The Role of Semilabile Oxygen Atoms for Intercalation Chemistry of the Metal-Ion Battery Polyanion Cathodes

Abstract

Using the orthorhombic layered Na₂FePO₄F cathode material as a model system we identify the bonding of the alkali metal cations to the semilabile oxygen atoms as an important factor affecting electrochemical activity of alkali cations in polyanion structures. The semilabile oxygens, bonded to the P and alkali cations, but not included into the FeO₄F₂ octahedra, experience severe undercoordination upon alkali cation deintercalation, causing an energy penalty for removing the alkali cations located in the proximity of such semilabile oxygens. Desodiation of Na₂FePO₄F proceeds through a two-phase mechanism in the Na-ion cell with a formation of an intermediate monoclinic Na_1.55FePO₄F phase with coupled Na/vacancy and Fe²⁺/Fe³⁺ charge ordering at 50% state of charge. In contrast, desodiation of Na₂FePO₄F in the Li-ion cell demonstrates a sloping charge profile suggesting a solid solution mechanism without formation of a charge-ordered intermediate phase. A combination of a comprehensive crystallographic study and extensive DFT-based calculations demonstrates that the difference in electrochemical behavior of the alkali cation positions is largely related to the different number of the nearest neighbor semilabile oxygen atoms, influencing their desodiation potential and accessibility for the Na/Li chemical exchange, triggering coupled alkali cation-vacancy ordering and Fe²⁺/Fe³⁺ charge ordering, as well as switching between the "solid solution" and "two-phase" charging mechanistic regimes.