Theoretical study on the structural evolution and hydrogen storage in NbHn (n = 2–15) clusters

Niobium hydrides are attractive superconductors. Exploring the formation process of niobium hydrides is essential to elucidate the mechanism of superconductivity. One of the key issues is to clarify the atomic stacking patterns of Nb and H atoms, i.e., the structural evolution of Nb–H clusters. Here, the low-energy structural isomers of NbH_n (n = 2–15) clusters are determined using the CALYPSO method combined with density functional theory calculations. Geometries were fully optimized at the B3LYP/LANL2DZ/6–311++G(d) level of theory to determine global minimum structures for each size. The results indicate that NbH₁₃ is the most stable cluster in this size range. The 4d atomic orbital of Nb and the hydrogen 1s atomic orbital participate largely to the internal binding of the NbH₁₃ cluster. They hydrogen storage density and adsorption energy of this cluster are calculated to be 12.4 wt% and 2.58 eV, respectively. The high hydrogen storage density, suitable hydrogen adsorption energy, and high stability of NbH₁₃ shows promise as a hydrogen storage material. These results provide fundamental information for further design of metal hydrogen storage materials.     

Lithium metal hydrides (Li2CaH4 and Li2SrH4) for hydrogen storage; mechanical,electronic and optical properties

Hydrogen storage is a critical step for commercialisation of hydrogen consumed energy production. Among other storage methods, solid state storage of hydrogen attracts much attention and requires extensive research. This study rationally and systematically designs novel solid state hydrides; Li₂CaH₄ (GHD is obtained as −6.95 wt %) and Li₂SrH₄ (GHD is obtained as −3.83 wt %) using computational method. As a first step, we suggest and predict crystal structures of solid state Li₂CaH₄ and Li₂SrH₄ hydrides and look for synthesizability. Then, the mechanical stabilities of hydrides are identified using elastic constants. Both hydrides fulfil the well-known Born stability criteria, indicating that both Li₂CaH₄ and Li₂SrH₄ are mechanically stable materials. Several critical parameters, bulk modulus, shear modulus, Cauchy pressures, anisotropy factors of hydrides and bonding characteristics are obtained and evaluated. Furthermore, electronic and optical band structures of hydrides are computed. Both Li₂CaH₄ and Li₂SrH₄ have indirect bands gaps as 0.96 eV (Г-U) and 1.10 eV (Г-R). Thus, both materials are electronically semiconducting. Also, Bader charge analysis of hydrides have been carried out. Charge density distribution suggests an ionic-like (or polarized covalent) bonding interaction between the atoms.     

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.     

Efficient and highly rapid hydrogen release from ball-milled 3NH3BH3/MMgH3 (M = Na,K, Rb) mixtures at low temperatures

The stoichiometric reactions of ammonia borane (NH₃BH₃, AB) and selected alkali or alkaline-earth metal hydrides produce metal amidoboranes, which possess dehydrogenation property advantages over their parent AB. However, the losses of hydrogen capacity and chemical energy in the preparation process make metal amidoboranes less energy-effective for hydrogen storage application. In the present study, by combining the M⁺–Mg²⁺ double cations remarkably lowers the reactivity of the alkali metal hydrides toward AB. As a result, the starting Mg-based ternary hydrides MMgH₃ (M = Na, K, Rb) and AB phases are largely stable in the mechanical milling process, but transform to the corresponding mixed-cation amidoboranes in the subsequent heating process. Importantly, when the post-milled 3AB/MMgH₃ mixtures are isothermally heated at above 60 °C using water bath, the formation and decomposition processes of the mixed-cation amidoboranes can be favorably combined, giving rise to rapid and efficient dehydrogenation performances at the mild temperatures (60–80 °C). The results acquired may provide a generalized reactions coupling strategy for designing and synthesis other potentially efficient hydrogen storage system.     

