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Effect of Hf-doping on electrochemical performance of anatase TiO(2) as an anode material for lithium storage

Hafnium-doped titania (Hf/Ti = 0.01; 0.03; 0.05) had been facilely synthesized via a template sol–gel method on carbon fibre. Physico-chemical properties of the as-synthesized materials were characterized by X-ray diffraction, Raman spectroscopy, scanning electron microscopy, energy-dispersive X-ray...

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Autores principales: Gnedenkov, Sergey V., Sinebryukhov, Sergey L., Zheleznov, Veniamin V., Opra, Denis P., Voit, Elena I., Modin, Evgeny B., Sokolov, Alexander A., Yu. Ustinov, Alexander, Sergienko, Valentin I.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society Publishing 2018
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6030266/
https://www.ncbi.nlm.nih.gov/pubmed/30110421
http://dx.doi.org/10.1098/rsos.171811
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author Gnedenkov, Sergey V.
Sinebryukhov, Sergey L.
Zheleznov, Veniamin V.
Opra, Denis P.
Voit, Elena I.
Modin, Evgeny B.
Sokolov, Alexander A.
Yu. Ustinov, Alexander
Sergienko, Valentin I.
author_facet Gnedenkov, Sergey V.
Sinebryukhov, Sergey L.
Zheleznov, Veniamin V.
Opra, Denis P.
Voit, Elena I.
Modin, Evgeny B.
Sokolov, Alexander A.
Yu. Ustinov, Alexander
Sergienko, Valentin I.
author_sort Gnedenkov, Sergey V.
collection PubMed
description Hafnium-doped titania (Hf/Ti = 0.01; 0.03; 0.05) had been facilely synthesized via a template sol–gel method on carbon fibre. Physico-chemical properties of the as-synthesized materials were characterized by X-ray diffraction, Raman spectroscopy, scanning electron microscopy, energy-dispersive X-ray analysis, scanning transmission electron microscopy, X-ray photoelectron spectroscopy, thermogravimetry analysis and Brunauer–Emmett–Teller measurements. It was confirmed that Hf(4+) substitute in the Ti(4+) sites, forming Ti(1–x)Hf(x)O(2) (x = 0.01; 0.03; 0.05) solid solutions with an anatase crystal structure. The Ti(1–x)Hf(x)O(2) materials are hollow microtubes (length of 10–100 µm, outer diameter of 1–5 µm) composed of nanoparticles (average size of 15–20 nm) with a surface area of 80–90 m(2) g(–1) and pore volume of 0.294–0.372 cm(3) g(–1). The effect of Hf ion incorporation on the electrochemical behaviour of anatase TiO(2) in the Li-ion battery anode was investigated by galvanostatic charge/discharge and electrochemical impedance spectroscopy. It was established that Ti(0.95)Hf(0.05)O(2) shows significantly higher reversibility (154.2 mAh g(–1)) after 35-fold cycling at a C/10 rate in comparison with undoped titania (55.9 mAh g(–1)). The better performance offered by Hf(4+) substitution of the Ti(4+) into anatase TiO(2) mainly results from a more open crystal structure, which has been achieved via the difference in ionic radius values of Ti(4+) (0.604 Å) and Hf(4+) (0.71 Å). The obtained results are in good accord with those for anatase TiO(2) doped with Zr(4+) (0.72 Å), published earlier. Furthermore, improved electrical conductivity of Hf-doped anatase TiO(2) materials owing to charge redistribution in the lattice and enhanced interfacial lithium storage owing to increased surface area directly depending on the Hf/Ti atomic ratio have a beneficial effect on electrochemical properties.
