CN102765723A - Method for synthesizing KSi hydrogen storage alloy - Google Patents
Method for synthesizing KSi hydrogen storage alloy Download PDFInfo
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- CN102765723A CN102765723A CN2012102550420A CN201210255042A CN102765723A CN 102765723 A CN102765723 A CN 102765723A CN 2012102550420 A CN2012102550420 A CN 2012102550420A CN 201210255042 A CN201210255042 A CN 201210255042A CN 102765723 A CN102765723 A CN 102765723A
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Abstract
The invention belongs to the technical field of preparation of materials, and particularly discloses a method for synthesizing KSi hydrogen storage alloy. According to the method, volatilization of metallic potassium at high temperature can be inhibited by using high-pressure inert gas, and the KSi alloy is synthesized by solid and liquid reaction and self-purification in the temperature reducing process. The method specifically comprises the following steps of: feeding mixture of metallic potassium and silica powder into a reactor with a self-refluxing structure under the condition that air is isolated; and in high-temperature inert gas atmosphere, raising temperature in the reactor to 500 DEG C, preserving heat for three days, reducing temperature to 150 DEG C, reducing pressure to normal pressure, and preserving heat for two hours. By the method, the KSi hydrogen storage alloy is synthesized; and the method has the advantages of simplicity and convenience in reaction, high yield and the like. The synthesized KSi alloy is a hydrogen storage material with excellent performance, hydrogenation can be performed at temperature of 150 DEG C and under the hydrogen pressure of 4MPa, dehydrogenation can be performed at the temperature of 250 DEG C and under the pressure of 0.1MPa, and the method is excellent in reverse circulation performance.
Description
Technical field
The invention belongs to technical field of material, be specifically related to the method for a kind of synthetic potassium silicon (KSi) hydrogen storage alloy, particularly utilize the method that high pressure is auxiliary and synthesize high-purity potassium silicon (KSi) hydrogen storage alloy from purification techniques.
Background technology
Hydrogen Energy becomes one of focus of green energy resource research now owing to advantages such as efficiency of combustion are high, and products of combustion is pollution-free.Hydrogen Energy mainly contains three kinds of storage modes: high-pressure gaseous storage hydrogen, low temperature liquid storage hydrogen and solid-state storage hydrogen.Store up hydrogen with traditional high-pressure gaseous storage hydrogen with low temperature liquid and compare, solid-state storage hydrogen has storage density height, safety, advantage such as portable, is a kind of hydrogen storage technology efficiently.[1,2] still, the hydrogen storage material of at present having developed because of working temperature higher or reversible cycle inhale problems such as putting stabilized hydrogen property difference, be difficult to satisfy requirement of actual application.Therefore, exploitation can become the emphasis of domestic and international research at the high power capacity storage hydrogen material that middle low temperature is put hydrogen.
The hydrogen storage material of studying at present mainly is divided into three kinds: ligand complex hydrogenate is (like LiBH
4And NaAlH
4), chemistry storage hydrogen hydrogen storage material is (like NH
3BH
3) and metal hydride (like LaNi
5H
6And MgH
2).Though ligand complex hydrogenate, chemistry storage hydrogen hydrogen storage material have higher weight hydrogen-storage density (6-13 wt%), their application be limited by desorption temperature too high, take off/problems such as the slow and reversibility difference of hydrogenation speed.[3,4] and in the traditional metal hydride, except magnesium and Magnuminium hydrogenate, the hydrogen storage capability of other metal hydrides generally lower (< 2 wt%).[5-7] though magnesium and Magnuminium hydrogenate have higher hydrogen storage capability (4-7 wt%), it takes off hydrogenation reaction temperature height, and problems such as dehydrogenation dynamic performance difference have hindered its practicability.[8,9] are discovered recently, and M-Si-H (M=Li, Mg and K) alloy hydride has higher hydrogen storage capability and suitable relatively hydrogenation temperature, the KSiH especially wherein of taking off
3Have more good reversible hydrogen adsorption and desorption performance.[10-12] KSiH
3Hydrogen storage capability with 4.3 wt% can reversible in 150-300 ℃ of scope, stablely be inhaled and put hydrogen, is a kind of hydrogen storage material of excellent property.At present to KSiH
3The hydrogen storage property research of alloy is less, mainly is because the fusing point gap of potassium metal and Pure Silicon Metal is big and problems such as saturated vapor pressure height potassium cause the KSi alloy to be difficult to synthesize through smelting process.The method of at present synthetic KSi alloy mainly adopts chemical method, promptly at subzero 78 ℃, and silane (SiH
4) and potassium metal in glycol dimethyl ether, react and form the KSi alloy.[13] the synthetic KSi alloy of chemical method needs low temperature and organic solvent, and cost is high, and purification step is complicated, is unfavorable for scale operation.Develop a kind of method simple and easy, the synthetic KSi alloy that is produced on a large scale and can greatly promote the research of KSi alloy hydrogen storage property, quicken its practicalization.
