CN102198933B - Method for preparing high-capacity composite hydrogen storage material calcium borohydride/lithium borohydride ammine - Google Patents
Method for preparing high-capacity composite hydrogen storage material calcium borohydride/lithium borohydride ammine Download PDFInfo
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- CN102198933B CN102198933B CN 201110098606 CN201110098606A CN102198933B CN 102198933 B CN102198933 B CN 102198933B CN 201110098606 CN201110098606 CN 201110098606 CN 201110098606 A CN201110098606 A CN 201110098606A CN 102198933 B CN102198933 B CN 102198933B
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- borohydride
- ammino
- lithium borohydride
- hydrogen
- storage material
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Abstract
The invention relates to a method for preparing a high-capacity composite hydrogen storage material calcium borohydride/lithium borohydride ammine (Ca(BH4)2/LiBH4.NH3), which comprises the following steps of: mixing calcium borohydride and lithium borohydride ammine in a molar ratio of 1:1, and grinding or ball-milling in inert gas to obtain the required product. The Ca(BH4)2/LiBH4.NH3 serving as a novel high-efficiency hydrogen storage material has high hydrogen release property, can slowly release hydrogen when heated to the temperature of 80 DEG C, and can release 12.3 weight percent of high-purity hydrogen before being heated to the temperature of 250 DEG C.
Description
Technical field
The invention belongs to the synthetic field of hydrogen memory technology and novel material, be specifically related to the preparation method of a kind of high-capacity composite hydrogen storage material calcium borohydride/ammino lithium borohydride.
Background technology
Hydrogen is a kind of clean fuel, and Hydrogen Energy is acknowledged as the desirable energy of human future, and the link of utilizing most critical of Hydrogen Energy is exactly the storage of Hydrogen Energy.The storage of hydrogen is the bottleneck of Hydrogen Energy present stage development and utilization.The storage method of hydrogen has 3 kinds of high-pressure gaseous storage, low temperature liquid storage and solid-state storages etc., and wherein high-pressure gaseous storage or low temperature liquid store and can not meet storage hydrogen target in the future.Solid-state storage hydrogen be by chemistry or physical adsorption by hydrogen storage in solid-state material, its energy density is high and security good, is considered to the most promising a kind of hydrogen storage mode
[1].
The hydroborates of light-weight metal is due to the large (Ca (BH of hydrogen-storage amount
4)
2for 11.4wt. %, LiBH
4for 18.4wt. % etc.), became in the last few years the study hotspot of hydrogen storage material.But at present higher hydrogen discharging temperature and the slower hydrogen power of putting have restricted its large-scale application
[2-3].In recent years, the compound hydrogen storage material of B-N-H system, won to have higher theoretical hydrogen content and lower initial hydrogen discharging temperature widely and paid close attention to
[4-5], such as, the metal ammonia borane complex compound
[6-7], ammino metal hydroborate
[8-11]deng.Wherein, an ammino lithium borohydride (LiBH
4 .nH
3, 18.2 wt. %) there is higher hydrogen richness and be considered to a kind of potential hydrogen storage material.Yet ammonias a large amount of in its pyrolytic process also are released together with hydrogen, this for its again the application of fuel cell aspect be very disadvantageous.
Recently, compound system is used successfully in the performance of improving the B-N-H based hydrogen storage material
[12-15], the excellent hydrogen discharging performance that this matrix material usually possesses starting material and do not had.We are by Ca (BH
4)
2and LiBH
4 .nH
3these two kinds of unsatisfactory materials of hydrogen discharging performance combine and are prepared into composite hydrogen storage material Ca (BH
4)
2/ LiBH
4 .nH
3.This material is at 80-250
ocan discharge the high-purity hydrogen of 12.3 wt.% between C.Wherein, LiBH
4nH
3the preparation method mainly with reference to the patent documentation of Yu Xuebin etc.
[16].
reference:
[1]?Schlapbach,?L.;?Züttel,?A.?
Nature 2001,?
414,?353-358.
[2]?R?ennebro,?E.;?Majzoub,?E.?
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[3]?Majzoub,?E.?H.;?R?nnebro,?E.?
