Modification of the Ni-Rich Layered Cathode Material by Hf Addition: Synergistic Microstructural Engineering and Surface Stabilization.

The rapid decline of the reversible capacity originating from microcracks and surface structural degradation during cycling is still a serious obstacle to the practical utilization of Ni-rich LiNi x Co y Al 1- x - y O 2 ( x ≥ 0.8) cathode materials. In this research, a feasible Hf-doping method is proposed to improve the electrochemical performance of LiNi 0.9 Co 0.08 Al 0.02 O 2 (NCA90) through microstructural optimization and structural enhancement. The addition of Hf refines the primary particles of NCA90 and develops them into a short rod shape, making them densely arranged along the radial direction, which increases the secondary particle toughness and reduces their internal porosity. Moreover, Hf-doping stabilizes the layered structure and suppresses the side reactions through the introduction of robust Hf-O bonding. Multiple advantages of Hf-doping allowed significant improvement of the cycling stability of LiNi 0.895 Co 0.08 Al 0.02 Hf 0.005 O 2 (NCA90-Hf0.5), with a reversible capacity retention rate of 95.3% after 100 cycles at 1 C, as compared with only 82.0% for the pristine NCA90. The proposed synergetic strategy combining microstructural engineering and crystal structure enhancement can effectively resolve the inherent capacity fading of Ni-rich layered cathodes, promoting their practical application for next-generation lithium-ion batteries.