Electronic Structure Modeling of Electrochemical Reactions at Electrode/Electrolyte Interfaces in Lithium Ion Batteries

TL;DR

This paper reviews ab initio molecular dynamics studies of electrode/electrolyte interfaces in lithium ion batteries, highlighting simulation techniques, reaction mechanisms, and future modeling challenges at atomic scales.

Contribution

It introduces simulation methods applicable to battery interfaces, emphasizing interdisciplinary approaches and identifying key reaction mechanisms in electrolyte decomposition.

Findings

Identification of kinetically controlled two-electron reactions

Discovery of a neglected chemical bond breaking in EC

Insights into electron tunneling at interfaces

Abstract

We review recent ab initio molecular dynamics studies of electrode/electrolyte interfaces in lithium ion batteries. Our goals are to introduce experimentalists to simulation techniques applicable to models which are arguably most faithful to experimental conditions so far, and to emphasize to theorists that the inherently interdisciplinary nature of this subject requires bridging the gap between solid and liquid state perspectives. We consider liquid ethylene carbonate (EC) decomposition on lithium intercalated graphite, lithium metal, oxide-coated graphite, and spinel manganese oxide surfaces. These calculations are put in the context of more widely studied water-solid interfaces. Our main themes include kinetically controlled two-electron-induced reactions, the breaking of a previously much neglected chemical bond in EC, and electron tunneling. Future work on modeling batteries at atomic lengthscales requires capabilities beyond state-of-the-art, which emphasizes that applied battery research can and should drive fundamental science development.