High-pressure synthesis of Mg2FeH6 complex hydride

We have designed a new synthesis method for the ternary metal hydride Mg₂FeH₆ based on the direct reaction of simple hydrides under high-pressure conditions. Well-crystallized samples were prepared in a piston-cylinder hydrostatic press at 2 GPa and temperatures around 750 °C from mixtures of MgH₂ and Fe enclosed in gold or platinum capsules. Seven different samples have been prepared under different conditions. X-ray powder diffraction analysis was used to identify and assess the purity of the samples, through Rietveld analyses of the crystal structure (K₂PtCl₆-type). Mg₂FeH₆ shows a cubic symmetry with space group Fm-3m. SEM images show an average particle size of 1–2 μm for Mg₂FeH₆; the microcrystals present well-grown faces and display a high homogeneity of shapes and sizes. Thermogravimetric analysis has been carried out to determine not only the hydrogen desorption temperature but also the hydrogen contents.     

Hydrogen generation by CaH2-induced hydrolysis of Mg17Al12 hydride

The Mg₁₇Al₁₂ intermetallic compound is brittle and easily pulverized and hydrogenated, which holds the promise as a hydrogen source because the theoretical hydrogen generation capacity by hydrolysis of Mg₁₇Al₁₂ hydride (MHA) is as high as 13.6 wt.%. However, it was found that the hydrolysis reaction of MHA without any additives would be rapidly interrupted because of the formation of a passive layer on the surface of the particles. The influence of CaH₂ on the hydrogen generation performances of the MHA + CaH₂ mixtures by hydrolysis was investigated in this paper. The result showed that the addition of CaH₂ by ball-milling is effective to improve the hydrolysis reactivity of the mixtures. The best was obtained by MHA+10wt.% CaH₂ mixture ball-milled for 1 h, which produces 1389 ml H₂/g at 70 °C after 1 h of hydrolysis in pure water, namely the hydrogen generation yield reaches 94.8%. In this paper, the reasons of the improvement and the reaction mechanism have also been discussed respectively.     

Reactivity of complex hydrides Mg2FeH6, Mg2CoH5 and Mg2NiH4 with lithium ion: Far from equilibrium electrochemically driven conversion reactions

The electrochemical reaction of lithium ion with Mg₂FeH₆, Mg₂CoH₅ and Mg₂NiH₄ complex hydrides prepared by reactive grinding is studied here. Plateaus at an average potential of 0.25 V, 0.24 V and 0.27 V corresponding to discharge capacities of 6.6, 5.5 and 3.6 Li can be achieved respectively for Mg₂FeH₆, Mg₂CoH₅ and Mg₂NiH₄. From in situ X-ray diffraction (XRD) characterizations of complex hydride based electrodes, dehydrogenation leads to a decrease of the intensities of the diffraction peaks suggesting a strong loss of crystallinity since formation of Mg and M (M = Fe, Co, Ni) peaks is not observed. ⁵⁷Fe Mössbauer spectroscopy confirms the formation of nanoscale Fe or an amorphous Mg–Fe alloy during the decomposition of Mg₂FeH_6. Interestingly, lattice parameter variations suggest phase transitions in the Mg₂NiH₄ system involving the formation of low hydrogen content hydride Mg₂NiH, while an increase of lattice parameters of Mg₂CoH₅ hydride could be attributed to the formation of a Mg₂CoH₅Li_x solid solution compound up to x = 1.     

The influence of aluminium on the properties of the Mg2Cu-H2 system

The addition of aluminium to a mixture of Mg-Cu (2:1 atomic ratio) leads by melting to the formation of increasing amounts of Mg(Cu,Al)₂ where aluminium substitutes for copper atoms in the MgCu₂ lattice, raising the lattice parameter. The hydrogen absorbed in this phase is strongly bounded, as proved by desorption isotherms and nuclear magnetic resonance data.     

Effect of Mg3MnNi2 on the electrochemical characteristics of Mg2Ni electrode alloy

Mg₂Ni–x mol% Mg₃MnNi₂ (x = 0, 15, 30, 60, 100), the novel composite alloys employed for hydrogen storage electrode, have been successfully synthesized by a method combining electric resistance melting with isothermal evaporation casting process (IECP). X-ray diffraction (XRD) analysis results show that the composite alloys are composed of Mg₂Ni phases and the new Mg₃MnNi₂ phases. It is found on the electrochemical studies that maximum discharge capacities of the composite alloys increase with the increasing content of the Mg₃MnNi₂ phase. The discharge capacity of the electrode alloy is effectively improved from 17 mAh g⁻¹ of the Mg₂Ni alloy to 166 mAh g⁻¹ of the Mg₃MnNi₂ alloy. Among these alloys, the Mg₃MnNi₂ phase possesses a positive effect on the retardation of cycling capacity degradation rate of the electrode materials. Cyclic voltammetry (CV) results confirm that the increasing content of the Mg₃MnNi₂ phase effectively improves the reaction activity of the electrode alloys. Surface analyses indicate that the Mg₃MnNi₂ phase can enhance the anti-corrosive performance of the particle surface of these composite alloys.     

