Free-Energy Profile of Li-Ion Insertion Reaction in Highly Concentrated Electrolytes: Impact of Destabilized Li-Ion on Electrode Reaction Thermodynamics.

Authors

Saki Sawayama, Misa Yamashita, Kenta Fujii

Published in

The journal of physical chemistry letters. Volume 17. Issue 33. Pages 9739-9745. Aug 20, 2026.

Abstract

Understanding the Li-ion insertion reaction at graphite electrodes as a chemical reaction requires a thermodynamic perspective, namely elucidating the underlying free-energy profile. In this study, we quantitatively constructed the free-energy profile of the Li-ion insertion reaction in highly concentrated electrolytes by combining activation thermodynamics derived from electrochemical impedance measurements with experimentally determined solvation free energies of Li+. The resulting free-energy profile revealed that the activation free energy (ΔG⧧) remains nearly constant across different solvent systems, whereas the solvation free energy of Li+ (ΔGLi) varies significantly depending on solvent properties and dominates the thermodynamics of the electrode reaction. Furthermore, high-energy X-ray total scattering and molecular dynamics simulations showed that Li+ forms ion-aggregate structures with anions and solvent molecules, where short-range Li+-Li+ configurations give rise to electrostatic repulsion, leading to destabilization of Li+. These results establish a direct link between solution structure and electrode reaction thermodynamics, providing new insights into the role of Li+ solvation in highly concentrated electrolytes.

PMID:
42622466
Bibliographic data and abstract were imported from PubMed on 20 Aug 2026.

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