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[4]?Custelcean,?R.;?Jackson,?J.?
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[5]?Hamilton,?C.;?Baker,?R.;?Staubitz,?A.;?Manners,?I.?
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38,?279-293.
[6]?Xiong,?Z.;?Yong,?C.;?Wu,?G.;?Chen,?P.;?Shaw,?W.;?Karkamkar,?A.;?Autrey,?T.;?Jones,?M.;?Johnson,?S.;?Edwards,?P.?
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7,?138-141.
[7]?Wu,?H.;?Zhou,?W.;?Yildirim,?T.?
J.?Am.?Chem.?Soc. 2008,?
130,?14834-14839.
[8]?Guo,?Y.?H.;?Yu,?X.?B.;?Sun,?W.?W.;?Sun,?D.?L.;?Yang,?W.?N.?
Angew.?Chem.?Int.?Ed. 2011,?
50,?1087-1091.
[9]?Chu,?H.?L.;?Wu,?G.?T.;?Xiong,?Z.?T.;?Guo,?J.?P.;?He,?T.;?Chen,?P.?
Chem.?mater. 2010,?
22,?6021-6028.
[10]?Soloveichik,?G.;?Her,?J.;?Stephens,?P.;?Gao,?Y.;?Rijssenbeek,?J.;?Andrus,?M.;?Zhao,?J.?
Inorg.?Chem. 2008,?
47,?4290-4298.
[11]?Guo,?Y.?H.;?Xia,?G.?L.;?Zhu,?Y.?H.;?Gao,?L.;?Yu,?X.?B.?
Chem.?Commun. 2010,?
46,?2599-2601.
[12]?Yu,?X.?B.;?Guo,?Y.?H.;?Sun,?D.?L.;?Yang,?Z.?X.;?Ranjbar,?A.;?Guo,?Z.?P.;?Liu,?H.?K.;?Dou,?S.?X.?
J.?Phys.?Chem.?C 2010,?
114,?4733-4737.
[13]?Tang,?Z.?W.;?Guo,?Y.?H.;?Li,?S.?F.;?Yu,?X.?B.?
J.?Phys.?Chem.?C 2011,?
115,?3188-3193.
[14]?Chu,?H.;?Xiong,?Z.;?Wu,?G.;?Guo,?J.;?Zheng,?X.;?He,?T.;?Wu,?C.;?Chen,?P.?
Chem.?Asian?J. 2010,?
5,?1594-1599.
[15]?Guo,?Y.?H.;?Gu,?Q.?F.;?Guo,?Z.?P.;?Mao,?J.?F.;?Liu,?H.?K.;?Dou,?S.?X.;?Yu,?X.?B.?
J.?Mater.?Chem.
2011,?in?press.
[16] a kind of LiBH for preparing
4xNH
3method; Contriver: Yu Xuebin, Guo Yanhui, Xia Guanglin, jowar; Accept numbering: 200810204191.8, authorize numbering: CN101746727A.
Summary of the invention
Purpose of the present invention provides the preparation method of a kind of novel high-capacity composite hydrogen storage material calcium borohydride/ammino lithium borohydride, and this material can be 250
odischarge the high-purity hydrogen of 12.3 wt.% before C.
The preparation method of the high-capacity composite hydrogen storage material calcium borohydride that the present invention proposes/ammino lithium borohydride, concrete steps are as follows:
The ratio that mol ratio that calcium borohydride be take with an ammino lithium borohydride is 1:1 is mixed, and in rare gas element, grinds or ball milling, obtains desired product.
In the present invention, while using polishing, calcium borohydride and an ammino lithium borohydride mixed grinding are no less than 1 hour; While using ball milled, ball material weight is 30:1, and rotating speed is 500 rev/mins, and Ball-milling Time is 1-2 hour.
In the present invention, Ca (BH
4)
2/ LiBH
4 .nH
3mainly put hydrogen methods for being heated, temperature is 80
oc-250
obetween C.
the present invention has the following aspects remarkable advantage:
1), use Ca (BH
4)
2/ LiBH
4 .nH
3as hydrogen source material, can under lower Heating temperature, obtain a large amount of high-purity hydrogens.
