Enhanced hydrogen desorption/absorption properties of magnesium hydride with CeF3@Gn

In order to improve the hydrogen storage performance of MgH₂, graphene and CeF₃ co-catalyzed MgH₂ (hereafter denoted as MgH₂+CeF₃@Gn) were prepared by wet method ball milling and hydriding, which is a simple and time-saving method. The effect of CeF₃@Gn on the hydrogen storage behavior of MgH₂ was investigated. The experimental results showed that co-addition of CeF₃@Gn greatly decreased the hydrogen desorption/absorption temperature of MgH₂, and remarkably improved the dehydriding/hydriding kinetics of MgH₂. The onset hydrogen desorption temperature of Mg + CeF₃@Gn is 232 °C,which is 86 °C lower than that of as-milled undoped MgH₂, and its hydrogen desorption capacity reaches 6.77 wt%, which is 99% of its theoretical capacity (6.84 wt%). At 300 °C and 200 °C the maximum hydrogen desorption rates are 79.5 and 118 times faster than that of the as-milled undoped MgH₂. Even at low temperature of 150 °C, the dedydrided sample (Mg + CeF₃@Gn) also showed excellent hydrogen absorption kinetics, it can absorb 5.71 wt% hydrogen within 50 s, and its maximum hydrogen absorption rate reached 15.0 wt% H₂/min, which is 1765 times faster than that of the undoped Mg. Moreover, no eminent degradation of hydrogen storage capacity occurred after 15 hydrogen desorption/absorption cycles. Mg + CeF₃@Gn showed excellent hydrogen de/absorption kinetics because of the MgF₂ and CeH_2-3 that are formed in situ, and the synergic catalytic effect of these by-products and unique structure of Gn.     

Hydrogen storage property of sandwiched magnesium hydride nanoparticle thin film

Hydrogen sorption property of magnesium (Mg) in the form of sandwiched Pd/Mg/Pd films is investigated. Pulsed laser deposition method was applied to deposit the samples consisting of films of nanoparticles. The enthalpy of formation of MgH₂ was found to be −68 kJ/mol H₂ for films with nanoparticle size on the order of 50 nm, which is smaller than the value for bulk MgH₂ and may be explained by the concept of excess volume.     

Enhanced hydrogen storage properties and mechanisms of magnesium hydride modified by transition metal dissolved magnesium oxides

Magnesium hydride (MgH₂) is a promising on-board hydrogen storage material due to its high capacity, low cost and abundant Mg resources. Nevertheless, the practical application of MgH₂ is hindered by its poor dehydrogenation ability and cycling stability. Herein, the influences and mechanisms of thin pristine magnesium oxide (MgO) and transition metals (TM) dissolved Mg(TM)O layers (TM = Ti, V, Nb, Fe, Co, Ni) on hydrogen desorption and reversible cycling properties of MgH₂ were investigated using first-principles calculations method. The results demonstrate that either thin pristine MgO or Mg(TM)O layer weakens the MgH bond strength, leading to the decreased structural stability and hydrogen desorption energy of MgH₂. Among them, the Mg(Nb)O layer exhibits the most pronounced destabilization effect on MgH₂. Moreover, the Mg(Nb)O layer presents a long-acting confinement effect on MgH₂ due to the stronger interfacial bonding strength of Mg(Nb)O/MgH₂ and the lower brittleness of Mg(Nb)O itself. Further analyses of electronic structures indicate that these thin oxide layers coating on MgH₂ surface reduce the bonding electron number of MgH₂, which essentially accounts for the weakened MgH bond strength and enhanced hydrogen desorption properties of modified MgH₂ systems. These findings provide a new avenue for enhancing the hydrogen desorption and reversible cycling properties of MgH₂ by designing and adding suitable MgO based oxides with high catalytic activity and low brittleness.     

