Hydrogen Storage Materials Research Articles

Magnesium hydrogen storage: Temperature control via particle swarm with nonlinear inertia strategy

Magnesium-based hydrogen storage has garnered significant attention in the field of hydrogen storage due to its notable advantages, including high hydrogen storage capacity and low material cost. However, the relatively high thermodynamic stability of magnesium-based hydrogen storage materials necessitates heating the material to a specific temperature during the hydrogen charging and discharging processes, severely limiting the practical application and further development of this technology.Therefore, this paper aims to design a temperature control system for a magnesium-based solid-state hydrogen storage bottle. The system employs an optimized particle swarm optimization (PSO) algorithm to determine PID parameters, enabling rapid preheating of the hydrogen storage bottle and maintaining a stable operating temperature. Furthermore, by incorporating an appropriate penalty function, the system effectively suppresses temperature overshoot, preventing adverse effects on hydrogen storage performance caused by transient high temperatures, thereby ensuring the safety and stability of the hydrogen storage process.

Mxene-supported NbVH nanoparticles as efficient catalysts for reversible hydrogen storage in magnesium borohydride

Bimetallic niobium vanadium hydride nanoparticles (NbVH NPs) anchored on Ti3C2 were synthesized using a facile ball milling method as an effective catalyst for the dehydrogenation kinetics and reversibility of Mg(BH4)2. It was found that the onset dehydrogenation temperature of the Mg(BH4)2 + 30NbVH NPs@Ti3C2 composite was 105.7 °C and released 9.07 wt% of hydrogen at 330 °C, while undoped Mg(BH4)2 only released 4.2 wt% of H2 from 248 °C to 330 °C. Additionally, the Mg(BH4)2 + 30NbVH NPs@Ti3C2 composite achieved remarkable hydrogen release of over 9.44 wt% at a temperature as low as 230 °C, indicating unexpected dehydrogenation kinetics. In the reversible hydrogen desorption tests, Mg(BH4)2 + 30NbVH NPs@Ti3C2 released 5.98 wt% of H2 in the 2nd cycle at 250 °C and maintained a reversible capacity of 4.35 wt% after 10 cycles, demonstrating a remarkable enhancement in reversibility. The enhancement in the dehydrogenation kinetics of Mg(BH4)2 could be attributed to the greatly reduced activation energies from 343 kJ·mol−1 and 138.3 kJ·mol−1 to 103.7 kJ·mol−1 and 124 kJ·mol−1. Investigations on the evaluation of catalyst and Mg(BH4)2 during reversible hydrogen storage have revealed that NbVH NPs actually acted as a “bidirectional hydrogen pump”, facilitating both the hydrogen release and uptake from Mg(BH4)2. This strategy of multi-component hydrides may show a new way to design effective catalysts for solid-state hydrogen storage materials.

Characterization of alane (AlH3) thin films grown by atomic layer deposition for hydrogen storage applications

Alane (AlH3) is an increasingly favored material for hydrogen and energy storage. It has demonstrated its potential in various applications, including rocket fuel, explosives, reducing agents, and serving as a viable source of hydrogen for portable fuel cells. In this study, we present the fabrication, morphology and elemental characterization of an AlH3 thin film grown through atomic layer deposition using a dimethylethylamine alane (DMEAA; AlH3N(CH3)2(CH2CH3)) precursor. The AlH3 thin film exhibited a rough surface with a white-like appearance, forming coarse grains as observed via scanning electron microscopy. X-ray diffraction confirmed the presence of AlH3 and it was compared with an aluminum thin film. Energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy confirmed the presence of pure AlH3 under a very thin aluminum oxide surface layer. Additionally, we propose a dissociation reaction mechanism based on the DMEAA precursor. Our work contributes to the advancement of hydrogen storage materials and energy-related applications that necessitate high hydrogen storage capacity and energy efficiency.

