Predicting the voltage dependence of interfacial electrochemical processes at lithium-intercalated graphite edge planes
Literature Information
The applied potential governs lithium-intercalation and electrode passivation reactions in lithium ion batteries, but are challenging to calibrate in condensed phase DFT calculations. In this work, the “anode potential” of charge-neutral lithium-intercalated graphite (LiC6) with oxidized edge planes is computed as a function of Li-content (nLi) at edge planes, using ab initio molecular dynamics (AIMD), a previously introduced Li+ transfer free energy method, and the experimental Li+/Li(s) value as reference. The voltage assignments are corroborated using explicit electron transfer from fluoroethylene carbonate radical anion markers. PF6− is shown to decompose electrochemically (i.e., not just thermally) at low potentials imposed by our voltage calibration technique. We demonstrate that excess electrons reside in localized states-in-the-gap in the organic carbonate liquid region, which is not semiconductor-like (band-state-like) as widely assumed in the literature.
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Source Journal
Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.














