WO2020207188A1 - 一种纳米氢化镁的原位制备方法 - Google Patents

一种纳米氢化镁的原位制备方法 Download PDF

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WO2020207188A1
WO2020207188A1 PCT/CN2020/079105 CN2020079105W WO2020207188A1 WO 2020207188 A1 WO2020207188 A1 WO 2020207188A1 CN 2020079105 W CN2020079105 W CN 2020079105W WO 2020207188 A1 WO2020207188 A1 WO 2020207188A1
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nano
magnesium
hydride
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magnesium hydride
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刘永锋
张欣
潘洪革
高明霞
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Zhejiang University
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    • C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
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    • C01B3/0005—Reversible storage of hydrogen, e.g. by hydrogen getters or electrodes
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    • C01P2004/00—Particle morphology
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    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
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    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/32—Hydrogen storage

Definitions

  • the invention relates to the technical field of hydrogen storage materials and nano materials, in particular to an in-situ preparation method of nano magnesium hydride.
  • MgH 2 is a typical light metal hydride hydrogen storage material, its theoretical hydrogen storage capacity is as high as 7.6% by weight, and its reversibility is good, and it has received extensive attention from researchers.
  • MgH 2 has high thermodynamic stability, the initial hydrogen release temperature is as high as 300°C, and the hydrogen release rate is slow, which is not conducive to the application of on-board hydrogen storage. Therefore, reducing the hydrogen absorption and desorption temperature of MgH 2 has always been the focus of research in this field.
  • the research on the modification of MgH 2 hydrogen storage materials mainly focuses on: (1) catalytic doping, (2) composition modulation, and (3) nanometerization.
  • Catalyst doping is currently the most studied modification method. This method can significantly improve the hydrogen absorption and desorption kinetic performance of MgH 2 on the basis of ensuring a certain hydrogen storage capacity.
  • This method can significantly improve the hydrogen absorption and desorption kinetic performance of MgH 2 on the basis of ensuring a certain hydrogen storage capacity.
  • people have successively found that Ti-, Zr-, V-, Nb-, Ni- and Co-based catalysts can significantly improve the performance of MgH 2 dehydrogenation/hydrogenation kinetics.
  • the thermodynamics of MgH 2 is relatively stable, the initial hydrogen release temperature is still high, and the existing catalysts are mainly based on transition metal oxides and halides, which easily react with MgH 2 to produce by-products MgCl 2 and MgO, etc., cause the loss of hydrogen storage capacity.
  • the purpose of the present invention is to provide an in-situ preparation method of catalyst-doped nano-magnesium hydride.
  • the method is based on the reaction [MgCl 2 -2LiH ⁇ MgH 2 +2LiCl] and utilizes the cavitation effect induced by ultrasonic waves in a liquid medium.
  • Add appropriate catalyst precursors during the preparation process It can realize in-situ catalytic doping.
  • the preparation method is simple and does not require a carrier.
  • the obtained catalyst-doped magnesium hydride hydrogen storage material has the advantages of high effective hydrogen storage capacity, low hydrogen absorption and desorption temperature, and fast hydrogen absorption and desorption rate.
  • An in-situ preparation method of nano-magnesium hydride includes the following steps:
  • the invention uses the cavitation effect induced by ultrasound in the liquid medium to provide energy, promote the chemical reaction between magnesium chloride and lithium hydride, and at the same time use the crushing effect of ultrasound to control the particle size of the product, inhibit nanoparticle agglomeration, and obtain nano-level hydrogenation magnesium.
  • the inert atmosphere refers to performing under an inert gas, and the inert gas is argon or the like.
  • the ingenuity of the invention is that ultrasonic treatment is used to accelerate the reaction of raw materials and control the particle size of the product, and realize the preparation of nano-magnesium hydride under the premise of simplifying the operation steps and reducing the energy consumption of the reaction.
  • step (1) before magnesium chloride and lithium hydride are added to the organic solvent, the magnesium chloride and lithium hydride are respectively ball-milled to obtain ball-milled magnesium chloride and ball-milled lithium hydride;
  • the rotation speed of the ball mill is 100 to 400 revolutions per hour, and the time is 3 to 12 hours.
  • the magnesium chloride is anhydrous magnesium chloride, and the molar ratio of magnesium chloride to lithium hydride is 1:2; selecting this ratio can fully convert magnesium chloride into magnesium hydride, and lithium hydride into lithium chloride , In line with the following reaction equation:
  • the organic solvent is ultra-dry tetrahydrofuran, ultra-dry cyclohexane or ultra-dry ethyl ether.
  • step (A) is used instead of step (1);
  • the transition metal chloride is a chloride without crystal water, specifically titanium tetrachloride, titanium trichloride, zirconium tetrachloride, vanadium trichloride, niobium pentachloride, nickel dichloride or cobalt dichloride .
  • the present invention uses transition metal chloride as the catalyst precursor, magnesium chloride as the magnesium source, lithium hydride as the hydrogen source and reducing agent, and the cavitation effect generated by ultrasonic waves as the energy source.
  • the powder is dispersed in an organic solvent for ultrasonic treatment to promote Lithium hydride chemically reacts with magnesium chloride to produce magnesium hydride and lithium chloride.
  • lithium hydride reduces transition metal chlorides to elemental metals to produce lithium chloride; the ultrasonic solid reaction product is cleaned by an organic solvent to dissolve and remove side effects.
  • the product lithium chloride is separated by centrifugation or suction filtration to obtain a solid powder material, which is further dried in a dynamic vacuum to obtain nano-magnesium hydride doped with a transition metal catalyst.
  • the applicable range of the molar ratio of transition metal chloride to magnesium chloride is slightly different.
  • the molar ratio of transition metal chloride to magnesium chloride is 0.01-0.05:1. This ratio can make the sample have better hydrogen absorption and desorption kinetics, and is good for storage. Hydrogen capacity has a small effect, and if it exceeds this range, the effect is not good; for zirconium tetrachloride, vanadium trichloride, niobium pentachloride, nickel dichloride and cobalt dichloride, the effect of transition metal chloride and magnesium chloride The molar ratio is 0.01 to 0.1:1.
  • the molar ratio of the lithium hydride to the chloride ion in the transition metal chloride is 1:1, and this ratio can be selected so that the metal chloride can be fully reduced, and all the lithium hydride can be converted into lithium chloride.
  • step (2) the power of the ultrasound is 100-600 W, the single ultrasound time is 0.5-1 hour, the intermittent is 10-30 minutes, and the cumulative ultrasound time is 3-24 hours.
  • the reaction degree of the raw materials gradually increases, and the output of MgH 2 also increases.
  • too long ultrasonic time will significantly increase the temperature of the system, causing the MgH 2 particles to grow up, and the resulting product will absorb and release hydrogen. Learning has slowed down; similar to prolonging the ultrasound time, too high power will cause excess energy, and increasing the temperature of the system will cause the particles of the product to increase, which is not conducive to the performance of the product.
  • the ultrasonic power is 210 W
  • the single ultrasonic time is 0.5 hour
  • the interval is 30 minutes
  • the cumulative ultrasonic time is 6 hours.
  • step (2) an ultrasonic rod is inserted into the organic suspension for ultrasonic treatment.
  • the results obtained are different; using an ultrasonic instrument equipped with an ultrasonic rod for preparation, the efficiency is higher, and the reaction rate is faster, while the use of an ultrasonic cleaning machine for preparation, the reaction acceleration effect is not good, and the reaction rate is slow .
  • the organic solvent is ultra-dry tetrahydrofuran or ultra-dry acetone; the cleaning time is 1 to 2 hours, which can ensure that the by-product lithium chloride is fully dissolved.
  • the drying is realized by heating under the protection of a vacuum environment (vacuum degree not less than 1 ⁇ 10 -3 Torr) or an inert atmosphere, and the treatment time is 1 to 2 hours.
  • the sample needs to be sealed in the centrifuge tube to prevent water and oxygen pollution, the centrifugal speed is 5000-10000 rpm, and the centrifugal time is 5-20 minutes.
