Precise Modulation of Surface Lattice to Reinforce Structural Stability of High-Nickel Layered Oxide Cathode by Hafnium Gradient Doping

The quest for high-energy lithium-ion batteries has intensified interest in high-nickel layered oxide cathode materials, while the rise in nickel content adversely impacts structural stability and cycling performance. Herein, Hafnium (Hf) anchored at nickel (Ni) site precisely modulates the surface crystal lattice of high-nickel cathode (LiNi0.9Co0.05Mn0.05O2, NCM90) that is confirmed by Rietveld refinement of neutron powder diffraction. Notably, the strengthened structural stability thanks to Hf gradient doping is firmly substantiated by in-situ X-ray diffraction and in-situ X-ray adsorption spectroscopy. This enhancement can be ascribed to the substantial atomic mass of Hf and large radius of Hf4+, facilitating the minimization of potential alterations of interlayer or intralayer. The intensified Hf-O bond significantly increases the formation energy of oxygen vacancies and efficiently restrains the detrimental Li+/Ni2+ disorder, thereby mitigating lattice oxygen loss and enhancing both cycling and thermal stability of high-nickel cathode. Consequently, the 0.3% Hf-doping cathode exhibits considerable improvement in electrochemical performance, delivering superior capacity retention of 95.0 % after 100 cycles at 1C (1 C = 200 mA g−1) and 83.9% after 500 cycles at 1C/5C in the voltage range of 3.0∼4.3 V. This work highlights the benefits of precise modulation strategy for high-nickel cathodes, offering a viable approach to enhance structural stability and electrochemical performance of high-nickel cathodes.