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Title: The electrochemical storage mechanism in oxy-hydroxyfluorinated anatase for sodium-ion batteries

Replacing lithium ions with sodium ions as the charge carriers in rechargeable batteries 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 TiO 2 affects the sodium storage mechanism. From pair distribution function analysis, we observe that sodium ions are inserted into 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 that the intercalation voltage is sensitive to the anion coordination environment of the vacancy. Sodiation to higher concentrations induces a phase transition toward a disordered rhombohedral structure, similar to that observed in defect-free TiO 2. Finally, we find that 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.
Authors:
 [1] ;  [2] ; ORCiD logo [3] ;  [4] ; ORCiD logo [5] ;  [5] ;  [1] ; ORCiD logo [2] ; ORCiD logo [6]
  1. Sorbonne Univ., Paris (France). Physico-chimie des électrolytes et nano-systèmes interfaciaux
  2. Tokyo Univ. of Science, Shinjuku (Japan). Dept.of Applied Chemistry
  3. Univ. of Bath, Claverton Down (United Kingdom). Dept. of Chemistry
  4. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS). X-ray Science Division
  5. Univ. de Caen, Caen (France). Lab. CRISMAT, ENSICAEN
  6. Sorbonne Univ., Paris (France). Physico-chimie des électrolytes et nano-systèmes interfaciaux; Réseau sur le Stockage Electrochimique de l'Energie (RS2E), Amiens (France)
Publication Date:
Grant/Contract Number:
AC02-06CH11357
Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry Frontiers (Online)
Additional Journal Information:
Journal Name: Inorganic Chemistry Frontiers (Online); Journal Volume: 5; Journal Issue: 5; Journal ID: ISSN 2052-1553
Publisher:
Royal Society of Chemistry
Research Org:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Scientific User Facilities Division
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE
OSTI Identifier:
1484019

Li, Wei, Fukunishi, Mika, Morgan, Benjamin J., Borkiewicz, Olaf. J., Pralong, Valérie, Maignan, Antoine, Groult, Henri, Komaba, Shinichi, and Dambournet, Damien. The electrochemical storage mechanism in oxy-hydroxyfluorinated anatase for sodium-ion batteries. United States: N. p., Web. doi:10.1039/c8qi00185e.
Li, Wei, Fukunishi, Mika, Morgan, Benjamin J., Borkiewicz, Olaf. J., Pralong, Valérie, Maignan, Antoine, Groult, Henri, Komaba, Shinichi, & Dambournet, Damien. The electrochemical storage mechanism in oxy-hydroxyfluorinated anatase for sodium-ion batteries. United States. doi:10.1039/c8qi00185e.
Li, Wei, Fukunishi, Mika, Morgan, Benjamin J., Borkiewicz, Olaf. J., Pralong, Valérie, Maignan, Antoine, Groult, Henri, Komaba, Shinichi, and Dambournet, Damien. 2018. "The electrochemical storage mechanism in oxy-hydroxyfluorinated anatase for sodium-ion batteries". United States. doi:10.1039/c8qi00185e.
@article{osti_1484019,
title = {The electrochemical storage mechanism in oxy-hydroxyfluorinated anatase for sodium-ion batteries},
author = {Li, Wei and Fukunishi, Mika and Morgan, Benjamin J. and Borkiewicz, Olaf. J. and Pralong, Valérie and Maignan, Antoine and Groult, Henri and Komaba, Shinichi and Dambournet, Damien},
abstractNote = {Replacing lithium ions with sodium ions as the charge carriers in rechargeable batteries 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 into 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 that the intercalation voltage is sensitive to the anion coordination environment of the vacancy. Sodiation to higher concentrations induces a phase transition toward a disordered rhombohedral structure, similar to that observed in defect-free TiO2. Finally, we find that 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.},
doi = {10.1039/c8qi00185e},
journal = {Inorganic Chemistry Frontiers (Online)},
number = 5,
volume = 5,
place = {United States},
year = {2018},
month = {3}
}

Works referenced in this record:

Rapid-acquisition pair distribution function (RA-PDF) analysis
journal, November 2003
  • Chupas, Peter J.; Qiu, Xiangyun; Hanson, Jonathan C.
  • Journal of Applied Crystallography, Vol. 36, Issue 6, p. 1342-1347
  • DOI: 10.1107/S0021889803017564

Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999

Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study
journal, January 1998
  • Dudarev, S. L.; Botton, G. A.; Savrasov, S. Y.
  • Physical Review B, Vol. 57, Issue 3, p. 1505-1509
  • DOI: 10.1103/PhysRevB.57.1505

PDFgetX2: a GUI-driven program to obtain the pair distribution function from X-ray powder diffraction data
journal, July 2004
  • Qiu, Xiangyun; Thompson, Jeroen W.; Billinge, Simon J. L.
  • Journal of Applied Crystallography, Vol. 37, Issue 4, p. 678-678
  • DOI: 10.1107/S0021889804011744

POWDER CELL � a program for the representation and manipulation of crystal structures and calculation of the resulting X-ray powder patterns
journal, June 1996

Two-dimensional detector software: From real detector to idealised image or two-theta scan
journal, January 1996
  • Hammersley, A. P.; Svensson, S. O.; Hanfland, M.
  • High Pressure Research, Vol. 14, Issue 4-6, p. 235-248
  • DOI: 10.1080/08957959608201408