Phase-Field Investigation of Lithium Electrodeposition at Different Applied Overpotentials and Operating Temperatures

Li metal is an exciting anode for high-energy Li-ion batteries and other future battery technologies due to its high energy density and low redox potential. Despite their high promise, the commercialization of Li-metal-based batteries has been hampered due to the formation of dendrites that lead to mechanical instability, energy loss, and eventual internal short circuits. In recent years, the mechanism of dendrite formation and the strategies to suppress their growth have been studied intensely. However, the effect of applied overpotential and operating temperature on dendrite formation and their growth rate remains to be fully understood. Here, we elucidate the correlation between the applied overpotential and operating temperature to the dendrite height and tortuosity of the Li-metal surface during electrodeposition using phase-field model simulations. We identify an optimal operating temperature of a half-cell consisting of a Li metal anode and 1 M LiPF₆ in EC/DMC (1/1), which increases gradually as the magnitude of the overpotential increases. The investigation reveals that the temperature dependence identified in the simulations and experiments often disagree because they are primarily conducted under galvanostatic and potentiostatic conditions, respectively. The temperature increase under potentiostatic conditions increases the induced current while it decreases the induced overpotential under galvanostatic conditions. Therefore, the analysis and comparison of temperature-dependent characteristics must be carried out with care.