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Research Papers

Crack Formation in Membrane Electrode Assembly Under Static and Cyclic Loadings

[+] Author and Article Information
Masaki Omiya

Department of Mechanical Engineering,
Keio University,
3-14-1, Hiyoshi, Kohoku-ku,
Yokohama, Kanagawa 223-8522, Japan

Toyota Motor Corporation,
Susono,
Shizuoka, Japan

1Corresponding author: oomiya@mech.keio.ac.jp

Contributed by the Advanced Energy Systems Division of ASME for publication in the Journal of Fuel Cell Science and Technology. Manuscript received December 20, 2012; final manuscript received January 18, 2013; published online March 25, 2013. Editor: Nigel M. Sammes.

J. Fuel Cell Sci. Technol 10(2), 021007 (Mar 25, 2013) (8 pages) Paper No: FC-12-1129; doi: 10.1115/1.4023878 History: Received December 20, 2012; Revised January 18, 2013

The mechanical reliability of membrane electrode assemblies (MEAs) in polymer electrolyte fuel cells (PEFCs) is a major concern for fuel cell vehicles. Hygrothermal cyclic conditions induce mechanical stress in MEAs and cracks form under operating conditions. This paper investigates the failure mechanism of MEAs under several mechanical and environmental conditions with the aim of designing durable PEFCs. We performed static tensile tests and low-cycle fatigue tests on MEAs. During the tensile tests, the temperature and humidity of the test chamber were controlled and surface crack formation of MEAs was observed in situ by a video microscope. Low-cycle fatigue tests were performed at ambient conditions and the number of cycles to crack formation was measured. The results reveal that the temperature and the humidity affect the mechanical properties of MEA. Observations of MEAs during tensile tests reveal that cracks form on the surface of catalyst layers immediately after the MEAs yield. These results indicate that reducing the deformation mismatch between the catalyst layer and the proton exchange membrane is important for suppressing crack formation in MEAs. The results of low-cycle fatigue tests reveal that the fatigue strength of a MEA follows the Coffin–Manson law so that fatigue design of MEAs based on the Coffin–Manson law is possible. This result is valuable for designing durable PEFCs.

Copyright © 2013 by ASME
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References

