CN102198933A - 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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- CN102198933A CN102198933A CN201110098606XA CN201110098606A CN102198933A CN 102198933 A CN102198933 A CN 102198933A CN 201110098606X A CN201110098606X A CN 201110098606XA CN 201110098606 A CN201110098606 A CN 201110098606A CN 102198933 A CN102198933 A CN 102198933A
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- lithium borohydride
- storage material
- hydrogen storage
- ammino
- hydrogen
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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 a kind of heavy body composite hydrogen storage material hydroboration calcium/ammino Preparation of Lithium Borohydride.
Background technology
Hydrogen is a kind of fuel of cleaning, and Hydrogen Energy is acknowledged as the human following desirable energy, 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 satisfy storage hydrogen target in the future.Solid-state storage hydrogen be by chemistry or physical adsorption with hydrogen storage in solid-state material, its energy density height and security are good, are considered to the most promising a kind of hydrogen storage mode
[1]
The hydroborates of light-weight metal is because the big (Ca (BH of hydrogen-storage amount
4)
2Be 11.4wt. %, LiBH
4Be 18.4wt. % etc.), became the research focus of hydrogen storage material in the last few years.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 has won concern widely to have high theoretical hydrogen content and lower initial hydrogen discharging temperature
[4-5], such as, the metal ammonia borane complex compound
[6-7], ammino metal hydroborate
[8-11]Deng.Wherein, an ammino lithium borohydride (LiBH
4NH
3, 18.2 wt. %) have 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 with Ca (BH
4)
2And LiBH
4NH
3These two kinds of unsatisfactory materials of hydrogen discharging performance combine and are prepared into composite hydrogen storage material Ca (BH
4)
2/ LiBH
4NH
3This material is at 80-250
oCan discharge the high-purity hydrogen of 12.3 wt.% between the C.Wherein, LiBH
4NH
3The patent documentation of the refined grade of surplus of preparation method's main reference
[16]
Reference:
[1]?Schlapbach,?L.;?Züttel,?A.?
Nature2001,?
414,?353-358.
[2]?R?ennebro,?E.;?Majzoub,?E.?
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[4]?Custelcean,?R.;?Jackson,?J.?
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38,?279-293.
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[8]?Guo,?Y.?H.;?Yu,?X.?B.;?Sun,?W.?W.;?Sun,?D.?L.;?Yang,?W.?N.?
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50,?1087-1091.
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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.?
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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.?
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114,?4733-4737.
[13]?Tang,?Z.?W.;?Guo,?Y.?H.;?Li,?S.?F.;?Yu,?X.?B.?
J.?Phys.?Chem.?C2011,?
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 preparation LiBH
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 a kind of novel high-capacity composite hydrogen storage material hydroboration calcium/ammino Preparation of Lithium Borohydride, and this material can be 250
oDischarge the high-purity hydrogen of 12.3 wt.% before the C.
Heavy body composite hydrogen storage material hydroboration calcium/ammino Preparation of Lithium Borohydride that the present invention proposes, concrete steps are as follows:
Is the mixed of 1:1 with a hydroboration calcium and an ammino lithium borohydride with the mol ratio, grinds or ball milling in rare gas element, promptly gets desired product.
Among the present invention, when using polishing, a hydroboration calcium and an ammino lithium borohydride mixed grinding are no less than 1 hour; When using ball milled, ball material weight is 30:1, and rotating speed is 500 rev/mins, and the ball milling time is 1-2 hour.
Among the present invention, Ca (BH
4)
2/ LiBH
4NH
3mainly put hydrogen methods for being heated, temperature is 80
oC-250
oBetween the C.
The present invention has the following aspects remarkable advantage:
1), uses Ca (BH
4)
2/ LiBH
4NH
3As hydrogen source material, can under lower Heating temperature, obtain a large amount of high-purity hydrogens.
2), Ca (BH
4)
2/ LiBH
4NH
3Preparation technology is simple, is easy to realize.
3), cost is moderate.
Description of drawings
Fig. 1 Ca (BH
4)
2/ LiBH
4NH
3Thermal decomposition performance spectrogram: (a) be the gas mass spectrum of raw material and product; (b) be the gas release curve of product.
Fig. 2 raw material Li BH
4NH
3, Ca (BH
4)
2And product C a (BH
4)
2/ LiBH
4NH
3The high resolution XRD spectra.
Fig. 3 Ca (BH
4)
2/ LiBH
4NH
3Differing temps under constant temperature discharge the gas curve.
Embodiment
Further specify the present invention below by embodiment.
