CN101920973A - Method for preparing porous aluminum diboride - Google Patents

Method for preparing porous aluminum diboride Download PDF

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Publication number
CN101920973A
CN101920973A CN 201010269894 CN201010269894A CN101920973A CN 101920973 A CN101920973 A CN 101920973A CN 201010269894 CN201010269894 CN 201010269894 CN 201010269894 A CN201010269894 A CN 201010269894A CN 101920973 A CN101920973 A CN 101920973A
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hydrogen
libh
alb
preparation
lialh
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CN101920973B (en
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陈如柑
王新华
陈立新
李寿权
葛红卫
陈长聘
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Zhejiang University ZJU
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Abstract

The invention discloses a method for preparing porous aluminum diboride (AlB2). The porous AlB2 is prepared from LiAlH4 and LiBH4 serving as raw materials, wherein the molar ratio of the LiAlH4 to the LiBH4 is 1:1-1:3. Through the method, the LiAlH4 is used as an initial raw material instead of pure Al and is heated and decomposed to generate Al particles with high degree of dispersion; and as the particles do not contain any oxide coating, the particles have remarkably high activity. Moreover, the AlB2 prepared by reacting the LiAlH4 instead of the Al with the LiBH4 is porous powder, the specific area is increased, and a channel for hydrogen to disperse from the surface toward the inside is provided, so the hydrogen absorption dynamic performance of the AlB2 is obviously improved.

