part in the metal hydride objects system and substitute, the high hydrogen storage capability characteristic that this had both kept the original bonding structure of hydrogenate to be had can be carried out the continuous regulation and control of hydrogen storage property to this hydrogenate again in the different application occasion.By this Li
1-xNa
xCaAlH
6It is AB that the light metal composite hydrogen storage material that metal hydride and fluoride catalysts are formed substitutes present rare earth
5The type hydrogen storage material both can further improve its storage hydrogen dynamic performance when effectively improving the material hydrogen storage capability, can reduce the cost of hydrogen storage material again.In addition, in the material prepn process, add certain amount of organic solvent (like THF, ether etc.), can effectively improve the efficient of reaction as the reactive behavior agent; If but used organic solvent can not obtain efficient recovery, both can improve the cost of building-up process, also environment is caused pollution to a certain degree.Preparing method provided by the invention adds thermal distillation to used organic solvent, and collects its cut at 68 ℃, and through cooling for reflux technology for recovery organic solvent, flow process is simple at last, and the recovery reaches more than 75%, can effectively reduce cost.
Embodiment
Below in conjunction with specific embodiment the present invention is described in further detail:
Embodiment 1
Light metal composite hydrogen storage material, its chemical formula are Li
1-xNa
xCaAlH
6Metal hydride is got x=0.2; Selecting catalyst is 2 mol% TiF
3, promptly constitute Li
0.8Na
0.2CaAlH
6+ 2 mol% TiF
3The metal coordinate hydride composite hydrogen storage material.
The preparation method of above-mentioned light metal composite hydrogen storage material is following:
At first; With LiH (purity is 95%), NaH (purity is 95%) and Al (purity is 99%) is raw material; Under protection of inert gas; According to LiH: NaH: Al=2.8: 0.2: 1 (mol ratio) uniform mixing, again mixed powder is placed the ball grinder of ball mill and ball grinder sealing is vacuumized; Utilize syringe to injecting the THF of 20ml in the ball grinder subsequently, charge into behind the hydrogen of 2MPa pressure ball milling 12h on ball mill again, (ball-to-powder weight ratio in the mechanical milling process is 40:1, and drum's speed of rotation is 480 rpm) can obtain Li
2.8Na
0.2AlH
6Middle hydrogenate;
Secondly, at synthetic Li
2.8Na
0.2AlH
6Ball grinder in further add the CaCl of equimolar amount
2Powder carries out ball milling 10h (ball-to-powder weight ratio in the mechanical milling process is 20:1, and drum's speed of rotation is 400 rpm), and then prepares NaCaAlH
6Metal hydride and LiCl by product filter, distill and purify the ball-milling reaction product subsequently, to remove the LiCl by product; And in the collection still-process at 68 ℃ cut, reclaim THF through the cooling for reflux method, can obtain purity up to 93% Li
0.8Na
0.2AlH
6Metal hydride;
At last, with the Li that is obtained
0.8Na
0.2AlH
6Metal hydride and the TiF that accounts for said metal hydride total amount 2 mol%
3Catalyzer is mechanical ball milling mixing 1h under the nitrogen atmosphere of 1MPa pressure, finally obtains Li
0.8Na
0.2AlH
6+ 2 mol% TiF
3The light metal composite hydrogen storage material.
To prepared Li
0.8Na
0.2AlH
6+ 2 mol% TiF
3Sample and the same terms be the Li of preparation down
3AlH
6The test of sample contrast carrying out hydrogen discharging performance, its result is as shown in table 1.Can find out Li
0.8Na
0.2AlH
6+ 2 mol% TiF
3Initial hydrogen discharging temperature (128 ℃) compare Li
3AlH
6Initial hydrogen discharging temperature (214 ℃) reduced by 86 ℃; And Li
0.8Na
0.2AlH
6+ 2 mol% TiF
3The Li of putting hydrogen total amount ratio
3AlH
6The hydrogen total amount of putting increased by 1.67 wt.%.In addition, under 200 ℃ of conditions of transferring hydrogen 30min, Li
0.8Na
0.2AlH
6+ 2 mol% TiF
3Can emit 6.05 wt.% hydrogen richnesss, have hydrogen desorption kinetics performance faster.
