CN105039815A - Preparation method of Mg-Li solid solution hydrogen storage material - Google Patents
Preparation method of Mg-Li solid solution hydrogen storage material Download PDFInfo
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- CN105039815A CN105039815A CN201510227212.8A CN201510227212A CN105039815A CN 105039815 A CN105039815 A CN 105039815A CN 201510227212 A CN201510227212 A CN 201510227212A CN 105039815 A CN105039815 A CN 105039815A
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Abstract
The invention discloses a preparation method of an Mg-Li solid solution hydrogen storage material. The preparation method comprises the steps of uniformly mixing magnesium powder, lithium hydride powder and silicon powder, pressing the mixture to form circular sheets, annealing the round sheets, crushing the annealed sample, and preparing the Mg-Li solid solution hydrogen storage material through a mechanical-alloying method. The invention is advantaged in that the composite in which Mg:Li:Si=90:(10-x):x is prepared through firstly annealing and then mechanical ball milling for 50 h, wherein the X=0,2,4,6. When the X=4 and the X=6, the alloy is high in hydrogen storage capacity, and the alloy is low in dehydrogenation activation energy, thereby providing a strong foundation for researching the solid solution hydrogen storage materials in future.
Description
Technical field
The invention belongs to hydrogen storage material technical field, specifically a kind of preparation method of Mg-Li solid solution hydrogen storage material, the method prepare a kind of have be easier to activate, reversible hydrogen storage capacity is high, dehydrogenation activation energy is low Mg-Li solid solution hydrogen storage material.
Background technology:
Mg and Li is light-weight metal element, their theoretical hydrogen storage capability is respectively 7.76wt% and 12.5wt%, it is the high-energy-density hydrogen storage material very with development prospect, but due to Mg and Li element too active, be combined with hydrogen atom and form comparatively stable hydride, cause their practical application to be restricted.At MgH
2with in LiH, hydrogen atom mainly occupies in the interstitial site between atoms metal, and therefore, the number of interstitial site directly affects the hydrogen-storage amount of metal hydride.Mg and Li is compounded in the hydrogen storage property that to a certain degree can improve Mg-Li system, but the thermodynamics of Mg-Li system composite hydrogen storage material is still comparatively stable, for improving the comprehensive hydrogen storage property of Mg-Li system, Mg-Li system mix element or more multielement be expected to solve the problem.Simultaneously for ensureing that Mg-Li system hydrogen storage capability reaches the requirement of practical application, Mg-Li system is prepared into solid-solution material to can yet be regarded as a kind of effective method, because the lattice types of sosoloid still keeps consistent with solvent lattice types, the position of hydrogen atom occupied by sosoloid is not reduced.Therefore prepare Mg-Li system solid-solution material using Mg or Li as matrix, the hydrogen storage capability of matrix material can be ensured to a great extent.Si, as a kind of special elements, has had both the feature of inorganic materials and organic materials, the compound of Mg, Li and Si ternary lightweight element, is expected to solve Mg-Li system hydrogen storage material thermodynamic stability high, not easily decomposes and inhale the feature of hydrogen desorption kinetics poor performance.
Summary of the invention
The object of this invention is to provide a kind of preparation method of Mg-Li solid solution hydrogen storage material.
The technical scheme that the present invention solves the problems of the technologies described above is as follows:
The processing step of a kind of preparation method of Mg-Li solid solution hydrogen storage material is as follows:
1. according to Mg:Li:Si=90:(10-X): be pressed into round sheet sample after the atomic ratio Homogeneous phase mixing of X, next round sheet sample is placed in vacuum annealing furnace, utilize argon shield, anneal 2h under temperature is 500 DEG C of conditions, and then round sheet sample broke, obtain composite powder; Described X=0,2,4,6.
2. under argon shield, utilizing planetary ball mill, is 40:1 by ratio of grinding media to material, with the rotating speed of 300 revs/min to step 1) composite powder carry out mechanical ball milling.
3. in mechanical milling process, under argon shield, sample was processed at interval of 5 hours, avoid composite powder to glue tank.
4. collected specimens after ball milling 50h, finally carries out XRD, PCT and DTA/TG test.
