The present invention provides methods and materials for the formation of hydrogen storage alanes, AlHx, where x is greater than 0 and less than or equal to 6 at reduced H2 pressures and temperatures. The methods rely upon reduction of the change in free energy of the reaction between aluminum and molecular H2. The change in free energy is reduced by lowering the entropy change during the reaction by providing aluminum in a state of high entropy, and by increasing the magnitude of the change in enthalpy of the reaction or combinations thereof.