Ternary Fe–Ni–B particles supported on Cu(OH)2–Cu foam: A highly efficient and stable catalyst for hydrolysis of ammonia borane

Ammonia borane (NH3BH3) as a solid chemical hydrogen storage material with a high hydrogen content can be hydrolyzed under mild conditions to release hydrogen. In this work, Fe–Ni–B/Cu(OH)2–Cu foam was synthesized by combining in situ growth and electroless plating. Compared with the binary Fe–B/Cu(OH)2–Cu foam and Ni–B/Cu(OH)2–Cu foam prepared by the same method, the ternary Fe–Ni–B/Cu(OH)2–Cu foam has superior catalytic performance. The Fe–Ni–B/Cu(OH)2–Cu foam catalyst was able to achieve a maximum hydrogen production rate of 5.6 ml min−1 cm−2 at 298 K with an activation energy as low as 46.3 kJ mol−1. And more importantly, its catalytic efficiency has hardly decayed after ten cycles. These excellent properties are due to its low activation energy and the large specific surface, multi–site Cu(OH)2–Cu–foam carrier.

Effects of Ti- and Nb-based transition element from single to multiple compound oxides and carbon-based composite additives on Mg-MgH2 hydrogen storage material

Effects of Ti- and Nb-based transition element from single to multiple compound oxides and carbon-based composite additives on Mg-MgH2 hydrogen storage material

Thermodynamic and Kinetic Regulation for Mg‐Based Hydrogen Storage Materials: Challenges, Strategies, and Perspectives

AbstractMg‐based hydrogen storage materials have drawn considerable attention as the solution for hydrogen storage and transportation due to their high hydrogen storage density, low cost, and high safety characteristics. However, their practical applications are hindered by the high dehydrogenation temperatures, low equilibrium pressure, and sluggish hydrogenation and dehydrogenation (de/hydrogenation) rates. These functionalities are typically determined by the thermodynamic and kinetic properties of de/hydrogenation reactions. This review comprehensively discusses how the compositeization, catalysts, alloying, and nanofabrication strategies can improve the thermodynamic and kinetic performances of Mg‐based hydrogen storage materials. Since the introduction of various additives leads the samples being a multiple‐phases and elements system, prediction methods of hydrogen storage properties are simultaneously introduced. In the last part of this review, the advantages and disadvantages of each approach are discussed and a summary of the emergence of new materials and potential strategies for realizing lower‐cost preparation, lower operation temperature, and long‐cycle properties is provided.

Exploring hydrogen storage safety research by bibliometric analysis

The application of hydrogen energy is affected by the safety of hydrogen storage system. To grasp the current status of research and application in the research field of hydrogen storage safety and explore its research development trend, data analysis techniques, such as co-occurrence, co-citation, and burst detection, were adopted to conduct bibliometric analysis of the relevant literature. The study results show that the research hotspots of hydrogen storage safety mainly concentrate on six aspects: the stability of metal hydride hydrogen storage materials, the study of thermal management and stress relief in metal hydride reactors, the safety analysis of hydrogen fuel cells and hydrogen leakage monitoring, the analysis of leakage and explosion risks in hydrogen refueling stations, the study of filling pressure and temperature distribution in hydrogen storage tanks, and the study of safety issues in underground hydrogen storage. Mg-based hydride stability and underground hydrogen storage risk analyses are current research frontiers in hydrogen storage safety.

