Details
Original language | English |
---|---|
Pages (from-to) | 1243-1262 |
Number of pages | 20 |
Journal | Zeitschrift für Physikalische Chemie |
Volume | 231 |
Issue number | 7-8 |
Publication status | Published - 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
- Chemistry(all)
- Physical and Theoretical Chemistry
Cite this
- Standard
- Harvard
- Apa
- Vancouver
- BibTeX
- RIS
In: Zeitschrift für Physikalische Chemie, Vol. 231, No. 7-8, 26.07.2017, p. 1243-1262.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
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.
AB - 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.
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
UR - http://www.scopus.com/inward/record.url?scp=85024928719&partnerID=8YFLogxK
U2 - 10.1515/zpch-2016-0948
DO - 10.1515/zpch-2016-0948
M3 - Article
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 -