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cc_2020_pbamilling.pdf (1.3 MB)

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

preprint
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.

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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