CN102225746B - Preparation method of high-efficient metal B-N-H system hydrogen storage material - Google Patents

Preparation method of high-efficient metal B-N-H system hydrogen storage material Download PDF

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CN102225746B
CN102225746B CN2011100986977A CN201110098697A CN102225746B CN 102225746 B CN102225746 B CN 102225746B CN 2011100986977 A CN2011100986977 A CN 2011100986977A CN 201110098697 A CN201110098697 A CN 201110098697A CN 102225746 B CN102225746 B CN 102225746B
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hydrogen storage
storage material
ammino
preparation
scium
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CN102225746A (en
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余学斌
唐子威
郭艳辉
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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-efficient metal B-N-H system hydrogen storage material. The structural formula of the metal B-N-H system hydrogen storage material is LixSc(BH4)y*ZNH3, wherein x=0, 1 or 2, y=3, 4 or 5, and z=4, 5 or 6; and the method particularly comprises the following steps: respectively mixing lithium borohydride with tetraammine scandium chloride, pentaammine scandium chloride, hexaammine scandium chloride with ratios of 3:1, 4:1, 5:1, and grinding or ball-milling the mixture in inert atmosphere to obtain the required product. The novel high-efficient hydrogen storage material has excellent hydrogen desorption performance, can release hydrogen slowly when heated to 80 DEG C, and can approximately release above 10 wt% of high-purity hydrogen before heated to 250 DEG C.

