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Sulfur-modulated FeNi nanoalloys as bifunctional oxygen electrode for efficient rechargeable aqueous Zn-air batteries

硫调控FeNi纳米合金作为双功能氧电极的研究

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Abstract

Currently, FeNi nanoalloys have received considerable attention for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in rechargeable aqueous zinc (Zn)-air batteries (ZABs) because of their high content and good chemical stability. However, their poor electronic conductivity, small surface area, and sluggish activity seriously hinder their catalytic performance. Herein, S-modulated FeNi nanoalloys supported by hierarchically porous carbon (S-FeNi/PC) are synthesized through the thermal treatment of metal-organic precursors for efficient bifunctional oxygen catalysis. S decoration endows S-FeNi/PC with a superior OER performance while maintaining an ORR performance that is comparable to that of Pt/C. Hence, S-FeNi/PC exhibits excellent bifunctional oxygen catalytic activity, outperforming the noble-metal-based composite catalysts of Pt/C and RuO2. Notably, the ZABs assembled with S-FeNi/PC exhibit high specific capacity (792 mA h g−1), high peak power density (123.5 mW cm−2), and remarkable durability for 700 charge/discharge cycles at 10 mA cm−2, which surpasses the performance of commercially available Pt/C-RuO2 and other catalysts in previously reported studies. This study will provide not only new bifunctional oxygen electrodes for efficient ZAB devices but also new insights into the design of FeNi-based materials for a wide range of catalytic applications.

摘要

当前, FeNi合金由于其含量丰富、化学稳定性好的优点, 在锌-空 气二次电池(ZABs)中的氧还原反应(ORR)和析氧反应(OER)方面受到 了广泛的关注. 然而, 传统FeNi合金还具有导电性差、比表面积小、活 性低等缺点, 严重阻碍了它们的催化性能. 我们通过对金属有机前驱体 进行热处理, 合成了以分级多孔碳为载体的S-调控FeNi纳米合金材料 (S-FeNi/PC), 以实现高效的双功能氧催化. S调控赋予了FeNi纳米合金 优越的OER性能, 同时还使材料保持了与Pt/C相当的ORR性能. 因此, SFeNi/PC具有很好的双功能氧催化活性, 优于商业的Pt/C和RuO2贵金 属基复合催化剂. 值得注意的是, 以S-FeNi/PC为电极组装的ZABs具有 较高的比容量(792 mA h g−1)、高峰值功率密度(123.5 mW cm−2), 以及 在10 mA cm−2电流密度下可700次放电/充电循环的优异耐久性, 这些 性能远高于商用Pt/C-RuO2催化剂, 甚至超过了许多先前报道的工作. 我们相信这项研究不仅为高效的ZABs装置提供了新的双功能氧电极 材料, 而且为具有广泛催化应用前景的FeNi基材料的设计提供了新的 见解.

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Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (22179087, 51903178, and 51803134), the Science and Technology Project of Sichuan Province (2021YFH0135), China Postdoctoral Science Foundation (2021M692303), and the Post-doctor Research Project, and Sichuan University (2021SCU12013). We thank our laboratory members for their generous help and gratefully acknowledge the help of the National Experimental Teaching Demonstration Center of Materials Science and Engineering at Sichuan University. We thank Zhongkebaice Technology Service Co., Ltd. for HR-TEM and XPS tests. We also appreciate the Analytical & Testing Center of Sichuan University.

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Authors and Affiliations

  1. College of Polymer Science and Engineering, State Key Laboratory of Polymer Materials Engineering, Sichuan University, Chengdu, 610065, China

    Hailin Yu  (余海林), Fei Fan  (范飞), Chao He  (何超), Tian Ma  (马田), Yinghan Wang  (汪映寒) & Chong Cheng  (程冲)

  2. Department of Ultrasound, West China Hospital, Sichuan University, Chengdu, 610065, China

    Tian Ma  (马田)

  3. College of Biomass Science and Engineering, Sichuan University, Chengdu, 610065, China

    Mi Zhou  (周密)

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  1. Hailin Yu  (余海林)
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Contributions

Yu H and Wang Y conceived the idea and designed the experiments. Yu H and Fan F conducted the synthesis experiments, electrochemical measurements, and data analysis. Zhou M performed the N2 adsorption experiments. He C performed the SEM. Yu H and Ma T wrote and edited the manuscript. Wang Y and Cheng C supervised the whole project. All authors discussed the results and commented on the manuscript.

Corresponding authors

Correspondence to Tian Ma  (马田) or Yinghan Wang  (汪映寒).

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Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary information

Experimental details and supporting data are available in the online version of the paper.

Hailin Yu is currently a doctoral student at the College of Polymer Science and Engineering, Sichuan University. His research interest is synthesizing functional materials related to electrocatalysis in energy conversion and protonexchange membrane fuel cells.

Tian Ma is now a postdoctoral research fellow at West China Hospital, Sichuan University. She obtained her PhD degree in chemistry from Jacobs University Bremen in 2019. Her current research interests include the design and fabrication of functionalized polyoxometalates-based/derived catalytic materials and their applications in electrocatalytic and energy fields, such as water splitting and fuel cells.

Yinghan Wang is a full professor at the Department of Polymer Science, Sichuan University. He received his B. Eng. degree from East China University of Science and Technology, his M.Eng. degree from Sichuan University, and his PhD degree from Tokyo Institute of Technology. He joined JSR Corporation and DIC Corporation as a research fellow. His main research interests include functional membrane materials, fuel-cell proton-exchange membranes, high-performance composite materials, and energy-storage and electrocatalytic materials.

Chong Cheng is currently a full professor in the Department of Polymer Science at Sichuan University. He obtained his BSc and PhD degrees from Sichuan University. After a research stay at the University of Michigan, USA, he joined the Freie Universität Berlin as an AvH research fellow. His current scientific interests include fabricating advanced low-dimensional materials for nanomedicines, antibacterial materials, stem cell scaffolds, energy storage devices, and electrocatalysts, especially the cutting-edge catalytic applications of metal-organic frameworks.

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Yu, H., Fan, F., He, C. et al. Sulfur-modulated FeNi nanoalloys as bifunctional oxygen electrode for efficient rechargeable aqueous Zn-air batteries. Sci. China Mater. 65, 3007–3016 (2022). https://doi.org/10.1007/s40843-022-2070-7

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