In this study, we have investigated the synthesis, microstructure and hydrogen storage properties of Mg-based nanocomposites containing different concentrations of TiCrV and TiCr1.2V0.8 alloys. The Mg-based nanocomposites of Mg containing Ti-Cr-V additives were prepared by reactive milling (RM) under hydrogen atmosphere. The structural characterization revealed the presence of the β-MgH2, γ-MgH2 and BCC phases in the powders samples after RM. In addition, a very refined and homogenous microstructure with average MgH2 crystallite size of around 10-12 nm was observed, including a nanometric dispersion of the additives in the magnesium hydride matrix. The doping with TiCrV and TiCr1,2V0,8 greatly improves the hydrogen desorption behavior of Mg in comparison with the sample without additive, resulting in the lowest onset temperature (240 ºC) for the sample containing 5%mol. of TiCrV. Very fast absorption and desorption kinetics at 275 ºC and 300 ºC (7 minutes and 5 minutes for full desorption and absorption, respectively) were observed in the samples containing TiCrV and TiCr1,2V0,8 without any notable difference between the type of additive used in comparison with the pure sample. However, a slight reduction in hydrogen capacity is observed in the mixtures than for the pure sample (6.7 wt.% against 7.3 wt.%).

In this paper we address some aspects of the kinetics of hydrogen absorption and desorption of Mg2FeH6 nanocomposite powder. The Mg2FeH6 material was prepared from a 2Mg-Fe composition by reactive milling under H2 pressure at room temperature. After mechano-chemical processing, the material was mainly constituted of Mg2FeH6 having a hydrogen gravimetric capacity corresponding to 94% of the theoretical capacity. The kinetics of hydrogen absorption at constant temperature and the transformation of phases during this process were studied. The kinetics of hydrogen absorption presented a two-step behaviour. First, β-MgH2 was formed with faster kinetics than Mg2FeH6 under constant temperature and H2 pressure. Then, β-MgH2 reacted with α-Fe forming Mg2FeH6 in a much slower reaction. Unexpectedly, reaction of hydrogen desorption showed an one-step kinetics, even if Mg2FeH6 and β-MgH2 phases were previously present in the powder.

The compound Mg2FeH6 was synthesized from a 2Mg-Fe mixture in a single process through high-energy ball milling under hydrogen atmosphere at room temperature. The complex hydride was prepared from Mg powder and granulated or powdered Fe using a planetary mill. The phase evolution during different milling times was performed by X-rays diffraction technique. The dehydrogenation behavior of the hydride was investigated through simultaneous thermal analyses of differential scanning calorimetry and thermogravimetry coupled with mass spectrometer. The use of powdered iron as starting material promoted conversion to complex hydride at shorter milling times than when granulated iron was used, nevertheless, after 24 hours of milling the 2Mg-Fe (powdered or granulated) mixtures presented similar dehydrogenation behavior. The hydrogen absorption during milling was on average 3.2 wt. (%), however, changing the proportions of the reagents to 3Mg-Fe a Mg2FeH6-MgH2 based nanocomposite with higher density of hydrogen (5.2 wt. (%)) was obtained.