  • the present invention provides a nano magnesium hydride prepared by the in-situ preparation method.
  • the present invention has the following beneficial effects:
  • the present invention uses the cavitation effect generated by ultrasound as the energy source to promote the chemical reaction between magnesium chloride and lithium hydride, and at the same time, uses the crushing effect of ultrasound to control the particle size of the product, inhibit nanoparticle agglomeration, and avoid the addition of various carriers
  • the material inhibits the side effects caused by the growth of particles, thereby obtaining nano-scale magnesium hydride, maintaining the high hydrogen storage capacity of the product.
  • the method of the present invention adds magnesium chloride, lithium hydride and transition metal chloride to an organic solvent for ultrasound, which can simultaneously realize the nanometerization of magnesium hydride and catalyst doping, and make full use of the nano effect and nano catalytic effect to make magnesium hydride
  • the hydrogen release temperature is greatly reduced.
  • the present invention uses LiH as a reducing agent, which can fully reduce high-valent metals while preparing nano-magnesium hydride.
  • the reaction precursor MgCl 2 is easily soluble in organic solvents such as tetrahydrofuran, and LiH has a low density and usually floats in the solvent.
  • LiH has a low density and usually floats in the solvent.
  • lithium chloride is soluble in a variety of organic solvents. The above-mentioned substances are easily removed after the reaction is completed, which can ensure the purity of the final product.
  • the catalyst prepared by the method of the present invention is mixed with magnesium hydride hydrogen storage materials After that, no by-products like MgCl 2 or MgO will be produced, which is conducive to maintaining high capacity of hydrogen storage materials, and the catalyst is generated at the same time as nano-magnesium hydride. At the same time, nano-materials and catalyst doping are realized. The particles are evenly distributed, and the catalytic effect is excellent.
  • the nano-magnesium hydride prepared by the method of the present invention has a particle size maintained within 5 nm, a high hydrogen storage capacity, and the hydrogen absorption and desorption temperature is greatly reduced compared with conventional magnesium hydride.
  • Figure 1 shows the EDS spectrum (a) and XPS spectrum (b) of the nano-magnesium hydride prepared in Example 1.
  • Figure 2 is an SEM photograph of the nano-magnesium hydride prepared in Example 1.
  • Figure 3 is a TEM image (a) and a high resolution TEM image (b, c) of the nano-magnesium hydride prepared in Example 1.
  • Figure 4 shows the temperature-dependent degassing mass spectrum curves of the nano-magnesium hydride prepared in Example 1: (a) hydrogen evolution curve and (b) tetrahydrofuran evolution curve.
  • Fig. 5 is a comparison diagram of the mass spectrometry curves of the nano-magnesium hydride sample prepared in Example 1 and the magnesium hydride prepared in Comparative Example 2 and Comparative Example 3 with temperature.
  • Example 6 is an XRD pattern of the nano-magnesium hydride sample (a) prepared in Example 1 and the magnesium hydride (b) prepared in Comparative Example 2 and Comparative Example 3 to different stages.
  • Example 7 shows the EDS spectrum (a) and the Ti element XPS spectrum (b) of the Ti-catalyzed-doped nano-magnesium hydride sample prepared in Example 2.
  • Example 8 is a TEM image (a) and a high-resolution TEM image (b) of the Ti-catalyzed doped nano-magnesium hydride sample prepared in Example 2.
  • Example 9 is a comparison diagram of the temperature-dependent dehydrogenation mass spectra of the Ti-catalyzed-doped nano-magnesium hydride sample prepared in Example 2 and the TiCl 4 doped magnesium hydride prepared in Comparative Examples 4 and 5.
  • FIG. 10 is a comparison diagram of the temperature-dependent dehydrogenation mass spectra of magnesium hydride samples prepared in Example 2 and Comparative Example 6 with different amounts of Ti catalyst added.
  • Example 11 is an XRD comparison diagram of the dehydrogenation products of magnesium hydride samples prepared in Example 2 and Comparative Example 6 with different Ti catalyst addition amounts.
  • FIG 13 V catalyst prepared in Example 3 was doped with magnesium hydride nano comparative sample 7, for comparison FIG VCl ratio of 82 prepared magnesium hydride doped with temperature dehydrogenation mass profile.
  • Example 14 shows the EDS spectrum (a) and the XPS spectrum (b) of the Zr element of the Zr-catalyzed-doped nano-magnesium hydride sample prepared in Example 4.
  • Example 15 is a comparison diagram of the temperature-dependent dehydrogenation mass spectra of the Zr-catalyzed-doped nano-magnesium hydride sample prepared in Example 4 and the ZrCl 4 doped magnesium hydride prepared in Comparative Example 9 and Comparative Example 10.
  • Example 16 is a comparison diagram of the temperature-dependent dehydrogenation mass spectra of the Nb catalytically doped nano-magnesium hydride sample prepared in Example 5 and the NbCl 5 doped magnesium hydride prepared in Comparative Examples 11 and 12.
  • Figure 17 is the SEM photograph (a), TEM photograph (b) and high resolution TEM photograph (c, d) of the Ni-catalyzed-doped nano-magnesium hydride sample prepared in Example 6.
  • FIG 18 is a comparative sample prepared NiCl conventional method 6 Ni catalyst prepared in Example 2 doped with magnesium hydride nano magnesium hydride doped with temperature dehydrogenation mass profile embodiment.
  • step (4) Separate the solid powder obtained in step (4) by centrifugation (8000 revolutions/min), clean it with tetrahydrofuran again, and centrifuge to obtain the solid powder, in a dynamic vacuum (vacuum degree of 1 ⁇ 10 -3 Torr) Keep it dry for 2 hours to remove the remaining tetrahydrofuran to obtain a nano-magnesium hydride sample, and then store the sample in a glove box for later use.
  • a dynamic vacuum vacuum degree of 1 ⁇ 10 -3 Torr
  • the sample prepared in the above process is: nano-MgH 2 sample (nano-MgH 2 ). It can be seen from Figure 1a that the sample contains only magnesium. The weak oxygen signal and carbon signal are derived from carbon and oxygen pollution in the air or A trace of organic solvent remains, indicating that the sample is composed of magnesium; as can be seen from Figure 1b, the 2p spin orbit peak of magnesium in the obtained sample is located at: 50.2eV, indicating that the magnesium in the sample is all in the form of magnesium hydride .
  • the sample is made up of a large number of magnesium hydride nanoparticles, and the particles are mostly approximately spherical.
  • the magnesium hydride nanoparticles are basically maintained at 5nm, and the high-resolution transmission photos can indicate that the crystal plane spacing of the magnesium hydride particles of 0.225nm corresponds to the (200) crystal plane family.
  • the nano-magnesium hydride can be successfully prepared by this method. Heat the sample from room temperature to 400°C at 2°C/min, and use a mass spectrometer to analyze the degassing curve of the sample during heating (Figure 4). It can be seen from the figure that nano-magnesium hydride only releases hydrogen during heating. , Almost no tetrahydrofuran gas is released, indicating that the organic solvent has been completely removed in the dynamic vacuum. It can be seen from the hydrogen release curve that the initial hydrogen release temperature of the sample is lower than 100°C, and the peak temperature of hydrogen release in the first step is 190°C. The hydrogen release temperature is lower than that of magnesium hydride samples prepared by conventional methods.
  • step (3) Using centrifugation (8000 rpm), the solid matter in the ultrasonic product in step (3) is separated.
  • anhydrous magnesium chloride and lithium hydride (molar ratio 1:2) in total to a ball mill tank and perform ball milling on a high-energy ball mill.
  • the ball milling atmosphere is an argon atmosphere and the speed is 500
  • the ball-to-battery ratio is 120:1, and the milling time is 24 hours.
  • the sample after ball milling is placed in tetrahydrofuran under an inert atmosphere and washed twice to remove the by-product lithium chloride, and then the solid powder is obtained by centrifugation.
