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Title: Controlled Formation of Mixed Nanoscale Domains of High Capacity Fe 2O 3–FeF 3 Conversion Compounds by Direct Fluorination

Abstract

In this paper, we report a direct fluorination method under fluorine gas atmosphere using a fluidized bed reactor for converting nanophase iron oxide (n-Fe 2O 3) 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, Fe 2O 3-xF 2x (x < 1). At fluorination temperatures of 275 °C, STEM-EELS results showed porous interconnected nanodomains of FeF 3 and Fe 2O 3 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 FeF 3 + Fe 2O 3 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% FeF 3) and the absence of the expected oxyfluoride phase based on the relative formation energiesmore » of oxide, fluoride, and oxyfluorides.« less

Authors:
 [1];  [1];  [2];  [1];  [3];  [4]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science and Technology Division
  2. Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry
  3. Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry; Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
  4. 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
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1286723
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
ACS Nano
Additional Journal Information:
Journal Volume: 9; Journal Issue: 3; Journal ID: ISSN 1936-0851
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; conversion electrode; fluoride; fluorination; nano-Fe2O3

Citation Formats

Zhou, Hui, Ruther, Rose E., Adcock, Jamie, Zhou, Wu, Dai, Sheng, and Nanda, Jagjit. Controlled Formation of Mixed Nanoscale Domains of High Capacity Fe2O3–FeF3 Conversion Compounds by Direct Fluorination. United States: N. p., 2015. Web. doi:10.1021/acsnano.5b00191.
Zhou, Hui, Ruther, Rose E., Adcock, Jamie, Zhou, Wu, Dai, Sheng, & Nanda, Jagjit. Controlled Formation of Mixed Nanoscale Domains of High Capacity Fe2O3–FeF3 Conversion Compounds by Direct Fluorination. United States. doi:10.1021/acsnano.5b00191.
Zhou, Hui, Ruther, Rose E., Adcock, Jamie, Zhou, Wu, Dai, Sheng, and Nanda, Jagjit. Sun . "Controlled Formation of Mixed Nanoscale Domains of High Capacity Fe2O3–FeF3 Conversion Compounds by Direct Fluorination". United States. doi:10.1021/acsnano.5b00191. https://www.osti.gov/servlets/purl/1286723.
@article{osti_1286723,
title = {Controlled Formation of Mixed Nanoscale Domains of High Capacity Fe2O3–FeF3 Conversion Compounds by Direct Fluorination},
author = {Zhou, Hui and Ruther, Rose E. and Adcock, Jamie and Zhou, Wu and Dai, Sheng and Nanda, Jagjit},
abstractNote = {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, Fe2O3-xF2x (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.},
doi = {10.1021/acsnano.5b00191},
journal = {ACS Nano},
number = 3,
volume = 9,
place = {United States},
year = {2015},
month = {2}
}

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