Alternative Solid‐State Synthesis Route for Highly Fluorinated Disordered Rock‐Salt Cathode Materials for High‐Energy Lithium‐Ion Batteries
Year: 2025
Type: article
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.
Source: Advanced Energy Materials
Authors: 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
Institutions: Lawrence Berkeley National Laboratory, University of California, Santa Barbara, Advanced Light Source, Pacific Northwest National Laboratory, SLAC National Accelerator Laboratory, Stanford Synchrotron Radiation Lightsource, University of California, Berkeley, Environmental Molecular Sciences Laboratory
Language: English
Subfield: Electrical and Electronic Engineering
Field: Engineering
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $5,790
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
Awards: G1141670404, G1202769797, G125460123, G1286236842, G1337544421, G1369386836, G138090931, G1451874870, G1647566209, G1899721271, G223002938, G2232042528, G2506945562, G2510423872, G2758699378, G2820049545, G2988778103, G3083819904, G391136020, G3967535168, G401861217, G419881185, G4281768896, G42916606, G4501827968, G4796240486, G495867719, G498139845, G5321382714, G5373841109, G5726405315, G613759197, G6282714480, G6652958823, G7665161096, G7787287669, G8135867528, G821644656, G969889393
OpenAlex ID: W4409269652