Abstract
Lithium-ion capacitors (LICs) could combine the virtues of high power capability of conventional super-3capacitors and high energy density of lithium-ion batteries. However, the lack of high-performance electrode materials and the kinetic imbalance between the positive and negative electrodes are the major challenge. In this study, Fe3O4 nanoparticles encapsulated in nitrogen-rich carbon (Fe3O4@NC) were prepared through a self-assembly of the colloidal FeOOH with polyaniline (PANI) followed by pyrolysis. Due to the well-designed nanostructure, conductive nitrogen-rich carbon shells, abundant micropores and high specific surface area, Fe3O4@NC-700 delivers a high capacity, high rate capability and long cycling stability. Kinetic analyses of the redox reactions reveal the pseudocapacitive mechanism and the feasibility as negative material in LIC devices. A novel LIC was constructed with Fe3O4@NC-700 as the negative electrode and expanded graphene (EGN) as the positive electrode. The well-matched two electrodes effectively alleviate the kinetic imbalance between the positive and negative electrodes. As a result, Fe3O4@NC-700//EGN LIC exhibits a wide operating voltage window, and thus achieves an ultrahigh energy density of 137.5 W h kg−1. These results provide fundamental insights into the design of pseudocapacitive electrode and show future research directions towards the next generation energy storage devices.
摘要
锂离子电容器继承了超级电容器高功率性能和锂离子电池 高能量密度两者的优点. 然而, 高电化学性能电极材料的短缺以及 正负电极材料动力学的不匹配是构筑高能量/高功率密度锂离子电 池遇到的最大挑战. 我们通过简单的溶液组装和煅烧法得到了具 有核壳结构的Fe3O4@NC复合材料. 首先, 研究了不同热解温度得 到的Fe3O4@NC样品的储锂性能. 结构单元纳米化和丰富的微孔使 得Fe3O4@NC-700具有大比表面积, 同时暴露出更多的活性位点, 缩 短了离子传输路径, 表现出特殊的赝电容行为, 从而显著提高了储 锂动力学. 除此之外, N-掺杂的碳壳提供了较高的电子导电性并保 证了在循环测试中的结构完整性. 以Fe3O4@NC-700为负极, 膨胀石 墨烯EGN为正极, 1 mol L−1 LiPF6为电解液, 组装成锂离子电容器. 受益于正负电极相配的动力学以及Fe3O4@NC-700和EGN两者的 协同优势, Fe3O4@NC-700//EGN杂化离子电容器获得了较宽的工 作电压窗口(1.0–4.5 V), 比能量最高可达137 W h kg−1, 比功率最高 可达8.2 kW kg−1, 且循环稳定性出色. 本工作可为下一代兼具高比 能量和高比功率的新型混合能源存储系统的设计提供启示.
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Acknowledgements
The authors appreciate the financial support of the National Natural Science Foundation of China (21773116), the Specialized Research Fund for the Doctoral Program of Higher Education (SRFDP, 20130091110010), the Natural Science Foundation of Jiangsu Province (BK2011438), the National Science Fund for Talent Training in Basic Science (J1103310), the Modern Analysis Center of Nanjing University and Program B for Outstanding PhD candidate of Nanjing University.
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Zhou J and Hou W conceived the idea. Zhou J and Xu S carried out the sample synthesis, characterization and performance measurements and wrote the manuscript. Kang Q, Ni L, Chen N, Li X, Peng L, Wang X, Guo X and Ding W participated in the general discussion. Lu C helped with XPS measurement. Wang X helped with BET measurements. Zhou J edited the manuscript and Hou W revised the manuscript.
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Jinhua Zhou obtained her MSc degree from Nanjing University of Posts & Telecommunications in 2016. Currently, she is pursuing her PhD degree under the supervision of Prof. Wenhua Hou at Nanjing University. Her research is mainly focused on the synthesis of 2D layered transition metal oxide nanomaterials, and their application for energy conversion and storage devices.
Shuchi Xu received his BSc degree in chemistry from the School of Chemistry and Chemical Engineering, Nanjing University in 2019. He worked with Prof. Wenhua Hou at Nanjing University in the last two years, focusing on the application of transition metal oxide nanomaterials as electrode.
Wenhua Hou is a professor in the School of Chemistry and Chemical Engineering at Nanjing University. He received his BSc (1985) and PhD (1993) degrees in chemistry from Nanjing University. He once worked as visiting scholar at the State University of New York at Albany and the University of California, San Diego. His current research interests include the synthesis of 2D layered nanomaterials for potocatalysis and energy conversion and storage.
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Zhou, J., Xu, S., Kang, Q. et al. Iron oxide encapsulated in nitrogen-rich carbon enabling high-performance lithium-ion capacitor. Sci. China Mater. 63, 2289–2302 (2020). https://doi.org/10.1007/s40843-020-1414-0
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DOI: https://doi.org/10.1007/s40843-020-1414-0