Morphological peculiarities of the lithium electrode from the perspective of the Marcus-Hush-Chidsey model

Abstract

This study employs the kinetics framework of Marcus-Hush-Chidsey (MHC) to investigate the charge transfer at the interface of lithium electrode and electrolyte in lithium(ion)-batteries. The charge-transfer rate constant is evaluated for different facets of lithium, namely (1 0 0), (1 1 0), (1 0 1), and (1 1 1) as a function of surface charge density with the aid of density functional theory (DFT) calculations. The results highlight and quantify the sensitivity of the rate of lithium plating and stripping to the surface orientation, surface charge density, and charge-transfer over-potential. An intrinsic kinetics competition among the different surface orientations is identified together with an asymmetry between the lithium plating and stripping and showcased to influence the deposit morphology and surface protrusions and indentations.