Low dimensional nanostructures of fast ion conducting lithium nitride.

As the only stable binary compound formed between an alkali metal and nitrogen, lithium nitride possesses remarkable properties and is a model material for energy applications involving the transport of lithium ions. Following a materials design principle drawn from broad structural analogies to hexagonal graphene and boron nitride, we demonstrate that such low dimensional structures can also be formed from an s-block element and nitrogen. Both one- and two-dimensional nanostructures of lithium nitride, Li3N, can be grown despite the absence of an equivalent van der Waals gap. Lithium-ion diffusion is enhanced compared to the bulk compound, yielding materials with exceptional ionic mobility. Li3N demonstrates the conceptual assembly of ionic inorganic nanostructures from monolayers without the requirement of a van der Waals gap. Computational studies reveal an electronic structure mediated by the number of Li-N layers, with a transition from a bulk narrow-bandgap semiconductor to a metal at the nanoscale.

Pressure-dependent deuterium reaction pathways in the Li-N-D system.

Neutron diffraction data from in situ deuteration and dedeuteration of Li(3)N are presented under different pressure regimes, whereby reaction pathways differing from the widely reported stoichiometric pathway of Li(3)N + 2D(2)<--> Li(2)ND + LiD + D(2)<--> LiND(2) + 2LiD are observed. At sufficiently high pressures, where the deuterium chemical potential is comparable with the heat of amide formation, the reaction appears to be driven straight to the amide plus deuteride phase mixture. At lower pressures, a cubic phase exhibiting a concentration-dependent variation in lattice parameter is observed. In dedeuteration, two sets of reflections from cubic structures with distinct lattice parameters are observed, both of which exhibit a continual decrease in cell volume. The reaction pathways are discussed in terms of the compositional variation.

A mechanism for non-stoichiometry in the lithium amide/lithium imide hydrogen storage reaction.

We demonstrate, through structural refinement from synchrotron X-ray diffraction data, that the mechanism of the transformation between lithium amide and lithium imide during hydrogen cycling in the important Li-N-H hydrogen storage system is a bulk reversible reaction that occurs in a non-stoichiometric manner within the cubic anti-fluorite-like Li-N-H structure.