  • the remaining tetrahydrofuran can be removed to obtain the MgH 2 sample prepared by the ball milling method. Then the sample is heated to 400°C at a heating rate of 2°C/min and recorded by mass spectrometer The hydrogen release behavior of the sample during heating.
  • the speed is: 500 rpm, the ball The material ratio is 120:1, ball milled for 24 hours to obtain a magnesium hydride sample, and then the sample is heated to 400°C at a heating rate of 2°C/min, and the hydrogen release behavior of the sample during the heating process is recorded by a mass spectrometer.
  • step (4) Separate the solid powder obtained in step (4) by centrifugation (8000 revolutions/min), clean it with tetrahydrofuran again, and centrifuge to obtain the solid powder, in a dynamic vacuum (vacuum degree of 1 ⁇ 10 -3 Torr) Keeping for 2 hours to remove residual tetrahydrofuran, a Ti-catalyzed doped nano-magnesium hydride sample named nano-MgH 2 -0.03Ti can be obtained, and then the sample is stored in a glove box for later use.
  • the sample contains only magnesium and titanium elements.
  • the weak oxygen and carbon signals come from carbon and oxygen pollution in the air or trace organic solvent residues, indicating that the main phase of the sample is magnesium hydride and a small amount of titanium.
  • the Ti2p 3/2 -2p 1/2 dual spin orbit peaks of titanium in the obtained sample are located at 453.9 and 459.3 eV, respectively, indicating that TiCl 4 has been completely reduced by this method It is a simple substance of Ti. It can be seen that ultrasound can not only trigger the synthesis reaction of MgH 2 but also the reduction reaction of TiCl 4 by LiH.
  • the magnesium hydride nanoparticles are basically maintained at 5 nm. From the high-resolution transmission photos, it can be calibrated that the crystal plane spacing of the magnesium hydride particles of 0.225 nm corresponds to the (200) crystal plane family.
  • the degassing curve of the sample during the heating process was analyzed by a mass spectrometer.
  • the hydrogen release temperature is 35°C (0.01:1) and 50°C (0.05:1)
  • the peak temperature of hydrogen release in the first step is 90°C (0.01:1) and 125°C (0.05:1) ( Figure 9).
  • the sample after ball milling is placed in tetrahydrofuran under an inert atmosphere and washed twice to remove by-product chlorination Lithium is then centrifuged to obtain solid powder, and the residual tetrahydrofuran is removed under dynamic vacuum conditions (vacuum degree is 1 ⁇ 10 -3 Torr) to obtain titanium-catalyzed doped MgH 2 samples.
  • the molar ratio of titanium catalyst to magnesium chloride is 0.03:1, and then the sample is heated to 400°C at a heating rate of 2°C/min, and the hydrogen release behavior of the sample during the heating process is recorded by a mass spectrometer.
  • the Ti-catalyzed doped nano-magnesium hydride prepared by the ultrasonic-assisted method has a lower initial temperature of 140°C than that of the magnesium hydride prepared by the ball milling method, and the peak temperature of the hydrogen release in the first step is reduced by 143°C.
  • the performance is significantly better than the samples prepared by the ball milling method.
  • the molar ratio of titanium catalyst to MgH 2 is 0.03:1, and then The sample was heated to 400°C at a heating rate of 2°C/min, and the hydrogen release behavior of the sample during the heating process was recorded by a mass spectrometer.
  • the initial temperature of Ti-catalyzed-doped magnesium hydride prepared by the ultrasonic-assisted method is 120°C lower than that of Ti-catalyzed doped magnesium hydride prepared by the heating-ball milling method, and the peak temperature of hydrogen release in the first step
  • the hydrogen desorption performance is significantly improved when the temperature is reduced at 110°C.
  • the preparation method is the same as in Example 2, but the difference is that the transition metal catalyst used is: vanadium trichloride VCl 3.
  • Table 1 lists the corresponding raw material ratio and key process. The sample is named nano-MgH 2 -0.03 V.
  • the sample contains only magnesium and vanadium.
  • the weak oxygen and carbon signals come from carbon and oxygen pollution in the air or trace organic solvent residues, indicating that the main phase of the sample is magnesium hydride and a small amount of vanadium.
  • the V2p 3/2 -Vp 1/2 dual spin orbit peaks of the titanium element in the obtained sample are located at 512.5 and 519.7eV, respectively, indicating that the VCl 3 has been completely reduced by this method It is V simple substance.
  • the dehydrogenation curve (2°C/min) of the sample was analyzed by a mass spectrometer ( Figure 13).
  • the hydrogen desorption performance parameters of the sample in this example are summarized in Table 4. This sample has a lower hydrogen desorption temperature than the magnesium hydride sample prepared by the conventional method .
  • the method is the same as that used in Comparative Example 4, except that the transition metal chloride used is: vanadium trichloride.
  • Table 2 shows the ball milling process and the ratio of raw materials used in the Comparative Example:
  • Comparative Example 5 The method used in Comparative Example 5 is the same, but the difference is that the transition metal chloride used is: vanadium trichloride.
  • Table 3 shows the ball milling process and raw material ratio for the mixed catalyst and magnesium hydride in the Comparative Example:
  • the preparation method is the same as in Example 2, except that the transition metal catalyst used is: zirconium tetrachloride ZrCl 4.
  • Table 4 lists the corresponding raw material ratio and key processes. The sample is named nano-MgH 2 -0.03 Zr.
  • Figure 14a shows the energy spectrum data (EDS) of the sample. It can be seen from the figure that the sample contains only magnesium and zirconium. The weak oxygen and carbon signals come from carbon and oxygen pollution in the air or trace organic solvents. Residual, indicating that the main phase of the sample is magnesium hydride, and a small amount of zirconium is used as the catalyst;
  • Figure 14 shows the X-ray photoelectron spectroscopy (XPS spectrum) of titanium in the sample. It can be seen from the figure that the zirconium in the obtained sample The Zr3d 5/2 -3d 3/2 dual-spin orbit peaks are located at 177.6 and 181.1eV, respectively, indicating that ZrCl 4 has been completely reduced to Zr elementary substance by this method.
  • EDS energy spectrum data
  • the method can successfully prepare nano-magnesium hydride samples that can be doped with Zr catalytically.
  • the dehydrogenation curve (2°C/min) of the sample was analyzed by a mass spectrometer ( Figure 15).
  • the hydrogen release performance parameters of the sample are summarized in Table 8. The sample has a lower hydrogen release temperature than the magnesium hydride sample prepared by the conventional method.
  • the method is the same as that used in Comparative Example 4, except that the transition metal chloride used is: zirconium tetrachloride.
  • Table 6 shows the ball milling process and raw material ratio used in the Comparative Example:
  • FIG. 15 shows a comparison diagram of the hydrogen release curve of the sample of Example 4 and the sample of the comparative example.
  • the hydrogen release performance parameters of the sample of the comparative example are summarized in Table 8.
  • the method is the same as that used in Comparative Example 5, but the difference is that the transition metal chloride used is: zirconium tetrachloride.
  • Table 7 shows the ball milling process and raw material ratio for the mixed catalyst and magnesium hydride in the Comparative Example:
  • the preparation method is the same as in Example 2, but the difference is that the transition metal catalyst used is: zirconium tetrachloride NbCl 5.
  • Table 9 lists the corresponding raw material ratio and key technology. The sample is named nano-MgH 2 -0.03 Nb.
  • Figure 16 shows the dehydrogenation curve (2°C/min) of the sample during the heating process.
  • the hydrogen release performance parameters of the sample are summarized in Table 11. Compared with the magnesium hydride sample prepared by the conventional method, the hydrogen release temperature is lower.
  • the method is the same as that used in Comparative Example 4, but the difference is that the transition metal chloride used is: niobium pentachloride.
  • Table 10 shows the ball milling process and the ratio of raw materials used in the Comparative Example:
  • the method is the same as that used in Comparative Example 5, except that the transition metal chloride used is: niobium pentachloride.
