The electrochemical storage mechanism in oxy-hydroxyfluorinated anatase for sodium-ion batteries
Abstract
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.
- Authors:
-
[3];
[5];
[2];
[6]
- Sorbonne Univ., Paris (France). Physico-chimie des électrolytes et nano-systèmes interfaciaux
- Tokyo Univ. of Science, Shinjuku (Japan). Dept.of Applied Chemistry
- Univ. of Bath, Claverton Down (United Kingdom). Dept. of Chemistry
- Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS). X-ray Science Division
- Univ. de Caen, Caen (France). Lab. CRISMAT, ENSICAEN
- 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:
- Research Org.:
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division
- OSTI Identifier:
- 1484019
- Grant/Contract Number:
- AC02-06CH11357
- Resource 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
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE
Citation Formats
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., 2018.
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. https://doi.org/10.1039/c8qi00185e
Li, Wei, Fukunishi, Mika, Morgan, Benjamin J., Borkiewicz, Olaf. J., Pralong, Valérie, Maignan, Antoine, Groult, Henri, Komaba, Shinichi, and Dambournet, Damien. Thu .
"The electrochemical storage mechanism in oxy-hydroxyfluorinated anatase for sodium-ion batteries". United States. https://doi.org/10.1039/c8qi00185e. https://www.osti.gov/servlets/purl/1484019.
@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 = {Thu Mar 29 00:00:00 EDT 2018},
month = {Thu Mar 29 00:00:00 EDT 2018}
}
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Works referenced in this record:
Room-Temperature Synthesis of High Surface Area Anatase TiO 2 Exhibiting a Complete Lithium Insertion Solid Solution
journal, August 2013
- Patra, Snehangshu; Davoisne, Carine; Bruyère, Stéphanie
- Particle & Particle Systems Characterization, Vol. 30, Issue 12
On the electrochemical encounter between sodium and mesoporous anatase TiO 2 as a Na-ion electrode
journal, January 2016
- Louvain, N.; Henry, A.; Daenens, L.
- CrystEngComm, Vol. 18, Issue 23
A new sodium storage mechanism of TiO 2 for sodium ion batteries
journal, January 2016
- Yan, Dong; Pan, Likun
- Inorganic Chemistry Frontiers, Vol. 3, Issue 4
Rationalization of Intercalation Potential and Redox Mechanism for A 2 Ti 3 O 7 (A = Li, Na)
journal, December 2013
- Rousse, Gwenaelle; Arroyo-de Dompablo, M. Elena; Senguttuvan, Premkumar
- Chemistry of Materials, Vol. 25, Issue 24
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
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996
- Kresse, G.; Furthmüller, J.
- Computational Materials Science, Vol. 6, Issue 1, p. 15-50
NaTiO 2 : a layered anode material for sodium-ion batteries
journal, January 2015
- Wu, Di; Li, Xin; Xu, Bo
- Energy & Environmental Science, Vol. 8, Issue 1
The electronic structure and ionic diffusion of nanoscale LiTiO2 anatase
journal, January 2009
- Borghols, W. J. H.; Lützenkirchen-Hecht, D.; Haake, U.
- Physical Chemistry Chemical Physics, Vol. 11, Issue 27
description of lithium intercalation into anatase
journal, October 2010
- Morgan, Benjamin J.; Watson, Graeme W.
- Physical Review B, Vol. 82, Issue 14
Synthesis, Structure, and Magnetic Properties of NaTiO 2
journal, January 1998
- Clarke, S. J.; Fowkes, A. J.; Harrison, A.
- Chemistry of Materials, Vol. 10, Issue 1
From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999
- Kresse, G.; Joubert, D.
- Physical Review B, Vol. 59, Issue 3, p. 1758-1775
Extraordinary Performance of Carbon-Coated Anatase TiO 2 as Sodium-Ion Anode
journal, December 2015
- Tahir, Muhammad Nawaz; Oschmann, Bernd; Buchholz, Daniel
- Advanced Energy Materials, Vol. 6, Issue 4
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
Large Impact of Particle Size on Insertion Reactions. A Case for Anatase Li x TiO 2
journal, April 2007
- Wagemaker, Marnix; Borghols, Wouter J. H.; Mulder, Fokko M.
- Journal of the American Chemical Society, Vol. 129, Issue 14
Role of Lithium Ordering in the Li x TiO 2 Anatase → Titanate Phase Transition
journal, June 2011
- Morgan, Benjamin J.; Watson, Graeme W.
- The Journal of Physical Chemistry Letters, Vol. 2, Issue 14
Reversible magnesium and aluminium ions insertion in cation-deficient anatase TiO2
journal, September 2017
- Koketsu, Toshinari; Ma, Jiwei; Morgan, Benjamin J.
- Nature Materials, Vol. 16, Issue 11
Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces
journal, April 2008
- Perdew, John P.; Ruzsinszky, Adrienn; Csonka, Gábor I.
- Physical Review Letters, Vol. 100, Issue 13
Unfolding the Mechanism of Sodium Insertion in Anatase TiO 2 Nanoparticles
journal, August 2014
- Wu, Liming; Bresser, Dominic; Buchholz, Daniel
- Advanced Energy Materials, Vol. 5, Issue 2
Surface states on NiO (100) and the origin of the contrast reversal in atomically resolved scanning tunneling microscope images
journal, August 1997
- Dudarev, S. L.; Liechtenstein, A. I.; Castell, M. R.
- Physical Review B, Vol. 56, Issue 8
Toward a Better Understanding and Optimization of the Electrochemical Activity of Na-Ion TiO 2 Anatase Anodes Using Uniform Nanostructures and Ionic Liquid Electrolytes
journal, July 2017
- Vázquez-Santos, María B.; Morales, Enrique; Tartaj, Pedro
- ACS Omega, Vol. 2, Issue 7
Dft Data Analysis: Intercalation Of X=(Li, Na, Mg, Ca, Al) Into (F/Oh)-Substituted Anatase Tio2
software, March 2018
- Morgan, Benjamin J.