Reference:
(1) Schlapbach,?L.;?Zuttel,?A.?
Natrue 2001,?414,?353.
(2) Crabtree,?G.?W.;?Dresselhaus,?M.?S.;?Buchanan,?M.?V.?
Phys.?Today 2004,?57,?39.
(3)?Staubitz,?A.;?Robertson,?A.?P.?M.;?Manners,?I.?
Chem.?Rev.? 2010,?110,?4079–4124.
(4)?Dornheim,?M.;?Doppiu,?S.;?Barkhordarian,?G.;?Boesenberg,?U.;?Klassen,?T.;?Gutfleisch,?O.;?Bormann,?R.?
Scripta?Mater.? 2007,?56,?841–846.
(5) Gamo,?T.;?Moriwaki,?T.;?Yanagihara?N.;?Iwaki,?T.?
Int.?J.?Hy-drogen?Energy 1985,?10,?39.
(6) Latroche,?M.;?Baddour-Hadjean,?R.;?Percheron-Guégan,?A.?
J.?Solid?State?Chem. 2003,?173,?236.
(7) Klyarnkin,?S.?N.;?Verbetsky,?V.?N.;?Demidov,?V.?A.?
J.?Alloys?Compd. 1994 ,?L1,?205
.
(8)?Kojima,?Y.;?Kawai,?Y.;?Haga,?T.?
J.?Alloys?Compd. 2006 ,?424,?294–298
.
(9)?Jurczyk,?M.;?Smardz,?L.;?Okonska,?I.;?Jankowska,?E.;?Nowak,?M.;?Smardz,?K.?
Int.?J.?Hydrogen?Energy 2008,?33,?374–380.
(10)Doi,?K.;?Hino,?S.;?Miyaoka,?H.;?Ichikawa,?T.;?Kojima,?Y.
?J.?Power?Sources? 2011,?196,?504–507.
(11)Janot,?R.;?Cuevas,?F.;?Latroche,?M.?Percheron-Guégan,?A.?
Intermetallics 2006,?14,?163–169.
(12)Chotard,?J.;?Tang,?W.?S.;?Raybaud,?P.;?Janot,?R.
?Chem.?Eur.?J.? 2011,?17,?12302–12309.
(13)Ring,?M.?A.;?Ritter,?D.?M.
?J.?Am.?Chem.?Soc.?
1961,?83,?802–805。
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, a kind of method of synthetic potassium silicon hydrogen storage alloy is provided.
The method of synthetic potassium silicon hydrogen storage alloy provided by the invention; Be in the reactor drum of return-flow structure, to carry out alloying reaction having, the structure of reactor drum is made up of big reaction chamber 1, little reaction chamber 2, powder filter sheet 3, copper sealing ring 4, reaction chamber lid 5 and gas inlet and outlet 6 shown in accompanying drawing 1; Big reaction chamber 1 is connected to form by cylindrical shell and end cap; Little reaction chamber 2 inserts in the cylindrical shell of big reaction chamber 1, and the end cap of big reaction chamber 1 middle part is provided with the groove of annular, and powder filter sheet 3 is put in the groove of said annular with copper sealing ring 4 successively; Reaction chamber lid 5 is fixed on the end cap of big reaction chamber 1; The middle part of copper sealing ring 4 is provided with circular hole, and the middle part of reaction chamber lid 5 is provided with gas inlet and outlet 6, communicates on the circular hole on the copper sealing ring 4 and the gas inlet and outlet 6; Put into little reaction chamber 2 after potassium metal and silica flour mixed, under the high-pressure inert gas environment,, form potassium silicon (KSi) alloy through alloying process; Wherein:
The mol ratio of said potassium metal and silica flour is 1.01:1-1.05:1;
Alloying process is divided into high-temperature alloy reaction and low temperature from two steps of purified reaction; Wherein: in, the high-temperature alloy reaction is under 3-6 MPa high pressure argon gas atmosphere, and reactor drum is heated to 400-600 ℃ carries out 3-5 days alloying reactions; Low temperature is under 0.1 MPa argon gas atmosphere from purified reaction, reactor drum is maintained under the 100-200 ℃ of temperature keep being cooled to room temperature after 1.5-2.5 hour.
Among the present invention, said rare gas element be in nitrogen, argon gas or the helium any.
Among the present invention, low temperature is in the purified reaction process, and potassium metal raw material unnecessary in the little reaction chamber of reactor drum can exist with liquid form.Because potassium has very high saturated vapor pressure, so can the volatilize diffusion and in being cooled to the room temperature process subsequently, be condensed in the inwall of the big reaction chamber of reactor drum of these unnecessary potassium, thereby realize the potassium silicon alloy purification purpose in the little reaction chamber.
