An ab initio study of dissociative adsorption of H2 on FeTi surfaces

Dissociative adsorption of H₂ on clean FeTi (001), (110) and (111) surfaces is investigated via ab initio pseudopotential-plane wave method. Adsorption energies of H atom and H₂ molecule on Fe and Ti terminated (001) and (111) and FeTi (110) surfaces are calculated on high symmetry adsorption sites. It is shown that, top site is the most stable site for horizontal H₂ molecule adsorption on (001) and (111) surfaces for both terminations. The most favorable site for H atom adsorption on these surfaces however, is the bridge site. In (110) surface, the 3-fold hollow site which is composed of a long Ti–Ti bridge and an Fe atom, (Ti–Ti)_L–Fe, and again a 3-fold hollow site this time composed of a short Ti–Ti bridge and an Fe atom, (Ti–Ti)_S–Fe, are the most stable sites for H₂ and H adsorption, respectively. With the analysis of the above favorable adsorption sites, probable dissociation paths for H₂ molecule over these surfaces are proposed. Activation energies of these dissociations are also determined with the use of the dynamics of the H₂ relaxation and climbing image nudged elastic band method. It is found that H₂ dissociation on (110) and Fe terminated (111) surfaces has no activation energy barrier. On other surfaces however, activation energies are calculated to be 0.178 and 0.190 eV per H₂ molecule for Fe and Ti terminated (001) surfaces respectively, and 1.164 eV for Ti terminated (111) surface.     

Ab initio study on destabilizing mechanism of magnesium hydride by Ti and Fe co-doping

A first-principle calculation based on density functional theory (DFT) was performed to study the destabilizing mechanism of Ti and Fe co-doped MgH₂. The calculated heats of formation show that Ti and Fe co-doped MgH₂ system is thermo-dynamically favorable for practical hydrogen storage. The doping of Fe combined with Ti into the MgH₂ rutile type structure is more energetically favorable relative to Fe single-doping into the same structure. We calculated the electronic structure, bond lengths and Bader atomic charges of the co-doped system and compared with those of the pure MgH₂. Based on phonon calculation, we also estimated the thermo-dynamical properties such as entropy and specific heat capacity as well as lattice vibrations. The obtained results indicate that Ti and Fe co-doping is an effective method in order to destabilize magnesium hydride.     

Hydrogen adsorption on Li metal in boron-substituted graphene: An ab initio approach

The characteristics of hydrogen adsorption on Li metal atoms dispersed on graphene with boron substitution is investigated including Li clustering, hydrogen bonding characteristics, and the open metal states of Li adatom using density functional theory calculations. It is found that Li atoms are well dispersed on boron-substituted graphene and can form the (2 × 2) pattern because clustering of Li atoms is hindered by the repulsive Coulomb interaction between Li atoms. One Li adatom dispersed on the double side of graphene can absorb up to 8 hydrogen molecules corresponding to a 13.2% hydrogen storage capacity. In addition, the adsorption behaviors of non-hydrogen atoms such as C and B are calculated to determine whether Li atoms can remain as the open metal state in boron-substituted graphene.     

Hydrogen capability of bimetallic boron cycles: A DFT and ab initio MD study

Bimetallic boron cycle, B₆C₂TM₂ (TM = scandium, titanium), was recently predicted to have high stability and aromaticity. The hydrogen capabilities of these clusters were studied in the present work. Our computational results indicate that the gravimetric hydrogen uptake capacity of B₆C₂Sc₂ and B₆C₂Ti₂ and clusters are 11.7% and 11.4%, respectively. The adsorption energies of H₂ molecules on B₆C₂Sc₂ and B₆C₂Ti₂ clusters are predicted with different calculational schemes to meet the criteria of reversible hydrogen storage. The interaction of H₂ with B₆C₂Ti₂ cluster is a little stronger than that with B₆C₂Sc₂. Ab initio molecular dynamics simulations indicate that H₂ molecules can be efficiently released from the metal sites of B₆C₂TM₂ clusters at room temperature. The bulk-like B₆C₂Sc₂ and B₆C₂Ti₂ tetramer can also efficiently adsorb H₂ molecules.     

