Abstract
Nickle sulfides are attractive anode materials for sodium-ion batteries (SIBs) due to their rich structures and natural abundance. However, their applications are greatly hindered by the large volume expansion and poor cycling properties. The introduction of hollow structures and heteroatom-doped carbon layers are effective ways to solve these issues. Here, nitrogen, sulfur co-doped carbon coated Ni3S2 (abbreviated as, Ni3S2@NSC) nanotubes were prepared by a novel templating route. During the annealing process, NiS2 acts as both a precursor to Ni3S2 and an S-doped sulfur source. No additional sulfur source was used during the S-doping procedure, suggesting an atomically economic synthesis process. As anodes for sodium-ion half-cells, Ni3S2@NSCs exhibited high discharge capacity of 481 mA h g-1 at 0.1 A g-1 after 100 cycles with exceptional capacity retention of 98.6%. Furthermore, they maintained excellent rate capability of 318 mA h g-1 even at elevated current density of 5 A g-1. Sodium-ion full-cells assembled from the Ni3S2@NSC anodes and Na3V2(PO4)3 (NVP@C) cathodes also presented superior capacities and cyclabilities. These features can be attributed to the N, S co-doped carbon coated hollow structure that provided sufficient contact between the electrode and electrolyte, enhanced surface ion storage performance (capacitive effect), and improved structural stability of electrode materials.
摘要
样性和丰富的自然储量, 硫化镍是钠离子电池极具潜力的负极材料. 然而, 大体积膨胀和差的循环性能阻碍了它们的应用. 引入中空结构和杂原子掺杂碳层是解决这些问题的有效方法. 本文通过新颖的模板法制备了氮、硫共掺杂碳层包覆的Ni3S2纳米管(Ni3S2@NSCs). 在退火过程中, NiS2既作为形成Ni3S2的前体又作为S掺杂的硫源. 在S掺杂过程中没有使用额外的硫源, 这表明合成过程具有原子经济性. 作为钠离子半电池的阳极, Ni3S2@NSCs在0.1 A g-1的电流密度下循环100次后表现出481 mA h g-1的高放电容量, 具有98.6%的优异容量保持率. 此外, 即使在5 A g-1的高电流密度下, 它们仍保持318 mA h g-1的优异倍率性能. 由Ni3S2阳极和@NSC阳极和Na3V2(PO4)3 (NVP@C)阴极组装的钠离子全电池也具有优异的容量和循环稳定性. 这些特征可归因于N, S共掺杂碳涂覆的中空结构. 此结构可使电极和电解质之间充分接触, 增强表面离子存储性能(电容效应), 并改善电极材料的结构稳定性.
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Acknowledgements
This work was supported by the National Natural Science Foundation of China (51772082, 51804106 and 51574117), the Natural Science Foundation of Hunan Province (2019JJ30002 and 2019JJ50061), and the China Postdoctoral Science Foundation (2018T110822 and 2017M610495).
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He H designed and performed the experiments, analyzed the data, and wrote the paper; Chen C gave pivotal advising; Chen Z, Li P and Ding S analyzed the data; Zhang M conceived the framework of this paper and wrote the paper. All authors contributed to the general discussion.
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Hongcheng He is currently a PhD student at the Key Laboratory for Micro/Nano Optoelectronic Devices of Ministry of Education, Hunan Provincial Key Laboratory of Low-Dimensional Structural Physics & Devices, School of Physics and Electronics, Hunan University. His research interests focus on the design and fabrication of advanced energy storage materials.
Changmiao Chen is currently a PhD student at the Key Laboratory for Micro/Nano Optoelectronic Devices of Ministry of Education, Hunan Provincial Key Laboratory of Low-Dimensional Structural Physics & Devices, School of Physics and Electronics, Hunan University. His research interests focus on the design and fabrication of advanced energy storage materials.
Ming Zhang has been an associated professor in Hunan University since 2012. His research is focused on the design and synthesis of nanocomposites for supercapacitors, Na/K-ion batteries, and gas sensors. He has published more than 50 papers which have been cited more than 2600 times.
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Ni3S2@S-carbon nanotubes synthesized using NiS2 as sulfur source and precursor for high performance sodium-ion half/full cells
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He, H., Chen, C., Chen, Z. et al. Ni3S2@S-carbon nanotubes synthesized using NiS2 as sulfur source and precursor for high performance sodium-ion half/full cells. Sci. China Mater. 63, 216–228 (2020). https://doi.org/10.1007/s40843-019-1175-9
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DOI: https://doi.org/10.1007/s40843-019-1175-9