Recent investigations showed the formation of new amide-chloride phases between LiNH2and AlCl3after milling and/or heating under hydrogen pressure. These phases exhibited a key role in the improvement of the hydrogen storage properties of the LiNH2-LiH composite. In the present work, we studied the effects of Al and AlCl3additives on the hydrogen storage behavior of the Li-Mg-N-H system. The dehydrogenation kinetics and the reaction pathway of Al and AlCl3modified LiNH2-MgH2composite were investigated through a combination of kinetic measurements and structural analyses. During the first cycle, the addition of Al catalytically accelerates the hydrogen release at 200 °C. In the subsequent cycles, the formation of a new phase of unknown nature is probably responsible for both increased equilibrium hydrogen pressure and decreased dehydrogenation rate. In contrast, AlCl3additive reacts with LiNH2-MgH2through the milling and continues during heating under hydrogen pressure. Addition of AlCl3leads to the formation of two cubic structures identified in the Li-Al-N-H-Cl system, which improves dehydrogenation rate by modifying the thermodynamic stability of the material. This study evidences positive effect of cation and/or anion substitution on hydrogen storage properties of the Li-Mg-N-H system.
Kinetics and hydrogen storage performance of Li-Mg-N-H systems doped with Al and AlCl3 / Senes, Nina; Fernández Albanesi, Luisa; Garroni, Sebastiano; Santoru, Antonio; Pistidda, Claudio; Mulas, Gabriele; Enzo, Stefano; Gennari, Fabiana. - In: JOURNAL OF ALLOYS AND COMPOUNDS. - ISSN 0925-8388. - 765:(2018), pp. 635-643. [10.1016/j.jallcom.2018.06.262]