Cathodes Coating Layer with Li‐Ion Diffusion Selectivity Employing Interactive Network of Metal‐Organic Polyhedras for Li‐Ion Batteries

Surface modification of cathodes using Ni‐rich coating layers prevents bulk and surface degradation for the stable operation of Li–ion batteries at high voltages. However, insulating and dense inorganic coating layers often impede charge transfer and ion diffusion kinetics. In this study, the fabrication of dual functional coating materials using metal–organic polyhedra (MOP) with 3D networks within microporous units of Li–ion batteries for surface stabilization and facile ion diffusion is proposed. Zr‐based MOP is modified by introducing acyl groups as a chemical linkage (MOPAC), and MOPAC layers are homogenously coated by simple spray coating on the cathode. The coating allow the smooth transport of electrons and ions. MOPAC effectively suppress side reactions between the cathode and electrolyte and protect active materials against aggressive fluoride ions by forming a Li–ion selective passivation film. The MOPAC‐coated Ni‐rich layered cathode exhibited better cycle retention and enhanced kinetic properties than pristine and MOP‐coated cathodes. Reduction of undesirable gas evolution on the cathode by MOPAC is also verified. Microporous MOPAC coating can simultaneously stabilize both the bulk and surface of the Ni‐rich layered cathode and maintain good electrochemical reaction kinetics for high‐performance Li–ion batteries. A cathode coating material using metal‐organic polyhedra modified by introducing acyl groups as a chemical linkage (MOPAC) with 3D networks within microporous units for selective Li‐ion diffusion and surface stabilization in Li‐ion batteries is reported. The MOPAC layers are homogenously coated by simple spray coating on the cathode and the MOPAC‐coated Ni‐rich layered cathodes exhibit enhanced cell performance.