Probing the Impact of Vacancy Diffusion on Void Dynamics at the Lithium Metal–Solid Electrolyte Interface

Understanding void formation at the lithium(Li) metal–solid electrolyte (SE) interface is crucial to improving interfacial stability in solid‐state batteries(SSBs). In this work, the competing electrochemical interactions, including surface diffusion modes are studied in dictating interface evolution during electro‐dissolution. A distinct surface diffusion mode for stable contact is identified, and the role of temperature and overpotential is explored. Abstract Lithium (Li) metal‐based solid‐state batteries (SSBs) are considered promising candidates for next‐generation energy storage due to their superior energy density and enhanced safety compared to conventional Li‐ion systems. However, their practical application is limited by challenges such as void formation at the Li‐solid electrolyte (SE) interface, which disrupts ion transport and accelerates interfacial degradation. This work investigates how the coupled effects of electro‐dissolution kinetics and surface diffusion at the Li metal surface govern the evolution of interfacial morphology during stripping. This work examines the influence of three distinct surface diffusion modes, which are terrace diffusion, step diffusion, and interlayer diffusion, on maintaining interfacial stability. In addition, how the dominant surface diffusion mechanism can overcome the contact loss due to high reaction kinetics is explored. Furthermore, the roughness of the Li metal anode surface is quantified, and the influence of different diffusion mechanisms on the evolution of the dynamic solid–solid interface is examined. The critical role of temperature in enhancing Li surface diffusivity and expanding the regime of stable contact is highlighted. By identifying distinct regimes of interface stability, this study analyzes how non‐uniform electrochemical dynamics dictate void morphology evolution and interfacial contact. These insights offer guiding principles for engineering robust Li–SE interfaces in SSBs. Understanding void formation at the lithium(Li) metal–solid electrolyte (SE) interface is crucial to improving interfacial stability in solid-state batteries(SSBs). In this work, the competing electrochemical interactions, including surface diffusion modes are studied in dictating interface evolution during electro-dissolution. A distinct surface diffusion mode for stable contact is identified, and the role of temperature and overpotential is explored. Abstract Lithium (Li) metal-based solid-state batteries (SSBs) are considered promising candidates for next-generation energy storage due to their superior energy density and enhanced safety compared to conventional Li-ion systems. However, their practical application is limited by challenges such as void formation at the Li-solid electrolyte (SE) interface, which disrupts ion transport and accelerates interfacial degradation. This work investigates how the coupled effects of electro-dissolution kinetics and surface diffusion at the Li metal surface govern the evolution of interfacial morphology during stripping. This work examines the influence of three distinct surface diffusion modes, which are terrace diffusion, step diffusion, and interlayer diffusion, on maintaining interfacial stability. In addition, how the dominant surface diffusion mechanism can overcome the contact loss due to high reaction kinetics is explored. Furthermore, the roughness of the Li metal anode surface is quantified, and the influence of different diffusion mechanisms on the evolution of the dynamic solid–solid interface is examined. The critical role of temperature in enhancing Li surface diffusivity and expanding the regime of stable contact is highlighted. By identifying distinct regimes of interface stability, this study analyzes how non-uniform electrochemical dynamics dictate void morphology evolution and interfacial contact. These insights offer guiding principles for engineering robust Li–SE interfaces in SSBs. Advanced Science, EarlyView.