Layered Transition Metal Oxides as Ca Intercalation Cathodes: A Systematic First‐Principles Evaluation

Abstract Finding high‐voltage Ca cathode materials is a critical step to unleashing the full potential of high‐energy‐density Ca‐ion batteries. First‐principles calculations are used to demonstrate that P‐type layered calcium transition metal (TM) oxide materials (CaTM 2 O 4 ) with a range of TM substitutions (TM = Ti, V, Cr, Mn, Fe, Co, and Ni) have excellent battery‐related properties including thermodynamic stability, average voltage, energy density, synthesizability, ionic mobility, and electronic structure. However, the thermodynamic stability of the charged phase and TM redox activity are shown to be sensitive to TM selection, with CaCo 2 O 4 having the best balance of all considered properties. The utility of combining multiple TMs to expand the chemical search space for TM substitutions is demonstrated by mixing Co and Ni in layered CaTM 2 O 4 .