- Zenodo , 1 zip file (3.1 MB)
Anatase TiO2 nanoparticles for high power sodium-ion anodes
journal, April 2014
- Wu, Liming; Buchholz, Daniel; Bresser, Dominic
- Journal of Power Sources, Vol. 251
DFT dataset: X=(Li,Na,Ca,Mg,Al) Intercalation into (F/OH)-Substituted Anatase TiO2
dataset, January 2018
- Morgan, Benjamin
- University of Bath
Sodium carboxymethyl cellulose as a potential binder for hard-carbon negative electrodes in sodium-ion batteries
journal, July 2014
- Dahbi, Mouad; Nakano, Takeshi; Yabuuchi, Naoaki
- Electrochemistry Communications, Vol. 44
Self-Supported Nanotube Arrays of Sulfur-Doped TiO 2 Enabling Ultrastable and Robust Sodium Storage
journal, January 2016
- Ni, Jiangfeng; Fu, Shidong; Wu, Chao
- Advanced Materials, Vol. 28, Issue 11
A Reversible Phase Transition for Sodium Insertion in Anatase TiO 2
journal, February 2017
- Li, Wei; Fukunishi, Mika; Morgan, Benjamin. J.
- Chemistry of Materials, Vol. 29, Issue 4
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
A new sodiation–desodiation mechanism of the titania-based negative electrode for sodium-ion batteries
journal, January 2016
- Ding, Changsheng; Nohira, Toshiyuki; Hagiwara, Rika
- Physical Chemistry Chemical Physics, Vol. 18, Issue 44
Impact of Particle Size on the Non-Equilibrium Phase Transition of Lithium-Inserted Anatase TiO 2
journal, February 2014
- Shen, Kun; Chen, Hao; Klaver, Frits
- Chemistry of Materials, Vol. 26, Issue 4
A study of the Na x TiO2 system by electrochemical deintercalation
journal, January 1983
- Maazaz, A.; Delmas, C.; Hagenmuller, P.
- Journal of Inclusion Phenomena, Vol. 1, Issue 1
Growth and structure analysis of nonstoichiometric single crystalNaxTiO2 (x ∼ 0.5)with the α-NaFeO2-type structure
journal, March 1990
- Akimoto, Junji; Takei, Humihiko
- Journal of Solid State Chemistry, Vol. 85, Issue 1
POWDER CELL – a program for the representation and manipulation of crystal structures and calculation of the resulting X-ray powder patterns
journal, June 1996
- Kraus, W.; Nolze, G.
- Journal of Applied Crystallography, Vol. 29, Issue 3, p. 301-303
A cost and resource analysis of sodium-ion batteries
journal, March 2018
- Vaalma, Christoph; Buchholz, Daniel; Weil, Marcel
- Nature Reviews Materials, Vol. 3, Issue 4
Titanium(III) Sulfate as New Negative Electrode for Sodium-Ion Batteries
journal, May 2013
- Senguttuvan, P.; Rousse, G.; Vezin, H.
- Chemistry of Materials, Vol. 25, Issue 12
Ultrafast sodium storage in anatase TiO2 nanoparticles embedded on carbon nanotubes
journal, September 2015
- Hwang, Jang-Yeon; Myung, Seung-Taek; Lee, Joo-Hyeong
- Nano Energy, Vol. 16
Shape-Controlled TiO 2 Nanocrystals for Na-Ion Battery Electrodes: The Role of Different Exposed Crystal Facets on the Electrochemical Properties
journal, January 2017
- Longoni, Gianluca; Pena Cabrera, Rosita Lissette; Polizzi, Stefano
- Nano Letters, Vol. 17, Issue 2
Applications of an amorphous silicon-based area detector for high-resolution, high-sensitivity and fast time-resolved pair distribution function measurements
journal, May 2007
- Chupas, Peter J.; Chapman, Karena W.; Lee, Peter L.
- Journal of Applied Crystallography, Vol. 40, Issue 3
High Substitution Rate in TiO 2 Anatase Nanoparticles with Cationic Vacancies for Fast Lithium Storage
journal, July 2015
- Li, Wei; Corradini, Dario; Body, Monique
- Chemistry of Materials, Vol. 27, Issue 14
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
Research Development on Sodium-Ion Batteries
journal, October 2014
- Yabuuchi, Naoaki; Kubota, Kei; Dahbi, Mouad
- Chemical Reviews, Vol. 114, Issue 23
Voltage- and time-dependent valence state transition in cobalt oxide catalysts during the oxygen evolution reaction
journal, April 2020
- Zhou, Jing; Zhang, Linjuan; Huang, Yu-Cheng
- Nature Communications, Vol. 11, Issue 1
Reducing Dzyaloshinskii-Moriya interaction and field-free spin-orbit torque switching in synthetic antiferromagnets
journal, May 2021
- Chen, Ruyi; Cui, Qirui; Liao, Liyang
- Nature Communications, Vol. 12, Issue 1
High-resolution X-ray luminescence extension imaging
journal, February 2021
- Ou, Xiangyu; Qin, Xian; Huang, Bolong
- Nature, Vol. 590, Issue 7846
Works referencing / citing this record:
Controlled hydroxy-fluorination reaction of anatase to promote Mg 2+ mobility in rechargeable magnesium batteries
journal, January 2018
- Ma, Jiwei; Koketsu, Toshinari; Morgan, Benjamin. J.
- Chemical Communications, Vol. 54, Issue 72