Correlating Kinetics to Cyclability Reveals Thermodynamic Origin of Lithium Anode Morphology in Liquid Electrolytes

The rechargeability of lithium metal batteries strongly depends on the electrolyte. The uniformity of the electroplated Li anode morphology underlies this dependence, so understanding the main drivers of uniform plating is critical for further electrolyte discovery. Here, we correlate electroplating kinetics with cyclability across several classes of electrolytes to reveal the mechanistic influence electrolytes have on morphology. Fast charge-transfer kinetics at fresh Li-electrolyte interfaces correlate well with uniform morphology and cyclability, whereas the resistance of Li⁺ transport through the solid electrolyte interphase (SEI) weakly correlates with cyclability. These trends contrast with the conventional thought that Li⁺ transport through the electrolyte or SEI is the main driver of morphological differences between classes of electrolytes. Relating these trends to Li⁺ solvation, Li nucleation, and the charge-transfer mechanism instead suggests that the Li/Li⁺ equilibrium potential and the surface energy─thermodynamic factors modulated by the strength of Li⁺ solvation─underlie electrolyte-dependent trends of Li morphology. Overall, this work provides an insight for discovering functional electrolytes, tuning kinetics in batteries, and explaining why weakly solvating fluorinated electrolytes favor uniform Li plating.