Kinetic Control of Long-Range Cationic Ordering in the Synthesis of Layered Ni-Rich Oxides

Deciphering the sophisticated interplay between thermodynamics and kinetics of high-temperature lithiation reaction is fundamentally significant for designing and preparing cathode materials. Here, the formation pathway of Ni-rich layered ordered LiNi_0.6Co_0.2Mn_0.2O₂ (O-LNCM622O) is carefully characterized using in situ synchrotron radiation diffraction. A fast nonequilibrium phase transition from the reactants to a metastable disordered Li_1−x(Ni_0.6Co_0.2Mn_0.2)_1+xO₂ (D-LNCM622O, 0 < x < 0.95) takes place while lithium/oxygen is incorporated during heating before the generation of the equilibrium phase (O-LNCM622O). The time evolution of the lattice parameters for layered nonstoichiometric D-LNCM622O is well-fitted to a model of first-order disorder-to-order transition. The long-range cation disordering parameter, Li/TM (TM = Ni, Co, Mn) ion exchange, decreases exponentially and finally reaches a steady-state as a function of heating time at selected temperatures. The dominant kinetic pathways revealed here will be instrumental in achieving high-performance cathode materials. Importantly, the O-LNCM622O tends to form the D-LNCM622O with Li/O loss above 850 °C. In situ XRD results exhibit that the long-range cationic (dis)ordering in the Ni-rich cathodes could affect the structural evolution during cycling and thus their electrochemical properties. These insights may open a new avenue for the kinetic control of the synthesis of advanced electrode materials.