介孔碳质子交换膜燃料电池结构与传输阻力仿真分析

doi:10.61558/2993-074X.3546

摘要/Abstract

摘要：

介孔碳载体可通过纳米孔限域Pt沉积缓解磺酸根中毒问题，但其形态特征对氧传输的影响机制尚不明确。本研究结合碳载体形态模拟与改进的催化层团聚体模型，构建了阐明催化层孔结构演化、Pt利用率及氧传输过程的数学模型。结果表明，局部传质阻力主要由三个因素主导：（1）决定氧通量的活性位点密度；（2）决定最短传输路径的离聚物膜厚度；（3）影响实际路径长度的离聚物-Pt表面积比。在低离聚物/碳比例（I/C比）条件下，活性位点不足导致局域传输阻力显著增加（因素1主导）；而高I/C比虽提升离聚物覆盖率，但膜厚增大会削弱传质（因素2-3主导）。大尺寸碳颗粒因降低外比表面积并增加离聚物厚度，导致局域传质阻力净升高。随着纳米孔内Pt占比或Pt质量分数增加，孔内Pt密度升高加剧孔道堵塞，导致活性位点减少并增加离聚物厚度及表面积，进一步增大传质阻力。同样地，Pt载量降低导致活性位点减少，氧传输阻力线性增加。本研究强调需协同优化载体形态、Pt分布及离聚物含量，在平衡催化活性与传质效率的同时抑制孔道堵塞，研究结果可以为高性能介孔碳催化剂设计提供系统化理论指导。

关键词: 介孔碳载体, 电化学活性面积, 铂覆盖率, 氧传输阻力, 孔体积分布

Abstract:

Mesoporous carbon supports mitigate Pt sulfonic poisoning through nanopore-confined Pt deposition, yet their morphological impacts on oxygen transport remain unclear. This study integrates carbon support morphology simulation with an enhanced agglomerate model to establish a mathematical framework elucidating pore evolution, Pt utilization, and oxygen transport in catalyst layers. Results demonstrate dominant local mass transport resistance governed by three factors: (1) active site density dictating oxygen flux; (2) ionomer film thickness defining shortest transport path; (3) ionomer-to-Pt surface area ratio modulating practical pathway length. At low ionomer-to-carbon (I/C) ratios, limited active sites elevate resistance (Factor 1 dominant). Higher I/C ratios improve the ionomer coverage but eventually thicken ionomer films, degrading transport (Factors 2-3 dominant). The results indicate that larger carbon particles result in a net increase in local transport resistance by reducing external surface area and increasing ionomer thickness. As the proportion of Pt situated in nanopores or the Pt mass fraction increases, elevated Pt density inside the nanopores exacerbates pore blockage. This leads to the increased transport resistance by reducing active sites and increasing ionomer thickness and surface area. Lower Pt loading linearly intensifies oxygen flux resistance. The model underscores the necessity to optimize support morphology, Pt distribution, and ionomer content to prevent pore blockage while balancing catalytic activity and transport efficiency. These insights provide a systematic approach for designing high-performance mesoporous carbon catalysts.

Key words: mesoporous carbon support, electrochemical active surface area, Pt coverage, oxygen transport resistance, pore volume distribution

邓豪, 刘佳, 侯中军. 介孔碳质子交换膜燃料电池结构与传输阻力仿真分析[J]. 电化学（中英文）, 2025, 31(5): 2514001.

Hao Deng, Jia Liu, Zhong-Jun Hou. Understanding the Morphology and Mass Transport Resistance of Mesoporous Carbon-Supported PEMFC Based on Modeling Analysis[J]. Journal of Electrochemistry, 2025, 31(5): 2514001.

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://electrochem.xmu.edu.cn/CN/10.61558/2993-074X.3546

