Three-Dimensional Fast Na-Ion Transport in Sodium Titanate Nanoarchitectures via Engineering of Oxygen Vacancies and Bismuth Substitution

  • Jun Mei*
    Jun Mei
    Centre for Materials Science, Queensland University of Technology, 2 George Street, Brisbane, QLD 4000, Australia
    School of Chemistry and Physics, Queensland University of Technology, 2 George Street, Brisbane, QLD 4000, Australia
    *Email: [email protected] (J.M.).
    More by Jun Mei
  • Tiantian Wang
    Tiantian Wang
    School of Mechanical, Medical and Process Engineering, Queensland University of Technology, 2 George Street, Brisbane, QLD 4000, Australia
    State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
    University of Chinese Academy of Sciences, Beijing 100049, China
  • Dongchen Qi
    Dongchen Qi
    Centre for Materials Science, Queensland University of Technology, 2 George Street, Brisbane, QLD 4000, Australia
    School of Chemistry and Physics, Queensland University of Technology, 2 George Street, Brisbane, QLD 4000, Australia
    More by Dongchen Qi
  • Jianjun Liu
    Jianjun Liu
    State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
    More by Jianjun Liu
  • Ting Liao
    Ting Liao
    Centre for Materials Science, Queensland University of Technology, 2 George Street, Brisbane, QLD 4000, Australia
    School of Mechanical, Medical and Process Engineering, Queensland University of Technology, 2 George Street, Brisbane, QLD 4000, Australia
    More by Ting Liao
  • Yusuke Yamauchi
    Yusuke Yamauchi
    Australian Institute for Bioengineering and Nanotechnology and School of Chemical Engineering, The University of Queensland, St Lucia, QLD 4072, Australia
    JST-ERATO Yamauchi Materials Space-Tectonics and International Center for Materials Nanoarchitectonics (WPI-MANA), National Institute for Materials Science, 1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan
  • , and 
  • Ziqi Sun*
    Ziqi Sun
    Centre for Materials Science, Queensland University of Technology, 2 George Street, Brisbane, QLD 4000, Australia
    School of Chemistry and Physics, Queensland University of Technology, 2 George Street, Brisbane, QLD 4000, Australia
    *Email: [email protected] (Z.S.).
    More by Ziqi Sun
Cite this: ACS Nano 2021, 15, 8, 13604–13615
Publication Date (Web):August 6, 2021
https://doi.org/10.1021/acsnano.1c04479
Copyright © 2021 American Chemical Society
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Abstract

Layered sodium titanates (NTO), one of the most promising anode materials for advanced sodium-ion batteries (SIBs), feature high theoretical capacity and no serious safety concerns. The pristine NTO electrode, however, has unfavorable Na+ transport kinetics, due to the dominant two-dimensional (2D) Na-ion transport channels within the crystal along the low energy barrier octahedron layers, which impedes the practical application of this class of potential materials. Herein, an interesting concept of opening three-dimensional (3D) fast ion transport channels within the intrinsic NTO frameworks is proposed to enhance the electrochemical performance through a combination of oxygen vacancy generation and cation substitution strategies, by which the interlayer spacing of the NTO frameworks is expanded for fast 3D Na-ion transport. It is evidenced that the oxygen-deficient and bismuth-substituted HBNTO (BixNa2–xTi3Oy, 0 < x < 2, 0 < y < 7, HBNTO) exhibits obvious enhancements on the reversible capacity (∼145% enhancement at 20 mAh g–1 compared with NTO), the rate capability (∼200% enhancement at 500 mAh g–1 compared with NTO), and the cycling stability (∼210% enhancement of retention capacity after 150 cycles at 20 mAh g–1 compared with NTO). The molecular dynamic simulations and theoretical calculations demonstrate that the enhanced performance of HBNTO is contributed by the multiplied sodium diffusion pathways and the increased ion migration rates with the successful opening of 3D internal ion transport channels. This work demonstrates the effectiveness of the strategies in opening the 3D intercrystal ion transport channels for boosting the electrochemical performance of SIBs.

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The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsnano.1c04479.

  • Experimental details for materials characterizations and electrochemical tests, crystal structure of the pristine NTO structure, theoretical screen processes of HNTO structure, theoretical screen processes of BNTO structure, theoretical screen processes of HBNTO structure, Bader charge analysis on titanium atoms, Bader charge analysis on oxygen atoms, interlayer spacings along the [100] crystal face, calculated XRD spectrum, low-magnification SEM image of the pristine NTO and HNTO, low-magnification TEM images of NTO, HNTO, BNTO, and HBNTO nanostructures, XPS survey comparison of NTO, HNTO, BNTO, and HBNTO nanostructures, cyclic voltammetry (CV) curves in the initial five cycles of NTO-, HNTO-, BNTO-, and HBNTO-based electrodes, galvanostatic voltage profiles during the first three cycles, initial galvanostatic discharge and charge profiles of HBNTO anodes, the separated the surface-controlled capacitive current with the diffusion-controlled faradaic current of HBNTO electrode, EIS spectra before and after cycling of NTO, HNTO, BNTO, and HBNTO electrodes, typical single-cycle titration profile on discharge, table of the lattice parameters of the pristine NTO structure, table of the sodium migration barriers and diffusion coefficients in NTO and HBNTO (PDF)

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