Milling induced surface modification of V-based catalyst to improve sorption kinetics of KSiH3: An XPS investigation

Hydrogen as an energy carrier has shown promises for future energy infrastructure. Due to its light weight and explosive nature, hydrogen need to be stored in safe and efficient way. The storage in solid state materials has been proposed as the safest method, which can store hydrogen through chemical bonding. Among several studied materials so far, KSiH₃ is one of the leading contender with a total hydrogen capacity of 4.3 wt %, which is more than what is offered by its rivals such as BCC hydrides or AB₅ type hydrides. However, the high activation energy slows down the hydrogen charging/discharging rate and allow the working only at higher temperatures (～200 °C). The kinetics of hydrogen absorption and desorption intensely improved by the addition of a catalyst. In this work, vanadium based catalysts are added to KSiH₃ system to modify the surface and to enhance the kinetics of this system. Specially, V₂O₅ addition, as leading candidate among the studied catalyst, decreased the activation energy to 83 kJmol^-1 from 142 kJ/mol for pristine KSi. KSiH₃ system with catalyst V₂O₅ started desorbing at 100 °C and could achieve highest weight loss 3.7 wt % which is very close to theoretical value. No disproportionation phenomenon is detected which indicated that the reaction between KSiH₃ and KSi is flawlessly reversible with a hydrogen storage capacity of 3.7 wt % H₂. The XPS investigation suggested a partial reduction of +5 oxidation state (corresponding to V₂O₅) to metallic state, which is proposed as the possible cause of this improvement.     

Structures and hydrogen storage properties of AeVH3 (Ae = Be,Mg, Ca,Sr) perovskite hydrides by DFT calculations

The capability of hydrogen to be an energy source has made the hydrogen storage as one of the most investigated research fields during the recent years, and novel perovskite materials have become the current focus for hydrogen storage applications. Here we study the AeVH₃ (Ae = Be, Mg, Ca, Sr) perovskite-type hydrides to explorer their potential for hydrogen storage applications using the density functional theory (DFT) implemented CASTEP code along with exchange correlation potential. The study examines the electronic structure, optical properties, elastic features and mechanical stability of the materials. The crystal structure of AeVH₃ compounds is found to be cubic with lattice constant as 3.66, 3.48, 3.76 and 3.83 for Ae = Be, Mg, Ca and Sr compounds, respectively. The calculated electronic structures of these compounds show ionic bonding and no energy bandgap. The mechanical characteristics of compounds are also investigated as to meet the Born stability criterion, these compounds should be mechanically stable. The Cauchy pressure and Pugh criteria revealed that these materials have a brittle character and rather hard. In low energy range, all optical properties are found to be suitable as needed for storing the hydrogen. Furthermore, the gravimetric ratios suggested that all the compounds are suitable for hydrogen storage as a fuel for a longer time and may provide remarkable contributions in diversity of power and transportation applications.     

First-principle investigation for the hydrogen storage properties of NaXH3 (X= Mn,Fe, Co) perovskite type hydrides

In the present study, NaXH₃ (X = Mn, Fe, Co) perovskite type hydrides have been investigated by performing first-principles calculation. The results of the structural optimizations show that all these compounds have negative formation energy implying the thermodynamic stability and synthesisability. The mechanical stability of these compounds has been studied with the elastic constants. Moreover, the polycrystalline properties like bulk modulus, Poisson's ratio, etc. have been obtained using calculated elastic constants of interest compounds. The electronic properties have been studied and band structures have been drawn with the corresponding partial density of states. These plots indicated that NaXH₃ hydrides show metallic characteristics. The charge transfer characteristics in these compounds have been studied with the Bader partial charge analysis. The phonon dispersion curves and corresponding density of states indicated that NaXH₃ compounds are dynamically stable compounds. The investigation on hydrogen storage characteristics of NaXH₃ compounds resulted in hydrogen storage capacities of 3.74, 3.70 and 3.57 wt% for X = Mn, Fe and Co, respectively. The present study is the first investigation of NaXH₃ perovskite type hydrides as known up to date and may provide remarkable contribution to the future researches in hydrogen storage applications.     

