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In this investigation, the improved electrochemical behavior in Si-doped Li-rich cathodes is studied with scanning transmission electron microscopy (STEM) and electron energy loss spectroscopy (EELS). Z-contrast images show a layered structure that develops a thin, spinel-like surface layer after the first charge cycle. Si-doping increases discharge capacity by ∼25% and appears to retard the surface phase transformation. Based on electron energy loss spectra, the surface layer in the doped material has an altered oxygen electronic environment, which supports the STEM findings. Furthermore, Si-doping changes the redox behavior during the activation cycle. Density functional theory calculations indicate that Si-doping can increase oxygen vacancy formation, and change the sequence of the redox couples by introducing more oxygen vacancies before or during the typical high voltage activation process. The results of this work indicate that the type of doping employed here is an effective strategy for controlling the complex charge compensation mechanisms in lithium-rich cathodes. 

High-energy nickel (Ni)–rich cathode will play a key role in advanced lithium (Li)–ion batteries, but it suffers from moisture sensitivity, side reactions, and gas generation. Single-crystalline Ni-rich cathode has a great potential to address the challenges present in its polycrystalline counterpart by reducing phase boundaries and materials surfaces. However, synthesis of high-performance single-crystalline Ni-rich cathode is very challenging, notwithstanding a fundamental linkage between overpotential, microstructure, and electrochemical behaviors in single-crystalline Ni-rich cathodes. We observe reversible planar gliding and microcracking along the (003) plane in a single-crystalline Ni-rich cathode. The reversible formation of microstructure defects is correlated with the localized stresses induced by a concentration gradient of Li atoms in the lattice, providing clues to mitigate particle fracture from synthesis modifications.