Abstract
Aqueous Zn-ion hybrid supercapacitors (ZHSCs) hold great potential as next-generation energy storage devices due to their low cost, excellent rate capability, long cycling life, and high safety. Heteroatom-doped hierarchical porous carbons (HD-HPCs) with integrated high specific surface area, multiscale pores, and abundant defects have been regarded as promising cathode materials for ZHSCs. However, the in situ architecture of HD-HPCs with these multiple advantages via a sustainable and controllable method remains an arduous challenge. Herein, a novel molecular engineering strategy was proposed for the in situ construction of N/P/O-doped HD-HPCs via the direct carbonization of multiple-heteroatom-rich hypermolecules. Such a strategy has multiple advantages, including the exclusion of pore-making techniques, activation agents, templates, and complicated and hazard washing processes, demonstrating its green and sustainable properties. The highly active multiple-heteroatom-rich hypermolecular precursors contributed to the formation of abundant micro/mesopores due to the self-abscission of heteroatoms and heteroatom-contiguous carbon atoms at high carbonization temperatures. Consequently, these active structural/compositional features endowed the optimal cathodes with outstanding storage capacities of 139.2 and 88.9 mA h g−1 at 0.5 and 20 A g−1 for aqueous ZHSCs, respectively. They also delivered a superior storage performance in quasi-solid ZHSCs (QS-ZHSCs) with a high specific capacity of 111.5 mA h g−1 at 0.5 A g−1. Superior energy/power densities and long cycling stability were also achieved for aqueous and QS-ZHSCs. The theoretical calculation confirmed the synergetic effects of multiple-atom doping on enhancing the electronic conductivity and reducing the energy barrier between Zn ions and carbon, which promote the Zn-ion adsorption capability. These findings shed fresh light on the straightforward manufacture of superior HD-HPCs for electrochemical energy storage.
摘要
具备低价、优异倍率性能、长寿命、高安全性的水系锌离子混 合电容器(ZHSCs)是理想的下一代能量存储器件. 高比表面积、多级 孔、富缺陷的掺杂分级多孔碳(HD-HPCs)是非常有前景的ZHSCs正极 材料. 但是, 可持续且可控原位构筑同时具备多种结构组分优势的HDHPCs 仍然面临挑战. 本文提出一种新的分子工程化策略, 即直接碳化 富含多种异质原子的超分子前驱体, 便可实现原位构筑多元掺杂HDHPCs. 该绿色可持续策略具有多种优势, 包括不需要额外的成孔技 术、活化剂、模板剂、以及复杂且危险的清洗过程. 由于富杂原子超 分子前驱体具有较高的活性, 高温碳化过程中杂原子以及邻近杂原子 的碳原子很容易从碳骨架中脱离, 形成丰富的微介孔结构. 因此, 活性 结构与组分优化后的正极材料在水系ZHSCs中0.5和20 A g−1下容量分 别达到139.2和88.9 mA h g−1, 在准固态ZHSCs中0.5 A g−1下容量也能够 达到111.5 mA h g−1. 此外, 水系和准固态ZHSCs也具备高能量和功率密 度, 以及长循环稳定性. 理论计算表明多原子掺杂能够协同提升碳材料 的导电性, 且降低锌离子与碳之间的相互作用能垒, 因而提升锌离子的 吸附性能. 本工作为直接制备HD-HPCs及其电化学储能应用提供了新 思路.
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Acknowledgements
This work was supported by the National Natural Science Foundation of China (21975026), the Science and Technology Program of Guangdong Province (2020B0909030004), and the Graduate Interdisciplinary Innovation Project of Yangtze Delta Region Academy of Beijing Institute of Technology (Jiaxing, GIIP2021-002).
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Bai Y and Wu C proposed the research idea. Liu M, Bai Y, and Wu C designed the project and performed the experiments. Liu M performed the material fabrication, characterization, and battery testing. Feng X and Wang Y participated in material fabrications, data analyses, and schematic illustrations. Zheng L and Li X performed the theoretical calculations and data analysis. Li Y and Gong Y provided technique support, data analyses, and scientific discussions. Wu F, Bai Y, and Wu C supervised the research. Liu M, Bai Y, and Wu C wrote the manuscript. All authors discussed the results and commented on the manuscript.
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The authors declare that they have no conflict of interest.
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Experimental details and supporting data are available in the online version of the paper.
Mingquan Liu is currently a PhD candidate under the supervision of Prof. Feng Wu at the School of Materials Science and Engineering, Beijing Institute of Technology (BIT). His research interests focus on the structural engineering of carbon materials for supercapacitors and sodium-ion batteries.
Feng Wu is currently a professor at BIT. He is the director of the Green Energy Research Institute. As the chief scientist, he has undertaken studies on new secondary batteries and related energy materials for a long time.
Ying Bai is currently a professor at BIT. She earned her bachelor’s degree from Harbin Institute of Technology, China, in 1997. She completed her PhD degree at the School of Chemical Engineering and Materials Science, BIT in 2003. Her research interests focus on the electrochemical energy storage and conversion technology.
Chuan Wu is a professor at BIT. He received his PhD degree in applied chemistry from BIT in 2002, followed by a 2-year postdoctoral fellowship at Dalian Institute of Chemical Physics, Chinese Academy of Sciences. His interests are new energy materials and secondary batteries based on multielectron materials.
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Molecular engineering toward sustainable development of multiple-doped hierarchical porous carbons for superior zinc ion storage
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Liu, M., Wu, F., Feng, X. et al. Molecular engineering toward sustainable development of multiple-doped hierarchical porous carbons for superior zinc ion storage. Sci. China Mater. 66, 541–555 (2023). https://doi.org/10.1007/s40843-022-2176-6
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DOI: https://doi.org/10.1007/s40843-022-2176-6