WO2023071963A1 - 一种负载纳米氢化镁的复合材料及其制备方法 - Google Patents

一种负载纳米氢化镁的复合材料及其制备方法 Download PDF

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WO2023071963A1
WO2023071963A1 PCT/CN2022/126919 CN2022126919W WO2023071963A1 WO 2023071963 A1 WO2023071963 A1 WO 2023071963A1 CN 2022126919 W CN2022126919 W CN 2022126919W WO 2023071963 A1 WO2023071963 A1 WO 2023071963A1
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composite material
magnesium hydride
nano
transition metal
dimensional transition
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邹建新
朱文
任莉
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Shanghai Jiao Tong University
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Shanghai Jiao Tong University
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Priority to US18/557,452 priority patent/US12227413B2/en
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; Reversible storage of hydrogen
    • C01B3/0005—Reversible storage of hydrogen, e.g. by hydrogen getters or electrodes
    • C01B3/001—Reversible storage of hydrogen, e.g. by hydrogen getters or electrodes characterised by the uptaking media; Treatment thereof
    • C01B3/0078—Composite solid storage media, e.g. mixtures of polymers and metal hydrides, coated solid compounds or structurally heterogeneous solid compounds
    • 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

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  • the invention relates to the field of solid hydrogen storage materials, in particular to a composite material loaded with nanometer magnesium hydride and a preparation method thereof.
  • Magnesium-based solid-state hydrogen storage materials have the advantages of high hydrogen storage density, strong cycle reversibility, and abundant earth reserves, and are considered to be the most promising solid-state hydrogen storage materials.
  • the hydrogen absorption and desorption thermodynamic properties of magnesium-based hydrogen storage materials are too stable (the standard hydrogen absorption and desorption reaction enthalpy is ⁇ 75kJ/mol).
  • pure magnesium hydride needs to be above 350°C to achieve hydrogen desorption.
  • the performance of hydrogen dynamics is also poor, which greatly limits the practical application of magnesium-based hydrogen storage materials.
  • size nanosizing is considered to be one of the most effective strategies to improve the hydrogen storage performance of magnesium-based hydrogen storage materials.
  • Nano-sized magnesium-based hydrogen storage materials will directly obtain larger specific surface area, higher surface energy, and larger grain boundary density, which provides a shorter time for the diffusion of hydrogen atoms in magnesium-based hydrogen storage materials. Solid phase diffusion distance, lower diffusion energy barrier, and more diffusion channels, thus significantly improving its hydrogen absorption and desorption kinetics.
  • a large number of experimental and theoretical studies have shown that size nanoscale can also reduce the thermodynamic stability of magnesium-based hydrogen storage materials.
  • nanoscale particles tend to agglomerate and grow spontaneously, resulting in the rapid loss of nanostructure morphology and the continuous deterioration of hydrogen storage stability of magnesium-based hydrogen storage materials.
  • Confining nanoscale magnesium hydride/magnesium hydride in porous materials can effectively inhibit the movement, agglomeration, growth, etc. of nanoparticles, thereby obtaining stable hydrogen storage thermodynamic and kinetic properties.
  • carbon-based porous materials with high specific surface area, strong chemical stability, and light weight are often widely studied as support materials for nano-confinement.
  • porous activated carbon, carbon gel, graphene, carbon nanotubes, etc. are often widely studied as support materials for nano-confinement.
  • Due to the small intrinsic catalytic effect of carbon on the hydrogen absorption and desorption process of magnesium-based materials it is difficult to achieve a high level of hydrogen absorption and desorption kinetics, so it is usually necessary to obtain higher hydrogen absorption and desorption kinetics by adding additional catalysts. performance.
  • the technical problem to be solved by the present invention is to provide a composite material loaded with nano-magnesium hydride through two-dimensional transition metal carbides, which has high hydrogen storage capacity, fast hydrogen absorption and desorption kinetics, and cycle Excellent characteristics of strong stability.
  • the invention provides a method for preparing a composite material loaded with nano-magnesium hydride, comprising the following steps:
  • Step (1) adding a cationic surfactant to the aqueous dispersion of the two-dimensional transition metal carbide to wrinkle and agglomerate the two-dimensional transition metal carbide nanosheets, followed by washing and drying;
  • Step (2) put the product obtained in step (1) into a sealed container, evacuate the sealed container to a vacuum, then raise the temperature to 600-1000°C, keep it warm for 2-5 hours, and then fill the sealed container with 1 ⁇ 10MPa high-pressure hydrogen and heat preservation for 2 ⁇ 5h;
  • Step (3) adding the product obtained in step (2) and dibutylmagnesium into an organic solvent to obtain a mixture, and ultrasonically dispersing the mixture, and then in a hydrogen pressure of 3 to 6MPa and a temperature of 180 to 220°C Under the condition, stir and heat for 12-48 hours, centrifuge and dry to obtain the composite material loaded with nano-magnesium hydride.
