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Oxygen vacancies boosting ultra-stability of mesoporous ZnO-CoO@N-doped carbon microspheres for asymmetric supercapacitors

氧空位改善超稳定性氮掺杂碳包覆的氧化锌-氧化钴介孔微球应用于非对称超级电容器

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Abstract

Long-term cycling stability of pseudocapacitive materials is pursued for high-energy supercapacitors. Herein, the mesoporous zinc-cobalt oxide heterostructure@nitrogendoped carbon (ZnO-CoO@NC) microspheres with abundant oxygen vacancies are self-assembled through a hydrothermal method combined with an annealing post-treatment. The multifunctional polyvinyl pyrrolidone (PVP) is used as a structure-directing agent, the precursor of NC and the initiator of abundant oxygen vacancies in zinc-cobalt oxide microspheres. XPS demonstrates the generation of surface oxygen vacancies resulted from the reduction effect of conductive NC, and further confirms the weaker interaction between the metal ions and oxygen atoms. As a result, the electrode based on ZnO-CoO@NC in 2 mol L−1 KOH shows enhanced capacitive performance with an excellent cycle stability of 92% retention of the initial capacitance after 40,000 charge-discharge cycles at 2 A g−1, keeping the morphology unchanged. The assembled asymmetric supercapacitor, graphene//ZnO-CoO@NC, also performs good cyclic stability with 94% capacitance retention after 10,000 cycles at 2 A g−1. The remarkable electrochemical performance of the self-assembled ZnO-CoO@NC composite is attributed to the mesoporous architecture, abundant oxygen vacancies, conductive ZnO scaffold for CoO crystals forming heterostructure of ZnO-CoO and the high conductive NC layer covering outside of the multi-metal oxide nanoparticles. Hence, the ZnO-CoO@NC holds great promise for high-performance energy storage applications.

摘要

赝电容材料的周期循环稳定性是高性能超级电容器追求的 目标. 本文采用水热结合退火后处理的方法, 以聚乙烯吡咯烷酮 (PVP)为锌钴氧化物微球的结构导向剂、氮掺杂碳的前驱体以及 大量氧空位的还原剂前躯体, 自组装含有丰富氧空位且包覆氮掺 杂碳的介孔氧化锌-氧化钴微球(ZnO-CoO@NC). XPS结果证明了 材料表面氧空位的产生是由于导电氮掺杂碳的还原作用, 同时进 一步证实了金属离子与氧原子之间较弱的相互作用. 在2 mol L−1 KOH电解质中ZnO-CoO@NC电极表现出良好的电容性能, 特别是 在2 A g−1的电流密度下40000次充放电循环后, 电极材料仍保持 92%的初始电容, 显示出良好的循环稳定性, 同时材料的形貌不变. ZnO-CoO@NC正极与石墨烯负极组装的非对称超级电容器(ASC) 也具有良好的循环稳定性, 在2 A g−1的电流密度下循环10000次后, 可以保持94%的初始电容. 介孔结构、丰富的氧空位、导电氧化锌 支架与氧化钴形成的氧化锌-氧化钴异质结构以及覆盖在多金属氧 化物纳米颗粒表面的高导电性氮掺杂碳层使得自组装得到的ZnOCoO@NC复合材料具有优异的电化学性能. ZnO-CoO@NC有望应 用于高性能储能设备领域.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (21576138 and 51572127), China-Israel Cooperative Program (2016YFE0129900), the Program Foundation for Science and Technology of Changzhou, China (CZ20190001), the Priority Academic Program Development of Jiangsu Higher Education Institutions, and the Program for Science and Technology Innovative Research Team in the Universities of Jiangsu Province, China. We also thank Dr. Huaping Bai and Dr. Wanying Tang at the Analysis and Test Center, Nanjing University of Science and Technology for the XRD and Raman data collection.

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Authors and Affiliations

  1. Key Laboratory for Soft Chemistry and Functional Materials, Ministry of Education, School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing, 210094, China

    Di Yao  (姚迪), Fulei Wang  (王福蕾), Wu Lei  (雷武), Yan Hua  (华艳), Xifeng Xia  (夏锡锋) & Qingli Hao  (郝青丽)

  2. Chemical Engineering and Life Science and State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, WuHan University of Technology, Wuhan, 430070, China

    Jinping Liu  (刘金平)

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  1. Di Yao  (姚迪)
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  2. Fulei Wang  (王福蕾)
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  4. Yan Hua  (华艳)
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Contributions

Yao D, Lei W and Hao Q took part in the whole process of the research and article preparation. Wang F and Hua Y did the synthetic experiments of a part of materials and conducted part of the characterization. Xia X characterized the chemical structures of the materials. Liu J participated in the discussion and gave valuable suggestions.

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Correspondence to Wu Lei  (雷武) or Qingli Hao  (郝青丽).

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The authors declare no conflict of interest.

Supplementary information

Supplementary data are available in the online version of the paper.

Di Yao is a PhD candidate at the School of Chemical Engineering under the supervision of Prof. Qingli Hao at Nanjing University of Science and Technology. His research interests focus on the development of novel materials, structures and characterization methods for the application in electrochemical energy storage.

Qingli Hao is a professor in materials chemistry at Nanjing University of Science and Technology. She received her PhD degree in chemistry from the University of Regensburg, Germany, in 2003. Her research interest focuses on functional nanomaterials and their applications in energy storage and conversion systems and chemical sensors.

Wu Lei is a professor in applied chemistry at Nanjing University of Science and Technology. He received his PhD degree in applied chemistry from Nanjing University of Science and Technology in 2006. His research interest focuses on functional materials and their applications in environment and energy fields.

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40843_2020_1357_MOESM1_ESM.pdf

Oxygen vacancies boosting ultra-stability of mesoporous ZnO-CoO@N-doped carbon microspheres for asymmetric supercapacitors

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Yao, D., Wang, F., Lei, W. et al. Oxygen vacancies boosting ultra-stability of mesoporous ZnO-CoO@N-doped carbon microspheres for asymmetric supercapacitors. Sci. China Mater. 63, 2013–2027 (2020). https://doi.org/10.1007/s40843-020-1357-9

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