Experimental and Computational Analysis of the Solvent-Dependent O[subscript 2]/Li+-O[subscript 2][superpscript −] Redox Couple: Standard Potentials, Coupling Strength, and Implications for Lithium-Oxygen Batteries
Author(s)
Kwabi, David Gator
Bryantsev, Vyacheslav S.
Batcho, Thomas Peter
Itkis, Daniil M.
Thompson, Carl Vernette
Shao-Horn, Yang
Alternative Title
Experimental and Computational Analysis of the Solvent-Dependent O2/Li+-O2− Redox Couple: Standard Potentials, Coupling Strength, and Implications for Lithium-Oxygen Batteries
Date Issued
January 2016
Journal
Angewandte Chemie International Edition
Publisher
John Wiley & Sons
Citation
Kwabi, David G., Vyacheslav S. Bryantsev, Thomas P. Batcho, Daniil M. Itkis, Carl V. Thompson, and Yang Shao-Horn. “Experimental and Computational Analysis of the Solvent-Dependent O2/Li+-O2−Redox Couple: Standard Potentials, Coupling Strength, and Implications for Lithium-Oxygen Batteries.” Angew. Chem. Int. Ed. 55, no. 9 (January 28, 2016): 3129–3134.
Version
Author's final manuscript
Abstract
Understanding and controlling the kinetics of O[subscript 2] reduction in the presence of Li+-containing aprotic solvents, to either Li+-O[subscript 2]− by one-electron reduction or Li[subscript 2]O[subscript 2] by two-electron reduction, is instrumental to enhance the discharge voltage and capacity of aprotic Li-O[subscript 2] batteries. Standard potentials of O[subscript 2]/Li+-O[subscript 2]− and O[subscript 2]/O[subscript 2]− were experimentally measured and computed using a mixed cluster-continuum model of ion solvation. Increasing combined solvation of Li+ and O[subscript 2]− was found to lower the coupling of Li+-O[subscript 2]− and the difference between O[subscript 2]/Li+-O[subscript 2]− and O[subscript 2]/O[subscript 2]− potentials. The solvation energy of Li+ trended with donor number (DN), and varied greater than that of O[subscript 2]− ions, which correlated with acceptor number (AN), explaining a previously reported correlation between Li+-O[subscript 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.
MIT Department
Massachusetts Institute of Technology. Department of Materials Science and Engineering
Massachusetts Institute of Technology. Department of Mechanical Engineering
Terms of Use
Creative Commons Attribution-Noncommercial-Share Alike
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DOI of Published Version
https://doi.org/10.1002/anie.201509143
