The long-term hydriding and dehydriding stability of the nanoscale LiNH2+LiH hydrogen storage system.

The long-term cyclic durability of nano-engineered solid-state hydrogen storage systems is investigated using LiNH2+LiH as a model system. Through 60 hydriding and dehydriding cycles over the course of more than 200 h, a small decrease in the kinetics of the dehydrogenation reaction leads to a 10% reduction in the amount of hydrogen liberated during a 2.5 h desorption. Although a 75% loss in the specific surface area is encountered within the first 10 cycles, the crystallite size remains relatively stable near 20 nm while enduring 72% of the average melting temperature of the phases. The lack of microstructural growth is attributed to low packing efficiency of the ball milled powder in combination with the mixture of multiple phases present and repeated nucleation of fine grains during hydriding and dehydriding reactions.

Enhancement of lithium amide to lithium imide transition via mechanical activation.

The decomposition of lithium amide (LiNH2) to lithium imide (Li2NH) and ammonia (NH3) with and without high-energy ball milling is investigated to lay a foundation for identifying methods to enhance the hydrogen uptake/release of the lithium amide and lithium hydride mixture. A wide range of analytical instruments are utilized to provide unambiguous evidence of the effect of mechanical activation. It is shown that ball milling reduces the onset temperature for the decomposition of LiNH2 from 120 degrees C to room temperature. The enhanced decomposition via ball milling is attributed to mechanical activation related to the formation of nanocrystallites, the reduced particle size, the increased surface area, and the decreased activation energy. The more mechanical activation there is, then the more improvement there is in enhancing the decomposition of LiNH2. It also is found that the activation energy for the decomposition of LiNH2 without ball milling is 243.98 kJ/mol, which is reduced to 222.20 kJ/mol after ball milling at room temperature for 45 min and is further reduced to 138.05 kJ/mol after ball milling for 180 min. The rate of the isothermal decomposition at the later phase of the LiNH2 decomposition is controlled by diffusion of NH3 through the Li2NH layer.

Stability of lithium hydride in argon and air.

The oxidation behaviors of LiH under a high purity argon atmosphere, an argon atmosphere with some O2 and H2O impurities, and ambient air at both room and high temperatures, are investigated using a variety of analytical instruments including X-ray diffractometry, thermogravimetry, mass spectrometry, scanning electron microscopy, and specific surface area analysis. The oxidation behaviors of the ball-milled LiH under different atmospheres are also studied and compared with those without ball milling. It is shown that no oxidation of LiH occurs under a high-purity argon atmosphere. However, oxidation of LiH takes place when the argon atmosphere contains some H2O and O2 impurities. At temperatures higher than approximately 55 degrees C, oxidation of LiH proceeds via the reaction of LiH + 1/4 O2 = 1/2 Li2O + 1/2 H2, whereas at room temperature oxidation of LiH is likely caused by the simultaneous reactions of LiH + H2O = LiOH + H2 and LiH + 1/2 O2 = LiOH. The oxidation behavior of LiH in ambient air with a 27% relative humidity can be well described by the Johnson-Mehl-Avrami equation. Furthermore, the ball-milled LiH oxidizes faster than the unmilled one, which is due to the finer particle size and larger surface area of the ball-milled powder.