Description

A kind of preparation method of the B-N-H of metal efficiently system hydrogen storage material
Technical field
The present invention relates to the synthetic field of Hydrogen Storage technology and novel material, be specifically related to a kind of preparation method of the B-N-H of metal efficiently system hydrogen storage material.
Background technology
The mass-producing of Hydrogen Energy is used and must be solved the producing of hydrogen, accumulating and application three big correlation techniques.Because inflammable, explosive, easy diffusion that hydrogen exists, and the low problems such as (three per milles of having only gasoline) of the volume energy density under the normal temperature and pressure conditions, hydrogen storage technology has become the bottleneck of restriction Hydrogen Energy development.Therefore, the hydrogen storaging and transport technology of development high-energy-density, high-level efficiency and safety is the key technical problem that must solve.Hydrogen storage method has 3 kinds of high-pressure gaseous storage, low temperature liquid storage and solid-state storages etc.Wherein, high-pressure gaseous storage hydrogen is ripe relatively technically, and it is 6% re-set target that industry member has been formulated tolerance 70MPa pressure, quality hydrogen-storage density, but there is safety-problems in high-pressure gaseous storage hydrogen, and the energy consumption of compression process is bigger.The volume energy density of low temperature liquid storage hydrogen is high, but the required energy consumption of liquefaction process is 50% of storage of hydrogen calorific value approximately, and volatilization problem certainly is difficult to avoid; In addition, the adiabatic system technical sophistication of this method, cost height.Solid-state hydrogen storage material storage hydrogen be through chemical reaction 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 like lithium borohydride LiBH 4Because hydrogen-storage amount is (18.4wt.%) greatly, 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]The hydrogen richness of itself can reach 9.1wt.% in the ammonia, and through adding catalyzer, ammonia can be 347 oJust be converted into hydrogen and nitrogen before the C [3,4]So ammonia can be counted as a kind of up-and-coming hydrogen carrier [5]At present many reports about metal chloride suction ammonia think that the ammonia complex of metal chloride is a kind of reversible, the indirect hydrogen storage material that hydrogen content is high (Indirect hydrogen storage material) [6]But do not provide the method that directly muriatic ammonia complex is converted into hydrogen in the article, only propose to discharge ammonia through this complex compound of heating, the idea of further ammonia being decomposed again.But also there is insoluble problem in the ammonia catalytically decomposed, and higher and poisoning of catalyst etc. has limited on its large-scale car and used like temperature [5]
B-N-H system hydrogen storage material is because the big (NH of hydrogen-storage amount 3BH 3Be 19.6wt. % etc.) and lower initial hydrogen discharging temperature, became the research focus of hydrogen storage material in the last few years [7,8]Wherein, ammino metal hydroborate [9-12]Have excellent hydrogen storage property, it puts hydrogen combining based on these two two hydrogen bonds of electropositive N-H and electronegative B-H.Here, we are with LiBH 4With ScCl 3ZNH 3Be mixed with and obtain a kind of new and effective metal B-N-H system hydrogen storage material Li xSc (BH4) yZNH 3(x=0,1,2 y=3,4,5 z=4,5,6), this material is 250 oC discharges the high-purity hydrogen of 10wt. %.
Reference:
[1]?Crabtree,?G.;?Dresselhaus,?M.;?Buchanan,?M.? Phys.?Today 2004,? 57,?39-44.
[2]?Zuttel,?A.;?Wenger,?P.;?Rentsch,?S.;?Sudan,?P.;?Mauron,?Ph.;Emmenegger,?Ch.? J.?Power?Sources? 2003,? 118,?1-7.
[3]?Raro′g-Pilecka,?W.;?Szmigiel,?D.;?Kowalczyk,?Z.;?Jodzis,?S.;?Zielinski,?J.? J.?Catal.? 2003,? 218,?465–469;
[4]?Li,?X.-K.;?Ji,?W.-J.;?Zhao,?J.;?Wang,?S.-J.;?Au,?C.-T.? J.?Catal.? 2005, 236,?181–189
[5]?Dresselhaus,?M.;?Crabtree,?G.;?Buchanan,?M.?Basic?Research?Needs?for?the?Hydrogen?Economy;?U.S.?Department?of?Energy:?Washington,?DC,? 2003
[6]?Rasmus?Z.?S?rensen,?Jens?S.?Hummelsh?j,Asbj?rn?Klerke,Jacob?Birke?Reves,Tejs?Vegge,Jens?K.?N?rskov,nd?Claus?H.?Christense. J?Am?Chem?Soc.?, 2008,?130?(27),?8660-8668
[7]?Hamilton,?C.;?Baker,?R.;?Staubitz,?A.;?Manners,?I.? Chem.?Soc.?Rev. 2009,? 38,?279-293.
[8]?Staubitz,?A.;?Robertson,?A.?P.?M.;?Manners,?I.? Chem.?Rev. ?2010,? 110,?4079-4124.
[9]?Guo,?Y.?H.;?Yu,?X.?B.;?Sun,?W.?W.;?Sun,?D.?L.;?Yang,?W.?N.? Angew.?Chem.?Int.?Ed. 2011,? 50,?1087-1091.
[10]?Chu,?H.?L.;?Wu,?G.?T.;?Xiong,?Z.?T.;?Guo,?J.?P.;?He,?T.;?Chen,?P.? Chem.?mater. 2010,? 22,?6021-6028.
[11]?Soloveichik,?G.;?Her,?J.;?Stephens,?P.;?Gao,?Y.;?Rijssenbeek,?J.;?Andrus,?M.;?Zhao,?J.? Inorg.?Chem. 2008,? 47,?4290-4298.
[12]?Guo,?Y.?H.;?Xia,?G.?L.;?Zhu,?Y.?H.;?Gao,?L.;?Yu,?X.?B.? Chem.?Commun. 2010,? 46,?2599-2601。
Summary of the invention
The object of the invention provides a kind of preparation method of metal B-N-H system hydrogen storage material of novel high-capacity, and this material can be 250 oDischarge the high-purity hydrogen of 10 wt.% before the C.
The preparation method of the novel high-capacity metal B-N-H system hydrogen storage material that the present invention proposes, the structural formula of said B-N-H system hydrogen storage material is Li xSc (BH 4) yZNH 3, wherein x is 0,1 or 2, and y is 3,4 or 5, and z is 4,5 or 6, and concrete steps are following:
With lithium borohydride is the mixed of 3:1,4:1,5:1 with the mol ratio with four ammino Scium trichlorides, five ammino Scium trichlorides, six ammino Scium trichlorides respectively, and mixture grinds or ball milling in rare gas element, promptly gets desired product.
Among the present invention, when using polishing, two kinds of reaction mixed grindings 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.
Among the present invention, Li xSc (BH 4) yZNH 3(x=0,1,2 y=3,4,5 z=4,5,6) mainly 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 Li xSc (BH 4) yZNH 3(x=0,1,2 y=3,4,5 z=4,5,6) can obtain a large amount of high-purity hydrogens as hydrogen source material under lower Heating temperature.
2), Li xSc (BH 4) yZNH 3(x=0,1,2 y=3,4,5 z=4,5,6) preparation technology is simple, is easy to realize.
3), cost is moderate.
Description of drawings
Fig. 1 product S c (BH 4) 35NH 3, Sc (BH 4) 36NH 3, LiSc (BH 4) 46NH 3And Li 2Sc (BH 4) 56NH 3The high resolution XRD figure.
Fig. 2 product S c (BH4) 34NH 3, LiSc (BH4) 44NH 3, Li 2Sc (BH4) 54NH 3, Sc (BH4) 35NH 3, LiSc (BH4) 45NH 3, Li 2Sc (BH4) 55NH 3, Sc (BH4) 36NH 3, LiSc (BH4) 46NH 3And Li 2Sc (BH4) 56NH 3The gas release curve.
Fig. 3 product LiSc (BH 4) 45NH 3Thermal decomposition performance spectrogram: (a) gas mass spectrum and thermogravimetric analysis figure (little figure); (b) gas release curve.
Fig. 4 raw material ScCl 35NH 3, LiBH 4And product LiSc (BH 4) 45NH 3The high resolution XRD spectra.
Embodiment
Further specify the present invention through embodiment below.
Embodiment 1:
1, ScCl 3ZNH 3The preparation of (z=4,5,6)
Room temperature 25 oUnder the C, with the anhydrous ScCl of 1g 3In glove box, pack into and be with in the reactor drum of cock, take out enclosed reaction vessel, fill dry ammonia after vacuumizing, the quiescent period pats reactor drum acceleration ammino repeatedly and closes reaction, after 12 hours this product is heated to 25 respectively under the argon gas atmosphere of the 1bar left and right sides oC, 100 oC and 300 oAbout C, promptly prepare ScCl 36NH 3, ScCl 35NH 3And ScCl 34NH 3
2, Li xSc (BH 4) yZNH 3The preparation of (x=0,1,2 y=3,4,5 z=4,5,6)
In glove box, get 0.005mol ScCl 3ZNH 3(z=4,5,6) respectively with 0.015,0.020 with 0.025mol LiBH 4Mix, 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 Sc (BH 4) 34NH 3, LiSc (BH 4) 44NH 3, Li 2Sc (BH 4) 54NH 3, Sc (BH 4) 35NH 3, LiSc (BH 4) 45NH 3, Li 2Sc (BH 4) 55NH 3, Sc (BH 4) 36NH 3, LiSc (BH 4) 46NH 3And Li 2Sc (BH 4) 56NH 3

