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Research Papers

Using a Stack Shunt to Mitigate Catalyst Support Carbon Corrosion in Polymer Electrolyte Membrane Fuel Cell Stacks During Start-Stop Cycling

[+] Author and Article Information
Denis Bona

Department of Electronics
and Telecommunications,
Faculty of Engineering,
Politecnico di Torino,
Turin 10129, Italy;
Electro Power Systems SpA,
Via Livorno 60,
Turin 10144, Italy
e-mail: denis.bona@polito.it

Dennis E. Curtin

Consultant,
Fayetteville, NC 28304

Francesco Pedrazzo

Electro Power Systems SpA,
Via Livorno 60,
Turin 10144, Italy

Elena Maria Tresso

Department of Applied Science and Technology,
Faculty of Engineering,
Politecnico di Torino,
Turin 10129, Italy;
Italy Center for Space Human Robotics at Polito,
Istituto Italiano di Tecnologia,
Turin 10129, Italy

1Corresponding author.

Contributed by the Advanced Energy Systems Division of ASME for publication in the JOURNAL OF FUEL CELL SCIENCE AND TECHNOLOGY. Manuscript received July 21, 2013; final manuscript received August 13, 2013; published online November 8, 2013. Editor: Nigel M. Sammes.

J. Fuel Cell Sci. Technol 11(1), 011010 (Nov 08, 2013) (7 pages) Paper No: FC-13-1066; doi: 10.1115/1.4025535 History: Received July 21, 2013; Revised August 13, 2013

Carbon black based electrodes are generally recognized as state of the art for PEM fuel cell technology due to the high performance achieved with a relatively low Pt content. However, the catalyst carbon support is prone to carbon oxidation. This leads to a loss of the catalyst area and overall performance, along with a higher mass transport loss due to an increased flooding tendency. This phenomenon is particularly severe when the fuel cell experiences repetitive start-stop cycles. Therefore, specific countermeasures against catalyst layer carbon oxidation are required, especially for automotive and backup power applications, where the startup/shutdown rate is considerably high. The authors evaluated a basic design that uses a stack shunt. A properly modified control protocol, which includes the stack shunt, is able to avoid high cathode potential peaks, which are known to accelerate catalyst carbon support corrosion and its negative effects. During two separate durability tests, one adopting the shunt design and another using nonprotected shutdown, a 24-cell stack was subjected to continuous starts and stops for several months and its performance constantly monitored. The results show that when the shunt is used, there is a 37% reduction in the voltage degradation rate for each startup/shutdown cycle and a two-fold increase in the number of startup/shutdown cycles before an individual cell reached the specified “end of life” voltage criteria. Furthermore, ex situ FE-SEM analysis revealed cathode catalyst layer thinning, which is an indication that the emerging degradation mechanism is the catalyst support carbon corrosion, as expected. This provides further support that the constant voltage degradation rate typically experienced in PEMFCs can be primarily attributed to the catalyst support carbon corrosion rate. The proposed shunt protocol is very cost effective and does not require any substantial changes in the system. For this reason, its adoption is recommended as a viable method to decrease the catalyst support carbon corrosion rate and extend the operating life of the PEMFC stack.