  • the hydrogen pressure in the step (1) is 3-4.5 MPa.
  • the two-dimensional transition metal carbides in the step (1) are Ti 3 C 2 T x , Ti 2 CT x , V 2 CT x , Mo 3 C 2 T x , Nb 2 CT x , Nb 4 Any one of C 3 T x , Ta 2 CT x , V 4 C 3 T x , T x is a surface chemical group, such as O 2- , OH - , F - , NH 3 , NH 4 + etc.
  • aqueous dispersion of the two-dimensional transition metal carbide is a single-layer dispersion or a few-layer dispersion.
  • the cationic surfactant is cetyltrimethylammonium bromide (CTAB).
  • CTAB cetyltrimethylammonium bromide
  • the cationic surfactant is first dissolved in deionized water, and then added to the aqueous dispersion of the two-dimensional transition metal carbide under stirring conditions.
  • the purpose of adding a cationic surfactant is to wrinkle the two-dimensional transition metal carbide nanosheets dispersed in water, avoid the re-stacking of the nanosheets, and reduce the risk of interlayer stacking during the drying process.
  • the sealed container in the step (2) is a stainless steel sealed container.
  • the heating rate in the step (2) is 5-10° C./min.
  • the purpose of heat treatment at high temperature is to remove the surfactant and oxygen-containing groups remaining in the two-dimensional transition metal carbide.
  • the organic solvent in the step (3) includes one or more of cyclohexane, hexane and heptane.
  • the ultrasonic power of the ultrasonic dispersion in the step (3) is 200W, and the ultrasonic dispersion time is 2h.
  • the mass fraction of the magnesium hydride in the composite material is controlled to be 20-75%.
  • a preparation method of a composite material loaded with nano-magnesium hydride comprising the following steps:
  • Step (3) adding the product obtained in step (2) and dibutylmagnesium into an organic solvent to obtain a mixture, and ultrasonically dispersing the mixture, and then in a hydrogen pressure of 3 to 6MPa and a temperature of 180 to 220°C Under the condition, stir and heat for 12-48 hours, centrifuge and dry to obtain the composite material loaded with nano-magnesium hydride.
  • the present invention also provides a composite material loaded with nano-magnesium hydride prepared by the above method.
  • the nano-magnesium hydride is loaded on the surface of the two-dimensional transition metal carbide; the nano-sheets of the two-dimensional transition metal carbide have wrinkles.
  • the mass fraction of the magnesium hydride in the composite material is 20-75%.
  • the invention also provides the application of a composite material loaded with nano-magnesium hydride in hydrogen storage.
  • the two-dimensional transition metal carbide nanosheets tend to stack spontaneously, resulting in a significant decrease in their specific surface area; however, the present invention makes the two-dimensional transition metal carbide nanosheets The folds and agglomeration of the sheets occur, the interlayer stacking phenomenon of the two-dimensional transition metal carbide nanosheets is effectively suppressed, and there are more free surfaces for anchoring nano-magnesium hydride, so that the composite material has a higher loading rate of magnesium hydride;
  • Nanoscale magnesium hydride/magnesium hydride has good hydrogen absorption and desorption kinetics, but it is prone to agglomeration and growth of nanoparticles in the continuous hydrogen absorption and desorption process, resulting in continuous deterioration of its cycle stability; but the present invention adopts Two-dimensional transition metal carbides are used as nano-confined carrier materials, and nanoscale magnesium hydride is uniformly distributed on the surface of two-dimensional transition metal carbides. Effective suppression, the advantages of nanometerization are preserved;
  • the two-dimensional transition metal carbide nanosheets have high chemical and physical stability, which ensures that the composite material has good structural stability and performance stability in the process of hydrogen absorption and desorption at high temperature;
  • a nano-catalytic phase (such as TiH 2 ) is generated in situ at the interface between the two-dimensional transition metal carbide nanosheet and the nano-magnesium hydride, which can accelerate the hydrogen absorption and desorption rate of the composite material.
  • the present invention wrinkles the two-dimensional transition metal carbide nanosheets, and utilizes the confinement effect of the two-dimensional transition metal carbide on nano-magnesium hydride/magnesium and its in-situ hydrogen absorption and desorption process on magnesium hydride/magnesium Catalytic action makes this two-dimensional transition metal carbide-supported nano-magnesium hydride composite material have the advantages of high hydrogen storage density, fast hydrogen absorption and desorption kinetics, and excellent cycle stability.