First-principles investigation on the role of interstitial site preference on the hydrogen-induced disproportionation of ZrCo and its doped alloys

There are two phase structures involved in ZrCo hydrides (ZrCoH_x). When x ≤ 1, the α-phase hydride is generated when hydrogen atoms occupy the 3c and 12i sites. When 1 < x ≤ 3, three interstitial sites of 4c₂, 8f₁, and 8e are occupied by H, and in turn the β-phase hydride is formed. There is a disproportionation reaction in β-phase hydrides during hydrogen discharging process to produce the ZrH₂ phase with higher thermal stability, leading to inferior hydrogen storage performance. In this study, the influence of hydrogen storage capacity on thermodynamic and lattice stabilities of α- and β-phase hydrides for each occupancy position is investigated under the framework of the first-principles study. The results indicate that the binding energy in the 3c site is higher compared with the 12i site under the condition of identical hydrogen storage capacity. Similarly, the binding energy is the largest for the 8e site compared with the other two sites, indicating that there is the least energy released in the reaction process. Thus, the 8e site is proved as the most unfavorable site in β-phase ZrCo hydrides, which is due to its degraded thermodynamic stability. Also, comparisons of mechanical properties and total density of states for each site in two hydride phases are presented to demonstrate that compound lattice stability in the 8e site is the poorest, suggesting that it is more likely to produce disproportionation. Furthermore, the dependence of hydrogen storage performance of β-phase hydrides on Ti/Rh doping is examined as well. It is discovered that there is improved thermodynamic stability and lattice stability in the 8e site for Zr_0.875Ti_0.125Co after Zr is partially substituted by Ti, which significantly enhances the disproportionation resistance. In contrast, when Co is partially replaced by Rh, there is a deterioration in the thermodynamic stability of ZrCo_0.875Rh_0.125 in the 8e site, but its lattice stability is somewhat improved.     

Nanoconfinement effects on hydrogen storage properties of MgH2 and LiBH4

To find a solution to efficiently exploit renewable energy sources is a key step to achieve complete independence from fossil fuel energy sources. Hydrogen is considered by many as a suitable energy vector for efficiently exploiting intermittent and unevenly distributed renewable energy sources. However, although the production of hydrogen from renewable energy sources is technically feasible, the storage of large quantities of hydrogen is challenging. Comparing to conventional compressed and cryogenic hydrogen storage, the solid-state storage of hydrogen shows many advantages in terms of safety and volumetric energy density. Among the materials available to store hydrogen, metal hydrides and complex metal hydrides have been extensively investigated due to their appealing hydrogen storage properties. Among several potentials candidates, magnesium hydride (MgH₂) and lithium borohydride (LiBH₄) have been widely recognized as promising solid-state hydrogen storage materials. However, before considering these hydrides ready for real-scale applications, the issue of their high thermodynamic stability and of their poor hydrogenation/dehydrogenation kinetics must be solved. An approach to modify the hydrogen storage properties of these hydrides is nanoconfinement. This review summarizes and discusses recent findings on the use of porous scaffolds as nanostructured tools for improving the thermodynamics and kinetics of MgH₂ and LiBH₄.     

Effects of compaction pressure and graphite content on hydrogen storage properties of Mg(NH2)2–2LiH hydride

Preparation of hydride–graphite compacts serves as an effective method to improve the volumetric hydrogen storage density and the effective thermal conductivity for light complex hydrides. This paper presents the effects of compaction pressure and expanded natural graphite (ENG) content on the hydrogen storage properties of the Mg(NH₂)₂–2LiH–0.07KOH compacts. The results show that the hydrogen desorption kinetics of the 1st sorption cycle decreases with the increase of the compaction pressure. However, the compacts exhibit the similar hydrogen desorption kinetics and capacities from the 2nd sorption cycles on regardless of the compaction pressure. The ENG addition significantly enhances the desorption kinetics because of the improvement of the heat transfer performance of the hydride. Furthermore, the volumetric hydrogen storage density of the hydride reaches 47 g/L after the compaction at 365 MPa, but it reduces by increasing the ENG content.     

