Anode‐Free Li Metal Batteries: Feasibility Analysis and Practical Strategy

Abstract Energy storage devices are striving to achieve high energy density, long lifespan, and enhanced safety. In view of the current popular lithiated cathode, anode‐free lithium metal batteries (AFLMBs) will deliver the theoretical maximum energy density among all the battery chemistries. However, AFLMBs face challenges such as low plating‐stripping efficiency, significant volume change, and severe Li‐dendrite growth, which negatively impact their lifespan and safety. This study provides an overview and analysis of recent progress in electrode structure, characterization, performance, and practical challenges of AFLMBs. The deposition behavior of lithium is categorized into two stages: heterogeneous and homogeneous interface deposition. The feasibility and practical application value of AFLMBs are critically evaluated. Additionally, key test models, evaluation parameters, and advanced characterization techniques are discussed. Importantly, practical strategies of different battery components in AFLMBs, including current collector, interface layer, solid‐state electrolyte, liquid‐state electrolyte, cathode, and cycling protocol, are presented to address the challenges posed by the two types of deposition processes, lithium loss, crosstalk effect and volume change. Finally, the application prospects of AFLMBs are envisioned, with a focus on overcoming the current limitations and unlocking their full potential as high‐performance energy storage solutions.