Hydrogen sorption mechanisms in lithium amide and metal hydride reactive systems.

Abstract

Considerable effort has been devoted to the M-N-H system for solid-state hydrogen storage. However, the desorption mechanism is still unclear and the desorption temperature is too high for practical considerations. Here, the desorption characteristics of LiNH2 and a mixture of (LiNH2+LiH) were firstly comparatively studied by simultaneous then-nogravimetry, differential scanning calorimetry and mass spectrometry for further understanding of H2 desorption in the (LiNH2+LiH) system. Mass spectrometry and thermal analysis of (LiNH2+LiH) mixtures indicate that approximately 5 mass % of H2 is released at 180*C after four hours of milling without any apparent release of NH3, whereas insufficient mixing of the two compounds cannot stop the escaping of NH3 from the mixture. Non-unifon-ri mixing can lead to the escape of NH3 from the mixture. The evidence further supports the notion that NH3 intermediated reaction is a possible reaction path within the thermal desorption of the (LiNH2+ LiH) mixture. BN additive, among selected nitrides shows the best effect on desorption from (LiNH2+ LiH). (LiNH2+MgH2)materials with different molar ratios (4: 3,4: 2 and 4: 1) were also studied for their sorption properties and mechanisms. Results show that more than 6 mass% H2 is desorbed from 1500C for the (4LiNH2 +3MgH2)mixture, with two H2peaks at 200 and 320'C. Meanwhile, there is only -5 mass% for (4LiNH2 +2MgH2) mixture with one H2 peak at 200 T. Reversibility measurements suggest that LiNH2 and MgH2 cannot be recovered after absorption; instead, Li2NH and Mg(NH2)2 (or MgNH) take over to perform the H2 storage functions. The (4LiNH2+3MgH2 ) mixture possess a greater H2 capacity in first desorption, but shows less than 2 mass% reversible capacity in subsequent cycles. However, there is only about I mass% capacity loss during the reversibility measurement for the (4LiNH2 +2MgH2)mixture. Other M-N-H systems, mainly NaH, KH, AlH3 and CaH2, were also investigated, and only CaH2 shows the capability of reacting with LiNH2 to produce H2 among these candidates.