Milling and Additive Effects on Hydrogen Desorption Reactions of Li-N-H and Li-Mg-N-H Hydrogen Storage Systems

Abstract

ABSTRACTHydrogen desorption reactions of the mixtures of (i) lithium amide and lithium hydride (LiNH2/LiH), and (ii) magnesium amide and lithium hydride (Mg(NH2)2/4LiH) were studied. Titanium compounds and nano-particles including fullerene (C60), were doped to those hydrogen storage mixtures respectively. The hydrogen desorption reactions were monitored by means of temperature programmed desorption (TPD) technique under an Ar atmosphere. The reaction of LiNH2/LiH was accelerated by adding either 1 mol% of Ti species or 0.2 mol% of fullerene (C60), while those additives did not show significant acceleration effects on the reaction of Mg(NH2)2/4LiH. Kinetic studies revealed the enhanced hydrogen desorption reaction rate constant for TiCl3 doped LiNH2/LiH, k = 3.1 × 10−4 s−1 at 493 K, and the prolonged ball-milling further improved reaction rate, k = 1.1 × 10−3 s−1 at the same temperature. For the dehydrogenation reaction of TiCl3 doped LiNH2/LiH, the activation energies estimated by Kissinger plot (95 kJ mol−1) and Arrhenius plot (110 kJ mol−1) were in reasonable agreement each other. The LiNH2/LiH mixture without additive exhibited slower hydrogen desorption process and the kinetic traces deviated from single exponential behavior. The results indicated the Ti(III) additives change the hydrogen desorption reaction mechanism of LiNH2/LiH.