Impact of Anion Vacancies on the Local and Electronic Structures of Iron-Based Oxyfluoride Electrodes

Burbano, Mario; Duttine, Mathieu; Morgan, Benjamin J.; Borkiewicz, Olaf J.; Chapman, Karena W.; Wattiaux, Alain; Demourgues, Alain; Groult, Henri; Salanne, Mathieu; Dambournet, Damien

doi:10.1021/acs.jpclett.8b03503

Title: Impact of Anion Vacancies on the Local and Electronic Structures of Iron-Based Oxyfluoride Electrodes

Journal Article · Wed Dec 19 00:00:00 EST 2018 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.8b03503· OSTI ID:1504931

Burbano, Mario ^[1]; Duttine, Mathieu ^[2]; Morgan, Benjamin J. ^[3]; Borkiewicz, Olaf J. ^[4];

^[4]; Wattiaux, Alain ^[2]; Demourgues, Alain ^[2]; Groult, Henri ^[1];

^[1];

^[1]

Sorbonne Univ., Paris (France); Reseau sur le Stockage Electrochimique de l’Energie (RS2E), Amiens Cedex (France)
Univ. de Bordeaux, Pessac (France)
Univ. of Bath, Claverton Down (United Kingdom); The Faraday Institution, Didcot (United Kingdom)
Argonne National Lab. (ANL), Argonne, IL (United States)

The properties of crystalline solids can be significantly modified by deliberately introducing point defects. Understanding these effects, however, requires understanding the changes in geometry and electronic structure of the host material. Here we report the effect of forming anion vacancies, via dehydroxylation, in a hexagonal tungsten-bronze-structured iron oxyfluoride, which has potential use as a lithium-ion battery cathode. Our combined pair distribution function and density functional theory analysis indicates that oxygen vacancy formation is accompanied by spontaneous rearrangement of fluorine anions and vacancies, producing dual pyramidal (FeF₄)-O-(FeF₄) structural units containing 5-fold-coordinated Fe atoms. The addition of lattice oxygen introduces new electronic states above the top of the valence band, with a corresponding reduction in the optical band gap from 4.05 to 2.05 eV. In conclusion, this band gap reduction relative to the FeF₃ parent material is correlated with a significant improvement in lithium insertion capability relative to a defect-free compound.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division; Royal Society United Kingdom; The Faraday Institution

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1504931

Journal Information:: Journal of Physical Chemistry Letters, Vol. 10, Issue 1; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 13 works

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