Regeneration of Lithium Aluminum Hydride

Lithium aluminum hydride (LiAlH(4)) is a promising compound for hydrogen storage, with a high gravimetric and volumetric hydrogen density and a low decomposition temperature. Similar to other metastable hydrides, LiAlH(4) does not form by direct hydrogenation at reasonable hydrogen pressures; therefore, there is considerable interest in developing new routes to regenerate the material from the dehydrogenated products LiH and Al. Here we demonstrate a low-energy route to regenerate LiAlH(4) from LiH and Ti-catalyzed Al. The initial hydrogenation occurs in a tetrahydrofuran slurry and forms the adduct LiAlH(4).4THF. The thermodynamics of this reversible reaction were investigated by measuring pressure-composition isotherms, and the free energy was found to be small and slightly negative (DeltaG = -1.1 kJ/mol H(2)), suggesting an equilibrium hydrogen pressure of just under 1 bar at 300 K. We also demonstrate that the adduct LiAlH(4).4THF can be desolvated at low temperature to yield crystalline LiAlH(4).