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

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.
 [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:
Grant/Contract Number:
EE0006860; TG-DMR130142
Published Article
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Volume: 7; Journal Issue: 42; Journal ID: ISSN 1944-8244
American Chemical Society (ACS)
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)
Country of Publication:
United States
25 ENERGY STORAGE; electrochemical stability; first-principles calculations; lithium ionic conductor; passivation; solid electrolyte; solid-electrolyte-interphases
OSTI Identifier:
Alternate Identifier(s):
OSTI ID: 1433680