title: Cationically Substituted Bi0.7Fe0.3OCl Nanosheets as Li Ion Battery Anodes.
abstract: Cation substitution of Bi3+with Fe3+in BiOCl leads to the formation of ionically layered Bi0.7Fe0.3OCl nanosheets. The synthesis follows a hydrolysis route using bismuth(III) nitrate and iron(III) chloride, followed by postannealing at 500 °C. Room temperature electrical conductivity improves from 6.11 × 10-8S/m for BiOCl to 6.80 × 10-7S/m for Bi0.7Fe0.3OCl. Correspondingly, the activation energy for electrical conduction reduces from 862 meV for pure BiOCl to 310 meV for Bi0.7Fe0.3OCl. These data suggest improved charge mobility in Bi0.7Fe0.3OCl nanosheets. Density functional theory calculations confirm this behavior by predicting a high density of states near the Fermi level for Bi0.7Fe0.3OCl. The improvement in electrical conductivity is exploited in the electrochemical performance of Bi0.7Fe0.3OCl nanosheets. The insertion capacity of Li+ions shows an increase of 2.5×, from 215 mAh·.g-1for undoped BiOCl to 542 mAh·g-1for Bi0.7Fe0.3OCl after 50 cycles at a current density of 50 mA·g-1. Thus, the direct substitution of Bi3+sites with Fe3+in BiOCl results in nanosheets of an ionically layered ternary semiconductor compound which is attractive for Li ion battery anode applications.
authors.affiliation: Department of Mechanical Engineering and Materials Science, Washington University in St. Louis , St. Louis, Missouri 63130, United States.|Department of Nanotechnology and Advanced Materials Engineering, Sejong University , Seoul, 05006, Korea.
authors.forename: Yoon
authors.identifier: http://orcid.org/0000-0002-5774-6183
authors.initials: Y
authors.lastname: Myung
authors.affiliation: Department of Materials Science and Engineering, University of Illinois at Urbana-Champaign , Urbana, Illinois 61801, United States.|Department of Chemistry, Sungkyunkwan University , Suwon 16419, Korea.
authors.forename: Jaewon
authors.initials: J
authors.lastname: Choi
authors.affiliation: Department of Mechanical Engineering and Materials Science, Washington University in St. Louis , St. Louis, Missouri 63130, United States.
authors.forename: Fei
authors.initials: F
authors.lastname: Wu
authors.affiliation: Department of Mechanical Engineering and Materials Science, Washington University in St. Louis , St. Louis, Missouri 63130, United States.
authors.forename: Sriya
authors.initials: S
authors.lastname: Banerjee
authors.affiliation: Center for Nanoscience, Department of Physics and Astronomy, University of Missouri , St. Louis, Missouri 63121, United States.
authors.forename: Eric H
authors.initials: EH
authors.lastname: Majzoub
authors.affiliation: Department of Chemistry, Sungkyunkwan University , Suwon 16419, Korea.
authors.forename: Jaewon
authors.initials: J
authors.lastname: Jin
authors.affiliation: Department of Chemistry, Sungkyunkwan University , Suwon 16419, Korea.
authors.forename: Seung Uk
authors.initials: SU
authors.lastname: Son
authors.affiliation: Department of Materials Science and Engineering, University of Illinois at Urbana-Champaign , Urbana, Illinois 61801, United States.
authors.forename: Paul V
authors.identifier: http://orcid.org/0000-0003-4079-8160
authors.initials: PV
authors.lastname: Braun
authors.affiliation: Department of Mechanical Engineering and Materials Science, Washington University in St. Louis , St. Louis, Missouri 63130, United States.|Institute of Materials Science and Engineering, Washington University in St. Louis , St. Louis, Missouri 63130, United States.
authors.forename: Parag
authors.identifier: http://orcid.org/0000-0003-0401-8155
authors.initials: P
authors.lastname: Banerjee
keywords: Li ion batteries; doping; electrochemistry; hydrolysis; metal oxychloride