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Filling Vacancies in a Prussian Blue Analogue Using Mechanochemical Post-Synthetic Modification

submitted on 22.04.2020, 17:47 and posted on 23.04.2020, 12:39 by John Cattermull, Samuel Wheeler, Kevin Hurlbutt, Mauro Pasta, Andrew Goodwin

Mechanochemical grinding of polycrystalline powders of the Prussian blue analogue (PBA) Mn[Co(CN)$_{\textbf6}$]$_{\textbf{2/3}}\boldsymbol\Box_{\textbf{1/3}}\cdot\boldmath x$H$_{\textbf 2}$O and K$_{\textbf 3}$Co(CN)$_{\textbf 6}$ consumes the latter and chemically modifies the former. A combination of inductively-coupled plasma and X-ray powder diffraction measurements suggests the hexacyanometallate vacancy fraction in this modified PBA is reduced by approximately one third under the specific conditions we explore. We infer the mechanochemically-driven incorporation of [Co(CN)$_{\textbf 6}$]$^{\textbf 3-}$ ions onto the initially-vacant sites, coupled with intercalation of charge-balancing K$^+$ ions within the PBA framework cavities. Our results offer a new methodology for the synthesis of low vacancy PBAs, unlocking novel, high capacity PBA battery materials.


European research council (788144)


Email Address of Submitting Author


University of Oxford



ORCID For Submitting Author


Declaration of Conflict of Interest

No conflict of interest


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