https://electrochem.xmu.edu.cn/CN/Y2025/V31/I5/2514001

图/表 11

Parameters	Value	Unit
Active area $A CCL$	25	cm²
Pt loading $L Pt$	0.25	mg·cm^-2
Ionomer to catalyst (I/C) ratio $φ I/C$	0.9	/
Packing density of carbon particles $ε C,pack$	0.6	/
Pt mass fraction of catalyst $φ Pt,Pt/C$	50%	/
Median Pt particle size	2.0	nm
Standard deviation of Pt particle size	0.5	nm
Fraction of Pt inside the nanopores $φ Pt,in$	65%	/
Specific nanopore volume $V p,C total m C total$	1.3	$cm 3 ⋅ g C − 1$
Carbon particle diameter $d C$	400	nm
Pt density	21.45	g·cm^-3
Carbon density	1	g·cm^-3
Ionomer density	1.15	g·cm^-3
Interfacial coefficient $k 1$	0.15	/
Interfacial coefficient $k 2$	2500	/
Operating temperature T	353.15	K
Operating pressure P	1	atm
Water content in the ionomer λ	10	/
Oxygen diffusivity in the ionomer $D O 2,ion$ [27]	$1.14698 e − 10 λ 0.708$	m² s^-1

参考文献 51

[1]	Zhang G B, Qu Z G, Tao W Q, Mu Y T, Jiao K, Xu H, Wang Y. Advancing next-generation proton-exchange membrane fuel cell development in multi-physics transfer[J]. Joule, 2024, 8(1): 45-63. https://doi.org/10.1016/j.joule.2023.11.015.
[2]	Jiao K, Xuan J, Du Q, Bao Z M, Xie B, Wang B W, Zhao Y, Fan L H, Wang H Z, Hou Z J, Huo S, Brandon N P, Yin Y, Guiver M D. Designing the next generation of proton-exchange membrane fuel cells[J]. Nature, 2021, 595: 361-369. https://doi.org/10.1038/s41586-021-03482-7.
[3]	Ren P, Pei P C, Li Y H, Wu Z Y, Chen D F, Huang S W. Degradation mechanisms of proton exchange membrane fuel cell under typical automotive operating conditions[J]. Prog. Energ. Combust., 2020, 80: 100859. https://doi.org/10.1016/j.pecs.2020.100859.
[4]	Woo S, Lee S, Taning A Z, Yang T H, Park S H, Yim S D. Current understanding of catalyst/ionomer interfacial structure and phenomena affecting the oxygen reduction reaction in cathode catalyst layers of proton exchange membrane fuel cells[J]. Curr. Opin. Electroche., 2020, 21: 289-296. https://doi.org/10.1016/j.coelec.2020.03.006.
[5]	Jinnouchi R, Kudo K, Kodama K, Kitano N, Suzuki K, Minami S, Shinozaki K, Hasegawav N, Shinohara A. The role of oxygen-permeable ionomer for polymer electrolyte fuel cells[J]. Nat. Commun., 2021, 12: 4956-4964. https://doi.org/10.1038/s41467-021-25301-3. doi: 10.1038/s41467-021-25301-3 URL pmid: 34400643
[6]	Jiao K, Li X G. Water transport in polymer electrolyte membrane fuel cells[J]. Prog. Energ. Combust., 2011, 37(3): 221-291. https://doi.org/10.1016/j.pecs.2010.06.002.
[7]	Liang Z J, Hong Z B, Xie M Y, Gu D. Recent progress of mesoporous carbons applied in electrochemical catalysis[J]. New Carbon Mater., 2022, 37(1): 152-179. https://doi.org/10.1016/S1872-5805(22)60575-4.
[8]	Huang Y H, Gu J, Hu Y D, Lei Y J, Yu T, Wang C. Preparation of mesoporous carbon with adjustable diameter and pore size[J]. Diam. Relat. Mater., 2022, 130: 109515. https://doi.org/10.1016/j.diamond.2022.109515.
[9]	Wang G X, Zhao W, Mansoor M, Liu Y N, Wang X Y, Zhang K Y, Xiao C L, Liu Q S, Mao L L, Wang M, Lv H F. Recent progress in using mesoporous carbon materials as catalyst support for proton exchange membrane fuel cells[J]. Nanomaterials-Basel, 2023, 13(21): 2818-2827. https://doi.org/10.3390/nano13212818.
[10]	Ramaswamy N, Zulevi B, McCool G, Shi Z X, Chavez A, Muller D A, Kongkanand A, Kumaraguru S. Graphitized mesoporous engineered carbon support for fuel cell applications[J]. ACS Appl. Eng. Mater., 2023, 1(10): 2543-2554. https://doi.org/10.1021/acsaenm.3c00354.