Crystal Structure Prediction and Performance Assessment of Hydrogen Storage Materials: Insights from Computational Materials Science

Hydrogen storage materials play a pivotal role in the development of a sustainable hydrogen economy. However, the discovery and optimization of high-performance storage materials remain a significant challenge due to the complex interplay of structural, thermodynamic and kinetic factors. Computational materials science has emerged as a powerful tool to accelerate the design and development of novel hydrogen storage materials by providing atomic-level insights into the storage mechanisms and guiding experimental efforts. In this comprehensive review, we discuss the recent advances in crystal structure prediction and performance assessment of hydrogen storage materials from a computational perspective. We highlight the applications of state-of-the-art computational methods, including density functional theory (DFT), molecular dynamics (MD) simulations, and machine learning (ML) techniques, in screening, evaluating, and optimizing storage materials. Special emphasis is placed on the prediction of stable crystal structures, assessment of thermodynamic and kinetic properties, and high-throughput screening of material space. Furthermore, we discuss the importance of multiscale modeling approaches that bridge different length and time scales, providing a holistic understanding of the storage processes. The synergistic integration of computational and experimental studies is also highlighted, with a focus on experimental validation and collaborative material discovery. Finally, we present an outlook on the future directions of computationally driven materials design for hydrogen storage applications, discussing the challenges, opportunities, and strategies for accelerating the development of high-performance storage materials. This review aims to provide a comprehensive and up-to-date account of the field, stimulating further research efforts to leverage computational methods to unlock the full potential of hydrogen storage materials.

Synergetic enhancement of hydrogen concentration and heat transfer for triply periodic minimal surface based hydrogen storage reactor

Metal hydride hydrogen storage technology is considered a potential alternative energy and energy storage solution in promoting global economic decarbonization. However, the heat transfer coefficient between hydrogen storage materials and reactors is relatively low, which cannot meet the heat transfer and hydrogen storage requirements of the metal hydride tank. This study employs a triply periodic minimal surface (TPMS) based hydrogen storage reactor and design of experiments (DOE) to reveal the relationship between various parameters and their characteristics. The multi-physics coupling of fluid flow, heat transfer, chemical reactions, and stress in a metal hydride hydrogen storage reactor is also combined to promote the synergistic improvement of heat transfer and hydrogen storage efficiency. Numerical simulation results demonstrate that the hydrogen absorption volume fraction of tank equipped with TPMS is 0.926, which is significantly higher than that of conventional finned one. The absorption of hydrogen leads to volume expansion, resulting in a 30.61 % increase in expansion stress. Furthermore, the optimal hydrogen absorption volume fraction occurs at a temperature of 273.15 K, a pressure of 3.49 MPa, and a velocity of 5 m/s.

Efficient hydrogen absorption and dehydrogenation of synergistically catalyzed Mg10Fe by MoS2 and Y2O3 via one-step synthesis and multistage regulation

To effectively deal with the long preparation period and low hydrogen absorption capacity issue of Mg-based hydrogen storage materials. One-step multistage control strategy and high-pressure hydrogenation have been employed to prepare Mg10Fe-M (M = MoS2 or Y2O3 or both) composites. The phase composition, microstructure, morphology, non-isothermal dehydrogenation thermodynamics and isothermal dehydrogenation kinetics at different milling time (2, 4, 8 h) were explored, and the catalytic hydrogen absorption and discharge mechanism of Mg10Fe–MoS2–Y2O3 was proposed. The addition of MoS2 nanoflowers and Y2O3 powder can synergistically regulate and improve the hydrogenation capacity and dehydrogenation temperature of Mg10Fe. The hydrogen absorption and dehydrogenation of Mg10Fe–MoS2–Y2O3 in short time milling for 2 h are 3.64 wt% and 3.27 wt% respectively. After extending the milling time to 8 h, the thermodynamic and kinetic behavior of Mg10Fe-M (M = MoS2 or Y2O3 or both) is greatly improved. Kinetically, the hydrogenation or dehydrogenation capacity increases significantly, Mg10Fe–MoS2 doesn't need activation, and the hydrogenation capacity reaches 5.42 wt% at 623 K, with a yield of about 85.9 % in 60 min. Thermodynamically, the initial dehydrogenation peak temperature drops to about 310 °C, and the apparent activation energy also decreases significantly, among which Mg10Fe–MoS2–Y2O3 was 91.87 kJ/mol. These are attributed to the fact that MoS2 nanoflowers provide many active sites for H2 adsorption and H atom dissociation. Synchro-efficient synthesis and regulation of Mg-rich composite hydrogen storage materials are expected to shorten the synthesis cycle, improve the hydrogen storage performance, and lay a material foundation for the design and development of solid hydrogen storage devices.

