K-Ion Slides in Prussian Blue Analogues

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Abstract

We study the phenomenology of cooperative off-centering of K+ ions in potassiated Prussian blue analogues (PBAs). The principal distortion mechanism by which this off-centering occurs is termed a “K-ion slide”, and its origin is shown to lie in the interaction between local electrostatic dipoles that couple through a combination of electrostatics and elastic strain. Using synchrotron powder X-ray diffraction measurements, we determine the crystal structures of a range of low-vacancy K2M[Fe(CN)6] PBAs (M = Ni, Co, Fe, Mn, Cd) and establish an empirical link between composition, temperature, and slide-distortion magnitude. Our results reflect the common underlying physics responsible for K-ion slides and their evolution with temperature and composition. Monte Carlo simulations driven by a simple model of dipolar interactions and strain coupling reproduce the general features of the experimental phase behavior. We discuss the implications of our study for optimizing the performance of PBA K-ion battery cathode materials and also its relevance to distortions in other, conceptually related, hybrid perovskites.

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Cattermull, J., Roth, N., Cassidy, S. J., Pasta, M., & Goodwin, A. L. (2023). K-Ion Slides in Prussian Blue Analogues. Journal of the American Chemical Society, 145(44), 24249–24259. https://doi.org/10.1021/jacs.3c08751

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