Mesoscale-architecture-based crack evolution dictating cycling stability of advanced lithium ion batteries

The cracking phenomenon of Ni-rich NMC (LiNixMnyCo1−x−yO2, x ≥ 0.6) secondary particles is frequently discovered and believed to be one of critical reasons deteriorating the long-term cycling stability of NMC cathode in lithium ion batteries (LIBs). However, the initiation and evolution of those cracks is still controversial due to the limited quantification especially by in situ monitoring, leading to the challenge of identifying an efficient approach to inhibit the formation of the fractures during repeated cycling. Herein, the irreversible, anisotropic cycling lattice and mesoscale expansion/shrinkage of nano-grains during the first cycle, as revealed by in situ X-ray diffraction (XRD) and in situ atomic force microscopy (AFM), have been quantified and confirmed to be the dominant driving forces of microcracks initiation at the grain boundaries. These microcracks preferentially nucleate at the core region with random oriented nano-grains in early stage. The further growth and aggregation of microcracks into macrocrack eventually results in microfracture propagation radially outward to the periphery region with more uniform nano-grain orientation. This mesoscale nano-grain architecture controlled cracking process highlights the importance of predictive synthesis of cathode materials with controllable multiscale crystalline architecture for high-performance LIBs. [Display omitted] •In situ AFM quantifies the anisotropic expansion/shrinkage of NMC primary particles.•In situ XRD confirms the irreversible lattice and morphological changes induces microcracks.•Prove that microcracks originate from core of polycrystalline NMC and extend to surfaces.•Provide new insights on synthesis NMC with controllable crystalline architecture.