基于重整气的高温聚合物电解质膜燃料电池电化学阻抗谱弛豫时间分布研究

doi:10.11949/0438-1157.20241062

化工学报 ›› 2025, Vol. 76 ›› Issue (7): 3509-3520.DOI: 10.11949/0438-1157.20241062

基于重整气的高温聚合物电解质膜燃料电池电化学阻抗谱弛豫时间分布研究

王珺仪¹^,²^,³(), 夏章讯¹^,³, 景粉宁¹^,³, 王素力¹^,³()

^1.中国科学院大连化学物理研究所燃料电池部，辽宁大连 116023
^2.中国科学院大学化学工程学院，北京 100049
^3.中国科学院醇类燃料电池及复合电能源重点实验室，辽宁大连 116023

收稿日期:2024-09-23 修回日期:2024-12-23 出版日期:2025-07-25 发布日期:2025-08-13
通讯作者: 王素力
作者简介:王珺仪（1998—），女，硕士研究生，wangjunyi@dicp.ac.cn
基金资助:
国家自然科学基金项目(22179130);国家自然科学基金项目(22379143);国家重点研发计划项目(2021YFB4001200)

Study on the relaxation time distribution of electrochemical impedance spectroscopy in high temperature polymer electrolyte membrane fuel cells based on reformed hydrogen fuels

Junyi WANG¹^,²^,³(), Zhangxun XIA¹^,³, Fenning JING¹^,³, Suli WANG¹^,³()

^1.Division of Fuel Cell & Battery, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
^2.School of Chemical Engineering, University of Chinese Academy of Sciences, Beijing 100049, China
^3.Key Laboratory of Alcohols Fuel Cell & Hybrid Power Sources, Chinese Academy of Sciences, Dalian 116023, Liaoning, China

Received:2024-09-23 Revised:2024-12-23 Online:2025-07-25 Published:2025-08-13
Contact: Suli WANG

摘要/Abstract

摘要：

采用磷酸掺杂电解质膜的高温聚合物电解质膜燃料电池（HT-PEMFC），其阳极催化层中磷酸分布对电极界面处的CO、H₂的电化学过程产生重要影响。通过研究不同阳极催化层活性位点密度的HT-PEMFC电池在重整气进料条件下的性能，并引入电化学阻抗谱弛豫时间分布（DRT）分析手段，建立阳极电化学反应与物质传输过程定量描述方法，阐释重整气进料条件下CO毒化作用机制。结果表明，低阳极活性位点密度单体电池相较高密度样品，在重整气进料条件下传质极化阻力提高了531%。Pt活性位点密度的提升可筛分富氢重整气中的CO组分、降低局域CO组分浓度，缓解活性位点占据导致的H₂传质受限。

关键词: 高温聚合物电解质膜燃料电池, 膜电极, CO, 弛豫时间分布, 电化学阻抗谱, 物质传输

Abstract:

The competitive adsorption of carbon monoxide (CO) and hydrogen (H₂) on the surface of platinum (Pt) catalyst has been recognized to reduce the available active sites for the hydrogen oxidation reaction (HOR), which is considered as the primary cause of CO poisoning in proton exchange membrane fuel cells (PEMFCs). In high-temperature PEMFCs utilizing with phosphoric acid electrolyte, the distribution of phosphoric acid in the anode catalyst layer may significantly influence the mass transport and charge transfer processes of CO and H₂ at the electrode interface, making the CO poisoning mechanism even more intricate. Therefore, comprehending the process and mechanism of CO poisoning in high-temperature PEMFCs holds crucial importance in optimizing the structure of the membrane-electrode assembly and enhancing the efficiency of the cell operation when supplied with reformate gas. In this paper, we propose a novel approach to regulate the number density of active sites in the anode catalyst layer and introduce the utilization of electrochemical impedance spectroscopy (EIS) to analyze the distribution of relaxation time (DRT). By employing this method, we aim to establish a quantitative description of the anode electrochemical reaction and mass transport processes. This enables us to better elucidate the mechanism of CO poisoning under conditions where the fuel supply consists of reformate gas. The obtained results demonstrate that the primary reason behind the performance degradation caused by the presence of CO in the anode of high-temperature PEMFCs is the mass transport polarization. The increase in Pt active site density can screen CO components in hydrogen-rich reformed gas and reduce the local CO component concentration, ultimately alleviating the H₂ mass transfer limitation caused by active site occupancy.

