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Reversible Room-Temperature Fluoride-Ion Insertion in a Tunnel-Structured Transition Metal Oxide Host



Cherno Jaye, Wasif Zaheer, Justin L. Andrews, Forrest P. Hyler, Conan Weiland, David A. Shapiro, Jinghua Guo, Jesus M. Velazquez, Sarbajit Banerjee, Abhishek Parija, Daniel A. Fischer


An energy storage paradigm orthogonal to conventional Li-ion battery chemistries can be conceptualized by employing anions as the primary charge carriers. F-ion conversion chemistries show promise but have limited cyclability as a result of the significant change in volume of active electrodes upon metal–metal-fluoride interconversion and must further operate at elevated temperatures to achieve F-ion diffusion. In contrast, the exploration of intercalation chemistries as a means of mitigating volumetric expansion has been stymied by the lack of hosts amenable to reversible F-ion insertion at room temperature. Here we show the reversible and homogeneous topochemical insertion and deinsertion of F-ions within the 1D tunnels of submicron-sized FeSb2O4 particles at room temperature. The insertion of F-ions is evidenced by formal oxidation of the iron centers from Fe2+ to Fe3+ and is accompanied by a small lattice volume contraction of <1% at a capacity of one F-ion per iron center. The topochemical insertion of F-ions is further observed to be homogenous across the FeSb2O4 particles. The design principles developed from elucidation of F-ion insertion in FeSb2O4 suggest a route to designing oxidative insertion hosts that fulfill the distinctive needs of anion batteries.
ACS Energy Letters


Energy, Batteries, Intercalation, Fluoride-ion, Lithium-ion, XRD, XAS, HAXPES, STXM


Jaye, C. , Zaheer, W. , Andrews, J. , Hyler, F. , Weiland, C. , Shapiro, D. , Guo, J. , Velazquez, J. , Banerjee, S. , Parija, A. and Fischer, D. (2020), Reversible Room-Temperature Fluoride-Ion Insertion in a Tunnel-Structured Transition Metal Oxide Host, ACS Energy Letters, [online], (Accessed July 18, 2024)


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Created July 6, 2020, Updated December 31, 2022