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MgH2-based hydrogen storage materials are promising candidates for solid-state hydrogen storage allowing efficient thermal management in energy systems integrating metal hydride hydrogen store with a solid oxide fuel cell (SOFC) providing dissipated heat at temperatures between 400 and 600 °C. Recently, we have shown that graphite-modified composite of TiH2 and MgH2 prepared by high-energy reactive ball milling in hydrogen (HRBM), demonstrates a high reversible gravimetric H storage capacity exceeding 5 wt % H, fast hydrogenation/dehydrogenation kinetics and excellent cycle stability. In present study, 0.9 MgH2 + 0.1 TiH2 +5 wt %C nanocomposite with a maximum hydrogen storage capacity of 6.3 wt% H was prepared by HRBM preceded by a short homogenizing pre-milling in inert gas. 300 g of the composite was loaded into a storage tank accommodating an air-heated stainless steel metal hydride (MH) container equipped with transversal internal (copper) and external (aluminium) fins. Tests of the tank were carried out in a temperature range from 150 °C (H2 absorption) to 370 °C (H2 desorption) and showed its ability to deliver up to 185 NL H2 corresponding to a reversible H storage capacity of the MH material of appr. 5 wt% H. No significant deterioration of the reversible H storage capacity was observed during 20 heating/cooling H2 discharge/charge cycles. It was found that H2 desorption performance can be tailored by selecting appropriate thermal management conditions and an optimal operational regime has been proposed.

The strong interactions between Mg and Ni/NiH4 are attributed to harsh operating conditions and difficulties for H2 release, restricting the practical applications of the Mg-based hydrides. In this study, a new method of interstitial nonmetals co-doping was proposed to reduce the strong interactions. The calculation results showed that the method of interstitial nonmetals co-doping causes a more significant reduction in the thermal stability of Mg-based hydrides, as compared with the methods of either single transition metal or nonmetal doping. To determine the influence mechanism, a theoretical study was conducted based on the first-principles calculations. The computations demonstrated that the criss-cross action between B–Ni and N–Mg bonds weakens the bonding effects between Mg and Ni/NiH4. Besides, the mutual interactions between nonmetals and H atoms could weaken Ni–H bonding effects and stimulate the breaking of stable NiH4 clusters, thereby facilitating the release of H2 from the hydride.

TiH2-modified MgH2 was prepared by high energy reactive ball milling (HRBM) of Mg and Ti in hydrogen and showed high weight H storage capacity and fast hydrogenation/dehydrogenation kinetics. However, a decrease in the reversible H storage capacity on cycling at high temperatures takes place and is a major obstacle for its use in hydrogen and heat storage applications. Reversible hydrogen absorption/desorption cycling of the materials requires use of the working temperature ≥330 °C and results in a partial step-by-step loss of the recoverable hydrogen storage capacity, with less significant changes in the rates of hydrogenation/dehydrogenation. After hydrogen desorption at 330–350 °C, hydrogen absorption can proceed at much lower temperatures, down to 24 °C. However, a significant decay in the reversible hydrogen capacity takes place with increasing number of cycles. The observed deterioration is caused by cycling-induced drastic morphological changes in the studied composite material leading to a segregation of TiH2 particles in the cycled samples instead of their initial homogeneous distribution. However, the introduction of 5 wt% of graphite into the MgH2–TiH2 composite system prepared by HRBM leads to an outstanding improvement of the hydrogen storage performance. Indeed, hydrogen absorption and desorption characteristics remain stable through 100 hydrogen absorption/desorption cycles and are related to an effect of the added graphite. The TEM study showed that carbon is uniformly distributed between the MgH2 grains covering segregated TiH2, preventing the grain growth and thus keeping the reversible storage capacity and the rates of hydrogen charge and discharge unchanged. Modelling of the kinetics of hydrogen absorption and desorption in the Mg–Ti and Mg–Ti–C composites showed that the reaction mechanisms significantly change depending on the presence or absence of graphite, the number of absorption–desorption cycles and the operating temperature.

Mg-based materials have become the cornerstone of hydrogen storage applications and have shown recently promises in thermal energy storage applications. However, synthesis of some materials including Mg2FeH6 ternary hydride poses a number of challenges. In spite a variety of reports on various synthesis routes yielding Mg2FeH6, none of them produces a 100% pure Mg2FeH6. In this communication, we have attempted to synthesize Mg2FeH6 by high energy reactive ball milling (HERBM) performed in hydrogen gas. Prior to the ball milling, the starting stoichiometric 2:1 mixture of the initial materials Mg+Fe was heat treated through a judicious temperature program. It was found that the yield of Mg2FeH6 is related to the conditions of heat treatment, time and temperature, and the milling parameters such as ball to powder mass ratio (BPR) and rotation speed of the planetary mill. Moreover, it was found that the synthesis took place in less than 5 hours of milling with a maximum yield of Mg2FeH6 of 84 wt%, which is a noticeable improvement as compared to the reference data.

