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. Our finding calls for a reconsideration of the apparent facility of ionic transport in PBA materials and deeper analysis of the charge carrier-host interactions in PBAs.