Advantages of a Solid Solution over Biphasic Intercalation for Vanadium-Based Polyanion Cathodes in Na-Ion Batteries

The efficient operation of metal-ion batteries in harsh environments, such as at temperatures below -20 °C or at high charge/discharge rates required for EV applications, calls for a careful selection of electrode materials. In this study, we report advantages associated with the solid solution (de)intercalation over the two-phase (de)intercalation pathway and identify the main sources of performance limitations originating from the two mechanisms. To isolate the (de)intercalation pathway as the main variable, we focused on two cathode materials for Na-ion batteries: a recently developed KTiOPO₄-type NaVPO₄F and a well-studied Na₃V₂(PO₄)₂F₃. These materials have the same elemental composition, operate within the same potential range, and demonstrate very close ionic diffusivities, yet follow different (de)intercalation routes. To avoid any interpretation uncertainties, we obtained these materials in the form of particles with merely identical morphology and size. A detailed electrochemical study revealed a much lower capacity and energy density retention for phase-transforming Na₃V₂(PO₄)₂F₃ compared to NaVPO₄F, which exhibits a single-phase behavior over a wide range of Na concentrations. The reasons for the inferior rate capability and temperature tolerance for the phase-separating Na₃V₂(PO₄)₂F₃ material should be affiliated with slow phase boundary propagation. We hope that the comprehensive information on limiting factors provided for both mechanisms is useful for the further optimization of electrode materials toward a new generation of high-power and low-temperature metal-ion batteries.