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 KTiOPO-type NaVPOF and a well-studied NaV(PO)F.

Resolving the Seeming Contradiction between the Superior Rate Capability of Prussian Blue Analogues and the Extremely Slow Ionic Diffusion.

The superior rate capabilities of metal ion battery materials based on Prussian blue analogues (PBAs) are almost exclusively ascribed to the extremely fast solid-state ionic diffusion, which is possible due to structural voids and spacious three-dimensional channels in PBA structures. We performed a detailed electroanalytical study of alkali ion diffusivities in nanosized cation-rich and cation-poor PBAs obtained as particles or electrodeposited films in both aqueous and non-aqueous media, which resulted in a solid conclusion about the exceptionally slow ionic transport. We show that the impressive rate capability of PBA materials is determined solely by the small size of the primary particles of PBAs, while the apparent diffusion coefficients are 3-5 orders of magnitude lower than those reported in earlier studies.

The Misconception of Mg Insertion into Prussian Blue Analogue Structures from Aqueous Solution.

Prussian blue analogues (PBAs) are commonly believed to reversibly insert divalent ions, such as calcium and magnesium, rendering them as perspective cathode materials for aqueous magnesium-ion batteries. In this study, the occurrence of Mg insertion into nanosized PBA materials is shown to be a misconception and conclusive evidence is provided for the unfeasibility of this process for both cation-rich and cation-poor nickel, iron, and copper hexacyanoferrates. Based on structural, electrochemical, IR spectroscopy, and quartz crystal microbalance data, the charge compensation of PBA redox can be attributed to protons rather than to divalent ions in aqueous Mg solution.