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

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

doi:10.1021/acs.chemmater.2c01474

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

Journal Article · Mon Jul 18 00:00:00 EDT 2022 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.2c01474· OSTI ID:1963457

^[1]; Zeng, Yan ^[2]; Bennett, Tyler ^[3]; Patil, Shripad ^[4]; Keum, Jong K. ^[5]; ^[3]; ^[6]; ^[1]; Giovine, Raynald ^[7]; ^[1]; ^[8]; ^[1]; ^[7]; ^[9]; ^[3]; ^[1]

Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division; Univ. of Tennessee, Knoxville, TN (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences and Neutron Scattering Division
Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
Univ. of California, Santa Barbara, CA (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Energy Storage and Distributed Resources Division

Here, we have designed and tested several synthesis routes targeting a highly fluorinated disordered rocksalt (DRX) cathode, Li_1.2Mn_0.4Ti_0.4O_1.6F_0.4, 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 Li₂Mn_0.33Ti_0.66O₃ 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.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division; USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Vehicle Technologies Office (VTO); National Science Foundation (NSF)

Grant/Contract Number:: AC02-05CH11231; SC0012704

OSTI ID:: 1963457

Journal Information:: Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 15 Vol. 34; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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