Decomposition Kinetics of the AlH3 Polymorphs

Aluminum hydride polymorphs (α-AlH3, β-AlH3, and γ-AlH3) were prepared by organometallic synthesis. Hydrogen capacities approaching 10 wt % at desorption temperatures less than 100 °C have been demonstrated with freshly prepared AlH3. The temperature-dependent rate constants were determined by measuring the isothermal hydrogen evolution between 60 °C and 140 °C. Fractional decomposition curves showed good fits using both the second and third-order Avrami−Erofeyev equations, indicating that the decomposition kinetics are controlled by nucleation and growth of the aluminum phase in two and three dimensions. The large activation energies measured for the AlH3 polymorphs suggest that the decomposition occurs via an activated complex mechanism with complexes consisting of approximately nine AlH3 molecules (1−2 unit cells for α-AlH3).