  • Fig. 2 is the transmission electron micrograph of the composite material of two-dimensional transition metal carbide supported magnesium hydride of a preferred embodiment of the present invention
  • Fig. 3 is the scanning electron micrograph of the composite material of two-dimensional transition metal carbide supported magnesium hydride of a preferred embodiment of the present invention
  • Fig. 4 is a particle size distribution figure of nanometer magnesium hydride in the composite material of two-dimensional transition metal carbide supported magnesium hydride of a preferred embodiment of the present invention
  • Fig. 5 is the programmed temperature dehydrogenation curve of the composite material of the two-dimensional transition metal carbide supported magnesium hydride of a preferred embodiment of the present invention
  • Fig. 6 is the cycle dehydrogenation curve of the composite material of the two-dimensional transition metal carbide supported magnesium hydride of a preferred embodiment of the present invention.
  • Fig. 9 is a transmission electron microscope image of a composite material of two-dimensional transition metal carbide supporting magnesium hydride in a preferred embodiment of the present invention.
  • a preparation method of a composite material loaded with nano-magnesium hydride comprising the following steps:
  • Step (1) adding a cationic surfactant to the aqueous dispersion of the two-dimensional transition metal carbide to wrinkle and agglomerate the two-dimensional transition metal carbide nanosheets, followed by washing and drying;
  • Step (2) put the product obtained in step (1) into a sealed container, evacuate the sealed container to a vacuum, then raise the temperature to 600-1000°C, keep it warm for 2-5 hours, and then fill the sealed container with 1-10MPa High-pressure hydrogen and heat preservation for 2 to 5 hours;
  • the two-dimensional transition metal carbide in step (1) can be Ti 3 C 2 T x , Ti 2 CT x , V 2 CT x , Mo 3 C 2 T x , Nb 2 CT x , Any one of Nb 4 C 3 T x , Ta 2 CT x and V 4 C 3 T x (T x is a surface chemical group, such as O 2- , OH - , F - , NH 3 , NH 4 + , etc.) kind.
  • the cationic surfactant in step (1) is a nitrogen-containing organic amine derivative, preferably cetyltrimethylammonium bromide (CTAB).
  • CTAB cetyltrimethylammonium bromide
  • step (1) it is preferable to first dissolve the cationic surfactant in step (1) in deionized water, and then add it to the aqueous dispersion of the two-dimensional transition metal carbide under stirring conditions.
  • the sealed container in step (2) is a stainless steel sealed container.
  • the mass fraction of magnesium hydride in the composite material can be controlled to be 20-75% by adjusting the mass ratio of dibutylmagnesium and two-dimensional transition metal carbide.
  • CTAB solution prepared in step (1) is added dropwise to 500ml concentration of 2mg/ml Ti 3 C 2 T x water dispersion under stirring condition, centrifugal washing reaction product is 3 times, and centrifugal product is frozen Dry for 72 hours;
  • step (3) Put the product obtained in step (2) into a sealed stainless steel container. After the sealed stainless steel container is continuously evacuated, it is heated to 800° C. at a heating rate of 5° C./min, and then filled with 3 MPa of hydrogen after holding for 2 hours. Insulate for 2 hours, and finally cool down to room temperature with the furnace, and the product is denoted as Ti-MX1;
  • the XRD pattern of the two-dimensional transition metal carbide-loaded nano-magnesium hydride composite material 60MgH 2 @Ti-MX prepared in this example is shown in Figure 1. It can be seen from Figure 1 that the phase of the composite material is mainly composed of magnesium hydride and Ti-MX .
  • the transmission electron microscope image is shown in Figure 2, the scanning electron microscope image is shown in Figure 3, and the particle size distribution is shown in Figure 4. It can be seen from Figures 2 to 4 that there are wrinkles on the two-dimensional transition metal carbide nanosheets, and the nano-magnesium hydride is evenly distributed on the surface of the two-dimensional transition metal carbide, without obvious agglomeration phenomenon.
  • the average particle size of magnesium hydride is 15nm.
  • Figure 6 is the cyclic hydrogen desorption curve of 60MgH 2 @Ti-MX1 at 200°C. It can be seen from Figure 6 that the 60MgH 2 @Ti-MX1 composite material has excellent cyclic hydrogen absorption and desorption stability.
  • CTAB cetyltrimethylammonium bromide
  • CTAB solution prepared in step (1) is added dropwise to 500ml concentration of 2mg/ml Ti 3 C 2 T x water dispersion under stirring condition, centrifugal washing reaction product is 3 times, and centrifugal product is frozen Dry for 72 hours;
  • step (3) Put the product obtained in step (2) into a sealed stainless steel container, and after continuously vacuuming the sealed stainless steel container, heat it to 600°C at a heating rate of 5°C/min, keep it warm for 5h, then fill it with 3MPa hydrogen, keep it warm 5h, finally cooled to room temperature with the furnace, and the product was denoted as Ti-MX2;
  • the melamine solution prepared in the step (1) is added dropwise to 500ml concentration of 2mg/ml Ti3C2Tx water dispersion under stirring condition, centrifugal washing reaction product is 3 times, and centrifugal product is frozen Dry for 72 hours;
  • step (3) Put the product obtained in step (2) into a sealed stainless steel container, and after continuously vacuuming the sealed stainless steel container, heat it to 1000°C at a heating rate of 10°C/min, keep it warm for 3h, and then fill it with 4.5MPa hydrogen, Insulate for 2 hours, and finally cool down to room temperature with the furnace, and the product is recorded as Ti-MX3;
  • the transmission electron microscope image of the two-dimensional transition metal carbide-loaded nano-magnesium hydride composite material 60MgH 2 @Ti-MX3 prepared in this implementation example is shown in Figure 9. It can be seen from Figure 9 that there are wrinkles on the two-dimensional transition metal carbide nanosheets, 60MgH 2
  • the nano-magnesium hydride in @Ti-MX3 is evenly distributed on the surface of the two-dimensional transition metal carbide, with an average particle size of about 17nm.

