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

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 NO^₃– 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.