Description

A kind of preparation method of porous aluminum diboride
Technical field
The present invention relates to the preparation field of porous metal compound, be specifically related to a kind of preparation method of porous aluminum diboride.
Background technology
Hydrogen Energy is a kind of green, the reproducible energy, has a good application prospect.But Hydrogen Energy is before being able to widespread use, at first will search out the material of a large amount of hydrogen gas storages of a kind of energy.As a kind of new type of metal complex hydrides, lithium borohydride (LiBH 4) the Theoretical Mass hydrogen-storage density up to 18.3%, can satisfy the application demand that moves the storage hydrogen carrier well.But, LiBH 4The reversal condition harshness, lithium hydride (LiH) and pure boron (B) need just can react under the hydrogen condition of 600 ℃ and 35MPa and generate LiBH 4Intermetallic compound be meant metal and metal or and metalloid element between the compound that forms; Bibliographical information, intermetallic compound AlB 2Under comparatively gentle condition, can generate LiBH with LiH and hydrogen reaction 4(Friedrichs O, Kim JW, Remhof A, Buchter F, Borgschulte A, Wallacher D, Cho YW, Fichtner M, Oh KH, Zuttel A.Theeffect of Al on the hydrogen sorption mechanism of LiBH 4.PhysicalChemistry Chemical Physics, 2009 (11) 1515-1520).Present studies show that, the diffusion of hydrogen is restriction LiBH 4The regenerated principal element.Thereby, prepare AlB with vesicular structure 2, to improving LiBH 4Regenerative power is learned performance and is had material impact.
Pure aluminum and boron generate AlB 2Eutectic temperature be about 980 ℃.The fusing point of Al is about 660 ℃, far below 2027 ℃ of the fusing points of B, because fusing point difference great disparity prepares AlB by the fused method 2Feasibility is not high.Existing bibliographical information, pure aluminum and lithium borohydride can react and generate AlB 2(DjordjeMirkovic, Joachim Grobner, Rainer Schmid-Fetzer, Olga Fabrichnaya, HansLeo Lukas, Experimental study and thermodynamic re-assessment of Al-Bsystem.Journal of Alloys and Compounds, 384 (2004) 168-174.).Usually, common Al particle top layer is coated with the oxide film of one deck densification, has seriously reduced Al particulate activity; Simultaneously because common Al particulate granularity is bigger, disperse inhomogeneous, thereby can not same well LiBH 4Reaction generates AlB 2
Summary of the invention
The invention provides a kind of preparation method of porous aluminum diboride, this method is simple to operate, is suitable for suitability for industrialized production.
A kind of preparation method of porous aluminum diboride comprises:
With lithium aluminum hydride (LiAlH 4) and lithium borohydride (LiBH 4) be raw material, preparation has the aluminium diboride (AlB of vesicular structure 2); Described LiAlH 4And LiBH 4Mol ratio be 1: 1～1: 3.
The present invention finds to have the AlB of vesicular structure 2Can improve LiAlH well 4-LiBH 4Compound system is put the speed that the hydrogen sample is inhaled hydrogen again.If LiBH 4Amount very little, the AlB of Sheng Chenging then 2Porosity will reduce; On the contrary, if LiBH 4Amount too much, unnecessary B then is coated on the powder particle skin, can not generate this vesicular structure equally.
In order to economize on resources, and reach effect better, preferred:
Described porous Al B 2The preparation method, specifically comprise step:
(1) with LiAlH 4And LiBH 4After the mixing, mechanical ball milling mixes it under protection of inert gas, obtains LiAlH 4And LiBH 4Mixture;
(2) to above-mentioned LiAlH 4And LiBH 4Feed hydrogen in the mixture, be warming up to 450 ℃～550 ℃ (preferred 500 ℃), make AlB with vesicular structure 2
In the step (1), the time of mechanical ball milling is 4.5h～5.5h, further preferred 5h.
Described rare gas element comprises the rare gas element in the broad scope of this area, generally selects a kind of in nitrogen, helium, the argon gas etc. for use.
In the step (2), the temperature rise rate during intensification is 1 ℃/min～5 ℃/min.
The pressure of described hydrogen is 2atm～5atm; The pressure of hydrogen is too low, the more difficult same LiBH of Al 4React and generate AlB 2The pressure of hydrogen is too high, LiBH 4Decomposition temperature is too high, AlB 2Productive rate reduce equally.
