Cracking Mechanism and Inhibition Strategies of Polycrystalline NCM Electrode Particles

Developing a high-energy-density cathode material (LiNi1–x–yCoxMnyO2, NCM) for lithium-ion batteries is crucial to the electric vehicle and energy storage industries. However, the continuous insertion/extraction of Li+ generates diffusion-induced stress, causing NCM particles to crack or even pulverize, leading to battery capacity loss and limiting its wider commercial application. Current experimental studies are primarily postmortem examinations, and it is difficult to capture the particle cracking evolution. Simulation studies frequently ignore or simplify anisotropic volume contraction, demonstrating an insufficient understanding of the cracking mechanism of NCM polycrystalline particles, and cracking prevention strategies still need improvement. Therefore, we develop an anisotropic polycrystalline fracture phase-field model (AP-FPFM) that focuses on the anisotropic volume contraction of primary particles and precisely generates grain boundary distribution, coupling with Li+ diffusion, mechanical stress, and particle cracking. We employ AP-FPFM to demonstrate the behavior and mechanism of NCM polycrystalline particle cracking and illustrate the necessity and importance of anisotropic volume contraction to understand particle cracking. Furthermore, we explore the effects of average primary particle size, secondary particle size, and core–shell structure modulation on crack initiation and propagation and propose strategies to inhibit or migrate NCM polycrystalline particle cracking. This work provides theoretical support for revealing the cracking mechanism of anisotropic polycrystalline NCM particles and supplying optimization strategies to suppress particle cracking and improve the mechanical stability.