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.

Development of vanadium-based polyanion positive electrode active materials for high-voltage sodium-based batteries.

Polyanion compounds offer a playground for designing prospective electrode active materials for sodium-ion storage due to their structural diversity and chemical variety. Here, by combining a NaVPO4F composition and KTiOPO4-type framework via a low-temperature (e.g., 190 °C) ion-exchange synthesis approach, we develop a high-capacity and high-voltage positive electrode active material. When tested in a coin cell configuration in combination with a Na metal negative electrode and a NaPF6-based non-aqueous electrolyte solution, this cathode active material enables a discharge capacity of 136 mAh g-1 at 14.3 mA g-1 with an average cell discharge voltage of about 4.0 V. Furthermore, a specific discharge capacity of 123 mAh g-1 at 5.7 A g-1 is also reported for the same cell configuration. Through ex situ and operando structural characterizations, we also demonstrate that the reversible Na-ion storage at the positive electrode occurs mostly via a solid-solution de/insertion mechanism.