Solid-State NMR Spectroscopy Study of Cation Dynamics in Layered Na2Ti3O7 and Li2Ti3O7

Research output: Contribution to journalArticleResearchpeer review

Authors

  • Kai Volgmann
  • Vanessa Werth
  • Suliman Nakhal
  • Martin Lerch
  • Thomas Bredow
  • Paul Heitjans

External Research Organisations

  • University of Bonn
  • Technische Universität Berlin
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Details

Original languageEnglish
Pages (from-to)1243-1262
Number of pages20
JournalZeitschrift für Physikalische Chemie
Volume231
Issue number7-8
Publication statusPublished - 26 Jul 2017

Abstract

Ti-based materials exhibit suitable properties for usage in secondary Li-and Na-ion batteries and were in the focus of several electrochemical and ion conductivity studies. A material of such interest is layer-structured, monoclinic Na2Ti3O7. Additionally, the sodium in Na2Ti3O7 can be replaced completely with lithium to achieve monoclinic Li2Ti3O7, whose electrochemical properties were already investigated as well. Both materials exhibit interesting properties such as zero-strain behavior upon intercalation and high cycling stability. However, there is still a lack of fundamental understanding of the ion diffusivity of both Na and Li in the corresponding host structure. Solid-state nuclear magnetic resonance (NMR) spectroscopy is used here for the first time to reveal the cation dynamics in layered Na2Ti3O7 and Li2Ti3O7. This includes activation energies for the ionic motion and jump rates on the microscopic scale from NMR spin-lattice relaxation (SLR), spin-alignment echo (SAE), and 2D NMR exchange techniques. Moreover, the dimensionality of the ionic motion is investigated by frequency-dependent NMR SLR. Structural details are studied using magic-angle spinning (MAS) NMR spectroscopy. Results for the electric field gradient at the Na and Li site, respectively, are compared with those from theoretical calculations performed within this study. The dynamics are similar for both cations, and the frequency-dependence of the 7Li NMR SLR rate indicates Li motion confined to two dimensions. Thus, these two materials may be regarded a model system for low-dimensional diffusion of two different cations.

Keywords

    2D NMR EXSY, Na NMR, Li and Li NMR, diffusion, solid-state NMR, spin-alignment echo, spin-lattice relaxation

ASJC Scopus subject areas

Cite this

Solid-State NMR Spectroscopy Study of Cation Dynamics in Layered Na2Ti3O7 and Li2Ti3O7. / Volgmann, Kai; Werth, Vanessa; Nakhal, Suliman et al.
In: Zeitschrift für Physikalische Chemie, Vol. 231, No. 7-8, 26.07.2017, p. 1243-1262.

Research output: Contribution to journalArticleResearchpeer review

Volgmann K, Werth V, Nakhal S, Lerch M, Bredow T, Heitjans P. Solid-State NMR Spectroscopy Study of Cation Dynamics in Layered Na2Ti3O7 and Li2Ti3O7. Zeitschrift für Physikalische Chemie. 2017 Jul 26;231(7-8):1243-1262. doi: 10.1515/zpch-2016-0948
Volgmann, Kai ; Werth, Vanessa ; Nakhal, Suliman et al. / Solid-State NMR Spectroscopy Study of Cation Dynamics in Layered Na2Ti3O7 and Li2Ti3O7. In: Zeitschrift für Physikalische Chemie. 2017 ; Vol. 231, No. 7-8. pp. 1243-1262.
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title = "Solid-State NMR Spectroscopy Study of Cation Dynamics in Layered Na2Ti3O7 and Li2Ti3O7",
abstract = "Ti-based materials exhibit suitable properties for usage in secondary Li-and Na-ion batteries and were in the focus of several electrochemical and ion conductivity studies. A material of such interest is layer-structured, monoclinic Na2Ti3O7. Additionally, the sodium in Na2Ti3O7 can be replaced completely with lithium to achieve monoclinic Li2Ti3O7, whose electrochemical properties were already investigated as well. Both materials exhibit interesting properties such as zero-strain behavior upon intercalation and high cycling stability. However, there is still a lack of fundamental understanding of the ion diffusivity of both Na and Li in the corresponding host structure. Solid-state nuclear magnetic resonance (NMR) spectroscopy is used here for the first time to reveal the cation dynamics in layered Na2Ti3O7 and Li2Ti3O7. This includes activation energies for the ionic motion and jump rates on the microscopic scale from NMR spin-lattice relaxation (SLR), spin-alignment echo (SAE), and 2D NMR exchange techniques. Moreover, the dimensionality of the ionic motion is investigated by frequency-dependent NMR SLR. Structural details are studied using magic-angle spinning (MAS) NMR spectroscopy. Results for the electric field gradient at the Na and Li site, respectively, are compared with those from theoretical calculations performed within this study. The dynamics are similar for both cations, and the frequency-dependence of the 7Li NMR SLR rate indicates Li motion confined to two dimensions. Thus, these two materials may be regarded a model system for low-dimensional diffusion of two different cations.",
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T1 - Solid-State NMR Spectroscopy Study of Cation Dynamics in Layered Na2Ti3O7 and Li2Ti3O7

AU - Volgmann, Kai

AU - Werth, Vanessa

AU - Nakhal, Suliman

AU - Lerch, Martin

AU - Bredow, Thomas

AU - Heitjans, Paul

N1 - Publisher Copyright: © 2017 Walter de Gruyter GmbH, Berlin/Boston. Copyright: Copyright 2021 Elsevier B.V., All rights reserved.

PY - 2017/7/26

Y1 - 2017/7/26

N2 - Ti-based materials exhibit suitable properties for usage in secondary Li-and Na-ion batteries and were in the focus of several electrochemical and ion conductivity studies. A material of such interest is layer-structured, monoclinic Na2Ti3O7. Additionally, the sodium in Na2Ti3O7 can be replaced completely with lithium to achieve monoclinic Li2Ti3O7, whose electrochemical properties were already investigated as well. Both materials exhibit interesting properties such as zero-strain behavior upon intercalation and high cycling stability. However, there is still a lack of fundamental understanding of the ion diffusivity of both Na and Li in the corresponding host structure. Solid-state nuclear magnetic resonance (NMR) spectroscopy is used here for the first time to reveal the cation dynamics in layered Na2Ti3O7 and Li2Ti3O7. This includes activation energies for the ionic motion and jump rates on the microscopic scale from NMR spin-lattice relaxation (SLR), spin-alignment echo (SAE), and 2D NMR exchange techniques. Moreover, the dimensionality of the ionic motion is investigated by frequency-dependent NMR SLR. Structural details are studied using magic-angle spinning (MAS) NMR spectroscopy. Results for the electric field gradient at the Na and Li site, respectively, are compared with those from theoretical calculations performed within this study. The dynamics are similar for both cations, and the frequency-dependence of the 7Li NMR SLR rate indicates Li motion confined to two dimensions. Thus, these two materials may be regarded a model system for low-dimensional diffusion of two different cations.

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KW - 2D NMR EXSY

KW - Na NMR

KW - Li and Li NMR

KW - diffusion

KW - solid-state NMR

KW - spin-alignment echo

KW - spin-lattice relaxation

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DO - 10.1515/zpch-2016-0948

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AN - SCOPUS:85024928719

VL - 231

SP - 1243

EP - 1262

JO - Zeitschrift für Physikalische Chemie

JF - Zeitschrift für Physikalische Chemie

SN - 0942-9352

IS - 7-8

ER -

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