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References

Williams, B. D., and Kurani, K. S., 2007, “Commercializing Light-Duty Plug-In/Plug-Out Hydrogen-Fuel-Cell Vehicles: “Mobile Electricity” Technologies and Opportunities,” J. Power Sources, 166, pp. 549–566. [CrossRef]
Garde, R., Jiménez, F., Larriba, T., García, G., Aguado, M., and Martínez, M., 2012, “Development of a Fuel Cell-Based System for Refrigerated Transport,” Energy Procedia, 29, pp. 201–207. [CrossRef]
Andùjar, J. M., and Segura, F., 2009, “Fuel Cells: History and Updating. A Walk Along Two Centuries,” Renewable Sustainable Energy Rev., 13, pp. 2309–2322. [CrossRef]
San Martin, J. I., Zamora, I., San Martin, J. J., Aperribay, V., Torres, E., and Eguia, P., 2010, “Influence of the Rated Power in the Performance of Different Proton Exchange Membrane (PEM) Fuel Cells,” Energy, 35, pp. 1898–1907. [CrossRef]
Zhang, S., Yuan, X., Wang, H., Mérida, 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]
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 Mechanisms and Mitigation Strategies,” J. Power Sources, 184, pp. 104–119. [CrossRef]
Schmittinger, W., and Vahidi, A., 2008, “A Review of the Main Parameters Influencing Long-Term Performance and Durability of PEM Fuel Cells,” J. Power Sources, 180, pp. 1–14. [CrossRef]
Büchi, F. N., Inaba, M., and Schmidt, T. J., eds., 2009, Polymer Electrolyte Fuel Cell Durability (Part III—System Perspectives), Springer Science and Business Media, New York, pp. 467–482.
Litster, S., and McLean, G., 2004, “PEM Fuel Cell Electrodes,” J. Power Sources, 130, pp. 61–76. [CrossRef]
Chaparro, A. M., Mueller, N., Atienza, C., and Daza, L., 2006, “Study of Electrochemical Instabilities of PEMFC Electrodes in Aqueous Solution by Means of Membrane Inlet Mass Spectrometry,” J. Electroanal. Chem., 591, pp. 69–73. [CrossRef]
Reiser, C. A., Bregoli, L., Patterson, T. W., Yi, J. S., Yang, J. D., Perry, M. L., and Jarvi, T. D., 2005, “A Reverse-Current Decay Mechanism for Fuel Cells,” Electrochem. Solid-State Lett., 8, pp. A273–A276. [CrossRef]
Kim, J., Lee, J., and Tak, Y., 2009, “Relationship Between Carbon Corrosion and Positive Electrode Potential in a Proton-Exchange Membrane Fuel Cell During Start/Stop Operation,” J. Power Sources, 192, pp. 674–678. [CrossRef]
Hinds, G., and Brightman, E., 2012, “In Situ Mapping of Electrode Potential in a PEM Fuel Cell,” Electrochem. Commun., 17, pp. 26–29. [CrossRef]
Makharia, R., Kocha, S. S., Yu, P. T., Sweikart, M. A., Gu, W. T., Wagner, F. T., and Gasteiger, H. A., 2006, “Durable PEM Fuel Cell Electrode Materials: Requirements and Benchmarking Methodologies,” ECS Trans., 1, pp. 3–18. [CrossRef]
Hartnig, C., and Schmidt, T. J., 2011, “Simulated Start–Stop as a Rapid Aging Tool for Polymer Electrolyte Fuel Cell Electrodes,” J. Power Sources, 196, pp. 5564–5572. [CrossRef]
Avasarala, B., Moore, R., and Haldar, P., 2010, “Surface Oxidation of Carbon Supports Due to Potential Cycling Under PEM Fuel Cell Conditions,” Electrochim. Acta, 55, pp. 4765–4771. [CrossRef]
Fowler, M., Amphlett, J. C., Mann, R. F., Peppley, B. A., and Roberge, P. R., 2002, “Issues Associated With Voltage Degradation in a PEMFC,” J. New Mater. Electrochem. Syst., 5(4), pp. 255–262.
Atanassova, P., Rice, G., Shen, J. P., and Sun, P., 2007, “Carbon Corrosion Effects in Fuel Cells,” Gordon Research Conference on Fuel Cells, Bryant University, Smithfield, RI, July 22–27.
Tang, H., Qi, Z., Ramani, M., and Elter, J. F., 2006, “PEM Fuel Cell Cathode Carbon Corrosion Due to the Formation of Air/Fuel Boundary at the Anode,” J. Power Sources, 158, pp. 1306–1312. [CrossRef]
Bekkedahl.T. A., Bregoli, L. J., Breault, R. D., Dykeman, E. A., Meyers, J. P., Patterson, T. W., Skiba, T., Vargas, C., Yang, D., and Yi, J. S., 2005, “Reducing Fuel Cell Cathode Potential During Startup and Shutdown,” U.S. Patent No. 6,913,845 B2.
Van Dine, L. L., Steinbugler, M. M., Reiser, C. A., and Scheffler, G. W., 2003, “Procedure for Shutting Down a Fuel Cell System Having an Anode Exhaust Recycle Loop,” U.S. Patent No. 6,514,635 B2.
Condit, D. A., and Breault, R. D., 2003, “Shut-Down Procedure for Hydrogen-Air Fuel Cell System,” U.S. Patent No. 6,635,370 B2.
Balliet, R. J., and Reiser, C. A., 2004, “System and Method for Shutting Down a Fuel Cell Power Plant,” U.S. Patent No. 6,835,479 B2.
Reiser, C. A., Yang, D., and Sawyer, R. D., 2005, “Procedure for Shutting Down a Fuel Cell System Using Air Purge,” U.S. Patent No. 6,858,336 B2.
Reiser, C. A., Yang, D., and Sawyer, R. D., 2008, “Procedure for Starting Up a Fuel Cell System Using a Fuel Purge,” U.S. Patent No. 7,410,712 B2.
Mench, M. M., Kumbur, E. C., and Veziroglu, T. N., 2011, Polymer Electrolyte Degradation, 1st ed., Academic, New York.
Chen, J., Siegel, J. B., Matsuura, T., and Stefanopoulou, A. G., 2011, “Carbon Corrosion in PEM Fuel Cell Dead-Ended Anode Operations,” J. Electrochem. Soc., 158, pp. B1164–B1174. [CrossRef]
Baumgartner, W. R., Parz, P., Fraser, S. D., Wallnofer, E., and Hacker, V., 2008, “Polarization Study of a PEMFC With Four Reference Electrodes at Hydrogen Starvation Conditions,” J. Power Sources, 182, pp. 413–421. [CrossRef]

Figures

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Fig. 1

Schematic model of the reactions occurring in the cell when the anode is partially exposed to hydrogen and partially exposed to air

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Fig. 2

Schematic of the test bench used for the experiment with unprotected startups and shutdowns

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Fig. 3

Schematic of the test bench used for the experiment adopting the stack shunt protocol

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Fig. 4

Voltage graph of the cells with unprotected startups and shutdowns

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Fig. 5

Average and maximum cell voltage degradation rate with unprotected startups and shutdowns

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Fig. 6

Stack polarization curve at the BOL and at the EOL

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Fig. 7

(a) FE-SEM scan of an MEA at the BOL, and (b) FE-SEM scan of the MEA coming from cell no. 4 after the cycling test

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Fig. 8

Voltage graph of the cells using the stack shunt protocol

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Fig. 9

Average cell voltage and degradation rate using the stack shunt protocol

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Fig. 10

Comparison of the degradation rate/cycle with unprotected startups and shutdowns and using the stack shunt protocol

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