Crack-free single-crystalline Ni-rich layered NCM cathode enable superior cycling performance of lithium-ion batteries

Ni-rich layered oxides are extensively employed as a promising cathode material in lithium ion batteries (LIBs) due to their high energy density and reasonable cost. However, the hierarchical structure of secondary particles with grain boundaries inevitably induces the structural collapse and severe electrode/electrolyte interface parasitic reactions as the intergranular crack arises from the anisotropic shrink and expansion. Herein, the single-crystalline LiNi0.83Co0.11Mn0.06O2 (SC-NCM) with primary particles of 3–6 μm diameter is developed and comprehensively investigated, which exhibits superior cycling performance at both room temperature and elevated temperature (55 °C) as well as significantly improved structural integrity after long-term cycling. Remarkably, the SiO-C||SC-NCM pouch-type full cell with a practical loading (8.7 mAh cm−2) delivers a capacity retention of 84.8 % at 45 °C after 600 cycles at a current rate of 1C (1C = 200 mA g−1), retaining a high specific energy density of 225 Wh/kg. Using a combination of X-ray photoelectron spectroscopy, time-of-flight secondary-ion mass spectrometry and scanning transmission electron microscopy, we reveal that SC-NCM particles with micron-sizes effectively mitigate the undesired electrode/electrolyte side interactions and prevent the generation of intergranular cracks, thereby alleviating irreversible structural degradation. The strategy of developing single-crystalline micron-sized particles may offer a new path for maintaining the structural stability and improving cycling life of Ni-rich layered NCM cathodes even under high temperature.