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Solid-state hydrogen storage technology has emerged as a disruptive solution to the "last mile" challenge in large-scale hydrogen energy applications, garnering significant global research attention. This paper systematically reviews the Chinese research progress in solid-state hydrogen storage material systems, thermodynamic mechanisms, and system integration. It also quantitatively assesses the market potential of solid-state hydrogen storage across four major application scenarios: on-board hydrogen storage, hydrogen refueling stations, backup power supplies, and power grid peak shaving. Furthermore, it analyzes the bottlenecks and challenges in industrialization related to key materials, testing standards, and innovation platforms. While acknowledging that the cost and performance of solid-state hydrogen storage are not yet fully competitive, the paper highlights its unique advantages of high safety, energy density, and potentially lower costs, showing promise in new energy vehicles and distributed energy fields. Breakthroughs in new hydrogen storage materials like magnesium-based and vanadium-based materials, coupled with improved standards, specifications, and innovation mechanisms, are expected to propel solid-state hydrogen storage into a mainstream technology within 10-15 years, with a market scale exceeding USD 14.3 billion. To accelerate the leapfrog development of China's solid-state hydrogen storage industry, increased investment in basic research, focused efforts on key core technologies, and streamlining the industry chain from materials to systems are recommended. This includes addressing challenges in passenger vehicles, commercial vehicles, and hydrogen refueling stations, and building a collaborative innovation ecosystem involving government, industry, academia, research, finance, and intermediary entities to support the achievement of carbon peak and neutrality goals and foster a clean, low-carbon, safe, and efficient modern energy system.
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Developing solid-state hydrogen storage materials is as pressing as ever, which requires a comprehensive understanding of the dehydrogenation chemistry of a solid-state hydride. Transition state search and kinetics calculations are essential to understanding and designing high-performance solid-state hydrogen storage materials by filling in the knowledge gap that current experimental techniques cannot measure. However, the ab initio analysis of these processes is computationally expensive and time-consuming. Searching for descriptors to accurately predict the energy barrier is urgently needed, to accelerate the prediction of hydrogen storage material properties and identify the opportunities and challenges in this field. Herein, we develop a data-driven model to describe and predict the dehydrogenation barriers of a typical solid-state hydrogen storage material, magnesium hydride (MgH2), based on the combination of the crystal Hamilton population orbital of Mg-H bond and the distance between atomic hydrogen. By deriving the distance energy ratio, this model elucidates the key chemistry of the reaction kinetics. All the parameters in this model can be directly calculated with significantly less computational cost than conventional transition state search, so that the dehydrogenation performance of hydrogen storage materials can be predicted efficiently. Finally, we found that this model leads to excellent agreement with typical experimental measurements reported to date and provides clear design guidelines on how to propel the performance of MgH2 closer to the target set by the United States Department of Energy (US-DOE).
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In this article, the capabilities of soft and hard X-ray techniques, including X-ray absorption (XAS), soft X-ray emission spectroscopy (XES), resonant inelastic soft X-ray scattering (RIXS), X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD), and their application to solid-state hydrogen storage materials are presented. These characterization tools are indispensable for interrogating hydrogen storage materials at the relevant length scales of fundamental interest, which range from the micron scale to nanometer dimensions. Since nanostructuring is now well established as an avenue to improve the thermodynamics and kinetics of hydrogen release and uptake, due to properties such as reduced mean free paths of transport and increased surface-to-volume ratio, it becomes of critical importance to explicitly identify structure-property relationships on the nanometer scale. X-ray diffraction and spectroscopy are effective tools for probing size-, shape-, and structure-dependent material properties at the nanoscale. This article also discusses the recent development of in-situ soft X-ray spectroscopy cells, which enable investigation of critical solid/liquid or solid/gas interfaces under more practical conditions. These unique tools are providing a window into the thermodynamics and kinetics of hydrogenation and dehydrogenation reactions and informing a quantitative understanding of the fundamental energetics of hydrogen storage processes at the microscopic level. In particular, in-situ soft X-ray spectroscopies can be utilized to probe the formation of intermediate species, byproducts, as well as the changes in morphology and effect of additives, which all can greatly affect the hydrogen storage capacity, kinetics, thermodynamics, and reversibility. A few examples using soft X-ray spectroscopies to study these materials are discussed to demonstrate how these powerful characterization tools could be helpful to further understand the hydrogen storage systems.
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High-pressure torsion (HPT) is widely used as a severe plastic deformation technique to create ultrafine-grained structures with promising mechanical and functional properties. Since 2007, the method has been employed to enhance the hydrogenation kinetics in different Mg-based hydrogen storage materials. Recent studies showed that the method is effective not only for increasing the hydrogenation kinetics but also for improving the hydrogenation activity, for enhancing the air resistivity and more importantly for synthesizing new nanostructured hydrogen storage materials with high densities of lattice defects. This manuscript reviews some major findings on the impact of HPT process on the hydrogen storage performance of different titanium-based and magnesium-based materials.
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Due to its high gravimetric capacity of hydrogen (10.5 wt%), LiAlH4 has been regarded as a promising material for solid-state hydrogen storage material for onboard usage. However, high decomposition temperature, poor kinetics and irreversibility retard its application. To counter this problem, various weight percentages of BaMnO3 are introduced into the LiAlH4 system as an additive in this work. As a result, the starting hydrogen release of LiAlH4 was reduced to 109-115 °C and the second desorption temperature occurred at around 134-158 °C, much lower than pure LiAlH4. The isothermal desorption kinetics also proved that faster desorption kinetics can be observed at 90 °C for 80 min. About 2.00-2.60 wt% of H2 could be desorbed by the composite, whereas only <1.00 wt% of H2 was desorbed by undoped LiAlH4. Additionally, adding BaMnO3 reduced the activation energies by 30 kJ/mol for the first stages and 34 kJ/mol for the second stages. Based on the X-ray diffraction result, the active species formed of MnO2 and Ba or Ba-containing materials are believed to be responsible for the noticeable enhancement in the desorption properties of LiAlH4.
