Alternative Solid‐State Synthesis Route for Highly Fluorinated Disordered Rock‐Salt Cathode Materials for High‐Energy Lithium‐Ion Batteries
Abstract Fluorination has been identified as a key element for enabling the stable cycling of earth‐abundant manganese‐based disordered rock salt (DRX) cathodes. However, fluorination in the DRX bulk remains a challenge for scalable solid‐state synthesis. In this study, a tailored reaction pathway is proposed to synthesize a highly fluorinated DRX. It is demonstrated for the first time that the unconventional precursors, Li 6 MnO 4 , MnF 2 , and TiO 2 , can avoid the formation of Mn‐based intermediates (such as Li 2 (Mn,Ti)O 3, LiMnO 2 , and Mn 3 O 4 ), which, once formed, persist until the synthesis temperature reaches close to or above that required for fluorine volatility. Therefore, this method can form a highly fluorinated DRX with a composition of Li 1.23 Mn 0.40 Ti 0.37 O 2−y F y ( y = 0.29–0.34) at a low temperature (800 °C) relative to that required for conventional DRX solid‐state reactions (≥900 °C). Li 1.23 Mn 0.40 Ti 0.37 O 2−y F y ( y = 0.29–0.34) delivers a specific capacity above 300 mAh g −1 and a specific energy of 980 Wh kg −1 at 30 °C. Detailed characterization reveals that this DRX phase reversibly utilizes Mn 2+/3+ redox in the low‐voltage region and Mn 3+/4+ redox in the middle‐voltage range, whereas reversible oxygen redox is observed at high potentials.
Authors
- Yanbao Fu (ORCID: https://orcid.org/0000-0001-7752-680X)
- Nathan J. Szymanski (ORCID: https://orcid.org/0000-0003-2255-9676)
- Young‐Woon Byeon (ORCID: https://orcid.org/0000-0003-2684-7720)
- Seonghun Jeong (ORCID: https://orcid.org/0009-0002-4068-2854)
- Finn Babbe (ORCID: https://orcid.org/0000-0002-9131-638X)
- Raphaële J. Clément (ORCID: https://orcid.org/0000-0002-3611-1162)
- Johanna Nelson Weker (ORCID: https://orcid.org/0000-0001-6856-3203)
- Krishna Prasad Koirala (ORCID: https://orcid.org/0000-0002-9137-917X)
- Wanli Yang (ORCID: https://orcid.org/0000-0003-0666-8063)
- Bernardine L. D. Rinkel (ORCID: https://orcid.org/0000-0003-4455-7313)
- Haegyeom Kim (ORCID: https://orcid.org/0000-0002-5962-8244)
- Gi‐Hyeok Lee (ORCID: https://orcid.org/0000-0003-2516-2586)
- David Milsted (ORCID: https://orcid.org/0000-0003-0415-910X)
- Bryan D. McCloskey (ORCID: https://orcid.org/0000-0001-6599-2336)
- Martin Kunz (ORCID: https://orcid.org/0000-0001-9769-9900)
- Venkata Sai Avvaru (ORCID: https://orcid.org/0000-0001-8287-0621)
- Tianyu Li (ORCID: https://orcid.org/0000-0003-0142-7252)
- Chongmin Wang (ORCID: https://orcid.org/0000-0003-3327-0958)
- Eunryeol Lee (ORCID: https://orcid.org/0000-0003-2868-5649)
- Otávio Cabral-Marques (ORCID: https://orcid.org/0000-0002-3183-6236)
- Vincent Battaglia
Institutions
- Pacific Northwest National Laboratory (US)
- Lawrence Berkeley National Laboratory (US)
- University of California, Santa Barbara (US)
- Environmental Molecular Sciences Laboratory (US)
- SLAC National Accelerator Laboratory (US)
- Stanford Synchrotron Radiation Lightsource (US)
- University of California, Berkeley (US)
Publication Details
- Journal
- Advanced Energy Materials
- Published
- 2025-04-08
- DOI
- https://doi.org/10.1002/aenm.202500492
- Citations
- 6
- Primary Topic
- Advancements in Battery Materials
- Type
- article
- Field-Weighted Citation Impact
- 4.38
Funders
- U.S. Department of Energy
- U.S. Department of Commerce
- Battelle
- Washington State University
- Office of Science
- University of California, Santa Barbara
- Materials Research Science and Engineering Center, Harvard University
- Division of Materials Research
- Biological and Environmental Research
- Vehicle Technologies Office
- Pacific Northwest National Laboratory
- SLAC National Accelerator Laboratory