Thermo-chemical energy storage based on metal hydrides has gained tremendous interest in solar heat storage applications such as concentrated solar power systems (CSP) and parabolic troughs. In such systems, two metal hydride beds are connected and operating in an alternative way as energy storage or hydrogen storage. However, the selection of metal hydrides is essential for a smooth operation of these CSP systems in terms of energy storage efficiency and density. In this study, thermal energy storage systems using metal hydrides are modeled and analyzed in detail using first law of thermodynamics. For these purpose, four conventional metal hydrides are selected namely LaNi5, Mg, Mg2Ni and Mg2FeH6. The comparison of performance is made in terms of volumetric energy storage and energy storage efficiency. The effects of operating conditions (temperature, hydrogen pressure and heat transfer fluid mass flow rates) and reactor design on the aforementioned performance metrics are studied and discussed in detail. The preliminary results showed that Mg-based hydrides store energy ranging from 1.3 to 2.4 GJ m−3 while the energy storage can be as low as 30% due to their slow intrinsic kinetics. On the other hand, coupling Mg-based hydrides with LaNi5 allow us to recover heat at a useful temperature above 330 K with low energy density ca.500 MJ m−3 provided suitable operating conditions are selected. The results of this study will be helpful to screen out all potentially viable hydrides materials for heat storage applications.

In this study, the modified preparation method of combining planetary and vibratory ball milling was proposed to prepare Mg based hydrogen storage alloy powders. The comparison of micromorphology and hydrogen storage behaviour between Mg2Ni prepared using the modified and conventional preparation methods were investigated experimentally. The comparison results showed that the combination of first planetary and then vibratory ball milling has more favourable effect on improving both the kinetics and the thermodynamics of ball milled Mg2Ni alloys. The sample synthesised by first planetary milling for 40 h and then vibratory milling for 30 h has faster hydrogen absorption kinetics and lower dehydriding onset temperature than those prepared by the single method of planetary or vibratory milling and hydriding combustion synthesis owing to its popcorn-like microstructure. Moreover, this kind of modified method reduces the reaction enthalpy and activation energy by up to ∼18 and 22% respectively.

The effects of a small amount of nonmetal elements (N, F and Cl) with high electronegativity interstitially doping on improving the hydrogen storage characteristics of Mg-based metal hydrides were systematically investigated by first-principle calculations in this paper. The interstitial positions which the doping elements easily occupied were firstly determined. The calculation results showed that these elements are most likely to hold the center position of octahedral sites with two Ni and four Mg atoms. Based on this, the crystal structures, thermal stability, dehydrogenation energy and electronic structures of all the crystals, including Mg2Ni, Mg2NiN0.5, Mg2NiF0.5, Mg2NiCl0.5 and their hydrides, were further investigated. The nonmetals with high electronegativity exhibit the favorable effects on the characteristics of Mg-based metal hydrides. Doping F significantly reduces the dehydrogenation energy of Mg2NiH4 by about 25%, because of the strong hybridization between F and H atoms. When doping Cl into Mg2Ni and Mg2NiH4, the formation enthalpies decrease respectively by 0.047 and 0.024 eV atom−1, due to the reduction of integral intensity of the bonding electron. Among the three elements, N has the best effects on improving both kinetics and thermodynamics. Doping N not only causes the formation enthalpies of Mg2Ni and its hydride to decrease by 0.215 and 0.141 eV atom−1 respectively, but also reduces the dehydrogenation energy of Mg2NiH4.

Metal hydride systems are utilized in many practical applications such as hydrogen storage, heat pumps, etc. The establishment of a metal hydride system requires the expression of reaction rate for the first step design, from an engineering standpoint. However, improper experimental determination of intrinsic kinetics usually leads to significant errors in the kinetic data. This paper presents a novel methodology of estimating these errors based on the entropy generation analysis. For this purpose, numerical simulation is performed taking into account the experimental conditions for a real case. The results showed that if the operating conditions (i.e. hydrogen pressure, heat transfer coefficient) and the size of the experimental setup are not chosen properly, the kinetic data obtained from the experiments will be largely misled. Therefore it should be carefully taken into account in order to minimize the relative errors induced on the kinetic data.