Unveiling electrode microstructure governed lithium plating–relaxation–stripping dynamics in lithium-ion batteries

Lithium plating severely limits the fast-charging capability and safety of lithium-ion batteries, yet the role of electrode microstructure in governing the coupled plating–relaxation–stripping dynamics remains unclear. Despite significant progress, existing operando characterization methods remain fundamentally limited in resolving this challenge. Here, we integrate stochastic microstructure reconstruction with microstructure-resolved multiphysics modeling to elucidate the underlying linkage between electrode microstructure and lithium plating–relaxation–stripping dynamics. Our findings reveal that particle-size dispersity amplifies electrochemical heterogeneity and accelerates localized lithiation and lithium plating, while gradient-particle-size electrodes exhibit pronounced rate-dependent lithium plating behavior owing to the competition between kinetic redistribution and transport limitation. In contrast, porosity grading and oriented-pore structures suppress lithium plating through enhanced ionic transport and mitigated electrolyte depletion. Beyond lithium plating onset and total amount, electrode microstructure is found to fundamentally regulate the subsequent relaxation and stripping dynamics by controlling ionic redistribution pathways and electrochemical nonequilibrium. These findings further suggest that fast-charging strategies and post-charging resting protocols should be co-designed with electrode microstructure to simultaneously regulate lithium plating and relaxation-induced dynamics evolution.