Highly destabilized Mg-Ti-Ni-H system investigated by density functional theory and hydrogenography

Using hydrogenography, we recently mapped the thermodynamic properties of a large range of compositions in the quaternary Mg-Ti-Ni-H system. The enthalpy of hydride formation of Mg-Ni alloys is significantly altered upon Ti doping. For a small range of compositions, we find a hydrogenation enthalpy ΔH=-40 kJ (mol H2) -1, which is the desired enthalpy for hydrogen storage at moderate temperature and pressure. This enthalpy value is surprising since it is significantly less negative than the ΔH of the Mg-Ni and Mg-Ti hydrides. The nanostructure of the Mg-Ti-Ni-H films hinders a direct determination of the hydride phases involved by x-ray diffraction. Using density functional theory calculations for various hydrogenation reaction paths, we establish that the destabilization of the Mg-Ni-H system by Ti doping is due to the formation of Mg2 Ni and Ti-Ni intermetallics in the as-deposited state, which transform into a metastable Ti-doped Mg2 Ni H4 phase upon hydrogenation. The Ti-doped Mg2 Ni H4 phase can be considered as a heavily doped semiconductor. © 2008 The American Physical Society.