Anode‐Free Solid‐State Batteries: From Materials Innovation to System‐Level Sustainability—A Review

This critical review examines anode‐free solid‐state batteries (AFSSBs) as a promising next‐generation energy storage technology within the broader context of sustainable energy systems. Literature was systematically collected from the Scopus and Web of Science databases to evaluate AFSSB materials, cell architectures, performance challenges, and development pathways. AFSSBs offer important advantages, including higher energy density, improved safety through nonflammable solid–electrolytes (SEs), and lower material demand by eliminating the conventional anode. However, their practical application remains limited by short cycle life, dendrite formation, low Coulombic efficiency (CE), and parasitic interfacial reactions. The review summarizes key strategies proposed to overcome these barriers, including stabilizing lithium plating, engineering protective interphases, and optimizing SEs. Recent studies show that interface modification and coating strategies can significantly improve CE and cycling stability. Beyond technical performance, this review emphasizes the importance of integrating technoeconomic analysis (TEA) and life cycle assessment (LCA) at an early stage to identify cost drivers, evaluate environmental impacts, and guide sustainable development. Overall, AFSSBs show strong potential, but their successful commercialization will depend on coordinated advances in materials design, cell architecture, economic viability, and sustainability assessment.