[11]	Huang O, Hu L Y, Chen X C, Cai W J, Wang L, Wang B. Metal-organic framework-derived N-doped carbon with controllable mesopore sizes for low-Pt fuel cells[J]. Adv. Funct. Mater., 2023, 33(44): 2302582. https://doi.org/10.1002/adfm.202302582.
[12]	Xi M, Chu T K, Wang X L, Li B, Yan D J, Ming P W, Zhang C M. Effect of mesoporous carbon on oxygen reduction reaction activity as cathode catalyst support for proton exchange membrane fuel cell[J]. Int. J. Hydrogen Energ., 2022, 47(65): 28074-28085. https://doi.org/10.1016/j.ijhydene.2022.06.131.
[13]	Xi M, Chu T K, Wang X L, Li B, Yan D J, Ming P W, Zhang C M. Study on durability of proton exchange membrane fuel cell stack based on mesoporous carbon supported platinum catalysts under dynamic cycles conditions[J]. J. Power Sources, 2023, 553: 232277. https://doi.org/10.1016/j.jpowsour.2022.232277.
[14]	Gu K, Kim E J, Sharm S K, Sharm P R, Bliznakov S, Hsiao B S, Rafailovich M H. Mesoporous carbon aerogel with tunable porosity as the catalyst support for enhanced proton-exchange membrane fuel cell performance[J]. Mater. Today Energy, 2021, 19: 100560. https://doi.org/10.1016/j.mtener.2020.100560.
[15]	Sung M, Yi H, Han J, Lee J B, Yoon S H, Park T L. Enhanced performance and durability of proton exchange membrane fuel cell catalyst supports via nanodrilling-induced selective mesoporous carbon structures[J]. ACS Appl. Eng. Mater., 2025, 8(2): 1230-1240. https://doi.org/10.1021/acsaem.4c02713.
[16]	Yarlagadda V, Ramaswamy N, Kukreja R S, Kumaraguru S. Ordered mesoporous carbon supported fuel cell cathode catalyst for improved oxygen transport[J]. J. Power Sources, 2022, 532: 231349. https://doi.org/10.1016/j.jpowsour.2022.231349.
[17]	Wu M J, Meng Z H, Xiong Y F, Zhang H N, Zhang A J, Zhang H, Zhu L Y, Tang H B, Tian T, Tang H L. Structurally tunable graphitized mesoporous carbon for enhancing the accessibility and durability of cathode Pt-based catalysts for proton exchange membrane fuel cells[J]. Small Sci., 2024, 4(7): 2400016. https://doi.org/10.1002/smsc.202400016.
[18]	Liu J J, Zenyuk I V. Proton transport in ionomer-free regions of polymer electrolyte fuel cells and implications for oxygen reduction reaction[J]. Curr. Opin. Electroche., 2018, 12: 202-208. https://doi.org/10.1016/j.coelec.2018.11.015.
[19]	Tu W Y, Liu W J, Cha C S, Wu B L. Study of the powder/membrane interface by using the powder microelectrode technique I. The Pt-black/Nafion interfaces[J]. Electrochim. Acta, 1998, 43(24): 3731-3739. https://doi.org/10.1016/S0013-4686(98)00131-5.
[20]	Liu W J, Wu B L, Cha C S. Surface diffusion and the spillover of H-adatoms and oxygen-containing surface species on the surface of carbon black and Pt/C porous electrodes[J]. J. Electroanal. Chem., 1999, 476(2): 101-108. https://doi.org/10.1016/S0022-0728(99)00371-X.
[21]	Paulus U A, Veziridis Z, Schnyder B, Kuhnke M, Scherer G G, Wokaun A. Fundamental investigation of catalyst utilization at the electrode/solid polymer electrolyte interface Part I. Development of a model system[J]. J. Electroanal. Chem., 2003, 541: 77-91. https://doi.org/10.1016/S0022-0728(02)01416-X.
[22]	Tominaka S, Wub C W, Kurodaa K, Osaka T. Electrochemical analysis of perpendicular mesoporous Pt electrode filled with pure water for clarifying the active region in fuel cell catalyst layers[J]. J. Power Sources, 2010, 195(8): 2236-2240. https://doi.org/10.1016/j.jpowsour.2009.11.002.
[23]	Chan K, Eikerling M. A pore-scale model of oxygen reduction in ionomer-free catalyst layers of PEFCs[J]. J. Electrochem. Soc., 2011, 158(1): B18-B28. 10.1149/1.3505042.
