Tuning hydrogen storage properties and reactivity: Investigation of the LiBH4-NaAlH4 system

Tuning the hydrogen storage properties of complex metal hydrides is of vast interest. Here, we investigate the hydrogen release and uptake pathways for a reactive hydride composite, LiBH4-NaAlH4 utilizing in situ synchrotron radiation powder X-ray diffraction experiments. Sodium alanate transforms to sodium borohydride via a metathesis reaction during ball milling or by heating at T similar to 95 degrees C. NaBH4 decomposes at 340 degrees C in dynamic vacuum, apparently directly to solid amorphous boron and hydrogen and sodium gas and the latter two elements are lost from the sample. Under other conditions, T=400 degrees C and p(H-2)=similar to 1 bar, NaBH4 only partly decomposes to B and NaH. On the other hand, formation of LiAl is facilitated by dynamic vacuum conditions, which gives access to the full hydrogen contents in the LiBH4-NaAlH4 system. Formation of AlB2 is observed (T similar to 450 degrees C) and other phases, possibly AlBx or Al1-xLixB2, were observed for the more Li-rich samples. This may open new routes to the stabilization of boron in the solid state in the dehydrogenated state, which is a challenging and important issue for hydrogen storage systems based on borohydrides. (C) 2010 Elsevier Ltd. All rights reserved.