Understanding high-temperature cycling-induced crack evolution and associated atomic-scale structure in a Ni-rich LiNi0.8Co0.1Mn0.1O2 layered cathode material

X-ray nano-computed tomography (nano-CT) and deep learning combined with Cs-corrected scanning transmission electron microscopy (STEM) and electron energy loss spectroscopy were employed to investigate the atomic to microscopic structural evolution of LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM) upon cycling at 55 °C. Two types of intergranular cracks were clearly distinguished by nano-CT for cycled cathode particles; denoted open and closed cracks depending on whether or not the cracks reach the surface of the NCM secondary particles. The volume of high-temperature cycling-induced cracks quantified by deep learning increased drastically, particularly for the open cracks, and this phenomenon was accompanied by rapid degradation of capacity retention. Further precise STEM analysis of the crack regions revealed that migration of transition metal (TM) ions to the Li layer forms a rocksalt-like structure, and the associated reduction of TM ions, e.g., Ni 3+ to Ni 2+ , predominately occurred in the open crack regions in the presence of penetrated electrolyte, even for regions extending to the center of the secondary particle. In contrast, in the closed crack regions, no significant atomic-scale structure distortion and limited reduction of TM ions was observed. Thus, our results provide fundamental guidance for improving the electrochemical performance of Ni-rich layered cathode materials for cycling at elevated temperatures. A combined investigation of X-ray nano-computed tomography/deep learning and Cs-corrected scanning transmission electron microscopy/electron energy loss spectroscopy reveals the atomic to microscopic structural evolution in the closed and open crack regions of LiNi 0.8 Co 0.1 Mn 0.1 O 2 upon cycling at 55 °C. • Nano-CT and STEM are combined to investigate Ni-rich layered cathode material. • After cycling at 55 °C, intergranular open and closed cracks are induced. • Open cracks increase drastically, accompanied by decrease of capacity. • Structural distortion is predominately occurred in the open crack regions. • Formation of rocksalt and metal fluoride occurs in the open crack regions.