Ammonia as a hydrogen energy carrier

The gravimetric H₂ densities and the heats of combustion of tanks stored ammonia (ammonia storage tanks) were similar to those of the liquid H₂ tanks at the weight of 20–30ton, although the gravimetric H₂ density of liquid H₂ is 100 wt%. The volumetric H₂ densities and the heats of combustion of ammonia storage tanks were about 2 times higher than those of liquid H₂ tanks at 1–4 × 10⁴ m³. Gray ammonia is synthesized from hydrogen through process known as steam methane reforming, nitrogen separated from air and Haber-Bosch process. Blue ammonia is the same as gray ammonia, but with CO₂ emissions captured and stored. Green ammonia is produced by reacting hydrogen produced by electrolysis of water and nitrogen separated from air with Haber-Bosch process using renewable energies. The energy efficiencies of gray, blue and green ammonia were better than those of liquid hydrogen and methylcyclohexane (MCH) with high H₂ density and similar to the efficiency of H₂ gas. The energy efficiencies of ammonia decreased in the order, gray ammonia > blue ammonia > green ammonia. The production costs of green hydrogen energy carried increased in the order, ammonia < liquid H₂<MCH. The amounts of energy consumption by N₂ production and Haber-Bosch process were below 10% compared with the value of H₂ production from water electrolysis.     

Effects of NH4+ doping on the hydrogen storage properties of metal hydrides

Doping can modify the properties of metal hydrogen storage materials significantly. Currently, the metal doping is a frequent strategy, while the non-metal cation doping has not been examined extensively so far. In this study, the effects of NH₄⁺ doping on the hydrogen storage properties of different metal hydrides, including TiH₂, Ti_0·25V_0·25Nb_0·25Zr_0·25H₂, Ti_0·5V_0·5H₂ and VH₂, are investigated by first-principles calculations. It is found that the NH₄⁺ presents a good affinity for metal hydrides and the NH₄⁺ incorporation leads to charge redistribution and formation of dihydrogen bond. Furthermore, the NH₄⁺ doping in metal hydrides is favorable for enhancing the hydrogen storage capacity and decreasing the thermal stability simultaneously. The possible reason for the NH₄⁺ doping induced destabilization in metal hydrides is the relatively weak interaction between NH₄⁺ and hydrogen atoms.     

Thermodynamics analysis of hydrogen storage based on compressed gaseous hydrogen,liquid hydrogen and cryo-compressed hydrogen

Safe, reliable, and economic hydrogen storage is a bottleneck for large-scale hydrogen utilization. In this paper, hydrogen storage methods based on the ambient temperature compressed gaseous hydrogen (CGH₂), liquid hydrogen (LH₂) and cryo-compressed hydrogen (CcH₂) are analyzed. There exists the optimal states, defined by temperature and pressure, for hydrogen storage in CcH₂ method. The ratio of the hydrogen density obtained to the electrical energy consumed exhibits a maximum value at the pressures above 15 MPa. The electrical energy consumed consists of compression and cooling down processes from 0.1 MPa at 300 K to the optimal states. The recommended parameters for hydrogen storage are at 35–110 K and 5–70 MPa regardless of ortho-to parahydrogen conversion. The corresponding hydrogen density at the optimal states range from 60.0 to 71.5 kg m⁻³ and the ratio of the hydrogen density obtained to the electrical energy consumed ranges from 1.50 to 2.30 kg m⁻³ kW⁻¹. While the ortho-to para-hydrogen conversion is considered, the optimal states move to a slightly higher temperatures comparing to calculations without ortho-to para-hydrogen conversion.     