Adopt the synthetic potassium silicon alloy of the inventive method in building-up process, to need not organic solvent, required top temperature is merely 600 ℃ and is merely 6 MPa with peak pressure, all is to be prone to realization in industrial production and prepared in laboratory.Adopt the inventive method synthetic potassium silicon alloy to inhale 150-300 ℃ of reversible cycle and put hydrogen, the actual measurement hydrogen storage capability is about 4.1 wt%, is a kind of hydrogen storage material of excellent property.
Description of drawings
Fig. 1 is the structure of reactor synoptic diagram.
Fig. 2 is for being that K and the Si mixed powder of 1.02:1 is KSiH behind raw material synthetic KSi alloy (a) and the suction hydrogen thereof with the mol ratio
3(b) X-ray diffraction spectrogram.
Fig. 3 is KSiH
3Differential thermal-thermogravimetric-mass spectrum curve.
Fig. 4 is KSiH
3The dehydrogenation capacity comparison repeatedly circulates.
Fig. 5 is for being that K and the Si mixed powder of 1.05:1 is KSiH behind raw material synthetic KSi alloy (a) and the suction hydrogen thereof with the mol ratio
3(b) X-ray diffraction spectrogram.
Label among the figure: 1 is big reaction chamber, and 2 is little reaction chamber, and 3 is the powder filter sheet, and 4 is copper sealing ring, and 5 are the reaction chamber lid, and 6 is gas inlet and outlet.
Embodiment
Further specify the present invention through embodiment below.
Embodiment 1:
(1) the KSi alloy is synthetic
Under inert atmosphere glove box, in the little reaction chamber with the reactor drum of packing into after potassium metal block materials and the mixed of silica flour (300 order) according to mol ratio 1.02:1, the structure of reactor drum is as shown in Figure 1.In reactor drum, feed 5 MPa argon gas, and be warming up to 500 ℃ gradually, temperature rise rate is 1 ℃/minute.500 ℃ keep 3 days after, be cooled to 150 ℃, be depressurized to 0.1 MPa and kept 2 hours.After cooling to room temperature with the furnace at last, little reaction chamber is opened and taken out to reactor drum in inert atmosphere glove box, promptly get the KSi alloy.The XRD figure of synthetic KSi alloy is composed shown in Fig. 2 (a),
(2) KSi absorption hydrogen reaction
Under 4 MPa hydrogen pressures, 150 ℃ of insulations promptly got KSiH in 24 hours with the KSi alloy
3KSiH
3XRD figure spectrum shown in Fig. 2 (b).
(3) hydrogen storage property characterizes
Use differential thermal-thermogravimetric-mass spectrometry method to characterize KSiH
3Dehydrogenation, the result is as shown in Figure 3.From figure, can see KSiH
3Between 200-300 ℃, decompose, discharge 4.1 wt% hydrogen.Constant temperature PCT circulation is inhaled and is put the hydrogen experiment and show, this alloy was inhaled hydrogen 24 hours in 150 ℃, 4 MPa hydrogen, and dehydrogenase 35 hour can be realized the reversible cycle hydrogen storage capability of about 4 wt% in 200 ℃, vacuum, and the result is as shown in Figure 4.
Embodiment 2:
(1) the KSi alloy is synthetic
Under inert atmosphere glove box, in the little reaction chamber with the reactor drum of packing into after potassium metal block materials and the mixed of silica flour (300 order) according to mol ratio 1.05:1.In reactor drum, feed 6 MPa argon gas, and be warming up to 500 ℃ gradually, temperature rise rate is 1 ℃/minute.500 ℃ keep 3 days after, be cooled to 200 ℃, be depressurized to 0.1 MPa and kept 2 hours.After cooling to room temperature with the furnace at last, little reaction chamber is opened and taken out to reactor drum in inert atmosphere glove box, promptly get the KSi alloy.The XRD figure of synthetic KSi alloy is composed shown in Fig. 5 (a),
(2) KSi absorption hydrogen reaction
Under 4 MPa hydrogen pressures, 200 ℃ of insulations promptly got KSiH in 24 hours with the KSi alloy
3KSiH
3XRD figure spectrum shown in Fig. 5 (b).
(3) hydrogen storage property characterizes
Using differential thermal-thermogravimetric-mass spectrum and constant temperature PCT circulation suction to put hydrogen tests and characterizes KSiH
3Hydrogen storage property.Test result is identical with embodiment 1, and concrete outcome is referring to Fig. 3 and Fig. 4.
