Recent progress of nanotechnology in enhancing hydrogen storage performance of magnesium-based materials: A review

Hydrogen has attracted wide attention in the field of new energy, triggering a comprehensive study of hydrogen production, storage and application. This paper mainly studies the hydrogen storage capacity of magnesium-based materials with nanostructure. The reversible hydrogen capacity of Mg-based hydrogen storage materials can reach 7.6 wt%, but due to its poor kinetic and thermodynamic properties, its hydrogen storage performance is not as good as other hydrogen storage materials. In order to reduce the desorption temperature of materials, many studies have been carried out. Alloying, nanostructure and adding catalyst are feasible methods to improve the properties of Mg-based hydrogen storage alloys. By adding catalyst and alloy with other transition elements, the dehydrogenation temperature of magnesium-based materials has been reduced to less than 200 °C. The hydrogen storage of magnesium-based alloys has been practically applied.     

Mg-based metastable nano alloys for hydrogen storage

Mg-based materials have been widely researched for hydrogen storage development due to the low price of Mg, abundant resources of Mg element in the earth's crust and the high hydrogen capacity (ca. 7.7 mass% for MgH₂). However, the challenges of poor kinetics, unsuitable thermodynamic properties, large volume change during hydrogen sorption cycles have greatly hindered the practical applications. Here in this review, our recent achievements of a new research direction on Mg-based metastable nano alloys with a Body-Centered Cubic (BCC) lattice structure are summarized. Different with other metals/alloys/complex hydrides etc. which involve significant lattice structure and volume change from hydrogen introduction and release, one unique nature of this kind of metastable nano alloys is that the lattice structure does not change obviously with hydrogen absorption and desorption, which brings interesting phenomenon in microstructure properties and hydrogen storage performances (outstanding kinetics at low temperature and super high hydrogen capacity potential). The synthesis results, morphology and microstructure characterization, formation evolution mechanisms, hydrogen storage performances and geometrical effect of these metastable nano alloys are discussed. The nanostructure, fresh surface from ball milling process and fast hydrogen diffusion rate in BCC lattice structure, as well as the unique nature of maintaining original BCC metal lattice during hydrogenation result in outstanding hydrogen storage performances for Mg-based metastable nano alloys. This work may open a new sight to develop new generation hydrogen storage materials.     

Magnesium-based alloys for solid-state hydrogen storage applications: A review

Magnesium hydrides (MgH₂) have attracted extensive attention as solid-state H₂ storage, owing to their low cost, abundance, excellent reversibility, and high H₂ storage capacity. This review comprehensively explores the synthesis and performance of Mg-based alloys. Several factors affecting their hydrogen storage performance were also reviewed. The metals addition led to destabilization of Mg–H bonds to boost the dehydrogenation process. A unique morphology could provide more available active sites for the dissociation/recombination of H₂ and allow the activation energy reduction. Also, an appropriate support prevent the agglomeration of Mg particles, hence, sustains their nanosize particles. Moreover, the perspective of avenues for future research presented in this review is expected to act as a guide for the development of novel Mg-based H₂ storage systems. New morphological shape of catalysts, more unexplored and highly potential waste materials, and numerous synthesis procedures should be explored to further enhance the H₂ storage of Mg-based alloys.     

Mg-based composites for enhanced hydrogen storage performance

Hydrogen storage in solids of hydrides is advantageous in comparison to gaseous or liquid storage. Magnesium based materials are being studies for solid-state hydrogen storage due to their advantages of high volumetric and gravimetric hydrogen storage capacity. However, unfavorable thermodynamic and kinetic barriers hinder its practical application. In this work, we presented that kinetics of Mg-based composites were significantly improved during high energy ball milling in presence of various types of carbon, including plasma carbon produced by plasma-reforming of hydrocarbons, activated carbon, and carbon nanotubes. The improvement of the kinetics and de-/re-hydrogenation performance of MgH₂ and TiC-catalysed MgH₂ by introduction of carbon are strongly dependent on the milling time, amount of carbon and carbon structure. The lowest dehydrogenation temperature was observed at 180 °C by the plasma carbon–modified MgH₂/TiC. We found that nanoconfinement of carbon structures stabilised Mg-based nanocomposites and hinders the nanoparticles growth and agglomeration. Plasma carbon was found to show better effects than the other two carbon structures because the plasma carbon contained both few layer graphene sheets that served as an active dispersion matrix and amorphous activated carbons that promoted the spill-over effect of TiC catalysed MgH₂. The strategy in enhancing the kinetics and thermodynamics of Mg-based composites is leading to a better design of metal hydride composites for hydrogen storage.     

