DataVXChemistry of MaterialsPaper
journal article·2022-08-09Open access

Understanding the Fluorination of Disordered Rocksalt Cathodes through Rational Exploration of Synthesis Pathways

Nathan J. Szymanski, Yan Zeng, Tyler Bennett, Shripad Patil, Jong K. Keum, Ethan C. Self, Jianming Bai, Zijian Cai, Raynald Giovine, Bin Ouyang, Feng Wang, Christopher J. Bartel, Raphaële J. Clément, Wei Tong, Jagjit Nanda, Gerbrand Ceder

Chemistry of Materials· Volume 34· Issue 15
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Source abstract

Abstract

We have designed and tested several synthesis routes targeting a highly fluorinated disordered rocksalt (DRX) cathode, Li1.2Mn0.4Ti0.4O1.6F0.4, with each route rationalized by thermochemical analysis. Precursor combinations were screened to raise the F chemical potential and avoid the formation of LiF, which inhibits fluorination of the targeted DRX phase. MnF2 was used as a reactive source of F, and Li6MnO4, LiMnO2, and Li2Mn0.33Ti0.66O3 were tested as alternative Li sources. Each synthesis procedure was monitored using a multi-modal suite of characterization techniques including X-ray diffraction, nuclear magnetic resonance, thermogravimetric analysis, and differential scanning calorimetry. From the resulting data, we advance the understanding of oxyfluoride synthesis by outlining the key factors limiting F solubility. At low temperatures, MnF2 consistently reacts with the Li source to form LiF as an intermediate phase, thereby trapping F in strong Li–F bonds. LiF can react with Li2TiO3 to form a highly lithiated and fluorinated DRX (Li3TiO3F); however, MnO is not easily incorporated into this DRX phase. Although higher temperatures typically increase solubility, the volatility of LiF above its melting point (848 °C) inhibits fluorination of the DRX phase. Based on these findings, metastable synthesis techniques are suggested for future work on DRX fluorination.
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Research context

Energy storage

OpenAlex topics: Advancements in Battery Materials · Inorganic Fluorides and Related Compounds · Inorganic Chemistry and Materials

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

Affiliations

Department of Materials Science & Engineering, UC Berkeley, Berkeley, California 94720, United States

Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States

Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37830, United States

Bredesen Center for Interdisciplinary Research and Graduate Education, University of Tennessee Knoxville, Knoxville, Tennessee 37996, United States

Center for Nanophase Materials Sciences and Neutron Scattering Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37830, United States

National Synchrotron Light Source II, Brookhaven National Laboratory, Upton, New York 11973, United States

Materials Department, UC Santa Barbara, Santa Barbara, California 93106, United States

Materials Research Laboratory, UC Santa Barbara, Santa Barbara, California 93106, United States

Energy & Photon Science Directorate, Brookhaven National Laboratory, Upton, New York 11973, United States

Energy Storage and Distributed Resources Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States

Funding

Vehicle Technologies Program · Umicore · National Science Foundation

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