CN102765723B - Method for synthesizing KSi hydrogen storage alloy - Google Patents
Method for synthesizing KSi hydrogen storage alloy Download PDFInfo
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- CN102765723B CN102765723B CN201210255042.0A CN201210255042A CN102765723B CN 102765723 B CN102765723 B CN 102765723B CN 201210255042 A CN201210255042 A CN 201210255042A CN 102765723 B CN102765723 B CN 102765723B
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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 a kind of method 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
Advantages such as Hydrogen Energy is because efficiency of combustion is high, and products of combustion is pollution-free and become one of focus of green energy resource research now.Hydrogen Energy mainly contains three kinds of storage modes: high-pressure gaseous storage hydrogen, low temperature liquid storage hydrogen and solid-state storage hydrogen.Compare with low temperature liquid storage hydrogen with traditional high-pressure gaseous storage hydrogen, solid-state storage hydrogen has the advantages such as storage density is high, safe, portable, is a kind of hydrogen storage technology efficiently.[1,2] still, the hydrogen storage material of now having developed, because working temperature is higher or reversible cycle is inhaled and put the problems such as stabilized hydrogen is poor, is difficult to meet the requirement of practical application.Therefore the high power capacity storage hydrogen material that, exploitation can be put hydrogen at middle low temperature becomes the emphasis of domestic and international research.
The hydrogen storage material of studying at present is mainly divided into three kinds: ligand complex hydride is (as LiBH
4and NaAlH
4), chemistry storage hydrogen hydrogen storage material is (as NH
3bH
3) and metal hydride (as LaNi
5h
6and MgH
2).Though ligand complex hydride, chemistry storage hydrogen hydrogen storage material have higher weight hydrogen-storage density (6-13 wt%), their application is limited by that desorption temperature is too high, de-/hydrogenation speed is slow and the problem such as reversibility is poor.[3,4] and in traditional metal hydride, except magnesium and magnesium based alloys hydride, the hydrogen storage capability of other metal hydrides is lower (< 2 wt%) generally.[5-7] problem has hindered that it is practical although magnesium and Magnuminium hydride have higher hydrogen storage capability (4-7 wt%), and its de-hydrogenation reaction temperature is high, and dehydrogenation dynamic performance is poor etc.[8,9] recently research are found, M-Si-H(M=Li, Mg and K) alloy hydride has higher hydrogen storage capability and relative suitable de-hydrogenation temperature, KSiH especially wherein
3have more good reversible hydrogen adsorption and desorption performance.[10-12] KSiH
3having the hydrogen storage capability of 4.3 wt%, can reversible within the scope of 150-300 ℃, stablely inhale and put hydrogen, is a kind of hydrogen storage material of excellent property.At present for KSiH
3the hydrogen storage property research of alloy is less, is mainly because the fusing point gap of potassium metal and Pure Silicon Metal is large and the problem such as the saturated vapor pressure height of potassium causes KSi alloy to be difficult to synthesize by smelting process.The method of at present synthetic KSi alloy mainly adopts chemical method, at subzero 78 ℃, and silane (SiH
4) and potassium metal in glycol dimethyl ether, react and form KSi alloy.[13] the synthetic KSi alloy of chemical method needs low temperature and organic solvent, and cost is high, and purification step complexity, 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, accelerate 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 object of the invention is to overcome the deficiencies in the 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, in the reactor of return-flow structure, to carry out alloying reaction having, the structure of reactor as shown in Figure 1, by large 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 form, large reaction chamber 1 is connected to form by cylindrical shell and end cap, little reaction chamber 2 inserts in the cylindrical shell of large reaction chamber 1, the end cap middle part of large 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 described annular successively, reaction chamber lid 5 is fixed on the end cap of large reaction chamber 1, 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, circular hole on copper sealing ring 4 communicates with on gas inlet and outlet 6, after potassium metal and silica flour are mixed, put into little reaction chamber 2, under high-pressure inert gas environment, through alloying process, form potassium silicon (KSi) alloy, wherein:
The mol ratio of described 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 purified reaction two steps; Wherein: high-temperature alloy reaction is under 3-6 MPa high pressure argon gas atmosphere, and reactor 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, and reactor is maintained and at 100-200 ℃ of temperature, keeps after 1.5-2.5 hour being cooled to room temperature.
In the present invention, described rare gas element be in nitrogen, argon gas or helium any.
In the present invention, low temperature is in purified reaction process, and potassium metal raw material unnecessary in the little reaction chamber of reactor can exist with liquid form.Because potassium has very high saturated vapor pressure, therefore can volatilize diffusion being cooled to subsequently the inwall that is condensed in the large reaction chamber of reactor in room temperature process of these unnecessary potassium, thus realize the potassium silicon alloy purification object in little reaction chamber.
Adopt the synthetic potassium silicon alloy of the inventive method in building-up process without organic solvent, required top temperature is only that 600 ℃ and peak pressure are only 6 MPa, in industrial production and laboratory preparation, is all easily to realize.Adopt the synthetic potassium silicon alloy of the inventive method to inhale and to put hydrogen 150-300 ℃ of reversible cycle, actual measurement hydrogen storage capability is about 4.1 wt%, is a kind of hydrogen storage material of excellent property.
Accompanying drawing explanation
Fig. 1 is structure of reactor schematic diagram.
Fig. 2 is K and the Si mixed powder KSiH after the synthetic KSi alloy (a) of raw material and suction hydrogen thereof take mol ratio as 1.02:1
3(b) X-ray diffraction spectrogram.