A critical review on improving hydrogen storage properties of metal hydride via nanostructuring and integrating carbonaceous materials

Hydrogen-based economy has a great potential for addressing the world's environmental concerns by using hydrogen as its future energy carrier. Hydrogen can be stored in gaseous, liquid and solid-state form, but among all solid-state hydrogen storage materials (metal hydrides) have the highest energy density. However, hydrogen accessibility is a challenging step in metal hydride-based materials. To improve the hydrogen storage kinetics, effects of functionalized catalysts/dopants on metal atoms have been extensively studied. The nanostructuring of metal hydrides is a new focus and has enhanced hydrogen storage properties by allowing higher surface area and thus reversibility, hydrogen storage density, faster and tunable kinetics, lower absorption and desorption temperatures, and durability. The effect of incorporating nanoparticles of carbon-based materials (graphene, C60, carbon nanotubes (CNTs), carbon black, and carbon aerogel) showed improved hydrogen storage characteristics of metal hydrides. In this critical review, the effects of various carbon-based materials, catalysts, and dopants are summarized in terms of hydrogen-storage capacity and kinetics. This review also highlights the effects of carbon nanomaterials on metal hydrides along with advanced synthesis routes, and analysis techniques to explore the effects of encapsulated metal hydrides and carbon particles. In addition, effects of carbon composites in polymeric composites for improved hydrogen storage properties in solid-state forms, and new characterization techniques are also discussed. As is known, the nanomaterials have extremely higher surface area (100–1000 time more surface area in m²/g) when compared to the bulk scale materials; thus, hydrogen absorption and desorption can be tuned in nanoscale structures for various industrial applications. The nanoscale tailoring of metal hydrides with carbon materials is a promising strategy for the next generation of solid-state hydrogen storage systems for different industries.     

Mg-based nanocomposites with improved hydrogen storage performances

MgH₂ is one of the most attractive candidates for on-board H₂ storage. However, the practical application of MgH₂ has not been achieved due to its slow hydrogenation/dehydrogenation kinetics and high thermodynamic stability. Many strategies have been adopted to improve the hydrogen storage properties of Mg-based materials, including modifying microstructure by ball milling, alloying with other elements, doping with catalysts, and nanosizing. To further improve the hydrogen storage properties, the nanostructured Mg is combined with other materials to form nanocomposite. Herein, we review the recent development of the Mg-based nanocomposites produced by hydrogen plasma-metal reaction (HPMR), rapid solidification (RS) technique, and other approaches. These nanocomposites effectively enhance the sorption kinetics of Mg by facilitating hydrogen dissociation and diffusion, and prevent particle sintering and grain growth of Mg during hydrogenation/dehydrogenation process.     

Defect-rich MoS2 nanosheets vertically grown on graphene-protected Ni foams for high efficient electrocatalytic hydrogen evolution

Defect-rich MoS₂ nanosheets are vertically grown on graphene-protected Ni foam by a facial hydrothermal route. The vertically aligned MoS₂ nanosheets with defects such as cracks, amorphousness and oxygen-incorporated disorders endow these as-synthesized catalysts with rich active sites, high conductivity and good stability. The graphene deposited on Ni foam increases its stability in acid. The optimized catalyst exhibits high activity for hydrogen evolution with a quite low overpotential of 140 mV at 10 mA cm^?2, a small Tafel slope of 42 mV decade^?1, and a large exchange current density of 63 μA/cm², as well as excellent stability. This performance is superior to most of its analogue MoS₂ and many transition metal sulfides. This work will broaden the vision to improve the activity of self-supported electrocatalysts by carefully designing the anchored catalysts.     

Selection of metal hydrides-based thermal energy storage: Energy storage efficiency and density targets

Thermo-chemical energy storage based on metal hydrides has gained tremendous interest in solar heat storage applications such as concentrated solar power systems (CSP) and parabolic troughs. In such systems, two metal hydride beds are connected and operating in an alternative way as energy storage or hydrogen storage. However, the selection of metal hydrides is essential for a smooth operation of these CSP systems in terms of energy storage efficiency and density. In this study, thermal energy storage systems using metal hydrides are modeled and analyzed in detail using first law of thermodynamics. For these purpose, four conventional metal hydrides are selected namely LaNi₅, Mg, Mg₂Ni and Mg₂FeH₆. The comparison of performance is made in terms of volumetric energy storage and energy storage efficiency. The effects of operating conditions (temperature, hydrogen pressure and heat transfer fluid mass flow rates) and reactor design on the aforementioned performance metrics are studied and discussed in detail. The preliminary results showed that Mg-based hydrides store energy ranging from 1.3 to 2.4 GJ m^?3 while the energy storage can be as low as 30% due to their slow intrinsic kinetics. On the other hand, coupling Mg-based hydrides with LaNi₅ allow us to recover heat at a useful temperature above 330 K with low energy density ca.500 MJ m^?3 provided suitable operating conditions are selected. The results of this study will be helpful to screen out all potentially viable hydrides materials for heat storage applications.     