Effect of Ni/tubular g-C3N4 on hydrogen storage properties of MgH2

Additive doping is one of the effective methods to overcome the shortcomings of MgH₂ on the aspect of relatively high operating temperatures and slow desorption kinetics. In this paper, hollow g-C₃N₄ (TCN) tubes with a diameter of 2 μm are synthesized through the hydrothermal and high-temperature pyrolysis methods, and then nickel is chemically reduced onto TCN to form Ni/TCN composite at 278 K. Ni/TCN is then introduced into the MgH₂/Mg system by means of hydriding combustion and ball milling. The MgH₂–Ni/TCN composite starts to release hydrogen at 535 K, which is 116 K lower than the as-milled MgH₂ (651 K). The MgH₂–Ni/TCN composite absorbs 5.24 wt% H₂ within 3500 s at 423 K, and takes up 3.56 wt% H₂ within 3500 s, even at a temperature as low as 373 K. The apparent activation energy (E_a) of the MgH₂ decreases from 161.1 to 82.6 kJ/mol by the addition of Ni/TCN. Moreover, the MgH₂–Ni/TCN sample shows excellent cycle stability, with a dehydrogenation capacity retention rate of 98.0% after 10 cycles. The carbon material enhances sorption kinetics by dispersing and stabilizating MgH₂. Otherwise, the phase transformation between Mg₂NiH₄ and Mg₂NiH_0.3 accelerates the re/dehydrogenation reaction of the composite.     

Hydrogen storage behaviors of magnesium hydride catalyzed by transition metal carbides

In this study, some transitional metal carbides (Ti₃C₂, Ni₃C, Mo₂C, Cr₃C₂ and NbC) were prepared to enhance the hydrogen storage behaviors of magnesium-based materials. The carbides with a weight ratio of 5 wt% were introduced into magnesium hydride (MgH₂) by mechanical ball milling, and the microstructure, phase composition and hydrogen storage properties of the composites were studied in detail. The phase compositions of Ni₃C, Mo₂C, Cr₃C₂ and NbC in the ball-milled composites have not changed during hydrogen absorption and desorption cycles. However, Ti₃C₂ decompose into multivalent Ti during hydrogenation process. All of these metal carbides can enhance the hydrogen absorption and desorption kinetics of MgH₂. Among them, Ti₃C₂ shows the best catalytic effect on dehydrogenation kinetic properties of MgH₂, followed by the Ni₃C, NbC, Mo₂C and Cr₃C₂.     

Effect of in-situ formed Mg2Ni/Mg2NiH4 compounds on hydrogen storage performance of MgH2

Magnesium-based hydrogen storage materials (MgH₂) are promising hydrogen carrier due to the high gravimetric hydrogen density; however, the undesirable thermodynamic stability and slow kinetics restrict its utilization. In this work, we assist the de/hydrogenation of MgH₂ via in situ formed additives from the conversion of an MgNi₂ alloy upon de/hydrogenation. The MgH₂–16.7 wt%MgNi₂ composite was synthesized by ball milling of Mg powder and MgNi₂ alloy followed by a hydrogen combustion synthesis method, where most of the Mg converted to MgH₂, and the others reacted with the MgNi₂ generating Mg₂NiH₄, which produced in situ Mg₂Ni during dehydrogenation. Results showed that the Mg₂Ni and Mg₂NiH₄ could induce hydrogen absorption and desorption of the MgH₂, that it absorbed 2.5 wt% H₂ at 473 K, much higher than that of pure Mg, and the dehydrogenation capacity increased by 2.6 wt% at 573 K. Besides, the initial dehydrogenation temperature of the composite under the promotion of Mg₂NiH₄ decreased greatly by 100 K, whereas it is 623 K for MgH₂. Furthermore, benefiting from the catalyst effect of Mg₂NiH₄ during dehydrogenation, the apparent activation energy of the composite reduced to 73.2 kJ mol⁻¹ H₂ from 129.5 kJ mol⁻¹ H₂.     