2), Ca (BH
4)
2/ LiBH
4 .nH
3preparation technology is simple, is easy to realize.
3), cost is moderate.
The accompanying drawing explanation
Fig. 1 Ca (BH
4)
2/ LiBH
4 .nH
3thermal decomposition performance spectrogram: (a) be the gas mass spectrum of raw material and product; (b) be the air release curve of product.
Fig. 2 raw material Li BH
4 .nH
3, Ca (BH
4)
2and product C a (BH
4)
2/ LiBH
4 .nH
3the high resolution XRD spectra.
Fig. 3 Ca (BH
4)
2/ LiBH
4 .nH
3differing temps under constant temperature discharge the gas curve.
Embodiment
Further illustrate the present invention below by embodiment.
Embodiment 1: under 25 ℃ of room temperatures, by 1g LiBH
4put in argon gas in the Schlenk test tube, after test tube is vacuumized, slowly pass into ammonia, stop passing into ammonia while reaching 0.8atm, react, after 20 minutes, test tube is evacuated to vacuum state, lasting vacuum stopped reaction after 3 hours takes out product and obtains LiBH in argon gas
4 .nH
3.Get 0.50g LiBH in glove box
4 .nH
3with 0.90g Ca (BH
4)
2mix, after the ball grinder of packing into, ball milling is taken out in sealing.Ball milling condition is: revolution is 400-450 rpm, joins the stainless steel ball-milling steel ball, and diameter is at 0.5-2cm, and Ball-milling Time is 1 hour, and operational mode is for alternately restarting, and alternately the time is 6 minutes.Complete Ca (the BH that obtains of ball milling
4)
2/ LiBH
4 .nH
3.Sample after ball milling is done to the test of mass spectrum and volumetric method, test result as shown in Figure 1, raw material, the high resolution XRD figure spectrum of product as shown in Figure 2.Ca (BH
4)
2/ LiBH
4 .nH
3differing temps under constant temperature discharge the gas curve as shown in Figure 3.
Claims (2)
1. the preparation method of high-capacity composite hydrogen storage material calcium borohydride/ammino lithium borohydride is characterized in that concrete steps are as follows:
The ratio that mol ratio that calcium borohydride be take with an ammino lithium borohydride is 1:1 is mixed, and in rare gas element, grinds or ball milling, obtains desired product; Wherein: while using polishing, calcium borohydride and an ammino lithium borohydride mixed grinding are no less than 1 hour; While using ball milled, ball material weight ratio is 30:1, and rotating speed is 500 rev/mins, and Ball-milling Time is 1-2 hour.
2. the preparation method of high-capacity composite hydrogen storage material calcium borohydride according to claim 1/ammino lithium borohydride, is characterized in that the preparation method of a described ammino lithium borohydride is: by LiBH
4in argon gas, put in the Schlenk test tube, after test tube is vacuumized, slowly pass into ammonia, stop passing into ammonia while reaching 0.6-1.0atm, react, after 20-30 minute, test tube is evacuated to vacuum state, stopped reaction after continuing to vacuumize 2.5-3.5 hour takes out product in argon gas, obtains LiBH
4nH
3white crystal.
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|---|---|---|---|
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|---|---|---|---|---|
| CN102826511B (en) * | 2012-09-06 | 2014-04-30 | 浙江华康药业股份有限公司 | Method and device for preparing active calcium hydride |
| CN103011078A (en) * | 2012-11-28 | 2013-04-03 | 复旦大学 | Preparation method and application of novel and efficient metal B-N-H system hydrogen storage material |
| CN104030239B (en) * | 2014-05-28 | 2016-04-06 | 桂林电子科技大学 | A kind of heavy body light-weight metal composite hydrogen storage material and preparation method |
| CN105060246B (en) * | 2015-09-01 | 2017-03-29 | 中国船舶重工集团公司第七一二研究所 | It is a kind of to improve the method that lithium borohydride puts hydrogen |
| CN112158868B (en) * | 2020-09-29 | 2021-09-17 | 四川大学 | Nano oxide/lithium borohydride amide high-conductivity solid electrolyte material and preparation method thereof |
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