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Abstract

本发明公开了一种负载纳米氢化镁的复合材料的制备方法，包括以下步骤：在二维过渡金属碳化物的水分散液中加入阳离子型表面活性剂，使二维过渡金属碳化物纳米片发生褶皱，避免重新堆叠，然后进行洗涤干燥；将干燥后的产物装入密封容器中，并将其抽至真空后升至高温，保温一段时间后在所述密封容器中充入高压氢气并保温一段时间；最后将热处理后的产物和二丁基镁加入到有机溶剂中得到混合物并进行超声分散，然后在氢压为3～6MPa，温度为180～220℃的条件下，搅拌加热12～48h，离心干燥后得到负载纳米氢化镁的复合材料。本发明制备的二维过渡金属碳化物负载纳米氢化镁的复合材料具有高的储氢密度、快速的吸放氢动力学性能和优异的循环稳定性等优点。

Description

一种负载纳米氢化镁的复合材料及其制备方法 技术领域
本发明涉及固态储氢材料领域，尤其涉及一种负载纳米氢化镁的复合材料及其制备方法。
背景技术
镁基固态储氢材料具有储氢密度高、循环可逆性强、地球储量丰富的等优势，被认为是最具应用前景的固态储氢材料。但是镁基储氢材料的吸放氢热力学性能过于稳定(标准吸放氢反应生成焓为±75kJ/mol)，一般情况下，纯氢化镁需要在350℃以上才能实现放氢，另外其吸放氢动力学方面表现同样较差，这就大大限制了镁基储氢材料的实际应用。目前，尺寸纳米化被认为是提高镁基储氢材料储氢性能最有效的策略之一。镁基储氢材料实现尺寸纳米化，将直接获得更大的比表面积、更高的表面能、及更大的晶界密度，这为氢原子在镁基储氢材料中的扩散提供更短的固相扩散距离、更低的扩散能垒，及更多的扩散通道，从而显著提高其吸放氢动力学性能。大量的实验和理论研究表明，尺寸纳米化同时也能降低镁基储氢材料的热力学稳定性。然而，由于其高表面能，纳米尺度的颗粒有自发团聚长大的趋势，导致镁基储氢材料纳米结构形态的迅速损失与储氢稳定性的持续恶化。将纳米尺度的氢化镁/镁限域在多孔材料中，可以有效地抑制纳米粒子的移动、团聚、长大等，从而获得稳定的储氢热力学及动力学性能。一般的，具有高比表面积、化学稳定性强、质轻的碳基多孔材料(如多孔活性炭、碳凝胶、石墨烯、碳纳米管等)常被作为纳米限域的支撑材料进行广泛研究。但由于碳对镁基材料吸放氢过程的本征催化作用较小，导致其吸放氢动力学很难达到较高水准，所以通常需要通过额外添加催化剂来获得更高的吸放氢动力学性能。另外碳材料-氢化镁复合材料中的氢化镁(镁)的装载率通常较低。因此，开发一种既能保证合适的氢化镁/镁装载效率，又能兼具良好的催化效应的支撑材料，对于发展镁基储氢材料具有十分重要的意义。
二维过渡金属碳化物(MXenes)作为一种新兴的二维材料，其在能量存储、催化、传感器等领域获得广泛研究，其化学通式可用M n+1X nT z表示，其中M指过渡族金属(如Ti、Zr、Hf、V、Nb、Ta、Cr、Sc等)，X为C，n一般为1，2或3，T z指表面化学基团(如O 2-、OH -、F -、NH 3、NH 4 +等)。二维过渡金属碳化物具有比表面积大、化学稳定及物理稳定的优势，另外其对镁基储氢材料吸放氢过程具有优异的催化作用，因此二维过渡金属碳化物被认为是一种兼具高装载率与催化效应的潜力支撑材料。然而由于二维过渡金属碳化物(MXenes)纳米片层间的范德华力作用，其容易发生严重 的层间堆叠现象，从而造成用于锚定纳米氢化镁的自由表面大量损失。另外，MXenes表面的大量含氧官能团会使氢化镁/镁在高温吸放氢过程中发生严重的氧化现象，导致储氢容量及吸放氢动力学性能恶化。基于上述原因，目前还没有利用二维过渡金属碳化物作为镁基储氢材料的支撑材料研究的相关报道。
因此，本领域的技术人员致力于开发一种通过二维过渡金属碳化物负载纳米氢化镁的复合材料，其兼具高氢化镁装载容量及优异的吸放氢动力学性能。
发明内容
有鉴于现有技术的上述缺陷，本发明所要解决的技术问题是提供一种通过二维过渡金属碳化物负载纳米氢化镁的复合材料，其具有储氢容量高、吸放氢动力学快、循环稳定性强的优异特性。
