Unraveling the Rapid Performance Decay of Layered High-Energy Cathodes: From Nanoscale Degradation to Drastic Bulk Evolution

Lithium-rich layered oxides are promising cathode candidates because of their exceptional high capacity. The commercial application of these high-energy cathodes, however, is thwarted by the undesired rapid performance decay during cycling. Surface degradation has been widely considered to correlate with the performance decay of the cathodes, whereas, in this work, we demonstrate that the degradation of Li-rich high-energy Li1.2Ni0.13Mn0.54Co0.13O2 (HENMC) cathode material not only takes place at surfaces but also proceeds from its internal structure. In addition to demonstrating the surface reconstruction and the formation of a cathode–electrolyte interphase (CEI) layer of cycled HENMC cathode, this study uncovers the irreversible bulk phase transition from a Li-excess monoclinic (C2/m) solid solution into a conventional “layered” (R3？m) phase, accompanied by complete loss of Li+ from the TM layers during cycling. Furthermore, the internal grains of HENMC bear lattice distortions, leading to the formation of “nano-defect” domains, which could limit the Li+ diffusion inside the grains. More prominently, the layered-to-spinel transition in the form of large spinel grains (Fd3？m), hundreds of nanometers across, is discovered, and their detailed atomic arrangement is studied. The findings suggest that, instead of attributing the overall capacity fade to the surface degradation, these drastic bulk evolutions would be the main degradation mechanisms at the source of the rapid failure of Li-rich cathodes