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Correlated polyhedral rotations in the absence of polarons during electrochemical insertion of lithium in ReO3

DOI: 10.1021/acsenergylett.8b01179 DOI Help

Authors: Nicholas H. Bashian (University of Southern California) , Shiliang Zhou (University of Southern California) , Mateusz Zuba (Binghamton University) , Alex M. Ganose (University College London; Diamond Light Source) , Joseph W. Stiles (University of Southern California) , Allyson Ee (University of Southern California) , David S. Ashby (University of California, Los Angeles,) , David O. Scanlon (University College London; Diamond Light Source; The Faraday Institution) , Louis F. J. Piper (Binghamton University) , Bruce S. Dunn (University of California, Los Angeles) , Brent C. Melot (University of Southern California)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Acs Energy Letters

State: Published (Approved)
Published: September 2018

Abstract: Understanding the structural transformations that materials undergo during the insertion and deinsertion of Li-ions is crucial for designing high performance intercalation hosts as these deformations can lead to significant capacity fade over time. Here we present a study of the metallic defect perovskite ReO3, with the goal of determining whether these distortions are driven by polaronic charge transport (i.e. the electrons and ions moving through the lattice in a coupled way) due to the semiconducting nature of most oxide hosts. Employing a range of techniques including galvanostatic/potentiometric electrochemical probes, operando X-ray diffraction, X-ray photoelectron spectroscopy, and density functional theory calculations we nd that the cubic structure of ReO3 experiences multiple phase changes involving the correlated twisting of rigid octahedral subunits during the insertion of two equivalents of Li-ions. This extensive rearrangement of the structure results in exceptionally poor long-term cyclability due to large strains that result within the structure, all in spite of the fact that the phase retains its metallic character for all values of Li content from ReO3 to Li2ReO3. These results suggest that phase transformations during alkali ion intercalation are the result of local strains in the lattice and not exclusively due to polaron migration.

Subject Areas: Chemistry, Materials, Energy

Facility: Advanced Photon Source