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spelling pubmed-60302662018-07-17 Effect of Hf-doping on electrochemical performance of anatase TiO(2) as an anode material for lithium storage Gnedenkov, Sergey V. Sinebryukhov, Sergey L. Zheleznov, Veniamin V. Opra, Denis P. Voit, Elena I. Modin, Evgeny B. Sokolov, Alexander A. Yu. Ustinov, Alexander Sergienko, Valentin I. R Soc Open Sci Chemistry Hafnium-doped titania (Hf/Ti = 0.01; 0.03; 0.05) had been facilely synthesized via a template sol–gel method on carbon fibre. Physico-chemical properties of the as-synthesized materials were characterized by X-ray diffraction, Raman spectroscopy, scanning electron microscopy, energy-dispersive X-ray analysis, scanning transmission electron microscopy, X-ray photoelectron spectroscopy, thermogravimetry analysis and Brunauer–Emmett–Teller measurements. It was confirmed that Hf(4+) substitute in the Ti(4+) sites, forming Ti(1–x)Hf(x)O(2) (x = 0.01; 0.03; 0.05) solid solutions with an anatase crystal structure. The Ti(1–x)Hf(x)O(2) materials are hollow microtubes (length of 10–100 µm, outer diameter of 1–5 µm) composed of nanoparticles (average size of 15–20 nm) with a surface area of 80–90 m(2) g(–1) and pore volume of 0.294–0.372 cm(3) g(–1). The effect of Hf ion incorporation on the electrochemical behaviour of anatase TiO(2) in the Li-ion battery anode was investigated by galvanostatic charge/discharge and electrochemical impedance spectroscopy. It was established that Ti(0.95)Hf(0.05)O(2) shows significantly higher reversibility (154.2 mAh g(–1)) after 35-fold cycling at a C/10 rate in comparison with undoped titania (55.9 mAh g(–1)). The better performance offered by Hf(4+) substitution of the Ti(4+) into anatase TiO(2) mainly results from a more open crystal structure, which has been achieved via the difference in ionic radius values of Ti(4+) (0.604 Å) and Hf(4+) (0.71 Å). The obtained results are in good accord with those for anatase TiO(2) doped with Zr(4+) (0.72 Å), published earlier. Furthermore, improved electrical conductivity of Hf-doped anatase TiO(2) materials owing to charge redistribution in the lattice and enhanced interfacial lithium storage owing to increased surface area directly depending on the Hf/Ti atomic ratio have a beneficial effect on electrochemical properties. The Royal Society Publishing 2018-06-06 /pmc/articles/PMC6030266/ /pubmed/30110421 http://dx.doi.org/10.1098/rsos.171811 Text en © 2018 The Authors. http://creativecommons.org/licenses/by/4.0/ Published by the Royal Society under the terms of the Creative Commons Attribution License http://creativecommons.org/licenses/by/4.0/, which permits unrestricted use, provided the original author and source are credited.
spellingShingle Chemistry
Gnedenkov, Sergey V.
Sinebryukhov, Sergey L.
Zheleznov, Veniamin V.
Opra, Denis P.
Voit, Elena I.
Modin, Evgeny B.
Sokolov, Alexander A.
Yu. Ustinov, Alexander
Sergienko, Valentin I.
Effect of Hf-doping on electrochemical performance of anatase TiO(2) as an anode material for lithium storage
title Effect of Hf-doping on electrochemical performance of anatase TiO(2) as an anode material for lithium storage
title_full Effect of Hf-doping on electrochemical performance of anatase TiO(2) as an anode material for lithium storage
title_fullStr Effect of Hf-doping on electrochemical performance of anatase TiO(2) as an anode material for lithium storage
title_full_unstemmed Effect of Hf-doping on electrochemical performance of anatase TiO(2) as an anode material for lithium storage
title_short Effect of Hf-doping on electrochemical performance of anatase TiO(2) as an anode material for lithium storage
title_sort effect of hf-doping on electrochemical performance of anatase tio(2) as an anode material for lithium storage
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6030266/
https://www.ncbi.nlm.nih.gov/pubmed/30110421
http://dx.doi.org/10.1098/rsos.171811
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