Unveiling the Onset, Evolution, and Kinetic Factors Associated with Lithium Plating on Graphite Electrodes in Lithium‐ion Batteries

Abstract Lithium plating on graphite anodes severely degrades the cycling performance and safety of lithium‐ion batteries (LIBs), fundamentally limiting their fast‐charging capabilities. Despite its critical implications, the operando quantification and probing of the dynamic evolution of lithium plating remain challenging, impeding the effective suppression of lithium dendrite formation—a primary cause of rapid battery degradation and failure. Here, an operando nuclear magnetic resonance (NMR) study is presented to track the onset state of charge (SoC) and the evolution of lithium plating on graphite electrodes across varying charging rates. By integrating operando NMR with X‐ray diffraction (XRD) and finite element modeling (FEM), a comprehensive analysis of electrolyte additives' impact on fast‐charging performance is performed. Beyond enhancing lithium plating reversibility, our findings reveal that accelerated interfacial lithium‐ion transfer kinetics promote lithiation uniformity, thereby suppressing lithium plating while ensuring a more even distribution of plated lithium. In contrast, sluggish interfacial kinetics, exacerbated by particle size heterogeneity, induce spatial lithiation heterogeneity, leading to clustered lithium plating. Building on these findings, particle size uniformity emerges as a critical microstructural parameter governing lithium plating behavior. These insights elucidate the interplay between interfacial kinetics and lithium plating mechanisms, offering actionable strategies for the rational design of fast‐charging LIBs with enhanced safety and durability.