Iron and niobium based additives in magnesium hydride: Microstructure and hydrogen storage properties

In this study, powder mixtures of MgH₂ + 2 mol.% X, with X = Nb, Nb₂O₅, NbF₅, Fe, Fe₂O₃, FeF₃, were processed by mechanical milling at liquid nitrogen temperature (cryomilling). The effect of additives on crystalline structure, thermal properties and hydrogen storage properties of the mixtures were investigated. Morphological investigations indicated a heterogeneous particle size distribution of the powder mixtures and a fine dispersion of additive particles (FeF₃) in the MgH₂ matrix. High resolution synchrotron radiation X-ray diffraction (SR-XRD) data followed by Rietveld refinements showed a significant reduction on crystallite size for the samples containing fluorides (11 nm) in comparison with the pure MgH₂ sample (29 nm). This was related to the mechanical behavior of fluorides during milling with MgH₂, which act as a lubricant, dispersing and/or cracking agent during milling, and thus helping to further reduce MgH₂ particle size. DSC analysis revealed that fluorides (NbF₅, FeF₃) are much more effective than oxides (Nb₂O₅, Fe₂O₃) and the transition metals (Nb and Fe), respectively, in reduction the desorption temperature. Furthermore, Nb₂O₅ is more efficient than Fe₂O₃. Finally, the best results for desorption kinetics were observed for the fluorides: NbF₅ and FeF₃ (equivalent effect and consistent to the DSC analysis) followed by the oxides: Nb₂O₅, Fe₂O₃ and Nb. The addition of Fe was not efficient in comparison with the pure cryomilled sample.     

Scaling up effects of Mg hydride in a temperature and pressure-controlled hydrogen storage device

A research program addressed to evaluate the magnesium hydride storage scaling up effects is being developed by CESI RICERCA, Milano, and the Hydrogen Group of Padova University. A storage device containing 500 g of magnesium hydride powder (manufactured by Venezia Tecnologie S.p.A. using high-energy ball milling) has been designed and tested in different operating conditions. A number of absorption and desorption cycles at different temperatures and pressures has been carried out in order to see if the results are comparable with laboratory data obtained on small amounts (fractions of grams) of powder samples. A sensible performance degradation that reduced the overall storage capacity of about 50% has been noticed after 20 cycles, presumably due to local powder heating, fragmentation and subsequent compaction. Further tests on a smaller tank equipped also with a porous baffle gave useful indications for the design of an improved large hydrogen reservoir.     

Excellent catalytic effect of LaNi5 on hydrogen storage properties for aluminium hydride at mild temperature

The catalytic effect of rare-earth hydrogen storage alloy is investigated for dehydrogenation of alane, which shows a significantly reduced onset dehydrogenation temperature (86 °C) with a high-purity hydrogen storage capacity of 8.6 wt% and an improved dehydrogenation kinetics property (6.3 wt% of dehydrogenation at 100 °C within 60 min). The related mechanism is that the catalytic sites on the surface of the hydrogen storage alloy and the hydrogen storage sites of the entire bulk phase of the hydrogen storage reduce the dehydrogenation temperature of AlH₃ and improve the dehydrogenation kinetic performance of AlH₃. This facile and effective method significantly improves the dehydrogenation of AlH₃ and provides a promising strategy for metal hydride modification.     

Ultrasonic irradiation on hydrolysis of magnesium hydride to enhance hydrogen generation

This paper describes the ultrasonic irradiation on the hydrolysis of magnesium hydride to enhance hydrogen generation; the effects of the ultrasonic frequency and the sample size on the hydrogen generation were mainly examined. In the experiments, three MgH₂ particle and nanofiber samples were soaked in distilled water and ultrasonically irradiated at frequencies of 28, 45, and 100 kHz. Then, the amount of hydrogen generated was measured. We found that the low frequency of ultrasonic irradiation and the relatively small sample size accelerated the hydrolysis reaction MgH₂ + 2H₂O = Mg(OH)₂ + 2H₂ + 277 kJ. In particular, the MgH₂ nanofibers exhibited the maximum hydrogen storage capacity of 14.4 mass% at room temperature at a frequency of 28 kHz (ultrasound irradiation). The results also experimentally validated that a combination of ultrasonic irradiation and MgH₂ hydrolysis is considerably effective for efficiently generating hydrogen without heating and adding any agent.     

