TY - JOUR
T1 - Competing Effects in the Hydration Mechanism of a Garnet-Type Li7La3Zr2O12 Electrolyte
AU - Arinicheva, Yulia
AU - Guo, Xin
AU - Gerhards, Marie Theres
AU - Tietz, Frank
AU - Fattakhova-Rohlfing, Dina
AU - Finsterbusch, Martin
AU - Navrotsky, Alexandra
AU - Guillon, Olivier
N1 - Funding Information:
The work at Forschungszentrum Jülich was funded by the Federal Ministry of Education and Research of Germany (BMBF, Project 03XP0084A) and the German Research Foundation (DFG, Project 429409150). The work at Arizona State University was supported by the U.S. Department of Energy, Office of Basic Energy Sciences, via Grant DE-FG02-03ER46053.
Publisher Copyright:
© 2022 American Chemical Society
PY - 2022/2/22
Y1 - 2022/2/22
N2 - Li-ion conducting oxides (Li7La3Zr2O12, LLZO) with a cubic garnet-type structure are among the most promising candidates to be used as solid electrolytes in all-solid-state Li batteries. However, the environmental instability of the electrolyte, induced by interaction between the material and gas molecules commonly found in air, namely, water and carbon dioxide, poses challenges for its manufacture and application. Herein, a combined experimental kinetic and thermodynamic study was performed as a function of temperature to clarify the mechanism of hydration of a garnet-type LLZO electrolyte in moist air. It was found that the kinetics of LLZO hydration is diffusion-limited and the hydration mechanism at room temperature and at higher temperatures differs. The hydration of LLZO increases up to 200 °C. Above this temperature, stagnation of water uptake is observed due to the onset of a competing dehydration process. The dehydration of LLZO takes place up to 400 °C. The partial pressure of water significantly affects the extent of hydration. Expanding this combined kinetic and thermodynamic approach to LLZO materials with a variety of chemical compositions and morphologies would allow prediction of their reactivity in a humid atmosphere and adjustment of the processing conditions accordingly to meet the requirements of technological applications.
AB - Li-ion conducting oxides (Li7La3Zr2O12, LLZO) with a cubic garnet-type structure are among the most promising candidates to be used as solid electrolytes in all-solid-state Li batteries. However, the environmental instability of the electrolyte, induced by interaction between the material and gas molecules commonly found in air, namely, water and carbon dioxide, poses challenges for its manufacture and application. Herein, a combined experimental kinetic and thermodynamic study was performed as a function of temperature to clarify the mechanism of hydration of a garnet-type LLZO electrolyte in moist air. It was found that the kinetics of LLZO hydration is diffusion-limited and the hydration mechanism at room temperature and at higher temperatures differs. The hydration of LLZO increases up to 200 °C. Above this temperature, stagnation of water uptake is observed due to the onset of a competing dehydration process. The dehydration of LLZO takes place up to 400 °C. The partial pressure of water significantly affects the extent of hydration. Expanding this combined kinetic and thermodynamic approach to LLZO materials with a variety of chemical compositions and morphologies would allow prediction of their reactivity in a humid atmosphere and adjustment of the processing conditions accordingly to meet the requirements of technological applications.
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U2 - 10.1021/acs.chemmater.1c02581
DO - 10.1021/acs.chemmater.1c02581
M3 - Article
AN - SCOPUS:85124951869
SN - 0897-4756
VL - 34
SP - 1473
EP - 1480
JO - Chemistry of Materials
JF - Chemistry of Materials
IS - 4
ER -