The lithium amide-lithium hydride system (LiNH2-LiH) is one of the most attractive lightweight materials for hydrogen storage. In an effort to improve its hydrogen sorption kinetics, the effect of 1 mol% AlCl3 addition to LiNH2-LiH system was systematically investigated by differential scanning calorimetry, X-ray diffraction, Fourier transform infrared analysis and hydrogen volumetric measurements. It is shown that Al3+ is incorporated into the LiNH2 structure by partial substitution of Li+ forming a new amide in the Li-Al-N-H system, which is reversible under hydriding/dehydriding cycles. This new substituted amide displays improved hydrogen storage properties with respect to LiNH2-LiH. In fact, a stable hydrogen storage capacity of about 4.5-5.0 wt% is observed under cycling and is completely desorbed in 30 min at 275 degrees C for the Li-Al-N-H system. Moreover, the concurrent incorporation of Al3+ and the presence of LiH are effective for mitigating the ammonia release. The results reveal a common reaction pathway for LiNH2-LiH and LiNH2-LiH plus 1 mol% AlCl3 systems, but the thermodynamic properties are changed by the inclusion of Al3+ in the LiNH2 structure. These findings have important implications for tailoring the properties of the Li-N-H system. Copyright (C) 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.