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Highly flexible, mechanically strengthened metallic glass-based composite electrode with enhanced capacitance and cyclic stability

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Abstract

The design of flexible composite electrodes has become the top priority in energy storage devices for the development of future wearable intelligent electronics. However, searching for fully integrated, ultrathin flexible composite electrodes with satisfying electrochemical performance is still a major challenge. Herein, we introduce a nanoporous gold metallic glass (MG) ribbon-based composite electrode with excellent electric conductivity, mechanical flexibility, and extra capacitance by integrating polypyrrole (PPy) into wrinkled nanoporous ribbon (NPG@MG). The “freestanding, ultrathin, highly conductive and flexible” nature of the composite electrode prevents the conducting polymer from structural instability resulting from the volume swell and shrink during the charging/discharging circulation, and the packed PPy provides protection for the wrinkled topology on the surface of the MG ribbon. The capacitance of pure NPG@MG-PPy composite electrode reached 393 mF·cm−2. The ultra-thin all-solid-state flexible supercapacitor demonstrates an excellent capacitance of 172 mF·cm−2 (14.8 F·cm−3), accompanied by a superior cycling capability after 8000 charge/discharge cycles attributed to mechanical flexibility. The areal energy density also reached 0.74 mWh·cm−3 (9 μWh·cm−2) at a power density of 1 μW·cm−2. This work provides valuable concepts on the design of PPy-based hybrid materials for flexible energy storage systems with greatly enhanced electrochemical performances.

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摘要

完全集成的超薄柔性超级电容器由于其高功率密度和出色的循环性能, 在可穿戴智能电子产品的日益受到关注。其中聚吡咯 (PPy) 是用于制造柔性超级电容器的超级电容器电极比较有前景的赝电容电极材料, 但由于其有限的电容和较差的循环稳定性, 仍然阻碍了其实际应用。我们在此报告了一种通过将 PPy 结合褶皱纳米多孔金金属玻璃带 (NPG@MG) 作为集流体来开发独立导电复合电极来提高 PPy 电容和循环稳定性的简易策略。具有褶皱突起结构的纳米多孔金非晶玻璃条带表现出高导电性、有效的电荷转移骨架、机械柔韧性、足够的活性表面积和额外的电容提升, 而沉积的 PPy 为金属玻璃带表面的皱纹拓扑结构提供保护。NPG@MG-PPy 复合电极的电容达到 393 mF·cm−2 (33.6 F·cm−3)。使用 NPG@MG-PPy复合电极的全固态柔性超级电容器表现出 172 mF·cm−2 (14.8 F·cm−3) 的优异电容和0.74 mWh·cm−3 (9 μWh·cm−2) 的面能量密度。 在 1 μW·cm−2 的功率密度下, 具有优异的循环能力和机械灵活性。这项工作为设计用于柔性储能系统的 PPy 基杂化材料提供了有价值的概念, 其电化学性能够大大增强。

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Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (Nos. 21905180 and 51873108), Shenzhen Science and Technology Planning Project (Nos. JCYJ20200109141640095 and JCYJ20170817110251498) and Guangdong-Hong Kong-Macao Joint Laboratory (No. 2019B121205001). All HAADF-STEM, and EDS mapping were supported by Centre for Advanced Research of Energy and Materials in Division of Quantum Science and Engineering, Faculty of Engineering, Hokkaido University. We acknowledge Dr. Yukun Wang and Dr. Zhuoxin Liu of Prof. Chunyi Zhi’s group in City University of Hong Kong for the discussion and support of PPy deposition.

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Authors and Affiliations

  1. Guangdong Research Center for Interfacial Engineering of Functional Materials, College of Materials Science and Engineering, Shenzhen University, Shenzhen, 518060, China

    Yi Xu, Da-Zhu Chen & Chen Liu

  2. Guangdong-Hong Kong-Macao Joint Laboratory for Photonic-Thermal-Electrical Energy Materials and Devices, Department of Materials Science and Engineering, Southern University of Science and Technology, Shenzhen, 518060, China

    Hua Cheng & Zhou-Guang Lu

  3. College of Physics and Optoelectronic Engineering, Shenzhen University, Shenzhen, 518060, China

    Yi Xu

  4. Department of Materials Science and Engineering, City University of Hong Kong, Hong Kong, 999077, China

    Pak Man Yiu, Yu-Kun Wang, Xiao-Meng Qin & Chan-Hung Shek

  5. Division of Quantum Science and Engineering, Faculty of Engineering, Centre for Advanced Research of Energy and Materials, Hokkaido University, Sapporo, 0608628, Japan

    Tamaki Shibayama, Seiichi Watanabe & Masato Ohnuma

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  1. Yi Xu
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Xu, Y., Yiu, P.M., Wang, YK. et al. Highly flexible, mechanically strengthened metallic glass-based composite electrode with enhanced capacitance and cyclic stability. Rare Met. 41, 3717–3728 (2022). https://doi.org/10.1007/s12598-022-02060-8

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