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Cationically Substituted Bi0.7Fe0.3OCl Nanosheets as Li Ion Battery Anodes

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journal contribution
posted on 2017-04-07, 00:00 authored by Yoon Myung, Jaewon Choi, Fei Wu, Sriya Banerjee, Eric H. Majzoub, Jaewon Jin, Seung Uk Son, Paul V. Braun, Parag Banerjee
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 × 10–8 S/m for BiOCl to 6.80 × 10–7 S/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–1 for undoped BiOCl to 542 mAh·g–1 for 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.

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