Incorporating Solvation Effects in Oxidative Stability Predictions of Battery Electrolytes

Area of Science:

• Electrochemistry
• Computational Chemistry
• Materials Science

Background:

• Accurate prediction of battery electrolyte oxidative stability is vital for high-voltage systems.
• Current methods using density functional theory (DFT) often neglect crucial solvation and interfacial effects.
• Understanding these factors is key for designing next-generation battery chemistries.

Purpose of the Study:

• To develop and apply an advanced computational methodology for predicting electrolyte oxidative stability.
• To account for many-body solvation and interfacial effects in electrochemical systems.
• To provide more accurate predictions than conventional computational strategies.

Main Methods:

• Integration of molecular dynamics (MD) sampling for local solvation environments.
• Explicit calculation of vertical ionization potentials (IP) to capture electronic effects.
• Application to various electrolytes based on common lithium salts and solvents.

Main Results:

• The new methodology provides statistical distributions of IPs and identifies oxidized species.
• Results offer more detailed conclusions compared to conventional DFT calculations.
• The method captures IP variations with salt concentration and near electrified interfaces.

Conclusions:

• The developed computational approach offers a more comprehensive understanding of electrolyte stability.
• It accurately accounts for microscopic factors and electronic structure in electrochemical systems.
• This work enables more rational design of advanced battery electrolytes.