Effects of Mg and Al doping on the desorption energetics and electronic structure of a Ti-V-Zr-Nb alloy hydride

Refractory high-entropy alloys (HEAs) show promise for novel hydrogen storage technology, but addressing their limited gravimetric hydrogen storage capacity necessitates exploration of light alloying elements including Mg and Al. Here, we employ density-functional theory to investigate the hydrogen desorption energetics of Ti0.325V0.275Zr0.125Nb0.275 alloy and the impact of doping with Mg and Al. Our analysis reveals that Mg and Al addition thermodynamically destabilize the Ti0.325V0.275Zr0.125Nb0.275-hydride and lower its storage capacity. The observed destabilization is attributed to reduced chemical contributions to the desorption enthalpy in the Mg and Al-doped hydrides. Detailed examination of the electronic density of states, electron localization function, and crystal orbital Hamilton population analysis unveils fundamental features of chemical bonding in these hydrides. Notably, H-H antibonding states occur for hydrogen atoms located in the nearest-neighbor interstices of Mg and Al atoms. Charge transfer facilitates formation of these antibonding states. This comprehensive analysis enhances our understanding of the intricate interplay between electronic structure, hydrogen desorption energetics, and chemical bonding in HEA hydrides, offering valuable insights for the design and optimization of advanced hydrogen storage materials.

Hydrogen adsorption, desorption, sensor and storage properties of Cu doped / decorated boron nitride nanocone materials: A density functional theory and molecular dynamic study

The hydrogen storage and sensor properties of Cu-modified boron nitride nanocone (BNNC) structure were comprehensively investigated using the density functional theory method (DFT). By replacing nitrogen atoms with copper atoms on the BNNC structure, the hydrogen molecule's adsorption enthalpy and Gibbs free energy values were calculated as −48.6 and −16.9 kJ/mol, respectively. 4 Cu-doped BNNC structure achieved a notable hydrogen storage capacity of 5.38 wt%. The molecular dynamics calculations demonstrate that the structure modified with four Cu atoms maintains its dynamic stability. Furthermore, this study reveals that the desorption temperatures tend to rise with an increase in the number of adsorbed hydrogen molecules, and the average desorption temperature under 1 atm pressure is determined to be 332 K. The changes of work function values after hydrogen adsorption point out that the Cu-modified BNNC has Φ-sensor feature. Overall, Cu-modified BNNC structures show promising potential as hydrogen storage materials in ambient conditions.

Chemical effect of alkaline-earth metals (Be, Mg, Ca) substitution of BFe2XH hydride perovskites for applications as hydrogen storage materials: A DFT perspective

This study investigated the effect of alkaline-earth metals (X = Be, Mg, Ca) substitution of BFe2XH perovskite materials and the potential applications for hydrogen storage utilizing density functional theory (DFT) approach at the GGA-PBE and the HSE06 methods. The mechanical properties of the studied systems demonstrate the mechanical stability of BFe2MgH, making it the most mechanically robust compound. While the Pugh ratio suggests that BFe2BeH was brittle, while BFe2CaH showed greater ductility, anisotropic factors confirm that all compounds are anisotropic, indicating directional dependence in their properties. The electronic band structure analysis using the HSE06 and the GGA-PBE suggests that the studied perovskites are metallic due to a calculated bandgap of zero. In terms of optical/optoelectronic properties, BFe2MgH exhibits the highest optical conductivity, absorption coefficient, and energy loss function, indicating its superior ability to absorb light and transfer electrons. For practical applications, the hydrogen storage capacity is assessed, with BFe2BeH showing the highest gravimetric and volumetric capacities. These promising results suggest the potential use of BFe2BeH as an efficient material for hydrogen storage.

