Abstract
Highly efficient platinum-group metal (PGM)-free electrocatalysts are essential for the large-scale utilization of Zn-air batteries (ZABs). Herein, we report the simple fabrication of a single atomic PGM-free electrocatalyst, Fe-SA/N-C, via a post-synthetic electrostatic absorption (PSEA) strategy. The single Fe atoms are anchored on the three-dimensiaonal (3D) porous carbon with adjacent N atoms, forming atomic Fe-N4 active sites. Fe-SA/N-C exhibits excellent ORR activity in 0.1 mol L−1 KOH aqueous solution (E1/2 = 0.92 V) and 0.5 mol L−1 H2SO4 aqueous solution (E1/2 = 0.77 V), superior to those of commercial Pt/C (0.85 and 0.79 V, respectively). As a proof of concept, homemade liquid ZAB with Fe-SA/N-C catalyst displays outstanding discharging specific capacity and peak power density, outperforming the commercial Pt/C. According to the density functional theory calculation, the Fe-N4 sites with graphitic N dopant can improve the activation of intermediates and decrease the energy barrier of the rate-determining step. This work highlights new insights for the experimental and theoretical guidance of PGM-free electrocatalysts and prescribes a general strategy for the rational design of PGM-free electrocatalysts used in ZABs.
摘要
设计和制备高效的非铂族催化剂对锌-空气电池的大规模应用至关重要. 本文采用简单的后合成静电吸附策略制备了Fe-N-C单原子催化剂(Fe-SA/N-C). 其中, Fe原子与相邻的氮原子形成Fe-N4活性位点并锚定在三维多孔碳上. 该催化剂在0.1 mol L−1 KOH (E1/2 = 0.92 V)和 0.5 mol L−1 H2SO4 (E1/2 = 0.77 V)中均表现出优异的氧化还原活性, 性能优于商业Pt/C催化剂(0.1 mol L−1 KOH, E1/2 = 0.85 V; 0.5 mol L−1 H2SO4, E1/2 = 0.79 V). 此外, 以Fe-SA/N-C作为阴极催化剂自组装的液体锌-空气电池具有优异的放电比容量和峰值功率密度, 优于商业Pt/C 催化剂. 密度泛函理论计算结果表明, 石墨化氮掺杂的Fe-N4位点能有效提高ORR中间产物的活化程度, 降低速率决定步骤的能垒. 本工作对非铂族催化剂的实验制备和理论研究提出了新的见解, 为锌-空气电池中使用的非铂族催化剂的合理设计提供了一般策略.
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Acknowledgements
This work was supported by the National Natural Science Foundation of China (22078028 and 21978026). The authors would like to thank the Shiyanjia lab (https://www.shiyanjia.com) for materials characterization, Prof. Yin for the support of VASP software, and Changzhou University Computer Center for computing services.
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Author contributions Li L designed the research. Li L and Li N performed the experiments and wrote the original draft. Xing H conducted the model optimization and performed DFT calculations. Li L, Xia J, Arif M, and Zhao Y made formal analysis and editing. He G and Chen H supervised the research.
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Supplementary information Experimental details and supporting data are available in the online version of the paper.
Le Li received his master degree from Changzhou University in 2018, and now he is a PhD student at Changzhou University. His current research focuses on the design and synthesis of single-atom catalysts for electrochemical applications.
Guangyu He is a professor at Changzhou University. She received her PhD degree from Nanjing University of Science and Technology. Her research mainly focuses on graphene-based functional materials for applications in advanced energy storage materials and devices and environmental engineering.
Haiqun Chen is a professor at Changzhou University. He received his PhD degree from Nanjing University of Science and Technology. His research mainly focuses on graphene-based functional materials for applications in environmental engineering, catalytic chemistry, and supercapacitors.
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Post-synthetic electrostatic adsorption-assisted fabrication of efficient single-atom Fe-N-C oxygen reduction catalysts for Zn-air batteries
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Li, L., Li, N., Xia, J. et al. Post-synthetic electrostatic adsorption-assisted fabrication of efficient single-atom Fe-N-C oxygen reduction catalysts for Zn-air batteries. Sci. China Mater. 66, 992–1001 (2023). https://doi.org/10.1007/s40843-022-2207-x
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DOI: https://doi.org/10.1007/s40843-022-2207-x