Revisiting Conversion Reaction Mechanisms in Lithium Batteries: Lithiation-Driven Topotactic Transformation in FeF2

Karki, Khim; Wu, Lijun; Ma, Ying; Armstrong, Mark J.; Holmes, Justin D.; Garofalini, Stephen H.; Zhu, Yimei; Stach, Eric A.; Wang, Feng

doi:10.1021/jacs.8b07740

Title: Revisiting Conversion Reaction Mechanisms in Lithium Batteries: Lithiation-Driven Topotactic Transformation in FeF₂

Journal Article · Tue Nov 20 00:00:00 EST 2018 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.8b07740· OSTI ID:1492791

Karki, Khim ^[1]; Wu, Lijun ^[2]; Ma, Ying ^[3]; Armstrong, Mark J. ^[4];

^[4]; Garofalini, Stephen H. ^[5];

^[2];

^[6];

^[1]

Brookhaven National Lab. (BNL), Upton, NY (United States). Sustainable Energy Technologies Dept.
Brookhaven National Lab. (BNL), Upton, NY (United States). Dept. of Condensed Matter Physics and Materials Science
Univ. of Wisconsin, Eau Claire, WI (United States). Materials Science & Engineering
Univ. College Cork, Cork (Ireland). School of Chemistry and the Tyndall National Inst.; Trinity College Dublin, Dublin (Ireland)
Rutgers Univ., Piscataway, NJ (United States). Dept. of Materials Science and Engineering
Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN); Univ. of Pennsylvania, Philadelphia, PA (United States). Dept. of Materials Science and Engineering

Intercalation-type electrodes have now been commonly employed in today’s batteries as such materials are capable of storing and releasing lithium reversibly via topotactic transformation, conducive to small structural change, but they have limited interstitial sites to hold Li. In contrast, conversion electrodes feature high Li-storage capacity, but often undergo large structural change during (de)lithiation, resulting in cycling instability. One exception is iron fluoride (FeF₂), a conversion-type cathode that exhibits both high capacity and high cycling stability. Herein, we report a lithiation-driven topotactic transformation in a single crystal of FeF2, unveiled by in situ visualization of the spatial and crystallographic correlation between the parent and converted phases. Specifically, conversion in FeF₂ resembles the intercalation process but involves transport of both Li⁺ and Fe²⁺ ions within the F-anion array, leading to formation of Fe preferentially along specific crystallographic orientations of FeF₂. Throughout the process, the F-anion framework is retained, creating a checkerboard-like structure, within which the volume change is largely compensated, thereby enabling the high cyclability in FeF₂. Lastly, findings from this study, with unique insights into conversion reaction mechanisms, may help to pave the way for designing conversion-type electrodes for the next-generation high energy lithium batteries.

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Research Organization:: Brookhaven National Lab. (BNL), Upton, NY (United States)

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

Grant/Contract Number:: SC0012704

OSTI ID:: 1492791

Report Number(s):: BNL-210929-2019-JAAM

Journal Information:: Journal of the American Chemical Society, Vol. 140, Issue 51; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 29 works

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Title: Revisiting Conversion Reaction Mechanisms in Lithium Batteries: Lithiation-Driven Topotactic Transformation in FeF2

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