Enhancing hydrogen storage performance of MgH2 through the addition of BaMnO3 synthesized via solid-state method

Currently, magnesium hydride (MgH₂) as a solid-state hydrogen storage material has become the subject of major research owing to its good reversibility, large hydrogen storage capacity (7.6 wt%) and affordability. However, MgH₂ has a high decomposition temperature (>400 °C) and slow desorption and absorption kinetics. In this work, BaMnO₃ was synthesized using the solid-state method and was used as an additive to overcome the drawbacks of MgH₂. Interestingly, after adding 10 wt% of BaMnO₃, the initial desorption temperature of MgH₂ decreased to 282 °C, which was 138 °C lower than that of pure MgH₂ and 61 °C lower than that of milled MgH₂. For absorption kinetics, at 250 °C in 2 min, 10 wt% of BaMnO₃-doped MgH₂ absorbed 5.22 wt% of H₂ compared to milled MgH₂ (3.48 wt%). Conversely, the desorption kinetics also demonstrated that 10 wt% of BaMnO₃-doped MgH₂ samples desorbed 5.36 wt% of H₂ at 300 °C within 1 h whereas milled MgH₂ only released less than 0.32 wt% of H₂. The activation energy was lowered by 45 kJ/mol compared to that of MgH₂ after the addition of 10 wt% of BaMnO₃. Further analyzed by using XRD revealed that the formation of Mg_0·9Mn_0·1O, Mn₃O₄ and Ba or Ba-containing enhanced the performance of MgH₂.     

Scaled-up production of a promising Mg-based hydride for hydrogen storage

The feasibility of scaling up the production of a Mg-based hydride as material for solid state hydrogen storage is demonstrated in the present work. Magnesium hydride, added with a Zr–Ni alloy as catalyst, was treated in an attritor-type ball mill, suitable to process a quantity of 0.5–1 kg of material. SEM–EDS examination showed that after milling the catalyst was well distributed among the magnesium hydride crystallites. Thermodynamic and kinetic properties determined by a Sievert's type apparatus showed that the semi-industrial product kept the main properties of the material prepared at the laboratory scale. The maximum amount of stored hydrogen reached values between 5.3 and 5.6 wt% and the hydriding and dehydriding times were of the order of few minutes at about 300 °C.     

Electrochemical performance of metal-organic framework MOF(Ni) doped graphene

In the paper, MOF(Ni) and MOF(Ni) complex with graphene MOF(Ni)-GR(w%) are synthesized by solvothermal method. The structure, morphology and elemental composition of samples are analyzed by physical characterization such as SEM, XRD, EDS and XPS. The results show that MOF(Ni) and MOF(Ni)-GR(w%) with high crystallinity and less impurities are successfully synthesized. Different samples are loaded on the electrodes and their electrochemical performances are tested by electrochemical workstation. The results show that doping appropriate graphene in MOF(Ni) can effectively improve the electrochemical catalytic activity of the composites. When the content of graphene is 4%, MOF(Ni)-GR(4%) is of the highest electrochemical catalytic activity, its overpotential is 268 mV, the Tafel slope is 108 mV·dec^?1, and it has better electrochemical stability compared with that of Pt/C electrode. The ECSA and EIS of MOF(Ni)-GR(4%) are superior to that of MOF(Ni) in exploring the reasons for enhancing catalytic hydrogen evolution. The reason is that the addition of graphene enhances the conductivity of the composites and reduces the resistance of catalyst transportation. Moreover, the doping of graphene improves the specific surface area of the composites, and provides enough active sites for hydrogen evolution reaction (HER).     

