Peer-Reviewed Journal Details
Mandatory Fields
Karki, K.; Wu, L.; Ma, Y.; Armstrong, M. J.; Holmes, J. D.; Garofalini, S. H.; Zhu, Y.; Stach, E. A.; Wang, F.
2018
December
Journal of the American Chemical Society
Revisiting Conversion Reaction Mechanisms in Lithium Batteries: Lithiation-Driven Topotactic Transformation in FeF2
Published
Optional Fields
140
51
17915
17922
Intercalation-type electrodes have now been commonly employed in today’s batteries due to their capability 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 phas-es. 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 ori-entations 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. 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 lithium batteries.
Washington, DC, USA
0002-7863
https://doi.org/10.1021/jacs.8b07740
10.1021/jacs.8b07740
Grant Details