Synthesis and Mechanism of High Structural Stability of Nickel-Rich Cathode Materials by Adjusting Li-Excess

It has been a long-term challenge to improve the phase stability of Ni-rich LiNixMnyCo1-x-yO2 (x ≥ 0.6) transition metal (TM) oxides for large-scale applications. Herein, a new structure engineering strategy is utilized to optimize the structural arrangement of Li1+x(Ni0.88Mn0.06Co0.06)1-xO2 (NMC88) with a different Li-excess content. It was found that structure stability and particle sizes can be tuned with suitable Li-excess contents. NMC88 with an actual Li-excess of 2.7% (x = 0.027, Li/TM = 1.055) exhibits a high discharge capacity (209.1 mAh g-1 at 3.0-4.3 V, 0.1 C) and maintains 91.7% after the 100th cycle at 1 C compared with the NMC88 sample free of Li-excess. It also performs a delayed voltage decay and a good rate capacity, delivering 145.8 mAh g-1 at a high rate of 10 C. Multiscale characterization technologies including ex/in situ X-ray diffraction (XRD), focused ion beam (FIB) cutting-scanning electronic microscopy (SEM), and transmission electron microscopy (TEM) results show that a proper Li-excess (2.7%) content contributes to the formation of a broader Li slab, optimized cation mixing ratio, and even particle sizes. Therefore, NMC88 with a proper Li-excess is a good choice for next-generation cathode materials.