Emergence of carbonaceous material for hydrogen storage: an overview

Emergence of carbonaceous material for hydrogen storage: an overview

Simulation of Hydrogen Adsorption in Hierarchical Silicalite: Role of Electrostatics and Surface Chemistry.

Adsorption in nanoporous materials is one strategy that can be used to store hydrogen at conditions of temperature and pressure that are economically viable. Adsorption capacity of nanoporous materials depends on surface area which can be enhanced by incorporating a hierarchical pore structure. We report grand canonical Monte Carlo (GCMC) simulation results on the adsorption of hydrogen in hierarchical models of silicalite that incorporate 4 nm wide mesopores in addition to the 0.5 nm wide micropores at 298 K, using different force fields to model hydrogen. Our results suggest that incorporating mesopores in silicalite can enhance adsorption by at least 20 % if electrostatic interactions are not included and up to 100 % otherwise. Incorporating electrostatic interactions results in higher adsorption by close to 100 % at lower pressures for hierarchical silicalite whereas for unmodified silicalite, it is less significant at all pressures. Hydroxylating the mesopore surface in hierarchical silicalite results in an enhancement in adsorption at pressures below 1 atm and suppression by up to 20 % at higher pressures. Temperature dependence at selected pressures exhibits expected decrease in adsorption amounts at higher temperatures. These findings can be useful in the engineering, selection, and optimization of nanoporous materials for hydrogen storage.

Efficient Hydrogen Generation from Ammonia Borane Hydrolysis on a Tandem Ruthenium–Platinum–Titanium Catalyst

AbstractHydrolysis of ammonia borane (NH3BH3, AB) involves multiple undefined steps and complex adsorption and activation, so single or dual sites are not enough to rapidly achieve the multi‐step catalytic processes. Designing multi‐site catalysts is necessary to enhance the catalytic performance of AB hydrolysis reactions but revealing the matching reaction mechanisms of AB hydrolysis is a great challenge. In this work, we propose to construct RuPt−Ti multi‐site catalysts to clarify the multi‐site tandem activation mechanism of AB hydrolysis. Experimental and theoretical studies reveal that the multi‐site tandem mode can respectively promote the activation of NH3BH3 and H2O molecules on the Ru and Pt sites as well as facilitate the fast transfer of *H and the desorption of H2 on Ti sites at the same time. RuPt−Ti multi‐site catalysts exhibit the highest turnover frequency (TOF) of 1293 min−1 for AB hydrolysis reaction, outperforming the single‐site Ru, dual‐site RuPt and Ru−Ti catalysts. This study proposes a multi‐site tandem concept for accelerating the dehydrogenation of hydrogen storage material, aiming to contribute to the development of cleaner, low‐carbon, and high‐performance hydrogen production systems.

Efficient Hydrogen Generation from Ammonia Borane Hydrolysis on a Tandem Ruthenium-Platinum-Titanium Catalyst.

Hydrolysis of ammonia borane (NH3BH3, AB) involves multiple undefined steps and complex adsorption and activation, so single or dual sites are not enough to rapidly achieve the multi-step catalytic processes. Designing multi-site catalysts is necessary to enhance the catalytic performance of AB hydrolysis reactions but revealing the matching reaction mechanisms of AB hydrolysis is a great challenge. In this work, we propose to construct RuPt-Ti multi-site catalysts to clarify the multi-site tandem activation mechanism of AB hydrolysis. Experimental and theoretical studies reveal that the multi-site tandem mode can respectively promote the activation of NH3BH3 and H2O molecules on the Ru and Pt sites as well as facilitate the fast transfer of *H and the desorption of H2 on Ti sites at the same time. RuPt-Ti multi-site catalysts exhibit the highest turnover frequency (TOF) of 1293 min-1 for AB hydrolysis reaction, outperforming the single-site Ru, dual-site RuPt and Ru-Ti catalysts. This study proposes a multi-site tandem concept for accelerating the dehydrogenation of hydrogen storage material, aiming to contribute to the development of cleaner, low-carbon, and high-performance hydrogen production systems.