Catalytic effect of Ni, Mg2Ni and Mg2NiH4 upon hydrogen desorption from MgH2

MgH₂ is a perspective hydrogen storage material whose main advantage is a relatively high hydrogen storage capacity (theoretically, 7.6 wt.% H₂). This compound, however, shows poor hydrogen desorption kinetics. Much effort was devoted in the past to finding possible ways of enhancing hydrogen desorption rate from MgH₂, which would bring this material closer to technical applications. One possible way is catalysis of hydrogen desorption. This paper investigates separate catalytic effects of Ni, Mg₂Ni and Mg₂NiH₄ on the hydrogen desorption characteristics of MgH₂. It was observed that the catalytic efficiency of Mg₂NiH₄ was considerably higher than that of pure Ni and non-hydrated intermetallic Mg₂Ni. The Mg₂NiH₄ phase has two low-temperature modifications below 508 K: un-twinned phase LT1 and micro-twinned phase LT2. LT1 was observed to have significantly higher catalytic efficiency than LT2.     

Prediction of hydrogen desorption performance of Mg2Ni hydride reactors

This work performs the simulation of hydrogen desorption processes with Mg₂Ni hydrogen storage alloy to investigate the canister designs. Reaction rates and equilibrium pressures of Mg₂Ni alloy were calculated by fitting experimental data in literature using least squares regression. The obtained reaction kinetics was used to model the thermalfluid behavior of hydrogen desorption. Since the alloy powders will expand and shrink during the absorption and desorption cycle, the canisters considered are comprised of expansion volume atop the metal bed. In order to enhance the heat transfer performance of the canister, an air pipe is equipped at the canister centre line with/without internal fins. Detailed equations that describe the force convection of the heat exchange pipe and the natural convection at the reactor wall are carefully incorporated in the model. Simulation results show that the bare cylindrical canister can not complete the desorption process in 2.8 h, while the canister equipped with the concentric heat exchanger pipe and fins can complete desorption within 1.7 h.Results also demonstrate that the reaction rates can be further increased by increasing the pipe flow velocity and/or increasing the fin volume.     

Dynamic synthesis of ternary Mg2FeH6

This work presents new results on the dynamic synthesis and decomposition of ternary Mg₂FeH₆. A novel synthesis method was applied for the rapid and effective synthesis of a ternary Mg–Fe hydride. This method consists of two processing routes. The first route involves high-energy ball milling of the initial MgH₂–Fe powder mixture, while the second is composed of a unique pressurizing and heating cycle route to obtain a full phase transformation within half an hour. The structural investigations carried out by X-ray diffraction revealed that almost all of the initial powder mixture transforms into the ternary hydride. Furthermore, the sample, which was synthesized, was also decomposed and reloaded with hydrogen. The formation of Mg₂FeH₆ consists of two steps that involve MgH₂ as an intermediate compound. In contrast, the decomposition of Mg₂FeH₆ consists of only one step and does not follow the inverse route. Some traces of iron were found in the reaction products. TDP results show that a desorption peak occurs at 315 °C, and this is in good agreement with DSC measurements showing only a single endothermic peak around 340 °C. Microstructural examinations revealed that the synthesized Mg₂FeH₆ powder generally exhibits a duplex structure that consists of plate-like particles larger than 1 μm in diameter and spherical particles smaller than 50 nm that show a tendency to agglomerate and form larger particles exhibiting a sponge-like structure. The formation of Mg₂FeH₆ takes place at the phase boundary between Fe seeds and the growing hydride phase. In contrast, the decomposition of the Mg₂FeH₆ phase takes place with the formation of the separate nanosized Mg and Fe phases. The dehydrogenated powder sample shows oval Fe precipitates of 10–100 nm in size that are embedded in the Mg-based matrix.     

Mg2NiH4 synthesis and decomposition reactions

A ternary Mg₂NiH₄ hydride was synthesized using method that relies on a relatively short mechanical milling time (one hour) of a 2:1 MgH₂–Ni powder mixture followed by sintering at a sufficiently high hydrogen pressure (>85 bar) and temperature (>400 °C). The ternary hydride forms in less than 2.5 h (including the milling time) with a yield of ∼90% as a mixture of two polymorphic forms. The mechanisms of formation and decomposition of ternary Mg₂NiH₄ under different hydrogen pressures were studied in detail using an in situ synchrotron radiation powder X-ray diffraction (SR-PXD) and high pressure DSC. The obtained experimental results are supported by morphological and microstructural investigations performed using SEM and high resolution STEM. Additionally, effects occurring during the desorption reaction were studied using DSC coupled with mass spectrometry.     

