The role of native defects in the transport of charge and mass and the decomposition of Li4BN3H10

Li4BN3H10 is of great interest for hydrogen storage and for lithium-ion battery solid electrolytes because of its high hydrogen content and high lithium-ion conductivity, respectively. The practical hydrogen storage application of this complex hydride is, however, limited due to irreversibility and cogeneration of ammonia (NH3) during the decomposition. We report a first-principles density-functional theory study of native point defects and defect complexes in Li4BN3H10, and propose an atomistic mechanism for the material's decomposition that involves mass transport mediated by native defects. In light of this specific mechanism, we argue that the release of NH3 is associated with the formation and migration of negatively charged hydrogen vacancies inside the material, and it can be manipulated by the incorporation of suitable electrically active impurities. We also find that Li4BN3H10 is prone to Frenkel disorder on the Li sublattice; lithium vacancies and interstitials are highly mobile and play an important role in mass transport and ionic conduction.