Relieving Stress Concentration through Anion–Cation Codoping toward Highly Stable Nickel-Rich Cathode
Yu Zhou, Hanwei Zhang, Yinglei Wang, Tao Wan, Peiyuan Guan, Xindong Zhou, Xuri Wang, Yi-Chang Chen, Hancheng Shi, Aichun Dou, Mingru Su, Ruiqiang Guo, Yunjian Liu, Liming Dai, Dewei Chu
Abstract
Nickel-rich LiNi 0.8 Co 0.15 Al 0.015 O 2 (NCA) with excellent energy density is considered one of the most promising cathodes for lithium-ion batteries. Nevertheless, the stress concentration caused by Li + /Ni 2+ mixing and oxygen vacancies leads to the structural collapse and obvious capacity degradation of NCA. Herein, a facile codoping of anion (F – )-cation (Mg 2+ ) strategy is proposed to address these problems. Benefiting from the synergistic effect of F – and Mg 2+, the codoped material exhibits alleviated Li + /Ni 2+ mixing and demonstrates enhanced electrochemical performance at high voltage (≥4.5 V), outperformed the pristine and F – /Mg 2+ single-doped counterparts. Combined experimental and theoretical studies reveal that Mg 2+ and F – codoping decreases the Li + diffusion energy barrier and enhances the Li + transport kinetics. In particular, the codoping synergistically suppresses the Li + /Ni 2+ mixing and lattice oxygen escape, and alleviates the stress–strain accumulation, thereby inhibiting crack propagation and improving the electrochemical performance of the NCA. As a consequence, the designed Li 0.99 Mg 0.01 Ni 0.8 Co 0.15 Al 0.05 O 0.98 F 0.02 (Mg1+F2) demonstrates a much higher capacity retention of 82.65% than NCA (55.69%) even after 200 cycles at 2.8–4.5 V under 1 C. Furthermore, the capacity retention rate of the Mg1+F2||graphite pouch cell after 500 cycles is 89.6% compared to that of the NCA (only 79.4%).