DataVXAdvanced Energy MaterialsPaper
journal article·2025-07Open access

Alternative Solid‐State Synthesis Route for Highly Fluorinated Disordered Rock‐Salt Cathode Materials for High‐Energy Lithium‐Ion Batteries

Venkata Sai Avvaru, Tianyu Li, Gi‐Hyeok Lee, Young‐Woon Byeon, Krishna Prasad Koirala, Otavio Jovino Marques, Bernardine L. D. Rinkel, Yanbao Fu, David Milsted, Seonghun Jeong, Nathan J. Szymanski, Martin Kunz, Finn Babbe, Eunryeol Lee, Vincent Battaglia, Bryan D. McCloskey, Johanna Nelson Weker, Chongmin Wang, Wanli Yang, Raphaële J. Clément, Haegyeom Kim

Advanced Energy Materials· Volume 15· Issue 28
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Abstract

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, Li6MnO4, MnF2, and TiO2, can avoid the formation of Mn‐based intermediates (such as Li2(Mn,Ti)O3, LiMnO2, and Mn3O4), 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 Li1.23Mn0.40Ti0.37O2−yFy (y = 0.29–0.34) at a low temperature (800 °C) relative to that required for conventional DRX solid‐state reactions (≥900 °C). Li1.23Mn0.40Ti0.37O2−yFy (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 Mn2+/3+ redox in the low‐voltage region and Mn3+/4+ redox in the middle‐voltage range, whereas reversible oxygen redox is observed at high potentials.
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Research context

Energy storage

OpenAlex topics: Advancements in Battery Materials · Advanced Battery Materials and Technologies · Extraction and Separation Processes

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

Materials Sciences Division Lawrence Berkeley National Laboratory Berkeley CA 94720 USA

Materials Department and Materials Research Laboratory University of California Santa Barbara CA 93106 USA

Advanced Light Source Lawrence Berkeley National Laboratory Berkeley CA 94720 USA

Physical and Computational Sciences Directorate Pacific Northwest National Laboratory Richland WA 99354 USA

Stanford Synchrotron Radiation Lightsource SLAC National Accelerator Laboratory Menlo Park CA 94025 USA

Energy Storage and Distributed Resources Division Lawrence Berkeley National Laboratory Berkeley CA 94720 USA

Department of Materials Science and Engineering University of California Berkeley CA 94720 USA

Chemical Sciences Division Lawrence Berkeley National Laboratory Berkeley CA 94720 USA

Department of Chemical and Biomolecular Engineering University of California Berkeley CA 94720 USA

Environmental Molecular Sciences Division Pacific Northwest National Laboratory Richland WA 99354 USA

Funding

Vehicle Technologies Office

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