工作电压对PEMFC膜电极衰退影响模拟研究

doi:10.11949/0438-1157.20231344

摘要/Abstract

摘要：

为研究长期稳定运行条件下，工作电压对质子交换膜燃料电池膜电极衰退状况的影响，建立了包含碳腐蚀、Pt氧化与溶解以及离聚物降解的PEMFC多物理场耦合模型进行数值模拟。研究结果表明：随着工作电压增加，阴极催化层中Pt溶解与碳腐蚀速率加快，500 h后Pt表面氧化的区域大幅增加，阴极催化层中团聚体半径与质子交换膜中磺酸基团浓度剧烈减小，衰退区域主要集中在阴极入口处且高电压下衰退程度急剧增加。电池在0.8 V下运行500 h后，阴极入口处阴极催化层与膜厚度显著减小，分别降低13.62%与35.30%；阴极催化层电化学活性面积和膜的离子电导率分别减小59.9%与6.9%，膜的当量质量增加7.4%，且上述指标前100 h内衰退剧烈，随后逐渐趋于平缓。可为膜电极材料设计与控制策略的优化提供参考。

关键词: 质子交换膜燃料电池, 膜电极, 工作电压, 计算流体力学, 衰退, 模拟

Abstract:

To study the effect of operating voltage on the degradation of membrane electrodes of proton exchange membrane fuel cell (PEMFC) under long-term stable operation conditions, a coupled multi-physics field PEMFC model including carbon corrosion, Pt oxidation, dissolution and ionomer degradation is established for numerical simulation. The results show that as the operating voltage increases, the Pt dissolution and carbon corrosion rates in the cathode catalytic layer accelerate. After 500 h, the oxidized area of the Pt surface increases significantly. The radius of the agglomerates in CCL and the concentration of sulfonic acid groups in the proton exchange membrane decrease drastically, and the recession area is mainly concentrated in the cathode inlet and the degree of the recession is increased drastically at a high voltage. When the cell is operated at 0.8 V for 500 h, the thickness of CCL and membrane at the cathode inlet decreased significantly by 13.62% and 35.30%, respectively. The electrochemcial active surface area of CCL and the ionic conductivity of the membrane decreased by 59.9% and 6.9%, respectively, and the equivalent weight of the membrane increased by 7.4%, and the above indexes declined drastically in the first 100 h, and then gradually stabilized. The conclusion can provide a guideline for the optimization of membrane electrode material design and control strategy.

Key words: PEMFC, membrane electrode, operating voltage, CFD, degradation, simulation

中图分类号:

TM 911.4

谭耀文, 姜攀星, 杜青, 余婉秋, 温小飞, 詹志刚. 工作电压对PEMFC膜电极衰退影响模拟研究[J]. 化工学报, 2024, 75(3): 974-986.

Yaowen TAN, Panxing JIANG, Qing DU, Wanqiu YU, Xiaofei WEN, Zhigang ZHAN. Numerical study of the effects of operating voltage on the degradation of membrane electrodes of PEMFC[J]. CIESC Journal, 2024, 75(3): 974-986.

图/表 16

图1 PEMFC几何模型示意图

Fig.1 Schematic of the PEMFC model

表1 结构参数

Table 1 Structural parameters

参数	数值/ $m m$
电池总长/宽/高	60/2/2.407
流道深度	0.5
流道宽度	0.8
岸宽	0.6
阴/阳极GDL厚度	0.16
阴/阳极MPL厚度	0.03
阴/阳极CL厚度	0.009/0.006
质子交换膜厚度	0.012

表1 结构参数

Table 1 Structural parameters

参数	数值/ $m m$
电池总长/宽/高	60/2/2.407
流道深度	0.5
流道宽度	0.8
岸宽	0.6
阴/阳极GDL厚度	0.16
阴/阳极MPL厚度	0.03
阴/阳极CL厚度	0.009/0.006
质子交换膜厚度	0.012

图2 离聚物降解机制示意图

Fig.2 Schematic diagram of ionomer degradation mechanism

表2 操作条件

Table 2 Operating conditions

参数	数值
温度/K	348.15
阴/阳极出口背压/kPa	150/150
阴/阳极进口加湿度/%	70/50
阴/阳极化学计量比	2/2

表3 物性参数［30］及电化学参数［20］

Table 3 Physical parameters［30］ and electrochemical parameters［20］

参数	数值
GDL/MPL/CL接触角/(°)	130/140/120
GDL/MPL/CL孔隙率	0.7/0.6/0.5
GDL/MPL/CL/PEM密度/(kg/m³)	2000/2000/1350/1980
GDL/MPL/CL/PEM比热容/(J/(kg·K))	1000/1000/680/1090
GDL/MPL/CL渗透率(厚度方向)/m²	6.5×10^-12/3.4×10^-12/2×10^-15
GDL/MPL/CL渗透率(平面方向)/m²	1.9×10^-12/3.4×10^-12/2×10^-15
GDL/MPL/CL/PEM电导率(厚度方向)/(S/m)	358/358/13514/0
GDL/MPL/CL/PEM电导率(平面方向)/(S/m)	27500/358/13514/0
GDL/MPL/CL/PEM热导率(厚度方向)/ (W/(m·K))	0.83/0.83/2.74/0.2
GDL/MPL/CL/PEM热导率(平面方向)/ (W/(m·K))	8.33/0.83/2.74/0.2
阴/阳极交换电流密度/(A/m³)	900/5×10⁸
阴/阳极电荷传递系数	0.65/0.5