Claims (3)

1. the preparation method of a heavy body metal B-N-H system hydrogen storage material, the structural formula that it is characterized in that said B-N-H system hydrogen storage material is Li xSc (BH 4) yZNH 3, wherein x is 0,1 or 2, and y is 3,4 or 5, and z is 4,5 or 6, and concrete steps are following:
With lithium borohydride is the mixed of 3:1,4:1,5:1 with the mol ratio respectively all with four ammino Scium trichlorides, five ammino Scium trichlorides, six ammino Scium trichlorides respectively, and mixture grinds or ball milling in rare gas element, promptly gets desired product.
2. the preparation method of heavy body metal B-N-H system hydrogen storage material according to claim 1 when it is characterized in that using polishing, is no less than 1 hour with two kinds of reaction mixed grindings; 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 heavy body metal B-N-H system hydrogen storage material according to claim 1 is characterized in that the preparation method of said six ammino Scium trichlorides, five ammino Scium trichlorides, four ammino Scium trichlorides is: with anhydrous ScCl 3In glove box, pack into and be with in the reactor drum of cock, take out enclosed reaction vessel, fill dry ammonia after vacuumizing, the quiescent period pats reactor drum acceleration ammino repeatedly and closes reaction, after 10 ~ 12 hours this product is heated to 25 respectively under the 1bar argon gas atmosphere oC, 100 oC and 300 oC promptly prepares ScCl 3 6NH 3, ScCl 3 5NH 3And ScCl 3 4NH 3
CN2011100986977A 2011-04-20 2011-04-20 Preparation method of high-efficient metal B-N-H system hydrogen storage material Expired - Fee Related CN102225746B (en)

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CN103496669B (en) * 2013-09-05 2015-06-03 华南理工大学 B-N-H system hydrogen storage material and preparation method thereof
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