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Room-temperature electrochemical fluoride (de)insertion into CsMnFeF6
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Andrews, Jessica L., McClure, Eric T., Jew, Kenneth K., Preefer, Molleigh B., Irshad, Ahamed, Lertola, Matthew J., Robertson, Daniel D., Salamat, Charlene Z., Brady, Michael J., Piper, Louis F. J., Tolbert, Sarah H., Nelson Weker, Johanna, Chmelka, Bradley F., Dunn, Bruce S., Narayan, Sri R., West, William C. and Melot, Brent C. (2022) Room-temperature electrochemical fluoride (de)insertion into CsMnFeF6. ACS Energy Letters (7). pp. 2340-2348. doi:10.1021/acsenergylett.2c01324 ISSN 2380-8195.
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WRAP-Room-temperature-electrochemical-fluoride-de-insertion-defect-pyrochlore-2022.pdf - Accepted Version - Requires a PDF viewer. Download (4Mb) | Preview |
Official URL: https://doi.org/10.1021/acsenergylett.2c01324
Abstract
We report on the reversible, electrochemical (de)fluorination of CsMnFeF6 at room temperature using a liquid electrolyte. CsMnFeF6 was synthesized via three methods (hydrothermal, ceramic, and mechanochemical), each of which yields products in a defect pyrochlore structure with varying particle sizes and phase purities. After three galvanostatic cycles, approximately one fluoride ion can be reversibly (de)inserted into mechanochemical CsMnFeF6 for multiple cycles. Ex situ X-ray absorption spectroscopy confirmed that both Mn2+ and Fe3+ are redox active. The cell impedance decreases after one cycle, suggesting that the formation of fluoride vacancies in early cycles generates mixed-valent Fe and enhances the material’s conductivity. Ex situ synchrotron diffraction revealed subtle expansion and contraction of the CsMnFeF6 cubic lattice on insertion and removal, respectively, during the first two cycles. New reflections intensify in the ex situ diffraction patterns from cycle 3, corresponding to a topotactic transformation of CsMnFeF6 from the pyrochlore structure into an orthorhombic polytype that continues cycling fluoride ions reversibly.
| Item Type: | Journal Article | ||||||||||||
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| Subjects: | Q Science > QD Chemistry T Technology > TJ Mechanical engineering and machinery T Technology > TK Electrical engineering. Electronics Nuclear engineering |
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| Divisions: | Faculty of Science, Engineering and Medicine > Engineering > WMG (Formerly the Warwick Manufacturing Group) | ||||||||||||
| SWORD Depositor: | Library Publications Router | ||||||||||||
| Library of Congress Subject Headings (LCSH): | Lithium ion batteries , Lithium ion batteries -- Materials, Electrodes , Fluorine, Electrochemistry , Solid state batteries -- Materials, Energy storage | ||||||||||||
| Journal or Publication Title: | ACS Energy Letters | ||||||||||||
| Publisher: | American Chemical Society (ACS) | ||||||||||||
| ISSN: | 2380-8195 | ||||||||||||
| Official Date: | 21 June 2022 | ||||||||||||
| Dates: |
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| Number: | 7 | ||||||||||||
| Page Range: | pp. 2340-2348 | ||||||||||||
| DOI: | 10.1021/acsenergylett.2c01324 | ||||||||||||
| Status: | Peer Reviewed | ||||||||||||
| Publication Status: | Published | ||||||||||||
| Access rights to Published version: | Restricted or Subscription Access | ||||||||||||
| Date of first compliant deposit: | 7 July 2022 | ||||||||||||
| Date of first compliant Open Access: | 21 June 2023 | ||||||||||||
| RIOXX Funder/Project Grant: |
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