@article{35917, author = {Balachandran Radhakrishnan and Justin B Haskins and Kristian B Knudsen and Bryan D McCloskey and John W Lawson}, title = {First-Principles Computational and Experimental Investigation of Molten-Salt Electrolytes: Implications for Li–O2 Battery}, abstract = {

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.

}, year = {2021}, journal = {The Journal of Physical Chemistry C}, volume = {125}, pages = {3698 - 3705}, month = {02/2021}, issn = {1932-7447}, url = {https://pubs.acs.org/doi/10.1021/acs.jpcc.0c09755}, doi = {10.1021/acs.jpcc.0c09755}, language = {eng}, }