CN102320570B - Preparation method of high-hydrogen-storage-quantity boron ammonate aluminum hydride series hydrogen storage material - Google Patents

Preparation method of high-hydrogen-storage-quantity boron ammonate aluminum hydride series hydrogen storage material Download PDF

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CN102320570B
CN102320570B CN 201110163002 CN201110163002A CN102320570B CN 102320570 B CN102320570 B CN 102320570B CN 201110163002 CN201110163002 CN 201110163002 CN 201110163002 A CN201110163002 A CN 201110163002A CN 102320570 B CN102320570 B CN 102320570B
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CN102320570A (en
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余学斌
郭艳辉
江亦潇
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Fudan University
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Fudan University
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Abstract

The invention relates to a preparation method of a high-hydrogen-storage-quantity boron ammonate aluminum hydride series hydrogen storage material, which has a structural formula of Al(BH4)3.nNH3, wherein n is smaller or equal to 5 but greater than 1, in the method, Al(BH4)3 gas obtained through the mixed heating reaction of hydroborate, anhydrous aluminum salts and aluminum powder takes contact reaction with Al(BH4)3.6NH3, and the Al(BH4)3.nNH3 high-hydrogen-storage-quantity hydrogen storage material with different n values is prepared through controlling the preparation conditions and processing the products. Further, the prepared Al(BH4)3.nNH3 takes ball mill reaction with the LiBH4, and an Al(BH4)3.nNH3+xLiBH4 composite hydrogen storage system is prepared.