Mg3Cd: A model alloy for studying the destabilization of magnesium hydride

We prepared an ordered Mg₃Cd alloy by high energy ball milling of elemental powders. The synthesized alloy exhibited good hydrogenation kinetics and reversibly absorbed about 2.8 wt. % of hydrogen. The temperature dependence of hydrogenation kinetics of the alloy measured in the range of temperatures covering the order-disorder phase transformations in the Mg₃Cd and MgCd phases did not exhibit any anomalies and could be fitted with a single Arrhenius line. The measured apparent activation energy (69 ± 2 kJ/mol) hinted that hydrogenation process was controlled by diffusion of Cd in metallic phase. The pressure-composition isotherms exhibited negligible pressure hysteresis and sloping pressure plateau. Based on microstructural evidence obtained with the aid of X-ray diffraction and scanning electron microscopy, we built a thermodynamic model predicting the plateau hydrogen pressure for partially hydrogenated alloy. The predictions of the model were in a good agreement with the experimental data. Finally, we discussed the origins and the growth mechanisms of Cd whiskers observed in the alloys after full hydrogenation cycle.     

Hydrogen storage in Mg51Zn20

The hydrogen absorption capacity of the Mg₅₁Zn₂₀ intermetallic compound was investigated. The equilibrium pressures at 300, 330 and 380°C were found to be 3.6, 8.05 and 31.0 atm., respectively. The highest hydrogen content in Mg₅₁Zn₂₀ corresponds to the nominal composition Mg₅₁Zn₂₀H₉₅ (3.62 wt % hydrogen). Evidence of MgH₂ formation in the hydrided material was found.     

Enhanced electrochemical lithium storage performance of Mg2FeH6 anode with TiO2 coating

Light-weight metal hydrides are potential high-capacity conversion anode materials for lithium-ion batteries, but the poor reaction reversibility and cyclic stability of hydride anodes need to be improved. In this work, the ternary hydride Mg₂FeH₆ was composited with the graphite (G) by ball-milling, and the Mg₂FeH₆-G composite electrode was further coated with amorphous TiO₂ film by magnetron sputtering. The resultant Mg₂FeH₆-G/TiO₂ electrode exhibited a stable charge capacity of 412 mAh g^?1 over 100 cycles, which is much higher than 46 mAh g^?1 at 20th cycle for the pure Mg₂FeH₆ electrode, or 185 mAh g^?1 at 100th cycle for the Mg₂FeH₆-G electrode. There is only little capacity degradation after 20 cycles for the Mg₂FeH₆-G/TiO₂ electrode and the charge capacity retention is 84.7% after 100 cycles. The remarkable improvement in the cyclic stability of Mg₂FeH₆-G/TiO₂ electrode is mainly attributed to the dense TiO₂ coating that maintains the structural integrity of electrode during cycling. The TiO₂ coating also prevents the direct contact of high active LiH/MgH₂ with the liquid electrolyte, and thus ensures the high reversibility of conversion reaction of MgH₂ during cycling.     

Hydrogen storage performance of 5LiBH4 + Mg2FeH6 composite system

The hydrogen storage properties of 5LiBH₄ + Mg₂FeH₆ reactive hydride composites for reversible hydrogen storage were investigated by comparing with the 2LiBH₄ + MgH₂ composite in the present work. The dehydrogenation pathway and reaction mechanism of 5LiBH₄ + Mg₂FeH₆ composite were also investigated and elucidated. The self-decomposition of Mg₂FeH₆ leads to the in situ formation of Mg and Fe particles on the surface of LiBH₄, resulting in a well dispersion between different reacting phases. The formation of FeB is observed during the dehydrogenation of 5LiBH₄ + Mg₂FeH₆ composite, which might supplies nucleation sites of MgB₂ during the dehydrogenation process, but is not an ascendant catalyst for the self-decomposition of LiBH₄. And FeB can also transform to the LiBH₄ and Fe by reacting with LiH and H₂ during the rehydrogenation process. The dehydrogenation capacity for 5LiBH₄ + Mg₂FeH₆ composite still gets to 6.5 wt% even after four cycles. The X-ray diffraction analyses reveal the phase transitions during the hydriding and dehydriding cycle. The formed FeB in the composite maintains a nanostructure after four hydriding-dehydriding cycles. The loss of hydrogen storage capacity and de-/rehydrogenation kinetics can be attributed to the incomplete generation of Mg₂FeH₆ during the rehydrogenation process.     

