Lattice‐Matched Interfacial Modulation Based on Olivine Enamel‐Like Front‐Face Fabrication for High‐Voltage LiCoO2

Abstract

AbstractThe high‐voltage induced undesirable surface passivation bilayer (cathode/electrolyte interface and cation‐densified surface phase) of LiCoO2 inevitably leads to battery degradation. Herein, a continual/uniform enamel‐like olivine layer on LiCoO2 surface is fabricated by employing a high‐speed mechanical fusion method . The enamel‐like layer suppresses interfacial side reactions by tuning EC dehydrogenation, contributing to an ultrathin and stable cathode/electrolyte interface. The strong bonding affinity between LiCoO2 and enamel‐like layer restrains both lattice oxygen loss and associated layered‐to‐spinel structural distortion. Moreover, the thermal stability of highly delithiated LiCoO2 is improved, as both the onset temperatures of layered‐to‐spinel transition and O2 evolution are simultaneously postponed. Stable operation of LiCoO2 at 4.6 V high‐voltage and 55 °C elevated temperature (both >85% capacity retention after 200 cycles) is achieved. This facile and scalable high‐speed solid‐phase coating strategy establishes a technical paradigm to enhance surface/interface stability of high‐energy‐density cathode candidates by constructing an ideal enamel‐like surface layer.