Abstract
New energy storage methods are emerging to increase the energy density of state-of-the-art battery systems beyond conventional intercalation electrode materials. For instance, employing anion redox can yield higher capacities compared with transition metal redox alone. Anion redox in sulfides has been recognized since the early days of rechargeable battery research. Here, we study the effect of d-p overlap in controlling anion redox by shifting the metal d band position relative to the S p band. We aim to determine the effect of shifting the d band position on the electronic structure and, ultimately, on charge compensation. Two isostructural sulfides LiNaFeS2 and LiNaCoS2 are directly compared to the hypothesis that the Co material should yield more covalent metal-anion bonds. LiNaCoS2 exhibits a multielectron capacity of ≥1.7 electrons per formula unit, but despite the lowered Co d band, the voltage of anion redox is close to that of LiNaFeS2. Interestingly, the material suffers from rapid capacity fade. Through a combination of solid-state nuclear magnetic resonance spectroscopy, Co and S X-ray absorption spectroscopy, X-ray diffraction, and partial density of states calculations, we demonstrate that oxidation of S nonbonding p states to S2 2- occurs in early states of charge, which leads to an irreversible phase transition. We conclude that the lower energy of Co d bands increases their overlap with S p bands while maintaining S nonbonding p states at the same higher energy level, thus causing no alteration in the oxidation potential. Further, the higher crystal field stabilization energy for octahedral coordination over tetrahedral coordination is proposed to cause the irreversible phase transition in LiNaCoS2.