Electrode Potential in Ionic Liquid Enlightened by Liquid Madelung Theory.
- 1Department of Chemical System Engineering, School of Engineering, The University of Tokyo, Hongo 7-3-1, Bunkyo-Ku, Tokyo113-8656, Japan.
- 2Sungkyunkwan University Institute of Energy Science & Technology (SIEST), Sungkyunkwan University, Suwon16419, Korea.
Abstract
Electrode potentials in electrolytes vary systematically with salt concentration, yet establishing a quantitative connection between electrolyte structure and electrode potential remains a longstanding challenge. Here, we demonstrate that the liquid Madelung energy─an atomistically resolved Coulombic descriptor obtained from simulations of all constituent molecules and ions─quantitatively accounts for electrode-potential shifts observed for the solvent-based and ionic liquid electrolytes investigated in the present study, the latter representing the concentrated limit. Decomposition of the Li+ electrostatic energy into contributions from surrounding species reveals two key electrostatic factors governing the potential shift: reduced electrostatic stabilization arising from Li+-anion coordination in the first coordination shell and enhanced Li+-Li+ repulsion emerging in the second coordination shell at high concentrations. This atomistic framework captures structural fluctuations inaccessible to classical Debye-Hückel and pseudo-lattice theories, and can be applied to ionic liquids exhibiting apparent nanoscale heterogeneity. These results demonstrate that the liquid Madelung framework can be extended from conventional solvent-based to ionic liquid electrolytes and provide an atomistic electrostatic perspective for the rational design of next-generation electrolytes composed of complex polyatomic species.
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BibTeX
@article{irie2026electrode,
title = {{Electrode Potential in Ionic Liquid Enlightened by Liquid Madelung Theory.}},
author = {Yusuke Irie and Atsushi Kitada and Longjie Liu and Norio Takenaka and Atsuo Yamada},
journal = {Journal of the American Chemical Society},
year = {2026},
month = sep,
doi = {10.1021/jacs.6c09488},
url = {https://europepmc.org/article/MED/42915527},
note = {CC BY-NC-ND},
}
RIS
TY - JOUR
TI - Electrode Potential in Ionic Liquid Enlightened by Liquid Madelung Theory.
AU - Yusuke Irie
AU - Atsushi Kitada
AU - Longjie Liu
AU - Norio Takenaka
AU - Atsuo Yamada
PY - 2026
DA - 2026/09/01
JO - Journal of the American Chemical Society
DO - 10.1021/jacs.6c09488
UR - https://europepmc.org/article/MED/42915527
AB - Electrode potentials in electrolytes vary systematically with salt concentration, yet establishing a quantitative connection between electrolyte structure and electrode potential remains a longstanding challenge. Here, we demonstrate that the liquid Madelung energy─an atomistically resolved Coulombic descriptor obtained from simulations of all constituent molecules and ions─quantitatively accounts for electrode-potential shifts observed for the solvent-based and ionic liquid electrolytes investigated in the present study, the latter representing the concentrated limit. Decomposition of the Li+ electrostatic energy into contributions from surrounding species reveals two key electrostatic factors governing the potential shift: reduced electrostatic stabilization arising from Li+-anion coordination in the first coordination shell and enhanced Li+-Li+ repulsion emerging in the second coordination shell at high concentrations. This atomistic framework captures structural fluctuations inaccessible to classical Debye-Hückel and pseudo-lattice theories, and can be applied to ionic liquids exhibiting apparent nanoscale heterogeneity. These results demonstrate that the liquid Madelung framework can be extended from conventional solvent-based to ionic liquid electrolytes and provide an atomistic electrostatic perspective for the rational design of next-generation electrolytes composed of complex polyatomic species.
SN - 0002-7863
SN - 1520-5126
ER -