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 V,Nb, Ti and graphite additions on the hydrogen desorption temperature of magnesium hydride

In this study the effects of mechanical milling with 5 wt.% of additives (V, Nb, Ti and Graphite) on the hydrogen desorption temperature of the magnesium hydride (MgH₂) were studied. The powder mixtures were mechanically milled for 2 h. X-ray diffraction (XRD), scanning electron microscope (SEM), and optical microscope (OM) techniques were used for the structural and morphological characterization of powders. Differential scanning calorimeter (DSC) was used to investigate the effects of the mechanical milling with additives on the hydrogen desorption temperature of the magnesium hydride powder. DSC results show that the hydrogen desorption temperatures of mechanically milled MgH₂ with additives are depressed about ∼40–50 °C compared with that of as-received MgH₂. The particle size analysis results indicate that decrease of the particle size of powders leads to a decrease of the hydrogen desorption temperature. Moreover, increasing specific surface area can also contribute to a decrease on the hydrogen desorption temperature.     

Catalytic effect of halide additives ball milled with magnesium hydride

The influence of various halide additives milled with magnesium hydride (MgH₂) on its decomposition temperature was studied. The optimum amount of halide additive and milling conditions were evaluated.     

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.     

Characterization of Mg–20 wt% Ni–Y hydrogen storage composite prepared by reactive mechanical alloying

Mg–20 wt% Ni–Y composite was successfully prepared by reactive mechanical alloying (RMA). X-ray diffraction (XRD) measurement showed that both MgH₂ and Mg₂NiH₄ co-exist in the milled composite. The composite exhibits excellent hydrogen sorption kinetics and does not need activation on the first hydrogen storage process. It can absorb 3.92 and 5.59 wt% hydrogen under 3.0 MPa hydrogen pressure at 293 and 473 K in 10 min, respectively, and desorb 4.67wt% hydrogen at 523 K in 30 min under 0.02 MPa hydrogen pressure. The equilibrium desorption pressure of the composite are 0.142, 0.051 and 0.025 MPa at 573, 543 and 523 K, respectively. The differential scanning calorimetry (DSC) measurement showed that dehydrogenation of Mg–20 wt% Ni–Y composite was depressed about 100 K comparing to that of milled pure MgH₂. It is deduced that both the catalysis effect of Mg₂Ni and YH₃ distributed in Mg substrate and the crystal defects formed by RMA are the main reason for improving hydrogen sorption kinetics of the Mg–20 wt% Ni–Y composite.     

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.     

Catalysis derived from flower-like Ni MOF towards the hydrogen storage performance of magnesium hydride

Herein, a novel flower-like Ni MOF with good thermostability is introduced into MgH₂ for the first time, and which demonstrates excellent catalytic activity on improving hydrogen storage performance of MgH₂. The peak dehydrogenation temperature of MgH₂-5 wt.% Ni MOF is 78 °C lower than that of pure MgH₂. Besides, MgH₂-5 wt.% Ni MOF shows faster de/hydrogenation kinetics, releasing 6.4 wt% hydrogen at 300 °C within 600 s and restoring about 5.7 wt% hydrogen at 150 °C after dehydrogenation. The apparent activation energy for de/hydrogenation reactions are calculated to be 107.8 and 42.8 kJ/mol H₂ respectively, which are much lower than that of MgH₂ doped with other MOFs. In addition, the catalytic mechanism of flower-like Ni MOF is investigated in depth, through XRD, XPS and TEM methods. The high catalytic activity of flower-like Ni MOF can be attributed to the combining effect of in-situ generated Mg₂Ni/Mg₂NiH₄, MgO nanoparticles, amorphous C and remaining layered Ni MOF. This research extends the knowledge of elaborating efficient catalysts via MOFs in hydrogen storage materials.     

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.     

New horizon in mechanochemistry—high-temperature,high-pressure mechanical synthesis in a planetary ball mill—with magnesium hydride synthesis as an example

A new route of materials synthesis, namely, high-temperature, high-pressure reactive planetary ball milling (HTPRM), is presented. HTPRM allows for the mechanosynthesis of materials at fully controlled temperatures of up to 450 °C and pressures of up to 100 bar of hydrogen. As an example of this application, a successful synthesis of magnesium hydride is presented. The synthesis was performed at controlled temperatures (room temperature (RT), 100, 150, 200, 250, 300, and 325 °C) while milling in a planetary ball mill under hydrogen pressure ($>$50 bar). Very mild milling conditions (250 rpm) were applied for a total milling time of 2 h, and a milling vial with a relatively small diameter (φ = 53 mm, V = ～0.06 dm³) was used. The effect of different temperatures on the synthesis kinetics and outcome were examined. The particle morphology, phase composition, reaction yield, and particle size were measured and analysed by scanning electron microscopy, X-ray diffraction, differential scanning calorimetry (DSC) techniques. The obtained results showed that increasing the temperature of the process significantly improved the reaction rate, which suggested the great potential of this technique for the mechanochemical synthesis of materials.     