Porous Al B of the present invention 2Under 400 ℃～500 ℃ (preferred 450 ℃) and 7MPa～10MPa (preferred 8MPa) hydrogen pressure, inhale hydrogen again, can generate LiBH 4General adopt existing method, as with AlB 2With LiH be raw material, in hydrogen, react, make the LiBH of hydrogen gas storage 4Concrete reaction equation is as follows:
AlB 2+2LiH+3H 2→2LiBH 4+Al
Compared with prior art, the present invention has following advantage:
The present invention LiAlH 4Instead of pure Al is as initial feed, LiAlH 4Decomposes will produce the Al particle of high diffusive degree, because these particles do not contain the oxide compound coating layer, thereby have very high activity.In addition, with LiAlH 4Substitute for Al and LiBH 4The AlB of prepared in reaction 2Be a kind of body of powder, also for hydrogen diffusion from the surface to the internal provides passage, thereby significantly improve AlB when increasing reference area with vesicular structure 2Suction hydrogen dynamic performance.
Description of drawings
Fig. 1 is the X ray diffracting spectrum of different steps product among the embodiment 1;
Fig. 2 is the AlB of embodiment 1 preparation 2Suction hydrogen curve;
Fig. 3 is the AlB of embodiment 4 preparations 2Microscopic appearance figure;
Fig. 4 is the AlB of embodiment 5 preparations 2Microscopic appearance figure;
Fig. 5 is the AlB of embodiment 6 preparations 2Microscopic appearance figure;
Fig. 6 is the AlB of Comparative Examples 1 preparation 2Microscopic appearance figure.
Embodiment
In following each embodiment and the Comparative Examples, productive rate is meant AlB 2Shared weight percentage in product.
Embodiment 1
With LiAlH 4, LiBH 4Be 1: 2 mixed in molar ratio, put into a stainless steel jar mill together with hard ball, feed argon gas as protection gas, mechanical ball milling mixed it in 5 hours.The mixture that mechanical ball milling is good joins reactor, feeds the hydrogen of 2atm, progressively is heated to 500 ℃ with the temperature rise rate of 1 ℃/min, makes the AlB with vesicular structure 2, its productive rate is 72.1%, finds out the AlB that makes from its microscopic appearance figure 2Has vesicular structure.
With the above-mentioned AlB for preparing 2And LiH (AlB 2With the mol ratio of LiH be 1: 2) under 450 ℃ and 8MPa hydrogen pressure, inhale hydrogen again, generate LiBH 4
The X ray diffracting spectrum of the mixture that above-mentioned mechanical ball milling is good has the AlB of vesicular structure shown in Fig. 1 (a) 2X ray diffracting spectrum shown in Fig. 1 (b), AlB 2Again inhale the LiBH that hydrogen generates 4X ray diffracting spectrum shown in Fig. 1 (c).Above-mentioned AlB 2Suction hydrogen curve such as Fig. 2.
By Fig. 1 (b) as can be known, LiAlH 4Decompose to produce evenly, the Al particle of disperse fully and LiBH 4React, the product that obtains at last is the higher AlB of purity 2
By Fig. 1 (c) as can be known, the AlB for preparing 2Generated LiBH after under 450 ℃ and 8MPa condition, inhaling hydrogen 4, this generates LiBH far below LiH and pure boron reaction 4Required 600 ℃ and the condition of 35MPa hydrogen pressure.
As shown in Figure 2, the AlB of this vesicular structure 2Have quick hydrogen-absorbing ability, preceding 50 minutes hydrogen (weight percentage) is that 4.88%, 600 minute hydrogen (weight percentage) is 6.80%.
Embodiment 2
With LiAlH 4, LiBH 4Be 1: 2 mixed in molar ratio, put into a stainless steel jar mill together with hard ball, feed nitrogen as protection gas, mechanical ball milling mixed it in 5 hours.The mixture that mechanical ball milling is good joins reactor, feeds the hydrogen of 3.5atm, progressively is heated to 500 ℃ with the temperature rise rate of 5 ℃/min, makes the AlB with vesicular structure 2, its productive rate is 72.8%, finds out the AlB that makes from its microscopic appearance figure 2Has vesicular structure.
With the above-mentioned AlB for preparing 2And LiH (AlB 2With the mol ratio of LiH be 1: 2) under 450 ℃ and 8MPa hydrogen pressure, inhale hydrogen again, generate LiBH 4
The preceding 50 minutes hydrogen (weight percentage) of this sample is that 5.02%, 600 minute hydrogen (weight percentage) is 6.97%.
Embodiment 3
With LiAlH 4, LiBH 4Be 1: 2 mixed in molar ratio, put into a stainless steel jar mill together with hard ball, feed argon gas as protection gas, mechanical ball milling mixed it in 5 hours.The mixture that mechanical ball milling is good joins reactor, feeds the hydrogen of 5atm, progressively is heated to 500 ℃ with the temperature rise rate of 3 ℃/min, makes the AlB with vesicular structure 2, its productive rate is 71.6%, finds out the AlB that makes from its microscopic appearance figure 2Has vesicular structure.