Adjustment of the decomposition path for Na2LiAlH6 by TiF3 addition

The decomposition of Na₂LiAlH₆ is studied by in-situ synchrotron diffraction. By addition of TiF₃ and dehydrogenation-rehydrogenation cycling of the samples new decomposition paths are found. Na₃AlH₆ is formed on decomposition in the presence of TiF₃. The additive brings the system closer to equilibrium, and decomposition through Na₃AlH₆ is demonstrated for the first time. The results are in agreement with previously published computational data. For a cycled sample with 10 mol% TiF₃ Na₂LiAlH₆ decomposes fully into Na₃AlH₆ before further decomposition to NaH and Al. This shows clear changes in the kinetics of the system, and may open possibilities of tailoring the decomposition path by the use of additives.     

An investigation on the thermodynamics and kinetics of magnesium hydride decomposition based on isotope effects

This work investigates the thermodynamics and kinetics of magnesium hydride decomposition by analyzing isotope effects in hydride and deuteride samples. Complete pressure composition desorption isotherm measurements of MgD₂ are reported for the first time. Deuterium desorption enthalpy and entropy obtained from the van’t Hoff plot of the middle plateau fugacities are 73.8 ± 0.4 kJ/mol and 135.5 ± 0.6 J/mol K, respectively, which are in good accordance with the values obtained more than fifty years ago from plateau pressure measurements. This result reveals that the enthalpy of desorption of MgD₂ is slightly lower than that of MgH₂, whereas the entropy change is higher for the deuteride than for the hydride. Although the differences in the enthalpy and entropy of both isotopes are weak, the synergy of both effects is capable of explaining the higher equilibrium pressures for the deuteride than for the hydride.On the other hand, kinetics of magnesium hydride decomposition has been investigated by simultaneous H and D desorption experiments from mixed hydride-deuteride samples. The obtained results reveal that that decomposition is controlled by the nucleation and growth of the Mg phase. Because this reaction step is not affected by the isotopic replacement of H for D no isotope effect is observed in the kinetics of magnesium hydride decomposition. On the contrary, a marked isotope effect is observed in the kinetics of H₂(D₂) absorption by magnesium. In this case, the lighter isotope shows faster kinetics than the heavier one, what has been related to the fact that absorption is rate limited by H(D) diffusion through the hydride(deuteride) phase.     

The hydrogen storage properties of Mg-intermetallic-hydrides by ab initio calculations and kinetic Monte Carlo simulations

First-principle calculations and kinetic Monte-Carlo simulations were performed to study the hydrogen storage properties of the intermetallic hydrides MgNiH₃, MgCoH₃ and thier mixture namely MgCo_0.5Ni_0.5H₃.Based on the heat of formation, desoprtion temperature, activation energies computed from DFT calculations and KMC simulations, we show that the MgNiH₃ involves a fast kinetic while it is thermodynamically unstable (−9.96 kJ/mol.H₂; 76.61 K) whereas MgCoH₃ has a high thermodynamic stability (−73.32 kJ/mol.H₂; 560.97 K) which prevents their application for mobile hydrogen storage.On the other hand, the electronic structures show that the Ni weakens the strong CoH bonding of the mixture MgCo_0.5Ni_0.5H₃, which enhances significantly its stability and its desorption temperature (−45.92 kJ/mol.H₂ and 351.33 K) without reducing its high volumetric capacity 133.73 g.H₂/l. Kinetic Monte-Carlo simulations show that MgCo_0.5Ni_0.5H₃ exhibits a fast charging time (only 4.6 min at 400 K and 10 bar).Thermodynamic properties including entropy S, Gibbs free energy G and thermal expansion coefficient are predicted within the quasi-harmonic approximation. It is verified that crystal structure of MgCo_0.5Ni_0.5H₃ is stable.     

