Nonstoichiometry-Induced Enhancement of Electrochemical Capacitance in Anodic TiO2 Nanotubes with Controlled Pore Diameter

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School of Mechanical Engineering, Yeungnam University, Gyeongsan 712-749, South Korea
Center for Research Facilities, Yeungnam University, Gyeongsan 712-749, South Korea
*E-mail: [email protected]; [email protected]. Telephone: +82-53-810-2453; Fax: +82-53-810-2062 (A.N.B.).
*E-mail: [email protected]. Telephone: +82-53-810-3239. Fax: +82-53-810-2062 (S.W.J.).
Cite this: J. Phys. Chem. C 2016, 120, 18, 9569–9580
Publication Date (Web):April 25, 2016
https://doi.org/10.1021/acs.jpcc.6b01171
Copyright © 2016 American Chemical Society
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Abstract

We report the fabrication of self-organized titania (TiO2) nanotubes (TNTs) with controlled pore diameters (140–20 nm) by anodization for the application of electrochemical capacitor electrodes. The areal capacitances obtained for 140 nm TNTs as 0.23/0.13 mF cm–2 at a scan rate of 1/5 mV s–1 and it is enhanced to 5.5/2.9 mF cm–2 (at the same scan rates) by controlling the pore diameter to 20 nm. In this study, role of pore diameter in the capacitance behavior of TNTs is explained on the basis of effective surface area and presence of oxygen vacancies/titanium interstitials. With a decrease in the pore diameter, the surface area-to-volume ratio (and hence, active surface sites) increases, which leads to greater dissociation of Ti4+ into Ti3+ under high temperature annealing and thus brings more nonstoichiometric defects like Ti3+ interstitials and oxygen deficiency within the lower dimensional TNTs. This manifests higher charge conductivity and greater electrochemical performance of TNTs with lower diameters. The simplicity of anodization method and the excellent electrochemical properties make these vertical TNTs as an alternative candidate for use in energy storage applications.

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jpcc.6b01171.

  • Variation of nanotube’s pore diameter size distribution, shift of Raman peak at anatase and rutile peak with pore diameter of titania nanotubes, variation of Ti3+/Ti ratio, oxygen vacancy, and O/Ti ratio, and schematic diagram depicting the desorption of surface oxygen under annealing in higher and smaller pore diameter of nanotubes (PDF)

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