First-principles study of iron oxyfluorides and lithiation of FeOF
Author(s)Chevrier, Vincent L.; Hautier, Geoffroy; Ong, Shyue Ping; Doe, Robert E.; Ceder, Gerbrand
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First-principles studies of iron oxyfluorides in the FeF[subscript 2] rutile framework (FeO[subscript x]F[subscript 2−x], 0≤x≤1) are performed using density functional theory (DFT) in the general gradient approximation (GGA) with a Hubbard U correction. Studies of O/F orderings reveal FeOF to be particularly stable compared to other FeO[subscript x]F[subscript 2−x] (x≠1) structures, where FeF[subscript 2]-FeOF mixing is not energetically favored. The band gap of FeF[subscript 2] is found to decrease as oxygen is substituted into its structure. The GGA + U electronic structure evolves from that of a Mott-Hubbard insulator (x=0) to a charge transfer semiconductor (x=1). Lithiation studies reveal that lithiation sites offering mixed O/F environments are the most stable. An insertion voltage plateau up to Li[subscript 0.5]FeOF on lithiation is found, in agreement with recent Li-ion battery experiments. The energetics of further lithiation with respect to conversion scenarios are discussed.
DepartmentMassachusetts Institute of Technology. Department of Materials Science and Engineering
Physical Review B
American Physical Society
Chevrier, Vincent L., Geoffroy Hautier, Shyue Ping Ong, Robert E. Doe, and Gerbrand Ceder. “First-principles study of iron oxyfluorides and lithiation of FeOF.” Physical Review B 87, no. 9 (March 2013).
Author's final manuscript