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 LiNixCoyAl1–x–yO2 (x ≥ 0.8) cathode materials. In this research, a feasible Hf-doping method is proposed to improve the electrochemical performance of LiNi0.9Co0.08Al0.02O2 (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 LiNi0.895Co0.08Al0.02Hf0.005O2 (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.