First-Principles Computational and Experimental Investigation of Molten-Salt Electrolytes: Implications for Li–O2 Battery

• Published in: Journal of physical chemistry. C Vol. 125; no. 7; pp. 3698 - 3705
• Main Authors: Radhakrishnan, Balachandran, Haskins, Justin B, Knudsen, Kristian B, McCloskey, Bryan D, Lawson, John W
• Format: Journal Article
• Language: English
• Published: American Chemical Society 25.02.2021
• Subjects: C: Energy Conversion and Storage
• ISSN: 1932-7447; 1932-7455
• DOI: 10.1021/acs.jpcc.0c09755

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.