Predicting Lithium Iron Oxysulfides for Battery Cathodes

Cathode materials that have high specific energies and low manufacturing costs are vital for the scaling up of lithium-ion batteries (LIBs) as energy storage solutions. Fe-based intercalation cathodes are highly attractive because of the low cost and the abundance of raw materials. However, existing Fe-based materials, such as LiFePO4, suffer from low capacity due to the large size of the polyanions. Turning to mixed anion systems can be a promising strategy to achieve higher specific capacity. Recently, antiperovskite-structured oxysulfide Li2FeSO has been synthesized and reported to be electrochemically active. In this work, we perform an extensive computational search for iron-based oxysulfides using ab initio random structure searching (AIRSS). By performing an unbiased sampling of the Li–Fe–S–O chemical space, several oxysulfide phases have been discovered, which are predicted to be less than 50 meV/atom from the convex hull and potentially accessible for synthesis. Among the predicted phases, two anti-Ruddlesden–Popper-structured materials Li2Fe2S2O and Li4Fe3S3O2 have been found to be attractive as they have high theoretical capacities with calculated average voltages of 2.9 and 2.5 V, respectively, and their distances to hull are less than 5 meV/atom. By performing nudged-elastic band calculations, we show that the Li-ion transport in these materials takes place by hopping between the nearest neighboring sites with low activation barriers between 0.3 and 0.5 eV. The richness of materials yet to be synthesized in the Li–Fe–S–O phase field illustrates the great opportunity in these mixed anion systems for energy storage applications and beyond.