Solid-State NMR Spectroscopy Study of Cation Dynamics in Layered Na2Ti3O7 and Li2Ti3O7
-
Kai Volgmann
,
Vanessa Werth
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.
Acknowledgement
We thank Prof. Feldhoff for access to the scanning electron microscope and Dr. Licht for carrying out the measurements at the SEM. Financial support by the DFG in the frame of the Research Unit FOR 1277 (molife) is gratefully acknowledged.
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©2017 Walter de Gruyter GmbH, Berlin/Boston
Artikel in diesem Heft
- Frontmatter
- Preface
- Mobility of Ions in Solids
- Solid-State NMR to Study Translational Li Ion Dynamics in Solids with Low-Dimensional Diffusion Pathways
- Solid-State NMR Spectroscopy Study of Cation Dynamics in Layered Na2Ti3O7 and Li2Ti3O7
- Density Functional Theory Evaluated for Structural and Electronic Properties of 1T-LixTiS2 and Lithium Ion Migration in 1T-Li0.94TiS2
- Diffusion Pathways and Activation Energies in Crystalline Lithium-Ion Conductors
- Lithium Mobility in Borate and Phosphate Glass Networks
- Effect of Particle Size and Pretreatment on the Conductivity of Glass Powder during Compaction
- On the Mechanisms of Chemical Intercalation of Lithium in Electrode Materials
- Nanostructured Ceramics: Ionic Transport and Electrochemical Activity
- Lithium Insertion into Mixed Phase Titania Nanotubes
- Slow Lithium Transport in Metal Oxides on the Nanoscale
- Local Ion Dynamics in Polycrystalline β-LiGaO2: A Solid-State NMR Study
- NMR Studies of Lithium Diffusion in Li3(NH2)2I Over Wide Range of Li+ Jump Rates
Artikel in diesem Heft
- Frontmatter
- Preface
- Mobility of Ions in Solids
- Solid-State NMR to Study Translational Li Ion Dynamics in Solids with Low-Dimensional Diffusion Pathways
- Solid-State NMR Spectroscopy Study of Cation Dynamics in Layered Na2Ti3O7 and Li2Ti3O7
- Density Functional Theory Evaluated for Structural and Electronic Properties of 1T-LixTiS2 and Lithium Ion Migration in 1T-Li0.94TiS2
- Diffusion Pathways and Activation Energies in Crystalline Lithium-Ion Conductors
- Lithium Mobility in Borate and Phosphate Glass Networks
- Effect of Particle Size and Pretreatment on the Conductivity of Glass Powder during Compaction
- On the Mechanisms of Chemical Intercalation of Lithium in Electrode Materials
- Nanostructured Ceramics: Ionic Transport and Electrochemical Activity
- Lithium Insertion into Mixed Phase Titania Nanotubes
- Slow Lithium Transport in Metal Oxides on the Nanoscale
- Local Ion Dynamics in Polycrystalline β-LiGaO2: A Solid-State NMR Study
- NMR Studies of Lithium Diffusion in Li3(NH2)2I Over Wide Range of Li+ Jump Rates