One electron is enough: A chemical bonding approach on the hydrogen induced structural transformation in MPd3 (M = Mg, In, Tl) intermetallic compounds

It is crucial to understand the nature of the metal-hydrogen interactions in the intermetallic hydrides in order to develop new hydrogen storage materials with optimum metal-H interactions for desired hydrogen absorption-desorption kinetics. The MPd3 intermetallic compounds (M = Mg, In, Tl) transform to cubic anti-perovskite type (AuCu3-type with hydrogen in the octahedral intersect) structure from ZrAl3-type four-fold ccp-superstructure up on hydrogenation. According to the DFT-based orbital space electronic structure and chemical bonding analysis, this structural transformation is driven by maximizing the coordination of hydrogen surrounded by Pd, forming the Pd (4d) – H (1s), and … Pd–H–Pd … multicenter interactions. These interactions provide sufficient thermodynamic stability for the hydrides to form, with negative binding energies of hydrogen. The binding energies are found to be significantly low, with the possibility of the ease of hydrogen desorption within limited reaction conditions.

Metal-decorated M-graphene for high hydrogen storage capability and reversible hydrogen release

With the increasing demand for green energy, the design of effective hydrogen storage materials is becoming particularly important. In this work, the hydrogen storage performances of the metal atoms (Li, Ca, and Sc) decorated two–dimensional (2D) M-graphenes were investigated with density functional theory (DFT) calculations. The metal atoms can be substantially anchored on the M-graphene surface in single–atom formation revealed by the high binding energy, which is ascribed to the remarkable charge transfers between metal atom and M-graphene. Each metal atom can capture six H2 molecules at most in single–atom decorated M-graphene. The H2 adsorption energies are in the range from −0.139 to −0.375 eV, following an order of Sc@M-graphene > Ca@M-graphene > Li@M-graphene. The affinity ability of metal–decorated M-graphene for hydrogen can be enhanced by adding an external electric field. The multi–metal atoms decorated M-graphenes, Li4C16(H2)8, Ca4C16(H2)12, and Sc4C16(H2)12 complexes show high gravimetric densities (6.06 ∼ 6.78 wt%) and a favorable binding energy window (−0.167 to −0.418 eV), meeting the department of energy (DOE)’s criteria. The thermodynamic properties were in detail studied by considering temperature and pressure effects. AIMD simulations at different temperatures indicate that the efficient release of hydrogen can occur at room temperature. Our results show that the M-graphenes with Li, Ca, and Sc decorated have high hydrogen storage capacity and reversible hydrogen release performance. This work may be useful for designing novel 2D carbon–based materials for hydrogen storage.

Low-temperature hydrogen release exceeding 7 wt% from LiBH4-mannitol composites

Among conventional hydrogen storage materials, LiBH4 has been regarded as one of the best hydrogen transporters due to its relatively large hydrogen capacities. However, because of its extraordinarily high dehydrogenation temperatures, LiBH4 was not suitable for hydrogen storage due to its stable thermodynamic features. Herein, we present a novel approach to LiBH4 that uses solid-state multi-hydroxyl mannitol as a reactant, regulating hydrogen release below 69.9 °C. More than 7 wt% H2 could be released with ultra-fast rates at 140 °C from the LiBH4-mannitol composite. XRD, FTIR, and SEM tests revealed that the reaction between mannitol (Hδ+) and LiBH4 (Hδ−) to produce hydrogen was accompanied by the generation of large amounts of heat in situ, which further promoted the decomposition of LiBH4 for hydrogen production, exceeding the theoretical dehydrogenation amount of Hδ+- Hδ− reaction. This work indicates possibilities for the development of fast and easy high-capacity hydrogen generation systems based on complex hydrides.