Supervalent doping is predicted to most strongly increase the concentrations of both V Li and O Cl . The defect species with the higher concentration in the relevant undoped system undergoes the largest increase, and supervalent doping is therefore predicted to most effectively increase the concentration of lithium vacancies under Lipoor synthesis conditions. Subvalent doping principally increases the concentration of chlorine vacancies ahead of lithium interstitials under all considered synthesis conditions, due to the much higher concentration of chlorine vacancies with respect to lithium interstitials in undoped Li 3 OCl.