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.
Original language | English |
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Pages (from-to) | 2513-2519 |
Number of pages | 7 |
Journal | ACS Energy Letters |
Volume | 3 |
Issue number | 10 |
DOIs | |
Publication status | Published - 12 Oct 2018 |
Bibliographical note
Funding Information:B.C.M. acknowledges support through a CAREER award from the National Science Foundation under Grant No. DMR-1554204 for the electrochemical studies and Research Corporation for Science Advancement for a Cottrell Scholar award. B.C.M. and L.F.J.P also thank Research Corporation for Science Advancement for funding through the Scialog program. M.Z. was supported as part of the Multidisciplinary GAANN in Smart Energy Materials, a Graduate Areas of National Need, funded by the U.S. Department of Education, under Award No. P200A150135 This work made use of the ARCHER UK National Supercomputing Service (http://www. archer.ac.uk), via membership of the UK’s HEC Materials Chemistry Consortium, which is funded by EPSRC (EP/ L000202). D.O.S. acknowledges support from the EPSRC (EP/N001982/1 and EP/P00315X/1) and membership in the Materials Design Network. A.M.G. thanks Diamond Light Source for the cosponsorship of a studentship on the EPSRC Centre for Doctoral Training in Molecular Modeling and Materials Science (EP/L015862/1). Additional support was received from the Faraday Institution (Grant No. FIRG003). D.S.A. and B.D. were supported by the Nanostructures for Electrical Energy Storage (NEES), an Energy Frontier Research Center (EFRC) funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DESC0001160. Use of the Advanced Photon Source at Argonne National Laboratory was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357.
Publisher Copyright:
© Copyright 2018 American Chemical Society.
ASJC Scopus subject areas
- Chemistry (miscellaneous)
- Renewable Energy, Sustainability and the Environment
- Fuel Technology
- Energy Engineering and Power Technology
- Materials Chemistry