Structure and Interface Design Enable Stable Li-Rich Cathode

Li-rich layered-oxide cathodes have the highest theoretical energy density among all the intercalated cathodes, which have attracted intense interests for high-energy Li-ion batteries. However, O3-structured layered-oxide cathodes suffer from a low initial Coulombic efficiency (CE), severe voltage fade, and poor cycling stability because of the continuous oxygen release, structural rearrangements due to irreversible transition-metal migration, and serious side reactions between the delithiated cathode and electrolyte. Herein, we report that these challenges are migrated by using a stable O2-structured Li1.2Ni0.13Co0.13Mn0.54O2 (O2-LR-NCM) and all-fluorinated electrolyte. The O2-LR-NCM can restrict the transition metals migrating into the Li layer, and the in situ formed fluorinated cathode–electrolyte interphase (CEI) on the surface of the O2-LR-NCM from the decomposition of all-fluorinated electrolyte during initial cycles effectively restrains the structure transition, suppresses the O2 release, and thereby safeguards the transition metal redox couples, enabling a highly reversible and stable oxygen redox reaction. O2-LR-NCM in all fluorinated electrolytes achieves a high initial CE of 99.82%, a cycling CE of >99.9%, a high reversible capacity of 278 mAh/g, and high capacity retention of 83.3% after 100 cycles. The synergic design of electrolyte and cathode structure represents a promising direction to stabilize high-energy cathodes.