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Title: Origin of Outstanding Stability in the Lithium Solid Electrolyte Materials: Insights from Thermodynamic Analyses Based on First-Principles Calculations

Abstract

First-principles calculations were performed to investigate the electrochemical stability of lithium solid electrolyte materials in all-solid-state Li-ion batteries. The common solid electrolytes were found to have a limited electrochemical window. Our results suggest that the outstanding stability of the solid electrolyte materials is not thermodynamically intrinsic but is originated from kinetic stabilizations. The sluggish kinetics of the decomposition reactions cause a high overpotential leading to a nominally wide electrochemical window observed in many experiments. The decomposition products, similar to the solid-electrolyte-interphases, mitigate the extreme chemical potential from the electrodes and protect the solid electrolyte from further decompositions. With the aid of the first-principles calculations, we revealed the passivation mechanism of these decomposition interphases and quantified the extensions of the electrochemical window from the interphases. We also found that the artificial coating layers applied at the solid electrolyte and electrode interfaces have a similar effect of passivating the solid electrolyte. Our newly gained understanding provided general principles for developing solid electrolyte materials with enhanced stability and for engineering interfaces in all-solid-state Li-ion batteries.

Authors:
 [1];  [1];  [2]
  1. Univ. of Maryland, College Park, MD (United States). Dept. of Materials Science and Engineering
  2. Univ. of Maryland, College Park, MD (United States). Dept. of Materials Science and Engineering. Energy Research Center
Publication Date:
Research Org.:
Univ. of Maryland, College Park, MD (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); National Science Foundation (NSF)
OSTI Identifier:
1240024
Alternate Identifier(s):
OSTI ID: 1433680
Grant/Contract Number:  
EE0006860; TG-DMR130142
Resource Type:
Journal Article: Published Article
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Name: ACS Applied Materials and Interfaces Journal Volume: 7 Journal Issue: 42; Journal ID: ISSN 1944-8244
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; electrochemical stability; first-principles calculations; lithium ionic conductor; passivation; solid electrolyte; solid-electrolyte-interphases

Citation Formats

Zhu, Yizhou, He, Xingfeng, and Mo, Yifei. Origin of Outstanding Stability in the Lithium Solid Electrolyte Materials: Insights from Thermodynamic Analyses Based on First-Principles Calculations. United States: N. p., 2015. Web. doi:10.1021/acsami.5b07517.
Zhu, Yizhou, He, Xingfeng, & Mo, Yifei. Origin of Outstanding Stability in the Lithium Solid Electrolyte Materials: Insights from Thermodynamic Analyses Based on First-Principles Calculations. United States. https://doi.org/10.1021/acsami.5b07517
Zhu, Yizhou, He, Xingfeng, and Mo, Yifei. 2015. "Origin of Outstanding Stability in the Lithium Solid Electrolyte Materials: Insights from Thermodynamic Analyses Based on First-Principles Calculations". United States. https://doi.org/10.1021/acsami.5b07517.
@article{osti_1240024,
title = {Origin of Outstanding Stability in the Lithium Solid Electrolyte Materials: Insights from Thermodynamic Analyses Based on First-Principles Calculations},
author = {Zhu, Yizhou and He, Xingfeng and Mo, Yifei},
abstractNote = {First-principles calculations were performed to investigate the electrochemical stability of lithium solid electrolyte materials in all-solid-state Li-ion batteries. The common solid electrolytes were found to have a limited electrochemical window. Our results suggest that the outstanding stability of the solid electrolyte materials is not thermodynamically intrinsic but is originated from kinetic stabilizations. The sluggish kinetics of the decomposition reactions cause a high overpotential leading to a nominally wide electrochemical window observed in many experiments. The decomposition products, similar to the solid-electrolyte-interphases, mitigate the extreme chemical potential from the electrodes and protect the solid electrolyte from further decompositions. With the aid of the first-principles calculations, we revealed the passivation mechanism of these decomposition interphases and quantified the extensions of the electrochemical window from the interphases. We also found that the artificial coating layers applied at the solid electrolyte and electrode interfaces have a similar effect of passivating the solid electrolyte. Our newly gained understanding provided general principles for developing solid electrolyte materials with enhanced stability and for engineering interfaces in all-solid-state Li-ion batteries.},
doi = {10.1021/acsami.5b07517},
url = {https://www.osti.gov/biblio/1240024}, journal = {ACS Applied Materials and Interfaces},
issn = {1944-8244},
number = 42,
volume = 7,
place = {United States},
year = {Tue Oct 06 00:00:00 EDT 2015},
month = {Tue Oct 06 00:00:00 EDT 2015}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at https://doi.org/10.1021/acsami.5b07517

Citation Metrics:
Cited by: 1144 works
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