Interaction of zirconia with magnesium hydride and its influence on the hydrogen storage behavior of magnesium hydride

This study demonstrates how zirconia additive transforms to zirconium hydride and substantially lowers the dehydrogenation temperature of magnesium hydride. We prepared MgH₂+xZrO₂ (x = 0.125 and 0.5) powder samples reacted for 15 min, 1 h, 5 h, 10 h, 15 h, 20 h and 25 h, and monitored the phase changes at each stage of the reaction. Differential scanning calorimetry (DSC) study provides the first crucial evidence regarding the chemical transformation of zirconia. Subsequently, detailed additional sample testing by X-ray diffraction (XRD), energy dispersive x-ray spectroscopy and confocal Raman microscopy provide strong supports that low temperature dehydrogenation of magnesium hydride is a result of formation of an active in situ product (zirconium hydride). This observation is validated by the negative Gibbs free energy values obtained for the formation of zirconium hydride over a broad working temperature range of 0–600 °C. Scanning electron microscopy (SEM) results prove the high dispersion of tiny nanoparticles all across the surface after the chemical interaction between MgH₂ and ZrO₂ and atomic force microscopy (AFM) study further proves that objects with grain sizes of ～10 nm are abundant throughout the scanned surfaces. These observations reiterate that better metal oxide additives interact with MgH₂ and results to the evolution of highly active insitu nanocatalysts.     

Experimental study of hydrogen storage with reaction heat recovery using metal hydride in a totalized hydrogen energy utilization system

Experimental results for hydrogen storage tanks with metal hydrides used for load leveling of electricity in commercial buildings are described. Variability in electricity demand due to air conditioning of commercial buildings necessitates installation of on-site energy storage. Here, we propose a totalized hydrogen energy utilization system (THEUS) as an on-site energy storage system, present feasibility test results for this system with a metal hydride tank, and discuss the energy efficiency of the system. This system uses a water electrolyzer to store electricity energy via hydrogen at night and uses fuel cells to generate power during the day. The system also utilizes the cold heat of reaction heat during the hydrogen desorption process for air conditioning. The storage tank has a shell-like structure and tube heat exchangers and contains 50 kg of metal hydride. Experimental conditions were specifically designed to regulate the pressure and temperature range. Absorption and desorption of 5,400 NL of hydrogen was successfully attained when the absorption rate was 10 NL/min and desorption rate was 6.9 NL/min. A 24-h cycle experiment emulating hydrogen generation at night and power generation during the day revealed that the system achieved a ratio of recovered thermal energy to the entire reaction heat of the hydrogen storage system of 43.2% without heat loss.     

Thermodynamical properties of La–Ni–T (T = Mg, Bi and Sb) hydrogen storage systems

The hydrogen absorption properties of LaNi_4.8T_0.2 (T = Mg, Bi and Sb) alloys are reported. The effects of the substitution of Ni in the LaNi₅ compound with Mg, Bi and Sb are investigated. The ability of alloys to absorb hydrogen is characterized by the pressure–composition (p–c) isotherms. The p–c isotherms allow the determining thermodynamic parameters enthalpy (ΔH^des) and entropy (ΔS^des) of the dehydrogenation processes. The calculated ΔH^des and ΔS^des data helps to explain the decrease of hydrogen equilibrium pressure in alloys doped with Al, Mg and Bi and its increase in the Sb-doped LaNi₅ compound. Generally, partial substitution of Ni in LaNi₅ compound with Mg, Bi and Sb cause insignificant changes of hydrogen storage capacity compared to the hydrogen content in the initial LaNi₅H₆ hydride phase. However, it is worth to stress that, in the case of LaNi_4.8Bi_0.2, a small increase of H/f.u. up to 6.8 is observed. The obtained results in these investigations indicate that the LaNi_4.8T_0.2 (T = Al, Mg and Bi) alloys can be very attractive materials dedicated for negative electrodes in Ni/MH batteries.     

