Xu Zhe, Yang Haidi, Zhao Xuesen, Zheng Runguo, Song Zhishuang, Wang Zhiyuan, Sun Hongyu, Liu Yanguo, Wang Dan
School of Materials Science and Engineering, Northeastern University, Shenyang 110819, People's Republic of China.
School of Resources and Materials, Northeastern University at Qinhuangdao, Qinhuangdao 066004, People's Republic of China.
ACS Appl Mater Interfaces. 2025 Jan 8;17(1):1085-1096. doi: 10.1021/acsami.4c16665. Epub 2024 Dec 17.
O3-NaNiFeMnO has attracted much attention as a cathode for sodium-ion batteries, because of its low cost and high sodium-ion storage capacity. However, its slow Na diffusion kinetics and harmful P3-O3' phase transition with severe bulk strain at high voltage leads to poor rate capability and fast capacity fading. Herein, we propose a multivariate doping strategy with Cu, Mg, and Ti ions to solve the above problems of the O3-NaNiFeMnO cathode. The O3-Na(NiFeMn)CuMgTiO (NFMCMT) cathode exhibits enlarged Na diffusion channels and a strengthened layered structure, which improves the Na diffusion kinetics, suppresses the harmful P3-O3' phase transition at high voltages, and inhibits the intragranular fatigue cracks, leading to enhanced rate capability and cycling performance. As a result, the NFMCMT exhibits outstanding performance in the 2-4.1 V voltage window, delivers a discharge capacity of 151.2 mAh g with the 81.5% capacity retention for 100 cycles at 0.1 C, and 83.1% capacity retention for 300 cycles at 5 C. Especially in the rate performance, the NFMCMT delivers a 115.6 mAh g and 100.1 mAh g discharge capacity even at 5 and 10 C. This work provides an effective multivariate doping strategy for development of high-performance layered oxide cathodes for sodium-ion batteries.
O3-NaNiFeMnO作为钠离子电池的阴极受到了广泛关注，因为其成本低且钠离子存储容量高。然而，其缓慢的钠离子扩散动力学以及在高电压下伴随着严重体应变的有害P3-O3'相变导致倍率性能差和容量快速衰减。在此，我们提出一种用铜、镁和钛离子的多元掺杂策略来解决O3-NaNiFeMnO阴极的上述问题。O3-Na(NiFeMn)CuMgTiO（NFMCMT）阴极展现出扩大的钠离子扩散通道和强化的层状结构，这改善了钠离子扩散动力学，抑制了高电压下有害的P3-O3'相变，并抑制了晶内疲劳裂纹，从而提高了倍率性能和循环性能。结果，NFMCMT在2-4.1V电压窗口表现出优异性能，在0.1C下100次循环的放电容量为151.2mAh g，容量保持率为81.5%，在5C下300次循环的容量保持率为83.1%。特别是在倍率性能方面，NFMCMT即使在5C和10C时也能提供115.6mAh g和100.1mAh g的放电容量。这项工作为开发高性能钠离子电池层状氧化物阴极提供了一种有效的多元掺杂策略。
