Thermal regimes of Li‐ion conductivity in β‐eucryptite
Abstract
Abstract While it is well‐established that ionic conduction in lithium aluminosilicates proceeds via hopping of Li ions, the nature of the various hoping‐based mechanisms in different temperature regimes has not been fully elucidated. The difficulties associated with investigating the conduction have to do with the presence of grains and grain boundaries of different orientations in these usually polycrystalline materials. Herein, we use electrochemical impedance spectroscopy ( EIS ) to investigate the ion conduction mechanisms in β‐eucryptite, which is a prototypical lithium aluminosilicate. In the absence of significant structural transitions in grain boundaries, we find that there are three conduction regimes for the one‐dimensional ionic motion along the c axis channels in the grains, and determine the activation energies for each of these temperature regimes. Activation energies computed from molecular statics calculations of the potential energy landscape encountered by Li ions suggest that at temperatures below 440°C conduction proceeds via cooperative or correlated motion, in agreement with established literature. Between 440°C and 500°C, the activation barriers extracted from EIS measurements are large and consistent with those from atomistic calculations for uncorrelated Li ion hopping. Above 500°C the activation barriers decrease significantly, which indicates that after the transition to the Li‐disordered phasemore »
- Authors:
-
[2];
[1]
- Department of Metallurgical and Materials Engineering Colorado School of Mines Golden Colorado
- Department of Mechanical Engineering Colorado School of Mines Golden Colorado
- Publication Date:
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1378303
- Resource Type:
- Publisher's Accepted Manuscript
- Journal Name:
- Journal of the American Ceramic Society
- Additional Journal Information:
- Journal Name: Journal of the American Ceramic Society Journal Volume: 101 Journal Issue: 1; Journal ID: ISSN 0002-7820
- Publisher:
- Wiley-Blackwell
- Country of Publication:
- United States
- Language:
- English
Citation Formats
Chen, Yachao, Manna, Sukriti, Ciobanu, Cristian V., and Reimanis, Ivar E. Thermal regimes of Li‐ion conductivity in β‐eucryptite. United States: N. p., 2017.
Web. doi:10.1111/jace.15173.
Chen, Yachao, Manna, Sukriti, Ciobanu, Cristian V., & Reimanis, Ivar E. Thermal regimes of Li‐ion conductivity in β‐eucryptite. United States. https://doi.org/10.1111/jace.15173
Chen, Yachao, Manna, Sukriti, Ciobanu, Cristian V., and Reimanis, Ivar E. Mon .
"Thermal regimes of Li‐ion conductivity in β‐eucryptite". United States. https://doi.org/10.1111/jace.15173.
@article{osti_1378303,
title = {Thermal regimes of Li‐ion conductivity in β‐eucryptite},
author = {Chen, Yachao and Manna, Sukriti and Ciobanu, Cristian V. and Reimanis, Ivar E.},
abstractNote = {Abstract While it is well‐established that ionic conduction in lithium aluminosilicates proceeds via hopping of Li ions, the nature of the various hoping‐based mechanisms in different temperature regimes has not been fully elucidated. The difficulties associated with investigating the conduction have to do with the presence of grains and grain boundaries of different orientations in these usually polycrystalline materials. Herein, we use electrochemical impedance spectroscopy ( EIS ) to investigate the ion conduction mechanisms in β‐eucryptite, which is a prototypical lithium aluminosilicate. In the absence of significant structural transitions in grain boundaries, we find that there are three conduction regimes for the one‐dimensional ionic motion along the c axis channels in the grains, and determine the activation energies for each of these temperature regimes. Activation energies computed from molecular statics calculations of the potential energy landscape encountered by Li ions suggest that at temperatures below 440°C conduction proceeds via cooperative or correlated motion, in agreement with established literature. Between 440°C and 500°C, the activation barriers extracted from EIS measurements are large and consistent with those from atomistic calculations for uncorrelated Li ion hopping. Above 500°C the activation barriers decrease significantly, which indicates that after the transition to the Li‐disordered phase of β‐eucryptite, the Li ion motion largely regains the correlated character.},
doi = {10.1111/jace.15173},
journal = {Journal of the American Ceramic Society},
number = 1,
volume = 101,
place = {United States},
year = {Mon Sep 04 00:00:00 EDT 2017},
month = {Mon Sep 04 00:00:00 EDT 2017}
}
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