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Fluorination-enabled interface of PtNi electrocatalysts for high-performance high-temperature proton exchange membrane fuel cells

氟化物界面抑制PtNi电催化剂去合金化及其高温质子交换膜燃料电池性能研究

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Abstract

High-temperature proton exchange membrane fuel cells (HT-PEMFCs) bring new opportunities for portable power generation due to their outstanding advantages such as high tolerance to fuel/air impurities and simplified heat/water management. However, carbon-supported nanostructured Pt-based catalysts running at temperatures over 150°C are challenged by the severe aggregation and carbon corrosion, thus leading to poor durability. Herein, we demonstrate that dendritic Pt-Ni nanoparticles supported on fluorinated carbon black (white carbon black) could significantly enhance the performance and durability of HT-PEMFCs as the cathode catalysts running at 160°C due to the strong interaction of the F and Ni atoms to form a NixFy interface on Pt-Ni nanoparticles. With the formation of a stable NixFy interface, this integrated HT-PEMFC reached peak power densities of 906 mW cm−2 and demonstrated excellent durability at 160°C under anhydrous H2/O2 conditions. This mitigation strategy was applied to Pt-alloy/C electrocatalysts and resulted in the elimination of Pt dissolution in practical fuel cells.

摘要

高温质子交换膜燃料电池(HT-PEMFCs)以其杂质耐受性高、系统简化等突出优势为燃料电池的发展带来了新机遇. 目前广泛使用的铂碳催化剂存在严重的颗粒团聚、载体腐蚀等耐久性较差问题. 本文采用氟化碳黑(白碳黑)负载的枝状Pt-Ni纳米颗粒作为HT-PEMFCs阴极催化剂, 由于Ni、F强相互作用并在Pt-Ni合金表面形成了NixFy界面,可显著提升器件性能和耐受性, 在160°C、干燥H2/O2条件下峰功率密度可达906 mW cm−2. 本文成功利用NixFy界面提升合金催化剂的活性和稳定性, 对于HT-PEMFCs催化剂的设计具有指导意义.

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Acknowledgements

This work was supported by the National Key R&D Program of China (2020YFA0710000), the National Natural Science Foundation of China (21825201 and U19A2017), the Provincial Natural Science Foundation of Hunan (2019GK2031, 2016TP1009 and 2020JJ5045), China Postdoctoral Science Foundation (2020M682541), the Science and Technology Innovation Program of Hunan Province, China (2020RC2020), and Changsha Municipal Natural Science Foundation (kq2007009).

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Author notes

  1. These authors contributed equally to this work.

Authors and Affiliations

  1. State Key Laboratory of Chem/Bio-Sensing and Chemometrics, Provincial Hunan Key Laboratory for Graphene Materials and Devices, Advanced Catalytic Engineering Research Center of the Ministry of Education, College of Chemistry and Chemical Engineering, Hunan University, Changsha, 410082, China

    Peng Long  (龙鹏), Shiqian Du  (杜石谦), Qie Liu  (刘切), Li Tao  (陶李), Tehua Wang  (王特华), Kaizhi Gu  (顾开智), Chao Xie  (谢超), Ru Chen  (陈如), Yi Cheng  (程义) & Shuangyin Wang  (王双印)

  2. School of Materials Science and Engineering, Tianjin University, Tianjin, 300072, China

    Cong Peng  (彭聪) & Wei Feng  (封伟)

  3. College of Materials Science and Engineering, Changsha University of Science & Technology, Changsha, 410083, China

    Yiqiong Zhang  (张怡琼)

  4. Beijing Key Laboratory of Bioinspired Energy Materials and Devices, School of Space and Environment, Beihang University, Beijing, 100191, China

    Shanfu Lu  (卢善富)

Authors
  1. Peng Long  (龙鹏)
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  2. Shiqian Du  (杜石谦)
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  5. Cong Peng  (彭聪)
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Contributions

Author contributions Long P, Du S, and Liu Q conceived the idea and wrote the paper; Long P, Gu K and Liu Q performed the synthesis and basic characterization of the samples. Du S, Wang T, Xie C and Peng C conducted the fuel cell test. Tao L, Zhang Y, Chen R, Lu S, Cheng Y, Feng W and Wang S discussed the mechanism of action and directed the writing of the paper. All the authors contributed to the overall scientific interpretation and edited the manuscript.

Corresponding authors

Correspondence to Li Tao  (陶李), Shanfu Lu  (卢善富), Yi Cheng  (程义), Wei Feng  (封伟) or Shuangyin Wang  (王双印).

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Conflict of interest The authors declare that they have no conflict of interest.

Additional information

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

Peng Long received his Master degree in 2014 from Hunan University of Science and Technology and his PhD degree in 2018 from Tianjin University under the supervision of Prof. Wei Feng. He currently works at Hunan University as a postdoctoral researcher under the supervision of Prof. Shuangyin Wang. His research interests include the synthesis and characterization of nanomaterials as electrocatalysts for proton exchange membrane fuel cells.

Shiqian Du received his Master degree in 2016 from Beijing University of Chemical Technology, China. He is pursuing his PhD degree under the supervision of Prof. Shuangyin Wang at Hunan University. His research interests are electrochemical catalysis and related devices.

Qie Liu received her Bachelor’s degree in 2020 from Hunan University. She is pursuing her PhD degree under the supervision of Prof. Shuangyin Wang at Hunan University. Her research interest includes the design of electrocatalysts and their applications in high-temperature proton exchange membrane fuel cells.

Li Tao received his Master degree in 2016 and his PhD degree in 2019 from Hunan University under the supervision of Prof. Shuangyin Wang. He is currently an assistant professor at the Provincial Hunan Key Laboratory for Graphene Materials, College of Chemistry and Chemical Engineering, Hunan University. His research interests are in plasma technology, defect chemistry and fuel cells.

Shuangyin Wang received his BSc degree in 2006 from Zhejiang University and his PhD degree in 2010 from Nanyang Technological University, Singapore. He is currently a professor of the Key Provincial Hunan Key Laboratory for Graphene Materials, College of Chemistry and Chemical Engineering, Hunan University. His research interests are in plasma technology, defects in various crystals and their application for electrochemical energy storage and conversion.

Shanfu Lu received his PhD in physical chemistry from Wuhan University in 2008, and then joined Nanyang Technological University in Singapore as a postdoctoral researcher. He joined the Department of Environmental Science and Engineering of Beihang University as a professor in 2009. He is mainly engaged in the research of key materials and devices for polymer electrolyte membrane fuel cells and liquid flow batteries.

Wei Feng received his PhD degree in 2000 from Xi’an Jiaotong University of China after studying the optical-electrical properties and device applications of novel conducting polymers, and then worked at Osaka University and Tsinghua University as a Japan Science Promotion Society (JSPS) fellow and postdoctoral researcher, respectively. In 2004, he became a full professor at Tianjin University, where he has been working on functional nanocarbon materials.

Yi Cheng received his Master degree in environmental engineering from Central South University in 2006 and his PhD degree in 2014 from Curtin University. His research interests are environmental functional materials, clean energy materials and devices, electrochemical catalysts for pollutant degradation and mechanisms.

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Fluorination-enabled interface of PtNi electrocatalysts for high-performance high-temperature proton exchange membrane fuel cells

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Long, P., Du, S., Liu, Q. et al. Fluorination-enabled interface of PtNi electrocatalysts for high-performance high-temperature proton exchange membrane fuel cells. Sci. China Mater. 65, 904–912 (2022). https://doi.org/10.1007/s40843-021-1839-8

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