Garland, N. L., and Kopasz, J. P., 2007, “The United States Department of Energy's High Temperature, Low Relative Humidity Membrane Program,” J. Power Sources, 172(1), pp. 94–99. [CrossRef]
Tang, H., Peikang, S., Jiang, S. P., Wang, F., and Pan, M., 2007, “A Degradation Study of Nafion Proton Exchange Membrane of PEM Fuel Cells,” J. Power Sources, 170(1), pp. 85–92. [CrossRef]
Schulze, M., Schneider, A., and Gulzow, E., 2004, “Alteration of the Distribution of the Platinum Catalyst in Membrane-Electrode Assemblies During PEFC Operation,” J. Power Sources, 127(1–2), pp. 213–221. [CrossRef]
Ishigami, Y., Takada, K., Yano, H., Inukai, J., Uchida, M., Nagumo, Y., Hyakutake, T., Nishide, H., and Watanabe, M., 2011, “Corrosion of Carbon Supports at Cathode During Hydrogen/Air Replacement at Anode Studied by Visualization of Oxygen Partial Pressures in a PEFC—Start-Up/Shut-Down Simulation,” J. Power Sources, 196(6), pp. 3003–3008. [CrossRef]
Jun, C. Y., Kim, W. J., and Yi, S. C., 2009, “Computational Analysis of Polarizations in Membrane-Electrode-Assembly for Proton Exchange Membrane Fuel Cells,” J. Membrane Sci., 341, pp. 5–10. [CrossRef]
Berning, T., Lu, D. M., and Djilali, N., 2002, “Three-Dimensional Analysis of Transport Phenomena in a PEM Fuel Cell,” J. Power Sources, 106, pp. 284–294. [CrossRef]
Silva, R. A., Hashimoto, T., Thompson, G. E., and Rangel, C. M., 2012, “Characterization of MEA Degradation for an Open Air Cathode PEM Fuel Cell,” Int. J. Hydrogen Energy, 37(8), pp. 7298–7308. [CrossRef]
Luo, Z., Li, D., Tang, H., Pan, M., and Ruan, R., 2006, “Degradation Behavior of Membrane-Electrode-Assembly Materials in 10-Cell PEMFC Stack,” Int. J. Hydrogen Energy, 31, pp. 1831–1837. [CrossRef]
Thepkaew, J., Therdthianwong, A., and Therdthianwong, S., 2008, “Key Parameters of Active Layers Affecting Proton Exchange Membrane (PEM) Fuel Cell Performance,” Energy, 33, pp. 1794–1800. [CrossRef]
Liu, D., and Case, S., 2006, “Durability Study of Proton Exchange Membrane Fuel Cells Under Dynamic Testing Conditions With Cyclic Current Profile,” J. Power Sources, 162, pp. 521–531. [CrossRef]
Ye, S., Hall, M., Cao, H., and He, P., 2006, “Degradation Resistant Cathodes in Polymer Electrolyte Membrane Fuel Cells” ECS Trans., 3(1), pp. 657–666. [CrossRef]
Borup, R., Meyers, J., Pivovar, B., Kim, Y. S., Mukundan, R., Garland, N., Myers, D., Wilson, M., Garzon, F., Wood, D., Zelenay, P., More, K., Stroh, K., Zawodzinski, T., Boncella, J., McGrath, J. E., Inaba, M., Miyatake, K., Hori, M., Ota, K., Ogumi, Z., Miyata, S., Nishikata, A., Siroma, Z., Uchimoto, Y., Yasuda, K., Kimijima, K., and Iwashita, N., 2007 “Scientific Aspects of Polymer Electrolyte Fuel Cell Durability and Degradation,” Chem. Rev., 107(10), pp. 3904–3951. [CrossRef] [PubMed]
Wu, J., Yuan, X. Z., Martin, J. J., Wang, H., Zhang, J., Shen, J., Wu, S., and Merida, W., 2008, “A Review of PEM Fuel Cell Durability: Degradation Mechanism, Mitigation Strategies,” J. Power Sources, 184(1), pp. 104–119. [CrossRef]
Chen, C., and Fuller, T. F., 2009, “The Effect of Humidity on the Degradation of Nafion® Membrane,” Polymer Degradation Stability, 94(9), pp. 1436–1447. [CrossRef]
Li, H., Zhang, J., Fatih, K., Wang, Z., Tang, Y., Shi, Z., Wu, S., Song, D., Zhang, J., Jia, N., Wessel, S., Abouatallah, R., and Joos, N., 2008, “Polymer Electrolyte Membrane Fuel Cell Contamination: Testing and Diagnosis of Toluene-Induced Cathode Degradation,” J. Power Sources, 185, pp. 272–279. [CrossRef]
Yu, J., Matsuura, T., Yoshikawa, Y., Islam, M. N., and Hori, M., 2005, “Lifetime Behavior of a PEM Fuel Cell With Low Humidification of Feed Stream,” Phys. Chem. Chem. Phys., 7(2), pp. 373–378. [CrossRef]
Wang, Z. B., Zuo, P. J., Chu, Y. Y., Shao, Y. Y., and Yin, G. P., 2009, “Durability Studies on Performance Degradation of Pt/C Catalysts of Proton Exchange Membrane Fuel Cell,” Int. J. Hydrogen Energy, 34(10), pp. 4387–4394. [CrossRef]
Endoh, E., Terazono, S., Widjaja, H., and Takimoto, Y., 2004, “Degradation Study of MEA for PEMFCs Under Low Humidity Conditions,” Electrochem. Solid-State Lett., 7(7), pp. A209–A211. [CrossRef]
Silberstein, M. N., and Boyce, M. C., 2010, “Constitutive Modeling of the Rate, Temperature, and Hydration Dependent Deformation Response of Nafion to Monotonic and Cyclic Loading,” J. Power Sources, 195(17), pp. 5692–5706. [CrossRef]
Silberstein, M. N., and Boyce, M. C., 2011, “Biaxial Elastic Viscoplastic Behavior of Nafion Membranes,” Polymer, 52(2), pp. 529–539. [CrossRef]
Huang, X., Solasi, R., Zou, Y., Feshler, M., Reifsn, K., Condit, D., Burlatsky, S., and Madden, T., 2006, “Mechanical Endurance of Polymer Electrolyte and PEM Fuel Cell Durability,” J. Polymer Sci. Part B, 44(16), pp. 2346–2357. [CrossRef]
Tang, Y., Karlsson, A. M., Santare, M. H., Gilbert, M., Cleghorn, S., Johnson, W. B., 2006, “An Experimental Investigation of Humidity and Temperature Effects on the Mechanical Properties of Perfluorosulfonic Acid Membrane,” Mater. Sci. Eng. A, 425, pp. 297–304. [CrossRef]
Shao, Y. Y., Yin, G. P., Wang, Z. B., and Gao, Y. Z., 2007, “Proton Exchange Membrane Fuel Cell From Low Temperature to High Temperature: Material Challenges,” J. Power Sources, 167(2), pp. 235–242. [CrossRef]
Lai, Y. H., Mittelstedt, C. K., Gittleman, C. S., and Dillard, D. A., 2009, “Viscoelastic Stress Analysis of Constrained Proton Exchange Membranes Under Humidity Cycling,” ASME J. Fuel Cell Sci. Technol., 6(2), p. 021002. [CrossRef]
Dillard, D. A., Li, Y., Grohs, J. R., Case, S. W., Ellis, M. W., Lai, Y. H., Budinski, M., and Gittleman, C. S., 2009, “On the Use of Pressure-Loaded Blister Tests to Characterize the Strength and Durability of Proton Exchange Membranes,” ASME J. Fuel Cell Sci. Technol., 6, p. 031014. [CrossRef]
Li, Y., Dillard, D. A., Case, S. W., Ellis, M. W., Lai, Y. H., Gittleman, C. S., and Miller, D. P., 2009, “Fatigue and Creep to Leak Tests of Proton Exchange Membranes Using Pressure-Loaded Blisters,” J. Power Sources, 194(2), pp. 873–879. [CrossRef]
Grohs, J. R., Li, Y., Dillard, D. A., Case, S. W., Ellis, M. W., Lai, Y. H., and Gittleman, C. S., 2009, “Evaluating the Time and Temperature Dependent Biaxial Strength of Gore-Select® Series 57 Proton Exchange Membrane Using a Pressure Loaded Blister Test,” J. Power Sources, 195(2), pp. 527–531. [CrossRef]
Jia, R., Han, B., Levi, K., Hasegawa, T., Ye, J., and Dauskardt, R. H., 2011, “Mechanical Durability of Proton Exchange Membranes With Catalyst Platinum Dispersion,” J. Power Sources, 196, pp. 8234–8240. [CrossRef]
Silberstein, M. N., and Boyce, M. C., 2011 “Hygro-Thermal Mechanical Behavior of Nafion During Constrained Swelling,” J. Power Sources, 196, pp. 3452–3460. [CrossRef]
Pestrak, M., Li, Y., Case, S. W., Dillard, D. A., Ellis, M. W., Lai, Y. H., and Gittleman, C. S., 2010, “The Effect of Mechanical Fatigue on the Lifetimes of Membrane Electrode Assemblies,” ASME J. Fuel Cell Sci. Technol., 7(4), p. 041009. [CrossRef]
Hicks, M., Pierpont, D., Turner, P., and Watschke, T., 2006, “Accelerated Testing and Lifetime Modeling for the Development of Durable Fuel Cell MEAs,” ECS Trans., 1(8), pp. 229–237. [CrossRef]
Zhang, S., Yuan, X., Wang, H., Merida, W., Zhu, H., Shen, J., Wu, S., and Zhang, J., 2009, “A Review of Accelerated Stress Tests of MEA Durability in PEM Fuel Cells,” Int. J. Hydrogen Energy, 34, pp. 388–404. [CrossRef]
Kim, S., and Mench, M. M., 2007, “Physical Degradation of Membrane Electrode Assemblies Undergoing Freeze/Thaw Cycling: Micro-Structure Effects,” J. Power Sources, 174, pp. 206–220. [CrossRef]
Coffin, L. F., 1954, “A Study of the Effect of Cyclic Thermal Stresses on a Ductile Metal,” ASME J. Appl. Mech., 76, pp. 931–950.
Manson, S. S., 1953, “Behavior of Materials Under Conditions of Thermal Stress,” NACA Tech. Notes, Rep. 1170, pp. 317–350.

