%0 Journal Article %A Balachandran Radhakrishnan %A Justin B Haskins %A Kristian B Knudsen %A Bryan D McCloskey %A John W Lawson %B The Journal of Physical Chemistry C %D 2021 %G eng %N 7 %P 3698 - 3705 %R 10.1021/acs.jpcc.0c09755 %T First-Principles Computational and Experimental Investigation of Molten-Salt Electrolytes: Implications for Li–O2 Battery %U https://pubs.acs.org/doi/10.1021/acs.jpcc.0c09755 %V 125 %8 02/2021 %! J. Phys. Chem. C %X

Nitrate-based molten salts have been the most stable electrolytes in Li–O2 electrochemical systems. While the high temperature of operation is a disadvantage, the molten-salt electrolytes offer a compelling inorganic alternative to both organic electrolytes and inorganic solid electrolytes. In this article, we explore the electrochemical and transport properties of the eutectic binary mixture, Li–K/NO3, using ab initio simulations and compare against experimental studies. Our analysis of the eutectic mixture shows that the Li+ ions are the most mobile species while K+ and NO3– ions have lower, comparable mobilities. The high mobility of the Li+ ion is found to result from its small atomic radius, which allows more transport through “hopping” between solvation shells than larger ions such as K+. Furthermore, ab initio computations of band gaps show much larger stability windows than observed in experiments. Electrochemical stability analysis, performed for the first time using grand-potential analysis on liquid electrolytes, shows that the electrochemical window of the nitrate mixture is restricted by the interface reactions with the electrodes.