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The high hydrogen storage capacity (10.5 wt.%) and release of hydrogen at a moderate temperature make LiAlH4 an appealing material for hydrogen storage. However, LiAlH4 suffers from slow kinetics and irreversibility. Hence, LaCoO3 was selected as an additive to defeat the slow kinetics problems of LiAlH4. For the irreversibility part, it still required high pressure to absorb hydrogen. Thus, this study focused on the reduction of the onset desorption temperature and the quickening of the desorption kinetics of LiAlH4. Here, we report the different weight percentages of LaCoO3 mixed with LiAlH4 using the ball-milling method. Interestingly, the addition of 10 wt.% of LaCoO3 resulted in a decrease in the desorption temperature to 70 °C for the first stage and 156 °C for the second stage. In addition, at 90 °C, LiAlH4 + 10 wt.% LaCoO3 can desorb 3.37 wt.% of H2 in 80 min, which is 10 times faster than the unsubstituted samples. The activation energies values for this composite are greatly reduced to 71 kJ/mol for the first stages and 95 kJ/mol for the second stages compared to milled LiAlH4 (107 kJ/mol and 120 kJ/mol for the first two stages, respectively). The enhancement of hydrogen desorption kinetics of LiAlH4 is attributed to the in situ formation of AlCo and La or La-containing species in the presence of LaCoO3, which resulted in a reduction of the onset desorption temperature and activation energies of LiAlH4.
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Magnesium hydrides (MgH2) have drawn a lot of interest as a promising hydrogen storage material option due to their good reversibility and high hydrogen storage capacity (7.60 wt.%). However, the high hydrogen desorption temperature (more than 400 °C) and slow sorption kinetics of MgH2 are the main obstacles to its practical use. In this research, nickel zinc oxide (Ni0.6Zn0.4O) was synthesized via the solid-state method and doped into MgH2 to overcome the drawbacks of MgH2. The onset desorption temperature of the MgH2-10 wt.% Ni0.6Zn0.4O sample was reduced to 285 °C, 133 °C, and 56 °C lower than that of pure MgH2 and milled MgH2, respectively. Furthermore, at 250 °C, the MgH2-10 wt.% Ni0.6Zn0.4O sample could absorb 6.50 wt.% of H2 and desorbed 2.20 wt.% of H2 at 300 °C within 1 h. With the addition of 10 wt.% of Ni0.6Zn0.4O, the activation energy of MgH2 dropped from 133 kJ/mol to 97 kJ/mol. The morphology of the samples also demonstrated that the particle size is smaller compared with undoped samples. It is believed that in situ forms of NiO, ZnO, and MgO had good catalytic effects on MgH2, significantly reducing the activation energy and onset desorption temperature while improving the sorption kinetics of MgH2.
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One of the ideal energy carriers for the future is hydrogen. It has a high energy density and is a source of clean energy. A crucial step in the development of the hydrogen economy is the safety and affordable storage of a large amount of hydrogen. Thus, owing to its large storage capacity, good reversibility, and low cost, Magnesium hydride (MgH2) was taken into consideration. Unfortunately, MgH2 has a high desorption temperature and slow ab/desorption kinetics. Using the ball milling technique, adding cobalt lanthanum oxide (LaCoO3) to MgH2 improves its hydrogen storage performance. The results show that adding 10 wt.% LaCoO3 relatively lowers the starting hydrogen release, compared with pure MgH2 and milled MgH2. On the other hand, faster ab/desorption after the introduction of 10 wt.% LaCoO3 could be observed when compared with milled MgH2 under the same circumstances. Besides this, the apparent activation energy for MgH2-10 wt.% LaCoO3 was greatly reduced when compared with that of milled MgH2. From the X-ray diffraction analysis, it could be shown that in-situ forms of MgO, CoO, and La2O3, produced from the reactions between MgH2 and LaCoO3, play a vital role in enhancing the properties of hydrogen storage of MgH2.
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Magnesium hydride and selected magnesium-based ternary hydride (Mg2FeH6, Mg2NiH4, and Mg2CoH5) syntheses and modification methods, as well as the properties of the obtained materials, which are modified mostly by mechanical synthesis or milling, are reviewed in this work. The roles of selected additives (oxides, halides, and intermetallics), nanostructurization, polymorphic transformations, and cyclic stability are described. Despite the many years of investigations related to these hydrides and the significant number of different additives used, there are still many unknown factors that affect their hydrogen storage properties, reaction yield, and stability. The described compounds seem to be extremely interesting from a theoretical point of view. However, their practical application still remains debatable.
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The crystal structure of diethylaminoalane, [H2Al-N(C2H5)2]2, was determined by X-ray powder diffraction in conjunction with DFT calculations. Diethylaminoalane crystallizes in the monoclinic space group P21/c with a = 7.4020â (2), b = 12.9663â (3), c = 7.2878â (2)â Å and ß = 90.660â (2)° at 293â K. The crystal structure was confirmed by DFT calculations and Raman spectroscopy. The molecular structure of diethylaminoalane consists of dimers of [H2Al-N(CH2CH3)2] in which an Al2N2 four-membered ring is formed by a center of inversion. Such an arrangement of the aminoalane moieties in the crystal structure is well known for this class of compound, as shown by the comparison with ethylmethylaminoalane and diisopropylaminoalane.