Synthetical catalysis of nickel and graphene on enhanced hydrogen storage properties of magnesium

Reduced graphene-oxide-supported nickel (Ni@rGO) nanocomposite catalysts were synthesized, and incorporated into magnesium (Mg) hydrogen storage materials with the aim of improving the hydrogen storage properties of these materials. The experimental results revealed that the catalytic effect of the Ni@rGO nanocomposite on Mg was more effective than that of single nickel (Ni) nanoparticles or graphene. When heated at 100 °C, the Mg–Ni and Mg–Ni@rGO composites absorbed 4.70 wt% and 5.48 wt% of H₂, respectively, whereas the pure Mg and Mg@rGO composite absorbed almost no hydrogen. The addition of the Ni@rGO composite as a catalyst yielded significant improvement in the hydrogen storage property of the Mg hydrogen storage materials. The apparent activation energy of the pure Mg sample (i.e., 163.9 kJ mol⁻¹) decreased to 139.7 kJ mol⁻¹ and 123.4 kJ mol⁻¹, respectively, when the sample was modified with single rGO or Ni nanoparticles. Under the catalytic action of the Ni@rGO nanocomposites, the value decreased further to 103.5 kJ mol⁻¹. The excellent hydrogen storage properties of the Mg–Ni@rGO composite were attributed to the catalytic effects of the highly surface-active Ni nanoparticles and the unique structure of the composite nanosheets.     

Enhancement of hydrogen sorption in magnesium hydride using expanded natural graphite

Magnesium hydrogenation reaction being exothermic and limited by heat removal, the thermal conductivity of ball-milled magnesium hydride (BM MgH₂) powders has to be improved. The compression of BM MgH₂ associated to Expanded Natural Graphite (ENG) to form compacted disks has been investigated. Using BM MgH₂ without ENG, its compression reduces the porosity and increases its volumetric hydrogen storage capacity. Incorporating ENG before compression drastically improves the thermal conductivity in the direction normal to compression axis. Moreover, the thermal conductivity increases linearly with ENG content, and can be adjusted to fulfill the loading time requirements. The thermodynamic properties and intrinsic sorption kinetics remain unchanged. However, both compression and ENG incorporation reduce the hydrogen permeability, especially in the direction parallel to the compression axis, which imposes a limit to the disk thickness. A small-size instrumented tank has been loaded with either pure BM MgH₂ powder or with disks having different ENG contents. The results obtained for both cases are compared.     

Generation of hydrogen from magnesium hydride oxidation in water in presence of halides

We have performed a systematic analysis of magnesium hydride oxidation by water in presence of several transition, non-transition metals and ammonia halides. It was observed that the most effective catalysts of the process are ammonia chloride and bromide, magnesium chloride and a few mixed salts: magnesium chloride mixed with aqueous solutions of ammonium, copper or potassium chlorides. It was observed that solution amount impacts the reaction rate, but not the overall hydrogen yield. The fastest MgH₂ oxidation (120 min to completion; ~100% hydrogen yield) was observed when it was activated by the mixture of MgCl₂ and NH₄Cl).     

Effect of hydride nucleation rate on the hydrogen capacity of Mg

The hydrogen capacity of magnesium is usually below its theoretical value of 7.6 wt.% hydrogen. Based on the model that hydrogen capacity is reached when the hydride colonies/grains nucleated on the surface of Mg powders impinge on each other, we designed two hydrogenation methods in order to shed light on the effect of hydride nucleation rate on the hydrogen capacity of a commercial pure magnesium powder. We have demonstrated that increasing the nucleation rate significantly reduces the hydrogen capacity. It is elucidated that at a high nucleation rate, the complete coverage of the powder surface is reached at a smaller volume fraction of magnesium hydride. The results of the analysis of the hydrogenation curves using the Johnson–Mehl–Avrami (JMA) equation revealed three stages of hydrogenation. The modification of the nucleation rate was found to affect stages 1 and 2, where the nucleation and growth of the hydride take place, most significantly.     