Description

The preparation method of the ammino aluminum borohydride series hydrogen storage material of high hydrogen storage
Technical field
The invention belongs to technical field of material, be specifically related to a kind of preparation method of ammino aluminum borohydride series hydrogen storage material of high hydrogen storage.
Background technology
Along with the world energy sources consumption increases rapidly, face exhaustion as the Nonrenewable resources such as fossil oil of current energy main body, meanwhile other by products of greenhouse gases and fossil oil production capacity are more serious on the impact that global environment causes 1-4It is day by day urgent to set up the new energy system take renewable and clean energy resource as main body.
Hydrogen Energy is with its high element reserves, heats of combustion, and cleanliness without any pollution, the plurality of advantages such as renewable has critical role in the research of new forms of energy system development 2-4But because low density and the low condensing temperature of hydrogen, traditional high-pressure gaseous tank and low temperature liquid tank can't satisfy application demand 2,4-5, so solid-state hydrogen storage material becomes study hotspot in recent years.
Light metal hydroborate ammonia complex (M (BH 4) mNNH 3) having more superior hydrogen discharging performance, it mainly puts hydrogen mechanism and amino borane (NH 3BH 3) similar, for the negative valency hydrogen of the nominal price hydrogen in the hydrogen bound to nitrogen in the boron hydrogen bond is combined (N-H-H-B) again 6-11Such hydrogen storage material that present document has been reported mainly contains Mg (BH 4) 22NH 3, theoretical hydrogen content 16.0 wt % are at 150 ℃ of beginning decomposing hydrogen 6LiBH 4NH 3, theoretical hydrogen content 18.0 wt % 7-9, at 280 ℃ of beginning decomposing hydrogen 8-9Ca (BH 4) 22NH 3, theoretical hydrogen content 13.5 wt % are at 190 ℃ of beginning decomposing hydrogen 10Al (BH 4) 36NH 3, theoretical hydrogen content 17.4 wt %, beginning decomposing hydrogen between 60-180 ℃ 11
The common issue with that this class material faces is that the thermal degradation process also can discharge ammonia except release hydrogen 6-11We can be by making this class material thermal degradation under ammonia atmosphere 6,8-9And adding metal chloride (MCl x) or metal hydride (MH x) etc. component make the combination that ammonia in the method stable comple of mixture promotes two hydrogen bonds 8-9,11, make and put the hydrogen purity raising.Wherein because Al (BH 4) 36NH 3The ammonia number higher, nominal price hydrogen is more than negative valency hydrogen, superfluous ammonia discharges in the thermal degradation process 11, so we can be by reducing Al (BH 4) 36NH 3The ammonia number method of nominal price hydrogen and negative valency hydrogen equity is improved put hydrogen purity 6,10-11In the time of this external reduction ammonia number, begin to decompose hydrogen discharging temperature and also can decrease 11, be to kill two birds with one stone.
Reference:
1、Zuttel, A; Remhof, A; Borgschulte, A, et al., Phil. Trans. R. Soc. A (2010) 368, 3329–3342。
2、Deng, ZY; Ferreira, JMF; Sakka, Y, J. Am. Ceram. Soc., 91 [12] 3825–3834 (2008)。
3、Graetz, J, Chem. Soc. Rev., 2009, 38, 73–82。
4、Armaroli, N; Balzani, V, Chem Sus Chem 2011, 4, 21–36。
5、Lim, KL; Kazemian, H; Yaakob, Z, et al., Chem. Eng. Technol. 2010, 33, No. 2, 213–226。
6、Soloveichik, G; Her, JH; Stephens, PW, et al., Inorg. Chem. 2008, 47, 4290-4298。
7、Johnson, SR; David, WIF; Royse, DM, et al., Chem. Asian J. 2009, 4, 849 – 854。
8、Guo, YH; Xia, GL; Zhu, YH, et al., Chem. Commun., 2010, 46, 2599–2601。
9、Guo, YH; Sun, WW; Guo, ZP, et al., J. Phys. Chem. C 2010, 114, 12823–12827。
10、Chu, HL; Wu, GT; Xiong, ZT, et al., Chem. Mater. 2010, 22, 6021–6028。
11、Guo, YH; Yu, XB; Sun, WW, et al., Angew. Chem. Int. Ed. 2011, 50, 1087 –1091。
Summary of the invention
The object of the invention is to provide the preparation method of the ammino aluminum borohydride series hydrogen storage material of the simple high hydrogen storage of a kind of technique.
The preparation method of the ammino aluminum borohydride series hydrogen storage material of the high hydrogen storage that the present invention proposes, the structural formula of described hydrogen storage material is Al (BH 4) 3NNH 3, wherein: 5 〉=n〉and 1, concrete steps are as follows:
Under anhydrous and oxygen-free atmosphere, hydroborate, anhydrous aluminium salt are mixed with aluminium powder, reacting by heating discharges Al (BH under 10-80 ℃ of temperature 4) 3Gas, Al (BH 4) 3Gas and Al (BH 4) 36NH 3Contact reacts 4-8 hour, reduce the ammonia ligancy; Products therefrom carries out ball-milling processing, namely gets required product; Wherein: BH 4 -With Al 3+Mol ratio is 1:2.0-1:5, and aluminium powder accounts for the 5%-50% of raw material hydroborate, anhydrous aluminium salt and aluminium powder gross weight.
Pure Al (BH 4) 36NH 3Place Al (BH 4) 3React in the atmosphere, synthetic route is as follows:
5Al(BH 4) 3·6NH 3(s) +Al(BH 4) 3(g) → 6Al(BH 4) 3·5NH 3(s) (1)
4Al(BH 4) 3·5NH 3(s) +Al(BH 4) 3(g) → 5Al(BH 4) 3·4NH 3(s) (2)
3Al(BH 4) 3·4NH 3(s) +Al(BH 4) 3(g) → 4Al(BH 4) 3·3NH 3(s) (3)
2Al(BH 4) 3·3NH 3(s) +Al(BH 4) 3(g) → 3Al(BH 4) 3·2NH 3(s) (4)
Among the present invention, described hydroborate comprises in lithium borohydride, sodium borohydride, POTASSIUM BOROHYDRIDE or the calcium borohydride any.
Among the present invention, in the non-oxidizable aluminium salt such as halogenide, Tai-Ace S 150 or aluminium carbonate that described anhydrous aluminium salt is aluminium any.
Among the present invention, described Al (BH 4) 3Gas and Al (BH 4) 36NH 3The contact reacts temperature is 30-60 ℃.
Among the present invention, described ball-milling processing, ball material weight ratio 5:1-10:1, rotating speed 100-400 rev/min, Ball-milling Time is 1-5 hour.
Al (the BH that handy the inventive method obtains 4) 3NNH 3Can be for the synthesis of Al (BH 4) 3NNH 3+ xLiBH 4Compound system, concrete steps are: with the Al (BH that makes 4) 3NNH 3With LiBH 4Ball-milling reaction, when using ball milled, ball material weight ratio is 5:1-10:1, rotating speed 100-400 rev/min, Ball-milling Time is 1-12 hour.