Above-mentioned through annealing again mechanical ball milling after 50 hours, Mg
90li
6si
4and Mg
90li
4si
6alloy can be inhaled at a lower temperature and put hydrogen, and their dehydrogenation activation energy is lower.
Above-mentioned Mg-Li solid solution hydrogen storage material is prepared into fuel cell, is mainly used in Hydrogen Energy storage system.
Advantage of the present invention: the Mg:Li:Si=90:(10-X prepared through the mechanical ball milling 50h again that anneals): X matrix material, wherein: X=0,2,4,6, in the corresponding alloy of X=4 and X=6, there is higher hydrogen storage capability, and their dehydrogenation activation energy is lower, is the research establish a firm foundation of later solid solution hydrogen storage material.
Accompanying drawing explanation
Fig. 1 Mg
90li
10-xsi
xthe XRD figure of (X=0,2,4,6) matrix material.
Fig. 2 Mg
90li
10-xsi
xxRD figure after (X=0,2,4,6) matrix material hydrogenation.
Fig. 3 Mg
90li
10-xsi
xxRD figure after (X=0,2,4,6) matrix material dehydrogenation.
Fig. 4 Mg
90li
10-xsi
x(X=0,2,4,6) matrix material is at the P-C-T curve of 325 DEG C.
Fig. 5 Mg
90li
10-xsi
xthe alternating temperature Hydrogen desorption isotherms of (X=0,2,4,6) matrix material.
Fig. 6 Mg
90li
10-xsi
xthe Kissinger curve of (X=0,2,4,6) matrix material.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1
The processing step of the preparation method of Mg-Li solid solution hydrogen storage material is as follows:
The atomic ratio of Mg:Li=90:10 is configured sample; mix the rear powder compressing machine that utilizes and be pressed into the round sheet that radius is 1.6cm; and be placed in vacuum annealing furnace; anneal 2h under argon shield; then the round sheet sample broke of annealing gained; be 40:1 by ratio of grinding media to material; rotating speed is carry out mechanical ball milling in 300 revs/min of situations; during ball milling at interval of 5 hours under argon shield alloy powder process; collected specimens after ball milling 50h; finally carry out XRD, PCT and DTA/TG test.
Embodiment 2
The processing step of the preparation method of Mg-Li solid solution hydrogen storage material is as follows:
The atomic ratio of Mg:Li:Si=90:8:2 is configured sample; mix the rear powder compressing machine that utilizes and be pressed into the round sheet that radius is 1.6cm; and be placed in vacuum annealing furnace; anneal 2h under argon shield; then the round sheet sample broke of annealing gained; be 40:1 by ratio of grinding media to material; rotating speed is carry out mechanical ball milling in 300 revs/min of situations; during ball milling at interval of 5 hours under argon shield alloy powder process; collected specimens after ball milling 50h; finally carry out XRD, PCT and DTA/TG test.
Embodiment 3
The processing step of the preparation method of Mg-Li solid solution hydrogen storage material is as follows:
The atomic ratio of Mg:Li:Si=90:6:4 is configured sample; mix the rear powder compressing machine that utilizes and be pressed into the round sheet that radius is 1.6cm; and be placed in vacuum annealing furnace; anneal 2h under argon shield; then the round sheet sample broke of annealing gained; be 40:1 by ratio of grinding media to material; rotating speed is carry out mechanical ball milling in 300 revs/min of situations; during ball milling at interval of 5 hours under argon shield alloy powder process; collected specimens after ball milling 50h; finally carry out XRD, PCT and DTA/TG test.
Embodiment 4
The processing step of the preparation method of Mg-Li solid solution hydrogen storage material is as follows:
The atomic ratio of Mg:Li:Si=90:4:6 is configured sample; mix the rear powder compressing machine that utilizes and be pressed into the round sheet that radius is 1.6cm; and be placed in vacuum annealing furnace; anneal 2h under argon shield; then the round sheet sample broke of annealing gained; be 40:1 by ratio of grinding media to material; rotating speed is carry out mechanical ball milling in 300 revs/min of situations; during ball milling at interval of 5 hours under argon shield alloy powder process; collected specimens after ball milling 50h; finally carry out XRD, PCT and DTA/TG test.