表4 网格独立性检验

Table 4 Grid independence test

工况	网格数量/个	电流密度/(mA/cm²)	电压/V	计算时间/h
Case1	196964	800	0.731275	5.1
Case2	261492	800	0.731949	7.3
Case3	307831	800	0.732615	8.6
Case4	363158	800	0.732826	10.4
Case5	431285	800	0.732910	12.8

图3 模型验证

Fig.3 Model validation

图4 运行起始时刻阴极催化层中间平面局部电压及相对湿度

Fig.4 Local voltage and relative humidity of the mid-plane of CCL at the starting moment of the run

图5 运行起始时刻阴极催化层中间平面的碳腐蚀速率和Pt溶解速率

Fig.5 Carbon corrosion rate and dissolution rate of Pt in the mid-plane of CCL at the starting moment of the run

图6 运行500 h后Pt表面被氧化与未被氧化的面积占比

Fig.6 Ratio of oxidized to unoxidized area on Pt surface after 500 h of running

图7 阴极催化层ECSA随运行时间的变化

Fig.7 Variation of ECSA of CCL with operating time

图8 运行500 h后阴极催化层中团聚体的半径和阴极催化层厚度的减少率

Fig.8 The reduction rate of the radius of agglomerate in CLL and the thickness reduction of the catalytic layer after 500 h of running

图9 运行起始时刻阳极催化层中间平面的局部电压和膜态水含量

Fig.9 Local voltage and dissolved water content of the mid-plane of ACL at the starting moment of the run

图10 运行起始时刻O2从CCL渗透到ACL的速率

Fig.10 Gas crossover flux of O2 from CCL to ACL at the starting moment of the run

图11 运行500 h后膜中间平面磺酸基团浓度和膜厚度减少率

Fig. 11 Concentration of RfSO3- in mid-plane of PEM and PEM thickness reduction after 500 h of running

