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

  • Author(s): Zaheer, W;
  • Andrews, JL;
  • Parija, A;
  • Hyler, FP;
  • Jaye, C;
  • Weiland, C;
  • Yu, YS;
  • Shapiro, DA;
  • Fischer, DA;
  • Guo, J;
  • Velázquez, JM;
  • Banerjee, S
  • et al.
Abstract

An energy storage paradigm orthogonal to 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. In contrast, the exploration of insertion chemistries 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/deinsertion and bulk diffusion of F ions within the one-dimensional tunnels of submicrometer-sized FeSb2O4 particles at room temperature. The insertion of F ions is evidenced by formal oxidation of the iron centers from Fe2+ to Fe3+ with a lattice volume contraction of <1% at a capacity of one F ion per iron center. The topochemical insertion of F ions is observed to be homogeneous across the FeSb2O4 particles. An approach to screen F-ion insertion electrodes through solution-phase topochemical methods is further demonstrated.

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