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Electrochemical oxidative fluorination of an oxide perovskite

DOI: 10.1021/acs.chemmater.1c01594 DOI Help

Authors: Nicholas H. Bashian (University of Southern California) , Mateusz Zuba (Binghamton University) , Ahamed Irshad (University of Southern California) , Shona M. Becwar (University of California, Santa Barbara) , Julija Vinckeviciute (University of California, Santa Barbara) , Warda Rahim (University College London) , Kent J. Griffith (University of Cambridge) , Eric T. Mcclure (University of Southern California) , Joseph K. Papp (University of California, Berkeley) , Bryan D. Mccloskey (University of California, Berkeley) , David O. Scanlon (University College London; Diamond Light Source; he Faraday Institution) , Bradley F. Chmelka (University of California, Santa Barbara) , Anton Van Der Ven (University of California, Santa Barbara) , Sri R. Narayan (University of Southern California) , Louis F. J. Piper (University of Warwick) , Brent Melot (University of Southern California)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Chemistry Of Materials

State: Published (Approved)
Published: July 2021
Diamond Proposal Number(s): 22250

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

Journal Keywords: Anions; Electrodes; Chemical structure; Electrochemical cells; Electrolytes

Diamond Keywords: Batteries; Fluoride-ion

Subject Areas: Materials, Chemistry, Energy

Instruments: I09-Surface and Interface Structural Analysis

Other Facilities: Advanced Photon Source

Discipline Tags:

Energy Storage Energy Physical Chemistry Energy Materials Chemistry Material Sciences Perovskites Metallurgy

Technical Tags:

Spectroscopy X-ray Photoelectron Spectroscopy (XPS) Hard X-ray Photoelectron Spectroscopy (HAXPES)