Abstract
Sodium-ion batteries (SIBs) have been regarded as one of the most promising candidates for filling the application vacancy of lithium-ion batteries for large-scale electrical energy storage. However, anodes with high reversible capacities and fast reaction kinetics are lacking and must be investigated. In this study, a composite consisting of PbSe nanoparticles and carbon nanotubes (PbSe@CNTs) was prepared via a simple mechanical ball-milling method with the recovered Pb from lead-acid batteries and commercial Se powder. The introduced CNT networks can encompass and segregate PbSe nanoparticles, thus suppressing their aggregation and increasing the electronic conductivity. The nanosized PbSe and anfractuous CNTs benefit the electrolyte penetration, which shortens the diffusion distance of Na+ and electrons and relieves the strain upon the sodiation/desodiation process, resulting in an improved rate capability and long cycling. Therefore, the PbSe@CNTs electrodes exhibited a high reversible capacity of 597 mA h g−1 at 20 mA g−1 and 458.9 mA h g−1 for 100 cycles at 100 mA g−1 with a capacity retention of 88%. The two-step conversion-alloying mechanism of PbSe with Na to form Na2Se and Na15Pb4 was confirmed by ex situ X-ray diffraction and Raman spectroscopy. The results of this study provide valuable guidance for the design and synthesis of high-performance anodes for SIBs.
摘要
钠离子电池作为新型的储能电池体系因钠资源储量丰富、成本 低廉等优势有望填补锂离子电池在某些应用领域的空缺, 非常适用于 大规模储能领域. 然而, 高容量储钠负极材料仍然需要进一步研究. 本 文以废旧铅酸电池的回收铅和商业化硒粉为原料, 采用机械球磨法制 备了纳米硒化铅与碳纳米管(PbSe@CNTs)的复合材料. 碳纳米管网络 缠绕在PbSe纳米粒子上, 可有效抑制纳米粒子的团聚, 同时提高了电子 导电性. 纳米级的PbSe和拓扑结构的CNTs有利于电解液的渗透, 缩短 了Na+和电子的传输路径, 缓解了脱嵌钠过程中的机械应变, 提高了倍 率和长循环稳定性能. PbSe@CNTs电极在20 mA g−1电流密度下具有 597 mA h g−1 的可逆比容量, 在100 mA g−1 循环100 圈仍保持 458.9 mA h g−1的可逆比容量, 容量保持率为88%. 通过X射线衍射和拉 曼光谱分析, 证实了PbSe的储钠机理为两步转化-合金化过程, 反应方 程式为PbSe + 5.75Na+ + 5.75e− ↔ 0.25Na15Pb4 + Na2Se.
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Acknowledgements
This work was supported by the National Natural Science Foundation of China (22109037), the Natural Science Foundation of Hebei Province (B2020201001), the Advanced Talents Incubation Program of Hebei University (521000981408), the Young Elite Scientists Sponsorship Program by CAST (2021QNRC001), and the Research Innovation Team of the College of Chemistry and Environmental Science of Hebei University (hxkytd2102). Wang L thanks NaXun Energy Technology Co., LTD (China) for the technical support.
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Wang L proposed the concept. Wang L and Zhang N supervised the work; Zhao D, Zhao X, and Liu N carried out the experiments, characterizations, and electrochemical measurements; Zhao D and Wang L wrote the manuscript; Qin B, Qiu M, and Zhang N helped to discuss and analyze the data. All authors contributed to the general discussion.
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The authors declare that they have no conflict of interest.
Dongdong Zhao received her BSc degree from Tangshan Normal University. She is currently a master student at Hebei University. Her research interests mainly focus on high-performance electrode materials for sodium-ion batteries.
Ning Zhang received his BSc degree from Hebei University in 2012 and then obtained his PhD degree in inorganic chemistry from Nankai University in 2017. He is now a professor at the College of Chemistry & Environmental Science, Hebei University. His current research focuses on the design and synthesis of functional materials for applications in energy storage and conversion (lithium/sodium-ion batteries and aqueous zinc batteries).
Liubin Wang received his BE degree in materials science and engineering from Southwest Jiaotong University and PhD degree in physical chemistry from Nankai University. He worked as a visiting student at The University of Hong Kong in 2019. He joined Hebei University as a professor in 2020. His research interests focus on the design of electrodes and electrolytes for high-energy electrochemical devices, including metal-ion batteries, aqueous batteries, and photo-assisted rechargeable batteries.
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Zhao, D., Zhang, N., Zhao, X. et al. A novel PbSe@CNTs anode material based on dual conversion-alloying mechanism for sodium-ion batteries. Sci. China Mater. 66, 61–68 (2023). https://doi.org/10.1007/s40843-022-2129-1
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DOI: https://doi.org/10.1007/s40843-022-2129-1