As shown in Figures 1 to 3, sample is annealed at 773K temperature, and mechanical ball milling is after 50 hours again for 2h, and matrix material is mainly containing Mg phase, Li or LiH has been solidly soluted in Mg matrix completely, forms Mg-Li system sosoloid, except X=0, and Mg
90li
10-xsi
xalso there is Mg in (X=2,4,6) matrix material
2si phase, and Mg
2si phase does not change in the front and back of putting of matrix material.As shown in Figure 4, at 325 DEG C of temperature, Mg
90li
10-xsi
x(X=0,2,4,6) matrix material hydrogen－sucking amount is respectively 6.87wt.%, 6.69wt%, 5.78wt% and 5.28wt%, and the hydrogen storage capability increasing matrix material along with Si content declines, but the interpolation of Si effectively can reduce suction hydrogen platform pressure; Putting under hydrogen pressure is 0.06atm situation, due in the matrix material that X=2 is corresponding, Si content is too low, Mg
2si katalysis is not obvious, and the matrix material that the matrix material causing X=2 corresponding is corresponding with x=0 is the same, can not discharge hydrogen at 325 DEG C of temperature, but after the value of X is increased to 4 or 6, at Mg
2under the katalysis of Si, matrix material can discharge hydrogen at 325 DEG C of temperature.As shown in Figure 5, at ambient pressure, when being increased to 390 DEG C gradually from room temperature, Mg
90li
10-xsi
x(X=0,2,4,6) matrix material amount of dehydrogenation is followed successively by 4.39wt.%, 4.51wt.%, 4.57wt.% and 5.38wt.%, the amount of dehydrogenation of material increases gradually along with the increase of Si content, and initial dehydrogenated temperature obviously declines, especially as X=6, under normal pressure, the initial dehydrogenated temperature of matrix material have decreased to about 340 DEG C from 370 DEG C before interpolation Si, and initial dehydrogenated temperature have dropped 30 DEG C than the matrix material not adding Si.As shown in Figure 6, Mg
90li
10-xsi
x(X=0,2,4,6) apparent activation energy of matrix material is followed successively by 179.5,163.6,155.2 and 128.3Kj/mol, Si adds the apparent activation energy being conducive to reducing Mg-Li solid solution composite material, and especially the apparent activation energy of the corresponding matrix material of X=6 reduces 51.2kJ/mol than when not adding Si.
Claims (3)
1. a preparation method for Mg-Li solid solution hydrogen storage material, is characterized in that, the processing step of the method is as follows:
1) first according to Mg:Li:Si=90:(10-X): be pressed into round sheet sample after the atomic ratio Homogeneous phase mixing of X, next round sheet sample is placed in vacuum annealing furnace, utilize argon shield, anneal 2h under temperature is 500 DEG C of conditions, and then round sheet sample broke, obtain composite powder; Described X=0,2,4,6;
2) under argon shield, utilizing planetary ball mill, is 40:1 by ratio of grinding media to material, with the rotating speed of 300 revs/min to step 1) composite powder carry out mechanical ball milling;
3) in mechanical milling process, under argon shield, sample was processed at interval of 5 hours, avoid composite powder to glue tank;
4) collected specimens after ball milling 50h, finally carries out XRD, PCT and DTA/TG test.
2. press the preparation method of the Mg-Li solid solution hydrogen storage material described in claims 1, it is characterized in that, described through annealing again mechanical ball milling after 50 hours, Mg
90li
6si
4and Mg
90li
4si
6alloy can be inhaled at a lower temperature and put hydrogen, and their dehydrogenation activation energy is lower.
3. utilize the Mg-Li solid solution hydrogen storage material as described in claims 1 to be prepared into fuel cell, be mainly used in Hydrogen Energy storage system.
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| 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 |
| CN108467956A (en) * | 2018-03-22 | 2018-08-31 | 燕山大学 | A kind of Si/La15Fe2Ni72Mn7B2Mo2The preparation method of composite hydrogen occluding alloy material |
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