High-value utilization of intermetallic Cu9Al4 as an additive to improve the hydrogen storage performance of magnesium

As a product of in the preparation of Cu–Al clad composites, intermetallic Cu₉Al₄ greatly affects the mechanical properties of the composites due to its high hardness and poor plasticity, which limits its application. Here, Cu₉Al₄ is used as an additive to improve the hydrogen storage performance of Mg. Thereby, the Cu₉Al₄ was introduced into Mg to prepare the Mg‒x wt.% Cu₉Al₄ composites (x = 0, 5, 10, 15, 20 and 25) by high-energy ball milling. The microstructure and phase composition of the composites under different states were analyzed. The hydrogen absorption and desorption kinetics and thermodynamics of the composites at different temperatures are investigated. Compared with pure Mg, the addition of Cu₉Al₄ can significantly improve the dehydrogenation kinetics of Mg. With the increase of Cu₉Al₄ content, the hydrogen desorption rate gradually increased. When the Cu₉Al₄ content was 20 wt.%, the dehydrogenation activation energy calculated according to JMAK kinetic model and Arrhenius equation was the lowest (96.84 kJ mol⁻¹), and it had the best hydrogen desorption kinetics. Especially, the phase transition of the first hydrogen absorption process for the Mg‒20 wt.% Cu₉Al₄ was studied in detail. The results show that the Cu₉Al₄ phase first transforms into (Cu_1.3Al_0.7)Mg during the first hydrogenation, and then Mg reacts with H₂ to generate MgH₂. In the subsequent dehydrogenation and re-hydrogenation cycles, the (Cu_1.3Al_0.7)Mg is stable and does not change.     

MgH2-based nanocomposites prepared by short-time high energy ball milling followed by cold rolling: A new processing route

A new processing route consisting of a short-time high energy ball milling (HEBM) step followed by cold rolling (CR) to produce MgH₂-based nanocomposites was investigated. Samples of pure MgH₂ and MgH₂-mixtures containing 2 mol% of FeF₃ were processed under air atmosphere and their effects on the microstructure and the hydrogen storage properties were studied in detail. X-ray Diffraction (XRD) analysis on all samples revealed crystallite sizes in the nanometer range for the beta-MgH₂ and FeF₃ phases (beta (beta): ∼8–13 nm and FeF₃: ∼16–21 nm). No extra crystallite size reduction was observed for the HEBM + CR samples in comparison with those only cold rolled. Scanning electron microscopy (SEM) evaluation together with elemental composition analysis indicated a finer size distribution of additive particles and also a more intimate level of mixing for the HEBM + CR mixture than for the mixture obtained only by CR. These features were associated with the HEBM step applied before the CR. These characteristics led to a lower hydrogen desorption temperatures and enhanced desorption kinetics behavior for the HEBM + CR samples in comparison with the CR samples.     

Nanostructured hydrogen storage materials prepared by high-energy reactive ball milling of magnesium and ferrovanadium

Hydrogen storage nanocomposites prepared by high energy reactive ball milling of magnesium and vanadium alloys in hydrogen (HRBM) are characterised by exceptionally fast hydrogenation rates and a significantly decreased hydride decomposition temperature. Replacement of vanadium in these materials with vanadium-rich Ferrovanadium (FeV, V80Fe20) is very cost efficient and is suggested as a durable way towards large scale applications of Mg-based hydrogen storage materials. The current work presents the results of the experimental study of Mg–(FeV) hydrogen storage nanocomposites prepared by HRBM of Mg powder and FeV (0–50 mol.%). The additives of FeV were shown to improve hydrogen sorption performance of Mg including facilitation of the hydrogenation during the HRBM and improvements of the dehydrogenation/re-hydrogenation kinetics. The improvements resemble the behaviour of pure vanadium metal, and the Mg–(FeV) nanocomposites exhibited a good stability of the hydrogen sorption performance during hydrogen absorption – desorption cycling at T = 350 °C caused by a stability of the cycling performance of the nanostructured FeV acting as a catalyst. Further improvement of the cycle stability including the increase of the reversible hydrogen storage capacity and acceleration of H₂ absorption kinetics during the cycling was observed for the composites containing carbon additives (activated carbon, graphite or multi-walled carbon nanotubes; 5 wt%), with the best performance achieved for activated carbon.     

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.     

