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

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.