Desorption kinetics of lithium amide/magnesium hydride systems at constant pressure thermodynamic driving forces

Lithium amide and magnesium hydride are lightweight materials with high hydrogen-holding capacities and thus they are of interest for hydrogen storage. In the present work mixtures with initial molar compositions of (LiNH₂ + MgH₂) and (2LiNH₂ + MgH₂) were ball milled with and without the presence of 3.3 mol% potassium hydride dopant. Temperature programmed desorption, TPD, analyses of the mixtures showed that the potassium hydride doped samples had lower onset temperatures than their corresponding pristine samples. The dehydrogenation kinetics of the doped and pristine mixtures was compared at 210 °C. In each case a constant pressure thermodynamic driving force was applied in which the ratio of the plateau pressure to the applied hydrogen pressure was set at 10. Under equivalent conditions, the (LiNH₂ + MgH₂) mixture desorbed hydrogen about 4 times faster than the (2LiNH₂ + MgH₂) mixture. The addition of potassium hydride dopant was found to have a 25-fold increase on the desorption rates of the (2LiNH₂ + MgH₂) mixture, however it had almost no effect on the desorption rates of the (LiNH₂ + MgH₂) mixture. Activation energies were determined by the Kissinger method. Results showed the potassium hydride doped mixtures to have lower activation energies than the pristine mixtures.     

Comparisons between MgH2- and LiH-containing systems for hydrogen storage applications

The present study compares the dehydrogenation kinetics of (2_LiNH2+_MgH2)$(2{\mathrm{LiNH}}_2+{\mathrm{MgH}}_2)$ and (_LiNH2+LiH)$({\mathrm{LiNH}}_2+\mathrm{LiH})$ systems and their vulnerabilities to the NH₃ emission problem. The (2_LiNH2+_MgH2)$(2{\mathrm{LiNH}}_2+{\mathrm{MgH}}_2)$ and (_LiNH2+LiH)$({\mathrm{LiNH}}_2+\mathrm{LiH})$ mixtures with different degrees of mechanical activation are investigated in order to evaluate the effect of mechanical activation on the dehydrogenation kinetics and NH₃ emission rate. The activation energy for dehydrogenation, the phase changes at different stages of dehydrogenation, and the level of NH₃ emission during the dehydrogenation process are studied. It is found that the (2_LiNH2+_MgH2)$(2{\mathrm{LiNH}}_2+{\mathrm{MgH}}_2)$ mixture has a higher rate for hydrogen release, slower rate for approaching a certain percentage of its equilibrium pressure, higher activation energy, and more NH₃ emission than the (_LiNH2+LiH)$({\mathrm{LiNH}}_2+\mathrm{LiH})$ mixture. On the basis of the phenomena observed, the reaction mechanism for the dehydrogenation of the (2_LiNH2+_MgH2)$(2{\mathrm{LiNH}}_2+{\mathrm{MgH}}_2)$ system has been proposed for the first time. Approaches for further improving the hydrogen storage behavior of the (2_LiNH2+_MgH2)$(2{\mathrm{LiNH}}_2+{\mathrm{MgH}}_2)$ system are discussed in light of the newly proposed reaction mechanism.     

Thermal modeling and performance analysis of industrial-scale metal hydride based hydrogen storage container

In this paper, a performance analysis of a metal hydride based hydrogen storage container with embedded cooling tubes during absorption of hydrogen is presented. A 2-D mathematical model in cylindrical coordinates is developed using the commercial software COMSOL Multiphysics 4.2. Numerical results obtained are found in good agreement with experimental data available in the literature. Different container geometries, depending upon the number and arrangement of cooling tubes inside the hydride bed, are considered to obtain an optimum geometry. For this optimum geometry, the effects of various operating parameters viz. supply pressure, cooling fluid temperature and overall heat transfer coefficient on the hydriding characteristics of MmNi_4.6Al_0.4 are presented. Industrial-scale hydrogen storage container with the capacity of about 150 kg of alloy mass is also modeled. In summary, this paper demonstrates the modeling and the selection of optimum geometry of a metal hydride based hydrogen storage container (MHHSC) based on minimum absorption time and easy manufacturing aspects.