Yuan Siqi, Qi Jizhen, Jiang Meidan, Cui Guijia, Liao Xiao-Zhen, Liu Xi, Tan Guoqiang, Wen Wen, He Yu-Shi, Ma Zi-Feng
Shanghai Electrichemical Energy Devices Research Center, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China.
i-Lab, CAS center for Excellence in Nanoscience, Suzhou Institute of Nano-Tech and Nano bionics, Chinese Academy of Sciences, Suzhou 215123, China.
ACS Appl Mater Interfaces. 2021 Jan 27;13(3):3793-3804. doi: 10.1021/acsami.0c17080. Epub 2021 Jan 15.
P2-NaNiMnO presents high working voltage with a theoretical capacity of 173 mAh g. However, the lattice oxygen on the particle surface participates in the redox reactions when the material is charged over 4.22 V. The resulting oxidized oxygen aggravates the electrolyte decomposition and transition metal dissolution, which cause severe capacity decay. The commonly reported cation substitution methods enhance the cycle stability by suppressing the high voltage plateau but lead to lower average working voltage and reduced capacity. Herein, we stabilized the lattice oxygen by a small amount of Sn substitution based on the strong Sn-O bond without sacrificing the high voltage performance and further protected the particle surface by polypyrrole (PPy) coating. The obtained NaNiMnSnO@PPy (3.3 wt %) composite showed excellent cycling stability with a reversible capacity of 137.6 (10) and 120.0 mAh g (100 mA g) with a capacity retention of 95% (10 mA g, 50 cycles) and 82.5% (100 mA g, 100 cycles), respectively. The present work indicates that slight Sn substitution combined with PPy coating could be an effective approach to achieving superior cycling stability for high-voltage layered transition metal oxides.
P2-NaNiMnO具有较高的工作电压,理论容量为173 mAh g。然而,当材料充电超过4.22 V时,颗粒表面的晶格氧会参与氧化还原反应。生成的氧化氧会加剧电解质分解和过渡金属溶解,从而导致严重的容量衰减。通常报道的阳离子取代方法通过抑制高压平台来提高循环稳定性,但会导致平均工作电压降低和容量减小。在此,我们基于强Sn-O键通过少量Sn取代来稳定晶格氧,同时不牺牲高压性能,并通过聚吡咯(PPy)涂层进一步保护颗粒表面。所制备的NaNiMnSnO@PPy(3.3 wt%)复合材料表现出优异的循环稳定性,在10 mA g、50次循环时可逆容量为137.6 mAh g,容量保持率为95%;在100 mA g、100次循环时可逆容量为120.0 mAh g,容量保持率为82.5%。目前的工作表明,少量Sn取代与PPy涂层相结合可能是实现高压层状过渡金属氧化物优异循环稳定性的有效方法。