Syntheses of alkali-metal carbazolides for hydrogen storage

Metalorganic hydrides are a new class of hydrogen storage materials. Replacing the H of N–H or O–H functional groups using metal hydrides have been recently reported, which substantially improved the dehydrogenation properties of heteroaromatic organic hydrides by lowering their enthalpies of dehydrogenation (ΔH_d), enabling dehydrogenation at much lower temperatures. Among the reported metalorganic hydrides, lithium carbazolide and sodium carbazolide appear to be the most attractive hydrogen storage/delivery material owing to its high hydrogen capacity (>6.0 wt%) and ideal ΔH_d. Nevertheless, the interaction of carbazole and corresponding metal hydride to form metallo-carbazolide is a multistep process involving intensive ball milling and high temperature treatment, where the interaction was not investigated in detail. In this paper, both alkali metal hydrides and amides were employed to react with carbazole to synthesize corresponding carbazolides, aiming to broaden and optimize the synthetic method and understand the reaction mechanism. Our experimental results showed that around one equivalent of H₂ or NH₃ could be released from the reactions of carbazole and corresponding hydrides or amides, respectively. Instrumental spectroscopic analyses proved that metallo-carbazolides were successfully synthesized from all precursors. It is found that the alkali metal amides (i.e., LiNH₂ and NaNH₂) with stronger Lewis basicities as metal precursors could synthesize the metallo-carbazolides under milder conditions. Furthermore, quasi in situ nuclear magnetic resonance results revealed that alkali metal could replace H (H–N) gradually, donating more electrons to carbazole ring. Additionally, the solubilized alkali cation may unselectively interact with π-electron of aromatic systems of both carbazole molecules and carbazolide anions via electrostatic cation-π interactions.     

Effect of CO on hydrogen storage performance of 2LiNH2 + MgH2 system

(2LiNH₂ + MgH₂) system is one of the most promising hydrogen storage materials due to its suitable operation temperature and high reversible hydrogen storage capacity. In studies and applications, impurities such as CO, CO₂, O₂, N₂ and CH₄ are potential factors which may influence its performance. In the present work, hydrogen containing 1 mol% CO is employed as the hydrogenation gas source, and directly participates in the reaction to investigate the effect of CO on the hydrogen sorption properties of (2LiNH₂ + MgH₂) system. The results indicate that the hydrogen capacity of the (Mg(NH₂)₂ + 2LiH) system declines from 5 wt.% to 3.45 wt.% after 6 cycles of hydrogenation and dehydrogenation, and can not restore to its initial level when use purified hydrogen again. The hydrogen desorption kinetics decreases obviously and the dehydrogenation activation energy increases from 133.35 kJ/mol to 153.35 kJ/mol. The main reason for these is that two new products Li₂CN₂ and MgO appear after (2LiNH₂ + MgH₂) react with CO. They are formed on the surface of materials particles, which may not only cause a permanent loss of NH²⁻, but also prevent the substance transmission during the reaction process. After re-mechanically milling, both kinetics and dehydrogenation activation energy can be recovered to the initial level.     

Low-temperature hydrogen release through LiAlH4 and NH4F react in Et2O

The application of hydrogen energy urgently requires a high-capacity hydrogen storage technology that can release hydrogen at low temperature. The composite of LiAlH₄ and NH₄F has a hydrogen storage capacity of up to 8.06 wt%, but the release of hydrogen requires a reaction temperature of about 170 °C, and the reaction is difficult to control. In this work, the reaction between LiAlH₄ and NH₄F is proposed to be carried out in diethyl ether to improve its hydrogen release performance. It exhibits good hydrogen release performance over a wide temperature range of −40–25 °C, and the hydrogen release capacity at −40 °C, −20 °C, 0 °C and 25 °C can reach 4.41 wt%, 6.79 wt%, 6.85 wt% and 7.78 wt%, respectively. The activation energy of the reaction is 38.41 kJ mol⁻¹, which is much lower than many previously reported catalytic hydrolysis systems that can release hydrogen at room temperature. Our study demonstrates a high-performance hydrogen storage system with very low operating temperature, which may lay the foundation for the development of practical mobile/portable hydrogen source in the north and the Arctic.     

