Gradient‐Matched Microstructural Engineering for Fast‐Charging, Damage‐Tolerant Thick Electrodes of Lithium‐Ion Batteries

Abstract Gradient microstructure design has emerged as a promising strategy for developing high areal loading thick electrode batteries with both fast‐charging performance and mechanical integrity. However, it has largely been explored through trial‐and‐error approaches. In this study, a universal matching concept is introduced, wherein electrode microstructures—specifically the conductive network, porosity, and particle size—are gradiently distributed to align with the intrinsic gradients of electron, ion, and reaction‐driven fluxes, respectively. The electro‐chemo‐mechanical coupled modeling and simulations validate that multi‐gradient matched structures in thick electrodes lead to a synergistic enhancement of both fast‐charging performance and mechanical resilience, consistent with experimental observations. This study demonstrates how the gradient‐matched structure fosters collaborative electron/ion and reaction transport, optimizing the balance between these processes and further mitigating concentration polarization. The findings provide a comprehensive design principle for gradient architecture that enables fast‐charging, damage‐tolerant thick electrodes.