Effect of Ti-catalyst content on the reversible hydrogen storage properties of the sodium alanates

Abstract The reversible hydrogen storage properties of Ti-catalyzed NaAlH 4 (and associated Na 3 AlH 6 ) were studied as a function of Ti-content using a dry preparation technique consisting of the ball-milling of NaAlH 4 +TiCl 3 mixtures (0–9 mol.% TiCl 3 ). This process is believed to result in the in situ solid-state introduction of metallic Ti via the reduction of the TiCl 3 by the Na-component of NaAlH 4 (to form NaCl). Properties studied were hydriding and dehydriding rates and reversible gravimetric H-capacity as a function of starting TiCl 3 content. Detailed isothermal kinetic studies were done over a wide temperature range (20–225 °C) and treated by Arrhenius analysis. All kinetics were found to follow the Arrhenius equation and the changes of thermal activation energies and rate constants with TiCl 3 -content were observed that may give valuable insights into the as-yet unknown mechanistic factors that control H 2 desorption and absorption kinetics. Ti increases both dehydriding and hydriding kinetics (and associated practical engineering rates), but at the substantial expense of H-capacity. The finite room temperature decomposition of the catalyzed NaAlH 4 phase was reconfirmed and rates better quantified.