图12 质子交换膜物性随运行时间的变化

Fig.12 Variation in physical properties of PEM with running time

参考文献 31

1	Meyer Q, Zeng Y C, Zhao C. In situ and operando characterization of proton exchange membrane fuel cells[J]. Advanced Materials, 2019, 31(40): e1901900.
2	侯明, 邵志刚, 俞红梅, 等. 2019年氢燃料电池研发热点回眸[J]. 科技导报, 2020, 38(1): 137-150.
	Hou M, Shao Z G, Yu H M, et al. Review of hot topics on hydrogen fuel cell in 2019[J]. Science & Technology Review, 2020, 38(1): 137-150.
3	Nguyen H L, Han J, Nguyen X L, et al. Review of the durability of polymer electrolyte membrane fuel cell in long-term operation: main influencing parameters and testing protocols[J]. Energies, 2021, 14(13): 4048.
4	Okonkwo P C, Ige O O, Barhoumi E M, et al. Platinum degradation mechanisms in proton exchange membrane fuel cell (PEMFC) system: a review[J]. International Journal of Hydrogen Energy, 2021, 46(29): 15850-15865.
5	Gittleman C S, Coms F, Lai Y. Membrane durability: physical and chemical degradation[M]// Modern Topics in Polymer Electrolyte Full Cell. Boston: Elsevier Inc., 2011: 15-88.
6	Hong K, Li S, Zhu K, et al. Effects of relative humidification on durability of membrane electrode assembly of proton exchange membrane fuel cells[J]. Journal of the Electrochemical Society, 2021, 168(6): 064507.
7	Chen H C, Zhao X, Zhang T, et al. The reactant starvation of the proton exchange membrane fuel cells for vehicular applications: a review[J]. Energy Conversion & Management, 2019, 182: 282-298.
8	王诚, 王树博, 张剑波, 等. 车用燃料电池耐久性研究[J]. 化学进展, 2015, 27(4): 424-435.
	Wang C, Wang S B, Zhang J B, et al. The durability research on the proton exchange membrane fuel cell for automobile application[J]. Progress in Chemistry, 2015, 27(4): 424-435.
9	Ren P, Pei P C, Li Y H, et al. Degradation mechanisms of proton exchange membrane fuel cell under typical automotive operating conditions[J]. Progress in Energy and Combustion Science, 2020, 80: 100859.
10	Zhang Y L, Chen S G, Wang Y, et al. Study of the degradation mechanisms of carbon-supported platinum fuel cells catalyst via different accelerated stress test[J]. Journal of Power Sources, 2015, 273: 62-69.
11	Han M, Shul Y G, Lee H, et al. Accelerated testing of polymer electrolyte membranes under open-circuit voltage conditions for durable proton exchange membrane fuel cells[J]. International Journal of Hydrogen Energy, 2017, 42(52): 30787-30791.
12	Franck-Lacaze L, Bonnet C, Choi E, et al. Ageing of PEMFC’s due to operation at low current density: investigation of oxidative degradation[J]. International Journal of Hydrogen Energy, 2010, 35(19): 10472-10481.
13	Kneer A, Wagner N, Sadeler C, et al. Effect of dwell time and scan rate during voltage cycling on catalyst degradation in PEM fuel cells[J]. Journal of the Electrochemical Society, 2018, 165(10): F805-F812.
14	Kneer A, Wagner N. A semi-empirical catalyst degradation model based on voltage cycling under automotive operating conditions in PEM fuel cells[J]. Journal of the Electrochemical Society, 2019, 166(2): F120-F127.
15	罗马吉, 杨俊玮, 赵岩, 等. 不同衰退机理对PEMFC怠速工况性能衰退影响的模拟研究[J]. 太阳能学报, 2021, 42(3): 414-421.
	Luo M J, Yang J W, Zhao Y, et al. Simulation study on effect of different aging mechanisms on PEMFC performance degradation under idling condition[J]. Acta Energiae Solaris Sinica, 2021, 42(3): 414-421.
16	Kundu S, Fowler M W, Simon L C, et al. Degradation analysis and modeling of reinforced catalyst coated membranes operated under OCV conditions[J]. Journal of Power Sources, 2008, 183(2): 619-628.
17	Moein-Jahromi M, Kermani M J. Three-dimensional multiphase simulation and multi-objective optimization of PEM fuel cells degradation under automotive cyclic loads[J]. Energy Conversion and Management, 2021, 231: 113837.
18	Cullen D A, Neyerlin K C, Ahluwalia R K, et al. New roads and challenges for fuel cells in heavy-duty transportation[J]. Nature Energy, 2021, 6: 462-474.
19	Shao Y Y, Yin G P, Gao Y Z. Understanding and approaches for the durability issues of Pt-based catalysts for PEM fuel cell[J]. Journal of Power Sources, 2007, 171(2): 558-566.
20	Fink C, Karpenko-Jereb L, Ashton S. Advanced CFD analysis of an air-cooled PEM fuel cell stack predicting the loss of performance with time[J]. Fuel Cells, 2016, 16(4): 490-503.
21	Pandy A, Yang Z W, Gummalla M, et al. A carbon corrosion model to evaluate the effect of steady state and transient operation of a polymer electrolyte membrane fuel cell[J]. Journal of the Electrochemical Society, 2013, 160(9): F972-F979.
22	MacAuley N, Papadias D D, Fairweather J, et al. Carbon corrosion in PEM fuel cells and the development of accelerated stress tests[J]. Journal of the Electrochemical Society, 2018, 165(6): F3148-F3160.
23	Bi W, Fuller T F. Modeling of PEM fuel cell Pt/C catalyst degradation[J]. Journal of Power Sources, 2008, 178(1): 188-196.
24	Heyd D V, Harrington D A. Platinum oxide growth kinetics for cyclic voltammetry[J]. Journal of Electroanalytical Chemistry, 1992, 335(1/2): 19-31.
25	Darling R M, Meyers J P. Mathematical model of platinum movement in PEM fuel cells[J]. Journal of the Electrochemical Society, 2005, 152(1): A242.
26	Kregar A, Tavčar G, Kravos A, et al. Predictive system-level modeling framework for transient operation and cathode platinum degradation of high temperature proton exchange membrane fuel cells[J]. Applied Energy, 2020, 263: 114547.
27	Wong K H, Kjeang E. Mitigation of chemical membrane degradation in fuel cells: understanding the effect of cell voltage and iron ion redox cycle[J]. ChemSusChem, 2015, 8(6): 1072-1082.
28	Wong K H, Kjeang E. Macroscopic in-situ modeling of chemical membrane degradation in polymer electrolyte fuel cells[J]. Journal of the Electrochemical Society, 2014, 161(9): F823-F832.
29	Singh R, Sui P C, Wong K H, et al. Modeling the effect of chemical membrane degradation on PEMFC performance[J]. Journal of the Electrochemical Society, 2018, 165(6): F3328-F3336.
30	Fink C, Gößling S, Karpenko-Jereb L, et al. CFD simulation of an industrial PEM fuel cell with local degradation effects[J]. Fuel Cells, 2020, 20(4): 431-452.
31	Chen H, Zhan Z G, Jiang P X, et al. Whole life cycle performance degradation test and RUL prediction research of fuel cell MEA[J]. Applied Energy, 2022, 310: 118556.

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