Hydrogen storage in binary and ternary Mg-based alloys: A comprehensive experimental study

This study focused on hydrogen sorption properties of 1.5 μm thick Mg-based films with Al, Fe and Ti as alloying elements. The binary alloys are used to establish as baseline case for the ternary Mg–Al–Ti, Mg–Fe–Ti and Mg–Al–Fe compositions. We show that the ternary alloys in particular display remarkable sorption behavior: at 200 °C the films are capable of absorbing 4–6 wt% hydrogen in seconds, and desorbing in minutes. Furthermore, this sorption behavior is stable over cycling for the Mg–Al–Ti and Mg–Fe–Ti alloys. Even after 100 absorption/desorption cycles, no degradation in capacity or kinetics is observed. For Mg–Al–Fe, the properties are clearly worse compared to the other ternary combinations. These differences are explained by considering the properties of all the different phases present during cycling in terms of their hydrogen affinity and catalytic activity. Based on these considerations, some general design principles for Mg-based hydrogen storage alloys are suggested.     

The effect of Na addition on the first hydrogen absorption kinetics of cast hypoeutectic Mg–La alloys

With superior properties of Mg such as high hydrogen storage capacity (7.6 wt% H/MgH₂), low price, and low density, Mg has been widely studied as a promising candidate for solid-state hydrogen storage systems. However, a harsh activation procedure, slow hydrogenation/dehydrogenation process, and a high temperature for dehydrogenation prevent the use of Mg-based metal hydrides for practical applications. For these reasons, Mg-based alloys for hydrogen storage systems are generally alloyed with other elements to improve hydrogen sorption properties. In this article, we have added Na to cast Mg–La alloys and achieved a significant improvement in hydrogen absorption kinetics during the first activation cycle. The role of Na in Mg–La has been discussed based on the findings from microstructural observations, crystallography, and first principles calculations based on density functional theory. From our results in this study, we have found that the Na doped surface of Mg–La alloy systems have a lower adsorption energy for H₂ compared to Na-free surfaces which facilitates adsorption and dissociation of hydrogen molecules leading to improvement of absorption kinetic. The effect of Na on the microstructure of these alloys, such as eutectic refinement and a density of twins is not highly correlated with absorption kinetics.     

Effect of nitrogen and sulfur co-doping on the performance of electrochemical hydrogen storage of graphene

In recent decades, finding a solution to replace metal catalysts with inexpensive and available elements has been investigated extensively. Carbon nanomaterials doped with heteroatom such as (N, B and S) which do not have any metal content can provide sustainable materials with a remarkable electrocatalytic activity that can compete with their metal counterparts. Doped graphene has been considered as an electrode material for oxygen reduction reaction, supercapacitor and Li-ion batteries. In this present account, co-doped graphene with nitrogen and sulfur was studied in order to investigate their electrochemical hydrogen storage performance. The dual doped sample was prepared via a simple hydrothermal method, using thiourea as a nitrogen and sulfur source. The nitrogen and sulfur co-doped graphene (NSG) showed excellent electrical conductivity and electrochemical performance compared with the nitrogen doped graphene (NG) and graphene oxide (GO). Doping graphene with foreign atoms is a method to create a semiconducting gap in it and can act as an n-type semiconductor, therefore the electrochemical performance is remarkable when used as an electrode. According to the results by increasing the electrical conductivity of graphene, the storage capacity of hydrogen was increased. The discharge capacity of GO after 20 cycles was increased from 653 mAh/g to 1663 mAh/g (5.88 wt% hydrogen) and 2418 mAh/g (8.55 wt% hydrogen) in single doped graphene (NG) and co-doped graphene (NSG), respectively. The prepared samples were characterized via X-Ray Diffraction (XRD), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), Brunauer-Emmet-Teller analysis (BET), vibration sample magnetometer (VSM) and infrared spectrum (FT-IR).     

