Surface Engineering Strategy Using Urea To Improve the Rate Performance of Na2Ti3O7 in Na-Ion Batteries

Sara I.R. Costa; Yong Seok Choi; Alistair J. Fielding; Andrew J. Naylor; John M. Griffin; Zdeněk Sofer; David O. Scanlon; Nuria Tapia-Ruiz

doi:10.1002/chem.202003129

Surface Engineering Strategy Using Urea To Improve the Rate Performance of Na₂Ti₃O₇ in Na-Ion Batteries

Sara I.R. Costa, Yong Seok Choi, Alistair J. Fielding, Andrew J. Naylor, John M. Griffin, Zdeněk Sofer, David O. Scanlon, Nuria Tapia-Ruiz^*

^*Corresponding author for this work

Chemistry

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Abstract

Na₂Ti₃O₇ (NTO) is considered a promising anode material for Na-ion batteries due to its layered structure with an open framework and low and safe average operating voltage of 0.3 V vs. Na⁺/Na. However, its poor electronic conductivity needs to be addressed to make this material attractive for practical applications among other anode choices. Here, we report a safe, controllable and affordable method using urea that significantly improves the rate performance of NTO by producing surface defects such as oxygen vacancies and hydroxyl groups, and the secondary phase Na₂Ti₆O₁₃. The enhanced electrochemical performance agrees with the higher Na⁺ ion diffusion coefficient, higher charge carrier density and reduced bandgap observed in these samples, without the need of nanosizing and/or complex synthetic strategies. A comprehensive study using a combination of diffraction, microscopic, spectroscopic and electrochemical techniques supported by computational studies based on DFT calculations, was carried out to understand the effects of this treatment on the surface, chemistry and electronic and charge storage properties of NTO. This study underscores the benefits of using urea as a strategy for enhancing the charge storage properties of NTO and thus, unfolding the potential of this material in practical energy storage applications.

Original language	English
Pages (from-to)	3875-3886
Number of pages	12
Journal	Chemistry - A European Journal
Volume	27
Issue number	11
Early online date	27 Aug 2020
DOIs	https://doi.org/10.1002/chem.202003129
Publication status	Published - 19 Feb 2021

Bibliographical note

Funding Information:
N.T.R. and D.O.S. are indebted to the Faraday Institution NEXGENNA project (FIRG018) for financial support. N.T.R. would like to acknowledge Lancaster University for financial support. We are grateful to the EPSRC EPR service for the EPR measurements, Dr Keith Yendall (University of Loughborough) for the FESEM measurements and Dr. David Grandy (University of Loughborough) for the thermogravimetric measurements. Z.S. was supported by the project LTAUSA19034 from the Ministry of Education Youth and Sports (MEYS). YC and DOS are grateful to the Faraday Institution for funding the MICHAEL computing cluster hosted at University College London (UCL). The calculations have been also carried out on the Myriad High Performance Computing Facility (Myriad@UCL) provisioned by UCL. Via our membership of the UKs HEC Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202, EP/R029431), this work used the ARCHER UK National Supercomputing Service (http://www.archer.ac.uk). We are also grateful to the UK Materials and Molecular Modelling Hub for computational resources, which is partially funded by EPSRC (EP/P020194/1). STandUP for Energy (Sweden) is acknowledged for financial support.

Publisher Copyright:
© 2020 The Authors. Published by Wiley-VCH GmbH

Keywords

anode
NaTiO and NaTiO
oxygen vacancies
sodium titanate
sodium-ion batteries
urea

ASJC Scopus subject areas

Catalysis
General Chemistry
Organic Chemistry

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Cite this

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title = "Surface Engineering Strategy Using Urea To Improve the Rate Performance of Na2Ti3O7 in Na-Ion Batteries",

abstract = "Na2Ti3O7 (NTO) is considered a promising anode material for Na-ion batteries due to its layered structure with an open framework and low and safe average operating voltage of 0.3 V vs. Na+/Na. However, its poor electronic conductivity needs to be addressed to make this material attractive for practical applications among other anode choices. Here, we report a safe, controllable and affordable method using urea that significantly improves the rate performance of NTO by producing surface defects such as oxygen vacancies and hydroxyl groups, and the secondary phase Na2Ti6O13. The enhanced electrochemical performance agrees with the higher Na+ ion diffusion coefficient, higher charge carrier density and reduced bandgap observed in these samples, without the need of nanosizing and/or complex synthetic strategies. A comprehensive study using a combination of diffraction, microscopic, spectroscopic and electrochemical techniques supported by computational studies based on DFT calculations, was carried out to understand the effects of this treatment on the surface, chemistry and electronic and charge storage properties of NTO. This study underscores the benefits of using urea as a strategy for enhancing the charge storage properties of NTO and thus, unfolding the potential of this material in practical energy storage applications.",