为实现上述目的，本发明提供了一种负载纳米氢化镁的复合材料的制备方法，包括以下步骤：
步骤(1)、在二维过渡金属碳化物的水分散液中加入阳离子型表面活性剂，使二维过渡金属碳化物纳米片发生褶皱团聚，然后进行洗涤、干燥；
步骤(2)、将步骤(1)获得的产物装入密封容器中，将所述密封容器抽至真空后升温至600-1000℃，保温2～5h，然后在所述密封容器中充入1～10MPa高压氢气并保温2～5h；
步骤(3)、将步骤(2)获得的产物和二丁基镁加入到有机溶剂中得到混合物，将所述混合物进行超声分散，然后在氢压为3～6MPa，温度为180～220℃的条件下，搅拌加热12～48h，离心干燥后即得所述负载纳米氢化镁的复合材料。
优选地，所述步骤(1)中氢气压力为3～4.5MPa。
进一步地，所述步骤(1)中所述二维过渡金属碳化物为Ti 3C 2T x、Ti 2CT x、V 2CT x、Mo 3C 2T x、Nb 2CT x、Nb 4C 3T x、Ta 2CT x、V 4C 3T x中的任意一种，T x为表面化学基团，例如O 2-、OH -、F -、NH 3、NH 4 +等。
进一步地，所述二维过渡金属碳化物的水分散液为单层分散液或少层分散液。
进一步地，所述步骤(1)中的阳离子型表面活性剂为含氮有机胺衍生物。
优选地，所述阳离子型表面活性剂是十六烷基三甲基溴化铵(CTAB)、。
进一步地，在所述步骤(1)中，所述阳离子型表面活性剂先溶解在去离子水中，然后在搅拌条件下加入到所述二维过渡金属碳化物的水分散液中。加入阳离子型表面活性剂的目的是为了使分散在水中二维过渡金属碳化物纳米片发生褶皱，避免纳米片重新堆叠，从而降低其在干燥过程中发生层间堆叠的风险。
优选地，所述步骤(2)中所述密封容器为不锈钢密封容器。
进一步地，所述步骤(2)中的升温速率为5～10℃/min。步骤(2)中在高温下先进行热处理是为了除去残留在二维过渡金属碳化物的表面活性剂及含氧基团。
进一步地，所述步骤(3)中所述有机溶剂包括环己烷、己烷和庚烷中的一种或多种。
进一步地，所述步骤(3)中所述超声分散的超声功率为200W，所述超声分散的时间为2h。
进一步地，通过调整所述二丁基镁和所述二维过渡金属碳化物的质量比，控制所述复合材料中所述氢化镁的质量分数为20～75％。
还提供一种负载纳米氢化镁的复合材料的制备方法，包括以下步骤：
步骤(1)、在二维过渡金属碳化物的水分散液中加入酸化三聚氰胺，使二维过渡金属碳化物纳米片发生褶皱团聚，然后进行洗涤、干燥；
步骤(2)、将步骤(1)获得的产物装入密封容器中，将所述密封容器抽至真空后升温至600-1000℃，保温2～5h，然后在所述密封容器中充入1～10MPa高压氢气并保温2～5h；
步骤(3)、将步骤(2)获得的产物和二丁基镁加入到有机溶剂中得到混合物，将所述混合物进行超声分散，然后在氢压为3～6MPa，温度为180～220℃的条件下，搅拌加热12～48h，离心干燥后即得所述负载纳米氢化镁的复合材料。
本发明还提供了一种由上述方法制备的负载纳米氢化镁的复合材料，所述纳米氢化镁负载在二维过渡金属碳化物表面；所述二维过渡金属碳化物的纳米片上有褶皱。
进一步地，所述复合材料中所述氢化镁的质量分数为20～75％。
本发明还提供了一种负载纳米氢化镁的复合材料在储氢中的应用。
本发明具有以下的技术效果：
1、由于范德华力及氢键作用，二维过渡金属碳化物纳米片有自发堆叠的趋势，导致其比表面积大幅降低；然而本发明通过加入阳离子型表面活性剂，使得二维过渡金属碳化物纳米片发生褶皱团聚，二维过渡金属碳化物纳米片层间堆叠现象被有效抑制，具有更多自由表面用于锚定纳米氢化镁，从而使得复合材料具有较高的氢化镁装载率；
2、纳米尺度的氢化镁/镁具有良好的吸放氢动力学性能，但其在连续的吸放氢过程中纳米颗粒容易发生团聚长大，造成其循环稳定性持续恶化；但是通过本发明采用二维过渡金属碳化物作为纳米限域的载体材料，纳米尺度的氢化镁均匀分布在二维过渡金属碳化物的表面，在充放氢的过程中，氢化镁/镁颗粒的团聚长大趋势被有效抑制，纳米化优势得以保留；
