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High substitution rate in TiO2 anatase nanoparticles with cationic vacancies for fast lithium storage
hal.structure.identifier | PHysicochimie des Electrolytes et Nanosystèmes InterfaciauX [PHENIX] | |
dc.contributor.author | LI, Wei | |
hal.structure.identifier | PHysicochimie des Electrolytes et Nanosystèmes InterfaciauX [PHENIX] | |
dc.contributor.author | CORRADINI, Dario | |
hal.structure.identifier | Institut des Molécules et Matériaux du Mans [IMMM] | |
dc.contributor.author | BODY, Monique | |
hal.structure.identifier | Institut des Molécules et Matériaux du Mans [IMMM] | |
dc.contributor.author | LEGEIN, Christophe | |
hal.structure.identifier | PHysicochimie des Electrolytes et Nanosystèmes InterfaciauX [PHENIX] | |
hal.structure.identifier | Réseau sur le stockage électrochimique de l'énergie [RS2E] | |
dc.contributor.author | SALANNE, Mathieu | |
hal.structure.identifier | PHysicochimie des Electrolytes et Nanosystèmes InterfaciauX [PHENIX] | |
dc.contributor.author | MA, Jiwei | |
hal.structure.identifier | X-ray Science Division [XSD] | |
dc.contributor.author | CHAPMAN, Karena W. | |
hal.structure.identifier | X-ray Science Division [XSD] | |
dc.contributor.author | CHUPAS, Peter J. | |
hal.structure.identifier | PHysicochimie des Electrolytes et Nanosystèmes InterfaciauX [PHENIX] | |
dc.contributor.author | ROLLET, Anne-Laure | |
hal.structure.identifier | PHysicochimie des Electrolytes et Nanosystèmes InterfaciauX [PHENIX] | |
dc.contributor.author | JULIEN, Christian | |
hal.structure.identifier | Energy Storage and Conversion, Research Institute of Hydro-Québec | |
dc.contributor.author | ZHAGIB, Karim | |
hal.structure.identifier | PHysicochimie des Electrolytes et Nanosystèmes InterfaciauX [PHENIX] | |
hal.structure.identifier | Institut de Chimie de la Matière Condensée de Bordeaux [ICMCB] | |
dc.contributor.author | DUTTINE, Mathieu | |
hal.structure.identifier | Institut de Chimie de la Matière Condensée de Bordeaux [ICMCB] | |
dc.contributor.author | DEMOURGUES, Alain | |
hal.structure.identifier | PHysicochimie des Electrolytes et Nanosystèmes InterfaciauX [PHENIX] | |
dc.contributor.author | GROULT, Henri | |
hal.structure.identifier | PHysicochimie des Electrolytes et Nanosystèmes InterfaciauX [PHENIX] | |
dc.contributor.author | DAMBOURNET, Damien | |
dc.date.issued | 2015 | |
dc.identifier.issn | 0897-4756 | |
dc.description.abstractEn | 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 O2– anions by monovalent F– and OH– anions resulting in the formation of cationic Ti4+ vacancies (□) whose concentration can be controlled by the reaction temperature. The resulting polyanionic anatase has the general composition Ti1–x–y□x+yO2–4(x+y)F4x(OH)4y, reaching vacancy concentrations of up to 22%, i.e., Ti0.78□0.22O1.12F0.4(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□1-F, and Ti1□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. | |
dc.language.iso | en | |
dc.publisher | American Chemical Society | |
dc.subject.en | Oxides | |
dc.subject.en | Defects in solids | |
dc.subject.en | Anions | |
dc.subject.en | Minerals | |
dc.subject.en | Lithium | |
dc.title.en | High substitution rate in TiO2 anatase nanoparticles with cationic vacancies for fast lithium storage | |
dc.type | Article de revue | |
dc.identifier.doi | 10.1021/acs.chemmater.5b01407 | |
dc.subject.hal | Chimie/Matériaux | |
bordeaux.journal | Chemistry of Materials | |
bordeaux.page | 5014-5019 | |
bordeaux.volume | 27 | |
bordeaux.issue | 14 | |
bordeaux.peerReviewed | oui | |
hal.identifier | hal-01204724 | |
hal.version | 1 | |
hal.popular | non | |
hal.audience | Internationale | |
hal.origin.link | https://hal.archives-ouvertes.fr//hal-01204724v1 | |
bordeaux.COinS | ctx_ver=Z39.88-2004&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.jtitle=Chemistry%20of%20Materials&rft.date=2015&rft.volume=27&rft.issue=14&rft.spage=5014-5019&rft.epage=5014-5019&rft.eissn=0897-4756&rft.issn=0897-4756&rft.au=LI,%20Wei&CORRADINI,%20Dario&BODY,%20Monique&LEGEIN,%20Christophe&SALANNE,%20Mathieu&rft.genre=article |
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