Evidence of Bulk Proton Insertion in Nanostructured Anatase and Amorphous TiO2 Electrodes
| Autor: | Véronique Balland, Jae-Young Cho, Jean-Marie Tarascon, Benoît Limoges, Kenneth D. M. Harris, Nikolina Makivic |
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| Přispěvatelé: | Laboratoire d'Electrochimie Moléculaire (LEM (UMR_7591)), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Paris (UP), Chaire Chimie du solide et énergie, Chimie du solide et de l'énergie (CSE), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS) |
| Rok vydání: | 2021 |
| Předmět: |
Anatase
Materials science General Chemical Engineering Oxide [CHIM.MATE]Chemical Sciences/Material chemistry 02 engineering and technology General Chemistry 010402 general chemistry 021001 nanoscience & nanotechnology Electrochemistry 01 natural sciences 0104 chemical sciences Amorphous solid Crystallinity chemistry.chemical_compound chemistry Chemical engineering Materials Chemistry [CHIM]Chemical Sciences Gravimetric analysis Proton-coupled electron transfer [CHIM.OTHE]Chemical Sciences/Other 0210 nano-technology Faraday efficiency |
| Zdroj: | Chemistry of Materials Chemistry of Materials, American Chemical Society, 2021, 33 (9), pp.3436-3448. ⟨10.1021/acs.chemmater.1c00840⟩ |
| ISSN: | 1520-5002 0897-4756 |
| Popis: | Crystalline structures and lattice water molecules are believed to strongly influence the ability of metal oxides to reversibly and rapidly insert protons in aqueous batteries. In the present work, we performed a systematic analysis of the electrochemical charge storage properties of nanostructured TiO2 electrodes composed of either anatase or amorphous TiO2 in a mild buffered aqueous electrolyte. We demonstrate that both materials allow reversible bulk proton insertion up to a maximal reversible gravimetric capacity of ~150 mA·h·g-1. We also show that the TiO2 crystallinity governs the energetics of the charge storage process, with a phase transition for anatase, while having little effect on either the interfacial charge-transfer kinetics or the apparent rate of proton diffusivity within the metal oxide. Finally, with both TiO2 electrodes, reversible proton insertion leads to gravimetric capacities as high as 95 mA·h·g-1 at 75 C. We also reveal two competitive reactions decreasing the Coulombic efficiency at low rates, i.e. hydrogen evolution and a non-faradaic self-discharge reaction. Overall, this work provides a comprehensive overview of the proton-coupled electrochemical reactivity of TiO2 and highlights the key issues to be solved in order to truly benefit from the unique properties of protons as fast charge carriers in metal oxides. |
| Databáze: | OpenAIRE |
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