3、二维过渡金属碳化物纳米片化学及物理稳定性高，从而保证了复合材料在高温吸放氢过程中具有良好的结构稳定性及性能稳定性；
4、在复合材料中，二维过渡金属碳化物纳米片与纳米氢化镁界面处原位生成纳米催化相(如TiH 2)，其可以加速复合材料的吸放氢速率。
因此，本发明通过使二维过渡金属碳化物纳米片产生褶皱，并且利用二维过渡金 属碳化物对纳米氢化镁/镁的限域作用以及其对氢化镁/镁的吸放氢过程的原位催化作用，使得这种二维过渡金属碳化物负载纳米氢化镁的复合材料具有高的储氢密度、快速的吸放氢动力学性能和优异的循环稳定性等优点。
以下将结合附图对本发明的构思、具体结构及产生的技术效果作进一步说明，以充分地了解本发明的目的、特征和效果。
附图说明
图1是本发明一个较佳实施例的二维过渡金属碳化物负载氢化镁的复合材料的XRD图谱；
图2是本发明一个较佳实施例的二维过渡金属碳化物负载氢化镁的复合材料透射电镜图；
图3是本发明一个较佳实施例的二维过渡金属碳化物负载氢化镁的复合材料扫描电镜图；
图4是本发明一个较佳实施例的二维过渡金属碳化物负载氢化镁的复合材料中纳米氢化镁粒径分布图；
图5是本发明一个较佳实施例的二维过渡金属碳化物负载氢化镁的复合材料的程序控温脱氢曲线；
图6是本发明一个较佳实施例的二维过渡金属碳化物负载氢化镁的复合材料的循环放氢曲线；
图7是本发明一个较佳实施例的二维过渡金属碳化物负载氢化镁的复合材料的透射电镜图；
图8是本发明一个较佳实施例的二维过渡金属碳化物负载氢化镁的复合材料中纳米氢化镁的粒径分布图；
图9是本发明一个较佳实施例的二维过渡金属碳化物负载氢化镁的复合材料的透射电镜图。
具体实施方式
以下参考说明书附图介绍本发明的多个优选实施例，使其技术内容更加清楚和便于理解。本发明可以通过许多不同形式的实施例来得以体现，本发明的保护范围并非仅限于文中提到的实施例。
一种负载纳米氢化镁的复合材料的制备方法，包括以下步骤：
步骤(1)、在二维过渡金属碳化物的水分散液中加入阳离子型表面活性剂，使二维过渡金属碳化物纳米片发生褶皱团聚，然后进行洗涤、干燥；
步骤(2)、将步骤(1)获得的产物装入密封容器中，将所述密封容器抽至真空后升温至600-1000℃，保温2～5h，然后在密封容器中充入1～10MPa高压氢气并保温 2～5h；
步骤(3)、将步骤(2)获得的产物和二丁基镁加入到有机溶剂中得到混合物，将所述混合物进行超声分散，然后在氢压为3～6MPa，温度为180～220℃的条件下，搅拌加热12～48h，离心干燥后即得所述负载纳米氢化镁的复合材料。
在一些实施例中，步骤(1)中所述二维过渡金属碳化物可以是Ti 3C 2T x、Ti 2CT x、V 2CT x、Mo 3C 2T x、Nb 2CT x、Nb 4C 3T x、Ta 2CT x和V 4C 3T x(T x为表面化学基团，如O 2-、OH -、F -、NH 3、NH 4 +等)中的任意一种。
在一些实施例中，步骤(1)中的阳离子型表面活性剂为含氮有机胺衍生物，优选为十六烷基三甲基溴化铵(CTAB)。
在一些实施例中，最好将步骤(1)中阳离子型表面活性剂先溶解在去离子水中，然后在搅拌条件下加入到所述二维过渡金属碳化物的水分散液中。
在一些实施例中，步骤(2)中所述密封容器为不锈钢密封容器。
在一些实施例中，步骤(2)中的升温速率为5～10℃/min，升温后的温度可以为600℃，700℃，800℃，900℃或1000℃。
在一些实施例中，步骤(3)中有机溶剂可以是环己烷、己烷或庚烷，或其任意混合物。
在一些实施例中，步骤(3)中超声分散的功率为200W，时间为2h。
在一些实施例中，可以通过调整二丁基镁和二维过渡金属碳化物的质量比，控制复合材料中氢化镁的质量分数为20～75％。
实施例1
二维过渡金属碳化物负载纳米氢化镁的复合材料60MgH 2@Ti-MX1的制备：
(1)取5g十六烷基三甲基溴化铵(CTAB)溶解于100ml去离子水中；