Among the present invention, described anhydrous and oxygen-free atmosphere is vacuum or inert atmosphere, and described inert atmosphere is nitrogen or argon gas atmosphere.
The present invention has the following aspects remarkable advantage:
1) preparation technology is simple, and is synthetic convenient.
2) preparation technology is not high to equipment requirements, is easy to realize.
Description of drawings
Fig. 1 is Al (BH 4) 3NNH 3The XRD contrast spectrogram of (n=3,4,5,6).
Fig. 2 is Al (BH 4) 35NH 3Thermogravimetric-mass spectrum.Wherein: temperature rise rate 5 oC/min, argon gas atmosphere.Among the figure ● be H 2M/e=2, zero is NH 3M/e=16, ☆ are B 2H 6M/e=26.
Fig. 3 is Al (BH 4) 34NH 3Thermogravimetric-mass spectrum.Wherein: temperature rise rate 5 oC/min, argon gas atmosphere.Among the figure ● be H 2M/e=2, zero is NH 3M/e=16, ☆ are B 2H 6M/e=26.
Fig. 4 is Al (BH 4) 33NH 3Thermogravimetric-mass spectrum.Wherein: temperature rise rate 5 oC/min, argon gas atmosphere.Among the figure ● be H 2M/e=2, zero is NH 3M/e=16, ☆ are B 2H 6M/e=26.
Fig. 5 is Al (BH 4) 34NH 3-2LiBH 4Thermogravimetric-mass spectrum.Temperature rise rate 5 oC/min, argon gas atmosphere.
Embodiment
Further specify the present invention below by embodiment.
1, Al (BH 4) 35NH 3Preparation
In glove box under the argon gas atmosphere with 0.75gAlCl 3, 0.342gLiBH 4Place the heating of diameter 30mm test tube mixing with the 0.162gAl powder, again with 0.167g Al (BH 4) 36NH 3Place 25 * 25mm tall regular weighing bottle to hang on this test tube.20 ℃ of lower reactions are taken out in the weighing bottle product and are weighed after about 8 hours, it is about 8% to increase weight, and namely is mainly Al (BH 4) 35NH 3This product is sealed the taking-up ball milling behind the ball grinder of packing into.Ball milling condition is: frequency is 20-25Hz, joins the stainless steel ball-milling steel ball, and diameter is at 0.5-1cm, and Ball-milling Time is 2-3 hour, and operational mode is for alternately restarting, and alternately the time is 6 minutes.Fig. 1 Al (BH 4) 35NH 3XRD result and Fig. 2 Al (BH 4) 35NH 3Product thermogravimetric-mass spectrum result, all with Al (BH 4) 36NH 3Different, show Al (BH 4) 36NH 3With newly-generated Al (BH 4) 3Reaction has occured, and its decomposability also changes to some extent.
2, Al (BH 4) 34NH 3Preparation
In glove box under the argon gas atmosphere with 0.731gAlCl 3, 0.328gLiBH 4Place the heating of diameter 30mm test tube mixing with the 0.164gAl powder, again with 0.165g Al (BH 4) 36NH 3Place 25 * 25mm tall regular weighing bottle to hang on this test tube.30 ℃ of lower reactions are taken out in the weighing bottle product and are weighed after about 6 hours, it is about 21% to increase weight, and namely is mainly Al (BH 4) 34NH 3This product is sealed the taking-up ball milling behind the ball grinder of packing into.Ball milling condition is: frequency is 20-25Hz, joins the stainless steel ball-milling steel ball, and diameter is at 0.5-1cm, and Ball-milling Time is 2-3 hour, and operational mode is for alternately restarting, and alternately the time is 6 minutes.Fig. 1 Al (BH 4) 34NH 3XRD result to report that the result is similar, confirm to have occured corresponding reaction, Fig. 3 Al (BH 4) 34NH 3Thermogravimetric-mass spectrum result show that this material has excellent hydrogen discharging performance, is heated to 350 ℃ of pure hydrogen that can discharge about 15.5wt.%.
3, Al (BH 4) 33NH 3Preparation
In glove box under the argon gas atmosphere with 0.708gAlCl 3, 0.315gLiBH 4Place the heating of diameter 30mm test tube mixing with the 0.164gAl powder, again with 0.164g Al (BH 4) 36NH 3Place 25 * 25mm tall regular weighing bottle to hang on this test tube.35 ℃ of lower reactions are taken out in the weighing bottle product and are weighed after about 7 hours, about 41 % that increase weight namely are mainly Al (BH 4) 33NH 3This product is sealed the taking-up ball milling behind the ball grinder of packing into.Ball milling condition is: frequency is 20-25Hz, joins the stainless steel ball-milling steel ball, and diameter is at 0.5-1cm, and Ball-milling Time is 2-3 hour, and operational mode is for alternately restarting, and alternately the time is 6 minutes.Fig. 1 Al (BH 4) 33NH 3XRD result and Al (BH 4) 3NNH 3(n=4,5,6) are all not identical, confirmed the generation of novel substance; Fig. 4 is Al (BH 4) 33NH 3Thermogravimetric-mass spectrum result, this material has comparatively ideal hydrogen discharging temperature as seen from the figure, is heated to 90 ℃ and namely begins to put hydrogen, the hydrogen that heating discharges is gas free from foreign meter also, is heated to 350 ℃ of pure hydrogen that can discharge about 13.7wt.%, the hydrogen discharging performance excellence.
4, Al (BH 4) 32NH 3Preparation
In glove box under the argon gas atmosphere with 0.771gAlCl 3, 0.352gLiBH 4Place the heating of diameter 30mm test tube mixing with the 0.174gAl powder, again with 0.164g Al (BH 4) 36NH 3Place 25 * 25mm tall regular weighing bottle to hang on this test tube.40 ℃ of lower reactions are taken out in the weighing bottle product and are weighed after about 10 hours, it is about 82% to increase weight, and namely is mainly Al (BH 4) 32NH 3This product is ground aftertreatment.
5, Al (BH 4) 34NH 3+ 2LiBH 4The preparation of compound system
In glove box under the argon gas atmosphere with 0.155gAl (BH 4) 34NH 3And 0.048gLiBH 4The sealing of packing into behind the ball grinder is taken out the ball milling ball milling condition and is: frequency is 20-25Hz, joins the stainless steel ball-milling steel ball, and diameter is at 0.5-1cm, and Ball-milling Time is 2-3 hour, and operational mode is for alternately restarting, and the time of replacing is 6 minutes.Fig. 5 is Al (BH 4) 34NH 3-2LiBH 4Thermogravimetric-mass spectrum result, this material has comparatively ideal hydrogen discharging temperature as seen from the figure, is heated to 80 ℃ and namely begins to put hydrogen, the hydrogen that heating discharges is gas free from foreign meter also, is heated to 350 ℃ of pure hydrogen that can discharge about 15 wt.%, hydrogen discharging performance is excellent.