  • Table 11 shows the ball milling process and raw material ratio for the mixed catalyst and magnesium hydride in the Comparative Example:
  • the preparation method is the same as in Example 2, but the difference is that the transition metal catalyst used is: zirconium tetrachloride NiCl 2.
  • Table 13 lists the corresponding raw material ratio and key processes. The sample is named nano-MgH 2 -0.03 Ni.
  • Figure 17 shows the SEM and TEM pictures of the nano-MgH 2 -0.03Ni sample. It can be seen from the figure that the sample presents a layered structure similar to graphene. It can be seen from the TEM picture of the sample that each layer of the sample It contains a large number of overlapping nano-MgH 2 particles, and the particle size is maintained at about 3 nanometers. It can be seen that the morphology of the product can be adjusted to a certain extent by changing the composition of the additive.
  • Figure 18 shows the hydrogen release curve (2°C/min) of the sample of this example.
  • the hydrogen release performance parameters of the sample of this example are summarized in Table 16. Compared with the magnesium hydride sample prepared by the conventional method, the hydrogen release temperature is lower.
  • Comparative Example 4 The method used in Comparative Example 4 is the same, but the difference is that the transition metal chloride used is nickel dichloride.
  • Table 14 shows the ball milling process and the ratio of raw materials used in the Comparative Example:

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Abstract

一种纳米氢化镁的原位制备方法，包括在惰性气氛保护下，将氯化镁和氢化锂放置于有机溶剂中，搅拌，得到混合物的有机悬浊液；对该有机悬浊液进行超声处理，促进混合物发生化学反应，反应结束后，过滤；对固体反应产物进行清洗、离心和干燥，脱除残留有机物，得到纳米氢化镁。本方法以超声波在液体介质中产生的空化效应提供的能量促进氯化镁和氢化锂之间的化学反应。由于空化效应能够在极小的范围内瞬间提供大量的能量，相比传统的加热和机械力供能，所制备的产物颗粒不易长大；同时利用超声波的破碎作用抑制纳米颗粒团聚，避免了添加各类载体材料抑制颗粒长大所导致的副作用，从而获得有效储氢容量提高的纳米级的氢化镁。

Description

一种纳米氢化镁的原位制备方法 技术领域
本发明涉及储氢材料和纳米材料技术领域，尤其涉及一种纳米氢化镁的原位制备方法。
背景技术
能源危机的加剧和地球环境的恶化，促使人类加快可再生清洁能源的开发。氢能以其丰富的储量和清洁无污染的特点得到了人们的关注。目前，制约氢经济的瓶颈主要是氢气的储运，而开发基于化学储氢的固体储氢材料被誉为是解决车载储氢问题的最有效途径。
MgH 2是一种典型的轻金属氢化物储氢材料，其理论储氢容量高达7.6wt％，且可逆性好，受到了研究者的广泛的关注。但MgH 2的热力学稳定性较高，起始放氢温度高达300℃，放氢速率缓慢，不利于车载储氢的应用，因此，降低MgH 2的吸放氢温度一直是该领域研究的重点。
目前，针对MgH 2储氢材料的改性研究主要集中在：(1)催化掺杂，(2)成分调变，和(3)纳米化，这三个方面。
催化剂掺杂是目前研究最多的改性手段，该方法可以在确保一定储氢容量的基础上显著改善MgH 2的吸放氢动力学性能。基于催化改性的方法，人们陆续发现Ti-、Zr-、V-、Nb-、Ni-和Co-基催化剂对MgH 2的脱/加氢动力学性能有明显的改善作用。但MgH 2的热力学较为稳定，起始放氢温度仍然较高，而且现有的催化剂主要是基于过渡金属氧化物和卤化物的催化剂，在加热过程中容易与MgH 2反应产生副产物MgCl 2和MgO等，造成储氢容量的损失。
相比于添加催化剂，纳米化有望同时调变MgH 2的热力学性能和动力学性能，使MgH 2的起始放氢温度显著下降，放氢速率提升，但现有的MgH 2纳米化技术大都基于高比表面材料负载MgH 2纳米颗粒。为了避免纳米MgH 2在制备中发生颗粒长大或团聚需要引入大量的碳、介孔硅等载体材料对纳米产物进行分散，会显著降低材料的储氢容量，不利于实际应用。
因此，制备颗粒尺寸小，催化活性高的金属单质催化剂，同时开发无需载体的纳米MgH 2制备技术，并将催化掺杂与纳米化技术结合，开发无载体纳米氢化镁原位催化技术是当前进一步改善MgH 2基储氢材料最为可行的途径。
发明内容
本发明的目的在于提供一种催化剂掺杂纳米氢化镁的原位制备方法，该方法以反应[MgCl 2-2LiH→MgH 2+2LiCl]为基础，利用超声波在液体介质中引发的空化效应，在 极小范围内快速提供能量，从而促进反应进行；同时，利用超声波的分散效应控制产物的颗粒尺寸，避免颗粒团聚，能有效实现氢化镁的纳米化制备，在制备过程中加入适当的催化剂前驱体，可实现原位催化掺杂，制备方法简便，无需载体，所得催化剂掺杂的氢化镁储氢材料，具有有效储氢容量高，吸放氢温度低，吸放氢速率快的优点。
具体技术方案如下：
一种纳米氢化镁的原位制备方法，包括以下步骤：
(1)在惰性气氛保护下，将氯化镁和氢化锂放置于有机溶剂中，搅拌，得到混合物的有机悬浊液；
(2)在惰性气氛保护下，对所述有机悬浊液进行超声处理，促进混合物发生化学反应，反应结束后，过滤，得到固体反应产物；
(3)在惰性气氛保护下，利用有机溶剂对固体反应产物进行清洗、离心和干燥，脱除残留有机物，得到纳米氢化镁。