Effects of SiC nanoparticles with and without Ni on the hydrogen storage properties of MgH2

In this work, MgH₂–SiC–Ni was prepared by magneto-mechanical milling in hydrogen atmosphere. Scanning electron microscope mapping images showed a homogeneous dispersion of both Ni and SiC among MgH₂ particles. Based on the differential scanning calorimetry traces, the temperature of desorption is reduced by doping MgH₂ with SiC and Ni. Hydrogen absorption/desorption behaviour of the samples was investigated by Sievert's method at 300 °C, and the results showed that both capacity and kinetics were improved by adding SiC and Ni. The hydrogen desorption kinetic investigation indicated that for pure MgH₂, the rate-determining step is surface controlled and recombination, while for the MgH₂–SiC–Ni sample it is controlled as described by the Johnson–Mehl–Avrami 3D model (JMA 3D).     

The effect of storage time on the thermal behavior of nanocrystalline magnesium hydride with metal halide additives

This work presents results concerning the thermal stability of nanocrystalline magnesium hydride milled with 7 wt% of metal halide additives such as ZrF₄, NbF₅, TaF₅, FeF₂, FeF₃, TiCl₃ and VCl₃ after one year of storage in a glovebox under a continuously purified argon atmosphere. The amounts of oxygen and water in the glovebox were below 0.1 ppm. The gases released from the materials during the thermal decomposition of all samples were analyzed using a quadrupole mass spectrometer. The oxidation of MgH₂ at low oxygen and water vapor pressures leads to an increase in the hydride decomposition temperatures of the samples compared to their initial (as-prepared) counterparts, which are shown in Ref. [1]. The differences in the decomposition temperatures between the powders stored for one year in a glovebox and the initial as-prepared powders were greater than 60 °C for MgH₂ with NbF₅, ZrF_4, TaF₅, TiCl₃ and VCl₃. The release of water from all long-term-stored materials and the emission of hydrogen fluoride (HF) from MgH₂ with metal fluorides were observed during heating. The observed results demonstrate that even a protective argon atmosphere did not prevent the degradation of the nanocrystalline MgH₂ powders with various metal halide additives during their long-term storage in a professional glovebox, which is an important practical concern.     

Room temperature conversion of Mg to MgH2 assisted by low fractions of additives

In recent works, it was noticed that Mg/MgH₂ mixed with additives by high energy ball milling allows temperature reductions of H₂ absorption/desorption without necessarily changing thermodynamic properties. Thus, the objective of this work was to investigate which additives, mixed in low fractions with MgH₂ powder would act as efficient hydrogen absorption/desorption catalysts at low temperatures, mainly at room temperature (RT). MgH₂ mixtures with 2 mol% additives (Fe, Nb₂O₅, TiAl and TiFe) were prepared by high energy reactive ball milling (RM). MgH₂–TiFe mixture showed the best results, both during desorption at 330 °C and absorption at RT. The hydrogen absorption was ≈ 2.67 wt% H₂ in 1 h and ≈ 4.44 wt% H₂ in 16 h (40% and 67% of maximum theoretical capacity, respectively). The MgH₂–TiFe superior performance was attributed to the hydrogen attraction by the created high energy interfaces and strong TiFe catalytic action facilitating the H₂ flow during Mg/MgH₂ reactions.     

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.     

Microstructure and hydrogen storage properties of melt-spun Mg-Cu-Ni-Y alloys

Microstructural and hydrogen storage properties of three nanocrystalline melt-spun Mg-base alloys (Mg₉₀Cu_2.5Ni_2.5Y₅, Mg₈₅Cu₅Ni₅Y₅ and Mg₈₀Cu₅Ni₅Y₁₀) have been investigated in view of their application as reversible hydrogen storage materials. The activation procedure and the hydrogen sorption kinetics of these alloys were studied by thermogravimetry at different temperatures in the range from 100 °C to 380 °C. It has been found that these alloys can reach reversible gravimetric hydrogen storage densities of up to 4.8 wt.%-H₂. Even at a low temperature of 100 °C, the hydrogenation kinetics of the investigated alloys is rather high in the range of 1.5 wt.%-H₂ per hour. In the hydrogenated state, these alloys consist of MgH₂, high temperature Mg₂NiH₄, Mg₂NiH_0.3, YH₂, YH₃ as well as MgCu₂. The presence of MgCu₂ indicates the reaction of Mg₂Cu with hydrogen. After repeated hydrogenation/dehydrogenation the preservation of a nanocrystalline grain structure has been confirmed by scanning electron microscopy, energy-filtered and conventional transmission electron microscopy. Additionally, the distribution of hydrogen in the hydrogenated sample was mapped by means of electron energy loss spectroscopy.     

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.