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Molecule-assisted modulation of the high-valence Co3+ in 3D honeycomb-like CoxSy networks for high-performance solid-state asymmetric supercapacitors

分子辅助制备富含高价态Co3+的三维蜂窝状钴硫 化物网络结构用于高性能固态不对称超级电容器

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Abstract

Modulating the oxidation states of transition metal species has been regarded as a promising strategy to tune the redox activity and achieve more active sites in electrode materials. In this work, a unique three-dimensional (3D) honeycomb-like cobalt sulfide (CoxSy) network organized by cross-linked nanosheets (CoxSy-T NSs) was prepared via a simple triethanolamine (TEOA)-assisted self-templating strategy. Interestingly, it has been found for the first time that the introduction of TEOA in the reaction effectively increases the ratio of high-valence Co3+ in the final product. Benefiting from the synergetic effect of the tailored high-valence Co3+ with the 3D network structure, the CoxSy-T NS electrode exhibits a maximum specific capacity of 351 mAhg−1 (2635 F g−1) at 5 A g−1 as well as excellent cycling stability. Furthermore, with the solid-state asymmetric supercapacitor (ASC) constructed based on the CoxSy-T NSs and activated carbon (AC) electrodes, a high energy density up to 81.62 W h kg−1 has been achieved at the power density of 0.81 kW kg−1 and 96.2% capacitance is preserved after 7000 cycles, indicating robust cycling stability. This result high lights the simple approach of simultaneously tailoring high valence metal species and constructing 3D network structure toward high performance electrode materials for energy sto rage and conversion.

摘要

过渡金属氧化态调控工程是一种很有前景的改善电极材料的 氧化还原活性、增加活性位点的策略. 本文提出了一种简单的三乙 醇胺辅助自模板法, 制备了一种由交错钴硫化物纳米片(CoxSy-T NSs)组装而成的独特的三维蜂窝状网络结构. 有趣的是, 我们首次 发现在该体系中, 三乙醇胺可以有效地增加目标产物中的高价态 Co3+的比例. CoxSy-T NSs电极具有高含量的Co3+和三维网络结构, 使得其在5 A g−1的电流密度下表现出351 mA h g−1(2635 F g−1)的最 大比容量和优异的循环稳定性. 此外, 由CoxSy-T NSs和活性炭(AC) 电极组装的固态不对称超级电容器在0.81 kW kg−1功率密度下展现 出81.62 W h kg−1的高能量密度和卓越的长周期循环稳定性, 7000次 循环后仍有96.2%的容量保持率. 该结果证明同时调控高价态的金属 物种并构筑三维网络结构是一种简单而有效的制备用于能源存储 与转换的高活性电极材料的策略.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (21671173) and Zhejiang Provincial Ten Thousand Talent Program (2017R52043).

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  1. These authors contributed equally to this work.

Authors and Affiliations

  1. Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Department of Chemistry, Zhejiang Normal University, Jinhua, 321004, China

    Haiyan Wang  (王海燕), Ying Yang  (杨瑛), Qinghao Li  (李擎昊), Wen Lu  (陆雯), Yijun Zhong  (钟依均) & Yong Hu  (胡勇)

  2. Vacuum Interconnected Nanotech Workstation, Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences, Suzhou, 215123, China

    Jiqiang Ning  (宁吉强) & Ziyang Zhang  (张子旸)

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  1. Haiyan Wang  (王海燕)
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Contributions

Wang H and Hu Y designed the project; Wang H, Yang Y and Li Q performed the experiments; Wang H analyzed the data and wrote the paper with support from Hu Y; Lu W assisted in the data analysis; Ning J, Zhong Y, and Zhang Z gave pivotal advice. All authors contributed to the general discussion.

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Correspondence to Yong Hu  (胡勇).

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Conflict of interest

The authors declare that they have no conflict of interest.

Haiyan Wang received her PhD degree in 2018 from Zhejiang University. From 2018 to 2019, she was a postdoctoral fellow at Zhejiang University and then she joined Zhejiang Normal University as a lecturer in 2019. Her interests mainly focus on electrode materials for energy storage and conversion devices, including supercapacitors, Zn-air batteries and water splitting.

Ying Yang is currently a graduate student under the guidance of Professor Yong Hu from the Department of Chemistry, Zhejiang Normal University. Her research interests focus on the design and manufacture of inorganic nanomaterials for supercapacitors and ionic hybrid supercapacitors.

Qinghao Li received his B. Eng degree in chemical engineering from Jiangxi University of Science and Technology and his MSc degree in chemistry from Zhejiang Normal University. His research interests include supercapacitors and electrochemical water splitting.

Yong Hu obtained his PhD degree in 2006 in inorganic chemistry from the University of Science and Technology of China. He then worked as a research fellow at Nanyang Technological University. Since 2008, he has been a full professor at the College of Chemistry and Life Science, Zhejiang Normal University, China. His current research interests are focused on the design and syntheses of nanomaterials for energy and environmental applications.

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Molecule-assisted modulation of the high-valence Co3+ in 3D honeycomb-like CoxSy networks for high-performance solid-state asymmetric supercapacitors

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Wang, H., Yang, Y., Li, Q. et al. Molecule-assisted modulation of the high-valence Co3+ in 3D honeycomb-like CoxSy networks for high-performance solid-state asymmetric supercapacitors. Sci. China Mater. 64, 840–851 (2021). https://doi.org/10.1007/s40843-020-1476-2

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