本发明以超声波在液体介质中引发的空化效应提供能量，促进氯化镁和氢化锂之间的化学反应，同时利用超声波的破碎作用控制产物的颗粒尺寸，抑制纳米颗粒团聚，从而获得纳米级的氢化镁。所述惰性气氛是指在惰性气体下进行，所述惰性气体为氩气等。
本发明的巧妙之处在于利用超声处理既加速原料反应又控制产物粒径，在简化操作步骤、降低反应能耗的前提下，实现纳米氢化镁的制备。
为了能够将原材料进行充分的颗粒细化，以便原料能够在后续操作中更好地分散到有机溶剂里。作为优选，步骤(1)中，在将氯化镁和氢化锂加入至有机溶剂之前，分别将氯化镁和氢化锂进行球磨，得到球磨后的氯化镁和球磨后的氢化锂；
所述球磨的转速为100～400转/小时，时间为3～12小时。
进一步地，步骤(1)中，所述氯化镁为无水氯化镁，氯化镁与氢化锂的摩尔比为1:2；选择该配比可使氯化镁充分转变为氢化镁，且氢化锂转化为氯化锂，符合下述反应方程式：
MgCl 2+2LiH→MgH 2+2LiCl          (1)
进一步地，所述的有机溶剂为超干四氢呋喃、超干环己烷或超干乙醚。
进一步地，采用步骤(A)替代步骤(1)；
步骤(A)：将氯化镁、氢化锂和过渡金属氯化物一同放置于有机溶剂中，搅拌，得到有机悬浊液；再经步骤(2)和(3)，得到催化剂掺杂的纳米氢化镁；
所述过渡金属氯化物为无结晶水的氯化物，具体为四氯化钛、三氯化钛、四氯化锆、三氯化钒、五氯化铌、二氯化镍或二氯化钴。
本发明以过渡金属氯化物作为催化剂前驱体，氯化镁作为镁源，氢化锂作为氢源及还原剂，超声波产生的空化效应为能量源，通过将粉末分散在有机溶剂中，进行超声处理，促使氢化锂与氯化镁发生化学反应，生成氢化镁和氯化锂，与此同时，氢化锂将过渡金属氯化物还原为金属单质，生成氯化锂；通过有机溶剂清洗超声固体反应产物，可以溶解除去副产物氯化锂，然后离心或抽滤分离，得到固体粉末材料，进一 步在动态真空中干燥处理，获得过渡金属催化剂掺杂的纳米氢化镁。
进一步地，针对不同过渡金属氯化物，过渡金属氯化物与氯化镁摩尔比的适用范围略不同。其中，对于四氯化钛和三氯化钛而言，过渡金属氯化物与氯化镁的摩尔比为0.01～0.05:1，该配比可以使样品具有较好的吸放氢动力学，且对储氢容量影响较小，而超过该范围则效果不佳；对于四氯化锆、三氯化钒、五氯化铌、二氯化镍和二氯化钴而言，过渡金属氯化物与氯化镁的摩尔比为0.01～0.1:1。
进一步地，所述氢化锂与过渡金属氯化物中氯离子的摩尔比为1:1，选择该配比可以使金属氯化物充分被还原，且氢化锂全部转化为氯化锂。
进一步地，步骤(2)中，所述超声的功率为100～600W，单次超声时间为0.5-1小时，间歇10-30分钟，累计超声时间为3～24小时。随着超声时间的延长，原料的反应程度逐渐提高，MgH 2的产量也随之提高，但过长的超声时间会使体系温度明显提高，使MgH 2颗粒出现长大，所得产物吸放氢动力学有所减慢；与延长超声时间类似，过高的功率会造成能量过剩，升高体系的温度导致产物的颗粒增大，不利于产物的性能。
更优选，所述超声功率为210W，单次超声时间为0.5小时，间歇30分钟，累计超声时间为6小时。
进一步地，步骤(2)中，将超声杆插入所述有机悬浊液中，进行超声处理。采用不同超声仪器进行超声，得到的结果不同；利用配备超声杆的超声波仪器进行制备，效率较高，反应速率较快，而利用超声波清洗机进行制备，对反应的加速效果不好，反应速率慢。
进一步地，步骤(3)中，所述的有机溶剂为超干四氢呋喃或超干丙酮；清洗的时间为1～2小时，可以确保副产物氯化锂充分溶解。所述干燥在真空环境(真空度不低于1×10 -3Torr)或惰性气氛保护下加热实现，处理时间1～2小时。
步骤(3)的多次离心操作，需将样品装入离心管内密封，以防止水氧污染，离心转速为5000～10000转/分钟，离心时间为5～20分钟。
本发明提供了一种如所述的原位制备方法制得的纳米氢化镁。
与现有技术相比，本发明具有以下有益效果：
(1)本发明以超声波产生的空化效应为能量源促进氯化镁和氢化锂之间的化学反应，同时，利用超声波的破碎作用控制产物的颗粒尺寸，抑制纳米颗粒团聚，避免了添加各类载体材料抑制颗粒长大所导致的副作用，从而获得纳米级的氢化镁，保持了产物的高储氢容量。
(2)本发明方法将氯化镁、氢化锂和过渡金属氯化物一同加入至有机溶剂中进行超声，可同时实现氢化镁的纳米化和催化剂掺杂，充分利用纳米效应及纳米催化效应，使氢化镁的放氢温度大幅度降低。
(3)本发明利用LiH作为还原剂，在制备纳米氢化镁的同时，可以充分将高价态金属还原，此外，反应前驱体MgCl 2易溶于四氢呋喃等有机溶剂，LiH密度较低通常漂浮于溶剂表面，氯化锂作为副产物，可溶于多种有机溶剂，上述物质在反应结束 后易于除去，能够确保最终产物的纯度。
(4)与现有的金属氧化物(TiO 2、ZrO 2等)或卤化物(TiF、TiCl 3、ZrCl 4等)催化剂相比，使用本发明方法制备的催化剂，与氢化镁储氢材料混合后不会产生类似MgCl 2或MgO的副产物，有利于储氢材料保持高的容量，且催化剂与纳米氢化镁同时生成，同时实现了材料的纳米化和催化剂掺杂，而且催化剂在氢化镁纳米颗粒中分布均匀，催化效果优异。
(5)本发明方法制备的纳米氢化镁，颗粒尺寸维持在5nm以内，储氢容量高，吸放氢温度相比常规技术制备的氢化镁大幅度降低。
附图说明
图1为实施例1制备的纳米氢化镁的EDS图谱(a)和XPS图谱(b)。
图2为实施例1制备的纳米氢化镁的SEM照片。
图3为实施例1制备的纳米氢化镁的TEM图片(a)和高分辨TEM图片(b,c)。
图4为实施例1制备的纳米氢化镁的随温脱气质谱曲线：(a)氢气析出曲线和(b)四氢呋喃析出曲线。
图5为实施例1制备的纳米氢化镁样品与对比例2、对比例3制备的氢化镁随温脱氢质谱曲线的比较图。
图6为实施例1制备的纳米氢化镁样品(a)与对比例2、对比例3制备的氢化镁(b)放氢至不同阶段的XRD图。
图7为实施例2制备的Ti催化掺杂的纳米氢化镁样品的EDS图谱(a)和Ti元素XPS图谱(b)。
图8为实施例2制备的Ti催化掺杂的纳米氢化镁样品的TEM图片(a)和高分辨TEM图片(b)。
图9为实施例2制备的Ti催化掺杂的纳米氢化镁样品与对比例4、对比例5制备的TiCl 4掺杂的氢化镁随温脱氢质谱曲线的比较图。
图10为实施例2和对比例6制备的不同Ti催化剂添加量的氢化镁样品随温脱氢质谱曲线比较图。
图11为实施例2和对比例6制备的不同Ti催化剂添加量的氢化镁样品脱氢产物的XRD比较图。
图12为实施例3制备的V催化掺杂的纳米氢化镁样品的EDS图谱(a)和V元素XPS图谱(b)。
图13为实施例3制备的V催化掺杂的纳米氢化镁样品与对比例7、对比例8制备的VCl 2掺杂的氢化镁随温脱氢质谱曲线的比较图。
图14为实施例4制备的Zr催化掺杂的纳米氢化镁样品的EDS图谱(a)和Zr元素的XPS图谱(b)。
图15为实施例4制备的Zr催化掺杂的纳米氢化镁样品与对比例9、对比例10制备的ZrCl 4掺杂的氢化镁随温脱氢质谱曲线的比较图。
图16为实施例5制备的Nb催化掺杂的纳米氢化镁样品与对比例11、对比例12制备的NbCl 5掺杂的氢化镁随温脱氢质谱曲线的比较图。
图17为实施例6制备的Ni催化掺杂的纳米氢化镁样品的SEM照片(a)，TEM照片(b)和高分辨TEM照片(c,d)
图18为实施例6制备的Ni催化掺杂的纳米氢化镁样品与传统方法制备的NiCl 2掺杂的氢化镁随温脱氢质谱曲线的比较图。
具体实施方式
