High Substitution Rate in TiO2 Anatase Nanoparticles with Cationic Vacancies for Fast Lithium Storage

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• 作者：Wei Li ; Dario Corradini ; Monique Body ; Christophe Legein ; Mathieu Salanne ; Jiwei Ma ; Karena W. Chapman ; Peter J. Chupas ; Anne-Laure Rollet ; Christian Julien ; Karim Zhagib ; Mathieu Duttine ; Alain Demourgues ; Henri Groult ; Damien Dambournet
• 刊名：Chemistry of Materials
• 出版年：2015
• 出版时间：July 28, 2015
• 年：2015
• 卷：27
• 期：14
• 页码：5014-5019
• 全文大小：385K
• ISSN：1520-5002

文摘

Doping is generally used to tune and enhance the properties of metal oxides. However, their chemical composition cannot be readily modified beyond low dopant amounts without disrupting the crystalline atomic structure. In the case of anatase TiO₂, we introduce a new solution-based chemical route allowing the composition to be significantly modified, substituting the divalent O^{2鈥?/sup> anions by monovalent F鈥?/sup> and OH鈥?/sup> anions resulting in the formation of cationic Ti4+ vacancies (鈻? whose concentration can be controlled by the reaction temperature. The resulting polyanionic anatase has the general composition Ti_{1鈥?i>x鈥?i>y}鈻?sub>x+yO_2鈥?(x+y)F_4x(OH)_4y, reaching vacancy concentrations of up to 22%, i.e., Ti_0.78鈻?sub>0.22O_1.12F_0.4(OH)_0.48. Solid-state 19F NMR spectroscopy reveals that fluoride ions can accommodate up to three different environments, depending on Ti and vacancies (i.e. Ti₃-F, Ti₂鈻?sub>1-F, and Ti₁鈻?sub>2-F), with a preferential location close to vacancies. DFT calculations further confirm the fluoride/vacancy ordering. When its characteristics were evaluated as an electrode for reversible Li-ion storage, the material shows a modified lithium reaction mechanism, which has been rationalized by the occurrence of cationic vacancies acting as additional lithium hosting sites within the anatase framework. Finally, the material shows a fast discharging/charging behavior, compared to TiO₂, highlighting the benefits of the structural modifications and paving the way for the design of advanced electrode materials, based on a defect mediated mechanism.}