Structures and dynamic properties of the LiPF6 electrolytic solution under electric fields – a theoretical study

Fluorinated carbonates have attracted increasing attention in high-voltage lithium ion battery applications. Under free and electric fields, their structure-related solvent dynamic properties such as charge and discharge rate, however, are rarely reported. Herein, solutions including linear fluorinated carbonates have been simulated using joint MD/DFT calculations. For the first time, the dielectric constants of the four pure fluorinated carbonates have been predicted to be ca. 5.4 (4: ethyl-2,2,2-trifluoroethyl carbonate)–12.1 (7: di-1,1,2,2,2-pentafluoroethyl carbonate), which are dependent on the number of fluorine atoms. Minor difference in the solvation free energies and few contact ion associations were observed in the ETFEC and DTFEC solvents. Their comparable viscosity values were found through calculations of ion diffusivity and conductivity. In the electric fields, the Li+ mobilities in the two solutions have similar values, showing that the dynamic properties of the electrolytic solutions are almost independent of the number of fluorine atoms on these carbonates. There emerges an oriented and ordered arrangement of the solvent molecules and thus the largely decreased dielectric constants under the electric fields, even though the field strength is very low. These interesting phenomena should be relevant in the formation of contact and aggregate ion pairs, leading to unexpected reduction of the charge–discharge rate-related ion mobility in mixed solvents.