下面结合具体实施例对本发明作进一步描述，以下列举的仅是本发明的具体实施例，但本发明的保护范围不仅限于此。
实施例1纳米氢化镁的制备
(1)将500mg无水氯化镁与500mg氢化锂在氩气气氛手套箱内，分别装入球磨罐，以350转/分钟的转速球磨破碎3小时。
(2)在氩气气氛手套箱内，取球磨过的无水氯化镁和氢化锂(摩尔比1:2)共计600mg，装入250ml烧瓶内，随后，向烧瓶内注入150ml超干四氢呋喃，搅拌30min，待氯化镁充分溶解。
(3)将超声杆插入烧瓶内，保持超声杆末端位于烧瓶内混合物中部，以210W输出功率进行超声处理，超声过程中为保持样品温度不至升温过高，持续超声半小时间须间歇半小时，累计处理6小时获得超声产物。
(4)利用离心的方式(8000转/分钟)，分离出步骤(3)中超声产物中的固体粉末，装入100ml烧瓶内，并注入50ml超干四氢呋喃，搅拌2小时进行清洗，使副产物氯化锂充分溶解于四氢呋喃中。
(5)利用离心的方式(8000转/分钟)分离出步骤(4)中得到的固体粉末，再次利用四氢呋喃清洗后离心获得固体粉末，在动态真空(真空度为1×10 -3Torr)中保持2小时干燥，除去残留的四氢呋喃，可获得纳米氢化镁样品，随后将样品在手套箱内保存待用。
上述过程中制备的样品为：纳米氢化镁样品(nano-MgH 2)，从图1a中可以看出，样品中只含有镁元素，微弱的氧信号和碳信号来源于空气中的碳氧污染或微量的有机溶剂残留，表明样品是由镁组成；从图1b中可以看出，所得样品中镁元素的2p自旋轨道峰位于：50.2eV，表明样品中的镁元素全部以氢化镁的形式存在。
从图2中可以看出样品是由大量的氢化镁纳米颗粒堆积而成，颗粒多为近似球状。
从图3中可以看出，氢化镁纳米颗粒基本维持在5nm，从高分辨透射照片可以标定出氢化镁颗粒的晶面间距0.225nm对应为(200)晶面族。
从上述分析可以看出，利用本方法可以成功制备出的纳米氢化镁。将样品以2℃/min从室温加热至400℃，并利用质谱仪分析样品在加热过程中的脱气曲线(图4)，从图中可以看出，纳米氢化镁在加热过程中只放出氢气，几乎没有四氢呋喃气体放出，表明有机溶剂在动态真空中已经完全除掉，从放氢曲线可以看出，样品的起始 放氢温度低于100℃，第一步放氢峰值温度为190℃，相比常规方法制备的氢化镁样品放氢温度更低。
对比例1无反应促进机制条件下制备氢化镁
(1)将500mg无水氯化镁与500mg氢化锂在氩气气氛手套箱内，分别装入球磨罐，以350转/分钟的转速球磨破碎3小时。
(2)在氩气气氛手套箱内，取球磨过的无水氯化镁和氢化锂(摩尔比1:2)共计600mg，装入250ml烧瓶内，随后，向烧瓶内注入150ml超干四氢呋喃，搅拌12h。
(3)利用离心的方式(8000转/分钟)，分离出步骤(3)中超声产物中的固体物质。
经过上述实验后发现，离心无法收集到固体材料，由此可知，MgCl 2与LiH之间的反应有较高的能垒，在没有额外能量输入(超声波)的情况下，MgCl 2与LiH之间在常温常压下反应动力学过慢，因此，超声在本发明中，不但起到控制颗粒团聚长大的作用，还起到加速MgCl 2与LiH之间化学反应的作用。
对比例2
在充满氩气的手套箱内，将无水氯化镁和氢化锂(摩尔比1:2)共计1.2g，装入球磨罐中在高能球磨机上进行球磨，球磨气氛为氩气气氛，转速为：500转/分钟，球料比为：120:1，球磨时间为24小时，将球磨后的样品在惰性气氛下放入四氢呋喃中进行清洗两次除去副产物氯化锂，随后通过离心取得固体粉末，在动态真空条件下(真空度为1×10 -3Torr)除去残留的四氢呋喃可获得球磨法制备的MgH 2样品，随后将样品以2℃/min的升温速率加热至400℃，通过质谱仪记录样品在加热过程中的放氢行为。
从图5中可以看出，利用超声辅助方法制备的纳米氢化镁比球磨法制备的氢化镁起始温度降低了180℃，第一步放氢峰值温度降低了130℃放氢性能得到明显改善。
从图6a中可以看出所制备的氢化镁由于颗粒细小MgH 2的衍射峰强度较低，峰宽较大，在放氢过程中，Mg的衍射峰逐渐显现，并随着温度升高而加强，放氢产物经吸氢后，Mg的峰消失。与对比例2中传统方法制备的MgH 2放氢过程相比，超声制备的纳米氢化镁分解得到的金属镁，由于颗粒细小，表面原子所占比例较大，晶格有序度差，衍射峰较宽，与之相比传统方法制备的MgH 2放氢产物结晶性较好，峰型尖锐。
对比例3
在充满氩气的手套箱内，将1g镁粉装入不锈钢管式密闭反应器内，在反应器内充入20大气压的高纯氢气，随后将反应器加热至550和350℃，各保温4小时，将反应器内的镁粉充分氢化为氢化镁，随后将反应器内的氢化镁转移至球磨罐内并在球磨罐内充入50大气压高纯氢气，转速为：500转/分钟，球料比为：120:1，球磨24小时，得到氢化镁样品，随后将样品以2℃/min的升温速率加热至400℃，通过质谱仪记录样品在加热过程中的放氢行为。
从图5中可以看出，利用超声辅助方法制备的纳米氢化镁比加热-球磨法制备的氢化镁起始温度降低了125℃，第一步放氢峰值温度降低了90℃放氢性能得到明显改善。从图6b中可以看出，本实施例的MgH 2放氢过程中产生的Mg与超声制备的纳米氢化镁分解得到的金属镁晶格结构明显不同。
实施例2 Ti催化掺杂的纳米氢化镁样品的制备
(1)将无水氯化镁(500mg)和氢化锂(500mg)在氩气气氛手套箱内，分别装入球磨罐，以350转/分钟的转速球磨破碎3小时。
(2)在氩气气氛手套箱内，取球磨过的无水氯化镁和氢化锂(摩尔比1:2)共计600mg以及四氯化钛(TiCl 4)(16.4μL)，装入250ml烧瓶内，随后向烧瓶内注入100ml超干环己烷搅拌30min，本实施例的配比，Ti催化剂与氯化镁的摩尔比为0.03:1。
(3)将超声杆插入烧瓶内，保持超声杆末端位于烧瓶内混合物中部，以210W输出功率进行超声处理，超声过程中为保持样品温度不至升温过高，持续超声半小时间须间歇半小时，累计处理6小时获得超声产物。
(4)利用离心的方式(8000转/分钟)，分离出步骤(3)中超声产物中的固体粉末，然后装入100ml烧瓶内并注入50ml超干四氢呋喃，磁力搅拌2小时进行清洗，使副产物氯化锂充分溶解于四氢呋喃中。
(5)利用离心的方式(8000转/分钟)分离出步骤(4)中得到的固体粉末，再次利用四氢呋喃清洗后离心获得固体粉末，在动态真空(真空度为1×10 -3Torr)中保持2小时脱除残留的四氢呋喃，可获得Ti催化掺杂的纳米氢化镁样品命名为nano-MgH 2-0.03Ti，随后将样品在手套箱内保存待用。
从图7a中可以看出样品中只含有镁元素和钛元素，微弱的氧信号和碳信号来源于空气中的碳氧污染或微量的有机溶剂残留，表明样品的主相是氢化镁，少量钛作为催化剂；从图7b中可以看出，所得样品中钛元素的Ti2p 3/2-2p 1/2双重自旋轨道峰分别位于：453.9和459.3eV，表明利用本方法，TiCl 4已经完全被还原为Ti单质，由此可见，超声波不但能够引发MgH 2的合成反应，同样可以引发LiH对TiCl 4的还原反应。
从图8中可以看出，氢化镁纳米颗粒基本维持在5nm，从高分辨透射照片可以标定出氢化镁颗粒的晶面间距0.225nm对应为(200)晶面族。
从上述分析可以看出，利用本方法可以成功制备出Ti催化掺杂的纳米氢化镁样品。将样品以2℃/min从室温加热至400℃，并利用质谱仪分析样品在加热过程中的脱气曲线(图9)，从图中可以看出，样品的起始放氢温度为40℃，第一步放氢峰值温度为115℃，相比常规方法制备的氢化镁样品放氢温度更低。
