Cavity‐Engineered Polycrystalline Cathodes Resolve Stress Concentration Problem in All‐Solid‐State Lithium Metal Batteries

ABSTRACT The development of all‐solid‐state lithium metal batteries (ASSLMBs) has pushed beyond the energy density limit of conventional liquid systems. However, stress concentration remains a critical yet poorly understood cause of degradation in ASSLMBs, particularly in widely used polycrystalline (PC) Ni‐rich cathode systems. Herein, we design cavity‐contained PC LiNi 0.9 Co 0.05 Mn 0.05 O 2 (NCM) cathode particles to resolve the stress concentration problem in particle‐electrode‐battery multiscale by bottom‐up stress management. Synchrotron x‐ray tomography and multiscale finite element simulations disclose the cathode reaction heterogeneity initiates stress concentration and particle‐electrode‐battery multiscale mechanical‐electrochemical degradation. Compared to cavity‐free and multi‐cavity NCM, central‐cavity NCM suppressed cracking within the particles through shortened ionic transport distances and a built‐in stress‐relief space, enhanced (de)lithiation depth and uniformity at the cathode, reduced porosity and fracture in the electrolyte, and inhibited lithium dendrite formation at the anode, suggesting significantly improved stress uniformity in particle‐electrode‐battery levels. Consequently, ASSLMBs using the central‐cavity NCM deliver a superior cycling stability (86.4% after 200 cycles and 81.5% after 400 cycles), outperforming both the traditional cavity‐free NCM (51.6% after 200 cycles) and highly anticipated single crystal NCM (44.2% after 400 cycles). This work links particle‐electrode‐battery multiscale mechanical‐electrochemical behavior, providing valuable insights for designing ASSLMBs with long lifespan from a holistic perspective.