Synergetic effect of Ni and Nb2O5 on dehydrogenation properties of nanostructured MgH2 synthesized by high-energy mechanical alloying

Nanostructured MgH₂-Ni/Nb₂O₅ nanocomposite was synthesized by high-energy mechanical alloying. The effect of MgH₂ structure, i.e. crystallite size and lattice strain, and the presence of 0.5 mol% Ni and Nb₂O₅ on the hydrogen-desorption kinetics was investigated. It is shown that the dehydrogenation temperature of MgH₂ decreases from 426 °C to 327 °C after 4 h mechanical alloying. Here, the average crystallite size and accumulated lattice strain are 20 nm and 0.9%, respectively. Further improvement in the hydrogen desorption is attained in the presence of Ni and Nb₂O₅, i.e. the dehydrogenation temperature of MgH₂/Ni and MgH₂/Nb₂O₅ is measured to be 230 °C and 220 °C, respectively. Meanwhile, the dehydrogenation starts at 200 °C in MgH₂–Ni/Nb₂O₅ system, revealing synergetic effect of Ni and Nb₂O₅. The mechanism of the catalytic effect is presented.     

Hydrogen absorption and optical properties of Pd/Mg thin films prepared by DC magnetron sputtering

Hydrogen storage in metallic thin films in the form of metal hydride have a great potential to solve the hydrogen storage challenges and also thin films offer an opportunity to grow new samples fast with novel structures. In the present work the ex situ study on structural, optical and hydrogen storage properties of Pd-capped Mg thin films have been investigated. The nano structured Pd-capped Mg thin films have been prepared by DC magnetron sputtering on glass substrate. The as deposited and hydrogenated samples have been characterized by XRD and FESEM. The content of hydrogen in thin films has measured by using Elastic Recoil Detection Analysis (ERDA) technique with 120 MeV₁₀₇ Ag⁺⁹ ions. The temperature dependent hydrogen contents in thin film samples have been estimated and the saturation of hydrogen absorption has been observed at 250 °C among all studied samples. In the optical reflectance spectra, Mg hydride samples have been observed partially transparent in comparison to as deposited Mg film.     

Design of a large-scale metal hydride based hydrogen storage reactor: Simulation and heat transfer optimization

An optimized design for a 210 kg alloy, TiMn alloy based hydrogen storage system for stationary application is presented. A majority of the studies on metal hydride hydrogen systems reported in literature are based on system scale less than 10 kg, leaving questions on the design and performance of large-scale systems unanswered. On the basis of sensitivity to various design and operating parameters such as thermal conductivity, porosity, heat transfer coefficient etc., a comprehensive design methodology is suggested. Following a series of performance analyses, a multi-tubular shell and tube type storage system is selected for the present application which completes the absorption process in 900 s and the desorption process in 2000 s at a system gravimetric capacity of 0.7% which is a vast improvement over similar studies. The study also indicates that after fifty percent reaction completion, heat transfer ceases to be the major controlling factor in the reaction. This could help prevent over-designing systems on the basis of heat transfer, and ensure optimum system weight.     

High-pressure synthesis of novel compounds in an Mg–Ni system

High-pressure works are attractive techniques to obtain new compounds, such as alkali or alkaline earth metal-based systems. The atomic radius of Mg under GPa pressure is considerably smaller compared with transition metals; as such, it may be preferable to synthesize novel intermetallic compounds and hydrides by using high-pressure techniques. In this study, novel compounds were synthesized in an Mg–Ni system by a high-pressure technique using a cubic-anvil-type apparatus.A novel Mg₆Ni intermetallic compound was obtained by exposing a mixture of Mg and Ni to 6 GPa at 900 °C for 2 h. The crystal structure of the compound is a tetragonal F-43m structure with a lattice parameter of a=1.9987(1) nm. This compound decomposed to Mg and Mg₂Ni phases at 278 °C with exothermic reaction.As is well known, MgNi₂ does not form hydrides under conventional hydrogenation conditions, hence we investigated the reactivity of MgNi₂ with highly pressurized hydrogen. It was found that the MgNi₂ was able to form MgNi₂H_3.2 by treatment at 700 °C for 2 h under 5 GPa with a hydrogen source, leading to a hydrogen capacity of 2.23 mass%. This novel hydride was found to be a tetragonal MoSi₂-type structure (I4/mmm) with lattice parameters of a=0.327(3) nm and c=0.878(9) nm. The dehydrogenation of this hydride occurred at 187 °C with endothermic reaction, and caused decomposition into C36-type MgNi₂. This hydride had solubility of Ni content and its thermal stability decreased with increasing Ni content.     

