Controlled Formation of Mixed Nanoscale Domains of High Capacity Fe2O3–FeF3 Conversion Compounds by Direct Fluorination

Zhou, Hui; Ruther, Rose E.; Adcock, Jamie; Zhou, Wu; Dai, Sheng; Nanda, Jagjit

doi:10.1021/acsnano.5b00191

Controlled Formation of Mixed Nanoscale Domains of High Capacity Fe₂O₃–FeF₃ Conversion Compounds by Direct Fluorination

Journal Article · Sun Feb 22 00:00:00 EST 2015 · ACS Nano

DOI:https://doi.org/10.1021/acsnano.5b00191· OSTI ID:1286723

Zhou, Hui ^[1]; Ruther, Rose E. ^[1]; Adcock, Jamie ^[2]; Zhou, Wu ^[1]; Dai, Sheng ^[3]; Nanda, Jagjit ^[4]

Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science and Technology Division
Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry
Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry; Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science and Technology Division; Univ. of Tennessee, Knoxville, TN (United States). Bredesen Centre for Interdisciplinary Science and Graduate Education. Dept. of Chemical and Biomolecular Engineering

In this paper, we report a direct fluorination method under fluorine gas atmosphere using a fluidized bed reactor for converting nanophase iron oxide (n-Fe₂O₃) to an electrochemically stable and higher energy density iron oxyfluoride/fluoride phase. Interestingly, no noticeable bulk iron oxyfluoride phase (FeOF) phase was observed even at fluorination temperature close to 300 °C. Instead, at fluorination temperatures below 250 °C, scanning transmission electron microscopy coupled with electron energy loss spectroscopy (STEM-EELS) and X-ray photoelectron spectroscopy (XPS) analysis showed surface fluorination with nominal composition, Fe₂O_3-xF_2x (x < 1). At fluorination temperatures of 275 °C, STEM-EELS results showed porous interconnected nanodomains of FeF₃ and Fe₂O₃ coexisting within the same particle, and overall the particles become less dense after fluorination. We performed potentiometric intermittent titration and electrochemical impedance spectroscopy studies to understand the lithium diffusion (or apparent diffusion) in both the oxyfluoride and mixed phase FeF₃ + Fe₂O₃ composition, and correlate the results to their electrochemical performance. Finally and further, we analyze from a thermodynamical perspective, the observed formation of the majority fluoride phase (77% FeF₃) and the absence of the expected oxyfluoride phase based on the relative formation energies of oxide, fluoride, and oxyfluorides.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1286723

Journal Information:: ACS Nano, Journal Name: ACS Nano Journal Issue: 3 Vol. 9; ISSN 1936-0851

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
conversion electrode
fluoride
fluorination
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