A Reversible Phase Transition for Sodium Insertion in Anatase TiO2

Wei Li, Mika Fukunishi, Benjamin Morgan, Olaf Borkiewicz, Karena Chapman, Valérie Pralong, Antoine Maignan, Oleg Lebedev, Jiwei Ma, Henri Groult, Shinichi Komaba, Damien Dambournet

Research output: Contribution to journalArticle

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Abstract

Anatase TiO2 is a potential negative electrode for sodium-ion batteries. The
sodium storage mechanism is, however, still under debate, yet its comprehension is required to optimize the electrochemical properties. To clarify the sodium storage mechanism occurring in anatase, we have used both electrochemical and chemical routes from which we obtained similar trends. During the first discharge, an irreversible plateau region is observed which corresponds to the insertion of Na+ within the interstitial sites of anatase and is accompanied by a drastic loss of the long-range order as revealed by X-ray diffraction, high resolution of high angle annular dark-field scanning transmission electron microscope (HAADF-STEM), and pair distribution function (PDF) analysis. Further structural analysis of the total scattering data indicates that the sodiated phase displays a layered-like rhombohedral R3m structure built from the stacking of Ti and Na slabs. Because of the initial 3D network of anatase, the reduced phase shows strong disorder due to cationic intermixing between the Ti and Na slabs and the refined chemical formula is (Na0.43Ti0.57)3a0.22Na0.39Ti0.39)3bO2, where □ refers to vacancy. The presence of high valence Ti ions in the Na layers induces a contraction of the c-parameter as compared to the ordered phase. Upon desodiation, the structure further amorphized and the local structure probed by PDF is shown to be similar to the anatase TiO2, suggesting that the 3D network is recovered. The reversible sodium insertion/deinsertion is thus attributed to the rhombohedral active phase formed during the first discharge, and an oxidized phase featuring the local structure of anatase. Due to the amorphous nature of the two phases, the potential-composition curves are characterized by a sloping curve. Finally, a comparison between the intercalation of lithium and sodium into anatase TiO2 performed by DFT calculations confirmed that, for the sodiated phase, the rhombohedral structure is more stable than the tetragonal phase observed during the lithiation of nanoparticles.
LanguageEnglish
Pages1836-1844
JournalChemistry of Materials
Volume29
Issue number4
Early online date7 Feb 2017
DOIs
StatusPublished - 28 Feb 2017

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Titanium dioxide
Phase transitions
Sodium
Distribution functions
Ions
Intercalation
titanium dioxide
Electrochemical properties
Lithium
Discrete Fourier transforms
Structural analysis
Vacancies
Electron microscopes
Scattering
Nanoparticles
Scanning
X ray diffraction
Electrodes
Chemical analysis

Cite this

Li, W., Fukunishi, M., Morgan, B., Borkiewicz, O., Chapman, K., Pralong, V., ... Dambournet, D. (2017). A Reversible Phase Transition for Sodium Insertion in Anatase TiO2. Chemistry of Materials, 29(4), 1836-1844. https://doi.org/10.1021/acs.chemmater.7b00098

A Reversible Phase Transition for Sodium Insertion in Anatase TiO2. / Li, Wei; Fukunishi, Mika; Morgan, Benjamin; Borkiewicz, Olaf; Chapman, Karena; Pralong, Valérie; Maignan, Antoine; Lebedev, Oleg; Ma, Jiwei; Groult, Henri; Komaba, Shinichi; Dambournet, Damien.

In: Chemistry of Materials, Vol. 29, No. 4, 28.02.2017, p. 1836-1844.