Embodiment 2
Light metal composite hydrogen storage material, its chemical formula are Li
1-xNa
xCaAlH
6Metal hydride is got x=0.5; Selecting catalyst is 5 mol% NbF
5, promptly constitute Li
0.5Na
0.5CaAlH
6+ 5 mol% NbF
5The metal coordinate hydride composite hydrogen storage material.
The preparation method of above-mentioned light metal composite hydrogen storage material is following:
At first; With LiH (purity is 95%), NaH (purity is 95%) and Al (purity is 99%) is raw material, under protection of inert gas, according to LiH: NaH: Al=2.5: 0.5: 1 (mol ratio) uniform mixing; Addition and method that mixed powder places ball grinder and injects THF are with embodiment 1; Charge into hydrogen ball milling 20h (ball-to-powder weight ratio in the mechanical milling process is 20:1, and drum's speed of rotation is 300 rpm) on ball mill of 5MPa pressure again, can obtain Li
2.5Na
0.5AlH
6Middle hydrogenate;
Secondly, at synthetic Li
2.5Na
0.5AlH
6Ball grinder in further add the CaCl of equimolar amount
2Powder, other preparation parameter be with embodiment 1, can obtain purity subsequently up to 90% Li
0.5Na
0.5AlH
6Metal hydride;
At last, with the Li that is obtained
0.5Na
0.5AlH
6Metal hydride and the NbF that accounts for said metal hydride total amount 5 mol%
5Catalyzer is mechanical ball milling mixing 5h (ball-to-powder weight ratio in the mechanical milling process is 35:1, and drum's speed of rotation is 400 rpm) under the nitrogen atmosphere of 10MPa pressure, finally obtains Li
0.5Na
0.5AlH
6+ 5 mol% NbF
5The light metal composite hydrogen storage material.
To prepared Li
0.5Na
0.5AlH
6+ 5 mol% NbF
5Sample carries out the hydrogen discharging performance test, and its result is as shown in table 1.Can find out Li
0.8Na
0.2AlH
6+ 2 mol% NbF
3Initial hydrogen discharging temperature be merely 96 ℃, the hydrogen total amount of putting under 350 ℃ is 5.49 wt.%, and can reach 5.17 wt.% at 200 ℃ of hydrogen desorption capacities of transferring hydrogen 30min.
Embodiment 3
Light metal composite hydrogen storage material, its chemical formula are Li
1-xNa
xCaAlH
6Metal hydride is got x=1; Selecting catalyst is 1 mol% FeF
3, promptly constitute NaCaAlH
6+ 1 mol% FeF
3The metal coordinate hydride composite hydrogen storage material.
The preparation method of above-mentioned light metal composite hydrogen storage material is following:
At first; With LiH (purity is 95%), NaH (purity is 95%) and Al (purity is 99%) is raw material, under protection of inert gas, according to LiH: NaH: Al=2: 1: 1 (mol ratio) uniform mixing; Addition and method that mixed powder places ball grinder and injects ether are with embodiment 1; Charge into behind the hydrogen of 1MPa pressure ball milling 10h (ball-to-powder weight ratio in the mechanical milling process is 30:1, and drum's speed of rotation is 450 rpm) on ball mill again, can obtain Li
2NaAlH
6Middle hydrogenate;
Secondly, at synthetic Li
2NaAlH
6Ball grinder in further add the CaCl of equimolar amount
2, other preparation parameter is with embodiment 1, can obtain purity subsequently up to 95% NaCaAlH
6Metal hydride;
At last, with the NaCaAlH that is obtained
6Metal hydride and the FeF that accounts for said metal hydride total amount 1 mol%
3Catalyzer is mechanical ball milling mixing 3h (ball-to-powder weight ratio in the mechanical milling process is 30:1, and drum's speed of rotation is 300 rpm) under the nitrogen atmosphere of 5MPa pressure, finally obtains NaCaAlH
6+ 1 mol% FeF
3The light metal composite hydrogen storage material.
