Tuning hydrogen storage properties and reactivity: Investigation of the LiBH 4–NaAlH 4 system

Abstract

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, LiBH 4−NaAlH 4 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∼95 °C. NaBH 4 decomposes at ∼340 °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 °C and p(H 2)=∼1 bar, NaBH 4 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 LiBH 4−NaAlH 4 system. Formation of AlB 2 is observed ( T∼450 °C) and other phases, possibly AlB x or Al 1− x Li x B 2, 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.