Claims (2)
1. the method for a synthetic potassium silicon hydrogen storage alloy; It is characterized in that in the reactor drum of return-flow structure, carrying out alloying reaction having; Reactor drum is made up of big reaction chamber (1), little reaction chamber (2), powder filter sheet (3), copper sealing ring (4), reaction chamber lid (5) and gas inlet and outlet (6), and big reaction chamber (1) is connected to form by cylindrical shell and end cap, and little reaction chamber (2) inserts in the cylindrical shell of big reaction chamber (1); The end cap middle part of big reaction chamber (1) is provided with the groove of annular; Powder filter sheet (3) and copper sealing ring (4) are put in the groove of said annular successively, and reaction chamber lid (5) is fixed on the end cap of big reaction chamber (1), and the middle part of copper sealing ring (4) is provided with circular hole; The middle part of reaction chamber lid (5) is provided with gas inlet and outlet (6), communicates on the circular hole on the copper sealing ring (4) and the gas inlet and outlet (6); Put into little reaction chamber (2) after potassium metal and silica flour mixed, under the high-pressure inert gas environment,, form the potassium silicon alloy through alloying process; Wherein:
The mol ratio of said potassium metal and silica flour is 1.01:1-1.05:1;
Alloying process is divided into high-temperature alloy reaction and low temperature from two steps of purified reaction; Wherein: in, the high-temperature alloy reaction is under 3-6 MPa high pressure argon gas atmosphere, and reactor drum is heated to 400-600 ℃ carries out 3-5 days alloying reactions; Low temperature is under 0.1 MPa argon gas atmosphere from purified reaction, reactor drum is maintained under the 100-200 ℃ of temperature keep being cooled to room temperature after 1.5-2.5 hour.
2. the method for synthetic potassium silicon hydrogen storage alloy according to claim 1, it is characterized in that said rare gas element be in nitrogen, argon gas or the helium any.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107188123A (en) * | 2017-01-06 | 2017-09-22 | 中国计量大学 | A kind of preparation method of silicon/alkali metal hydrogen manufacturing material |
| CN107188124A (en) * | 2017-01-06 | 2017-09-22 | 中国计量大学 | A kind of preparation method of silicon substrate hydrogen manufacturing material |
| CN111943211A (en) * | 2020-08-21 | 2020-11-17 | 南方科技大学 | Metal silicide preparation method and preparation auxiliary device |
| CN113481383A (en) * | 2021-07-21 | 2021-10-08 | 合肥学院 | Preparation method of metal potassium |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050069489A1 (en) * | 2003-09-30 | 2005-03-31 | Ji-Cheng Zhao | Hydrogen storage compositions and methods of manufacture thereof |
| WO2005123586A2 (en) * | 2004-06-14 | 2005-12-29 | Signa Chemistry Llc | Silicide compositions containing alkali metals and methods of making the same |
| US20070014683A1 (en) * | 2003-09-30 | 2007-01-18 | General Electric Company | Hydrogen storage composition, and associated article and method |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050069489A1 (en) * | 2003-09-30 | 2005-03-31 | Ji-Cheng Zhao | Hydrogen storage compositions and methods of manufacture thereof |
| US20070014683A1 (en) * | 2003-09-30 | 2007-01-18 | General Electric Company | Hydrogen storage composition, and associated article and method |
| WO2005123586A2 (en) * | 2004-06-14 | 2005-12-29 | Signa Chemistry Llc | Silicide compositions containing alkali metals and methods of making the same |
Non-Patent Citations (2)
| Title |
|---|
| JEAN-NOEL CHOTARD ET AL.: "Potassium Silanide (KSiH3): A Reversible Hydrogen Storage Material", 《CHEMISTRY A EUROPEAN JOURNAL》, vol. 17, 27 September 2011 (2011-09-27), pages 12302 - 12309 * |
| KOICHI DOI ETAL.: "Hydrogen storage properties of lithium silicon alloy synthesized by mechanical alloying", 《JOURNAL OF POWDER SOURCES》, vol. 196, 26 June 2010 (2010-06-26), pages 504 - 507, XP027261361 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107188123A (en) * | 2017-01-06 | 2017-09-22 | 中国计量大学 | A kind of preparation method of silicon/alkali metal hydrogen manufacturing material |
| CN107188124A (en) * | 2017-01-06 | 2017-09-22 | 中国计量大学 | A kind of preparation method of silicon substrate hydrogen manufacturing material |
| CN107188124B (en) * | 2017-01-06 | 2019-01-25 | 中国计量大学 | A kind of preparation method of silicon substrate hydrogen manufacturing material |
| CN111943211A (en) * | 2020-08-21 | 2020-11-17 | 南方科技大学 | Metal silicide preparation method and preparation auxiliary device |
| CN113481383A (en) * | 2021-07-21 | 2021-10-08 | 合肥学院 | Preparation method of metal potassium |
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