物理化学学报 >> 2021, Vol. 37 >> Issue (9): 2010048.doi: 10.3866/PKU.WHXB202010048

所属专题: 燃料电池

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基于金属-氮-碳结构催化剂的质子交换膜燃料电池研究进展

丁亮1,2, 唐堂1,2, 胡劲松1,2,*()   

  1. 1 中国科学院化学研究所,中国科学院分子纳米结构与纳米技术重点实验室,北京分子科学国家研究中心,北京 100190
    2 中国科学院大学,北京 100049
  • 收稿日期:2020-10-22 录用日期:2020-11-16 发布日期:2020-11-25
  • 通讯作者: 胡劲松 E-mail:hujs@iccas.ac.cn
  • 作者简介:Jin-Song Hu received his Ph.D. degree in Physical Chemistry at the Institute of Chemistry, Chinese Academy of Sciences (ICCAS) in 2005. After that, he joined in ICCAS as an assistant professor and then was promoted as an associated professor in 2007. In 2008–2011, he worked in the research group of Charles M. Lieber at Harvard University. Then, he joined in ICCAS as a Full Professor. His current research interests focus on the development of non-precious electrocatalysts for electrochemical energy conversion and low-cost thin film solar cells
  • 基金资助:
    国家重点研发计划(2016YFB0101202);国家自然科学基金(21773263);国家自然科学基金(21972147)

Recent Progress in Proton-Exchange Membrane Fuel Cells Based on Metal-Nitrogen-Carbon Catalysts

Liang Ding1,2, Tang Tang1,2, Jin-Song Hu1,2,*()   

  1. 1 Beijing National Laboratory for Molecular Sciences (BNLMS), CAS Key Laboratory of Molecular Nanostructure and Nanotechnology, Institute of Chemistry, Chinese Academy of Sciences (CAS), Beijing 100190, China
    2 University of Chinese Academy of Sciences, Beijing 100049, China
  • Received:2020-10-22 Accepted:2020-11-16 Published:2020-11-25
  • Contact: Jin-Song Hu E-mail:hujs@iccas.ac.cn
  • About author:Jin-Song Hu, Email: hujs@iccas.ac.cn; Tel.: +86-10-82613929
  • Supported by:
    the National Key Research and Development Program of China(2016YFB0101202);the National Natural Science Foundation of China(21773263);the National Natural Science Foundation of China(21972147)

摘要:

质子交换膜燃料电池(PEMFC)可以直接将储存在氢中的化学能无污染地转化为电能,是实现碳减排和碳中和的关键新能源技术。目前的PEMFC技术,尤其是在发生氧还原反应的阴极,还严重依赖铂基贵金属催化剂,导致了燃料电池高昂的成本,限制了其大规模应用。因此,人们对于研究基于低成本非贵金属催化剂的PEMFC展现出了极大的兴趣。自从采用金属-氮-碳结构催化剂作为贵金属催化剂的替代品以来,非铂基PEMFC取得了很多突破,但是当前其在活性和稳定性的表现仍不能令人满意。本文总结了基于金属-氮-碳催化剂的PEMFC性能与活性位点、催化剂结构和催化层结构之间的关系,揭示了催化剂结构对于PEMFC中物质传输的重要作用。另外,为了满足实际需求,本文也总结并讨论了PEMFC可能的失活机理,包括脱金属作用,氮物种的质子化,碳载体腐蚀和孔道水淹等,以及目前发展的可能的解决方案。基于这些认识,本文最后介绍了在提升金属-氮-碳基PEMFC的活性和稳定性方面的最新进展与策略。

关键词: 质子交换膜燃料电池, 非贵金属催化剂, 金属-氮-碳, 氧还原反应, 电催化

Abstract:

Proton-exchange membrane fuel cells (PEMFCs) directly transform chemical energy into electrical energy with high energy density and zero carbon emissions, thereby offering a clean energy alternative for fossil fuels and vehicle electrification. However, the existing PEMFCs rely on Pt-based catalysts, especially at the cathode side wherein the sluggish oxygen reduction reaction (ORR) takes place, resulting in high cost and limiting their commercial applications. Therefore, there is a strong interest in developing platinum group metal-free (PGM-free) PEMFCs. Although impressive advancements have been made since metal-nitrogen-carbon (M-N-C) catalysts have been developed as promising candidates for low-cost cathode catalysts, PGM-free PEMFCs still suffer from insufficient activity and durability. Owing to the intricate structure of the tri-phase interface and mass transport limitation, the M-N-C catalysts with high ORR activity in rotating disk electrode (RDE) tests still suffer from unexpected problems such as showing low activity and undesired rapid degradation process in real fuel cell conditions. Therefore, a comprehensive understanding of the active sites and influences of the M-N-C catalyst structure and cathode structure on the PEMFC performance will promote the development of PGM-free PEMFCs. Herein, with an aim to increase the activity and durability of PEMFCs based on M-N-C catalysts, we summarize the recent progress in understanding the active sites of M-N-C catalysts and the relationships between the structures of catalysts/catalyst layers and device performances. At the catalyst level, multiple delicately designed synthetic strategies suggest that attractive device performances can be obtained by tailoring the intrinsic activity and density of the catalyst active sites while engineering the porosity of catalysts to improve the utilization of active sites. Additionally, integrating the catalyst ink into the cathode catalyst layers in PGM-free PEMFC is pivotal for transforming the impressive ORR performance of catalysts in the RDE test to fuel cell performance. Accordingly, the recent advances in the enhancement of mass transfer and charge transport to achieve remarkable fuel cell performance were also included by rationally designing ionomer contents, catalyst morphology, and fabrication process of cathodic catalyst layers. Moreover, durability is the Achilles heel of PEMFCs with M-N-C catalysts, which is currently far behind the commercial requirements. The possible degradation mechanisms and the recent progress in seeking the corresponding solutions are also discussed in this review, including the decomposition of metal species, protonation of nitrogen sites, corrosion of carbon support, and micropore flooding. Based on these insights, the perspective is proposed by articulating open challenges and opportunities in materials innovations and device engineering with an aim to achieve practical M-N-C based PEMFCs.

Key words: Proton-exchange membrane fuel cell, Platinum group metal-free catalyst, Metal-nitrogen-carbon, Oxygen reduction reaction, Electrolysis