Experimental and Computational Analysis of the Solvent‐Dependent O 2 /Li + ‐O 2 − Redox Couple: Standard Potentials, Coupling Strength, and Implications for Lithium–Oxygen Batteries

Kwabi, David G.; Bryantsev, Vyacheslav S.; Batcho, Thomas P.; Itkis, Daniil M.; Thompson, Carl V.; Shao‐Horn, Yang

doi:10.1002/anie.201509143

Title: Experimental and Computational Analysis of the Solvent‐Dependent O ₂ /Li ⁺ ‐O ₂ ⁻ Redox Couple: Standard Potentials, Coupling Strength, and Implications for Lithium–Oxygen Batteries

Journal Article · Thu Jan 28 00:00:00 EST 2016 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.201509143· OSTI ID:1400735

Kwabi, David G. ^[1]; Bryantsev, Vyacheslav S. ^[2]; Batcho, Thomas P. ^[3]; Itkis, Daniil M. ^[4]; Thompson, Carl V. ^[3]; Shao‐Horn, Yang ^[5]

Department of Mechanical Engineering Massachusetts Institute of Technology 77 Massachusetts Avenue Cambridge MA 02139 USA
Liox Power Inc 129 North Hill Ave, Suite 103 Pasadena CA 911106 USA, Oak Ridge National Lab Chemical Sciences Division 1 Bethel Valley Rd Oak Ridge TN 37831-6119 USA
Department of Materials Science and Engineering Massachusetts Institute of Technology 77 Massachusetts Avenue Cambridge MA 02139 USA
Department of Chemistry and Materials Science Moscow State University Moscow 119992 Russia
Department of Mechanical Engineering Massachusetts Institute of Technology 77 Massachusetts Avenue Cambridge MA 02139 USA, Department of Materials Science and Engineering Massachusetts Institute of Technology 77 Massachusetts Avenue Cambridge MA 02139 USA

Abstract Understanding and controlling the kinetics of O ₂ reduction in the presence of Li ⁺ ‐containing aprotic solvents, to either Li ⁺ ‐O ₂ ⁻ by one‐electron reduction or Li ₂ O ₂ by two‐electron reduction, is instrumental to enhance the discharge voltage and capacity of aprotic Li‐O ₂ batteries. Standard potentials of O ₂ /Li ⁺ ‐O ₂ ⁻ and O ₂ /O ₂ ⁻ were experimentally measured and computed using a mixed cluster‐continuum model of ion solvation. Increasing combined solvation of Li ⁺ and O ₂ ⁻ was found to lower the coupling of Li ⁺ ‐O ₂ ⁻ and the difference between O ₂ /Li ⁺ ‐O ₂ ⁻ and O ₂ /O ₂ ⁻ potentials. The solvation energy of Li ⁺ trended with donor number (DN), and varied greater than that of O ₂ ⁻ ions, which correlated with acceptor number (AN), explaining a previously reported correlation between Li ⁺ ‐O ₂ ⁻ solubility and DN. These results highlight the importance of the interplay between ion–solvent and ion–ion interactions for manipulating the energetics of intermediate species produced in aprotic metal–oxygen batteries.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: PI0000012

OSTI ID:: 1400735

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Vol. 55 Journal Issue: 9; ISSN 1433-7851

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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Cited by: 99 works

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Title: Experimental and Computational Analysis of the Solvent‐Dependent O ₂ /Li ⁺ ‐O ₂ ⁻ Redox Couple: Standard Potentials, Coupling Strength, and Implications for Lithium–Oxygen Batteries