Electrochemical Oxidative Fluorination of an Oxide Perovskite

We report on the electrochemical fluorination of A-site vacant perovskite ReO3 using high-temperature solid-state cells as well room-temperature liquid electrolytes. Using galvanostatic oxidation and impedance spectroscopy, we find that can be oxidized by approximately 0.5 equiv electrons when in contact with fluoride-rich Results from our density functional theory calculations clearly rule out most intuitive mechanism for charge compensation, whereby F-ions would simply insert onto structure. Operando X-ray diffraction, neutron total scattering measurements, 19F NMR magic-angle spinning were, therefore, used to explore which fluoride ions react electrode during oxidation. Taken together, results indicate a complex structural transformation occurs following stabilize resulting material. While this process fluorinating appears only partially reversible, work demonstrates practical electrolyte cell design evaluate mobility small anions like is robust at room temperature opens new opportunities exploring many materials.