Recent advances in magnesium-based hydrogen storage materials with multiple catalysts

The slow hydrogenation/dehydrogenation kinetics and high thermodynamic stability of MgH bond are the two major limitations for large-scale utilization of MgH₂. Constructing Mg nanoparticles (NPs) with large specific surface area and short hydrogen diffusion distance and adding effective catalysts to facilitate the sorption kinetics are the main ways to solve the remained shortages of Mg/MgH₂ system. This article reviews the recent advances in the Mg-based nanocomposites with multiple catalysts produced by different approaches. The multiple catalysts was classified into transition metals and/or their hydrides (TM and/or TMH), TM together with metal oxides, TM and/or TMH together with metal hadlies, TM and/or TMH together with metal sulfides, TM and/or TMH together with Mg₂M and other multiple catalysts systems. Compared with single catalyst, the multiple catalysts display enhanced synergistic catalytic effects on the hydrogen absorption and desorption rates.     

Geometrical effect in Mg-based metastable nano alloys with BCC structure for hydrogen storage

Mg-based materials are thought to be promising candidates for future hydrogen storage applications due to the low cost, abundant resources and large hydrogen storage capacity. However, they suffer from the challenges of sluggish kinetics and large volume change after hydriding/dehydriding (H/D) process. In order to address the problems, we successfully synthesized the Mg-based Body-Centered Cubic (BCC) metastable nano alloys with much improved kinetics while almost no obvious structure change after H/D process. In this work, the obtained Mg₅₅Co₄₅ metastable alloy with BCC structure can reach a hydrogen storage capacity of 3.24 wt% (hydrogen per metal or H/M = 1.28, H/Mg = 2.33) at −15 °C and this absorption temperature in Mg-based BCC structure is the lowest temperature reported for Mg-based materials to absorb hydrogen. Importantly, the BCC structure is maintained without obvious metal lattice change after H/D process. Nevertheless, the potential uptake of about 20 wt% theoretical hydrogen capacity (H/M = 9) for this unique BCC structure cannot be reached up to now. Herein, we discuss the mechanism from the geometrical effect aspect to figure out the difference between the experimental hydrogen storage capacity (H/M = 1.28) and the theoretical one (H/M = 9).     

Diatom frustule-graphene based nanomaterial for room temperature hydrogen storage

Development of a room temperature hydrogen storage material is vital for the realization of a hydrogen economy. Towards achieving this goal, we present the use of naturally occurring diatom frustule for the synthesis of a novel nanomaterial that can achieve a hydrogen storage capacity of ~4.83 wt% at 25 ^°C and ~20 bar H₂ equilibrium pressure. We have effectively combined the large surface area of few layer graphene(G), the unique physical and chemical properties of diatom frustules(D) such as chemical inertness and good porosity and the ability of transition metals and their alloys (Pd₃Co) to adsorb large amounts of hydrogen. The resulting nanomaterial (Pd₃Co-D(100)-G) has a surface area of 163.25 m²/g and pore volume of 0.84 cm³/g. The observations in the present study suggest that increased surface area and porosity play a key role in achieving high hydrogen storage capacity at relatively low H₂ equilibrium pressures and room temperature conditions.     

Synergetic catalytic effect of MWCNTs and TiF3 on hydrogenation properties of nanocrystalline Mg-10wt%Ni alloys

The Mg-10wt%Ni master alloy was firstly prepared using an electric resistance furnace under the protection of the cover reagent. Nanocrystalline alloys were obtained by spinning the molten alloy on a rotating copper wheel at a linear velocity of 35 m/s. Subsequently, the nanocrystalline alloy was high-energy ball milled (HEBM) with MWCNTs or TiF₃ or both. The catalytic effect of MWCNTs or TiF₃ and the synergetic catalytic effects on hydrogenation properties of Mg-based alloys were investigated. The alloys were characterized by X-ray diffraction (XRD), transition electron microscope (TEM), scanning electron microscope (SEM) equipped with an electron energy dispersion spectrum (EDS) to evaluate phase compositions, crystal structure, grain size, particle morphology and the distribution of catalyst element. Hydrogen storage capacities and the hydriding kinetics of the materials were measured using a Sievert's apparatus. Hydrogenation properties of the samples with and without catalysts were compared to understand the catalytic effect of MWCNTs and TiF₃ on the hydrogenation performance of Mg-based alloys.     

