Toward First Principles Prediction of Voltage Dependences of Electrolyte/Electrolyte Interfacial Processes in Lithium Ion Batteries

In lithium ion batteries, Li⁺ intercalation into electrodes is induced by applied voltages, which are in turn associated with free energy changes of Li⁺ transfer (Δ<i>G</i>_<i>t</i>) between the solid and liquid phases. Using <i>ab initio</i> molecular dynamics (AIMD) and thermodynamic integration techniques, we compute Δ<i>G</i>_<i>t</i> for the virtual transfer of a Li⁺ from a LiC₆ anode slab, with pristine basal planes exposed, to liquid ethylene carbonate confined in a nanogap. The onset of delithiation, at Δ<i>G</i>_<i>t</i> = 0, is found to occur on LiC₆ anodes with negatively charged basal surfaces. These negative surface charges are evidently needed to retain Li⁺ inside the electrode and should affect passivation (“SEI”) film formation processes. Fast electrolyte decomposition is observed at even larger electron surface densities. By assigning the experimentally known voltage (0.1 V vs Li⁺/Li metal) to the predicted delithiation onset, an absolute potential scale is obtained. This enables voltage calibrations in simulation cells used in AIMD studies and paves the way for future prediction of voltage dependences in interfacial processes in batteries