From Formation to Reactivation of Inactive Lithium in Lithium Metal Anodes

Inactive lithium (Li), often referred to as dead or isolated Li, consists of electrochemically disconnected metallic Li and Li‐containing compounds trapped within or beneath the solid–electrolyte interphase (SEI). It is widely recognized as a primary failure mode in lithium‐metal batteries (LMBs), contributing to performance degradation, safety concerns, and limited scalability. This review outlines the sequential processes of Li nucleation, growth of high‐surface‐area Li, and the formation of inactive Li, while identifying the key physicochemical factors influencing each stage. Li nucleation is governed by current density, temperature, electrolyte formulation, and interfacial properties, which collectively dictate the uniformity of Li plating. High‐surface‐area Li growth introduces mechanical and chemical instabilities, fractures and uneven stripping of these filamentous structures lead to Li isolation and inactive Li accumulation. To address these challenges, advanced characterization techniques, including solid‐state nuclear magnetic resonance spectroscopy, titration gas chromatography, inductively coupled plasma optical emission spectroscopy, and operando synchrotron X‐ray diffraction, offer critical insights into the formation and progression of inactive Li. Emerging reactivation strategies, such as redox mediators and tailored cycling protocols, show promise in recovering lost capacity. This review presents key mechanistic factors, advanced diagnostic tools, and emerging reactivation strategies to support a deeper understanding and control of failure mechanisms in LMBs systems.