此外，针对于Ti催化剂与氯化镁的摩尔比为0.01:1和0.05:1制备获得的Ti催化掺杂的纳米氢化镁样品，利用质谱仪分析样品在加热过程中的脱气曲线，样品的起始放氢温度为35℃(0.01:1)和50℃(0.05:1)，第一步放氢峰值温度为90℃(0.01:1)和125℃(0.05:1)(图9)。
对比例4
在充满氩气的手套箱内，将无水氯化镁和氢化锂(摩尔比1:2，共计1.2g)以及四氯化钛(32.5μL)装入球磨罐中在高能球磨机上进行球磨，球磨气氛为氩气气氛，转速为：500转/分钟，球料比为：120:1，球磨时间为24小时，将球磨后的样品在惰性气氛下放入四氢呋喃中进行清洗两次除去副产物氯化锂，随后通过离心取得固体粉末，在动态真空条件下(真空度为1×10 -3Torr)除去残留的四氢呋喃，可获得钛催化掺杂的MgH 2样品，本对比例所制备的样品中，钛催化剂与氯化镁的摩尔比为：0.03:1，随后将样品以2℃/min的升温速率加热至400℃，通过质谱仪记录样品在加热过程中的放氢行为。
从图9中可以看出，利用超声辅助方法制备的Ti催化掺杂的纳米氢化镁比球磨法制备的氢化镁起始温度降低了140℃，第一步放氢峰值温度降低了143℃放氢性能明显优于球磨法制备的样品。
对比例5
在充满氩气的手套箱内，将1g镁粉装入不锈钢管式密闭反应器内，在反应器内充入20大气压高纯氢气，随后将反应器加热至550和350℃各保温4小时，将反应器内的镁粉充分氢化为氢化镁，随后将反应器内的氢化镁转移至球磨罐内，并加入32.5μL四氯化钛后，充入50大气压高纯氢气，转速为：500转/分钟，球料比为：120:1，球磨24小时，得到钛催化掺杂的氢化镁样品，本对比例所制备的样品中，钛催化剂与MgH 2的摩尔比为：0.03:1，随后将样品以2℃/min的升温速率加热至400℃，通过质谱仪记录样品在加热过程中的放氢行为。
从图9中可以看出，利用超声辅助方法制备的Ti催化掺杂的纳米氢化镁比加热-球磨法制备的Ti催化掺杂氢化镁起始温度降低了120℃，第一步放氢峰值温度降低了110℃放氢性能得到明显改善。
对比例6
利用实施例3中所描述的相同的方法，超声波辅助制备Ti催化掺杂的纳米氢化镁，对其中的TiCl 4用量进行扩展，Ti催化剂与氯化镁的摩尔比为0.1:1。
从图10中可以发现，本对比例扩大TiCl 4的用量后，性能明显变差，主要的放氢峰向着高温区偏移，在低温区只有微弱的放氢，这表明添加过量的催化剂会对超声促进MgCl 2与LiH的反应产生不利影响，使得[MgCl 2+2LiH→MgH 2+2LiCl]反应的能垒下降，多余的能量促进产物结晶，MgH 2颗粒尺寸增大。从图11从可以看出，添加过量的催化剂后，样品放氢的产物Mg出现了与对比例2(传统方法)中样品放氢产物类似的峰型。
实施例3 V催化掺杂的纳米氢化镁样品的制备
与实施例2的制备方法相同，不同之处在于所用过渡金属催化剂为：三氯化钒VCl 3，表1列出了相应的原料配比及关键工艺，该样品命名为nano-MgH 2-0.03V。
表1 nano-MgH 2-0.03V样品的制备工艺及原料配比
超声功率(W) 超声时间(h) MgCl 2+LiH(mg) VCl 3(mg)
210 6 600 24
从图12a中可以看出样品中只含有镁元素和钒元素，微弱的氧信号和碳信号来源于空气中的碳氧污染或微量的有机溶剂残留，表明样品的主相是氢化镁，少量钒作为催化剂；从图12b中可以看出，所得样品中钛元素的V2p 3/2-Vp 1/2双重自旋轨道峰分别位于：512.5和519.7eV，表明利用本方法，VCl 3已经完全被还原为V单质。
利用质谱仪分析样品的脱氢曲线(2℃/min)(图13)，本实施例样品的放氢性能参数总结在表4，该样品相比常规方法制备的氢化镁样品放氢温度更低。
对比例7
与对比例4所用方法相同，不同之处在于所用过渡金属氯化物为：三氯化钒，表2所示为本对比例所用球磨工艺与原料配比：
表2对比例7样品的制备工艺及原料配比
转速(r/min) 球料比 球磨时间(h) MgCl 2+LiH(mg) VCl 3(mg)
500 120:1 24 1200 47
本对比例所制备的样品中，V催化剂与MgH 2的摩尔比为：0.03:1，图13所示为实施例3样品与本对比例样品的放氢曲线对比图，相关放氢性能参数总结于表4。
对比例8
与对比例5所用方法相同，不同之处在于所用过渡金属氯化物为：三氯化钒，表3所示为本对比例中混合催化剂与氢化镁所用球磨工艺与原料配比：
表3对比例8样品的制备工艺及原料配比
转速(r/min) 球料比 球磨时间(h) Mg粉(mg) VCl 3(mg)
500 120:1 24 1000 200
本对比例所制备的样品中，V催化剂与MgH 2的摩尔比为：0.03:1，图13所示为实施例3样品与本对比例样品的放氢曲线对比图，样品的放氢性能参数总结于表4。
表4 V催化MgH 2样品的性能对比
样品名 起始放氢温度(℃) 峰值温度(℃)
nano-MgH 2-0.03V 70 163
对比例7 245 293
对比例8 220 263
从表4总结的样品性能对比可以看出，超声辅助法制备的样品比传统方法制备的样品具有更优异的放氢动力学性能
实施例4 Zr催化掺杂的纳米氢化镁样品的制备
与实施例2的制备方法相同，不同之处在于所用过渡金属催化剂为：四氯化锆 ZrCl 4，表4列出了相应的原料配比及关键工艺，该样品命名为nano-MgH 2-0.03Zr。
表5 nano-MgH 2-0.03Zr样品的制备工艺及原料配比
超声功率(W) 超声时间(h) MgCl 2+LiH(mg) ZrCl 4(mg)
210 10 600 35
图14a所示为样品的能谱数据(EDS)，从图中可以看出样品中只含有镁元素和锆元素，微弱的氧信号和碳信号来源于空气中的碳氧污染或微量的有机溶剂残留，表明样品的主相是氢化镁，少量锆作为催化剂；图14所示为样品中钛元素的X射线光电子能谱分析图谱(XPS图谱)，从图中可以看出，所得样品中锆元素的Zr3d 5/2-3d 3/2双重自旋轨道峰分别位于：177.6和181.1eV，表明利用本方法，ZrCl 4已经完全被还原为Zr单质。
从上述分析可以看出，利用本方法可以成功制备出可获得Zr催化掺杂的纳米氢化镁样品。利用质谱仪分析样品的脱氢曲线(2℃/min)(图15)，样品的放氢性能参数总结在表8，该样品相比常规方法制备的氢化镁样品放氢温度更低。
对比例9
与对比例4所用方法相同，不同之处在于所用过渡金属氯化物为：四氯化锆，表6所示为本对比例所用球磨工艺与原料配比：
表6对比例9样品的制备工艺及原料配比
转速(r/min) 球料比 球磨时间(h) MgCl 2+LiH(mg) ZrCl 2(mg)
500 120:1 24 1200 70
图15所示为实施例4样品与本对比例样品放氢曲线对比图，本对比例样品的放氢性能参数总结于表8。
对比例10
与对比例5所用方法相同，不同之处在于所用过渡金属氯化物为：四氯化锆，表7所示为本对比例中混合催化剂与氢化镁所用球磨工艺与原料配比：
表7对比例10样品的制备工艺及原料配比
转速(r/min) 球料比 球磨时间(h) Mg粉(mg) ZrCl 4(mg)
500 120:1 24 1000 270
本对比例所制备的样品中，Zr催化剂与MgH 2的摩尔比为：0.03:1，图15所示为实施例4样品与本对比例样品放氢曲线对比图，本对比例样品的性能参数总结于表8。
