Revealing the Chemical and Structural Complexity of Electrochemical Ion Exchange in Layered Oxide Materials
Soft chemistry techniques, such as ion exchange, hold great potential for the development of battery electrode materials that cannot be stabilized via conventional equilibrium synthesis methods. Nevertheless, the intricate mechanisms governing ion exchange remain elusive. Herein, we investigate the evolution of the long-range and local structure, as well as the ion (de)intercalation mechanism during electrochemical Li-to-Na ion exchange initiated from an O3-type lithium-layered oxide cathode. The in situ-formed mixed-cation electrolyte leads to competitive intercalation of Li and Na ions. While Li ion intercalation predominates at the beginning of initial discharge, Na ion cointercalation into a different layer results in ion redistribution and phase separation, with the emergence of a P3–Na phase alongside an O3–Li phase. Further, this study spatially resolves the heterogeneous nature of electrochemical ion exchange reactions within individual particles and provides insights into the correlations between local Ni redox processes and phase separation. Overall, electrochemical ion exchange leads to a mixed-phase cathode and alters its reaction kinetics. Those findings have important implications for the development of new metastable materials for renewable energy devices and ion separation applications.
Authors
- Enyuan Hu (ORCID: https://orcid.org/0000-0002-1881-4534)
- Zhisen Jiang
- Jia‐Mian Hu (ORCID: https://orcid.org/0000-0002-7579-6440)
- Yanbao Fu (ORCID: https://orcid.org/0000-0001-7752-680X)
- Dennis Nordlund (ORCID: https://orcid.org/0000-0001-9524-6908)
- Muhammad Mominur Rahman (ORCID: https://orcid.org/0000-0001-6814-456X)
- Dong Hou (ORCID: https://orcid.org/0000-0002-0942-688X)
- Raphaële J. Clément (ORCID: https://orcid.org/0000-0002-3611-1162)
- Yijin Liu (ORCID: https://orcid.org/0000-0002-8417-2488)
- Linqin Mu (ORCID: https://orcid.org/0000-0003-4421-4820)
- Sami Sainio (ORCID: https://orcid.org/0000-0002-9268-0124)
- Lu‐Fang Ma (ORCID: https://orcid.org/0000-0002-5601-6437)
- Minyi Dai (ORCID: https://orcid.org/0000-0001-8908-7234)
- Feng Lin (ORCID: https://orcid.org/0000-0002-3729-3148)
- Emily Foley (ORCID: https://orcid.org/0000-0003-2173-7899)
- Jue Liu (ORCID: https://orcid.org/0000-0002-4453-910X)
- Jin Zhang (ORCID: https://orcid.org/0009-0008-7695-1415)
Institutions
- Oak Ridge National Laboratory (US)
- University of Wisconsin–Madison (US)
- Lawrence Berkeley National Laboratory (US)
- University of California, Santa Barbara (US)
- Brookhaven National Laboratory (US)
- SLAC National Accelerator Laboratory (US)
- Stanford Synchrotron Radiation Lightsource (US)
- Arizona State University (US)
- University of Louisiana at Lafayette (US)
- Virginia Tech (US)
Publication Details
- Journal
- Journal of the American Chemical Society
- Published
- 2024-09-17
- DOI
- https://doi.org/10.1021/jacs.4c08089
- Citations
- 13
- Primary Topic
- Advancements in Battery Materials
- Type
- article
- Field-Weighted Citation Impact
- 2.71
Funders
- National Science Foundation
- U.S. Department of Energy
- Arizona State University
- Office of Science
- American Chemical Society Petroleum Research Fund
- University of California, Santa Barbara
- Materials Research Science and Engineering Center, Harvard University
- Division of Materials Research
- Office of Advanced Cyberinfrastructure
- Division of Chemical, Bioengineering, Environmental, and Transport Systems
- Basic Energy Sciences
- Argonne National Laboratory
- Oak Ridge National Laboratory
- Brookhaven National Laboratory
- SLAC National Accelerator Laboratory