Research output: Contribution to journalArticle

Li, W, Fukunishi, M, Morgan, B, Borkiewicz, O, Chapman, K, Pralong, V, Maignan, A, Lebedev, O, Ma, J, Groult, H, Komaba, S & Dambournet, D 2017, 'A Reversible Phase Transition for Sodium Insertion in Anatase TiO2', Chemistry of Materials, vol. 29, no. 4, pp. 1836-1844. https://doi.org/10.1021/acs.chemmater.7b00098
Li, Wei ; Fukunishi, Mika ; Morgan, Benjamin ; Borkiewicz, Olaf ; Chapman, Karena ; Pralong, Valérie ; Maignan, Antoine ; Lebedev, Oleg ; Ma, Jiwei ; Groult, Henri ; Komaba, Shinichi ; Dambournet, Damien. / A Reversible Phase Transition for Sodium Insertion in Anatase TiO2. In: Chemistry of Materials. 2017 ; Vol. 29, No. 4. pp. 1836-1844.
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AU - Pralong, Valérie

AU - Maignan, Antoine

AU - Lebedev, Oleg

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N2 - Anatase TiO2 is a potential negative electrode for sodium-ion batteries. Thesodium storage mechanism is, however, still under debate, yet its comprehension is required to optimize the electrochemical properties. To clarify the sodium storage mechanism occurring in anatase, we have used both electrochemical and chemical routes from which we obtained similar trends. During the first discharge, an irreversible plateau region is observed which corresponds to the insertion of Na+ within the interstitial sites of anatase and is accompanied by a drastic loss of the long-range order as revealed by X-ray diffraction, high resolution of high angle annular dark-field scanning transmission electron microscope (HAADF-STEM), and pair distribution function (PDF) analysis. Further structural analysis of the total scattering data indicates that the sodiated phase displays a layered-like rhombohedral R3m structure built from the stacking of Ti and Na slabs. Because of the initial 3D network of anatase, the reduced phase shows strong disorder due to cationic intermixing between the Ti and Na slabs and the refined chemical formula is (Na0.43Ti0.57)3a□0.22Na0.39Ti0.39)3bO2, where □ refers to vacancy. The presence of high valence Ti ions in the Na layers induces a contraction of the c-parameter as compared to the ordered phase. Upon desodiation, the structure further amorphized and the local structure probed by PDF is shown to be similar to the anatase TiO2, suggesting that the 3D network is recovered. The reversible sodium insertion/deinsertion is thus attributed to the rhombohedral active phase formed during the first discharge, and an oxidized phase featuring the local structure of anatase. Due to the amorphous nature of the two phases, the potential-composition curves are characterized by a sloping curve. Finally, a comparison between the intercalation of lithium and sodium into anatase TiO2 performed by DFT calculations confirmed that, for the sodiated phase, the rhombohedral structure is more stable than the tetragonal phase observed during the lithiation of nanoparticles.

AB - Anatase TiO2 is a potential negative electrode for sodium-ion batteries. Thesodium storage mechanism is, however, still under debate, yet its comprehension is required to optimize the electrochemical properties. To clarify the sodium storage mechanism occurring in anatase, we have used both electrochemical and chemical routes from which we obtained similar trends. During the first discharge, an irreversible plateau region is observed which corresponds to the insertion of Na+ within the interstitial sites of anatase and is accompanied by a drastic loss of the long-range order as revealed by X-ray diffraction, high resolution of high angle annular dark-field scanning transmission electron microscope (HAADF-STEM), and pair distribution function (PDF) analysis. Further structural analysis of the total scattering data indicates that the sodiated phase displays a layered-like rhombohedral R3m structure built from the stacking of Ti and Na slabs. Because of the initial 3D network of anatase, the reduced phase shows strong disorder due to cationic intermixing between the Ti and Na slabs and the refined chemical formula is (Na0.43Ti0.57)3a□0.22Na0.39Ti0.39)3bO2, where □ refers to vacancy. The presence of high valence Ti ions in the Na layers induces a contraction of the c-parameter as compared to the ordered phase. Upon desodiation, the structure further amorphized and the local structure probed by PDF is shown to be similar to the anatase TiO2, suggesting that the 3D network is recovered. The reversible sodium insertion/deinsertion is thus attributed to the rhombohedral active phase formed during the first discharge, and an oxidized phase featuring the local structure of anatase. Due to the amorphous nature of the two phases, the potential-composition curves are characterized by a sloping curve. Finally, a comparison between the intercalation of lithium and sodium into anatase TiO2 performed by DFT calculations confirmed that, for the sodiated phase, the rhombohedral structure is more stable than the tetragonal phase observed during the lithiation of nanoparticles.

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