表8 V催化MgH 2样品的性能对比
样品名 起始放氢温度(℃) 峰值温度(℃)
nano-MgH 2-0.03Zr 75 185
对比例9 305 338
对比例10 250 294
从表8总结的样品性能对比可以看出，超声辅助法制备的样品比传统方法制备的 样品具有更优异的放氢动力学性能
实施例5 Nb催化掺杂的纳米氢化镁样品的制备
与实施例2的制备方法相同，不同之处在于所用过渡金属催化剂为：四氯化锆NbCl 5，表9列出了相应的原料配比及关键工艺，该样品命名为nano-MgH 2-0.03Nb。
表9 nano-MgH 2-0.03Nb样品的制备工艺及原料配比
超声功率(W) 超声时间(h) MgCl 2+LiH(mg) NbCl 5(mg)
210 10 600 40
图16所示为样品在加热过程中的脱氢曲线(2℃/min)，该样品的放氢性能参数总结于表11，相比常规方法制备的氢化镁样品放氢温度更低。
对比例11
与对比例4所用方法相同，不同之处在于所用过渡金属氯化物为：五氯化铌，表10所示为本对比例所用球磨工艺与原料配比：
表10对比例11样品的制备工艺及原料配比
转速(r/min) 球料比 球磨时间(h) MgCl 2+LiH(mg) NbCl 5(mg)
500 120:1 24 1200 80
本对比例所制备的样品中，Nb催化剂与MgH 2的摩尔比为：0.03:1，图16所示为实施例5样品与本对比例样品放氢曲线对比图，本对比例样品的放氢性能参数总结于表11。
对比例12
与对比例5所用方法相同，不同之处在于所用过渡金属氯化物为：五氯化铌，表11所示为本对比例中混合催化剂与氢化镁所用球磨工艺与原料配比：
表11对比例12样品的制备工艺及原料配比
转速(r/min) 球料比 球磨时间(h) Mg粉(mg) NbCl 5(mg)
500 120:1 24 1000 310
本对比例所制备的样品中，Nb催化剂与MgH 2的摩尔比为：0.03:1，图16所示为实施例5样品与本对比例样品放氢曲线对比图，本对比例样品的放氢性能参数总结于表12。
表12 V催化MgH 2样品的性能对比
样品名 起始放氢温度(℃) 峰值温度(℃)
nano-MgH 2-0.03Nb 65 137
对比例11 205 267
对比例12 210 247
从表12总结的样品性能对比可以看出，超声辅助法制备的样品比传统方法制备的样品具有更优异的放氢动力学性能
实施例6 Ni催化掺杂的纳米氢化镁样品的制备
与实施例2的制备方法相同，不同之处在于所用过渡金属催化剂为：四氯化锆NiCl 2，表13列出了相应的原料配比及关键工艺，该样品命名为nano-MgH 2-0.03Ni。
表13 nano-MgH 2-0.03Ni样品的制备工艺及原料配比
超声功率(W) 超声时间(h) MgCl 2+LiH(mg) NiCl 2(mg)
210 10 600 20
图17所示为nano-MgH 2-0.03Ni样品的SEM和TEM图片，从图中可以看出，样品呈现出类似石墨烯的层状结构，从样品的TEM照片可以看出，每层样品中包含大量相互交叠的纳米MgH 2颗粒，颗粒尺寸维持在3纳米左右，可以看出，通过改变添加剂的成分，对产物的形貌具有一定的调变作用。
图18所示为本实施例样品的放氢曲线(2℃/min)，本实施例样品的放氢性能参数总结于表16，相比常规方法制备的氢化镁样品放氢温度更低。
对比例13
与对比例4所用方法相同，不同之处在于所用过渡金属氯化物为：二氯化镍，表14所示为本对比例所用球磨工艺与原料配比：
表14对比例13样品的制备工艺及原料配比
转速(r/min) 球料比 球磨时间(h) MgCl 2+LiH(mg) NiCl 2(mg)
500 120:1 24 1200 80
本对比例所制备的样品中，Ni催化剂与MgH 2的摩尔比为：0.03:1，图18所示为实施例6样品与本对比例样品放氢曲线对比图，本对比例样品的放氢性能参数总结于表16。
对比例14
与对比例5所用方法相同，不同之处在于所用过渡金属氯化物为：二氯化镍，表15所示为本对比例中混合催化剂与氢化镁所用球磨工艺与原料配比：
表15对比例14样品的制备工艺及原料配比
转速(r/min) 球料比 球磨时间(h) Mg粉(mg) NiCl 2(mg)
500 120:1 24 1000 150
本对比例所制备的样品中，Ni催化剂与MgH 2的摩尔比为：0.03:1，图18所示为实施例6样品与本对比例样品放氢曲线对比图，本对比例样品的放氢性能参数总结于表16。
表16 V催化MgH 2样品的性能对比
样品名 起始放氢温度(℃) 峰值温度(℃)
nano-MgH 2-0.03Ni 55 175
对比例13 210 245
对比例14 210 254
从表12总结的样品性能对比可以看出，超声辅助法制备的样品比传统方法制备的样品具有更优异的放氢动力学性能。

Claims (10)

  1. 一种纳米氢化镁的原位制备方法，其特征在于，包括以下步骤：
    (1)在惰性气氛保护下，将氯化镁和氢化锂放置于有机溶剂中，搅拌，得到混合物的有机悬浊液；
    (2)在惰性气氛保护下，对所述有机悬浊液进行超声处理，促进混合物发生化学反应，反应结束后，过滤，得到固体反应产物；
    (3)在惰性气氛保护下，利用有机溶剂对固体反应产物进行清洗、离心和干燥，脱除残留有机物，得到纳米氢化镁。
  2. 如权利要求1所述的纳米氢化镁的原位制备方法，其特征在于，步骤(1)中，在将氯化镁和氢化锂放置于有机溶剂之前，将氯化镁和氢化锂分别进行球磨，得到球磨后的氯化镁和球磨后的氢化锂；
    所述球磨的转速为100～400转/小时，时间为3～12小时。
  3. 如权利要求1所述的纳米氢化镁的原位制备方法，其特征在于，步骤(1)中，所述氯化镁为无水氯化镁，氯化镁与氢化锂的摩尔比为1:2。
  4. 如权利要求1所述的纳米氢化镁的原位制备方法，其特征在于，步骤(1)，所述的有机溶剂为超干四氢呋喃、超干环己烷或超干乙醚。
  5. 如权利要求1所述的纳米氢化镁的原位制备方法，其特征在于，采用步骤(A)替代步骤(1)；
    步骤(A)：将氯化镁、氢化锂和过渡金属氯化物一同放置于有机溶剂中，搅拌，得到有机悬浊液；再经步骤(2)和(3)，得到催化剂掺杂的纳米氢化镁；
    所述过渡金属氯化物为无结晶水的氯化物，具体为四氯化钛、三氯化钛、四氯化锆、三氯化钒、五氯化铌、二氯化镍或二氯化钴。
  6. 如权利要求5所述的纳米氢化镁的原位制备方法，其特征在于，所述过渡金属氯化物与氯化镁的摩尔比为0.01～0.05:1；氢化锂与过渡金属氯化物中氯离子的摩尔比为1:1。
  7. 如权利要求1所述的纳米氢化镁的原位制备方法，其特征在于，步骤(2)中，所述超声的功率为100～600W，单次超声时间为0.5～1小时，间歇10～30分钟，累计超声时间为3～24小时。
  8. 如权利要求1所述的纳米氢化镁的原位制备方法，其特征在于，步骤(2)中，将超声杆插入所述有机悬浊液中，进行超声处理。
  9. 如权利要求1所述的纳米氢化镁的原位制备方法，其特征在于，步骤(3)中，所述的有机溶剂为超干四氢呋喃或超干丙酮；清洗的时间为1～2小时，所述干燥在真空环境或惰性气氛保护下加热实现。
  10. 一种如权利要求1～9任一项所述的原位制备方法制得的纳米氢化镁。
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