Key Anodic Interfacial Phenomena and their Control in Next‐Generation Lithium and Sodium Metal Batteries

Abstract Advancing next‐generation battery technologies requires a thorough understanding of the intricate phenomena occurring at anodic interfaces. This focused review explores key interfacial processes, examining their thermodynamics and consequences in ion transport and charge transfer kinetics. It begins with a discussion on the formation of the electro chemical double layer, based on the GuoyChapman model, and explores how charge carriers achieve equilibrium at the interface. This review then delves into essential interfacial processes, including metal nucleation and growth, the development and stability of the solid electrolyte interphase (SEI), and ion movement across the interface. In addition, it analyzes the impact of different electrolyte solutions—such as low‐ and high‐concentration electrolytes and localized high‐concentration electrolytes—on these interfacial processes. The role of additives, co‐solvents, and diluents in modifying these interfaces is also covered. This review further evaluates techniques for characterizing the SEI layer, highlighting their strengths and limitations in both aqueous and nonaqueous battery systems. By comparing the challenges and opportunities associated with interfaces next‐generation nonaqueous metal battery systems, this review aims to offer new insights into their respective advantages and limitations, ultimately guiding the design and optimization of anodic interfaces to enhance the safety and efficiency of future energy storage technologies.