[24]	Debe M K. Tutorial on the Fundamental characteristics and practical properties of nanostructured thin film (NSTF) catalysts[J]. J. Electrochem. Soc., 2013, 160(6): F522-F534. 10.1149/2.049306jes.
[25]	Kudo K, Jinnouchi R, Morimoto Y. Humidity and temperature dependences of oxygen transport resistance of Nafion thin film on platinum electrode[J]. Electrochim. Acta, 2016, 209: 682-690. https://doi.org/10.1016/j.electacta.2016.04.023.
[26]	Kudo K, Morimoto Y. Analysis of oxygen transport resistance of Nafion thin film on Pt electrode[J]. ECS Transactions, 2012, 50(2): 1487-1494. 10.1149/05002.1487ecst.
[27]	Suzuki T, Kudo K, Morimoto Y. Model for investigation of oxygen transport limitation in a polymer electrolyte fuel cell[J]. J. Power Sources, 2013, 222: 379-389. https://doi.org/10.1016/j.jpowsour.2012.08.068.
[28]	Parthasarathy A, Srinivasan S, Appleby A J, Martin C R. Temperature dependence of the electrode kinetics of oxygen reduction at the platinum/Nafion® interface—a microelectrode investigation[J]. J. Electrochem. Soc., 1992, 139(9): 2530-2537. 10.1149/1.2221258.
[29]	Soboleva T, Zhao X S, Malek K, Xie Z, Navessin T, Holdcroft S. On the micro-, meso-, and macroporous structures of polymer electrolyte membrane fuel cell catalyst layers[J]. ACS Appl. Mater. Interfaces, 2010, 2(2): 375-384. https://doi.org/10.1021/am900600y.
[30]	Park Y C, Tokiwa H, Kakinuma K, Watanabe M, Uchida M. Effects of carbon supports on Pt distribution, ionomer coverage and cathode performance for polymer electrolyte fuel cells[J]. J. Power Sources, 2016, 315: 179-191. https://doi.org/10.1016/j.jpowsour.2016.02.091.
[31]	Kobayashi A, Fujii T, Harada C, Yasumoto E, Takeda K, Kakinuma K, Uchida M. Effect of Pt and ionomer distribution on polymer electrolyte fuel cell performance and durability[J]. ACS Appl. Energy Mater., 2010, 4(3): 2307-2317. https://doi.org/10.1021/acsaem.0c02841.
[32]	Lopez-Haro M, Guetaz L, Printemps T, Morin A, Escribano S, Jouneau P H, Bayle-Guillemaud P, Chandezon F, Gebel G. Three-dimensional analysis of Naﬁon layers in fuel cell electrodes[J]. Nat. Commun., 2014, 5: 5229-5234. https://doi.org/10.1038/ncomms6229. doi: 10.1038/ncomms6229 URL pmid: 25354473
[33]	Zou G F, Chen W S, She J, Yang T Q, Chen B. Effects of water dynamic behavior on oxygen transport in catalyst layers: A pore-scale study of proton exchange membrane fuel cells[J]. Int. Commun. Heat. Mass., 2025, 164(Part A)108806. https://doi.org/10.1016/j.icheatmasstransfer.2025.108806.
[34]	Dou S J, Hao L, Wang Y H, Wang Q Q. Pore-scale study of coupled charge, gas, and liquid water transport in the catalyst layer of PEM fuel cells[J]. Fuel, 2025, 380: 133141.
[35]	Sun F, Di Q, Chen M, Liu H J, Wang H J. Exploring local oxygen transport in low-Pt loading proton exchange membrane fuel cells: A comprehensive review[J]. eTransportation, 2024, 20: 100327. https://doi.org/10.1016/j.etran.2024.100327.
[36]	Shin S, Kim A R, Um S. Computational prediction of nanoscale transport characteristics and catalyst utilization in fuel cell catalyst layers by the lattice Boltzmann method[J]. Electrochim. Acta, 2018, 275: 87-99. https://doi.org/10.1016/j.electacta.2018.04.138.
[37]	Zhao C F, Yuan S, Cheng X J, Zheng Z F, Liu J, Yin J W, Shen S Y, Yan X Y, Zhang J L. The effect of catalyst layer design on catalyst utilization in PEMFC studied via stochastic reconstruction method[J]. Energy Ai, 2023, 13: 100245. https://doi.org/10.1016/j.egyai.2023.100245.
