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Rapid microwave-assisted refluxing synthesis of hierarchical mulberry-shaped Na3V2(PO4)2O2F@C as high performance cathode for sodium & lithium-ion batteries

微波辅助回流法制备桑椹形Na3V2(PO4)2O2F@C正极材料用于高性能钠/锂离子电池

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Abstract

Unique hierarchical mulberry-shaped Na3V2(PO4)2O2F@C nanocomposite was fabricated by a rapid microwave-assisted low-temperature refluxing strategy. The V(acac)3 reverse micelle systems in the water-in-oil microemulsions played key roles in forming the self-assembly architectures. The prepared Na3V2(PO4)2O2F@C nanoparticles with the anisotropic growth along the [002] direction were in-situ encapsulated in carbon shells, which greatly contribute to fast Na+/e− transfer in electrodes. And the self-assemblies with high structure stability help to improve the cycle performance and mitigate voltage fading. The initial discharge capacity of Na3V2(PO4)2O2F@C as cathode for sodium ion batteries is about 127.9 mA h g−1 at 0.1 C. Besides, a high rate performance with a capacity of 88.1 mA h g−1 at 20 C has been achieved, and the capacity retains 82.1% after 2,000 cycles. In addition, the reaction kinetics and Na+ transportation mechanism of Na3V2(PO4)2O2F@C were preliminarily investigated by the ex situ X-ray diffraction, X-ray photoelectron spectroscopy and galvanostatic intermittent titration technique. More interestingly, when coupled with Li, the fabricated hybrid Li/Na-ion batteries also exhibit excellent rate and cycling performances. The proposed rapid refluxing strategy to synthesize mulberry-shaped Na3V2(PO4)2O2F@C opens up a new opportunity to develop high-performance electrode materials for the energy storage systems.

摘要

本论文采用快速微波辅助低温回流策略制备了桑椹形Na3V2(PO4)2O2F@C纳米复合材料. 研究表明微乳液中的V(acac)3反胶束体系 对该自组装结构的形成起到了关键作用. 制得的Na3V2(PO4)2O2F晶粒沿着[002]方向生长并被原位包封在碳壳中, 形成了高度稳定的自组装结构, 这不仅有利于Na+/e−的快速迁移, 而且能够有效改善电极材料的循环性能并抑制电压衰减. 作为钠离子电池正极材料, 在0.1C条件下, Na3V2(PO4)2O2F@C的初始放电容量约为127.9 mA h g−1. 在高倍率(20 C)条件下, 容量达88.1 mA h g−1, 2000次循环后容量保持率为 82.1%. 此外, 利用非原位X射线衍射, X射线光电子能谱和恒电流间歇滴定技术, 初步研究了Na3V2(PO4)2O2F@C在充放电过程中的反应机 理和Na+迁移机制. 同时, 在Li/Na离子混合电池当中, Na3V2(PO4)2O2F@C也表现出了优异的倍率和循环性能. 上述微波辅助低温回流合成 策略为开发高性能电化学储能材料开辟了新的途径.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (21303042, 21875097, 21671096 and 21603094), the Guangdong Special Support for the Science and Technology Leading Young Scientist (2016TQ03C919), and the Basic Research Project of the Science and Technology Innovation Commission of Shenzhen (JCYJ20170412153139454 and JCYJ20170817110251498).

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Authors and Affiliations

  1. Collaborative Innovation Center of Henan Province for Green Manufacturing of Fine Chemicals, School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, 453007, China

    Yan Hou  (侯燕), Shenglin Zhang  (张圣麟) & Zhaorong Chang  (常照荣)

  2. Department of Materials Science & Engineering, Southern University of Science and Technology, Shenzhen, 518055, China

    Yan Hou  (侯燕), Zhenyu Wang  (王振宇), Shuai Gu  (顾帅), Qiong Liu  (刘琼), Junjun Zhang  (张钧君), Hua Cheng  (程化) & Zhouguang Lu  (卢周广)

  3. National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki, 305-0044, Japan

    Kun Chang  (常焜)

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  1. Yan Hou  (侯燕)
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  8. Shenglin Zhang  (张圣麟)
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  9. Zhaorong Chang  (常照荣)
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  10. Zhouguang Lu  (卢周广)
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Corresponding authors

Correspondence to Zhaorong Chang  (常照荣) or Zhouguang Lu  (卢周广).

Additional information

Yan Hou is a PhD student at Henan Normal University. Her research focuses on the development of high-voltage cathode materials for lithium/sodium ion batteries.

Zhouguang Lu is now a Professor in the Department of Materials Science and Engineering, South University of Science and Technology of China. He obtained his BSc from the Central South University in 2001, his MSc degree, under the joint master program between Tsinghua University and Central South University in 2004, and PhD from City University of Hong Kong in 2009. He is the recipient of Fulbright Fellowship of USA Government in 2008–2009 and the Overseas High-Caliber Personnel (Level B) of Shenzhen Government in 2013. His research mainly covers the design and synthesis of nanostructures and their application in energy storage and conversion with focus on lithium/sodium ion batteries, and lithium-air batteries. He has authored more than 100 peer-review journal papers with total citations of more than 4000 and h-index of 38.

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Rapid Microwave-Assisted Refluxing Synthesis of Hierarchical Mulberry-Shaped Na3V2(PO4)2O2F@C as High Performance Cathode for Sodium & Lithium-Ion Batteries

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Hou, Y., Chang, K., Wang, Z. et al. Rapid microwave-assisted refluxing synthesis of hierarchical mulberry-shaped Na3V2(PO4)2O2F@C as high performance cathode for sodium & lithium-ion batteries. Sci. China Mater. 62, 474–486 (2019). https://doi.org/10.1007/s40843-018-9342-0

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