Mechanical and thermal dehydrogenation of lithium alanate (LiAlH4) and lithium amide (LiNH2) hydride composites

Abstract

Hydrogen storage properties of the (nLiAlH4 + LiNH2) hydride composite where n = 1, 3, 11.5 and 30, synthesized by high energy ball milling have been investigated. The composite with the molar ratio n = 1 releases large quantities of H2 (up to ~5 wt.%) during ball milling up to 100-150 min. The quantity of released H2 rapidly decreases for the molar ratio n = 3 and is not observed for n = 11.5 and 30. The XRD studies indicate that the H2 release is a result of a solid state decomposition of LiAlH4 into (1/3)Li3AlH6 + (2/3)Al + H2 and subsequently decomposition of (1/3)Li3AlH6 into LiH + (1/3)Al + 0.5H2. Apparently, LiAlH4 is profoundly destabilized during ball milling by the presence of a large quantity of LiNH2 (37.7 wt.%) in the n = 1 composite. The rate of dehydrogenation at 100-170 °C (at 1 bar H2) is adversely affected by insufficient microstructural refinement, as observed for the n = 1 composite, which was milled for only 2 min to avoid H2 discharge during milling. XRD studies show that isothermal dehydrogenation of (nLiAlH4 + LiNH2) occurs by the same LiAlH4 decomposition reactions as those found during ball milling. The ball milled n = 1 composite stored under Ar at 80 °C slowly discharges large quantities of H2 approaching 3.5 wt.% after 8 days of storage. © 2011 by the authors; licensee MDPI, Basel, Switzerland.