Hydrogenstorage and ionic mobility in amide–halide systems

Abstract

We report the results of a systematic study of the effect of halides on hydrogen release and uptake in lithium amide and lithium imide, respectively. The reaction of lithium amide and lithium imide with lithium or magnesium chloride, bromide and iodide resulted in a series of amide–halide and imide–halide phases, only two of which have been reported previously. On heating with LiH or MgH₂, the amide–halides synthesised all released hydrogen more rapidly than lithium amide itself, accompanied by much reduced, or in some cases undetectable, release of ammonia by-product. The imide–halides produced were found to hydrogenate more rapidly than lithium imide, reforming related amide–halide phases. The work was initiated to test the hypothesis that the incorporation of halide anions might improve the lithium ion conductivity of lithium amide and help maintain high lithium ion mobility at all stages of the de/rehydrogenation process, enhancing the bulk hydrogen storage properties of the system. Preliminary ionic conductivity measurements indicated that the most conducting amide– and imide–halide phases were also the quickest to release hydrogen on heating and to hydrogenate. We conclude that ionic conductivity may be an important parameter in optimising the materials properties of this and other hydrogen storage systems.