(2)将步骤(1)中制备的CTAB溶液在搅拌条件下逐滴加入到500ml浓度为2mg/ml的Ti 3C 2T x水分散液中，离心洗涤反应产物3次，将离心产物冷冻干燥72小时；
(3)将步骤(2)获得的产物装入密封的不锈钢容器中，将密封的不锈钢容器连续抽真空后，以5℃/min升温速率加热至800℃，保温2h后充入3MPa的氢气，保温2h，最后随炉冷却至室温，产物记为Ti-MX1；
(4)取30mg的Ti-MX1，3.5ml浓度为0.5M的二丁基镁庚烷溶液，及40ml环己烷加入内胆为聚四氟乙烯的不锈钢高压反应釜，然后进行探入式超声分散2h，超声功率为200W；
(5)对不锈钢高压反应釜充氢至4.5MPa，加热至200℃，在搅拌条件下反应12h，最后离心干燥获得氢化镁装载率为60wt％的二维过渡金属碳化物负载纳米氢化镁的复合材料60MgH 2@Ti-MX1。
本实施实例制备的二维过渡金属碳化物负载纳米氢化镁复合材料60MgH 2@Ti-MX的XRD图谱如图1所示，由图1可知复合材料的物相主要由氢化镁和Ti-MX组成。
透射电镜图如图2所示，扫描电镜图如图3所示，粒径分布如图4所示。由图2～4可知二维过渡金属碳化物纳米片上有褶皱，且纳米氢化镁均匀分布在二维过渡金属碳化物表面，无明显团聚现象，氢化镁的平均粒径为15nm。
本实施例制备的二维过渡金属碳化物负载纳米氢化镁复合材料60MgH 2@Ti-MX1的储氢性能测试：
图5为其程序控温脱附曲线(TPD)，由图5可知60MgH 2@Ti-MX1复合材料的起始放氢温度为140℃，储氢容量为4.2wt％H 2。
图6为60MgH 2@Ti-MX1在200℃循环放氢曲线，由图6可知60MgH 2@Ti-MX1复合材料具有优异的循环吸放氢稳定性。
实施例2
二维过渡金属碳化物负载纳米氢化镁复合材料35MgH 2@Ti-MX2的制备：
(1)取5g十六烷基三甲基溴化铵(CTAB)溶解于100ml去离子水中；
(2)将步骤(1)中制备的CTAB溶液在搅拌条件下逐滴加入到500ml浓度为2mg/ml的Ti 3C 2T x水分散液中，离心洗涤反应产物3次，将离心产物冷冻干燥72小时；
(3)将步骤(2)获得的产物装入密封的不锈钢容器，将密封的不锈钢容器连续抽真空后，以5℃/min升温速率加热至600℃，保温5h，然后充入3MPa氢气，保温5h，最后随炉冷却至室温，产物记为Ti-MX2；
(4)取30mg的Ti-MX2，1.3ml浓度为0.5M的二丁基镁庚烷溶液，及40ml环己烷加入内胆为聚四氟乙烯的不锈钢高压反应釜，然后进行探入式超声分散2h，超声功率为200W；
(5)对不锈钢高压反应釜充氢至3MPa，加热至180℃，在搅拌条件下反应24h，最后离心干燥获得氢化镁装载率为35wt％的二维过渡金属碳化物负载纳米氢化镁的复合材料35MgH 2@Ti-MX2。
本实施实例制备的二维过渡金属碳化物负载纳米氢化镁复合材料35MgH 2@Ti-MX2的透射电镜图如图7所示，粒径分布如图8所示，由图7～8可知二维过渡金属碳化物纳米片上有褶皱，35MgH 2@Ti-MX2中纳米氢化镁均匀分布在二维过渡金属碳化物表面，平均粒径为8nm左右。
实施例3
二维过渡金属碳化物负载纳米氢化镁复合材料60MgH 2@Ti-MX3的制备：
(1)取1.5g酸化三聚氰胺溶解于200ml去离子水中；
(2)将步骤(1)中制备的三聚氰胺溶液在搅拌条件下逐滴加入到500ml浓度为2mg/ml的Ti 3C 2T x水分散液中，离心洗涤反应产物3次，将离心产物冷冻干燥72小时；
(3)将步骤(2)获得的产物装入密封的不锈钢容器，将密封的不锈钢容器连续抽真空后，以10℃/min升温速率加热至1000℃，保温3h，然后充入4.5MPa氢气，保温2h，最后随炉冷却至室温，产物记为Ti-MX3；
(4)取30mg的Ti-MX3，3.5ml浓度为0.5M的二丁基镁庚烷溶液，及40ml环己烷加入内胆为聚四氟乙烯的不锈钢高压反应釜，探入式超声分散2h，超声功率200W；
