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

preprint
submitted on 22.04.2020 and posted on 23.04.2020 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.

Funding

European research council (788144)

History

Email Address of Submitting Author

andrew.goodwin@chem.ox.ac.uk

Institution

University of Oxford

Country

UK

ORCID For Submitting Author

0000-0001-9231-3749

Declaration of Conflict of Interest

No conflict of interest

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