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

Bashian, N. H. et al. (2018) Correlated polyhedral rotations in the absence of polarons during electrochemical insertion of lithium in ReO3. ACS Energy Letters, 3(10), pp. 2513-2519. (doi: 10.1021/acsenergylett.8b01179)

Abstract

Understanding the structural transformations that materials undergo during (de)insertion of Li ions is crucial for designing high-performance intercalation hosts as these deformations can lead to significant capacity fade. Herein, we present a study of the metallic defect perovskite ReO3 to determine 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 numerous techniques, including electrochemical probes, operando X-ray diffraction, X-ray photoelectron spectroscopy, and density functional theory calculations, we find that the cubic structure of ReO3 experiences multiple phase changes involving the correlated twisting of rigid octahedral subunits upon lithiation. This results in exceptionally poor long-term cyclability due to large strains upon lithiation, even though metallic character is maintained throughout. This suggests that phase transformations during alkali ion intercalation are the result of local strains in the lattice and not exclusively due to polaron migration.

• Item Type: Articles
• Status: Published
• Refereed: Yes
• Glasgow Author(s) Enlighten ID: UNSPECIFIED
• Authors: Bashian, N. H., Zhou, S., Zuba, M., Ganose, A. M., Stiles, J. W., Ee, A., Ashby, D. S., Scanlon, D. O., Piper, L. F.J., Dunn, B., and Melot, B. C.
• College/School: College of Science and Engineering > School of Chemistry
• Journal Name: ACS Energy Letters
• Publisher: American Chemical Society
• ISSN: 2380-8195
• ISSN (Online): 2380-8195
• Published Online: 12 September 2018
• Copyright Holders: Copyright © 2018 American Chemical Society
• First Published: First published in ACS Energy Letters 3(10): 2513-2519
• Publisher Policy: Reproduced under a Creative Commons License

Project Code	Award No	Project Name	Principal Investigator	Funder's Name	Funder Ref	Lead Dept
69353	1	High throughput microwave synthesis of Li-ion battery materials	Serena Corr	Engineering and Physical Sciences Research Council (EPSRC)	EP/N001982/1	SCHOOL OF CHEMISTRY
72707	1	(Iso)alloxazine incorporating electrodes as high-performance organic energy storage materials	Graeme Cooke	Engineering and Physical Sciences Research Council (EPSRC)	EP/P00315X/1	CHEM - CHEMISTRY