A thermodynamic analysis of the SO2/H2SO4 system in SO2-depolarized electrolysis

The hybrid sulfur thermochemical cycle has been proposed as a means to produce efficiently massive quantities of clean hydrogen using a high-temperature heat source like nuclear or solar. The cycle consists of two steps, one of which is electrolytic. The reversible cell potential for this step and, hence, the resulting operating potential will depend on the concentrations of dissolved SO₂ and sulfuric acid at the electrode. To understand better how these are related as functions of temperature and pressure, an Aspen Plus phase equilibrium model using the OLI Mixed Solvent Electrolyte physical properties method was employed to determine the activities of the species present in the system. These activities were used in conjunction with the Nernst equation to determine the reversible cell potential as a function of sulfuric acid concentration, temperature and pressure. A significant difference between the reversible and actual cell potentials was found, suggesting that there may be considerable room for reducing the operating potential.     

Reactivity of TiH2 hydride with lithium ion: Evidence for a new conversion mechanism

The electrochemical reactivity of the face centered cubic (fcc) TiH₂ hydride with lithium ion was studied. A full discharge capacity of 1072 mAh/g at an average potential of 0.2 V can be achieved when the TiH₂ hydride electrode is ground with 10wt% of carbon. From X-ray diffraction (XRD) characterization of the electrodes, dehydrogenation of the titanium hydride via an electrochemical process occurs following different reaction steps. From 0 to 0.34 Li, an fcc δ-TiH_2−x solid solution is formed according to the reaction δ-TiH₂ (fcc) + 0.34 Li → δ TiH_1.66 (fcc) + 0.34 LiH. Pursuing the dehydrogenation process from 0.34 to 1, the cubic solid solution δ-TiH_2−x reacts with lithium ion and transforms partially in a distorted face centered orthorhombic phase δ-TiH (fco). At this stage, the absence of hexagonal close-packed (hcp) α-Ti formation is attributed to the peritectic transformation: hcp α-Ti(H) + fcc δ-TiH_2−x → δ-TiH. From 1 to 2 Li, a usual conversion mechanism is observed leading to the formation of hcp α-Ti and LiH according to the reaction δ-TiH_2−x (fcc) ↔ δ-TiH (fco) + Li → α-Ti (hcp) + LiH.     

Effects of nano additives on hydrogen storage behavior of the multinary complex hydride LiBH4/LiNH2/MgH2

Multinary complex hydrides comprised of borohydrides, amides and metal hydrides have been synthesized using the solid state mechano-chemical process. After the optimization of the system, it was found that LiBH₄/LiNH₂/MgH₂ exhibits potential reversible hydrogen storage behavior (>6 wt.%) at temperatures of 125–175 °C. To further improve the hydrogen performance of the system, various nano additives namely, nickel, cobalt, iron, copper, and manganese were investigated. It was observed that some of these additives (Co, Ni) lowered the hydrogen release temperature at least 75–100 °C in the major hydrogen decomposition step. While other additives acted as catalysts and increased the rate at which hydrogen was released. Combinatorial addition of selected materials were also investigated and found to have both a positive effect on kinetics and reduction in hydrogen desorption temperature.     

First-principles study on the dehydrogenation properties and mechanism of Al-doped Mg2NiH4

Mg₂NiH₄, with fast sorption kinetics, is considered to be a promising hydrogen storage material. However, its hydrogen desorption enthalpy is too high for practical applications. In this paper, first-principles calculations based on density functional theory (DFT) were performed to systematically study the effects of Al doping on dehydrogenation properties of Mg₂NiH₄, and the underlying dehydrogenation mechanism was investigated. The energetic calculations reveal that partial component substitution of Mg by Al results in a stabilization of the alloy Mg₂Ni and a destabilization of the hydride Mg₂NiH₄, which significantly alters the hydrogen desorption enthalpy ΔH_des for the reaction Mg₂NiH₄ → Mg₂Ni + 2H₂. A desirable enthalpy value of ∼0.4 eV/H₂ for application can be obtained for a doping level of x ≥ 0.35 in Mg_2−xAl_xNi alloy. The stability calculations by considering possible decompositions indicate that the Al-doped Mg₂Ni and Mg₂NiH₄ exhibit thermodynamically unstable with respect to phase segregation, which explains well the experimental results that these doped materials are multiphase systems. The dehydrogenation reaction of Al-doped Mg₂NiH₄ is energetically favorable to perform from a metastable hydrogenated state to a multiphase dehydrogenated state composed of Mg₂Ni and Mg₃AlNi₂ as well as NiAl intermetallics. Further analysis of density of states (DOS) suggests the improving of dehydrogenation properties of Al-doped Mg₂NiH₄ can be attributed to the weakened Mg-Ni and Ni-H interactions and the decreasing bonding electrons number below Fermi level. The mechanistic understanding gained from this study can be applied to the selection and optimization of dopants for designing better hydrogen storage materials.