To prepared NaCaAlH
6+ 1 mol% FeF
3Sample and the same terms be the Na of preparation down
3AlH
6The test of sample contrast carrying out hydrogen discharging performance, its result is as shown in table 1.Can find out NaCaAlH
6+ 1 mol% FeF
3With Na
3AlH
6Initial hydrogen discharging temperature be respectively 147 ℃ and 248 ℃, i.e. NaCaAlH
6+ 1 mol% FeF
3Compare Na
3AlH
6Initial hydrogen discharging temperature reduce about 100 ℃.In addition, NaCaAlH
6+ 1 mol% FeF
3The hydrogen total amount of putting compare Na
3AlH
6The hydrogen total amount of putting increased by 2.28 wt.%.
The initial hydrogen discharging temperature of the various metal coordinate hydrides of table 1 and hydrogen discharging performance thereof are relatively
In a word, the above is merely preferred embodiment of the present invention, and all equalizations of doing according to claim of the present invention change and modify, and all should belong to the covering scope of patent of the present invention.
Claims (3)
1. light metal composite hydrogen-storage material preparation method for material is characterized in that: described metal composite hydrogen storage material comprises metal hydride and accounts for this metal hydride total amount 0 ~ 5mol%, does not comprise 0, fluoride catalysts, said metal hydride is Li
1-xNa
xCaAlH
6, wherein 0<x<1, described fluoride catalysts is TiF
3, LaF
3, CeF
3, NbF
5, FeF
3, CoF
2And NiF
2In any, said metal composite hydrogen storage material preparation method may further comprise the steps:
(1) under protection of inert gas atmosphere, with LiH, NaH and Al powder raw material according to Li
3-xNa
xAlH
6, 0<x<1, the proportion relation uniform mixing, again mixed powder is placed the ball grinder of ball mill and ball grinder sealing is vacuumized; Utilize syringe to injecting organic solvent in the ball grinder subsequently, charge into behind the hydrogen of 1 5MPa pressure ball milling 10 20h on ball mill again, can obtain Li at last
3-xNa
xAlH
6Middle hydrogenate;
(2) at synthetic Li
3-xNa
xAlH
6Ball grinder in further add the CaCl of equimolar amount
2Powder carries out ball milling 10h, can pass through Li
+And Ca
2+Ionic replacement(metathesis)reaction and prepare Li
1-xNa
xCaAlH
6Metal hydride and LiCl by product filter, distill and purify the ball-milling reaction product subsequently, remove the LiCl by product and organic solvent is reclaimed, and can obtain highly purified Li
1-xNa
xCaAlH
6Metal hydride;
(3) with the Li that is obtained
1-xNa
xCaAlH
6Metal hydride with account for said metal hydride total amount 0 ~ 5 mol%, do not comprise 0, fluoride catalysts mechanical ball milling under the nitrogen atmosphere of 1 ~ 10MPa pressure mix 1 ~ 5h, finally obtain the light metal composite hydrogen storage material.
2. light metal composite hydrogen-storage material preparation method for material according to claim 1 is characterized in that: the ball-to-powder weight ratio in the described mechanical milling process is 20 ~ 40:1, and drum's speed of rotation is 300 ~ 480rpm.
3. light metal composite hydrogen-storage material preparation method for material according to claim 1 is characterized in that: said organic solvent is any in THF and the ether.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104016302A (en) * | 2014-05-24 | 2014-09-03 | 罗文浪 | A rare earth alloy slurry hydrogen storage device and a hydrogen storage method thereof |
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2011
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| CN101264863A (en) * | 2008-04-18 | 2008-09-17 | 浙江大学 | Method for synthesizing metal coordinate hydride hydrogen-storing material directly by reaction ball milling |
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| CN104016302A (en) * | 2014-05-24 | 2014-09-03 | 罗文浪 | A rare earth alloy slurry hydrogen storage device and a hydrogen storage method thereof |
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