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Calculation of solvation free energies of Li+ and O2 − ions and neutral lithium–oxygen compounds in acetonitrile using mixed cluster/continuum models

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Abstract

Solvation effects play a major role in determining the cycling characteristics of the non-aqueous rechargeable Li-air battery. We use a mixed cluster/continuum solvent model with varying number of explicit solvent molecules (n = 4–10) to calculate the solvation free energies (\( \Updelta G_{\text{solv}}^{*} \)) of Li+ and O2 − ions and neutral LiO2, Li2O2, LiO, and Li2O species in acetonitrile solvent. Calculations for complexes with the full first solvation shell around Li+ (n = 4) and O2 − (n = 8) show excellent agreement with the solvation free energies obtained using the cluster pair approximation (the error is below 2.0 kcal/mol). The use of the pure continuum model fitted to reproduce the experimental values of \( \Updelta G_{\text{solv}}^{*} \)(Li+) and \( \Updelta G_{\text{solv}}^{*} \)(O2 −) gives the solvation free energies of various lithium–oxygen species (Li x O y ; x, y = 1, 2) that are in excellent agreement with the results obtained using mixed cluster/continuum models (n ≥ 8). This provides a theoretical framework for including solvent effects in the theoretical models of oxygen reduction and evolution reactions in the aprotic Li-air battery.

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Acknowledgments

I am indebted to Dr. Mario Blanco for providing me with the algorithm for sampling the initial configurations of solvated clusters. This work was supported by Liox Power, Inc., Pasadena, CA.

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  1. Liox Power, Inc., 129 N. Hill Ave., Suite 103, Pasadena, CA, 91106, USA

    Vyacheslav S. Bryantsev

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Correspondence to Vyacheslav S. Bryantsev.

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Bryantsev, V.S. Calculation of solvation free energies of Li+ and O2 − ions and neutral lithium–oxygen compounds in acetonitrile using mixed cluster/continuum models. Theor Chem Acc 131, 1250 (2012). https://doi.org/10.1007/s00214-012-1250-7

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