Experimental and Computational Analysis of the Solvent‐Dependent O2/Li+‐O2− Redox Couple: Standard Potentials,Coupling Strength,and Implications for Lithium–Oxygen Batteries |
| |
| Authors: | David G. Kwabi Vyacheslav S. Bryantsev Thomas P. Batcho Daniil M. Itkis Carl V. Thompson Yang Shao‐Horn |
| |
| Abstract: | ![]()
Understanding and controlling the kinetics of O2 reduction in the presence of Li+‐containing aprotic solvents, to either Li+‐O2− by one‐electron reduction or Li2O2 by two‐electron reduction, is instrumental to enhance the discharge voltage and capacity of aprotic Li‐O2 batteries. Standard potentials of O2/Li+‐O2− and O2/O2− were experimentally measured and computed using a mixed cluster‐continuum model of ion solvation. Increasing combined solvation of Li+ and O2− was found to lower the coupling of Li+‐O2− and the difference between O2/Li+‐O2− and O2/O2− potentials. The solvation energy of Li+ trended with donor number (DN), and varied greater than that of O2− ions, which correlated with acceptor number (AN), explaining a previously reported correlation between Li+‐O2− 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. |
| |
| Keywords: | Elektrochemie Lithium Sä ure-Base-Wechselwirkungen Solvatation Superoxid |
|
|