Key words: high temperature polymer electrolyte membrane fuel cell, membrane electrode, carbon monoxide, distribution of relaxation time, electrochemical impedance spectroscopy, mass transport

中图分类号:

TK 091

王珺仪, 夏章讯, 景粉宁, 王素力. 基于重整气的高温聚合物电解质膜燃料电池电化学阻抗谱弛豫时间分布研究[J]. 化工学报, 2025, 76(7): 3509-3520.

Junyi WANG, Zhangxun XIA, Fenning JING, Suli WANG. Study on the relaxation time distribution of electrochemical impedance spectroscopy in high temperature polymer electrolyte membrane fuel cells based on reformed hydrogen fuels[J]. CIESC Journal, 2025, 76(7): 3509-3520.

图/表 12

表1 MEA阳极结构信息

Table 1 Structural information of anode MEAs

样品名称	Pt载量/(mg·cm^-2)	炭粉/(mg·cm^-2)	PTFE/(mg·cm^-2)
MEA-A0.2	0.2	0.8	0.3
MEA-A0.6	0.6	0.5	0.3
MEA-A1.0	1.0	0.3	0.3
MEA-A1.4	1.4	0	0.3

表2 阳极电化学活性面积

Table 2 Electrochemical active surface area of anode

测试温度/℃	ECSA/cm²
测试温度/℃	MEA-A0.2	MEA-A0.6	MEA-A1.0	MEA-A1.4
160	12.47	18.55	29.70	46.08
170	14.26	33.31	60.48	61.90
180	17.65	51.61	85.40	60.00

图1 阳极Pt载量膜电极在不同温度、进气条件下的极化曲线及氢增益对比

Fig.1 Polarization curves and hydrogen gain of Pt-loaded anodes at different temperatures and gas flow settings

图2 四种阳极Pt载量膜电极在不同温度、进气条件下的Tafel曲线

Fig.2 Tafel plots of Pt-loaded anodes across varying temperatures and gas flow regimes

表3 Tafel曲线斜率

Table 3 Tafel slope of membrane electrodes

Gas	Tafel slop/(mV·dec^-1)
	160℃				180℃
	MEA-A0.2	MEA-A0.6	MEA-A1.0	MEA-A1.4	MEA-A0.2	MEA-A0.6	MEA-A1.0	MEA-A1.4
H₂	-115	-110	-113	-107	-119	-112	-111	-107
RE	-118	-114	-113	-109	-117	-104	-98	-98

表4 EIS 测试条件

Table 4 EIS testing conditions for membrane electrodes

氧气进料计量比	氢气进料计量比		温度/℃	电流密度/(mA·cm^-2)
氧气进料计量比	H₂进料	RE进料	温度/℃	电流密度/(mA·cm^-2)
2.0	18	—	160	200
4.0	18	—	160	200
10.0	1.8，2.0，2.2		160，180	200，400

图3 MEA-A0.6在不同条件下的EIS谱图对比

Fig.3 EIS spectra of MEA-A0.6 under specified conditions

图4 MEA-A0.6的DRT谱图及DRT峰值分布

Fig.4 DRT spectra of MEA-A0.6 under specified conditions

图5 膜电极的EIS测试及DRT拟合对比

Fig.5 EIS testing and DRT fitting comparison of membrane electrodes

图6 等效电路及ECM元件示意图

Fig.6 Schematic of the equivalent circuit and ECM components

图7 MEA-A0.2~MEA-A1.4的ECM拟合数据

Fig.7 ECM fitting data of EIS for MEA-A0.2 — MEA-A1.4

图8 不同活性位点密度HT-PEMFC阳极重整气进料电极过程示意图

Fig.8 The electrode process with different active site densities in HT-PEMFC while anode reformate gas feed

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基于重整气的高温聚合物电解质膜燃料电池电化学阻抗谱弛豫时间分布研究

Study on the relaxation time distribution of electrochemical impedance spectroscopy in high temperature polymer electrolyte membrane fuel cells based on reformed hydrogen fuels

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