[38]	Ishikawa H, Sugawara Y, Inoue G, Kawase M. Effects of Pt and ionomer ratios on the structure of catalyst layer: A theoretical model for polymer electrolyte fuel cells[J]. J. Power Sources, 2018, 374: 196-204. https://doi.org/10.1016/j.jpowsour.2017.11.026.
[39]	Hao L, Moriyama K, Gu W B, Wang C Y. Modeling and experimental validation of Pt loading and electrode composition effects in PEM fuel cells[J]. J. Electrochem. Soc., 2015, 16(88): F854-F867. 10.1149/2.0221508jes.
[40]	Xie B, Zhang G B, Xuan J, Jiao K. Three-dimensional multi-phase model of PEM fuel cell coupled with improved agglomerate sub-model of catalyst layer[J]. Energ. Convers. Manage., 2019, 199: 112051. https://doi.org/10.1016/j.enconman.2019.112051.
[41]	Wang N, Qu Z G, Jiang Z Y, Zhang G B. A unified catalyst layer design classification criterion on proton exchange membrane fuel cell performance based on a modified agglomerate model[J]. Chem. Eng. J., 2022, 447: 137489. https://doi.org/10.1016/j.cej.2022.137489.
[42]	Samris A, Mounir H. Using a three-dimensional computational fluid dynamics model and an agglomerate model to investigate the effect of varying agglomerate parameters and output voltages on proton exchange membrane fuel cell performance[J]. Heliyon, 2024, 10(11): e32277. https://doi.org/10.1016/j.heliyon.2024.e32277.
[43]	An K B, Fang W Z, Xuan Z H, Zhao G R, Ling H, Tao W Q. Mechanisms of oxygen transport resistance of mesoporous carbon-supported catalysts in fuel cells[J]. J. Mater. Chem. A, 2025, 13: 2143-2154. https://doi.org/10.1039/D4TA06413E.
[44]	Fan L H, Wang J Q, Diaz D F R, Li L C, Wang Y, Jiao K. Molecular dynamics modeling in catalyst layer development for PEM fuel cell[J]. Prog. Energ. Combust., 2025, 108: 101220. https://doi.org/10.1016/j.pecs.2025.101220.
[45]	Kikkawa N, Kimura M. Comprehensive molecular dynamics study of oxygen diffusion in carbon mesopores: Insights for designing fuel-cell catalyst supports[J]. Langmuir, 2024 40(3): 1674-1687. https://doi.org/10.1021/acs.langmuir.3c02627.
[46]	Scherzer A C, Schneider P, Herring P K, Klingele M, Zamel N, Gerteisen D. Modeling the morphological effects of catalyst and ionomer loading on porous carbon supports of PEMFC[J]. J. Electrochem. Soc., 2022, 169(3): 034509-034522. 10.1149/1945-7111/ac58c2.
[47]	Sabharwal M, Pant L M, Patel N, Secanell M. Computational analysis of gas transport in fuel cell catalyst layer under dry and partially saturated conditions[J]. J. Electrochem. Soc., 2019, 166(7): F3065-F3080. 10.1149/2.0081907jes.
[48]	Olbrich W, Kadyk T, Sauter U, Eikerling M. Review-wetting phenomena in catalyst layers of PEM fuel cells: Novel approaches for modeling and materials research[J]. J. Electrochem. Soc., 2022, 169(5): 054521-054531. 10.1149/1945-7111/ac6e8b.
[49]	Ren H, Teng Y, Meng X C, Fang D H, Huang He, Geng J T, Shao Z G. Ionomer network of catalyst layers for proton exchange membrane fuel cell[J]. J. Power Sources, 2021, 506: 230186. https://doi.org/10.1016/j.jpowsour.2021.230186.
[50]	Srouji A C, Zheng L J, Dross R, Aaron D, Mench M M. The role of water management on the oxygen transport resistance in polymer electrolyte fuel cell with ultra-low precious metal loading[J]. J. Power Sources, 2017, 364: 92-100. https://doi.org/10.1016/j.jpowsour.2017.07.036.
[51]	Salari S, Tam M, McCague C, Stumper J, Bahrami M. The ex-situ and in-situ gas diffusivities of polymer electrolyte membrane fuel cell catalyst layer and contribution of primary pores, secondary pores, ionomer and water to the total oxygen diffusion resistance[J]. J. Power Sources, 2020, 449: 227479. https://doi.org/10.1016/j.jpowsour.2019.227479.