Targeted masking enables stable cycling of LiNi0.6Co0.2Mn0.2O2 at 4.6V

• Published in: Nano energy 2022-06, Vol.96, p.107123, Article 107123
• Main Authors: Hu, Qiao, He, Yufang, Ren, Dongsheng, Song, Youzhi, Wu, Yanzhou, Liang, Hongmei, Gao, Jinhui, Xu, Gang, Cai, Jiyu, Li, Tianyi, Xu, Hong, Wang, Li, Chen, Zonghai, He, Xiangming
• Format: Article
• Language: English
• Subjects: ENERGY STORAGE; High voltage; NCM622; Parasitic reaction; Surface decoration; Thermal runaway
• ISSN: 2211-2855
• DOI: 10.1016/j.nanoen.2022.107123

Layered LiNixCoyMn1−x-yO2 (NCM, or NCMxy(1-x-y)) is a dominant family of cathode materials for lithium-ion batteries (LIBs) due to its high energy density. Among all NCM cathode materials, NCM622 possess the optimal energy density at high potential (≥ 4.6 V vs. Li/Li+). However, the practical application of NCM622 at high voltage (≥ 4.6 V) is limited by its parasitic reactions and associated safety concerns. Completely physical isolation has been considered as the main approach to mitigate the parasitic reaction. It has also been previously demonstrated that the interface reaction has active site selectivity, and that the reactivity of the active sites can effectively suppressed by blocking the chemically active sites. Herein, a targeted masking by LiFePO4 @C nanoplates is reported to unlock the stable performance of NCM622 up to 4.6 V vs. Li/Li+. The (targeted masked-NCM622)|graphite pouch cell shows 86.5% capacity retention after 1000 cycles and its maximum temperature during thermal runaway is dramatically reduced from 570 °C to 415 °C. Systematic in/ex situ characterizations, first-principles calculations and half/pouch targeted LiFePO4@C covers the surface of NCM partcell evaluation prove that PO43- is preferentially adsorbed on transition metal sites, stabilizing both the transition metal ions and oxygen ions on the surface against the ethylene carbonate-containing traditional electrolyte even under high voltage (≥ 4.6 V vs. Li/Li+). This work opens up new venue for rational design of high-performance cathode materials through a low-cost and scalable decoration process, and reveal a new understanding of interfacial activity of materials. [Display omitted] •A targeted LiFePO4@Ccovers the surface of NCM particles less than 30%, enables high-voltage (≥4.6 V) cycling of NCM622.•The PO43- is preferentially adsorbed on transition metal ion and prevents the subsequent carbonate catalytic oxidation.•The targeted self-repairing decorated-NCM622|graphite pouch cell shows 86.5% capacity retention after 1000 cycles.•The maximum temperature of NCM622|graphite pouch cell during thermal runaway is dramatically reduced from 570 °C to 415 °C.•This study breaks free from traditional cognition on surface modification of NCM materials