Metal (boro-) hydrides for high energy density storage and relevant emerging technologies

The current energy transition imposes a rapid implementation of energy storage systems with high energy density and eminent regeneration and cycling efficiency. Metal hydrides are potential candidates for generalized energy storage, when coupled with fuel cell units and/or batteries. An overview of ongoing research is reported and discussed in this review work on the light of application as hydrogen and heat storage matrices, as well as thin films for hydrogen optical sensors. These include a selection of single-metal hydrides, Ti–V(Fe) based intermetallics, multi-principal element alloys (high-entropy alloys), and a series of novel synthetically accessible metal borohydrides. Metal hydride materials can be as well of important usefulness for MH-based electrodes with high capacity (e.g. MgH₂ ~ 2000 mA h g⁻¹) and solid-state electrolytes displaying high ionic conductivity suitable, respectively, for Li-ion and Li/Mg battery technologies. To boost further research and development directions some characterization techniques dedicated to the study of M-H interactions, their equilibrium reactions, and additional quantification of hydrogen concentration in thin film and bulk hydrides are briefly discussed.     

Boosting the hydrogenation activity of dibenzyltoluene catalyzed by Mg-based metal hydrides

Hydrogenation of dibenzyltoluene (DBT) is of great significance for the application in liquid organic hydrogen carriers (LOHCs). We successfully develop Mg-based metal hydrides (Mg₂NiH₄, MgH₂, and LaH₃) reactive ball-milling for the hydrogenation of DBT. Mg-based metal hydrides milled with 500 min exhibit the best catalytic activity, the hydrogen uptake of DBT can reach 4.63 wt% at the first 4 h and finally achieve 5.70 wt% through 20 h, which is the first time to use hydrogen storage material as a catalyst for the hydrogenation of DBT. The excellent catalytic hydrogenation performance of Mg-based metal hydrides mostly originates from numerous catalytic activity centers formed at the surfaces of Mg₂NiH₄ nanoparticles in the MgH₂ matrix. Inspired by this mechanism, more general metal hydrides can be explored for catalyzing the hydrogenation of LOHCs. The new application of Mg-based metal hydrides is beneficial to developing efficient LOHC based hydrogen storage systems and offers novel insights to hydride-based catalysts.     

Iron based catalyst for the improvement of the sorption properties of KSiH3

Recently, silanides (MSiH₃) have been proposed as the possible hydrogen storage materials due to their hydrogen storage properties. Among these silanides, KSiH₃ has been considered as leading contender due to its high hydrogen storage capacity i.e. 4.3 wt% and suitable thermodynamic parameters. It can absorb and desorb hydrogen reversibly at near ambient temperature, however, a high activation barrier slows down its kinetics. To enhance its kinetic properties, several catalysts have been attempted so far. Nb₂O₅ has been proven as leading catalyst with significant improvement. In the present work, Fe based catalysts were chosen due to their suitability for hydrogen storage materials. Among all the studied catalysts in this work, Fe₂O₃ was found to be the most effective catalyst, reducing the activation energy down to 75 kJ mol⁻¹ from 142 kJ mol⁻¹ for pristine KSi.     

Composition dependent hydrogen storage performance and desorption factors of Mg–Ce based alloys

The widespread application of Mg as a hydrogen storage material has been limited by its slow absorption and desorption kinetics at moderate temperatures. Aiming at improving the de-/absorption kinetics of Mg-based alloys by in situ formed catalysts and understanding the desorption factors, Mg–Ce and Mg–Ce–Ni alloys with different Ce contents are prepared. The phase components, microstructure and hydrogen storage properties have been carefully investigated. It is shown that an 18R-type long-period stacking ordered (LPSO) phase is formed in as-melt Mg–Ce–Ni ternary alloy together with random stacking faults. Abundant in situ formed CeH_2.73 particles with particle size less than 100 nm are observed on the matrix after hydrogenation. It is found in isothermal hydrogenation and dehydrogenation kinetic curves that Ni significantly favors desorption process, while Ce is more conducive to absorption. After partial dehydrogenation of Mg–Ce binary alloy, the initial desorption temperature decreases significantly when desorbing again. The primary-formed Mg phase on the surface of MgH₂ accounts for the improved desorption performance.     

Enhanced hydrogen storage performance in Pd3Co decorated nitrogen/boron doped graphene composites

In order to harness the potential of hydrogen as an alternative energy carrier, overcoming the barrier related to its storage is of utmost importance. In this direction, it has been shown that dissociation of hydrogen molecules into atoms followed by their adsorption onto high surface area nanomaterials like reduced graphene oxide is a promising pathway. In the present study, we have exploited this pathway, commonly known as the “spillover mechanism” and achieved a hydrogen storage capacity of ～4.6 wt% at 30 bar and 25 °C in Pd₃Co decorated boron doped graphene composite. We demonstrate that optimum loading of transition metal alloy nanoparticles coupled with heteroatom (nitrogen or boron) doped graphene support is an efficient, easy and cost effective avenue towards meeting the US department of energy (DOE) targets for gravimetric hydrogen storage capacity at room temperature and moderate pressures.