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Electrochemical Oxidative Fluorination of an Oxide Perovskite

preprint
submitted on 23.10.2020, 19:01 and posted on 27.10.2020, 08:42 by Nicholas H. Bashian, Mateusz Zuba, Ahamed Irshad,, Shona Becwar, Julija Vinckeviciute, Warda Rahim, Kent Griffith, Eric T. McClure, Joseph K. Papp, Bryan D. McCloskey, David Scanlon, Bradley F. Chmelka, Anton Van der Ven, Sri Narayan, Louis Piper, Brent Melot
We report the successful electrochemical intercalation of F-ions into a densely packed perovskite oxide from a liquid electrolyte at room temperature. Using galvanostatic oxidation and electrochemical impedance spectroscopy coupled with operando X-ray diffraction, we show that roughly 0.5 equivalents of F-ions can be inserted onto the vacant A-site of the perovskite ReO3. Density functional theory calculations indicate that the intercalated phase is thermodynamically unfavorable compared to other less densely packed polymorphs of ReO3F. Pairing X-ray spectroscopy, neutron total scattering measurements, and magic-angle spinning 19F NMR confirms a rapid decomposition of the product on removal from the cell but nevertheless, these results clearly demonstrate that small anions like fluoride can be intercalated into solids as readily as alkali cations at room temperature, which opens new opportunities to electrochemically fluorinate many new materials.

Funding

EFRC Center for Synthetic Control Across Length-scales for Advancing Rechargeables (SCALAR)

Basic Energy Sciences

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The Faraday Institution

Engineering and Physical Sciences Research Council

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Design of Mixed Anion Inorganic Semiconductors for Energy Conversion

European Research Council

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MATERIALS CHEMISTRY HIGH END COMPUTING CONSORTIUM

Engineering and Physical Sciences Research Council

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HIGH END COMPUTING MATERIALS CHEMISTRY CONSORTIUM

Engineering and Physical Sciences Research Council

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Materials Research Science and Engineering Center at UCSB

Directorate for Mathematical & Physical Sciences

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History

Email Address of Submitting Author

melot@usc.edu

Institution

University of Southern California

Country

United States

ORCID For Submitting Author

0000-0002-7078-8206

Declaration of Conflict of Interest

no conflict of interest

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