Rational design of Li off-stoichiometric Ni-rich layered cathode materials for Li-ion batteries

The electrification trend in the automotive industry is fueling research on Ni-rich layered NCM cathode materials with high specific capacities. The simplest way to maximize the electrochemical performance of Ni-rich NCM is to tune the crystal structure by controlling the Li content and synthesis temperature. Herein, we demonstrate the critical roles of the Li content and synthesis temperature in determining the crystal structure of Li-excess Ni-rich NCM with enhanced electrochemical performance. The crystal structure of Li-excess Ni-rich NCM was systemically investigated using X-ray diffraction, neutron diffraction, and X-ray absorption spectroscopy, revealing that excess Li can be accommodated in Ni-rich NCM as the synthesis temperature decreases, resulting in stable cycle performance at high working voltage. We believe that our findings provide a rational reason for the excess amount Li required for optimization of the synthesis of Ni-rich NCM and offer insight for the simplest design of Ni-rich cathode materials that are stable under high-voltage operation.