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Synthesis of Ionic Liquid Based Electrolytes, Assembly of Li-ion Batteries, and Measurements of Performance at High Temperature
Published on: December 20, 2016
Electrode Potential in Ionic Liquid Enlightened by Liquid Madelung Theory
Yusuke Irie1, Atsushi Kitada1, Longjie Liu1
1Department of Chemical System Engineering, School of Engineering, The University of Tokyo, Hongo 7-3-1, Bunkyo-Ku, Tokyo113-8656, Japan.
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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