Figures

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Fig. 1

Experimental equipment. (a) Tensile testing machine, (b) tensile testing machine whose temperature and relative humidity can be controlled, and (c) cross section of experimental chamber.

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Fig. 2

Stress–strain curve of MEA in 25 °C and 50%RH

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Fig. 3

Effect of temperature and relative humidity on Young's modulus

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Fig. 4

Effect of temperature and humidity rate on yield stress

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Fig. 5

Effect of temperature and relative humidity on maximum stress

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Fig. 6

Effect of temperature and relative humidity on rupture strain

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Fig. 7

Surface observation results for ambient conditions (25 °C and 50%RH): (a) ε = 0.07, (b) ε = 0.1, (c) ε = 0.5, and (d) ε = 1.0

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Fig. 8

Relation between stress–strain curve and surface observation results at 25 °C and 50%RH

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Fig. 9

Surface observation results at 25 °C and 80%RH: (a) ε = 0.06, (b) ε = 0.1, (c) ε = 0.3, and (d) ε = 0.7

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Fig. 10

Relation between stress–strain curve and surface observations at 25 °C and 80%RH

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Fig. 11

Surface observation results at 80 °C and 50%RH: (a) ε = 0.03, (b) ε = 0.04, (c) ε = 0.08, and (d) ε = 0.3

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Fig. 12

Relation between stress–strain curve and surface observation results at 80 °C and 50%RH

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Fig. 13

Effect of temperature and relative humidity on crack initiation strain

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Fig. 14

Surface observations during fatigue test for a plastic strain range of 0.03 and a strain rate of 0.0025 s–1 at 25 °C and 50%RH

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Fig. 15

Relation between plastic strain range and number of cycles to crack initiation at 25 °C and 50%RH

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