Structural and electronic changes in induced by lithium intercalation
Phys. Rev. Materials 9, 125402 – Published 5 December, 2025
DOI: https://doi.org/10.1103/pk6l-ds6m
Abstract
Despite extensive research on oxide battery cathodes that transcend classical cationic redox activity, the detailed interplay between structural transformations and electronic redox processes remains insufficiently understood. We report a detailed study of the sequential structural and electronic changes in upon lithium intercalation, characterized by powder x-ray and neutron diffraction alongside Ru and O -edge x-ray absorption spectroscopy (XAS), and guided by operando synchrotron x-ray diffraction. During delithiation, evolves from a well-defined monoclinic state to a complex trigonal phase via multiple intermediate structures, marked by significant changes in Ru-O bond distances that closely track the transition from a classical cationic redox to an unconventional process centered at oxygen states. Armed with high-quality atomic structural descriptions, computational models of the O -edge XAS closely reproduce the experimentally observed spectral shifts. Lastly, we relate observations of electrochemical hysteresis with concurrent changes in the pathways of structural and electronic transitions. Our results not only clarify the mechanisms underpinning voltage hysteresis in a model for lattice oxygen redox but also underscore the importance of structural fidelity in modeling redox behavior when this type of complex reactivity is present.
Physics Subject Headings (PhySH)
Collections
This article appears in the following collection:
Functional Materials Through Electrochemical Ion Insertion
The Editors of Physical Review Materials are pleased to present the Collection on Functional Materials Through Electrochemical Ion Insertion, highlighting cutting-edge advances in the theory, synthesis, and structural and physical characterization of dynamic property modulation (e.g. optical, electrical, mechanical, chemical) using electrochemical ion insertion into solid state hosts. The Collection is being guest-edited by Veronica Augustyn and Nina Balke of North Carolina State University (USA). Every article published in this collection underwent a rigorous peer review process, adhering to the same high standards applied to all papers. The Physical Review Materials editorial team managed the peer review and made all editorial decisions.