Fig. 3 is KSiH
3differential thermal-thermogravimetric-mass spectrum curve.
Fig. 4 is KSiH
3dehydrogenation capacity comparison repeatedly circulates.
Fig. 5 is K and the Si mixed powder KSiH after the synthetic KSi alloy (a) of raw material and suction hydrogen thereof take mol ratio as 1.05:1
3(b) X-ray diffraction spectrogram.
Number in the figure: 1 is large reaction chamber, 2 is little reaction chamber, and 3 is powder filter sheet, and 4 is copper sealing ring, and 5 is reaction chamber lid, 6 is gas inlet and outlet.
Embodiment
Further illustrate the present invention below by embodiment.
Embodiment 1:
(1) KSi alloy is synthetic
Under inert atmosphere glove box, after being mixed according to the ratio of mol ratio 1.02:1, potassium metal block materials and silica flour (300 order) pack in the little reaction chamber of reactor, and the structure of reactor is as shown in Figure 1.In reactor, pass into 5 MPa argon gas, and be warming up to gradually 500 ℃, temperature rise rate is 1 ℃/min.Keep, after 3 days, being cooled to 150 ℃ at 500 ℃, be depressurized to 0.1 MPa and keep 2 hours.Finally cool to the furnace after room temperature, reactor is opened in inert atmosphere glove box and taken out little reaction chamber, obtain KSi alloy.The XRD figure of synthetic KSi alloy is composed as shown in Figure 2 (a) shows,
(2) KSi absorption hydrogen reaction
By KSi alloy, under 4 MPa hydrogen pressures, 150 ℃ of insulations obtain KSiH for 24 hours
3.KSiH
3xRD figure compose as shown in Fig. 2 (b).
(3) hydrogen storage property characterizes
Characterize KSiH with differential thermal-thermogravimetric-mass spectrometry method
3dehydrogenation, result is as shown in Figure 3.As we can see from the figure, KSiH
3between 200-300 ℃, decompose, discharge 4.1 wt% hydrogen.Constant temperature PCT circulation is inhaled and is put hydrogen experiment and show, this alloy is inhaled hydrogen 24 hours in 150 ℃, 4 MPa hydrogen, and in 200 ℃, vacuum, dehydrogenase 35 hour can be realized the reversible cycle hydrogen storage capability of approximately 4 wt%, and result as shown in Figure 4.
Embodiment 2:
(1) KSi alloy is synthetic
Under inert atmosphere glove box, after being mixed according to the ratio of mol ratio 1.05:1, potassium metal block materials and silica flour (300 order) pack in the little reaction chamber of reactor.In reactor, pass into 6 MPa argon gas, and be warming up to gradually 500 ℃, temperature rise rate is 1 ℃/min.Keep, after 3 days, being cooled to 200 ℃ at 500 ℃, be depressurized to 0.1 MPa and keep 2 hours.Finally cool to the furnace after room temperature, reactor is opened in inert atmosphere glove box and taken out little reaction chamber, obtain KSi alloy.The XRD figure of synthetic KSi alloy is composed as shown in Fig. 5 (a),
(2) KSi absorption hydrogen reaction
By KSi alloy, under 4 MPa hydrogen pressures, 200 ℃ of insulations obtain KSiH for 24 hours
3.KSiH
3xRD figure compose as shown in Fig. 5 (b).
(3) hydrogen storage property characterizes
Put hydrogen with differential thermal-thermogravimetric-mass spectrum and constant temperature PCT circulation suction and test to characterize 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 of return-flow structure, carrying out alloying reaction having, reactor is by large 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) composition, large reaction chamber (1) is connected to form by cylindrical shell and end cap, little reaction chamber (2) inserts in the cylindrical shell of large reaction chamber (1), the end cap middle part of large 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 described annular successively, reaction chamber lid (5) is fixed on the end cap of large reaction chamber (1), 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), circular hole on copper sealing ring (4) communicates with on gas inlet and outlet (6), after potassium metal and silica flour are mixed, put into little reaction chamber (2), under high-pressure inert gas environment, through alloying process, form potassium silicon alloy, wherein:
The mol ratio of described 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 purified reaction two steps; Wherein: high-temperature alloy reaction is under 3-6 MPa high pressure argon gas atmosphere, and reactor 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, and reactor is maintained and at 100-200 ℃ of temperature, keeps after 1.5-2.5 hour being cooled to room temperature.
2. the method for synthetic potassium silicon hydrogen storage alloy according to claim 1, it is characterized in that described rare gas element be in nitrogen, argon gas or helium any.
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| CN111943211B (en) * | 2020-08-21 | 2022-02-22 | 南方科技大学 | Metal silicide preparation method and preparation auxiliary device |
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Non-Patent Citations (4)
| Title |
|---|
| Hydrogen storage properties of lithium silicon alloy synthesized by mechanical alloying;Koichi Doi etal.;《Journal of Powder Sources》;20100626;第196卷;第504-507页 * |
| Jean-Noel Chotard et al..Potassium Silanide (KSiH3): A Reversible Hydrogen Storage Material.《CHEMISTRY A European Journal》.2011,第17卷第12302-12309页. |
| Koichi Doi etal..Hydrogen storage properties of lithium silicon alloy synthesized by mechanical alloying.《Journal of Powder Sources》.2010,第196卷第504-507页. |
| Potassium Silanide (KSiH3): A Reversible Hydrogen Storage Material;Jean-Noel Chotard et al.;《CHEMISTRY A European Journal》;20110927;第17卷;第12302-12309页 * |
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