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Effective enhancement of electrochemical energy storage of cobalt-based nanocrystals by hybridization with nitrogen-doped carbon nanocages

钴基纳米晶-氮掺杂碳纳米笼复合材料的构建与电化学储能性能研究

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Abstract

Cobalt-based oxygenic compounds Co(OH)2, CoO and Co3O4 are attractive for electrochemical energy storage owing to their high theoretical capacities and pseudocapacitive properties. Despite the great efforts to their compositional and morphological regulations, the performances to date are still quite limited owing to the low active surface area and sluggish charge transfer kinetics. Herein, different Co-based nanocrystals (Co-NCs) were conveniently anchored on the hierarchical nitrogen-doped carbon nanocages (hNCNCs) with high specific surface area and coexisting micro-meso-macropores to decrease the size and facilitate the charge transfer. Accordingly, a high specific capacity of 1170 F g−1 is achieved at 2 A g−1 for the Co(OH)2/hNCNCs hybrid, in which the capacitance of Co(OH)2 (2214 \({\rm{F\;g}}_{\rm{Co({OH})_2}}^{ - 1}\)) is approaching to its theoretical maximum (2595 F g−1), demonstrating the high utilization of active materials by the hybridization with N-doped nanocarbons. This study also reveals that these Co-NCs store/release electrical energy via the same reversible redox reaction despite their different pristine compositions. This insight on the energy storage of Co-based nanomaterials suggests that the commonly-employed transformation of the Co-NCs from Co(OH)2 to CoO and Co3O4 on carbon supports is unnecessary and even could be harmful to the energy storage performance. The result is instructive to develop high-energy-density electrodes from transition metal compounds.

摘要

Co(OH)2、CoO和Co3O4等钴基化合物因具有高理论容量和 赝电容性质而备受关注. 但受限于活性表面积小、电荷传输缓慢, 钴基纳米材料的实际储能性能却有限. 本文以我们前期开发的具 有大比表面积、高导电性和微孔-介孔-大孔共存的分级结构氮掺 杂碳纳米笼(hNCNCs)为载体, 成功构建了晶粒尺寸小、电荷转移 快的系列钴基纳米晶-hNCNCs复合材料, 有效地提高了活性材料 的利用率. 其中, Co(OH)2/hNCNCs在2 A g−1下表现出1170 F g−1的 高比容量, 基于活性物种Co(OH)2的比电容高达2214 F g−1, 接近其 理论值(2595 F g−1). 研究发现, 具有不同组成的Co(OH)2、CoO和 Co3O4纳米晶通过相同的可逆氧化还原反应存储/释放电能. 这种新 的储能机理表明将碳基载体上的Co(OH)2转化为CoO或Co3O4的策 略是提升储能性能的非必要条件, 还可能损害其储能性能. 本研究 可为开发过渡金属化合物基高能量密度电极材料提供借鉴.

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Acknowledgements

This work was jointly supported by the National Key Research and Development Program of China (2017YFA0206500 and 2018YFA0209103), the National Natural Science Foundation of China (21832003, 21773111, 51571110 and 21573107), and the Fundamental Research Funds for the Central Universities (020514380126).

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Authors and Affiliations

  1. Key Laboratory of Mesoscopic Chemistry of MOE and Jiangsu Provincial Lab for Nanotechnology, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210023, China

    Qingming Ma  (麻青明), Yuejian Yao  (姚月坚), Minglei Yan  (闫明磊), Jie Zhao  (赵杰), Chengxuan Ge  (葛承宣), Qiang Wu  (吴强), Lijun Yang  (杨立军), Xizhang Wang  (王喜章) & Zheng Hu  (胡征)

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  1. Qingming Ma  (麻青明)
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  2. Yuejian Yao  (姚月坚)
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  3. Minglei Yan  (闫明磊)
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  4. Jie Zhao  (赵杰)
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  5. Chengxuan Ge  (葛承宣)
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  6. Qiang Wu  (吴强)
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  8. Xizhang Wang  (王喜章)
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  9. Zheng Hu  (胡征)
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Contributions

Author contributions Wu Q and Hu Z conceived and supervised the project; Ma Q performed the experiments; Yao Y, Yan M, Zhao J, Ge C and Wang X helped to characterize the samples; Ma Q, Wu Q and Hu Z analyzed the data and wrote the paper with support from Yang L and Wang X. All authors contributed to the general discussion.

Corresponding authors

Correspondence to Qiang Wu  (吴强) or Zheng Hu  (胡征).

Additional information

Conflict of interest The authors declare no conflict of interest.

Qingming Ma received his Bachelor degree from the School of Chemistry and Chemical Engineering, Inner Mongolia University in 2016. He is currently a Master candidate in the School of Chemistry and Chemical Engineering, Nanjing University. His current research interest is the design of high-performance electrode nanomaterials for energy storage.

Qiang Wu obtained his BSc (1999) and PhD (2004) degrees in chemistry from Nanjing University. He was appointed an associate professor in 2006, and a professor at Nanjing University in 2015. As a Hua-Ying Scholar, he worked at Stanford University for one year. His scientific interest focuses on the rational design of nano-/ mesostructured materials and their applications in energy storage and conversion.

Zheng Hu received his BSc (1985) and PhD (1991) degrees in physics from Nanjing University. He became an associate professor of chemistry in 1993, and acquired the professor position in 1999, and Cheung Kong Scholar professor in 2007. He was awarded the National Natural Science Foundation of China for Outstanding Young Scientists (2005). He is engaged in the research of physical chemistry and materials chemistry addressing the growth mechanism, materials design and energy applications of a range of nano-/mesostructured materials, especially carbon-based materials, group III nitrides and transition metal oxides.

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40843_2019_9449_MOESM1_ESM.pdf

Effective enhancement of electrochemical energy storage of cobalt-based nanocrystals by hybridization with nitrogen-doped carbon nanocages

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Ma, Q., Yao, Y., Yan, M. et al. Effective enhancement of electrochemical energy storage of cobalt-based nanocrystals by hybridization with nitrogen-doped carbon nanocages. Sci. China Mater. 62, 1393–1402 (2019). https://doi.org/10.1007/s40843-019-9449-0

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