With the above-mentioned AlB for preparing 2And LiH (AlB 2With the mol ratio of LiH be 1: 2) under 450 ℃ and 8MPa hydrogen pressure, inhale hydrogen again, generate LiBH 4
The preceding 50 minutes hydrogen (weight percentage) of this sample is that 4.95%, 600 minute hydrogen (weight percentage) is 6.93%.
Embodiment 4
With LiAlH 4, LiBH 4Be 1: 1 mixed in molar ratio, put into a stainless steel jar mill together with hard ball, feed argon gas as protection gas, mechanical ball milling mixed it in 5 hours.The mixture that mechanical ball milling is good joins reactor, feeds the hydrogen of 2atm, progressively is heated to 500 ℃ with the temperature rise rate of 3 ℃/min, makes the AlB with vesicular structure 2, its productive rate is 45.8%, its microscopic appearance figure shows the AlB that makes as shown in Figure 3 2Has vesicular structure.
With the above-mentioned AlB for preparing 2And LiH (AlB 2With the mol ratio of LiH be 1: 2) under 450 ℃ and 8MPa hydrogen pressure, inhale hydrogen again, generate LiBH 4
The preceding 50 minutes hydrogen (weight percentage) of this sample is that 3.66%, 600 minute hydrogen (weight percentage) is 4.41%.
Embodiment 5
With LiAlH 4, LiBH 4Be 1: 2 mixed in molar ratio, put into a stainless steel jar mill together with hard ball, feed argon gas as protection gas, mechanical ball milling mixed it in 5 hours.The mixture that mechanical ball milling is good joins reactor, feeds the hydrogen of 2atm, progressively is heated to 500 ℃ with the temperature rise rate of 3 ℃/min, makes the AlB with vesicular structure 2, its productive rate is 71.7%, its microscopic appearance figure shows the AlB that makes as shown in Figure 4 2Has vesicular structure.
With the above-mentioned AlB for preparing 2And LiH (AlB 2With the mol ratio of LiH be 1: 2) under 450 ℃ and 8MPa hydrogen pressure, inhale hydrogen again, generate LiBH 4
The preceding 50 minutes hydrogen (weight percentage) of this sample is that 4.69%, 600 minute hydrogen (weight percentage) is 6.74%.
Embodiment 6
With LiAlH 4, LiBH 4Be 1: 3 mixed in molar ratio, put into a stainless steel jar mill together with hard ball, feed argon gas as protection gas, mechanical ball milling mixed it in 5 hours.The mixture that mechanical ball milling is good joins reactor, feeds the hydrogen of 2atm, progressively is heated to 500 ℃ with the temperature rise rate of 3 ℃/min.Because unnecessary B covers AlB 2The surface, the AlB that makes 2Vesicular structure is not obvious, and its productive rate is 48.2%, and its microscopic appearance figure as shown in Figure 5.
With the above-mentioned AlB for preparing 2And LiH (AlB 2With the mol ratio of LiH be 1: 2) under 450 ℃ and 8MPa hydrogen pressure, inhale hydrogen again, generate LiBH 4
The preceding 50 minutes hydrogen (weight percentage) of this sample is that 5.41%, 600 minute hydrogen (weight percentage) is 5.88%.
Comparative Examples 1
With Al, LiBH 4Be 1: 2 mixed in molar ratio, put into a stainless steel jar mill together with hard ball, feed argon gas as protection gas, mechanical ball milling mixed it in 5 hours.The mixture that mechanical ball milling is good joins reactor, feeds the hydrogen of 2atm, progressively is heated to 500 ℃ with the temperature rise rate of 3 ℃/min, makes blocky AlB 2, its productive rate is 8.1%, its microscopic appearance figure as shown in Figure 6, X ray diffracting spectrum is shown in Fig. 1 (d).
The above-mentioned AlB that obtains 2Be a kind of lumphy structure, as can be seen from Figure 6: because most Al particle and have neither part nor lot in reaction, LiBH 4Decompose the pure boron and the LiH that produce and be coated on Al particle top layer, form loose coating layer.
From Fig. 1 (d) as can be known, with Al and LiBH 4Can only obtain a spot of AlB by 1: 2 molar ratio reaction 2, this is because the Al particle size is bigger, disperses inhomogeneously, and simultaneously there is oxide skin on the top layer, and the lower reason of activity causes.
With the above-mentioned AlB for preparing 2And LiH (AlB 2With the mol ratio of LiH be 1: 2) under 450 ℃ and 8MPa hydrogen pressure, inhale hydrogen again, generate LiBH 4
The preceding 50 minutes hydrogen (weight percentage) of this sample is that 0.7%, 600 minute hydrogen (weight percentage) is 1.2%.

