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Mechanisms for the decomposition and dehydrogenation of Li amide/imide

Reversible reaction involving Li amide (LiNH$_{2}$) and Li imide (Li$_{2}$NH) is a potential mechanism for hydrogen storage. Recent synchrotron x-ray diffraction experiments [W. I. David et al., J. Am. Chem. Soc. 129, 1594 (2007)] suggest that the transformation between LiNH$_{2}$ and Li$_{2}$NH is a bulk reaction that occurs through non-stoichiometric processes and involves the migration of Li$^{+}$ and H$^{+}$ ions. In order to understand the atomistic mechanisms behind these processes, we carry out comprehensive first-principles studies of native point defects and defect complexes in the two compounds. We find that both LiNH$_{2}$ and Li$_{2}$NH are prone to Frenkel disorder on the Li sublattice. Lithium interstitials and vacancies have low formation energies and are highly mobile, and therefore play an important role in mass transport and ionic conduction. Hydrogen interstitials and vacancies, on the other hand, are responsible for forming and breaking N$-$H bonds, which is essential in the Li amide/imide reaction. Based on the structure, energetics, and migration of hydrogen-, lithium-, and nitrogen-related defects, we propose that LiNH$_{2}$ decomposes into Li$_{2}$NH and NH$_{3}$ according to two competing mechanisms with different activation energies: one mechanism involves the formation of native defects in the interior of the material, the other at the surface. As a result, the prevailing mechanism and hence the effective activation energy for decomposition depend on the surface-to-volume ratio or the specific surface area, which changes with particle size during ball milling. These mechanisms also provide an explanation for the dehydrogenation of LiNH$_{2}$+LiH mixtures.