Embodiment 1: under 25 ℃ of the room temperatures, with 1g LiBH
4In argon gas, put in the Schlenk test tube, after test tube is vacuumized, slowly feed ammonia, stop to feed ammonia when reaching 0.8atm, react and after 20 minutes test tube is evacuated to vacuum state, continue vacuum stopped reaction after 3 hours, product is taken out in argon gas promptly obtain LiBH
4NH
3In glove box, get 0.50g LiBH
4NH
3With 0.90g Ca (BH
4)
2Mix, ball milling is taken out in sealing behind the ball grinder of packing into.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 the ball milling time is 1 hour, and operational mode is for alternately restarting, and alternately the time is 6 minutes.Ball milling finishes and promptly obtains Ca (BH
4)
2/ LiBH
4NH
3Sample behind the ball milling is done 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
4NH
3Differing temps under constant temperature discharge the gas curve as shown in Figure 3.
Claims (3)
1. heavy body composite hydrogen storage material hydroboration calcium/ammino Preparation of Lithium Borohydride is characterized in that concrete steps are as follows:
Is the mixed of 1:1 with a hydroboration calcium and an ammino lithium borohydride with the mol ratio, grinds or ball milling in rare gas element, promptly gets desired product.
2. a heavy body composite hydrogen storage material hydroboration calcium according to claim 1/ammino Preparation of Lithium Borohydride, when it is characterized in that using polishing, a hydroboration calcium and an ammino lithium borohydride mixed grinding are no less than 1 hour; When using ball milled, ball material weight ratio is 30:1, and rotating speed is 500 rev/mins, and the ball milling time is 1-2 hour.
3. the preparation method of ammoniated compound ion hydrogen storage material according to claim 1 is characterized in that a described ammino Preparation of Lithium Borohydride is: with LiBH
4In argon gas, put in the Schlenk test tube, after test tube vacuumized, slowly feed ammonia, stop to feed ammonia when reaching 0.6-1.0atm, react and 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, promptly obtain LiBH
4NH
3White crystal.
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|---|---|---|---|
| CN 201110098606 CN102198933B (en) | 2011-04-20 | 2011-04-20 | Method for preparing high-capacity composite hydrogen storage material calcium borohydride/lithium borohydride ammine |
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|---|---|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102826511A (en) * | 2012-09-06 | 2012-12-19 | 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 |
| CN104030239A (en) * | 2014-05-28 | 2014-09-10 | 桂林电子科技大学 | High-capacity light metal composite hydrogen storage material and preparation method thereof |
| CN105060246A (en) * | 2015-09-01 | 2015-11-18 | 中国船舶重工集团公司第七一二研究所 | Method for improving lithium borohydride hydrogen |
| CN112158868A (en) * | 2020-09-29 | 2021-01-01 | 四川大学 | Nano oxide/lithium borohydride amide high-conductivity solid electrolyte material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101746727A (en) * | 2008-12-08 | 2010-06-23 | 复旦大学 | Method for preparing LiBH4 xNH3 compounds |
-
2011
- 2011-04-20 CN CN 201110098606 patent/CN102198933B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101746727A (en) * | 2008-12-08 | 2010-06-23 | 复旦大学 | Method for preparing LiBH4 xNH3 compounds |
Non-Patent Citations (3)
| Title |
|---|
| 《Chem.Asian J.》 20100507 Hailing Chu et al. Hydrogen Storage Properties of Ca(BH4)2-LiNH2 System 第1598页实验 1-3 第5卷, * |
| HAILING CHU ET AL.: "Hydrogen Storage Properties of Ca(BH4)2–LiNH2 System", 《CHEM.ASIAN J.》 * |
| ZHAN-ZHAO FANG ET AL.: "Unexpected dehydrogenation behavior of LiBH4/Mg(BH4)2 mixture associated with the in situ formation of dual-cation borohydride", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102826511A (en) * | 2012-09-06 | 2012-12-19 | 浙江华康药业股份有限公司 | Method and device for preparing active calcium hydride |
| 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 |
| CN104030239A (en) * | 2014-05-28 | 2014-09-10 | 桂林电子科技大学 | High-capacity light metal composite hydrogen storage material and preparation method thereof |
| CN105060246A (en) * | 2015-09-01 | 2015-11-18 | 中国船舶重工集团公司第七一二研究所 | Method for improving lithium borohydride hydrogen |
| CN112158868A (en) * | 2020-09-29 | 2021-01-01 | 四川大学 | Nano oxide/lithium borohydride amide high-conductivity solid electrolyte material and preparation method thereof |
| 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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