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Towards First Principles prediction of Voltage Dependences of Electrolyte/Electrolyte Interfacial Processes in Lithium Ion Batteries

In lithium ion batteries, Li+ intercalation and processes associated with passivation of electrodes are governed by applied voltages, which are in turn associated with free energy changes of Li+ transfer (Delta G_t) between the solid and liquid phases. Using ab initio molecular dynamics (AIMD) and thermodynamic integration techniques, we compute Delta G_t for the virtual transfer of a Li+ from a LiC(6) anode slab, with pristine basal planes exposed, to liquid ethylene carbonate confined in a nanogap. The onset of delithiation, at Delta G_t=0, is found to occur on LiC(6) 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.