Data repository for: Exploring the possibility of extrinsic anion vacancies in the lithium-argyrodite

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The search for highly conducting solid ionic conductors requires a deep understanding of the underlying crystal structure and local dynamic processes. Therefore, cationic and anionic substitutions are typically performed to monitor the resulting changes in the structure and ionic transport, ultimately drawing conclusions to find optimized Li⁺ conductors. Within a substitution series, the anionic framework is generally assumed to be non-changing. This study addresses the question whether the targeted introduction of extrinsic anion vacancies can be stabilized within the a Li⁺ argyrodite. Using diffraction and spectroscopic techniques, Monte Carlo simulations as well as density functional theory calculations, changes in crystal structure and ionic and electronic transport are monitored and the configurational stability is assessed. The structures with anion vacancies were found to have high formation energies, in agreement with the experimental observation. Instead, the phase formation of Li_6+xPS_5+xCl_1−x is observed, showing a decrease in Li⁺ conductivity related to the anion ordering.