Claims (6)

1. the preparation method of a porous aluminum diboride comprises: with LiAlH 4And LiBH 4Be raw material, preparation has the aluminium diboride of vesicular structure; Described LiAlH 4And LiBH 4Mol ratio be 1: 1～1: 3.
2. the preparation method of porous aluminum diboride according to claim 1 is characterized in that, comprises step:
(1) with LiAlH 4And LiBH 4After the mixing, mechanical ball milling mixes it under protection of inert gas, obtains LiAlH 4And LiBH 4Mixture;
(2) to above-mentioned LiAlH 4And LiBH 4Feed hydrogen in the mixture, be warming up to 450 ℃～550 ℃, make aluminium diboride with vesicular structure.
3. the preparation method of porous aluminum diboride according to claim 2 is characterized in that, in the step (1), the time of mechanical ball milling is 4.5h～5.5h.
4. the preparation method of porous aluminum diboride according to claim 2 is characterized in that, in the step (1), described rare gas element is a kind of in nitrogen, helium, the argon gas.
5. the preparation method of porous aluminum diboride according to claim 2 is characterized in that, in the step (2), the temperature rise rate during intensification is 1 ℃/min～5 ℃/min.
6. the preparation method of porous aluminum diboride according to claim 2 is characterized in that, in the step (2), the pressure of described hydrogen is 2atm～5atm.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102965685A (en) * 2012-12-19 2013-03-13 东北大学 Method for preparing aluminum dodecaboride
RU2603793C1 (en) * 2015-11-12 2016-11-27 Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский Томский государственный университет" (ТГУ) Method of producing aluminium diboride
CN108862298A (en) * 2018-05-28 2018-11-23 北京理工大学 A kind of aluminium diboride raw powder's production technology
CN111333077A (en) * 2020-02-14 2020-06-26 中国科学院金属研究所 Preparation method of high-purity aluminum diboride
CN115108817A (en) * 2022-06-17 2022-09-27 无锡畾田陶瓷科技有限公司 Environment-friendly wear-resistant ceramic brick and preparation process thereof

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US20060013766A1 (en) * 2004-03-26 2006-01-19 Vajo John J Methods for reversibly storing hydrogen
CN101734622A (en) * 2009-12-24 2010-06-16 浙江大学 Preparation method of hydrogen storage material of Li-Al-H complex hydride
CN101817504A (en) * 2010-04-20 2010-09-01 浙江大学 Solid-liquid borohydride composite hydrogen storage material and preparation method thereof

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Publication number Priority date Publication date Assignee Title
US20060013766A1 (en) * 2004-03-26 2006-01-19 Vajo John J Methods for reversibly storing hydrogen
CN101734622A (en) * 2009-12-24 2010-06-16 浙江大学 Preparation method of hydrogen storage material of Li-Al-H complex hydride
CN101817504A (en) * 2010-04-20 2010-09-01 浙江大学 Solid-liquid borohydride composite hydrogen storage material and preparation method thereof

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102965685A (en) * 2012-12-19 2013-03-13 东北大学 Method for preparing aluminum dodecaboride
RU2603793C1 (en) * 2015-11-12 2016-11-27 Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский Томский государственный университет" (ТГУ) Method of producing aluminium diboride
CN108862298A (en) * 2018-05-28 2018-11-23 北京理工大学 A kind of aluminium diboride raw powder's production technology
CN111333077A (en) * 2020-02-14 2020-06-26 中国科学院金属研究所 Preparation method of high-purity aluminum diboride
CN111333077B (en) * 2020-02-14 2022-11-22 中国科学院金属研究所 Preparation method of high-purity aluminum diboride
CN115108817A (en) * 2022-06-17 2022-09-27 无锡畾田陶瓷科技有限公司 Environment-friendly wear-resistant ceramic brick and preparation process thereof

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