Yue Ming, Zhong Longsheng, Sheng Yanzhe, He Hongxiao, Xiao Yanhe, Cheng Baochang, Chen Wen, Lei Shuijin
School of Physics and Materials Science, Nanchang University, Nanchang, 330031, China.
China State Key Laboratory of Marine Resource Utilization in South China Sea, Hainan Provincial Key Laboratory of Research on Utilization of Si-Zr-Ti Resources, Hainan University, Haikou, 570228, China.
Small. 2024 Nov;20(47):e2405262. doi: 10.1002/smll.202405262. Epub 2024 Aug 17.
Metal thiophosphites have recently emerged as a hot electrode material system for sodium-ion batteries because of their large theoretical capacity. Nevertheless, the sluggish electrochemical reaction kinetics and drastic volume expansion induced by the low conductivity and inherent conversion-alloying reaction mechanism, require urgent resolution. Herein, a distinctive porous core-shell structure, denoted as SnPS@C, is controllably synthesized by synchronously phosphor-sulfurizing resorcinol-formaldehyde-coated tin metal-organic framework cubes. Thanks to the 3D porous structure, the ion diffusion kinetics are accelerated. In addition, SnPS@C features a tough protective carbon layer, which improves the electrochemical activity and reduces the polarization. As expected, the as-prepared SnPS@C electrode exhibits superior electrochemical performance compared to pure SnPS, including excellent rate capability (1342.4 and 731.1 mAh g at 0.1 and 4 A g, respectively), and impressive long-term cycling stability (97.9% capacity retention after 1000 cycles at 1 A g). Moreover, the sodium storage mechanism is thoroughly studied by in-situ and ex-situ characterizations. This work offers an innovative approach to enhance the energy storage performance of metal thiophosphite materials through meticulous structural design, including the introduction of porous characteristics and core-shell structures.
金属硫代亚磷酸盐因其理论容量大,最近已成为钠离子电池的一种热门电极材料体系。然而,低电导率和固有的转化-合金化反应机制所导致的缓慢电化学反应动力学和剧烈的体积膨胀,亟待解决。在此,通过对间苯二酚-甲醛包覆的锡金属有机框架立方体进行同步磷硫化,可控地合成了一种独特的多孔核壳结构,记为SnPS@C。得益于三维多孔结构,离子扩散动力学得以加速。此外,SnPS@C具有一层坚韧的保护碳层,可提高电化学活性并降低极化。正如预期的那样,与纯SnPS相比,所制备的SnPS@C电极表现出优异的电化学性能,包括出色的倍率性能(在0.1和4 A g时分别为1342.4和731.1 mAh g)以及令人印象深刻的长期循环稳定性(在1 A g下1000次循环后容量保持率为97.9%)。此外,通过原位和非原位表征对储钠机制进行了深入研究。这项工作通过精心的结构设计,包括引入多孔特性和核壳结构