Investigation of ZrFe2-type materials for metal hydride hydrogen compressor systems by substituting Fe with Cr or V

In this study, the effects of partial substitution of Fe, in the ZrFe₂-system alloys, by Cr or V are presented. The two studied alloys, ZrFe_1.8V_0.2 and ZrFe_1.8Cr_0.2, have been synthesized by high frequency induction-levitation melting under inert Ar atmosphere. The induction furnace was equipped with a water-cooled copper crucible that permits the rapid solidification of the alloy after the melting. The crystal structures of the investigated alloys have been studied by the Rietveld analysis of the obtained X-ray diffraction (XRD) patterns. The microstructure has been observed by a scanning electron microscope (SEM) on polished samples of the alloys. Their hydriding properties have been studied with a high pressure Sievert's type apparatus, up to 200 bar. All pressure–composition–temperature (PCT) measurements have been obtained at 20, 60 and 90 °C. Two high temperature activation cycles have been conducted prior to PCT measurements. The results showed almost the same uptake for the alloys after identical activation and lowering of the plateau pressure in both cases.     

Simulation of heat transfer in a metal hydride reactor with aluminium foam

A 1-D model has been developed to evaluate various designs of metal hydride reactors with planar, cylindrical or spherical geometry. It simulates a cycling loop (absorption–desorption) focusing attention on the heat transfer inside the hydride bed, which is considered the rate-limiting factor. We have validated this model with experimental data collected on two reactors, respectively, containing 1 and 25 g of _LaNi5${\mathrm{LaNi}}_5$, the second being equipped with aluminium foam. The simulation program reproduces accurately our experimental results. The impact of the foam cell size has been studied. According to our model, the use of aluminium foam allows the reactor diameter to be increased by 7.5 times, without losing its performance.     

Studies of off-stoichiometric AB2 metal hydride alloy: Part 1. Structural characteristics

In Part 1 of this two-part series of papers, phase abundances, lattice parameters, crystallite sizes, and microstructures of three series of AB₂-based metal hydride alloys were studied. The base alloys with B/A stoichiometry of 2.0 in series 177, 190, and 193 are rich in C14, equal in C14/C15, and rich in C15 phases, respectively. In each series of alloys, the B/A stoichiometry varies from 1.8, 1.9, 2.0, 2.1, to 2.2. The effects of varying B/A stoichiometry to microstructures are the same for these three series of alloys. As the alloy formula changes from AB_1.8, AB_1.9, AB_2.0, AB_2.1, to AB_2.2, the following events occur: C14-to-C15 phase ratio decreases, both C14 and TiNi secondary phase lattice parameters and unit cell volume reduce; the a/c aspect ratio of C14 phase first decreases and then increases; abundances of non-Laves secondary phases decrease; and the Zr/Ti ratio in AB phase decreases. The C14/C15 ratio is closely related to the average electron density with a threshold that first decreases from 7.13 (AB_1.8) to 7.08 (AB_1.9) and to 7.06 (AB_2.0) and then increases to 7.08 (AB_2.1) and 7.09 (AB_2.2) as the stoichiometry increases. The distributions of B-site elements are not uniform with most of the V, Cr, Mn, Co residing in AB₂ phase and Sn in Zr₇Ni₁₀ phase.     

Interaction of H2 with fragments of MOF-5 and its implications for the design and development of new MOFs: A computational study

The interaction energies (IEs) of H₂ and various organic ligands have been computed using coupled-cluster method with singles, doubles, and noniterative triples (CCSD(T)) at the complete basis set (CBS) limit. The density fitting-density functional theory-symmetry adapted perturbation theory (DF-DFT-SAPT) approach has been used to probe the nature of interaction between H₂ and organic linkers. It has been found that dispersive interaction predominantly stabilizes the intermolecular complex formation of H₂ on a variety of organic linkers. Furthermore, H₂ binding affinity of inorganic connectors is improved by partial isomorphic substitution of Zn by different metal ions such as Fe, Co, Ni and Cu. A new modified metal-organic framework (MOF-5 M) has been designed based upon the insight from the organic and inorganic fragments. The present study provides valuable information required for the design of novel MOFs with improved affinity for H₂ adsorption.