Electrochemical Storage Mechanism in Oxy-Hydroxyfluorinated Anatase for Sodium-Ion Batteries

Wei Li, Mika Fukunishi, Benjamin J. Morgan, Olaf J. Borkiewicz, Valérie Pralong, Antoine Maignan, Henri Groult, Shinichi Komaba, Damien Dambournet

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Abstract

Replacing lithium ions as the charge carriers in rechargeable batteries with sodium ions can induce noticeable differences in the electrochemical storage mechanisms of electrode materials. Many material parameters, such as particle size, morphology, and the presence of defects are known to further affect the storage mechanism. Here, we report an investigation of how the introduction of titanium vacancies into anatase TiO2 affects the sodium storage-mechanism. From pair distribution function analysis, we observe that sodium ions are inserted in titanium vacancies at the early stage of the discharge process. This is supported by density functional theory calculations, which predict that sodium insertion is more favourable at vacancies than at interstitial sites. Our calculations also show the intercalation voltage is sensitive to the anion coordination environment of the. Sodiation to higher concentrations induces a phase transition toward a disordered rhombohedral structure, similar to that observed in defect-free TiO2. Finally, we find the x-ray diffraction pattern of the rhombohedral phase drastically changes depending on the composition and degree of disorder, providing further comprehension on the sodium storage mechanism of anatase.
Original languageEnglish
Pages (from-to)1100-1106
JournalInorganic Chemistry Frontiers
Volume5
Issue number5
Early online date29 Mar 2018
DOIs
Publication statusPublished - 1 May 2018

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Sodium
Ions
Vacancies
Titanium
Defects
Secondary batteries
Intercalation
Charge carriers
Lithium
Diffraction patterns
Distribution functions
Density functional theory
Anions
Phase transitions
Particle size
titanium dioxide
X rays
Electrodes
Electric potential
Chemical analysis

Cite this

Li, W., Fukunishi, M., Morgan, B. J., Borkiewicz, O. J., Pralong, V., Maignan, A., ... Dambournet, D. (2018). Electrochemical Storage Mechanism in Oxy-Hydroxyfluorinated Anatase for Sodium-Ion Batteries. Inorganic Chemistry Frontiers, 5(5), 1100-1106. https://doi.org/10.1039/c8qi00185e

Electrochemical Storage Mechanism in Oxy-Hydroxyfluorinated Anatase for Sodium-Ion Batteries. / Li, Wei; Fukunishi, Mika; Morgan, Benjamin J.; Borkiewicz, Olaf J.; Pralong, Valérie; Maignan, Antoine; Groult, Henri; Komaba, Shinichi; Dambournet, Damien.

In: Inorganic Chemistry Frontiers, Vol. 5, No. 5, 01.05.2018, p. 1100-1106.

Research output: Contribution to journalArticle

Li, W, Fukunishi, M, Morgan, BJ, Borkiewicz, OJ, Pralong, V, Maignan, A, Groult, H, Komaba, S & Dambournet, D 2018, 'Electrochemical Storage Mechanism in Oxy-Hydroxyfluorinated Anatase for Sodium-Ion Batteries', Inorganic Chemistry Frontiers, vol. 5, no. 5, pp. 1100-1106. https://doi.org/10.1039/c8qi00185e
Li, Wei ; Fukunishi, Mika ; Morgan, Benjamin J. ; Borkiewicz, Olaf J. ; Pralong, Valérie ; Maignan, Antoine ; Groult, Henri ; Komaba, Shinichi ; Dambournet, Damien. / Electrochemical Storage Mechanism in Oxy-Hydroxyfluorinated Anatase for Sodium-Ion Batteries. In: Inorganic Chemistry Frontiers. 2018 ; Vol. 5, No. 5. pp. 1100-1106.
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