Claims (7)

1. the preparation method of the ammino aluminum borohydride of high hydrogen storage series hydrogen storage material, the structural formula that it is characterized in that described hydrogen storage material is Al (BH 4) 3NNH 3, wherein: 5 〉=n〉and 1, concrete steps are as follows:
Under anhydrous and oxygen-free atmosphere, hydroborate, anhydrous aluminium salt are mixed with aluminium powder, reacting by heating discharges Al (BH under 10-80 ℃ of temperature 4) 3Gas, Al (BH 4) 3Gas and Al (BH 4) 36NH 3Contact reacts 4-8 hour, reduce the ammonia ligancy; Products therefrom carries out ball-milling processing, namely gets required product; Wherein: BH 4 -With Al 3+Mol ratio is 1:2.0-1:5, and aluminium powder accounts for the 5%-50% of raw material hydroborate, anhydrous aluminium salt and aluminium powder gross weight.
2. preparation method according to claim 1 is characterized in that described hydroborate comprises in lithium borohydride, sodium borohydride, POTASSIUM BOROHYDRIDE or the calcium borohydride any.
3. preparation method according to claim 1 is characterized in that in halogenide, Tai-Ace S 150 or the aluminium carbonate that described anhydrous aluminium salt is aluminium any.
4. preparation method according to claim 1 is characterized in that described Al (BH 4) 3Gas and Al (BH 4) 36NH 3The contact reacts temperature is 30-60 ℃.
5. preparation method according to claim 1 is characterized in that described ball-milling processing, ball material weight ratio 5:1-10:1, and rotating speed 100-400 rev/min, Ball-milling Time is 1-5 hour.
6. preparation method according to claim 1 is characterized in that the Al (BH of gained 4) 3NNH 3For the synthesis of Al (BH 4) 3NNH 3+ xLiBH 4Compound system, concrete steps are: with the Al (BH that makes 4) 3NNH 3With LiBH 4Ball-milling reaction, when using ball milled, ball material weight ratio is 5:1-10:1, rotating speed 100-400 rev/min, Ball-milling Time is 1-12 hour.
7. preparation method according to claim 1 is characterized in that described anhydrous and oxygen-free atmosphere is vacuum or inert atmosphere.
CN 201110163002 2011-06-17 2011-06-17 Preparation method of high-hydrogen-storage-quantity boron ammonate aluminum hydride series hydrogen storage material Expired - Fee Related CN102320570B (en)

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