The cycling stability of LiCoO2 under high voltages (>4.5 V) was plagued by hybrid anion- and cation-redox (HACR) induced oxygen escape and uncontrolled phase collapse. With DEMS and in situ XANES mapping at the NSLS-II, we demonstrate that oxygen escape triggers irreversible transformations into “bad” surface phases that rapidly propagate inward. Enabling HACR but stopping global oxygen migration is key to a stable high-energy cathode. Therefore, we developed ∼10 μm single crystals with LiCoO2 in the bulk smoothly transitioning to Co-free LiMn0.75Ni0.25O2 at the surface. By means of initial electrochemical formation, a semi-coherent LiMn1.5Ni0.5O4 spinel-like shell was established in operando with little oxygen loss to integrally wrap the LiCoO2 bulk. Then we obtained gradient-morph LiCoO2 single crystals to prevent the percolating migration of oxygen out of the particle and achieved enhanced HACR reversibility at high voltages. The gradient-morph HACR cathode undergoes substantially stabilized cycling when charged to above 4.6 V, and hence a stable cyclic volumetric energy density of >3400 W h L−1 has been achieved in a pouch full-cell coupled with a commercial graphite anode and lean electrolyte (2 g A h−1), exhibiting up to 2906 W h L−1 even after 300 cycles.