keywords = "anode, NaTiO and NaTiO, oxygen vacancies, sodium titanate, sodium-ion batteries, urea",

author = "Costa, {Sara I.R.} and Choi, {Yong Seok} and Fielding, {Alistair J.} and Naylor, {Andrew J.} and Griffin, {John M.} and Zden{\v e}k Sofer and Scanlon, {David O.} and Nuria Tapia-Ruiz",

note = "Funding Information: N.T.R. and D.O.S. are indebted to the Faraday Institution NEXGENNA project (FIRG018) for financial support. N.T.R. would like to acknowledge Lancaster University for financial support. We are grateful to the EPSRC EPR service for the EPR measurements, Dr Keith Yendall (University of Loughborough) for the FESEM measurements and Dr. David Grandy (University of Loughborough) for the thermogravimetric measurements. Z.S. was supported by the project LTAUSA19034 from the Ministry of Education Youth and Sports (MEYS). YC and DOS are grateful to the Faraday Institution for funding the MICHAEL computing cluster hosted at University College London (UCL). The calculations have been also carried out on the Myriad High Performance Computing Facility (Myriad@UCL) provisioned by UCL. Via our membership of the UKs HEC Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202, EP/R029431), this work used the ARCHER UK National Supercomputing Service (http://www.archer.ac.uk). We are also grateful to the UK Materials and Molecular Modelling Hub for computational resources, which is partially funded by EPSRC (EP/P020194/1). STandUP for Energy (Sweden) is acknowledged for financial support. Publisher Copyright: {\textcopyright} 2020 The Authors. Published by Wiley-VCH GmbH",

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AU - Naylor, Andrew J.

AU - Griffin, John M.

AU - Sofer, Zdeněk

AU - Scanlon, David O.

AU - Tapia-Ruiz, Nuria

N1 - Funding Information: N.T.R. and D.O.S. are indebted to the Faraday Institution NEXGENNA project (FIRG018) for financial support. N.T.R. would like to acknowledge Lancaster University for financial support. We are grateful to the EPSRC EPR service for the EPR measurements, Dr Keith Yendall (University of Loughborough) for the FESEM measurements and Dr. David Grandy (University of Loughborough) for the thermogravimetric measurements. Z.S. was supported by the project LTAUSA19034 from the Ministry of Education Youth and Sports (MEYS). YC and DOS are grateful to the Faraday Institution for funding the MICHAEL computing cluster hosted at University College London (UCL). The calculations have been also carried out on the Myriad High Performance Computing Facility (Myriad@UCL) provisioned by UCL. Via our membership of the UKs HEC Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202, EP/R029431), this work used the ARCHER UK National Supercomputing Service (http://www.archer.ac.uk). We are also grateful to the UK Materials and Molecular Modelling Hub for computational resources, which is partially funded by EPSRC (EP/P020194/1). STandUP for Energy (Sweden) is acknowledged for financial support. Publisher Copyright: © 2020 The Authors. Published by Wiley-VCH GmbH

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N2 - Na2Ti3O7 (NTO) is considered a promising anode material for Na-ion batteries due to its layered structure with an open framework and low and safe average operating voltage of 0.3 V vs. Na+/Na. However, its poor electronic conductivity needs to be addressed to make this material attractive for practical applications among other anode choices. Here, we report a safe, controllable and affordable method using urea that significantly improves the rate performance of NTO by producing surface defects such as oxygen vacancies and hydroxyl groups, and the secondary phase Na2Ti6O13. The enhanced electrochemical performance agrees with the higher Na+ ion diffusion coefficient, higher charge carrier density and reduced bandgap observed in these samples, without the need of nanosizing and/or complex synthetic strategies. A comprehensive study using a combination of diffraction, microscopic, spectroscopic and electrochemical techniques supported by computational studies based on DFT calculations, was carried out to understand the effects of this treatment on the surface, chemistry and electronic and charge storage properties of NTO. This study underscores the benefits of using urea as a strategy for enhancing the charge storage properties of NTO and thus, unfolding the potential of this material in practical energy storage applications.

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