Lithium Transport Pathways Guided by Grain Architectures in Ni-Rich Layered Cathodes

Ni-rich layered cathodes have been used in commercial Li-ion batteries because of their high capacity and low cost. However, they suffer from crack formation at the grain boundaries owing to heterogeneous large volume changes during the reactions. To improve their performance, a comprehensive understanding of the grain architecture, Li transport pathways, and phase transitions is essential. Here, we show the correlations between these factors using in situ transmission electron microscopy. The results show that Li ions are extracted through tortuous paths connecting the Li-containing a-b planes in the crystals. Moreover, the grain boundary resistance depends not only on the misorientations of the neighboring grains. Even twins with misorientation angles of 70° are not decisive factors in Li movement. We also show the existence of two-phase separation in single crystals between two hexagonal phases during fast charging. These results provide valuable information for determining the optimal grain architecture and for material design, helping enhance high capacity and high stability.