(5)对不锈钢高压反应釜充氢至6MPa，加热至220℃，搅拌条件下反应12h，最后离心干燥获得氢化镁装载率为60wt％的二维过渡金属碳化物负载纳米氢化镁的复合材料60MgH 2@Ti-MX3。
本实施实例制备的二维过渡金属碳化物负载纳米氢化镁复合材料60MgH 2@Ti-MX3的透射电镜图如图9所示，由图9可知二维过渡金属碳化物纳米片上有褶皱，60MgH 2@Ti-MX3中纳米氢化镁均匀分布在二维过渡金属碳化物表面，平均粒径为17nm左右。
以上详细描述了本发明的较佳具体实施例。应当理解，本领域的普通技术无需创造性劳动就可以根据本发明的构思作出诸多修改和变化。因此，凡本技术领域中技术人员依本发明的构思在现有技术的基础上通过逻辑分析、推理或者有限的实验可以得到的技术方案，皆应在由权利要求书所确定的保护范围内。

Claims (11)

  1. 一种负载纳米氢化镁的复合材料的制备方法，其特征在于，包括以下步骤：
    步骤(1)、在二维过渡金属碳化物的水分散液中加入阳离子型表面活性剂，使二维过渡金属碳化物纳米片发生褶皱，然后进行洗涤、干燥；
    步骤(2)、将步骤(1)获得的产物装入密封容器中，将所述密封容器抽至真空后升温至600-1000℃，保温2～5h，然后在所述密封容器中充入1～10MPa的氢气并保温2～5h；
    步骤(3)、将步骤(2)获得的产物和二丁基镁加入到有机溶剂中得到混合物，将所述混合物进行超声分散，然后在氢压为3～6MPa，温度为180～220℃的条件下，搅拌加热12～48h，离心干燥后即得所述负载纳米氢化镁的复合材料。
  2. 根据权利要求1所述的负载纳米氢化镁的复合材料的制备方法，其特征在于，所述步骤(1)中所述二维过渡金属碳化物为Ti 3C 2T x、Ti 2CT x、V 2CT x、Mo 3C 2T x、Nb 2CT x、Nb 4C 3T x、Ta 2CT x和V 4C 3T x中的任意一种。
  3. 根据权利要求1所述的负载纳米氢化镁的复合材料的制备方法，其特征在于，所述阳离子型表面活性剂为含氮有机胺衍生物。
  4. 根据权利要求3所述的负载纳米氢化镁的复合材料的制备方法，其特征在于，所述含氮有机胺衍生物是十六烷基三甲基溴化铵。
  5. 根据权利要求1所述的负载纳米氢化镁的复合材料的制备方法，其特征在于，在所述步骤(1)中，所述阳离子型表面活性剂先溶解在去离子水中，然后在搅拌条件下加入到所述二维过渡金属碳化物的水分散液中。
  6. 根据权利要求1所述的负载纳米氢化镁的复合材料的制备方法，其特征在于，所述步骤(2)中的升温速率为5～10℃/min。
  7. 根据权利要求1所述的负载纳米氢化镁的复合材料的制备方法，其特征在于，所述步骤(3)中所述有机溶剂包括环己烷、己烷和庚烷中的一种或多种。
  8. 一种负载纳米氢化镁的复合材料的制备方法，其特征在于，包括以下步骤：
    步骤(1)、在二维过渡金属碳化物的水分散液中加入酸化三聚氰胺，使二维过渡金属碳化物纳米片发生褶皱，然后进行洗涤、干燥；
    步骤(2)、将步骤(1)获得的产物装入密封容器中，将所述密封容器抽至真空后升温至600-1000℃，保温2～5h，然后在所述密封容器中充入1～10MPa的氢气并保温2～5h；
    步骤(3)、将步骤(2)获得的产物和二丁基镁加入到有机溶剂中得到混合物，将所述混合物进行超声分散，然后在氢压为3～6MPa，温度为180～220℃的条件下，搅拌加热12～48h，离心干燥后即得所述负载纳米氢化镁的复合材料。
  9. 一种根据权利要求1-8中任一项所述的方法制备的负载纳米氢化镁的复合材料，其特征在于，所述纳米氢化镁负载在二维过渡金属碳化物表面，所述二维过渡金属碳化物的纳米片上有褶皱。
  10. 根据权利要求9所述的负载纳米氢化镁的复合材料，其特征在于，所述复合材料中所述氢化镁的质量分数为20～75％。
  11. 一种根据权利要求9或10所述的负载纳米氢化镁的复合材料在储氢中的应用。
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