The potential of metal hydrides paired with compressed hydrogen as thermal energy storage for concentrating solar power plants

Concentrating solar power (CSP) plants require thermal energy storage (TES) systems to produce electricity during the night and periods of cloud cover. The high energy density of high-temperature metal hydrides (HTMHs) compared to state-of-the-art two-tank molten salt systems has recently promoted their investigation as TES systems. A common challenge associated with high-temperature metal hydride thermal energy storage systems (HTMH TES systems) is storing the hydrogen gas until it is required by the HTMH to generate heat. Low-temperature metal hydrides can be used to store the hydrogen but can comprise a significant proportion of the overall system cost and they also require thermal management, which increases the engineering complexity. In this work, the potential of using a hydrogen compressor and large-scale underground hydrogen gas storage using either salt caverns or lined rock caverns has been assessed for a number of magnesium- and sodium-based hydrides: MgH₂, Mg₂FeH₆, NaMgH₃, NaMgH₂F and NaH. Previous work has assumed that the sensible heat of the hydrogen released from the HTMH would be stored in a small, inexpensive regenerative material system. However, we show that storing the sensible heat of the hydrogen released would add between US$3.6 and US$7.5/kWh_th to the total system cost for HTMHs operating at 565 °C. If the sensible heat of released hydrogen is instead exploited to perform work then there is a flow-on cost reduction for each component of the system. The HTMHs combined with underground hydrogen storage all have specific installed costs that range between US$13.7 and US$26.7/kWh_th which is less than that for current state-of-the-art molten salt heat storage. Systems based on the HTMHs Mg₂FeH₆ or NaH have the most near term and long term potential to meet SunShot cost targets for CSP thermal energy storage. Increasing the operating temperature and hydrogen equilibrium pressure of the HTMH is the most effective means to reduce costs further.     

Complex quaternary hydrides Mg2(Fe,Co)Hy for hydrogen storage

Complex ternary hydrides based in Mg and transition metals are very attractive materials for hydrogen and energy storage due to their large volumetric capacity, up to 150 kgH₂/m³ in Mg₂FeH₆ and their high dissociation enthalpies. These compounds may be produced at room temperature by mechanical milling of the constituents in H₂ atmosphere. This technique has also served to explore the synthesis of quaternary hydrides Mg₂T_1−zT’_zH_y, combining two transition metals to optimize the properties of the resulting hydride. In the present work we analyze the mechanical synthesis of the compounds Mg₂Fe_1−zCo_zH_y (z = 0, ¼, ½, ¾, 1) by mechanical alloying at room temperature Mg-Fe-Co powder mixtures in adequate proportion, at 0.3 MPa H₂. We follow the mechanosynthesis process trough the analysis of the hydrogen absorption kinetic curves. Samples obtained after a steady state was reached were characterized by X ray diffraction and Mössbauer spectroscopy. The different stages in the mechanosynthesis of these complex hydrides are discussed in terms of the composition and initial state of the powder mixture.     

High-capacity hydrogen release through hydrolysis of NaB3H8

NaB₃H₈ has advantages over NaBH₄ and NH₃BH₃, two most widely studied chemical hydrides for hydrogen storage via hydrolysis. NaB₃H₈ has an extraordinary high solubility in water and thus possesses a high theoretical capacity of 10.5 wt% H via hydrolysis, in contrast to 7.5 wt% for NaBH₄ and 5.1 wt% for NH₃BH₃. NaB₃H₈ is reasonably stable in water which makes it unnecessary to add corrosive NaOH as a stabilizer as the case for NaBH₄. Furthermore, hydrolysis of NaB₃H₈ can be catalyzed by a Co-based catalyst with fast kinetics that is comparable to Ru-based catalysts. Therefore, cost-effective hydrolysis of NaB₃H₈ is possible for practical applications. A high capacity of 7.4 wt% H was achieved when water was included in the materials weight.