High Safety Electrolyte Design for Enabling High Energy‐Density System of LiNi0.8Co0.1Mn0.1O2//Phosphorus by Simultaneously Adjusting Dual Electrode/Electrolyte Interfaces

Abstract The demand for state‐of‐the‐art high‐energy‐density lithium‐ion batteries is increasing. However, the low specific capacity of electrode materials in conventional full‐cell systems cannot meet the requirements. Ni‐rich layered oxide cathodes such as Li(Ni 0.8 Co 0.1 Mn 0.1 )O 2 (NCM811) have a high theoretical specific capacity of 200 mAh g −1 , but it is always accompanied by side reactions on the electrode/electrolyte interface. Phosphorus anode possesses a high theoretical specific capacity of 2596 mAh g −1 , but it has a huge volume expansion (≈300%). Herein, a highly compatible and secure electrolyte is reported via introducing an additive with a narrow electrochemical window, Lithium difluoro(oxalato)borate (LiDFOB), into 1 m LiPF 6 EC/DMC with tris (2,2,2‐trifluoroethyl) phosphate (TFEP) as a cosolvent. LiDFOB participates in the formation of organic/inorganic hybrid electrode/electrolyte interface layers at both the cathode and anode sides. The side reactions on the surface of the NCM811 cathode and the volume expansion of the phosphorus anode are effectively alleviated. The NCM811//RP full cell in this electrolyte shows high capacity retention of 82% after 150 cycles at a 0.5C rate. Meanwhile, the electrolyte shows non‐flammability. This work highlights the importance of manipulating the electrode/electrolyte interface layers for the design of lithium‐ion batteries with high energy density.