Maintaining a Flat Li Surface during the Li Stripping Process via Interface Design

Electroplating has been the main focus in mitigating the dendrite growth on the Li-metal electrode; however, the stripping process is equally critical, since the nonsmooth Li surface during stripping will lead to nonuniform local current density, planting the seeds for dendrite growth. In this paper, density functional theory (DFT) and kinetic Monte Carlo (KMC) techniques were combined to investigate the vacancy evolution in Li interfaced with different solid–electrolyte interphase (SEI) materials. It was found that the lithiophilic interface, such as Li/Li₂O, repels vacancies into the bulk Li, so Li atoms can quickly fill the Li vacancies near the Li/Li₂O interface and maintain a smooth Li surface. In contrast, the lithiophobic interface, such as Li/LiF, traps Li vacancies toward the interface, and the accumulated Li vacancies form voids and roughen the surface. The predicted critical stripping current density, below which a smooth Li surface will be maintained, is therefore much faster at the lithiophilic interface than that at the lithiophobic interface. It was further revealed that the lithiophilicity at different SEI or coating materials can be ranked as Li/Li₂O > Li/LiPON > Li/Li₂CO₃ > Li/LiF based on the calculated interfacial adhesion and accumulation of electron density at the interface. This suggests that interface and coating design at nanoscale can be effective for maintaining a smooth Li surface during the stripping process, solving another challenge to achieving a dendrite-free Li-metal electrode in both liquid and solid electrolytes.