Despite the apparent stability of bulk LiNiO 2 to molecular oxygen formation, it is questionable as to what extent R 3m-NiO 2 is wholly representative of LiNiO 2 at the top of charge. LiNiO 2 is known to be highly defective: it can more accurately be described as Li 0 < x ≤ 0.3 . This off-stoichiometry is caused by asymmetric cation-antisite disorder, where a fraction of the lithium sites are occupied by Ni 2+ . This total off-stoichiometry leading to generally nickel-rich systems does not preclude the formation of locally nickel-deficient regions introduced by point defects. Such regions could act as nucleation points for oxygen oxidation and subsequent dimerization. To assess this possibility, we calculate point defect concentrations to examine how vacancies may be introduced into the nickel layer during the synthesis of "pristine" LiNiO 2 .