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Research Papers

In Situ and Ex Situ Studies on the Degradation of Pd/C Catalyst for Proton Exchange Membrane Fuel Cells

[+] Author and Article Information
Yongfu Tang

Hebei Key Laboratory of Applied Chemistry,
College of Environmental and Chemical Engineering,
Yanshan University,
Qinhuangdao, Hebei 066004, China
e-mail: tangyongfu@ysu.edu.cn

Shichun Mu

State Key Laboratory of Advanced Technology
for Materials Synthesis and Processing,
Wuhan University of Technology,
Wuhan 430070, China

Shengxue Yu, Yufeng Zhao, Hongchao Wang, Faming Gao

Hebei Key Laboratory of Applied Chemistry,
College of Environmental and Chemical Engineering,
Yanshan University,
Qinhuangdao, Hebei 066004, China

1Corresponding author.

Contributed by the Advanced Energy Systems Division of ASME for publication in the JOURNAL OF FUEL CELL SCIENCE AND TECHNOLOGY. Manuscript received August 30, 2013; final manuscript received April 12, 2014; published online June 10, 2014. Assoc. Editor: Umberto Desideri.

J. Fuel Cell Sci. Technol 11(5), 051004 (Jun 10, 2014) (7 pages) Paper No: FC-13-1079; doi: 10.1115/1.4027708 History: Received August 30, 2013; Revised April 12, 2014

To investigate the degradation mechanism of the as-prepared Pd/C catalyst, in situ and ex situ accelerated stress tests were carried out via potential cycling. Durability tests of the single cells with Pd/C catalysts were performed through an interval constant current density mode. Electrochemical impedance spectroscopy (EIS) was applied to measure the impedance of the single cell during degradation tests. Results indicate that the degradation of Pd/C catalyst may be attributed to the phase transition of absorbed α-phase PdH to β-phase PdH, the dissolution of Pd metal, and the size increase of Pd nanoparticles. Moreover, the degradation of single cell may be predominantly ascribed to the degradation of catalyst, the deterioration of contact between electronic/ionic conductors, as well as the flooding of gas diffusion channels.

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References

Service, R. F., 2009, “Hydrogen Cars: Fad or the Future?,” Science, 324(5932), pp. 1257–1259. [CrossRef] [PubMed]
Costamagna, P., and Srinivasan, S., 2001, “Quantum Jumps in the PEMFC Science and Technology From the 1960s to the Year 2000: Part I. Fundamental Scientific Aspects,” J. Power Sources, 102(1–2), pp. 242–252. [CrossRef]
Vielstich, W., Lamm, A., and Gasteiger, H. A., 2003, Handbook of Fuel Cells: Fundamentals, Technology, Applications, Wiley, New York, Chap. 3.
Shao, M. H., Sasaki, K., and Adzic, R. R., 2006, “Pd-Fe Nanoparticles as Electrocatalysts for Oxygen Reduction,” J. Am. Chem. Soc., 128(11), pp. 3526–3527. [CrossRef] [PubMed]
Fernández, J. L., Raghuveer, V., Manthiram, A., and Bard, A. J., 2005, “Pd-Ti and Pd-Co-Au Electrocatalysts as a Replacement for Platinum for Oxygen Reduction in Proton Exchange Membrane Fuel Cells,” J. Am. Chem. Soc., 127(38), pp. 13100–13101. [CrossRef] [PubMed]
Raghuveer, V., Manthiram, A., and Bard, A. J., 2005, “Pd-Co-Mo Electrocatalyst for the Oxygen Reduction Reaction in Proton Exchange Membrane Fuel Cells,” J. Phys. Chem. B, 109(48), pp. 22909–22912. [CrossRef] [PubMed]
Ren, M., Kang, Y., He, W., Zou, Z., Xue, X., Akins, D. L., Yang, H., and Feng, S., 2011, “Origin of Performance Degradation of Palladium-Based Direct Formic Acid Fuel Cells,” Appl. Catal. B: Environ., 104(1–2), pp. 49–53. [CrossRef]
Hartl, K., Hanzlik, M., and Arenz, M., 2011, “IL-TEM Investigations on the Degradation Mechanism of Pt/C Electrocatalysts With Different Carbon Supports,” Energy Environ. Sci., 4(1), pp. 234–238. [CrossRef]
Schlögl, K., Hanzlik, M., and Arenz, M., 2012, “Comparative IL-TEM Study Concerning the Degradation of Carbon Supported Pt-Based Electrocatalysts,” J. Electrochem. Soc., 159(6), pp. B677–B682. [CrossRef]
Uno, M., and Tanaka, K., 2011, “Pt/C Catalyst Degradation in Proton Exchange Membrane Fuel Cells Due to High-Frequency Potential Cycling Induced by Switching Power Converters,” J. Power Sources, 196(23), pp. 9884–9889. [CrossRef]
Xu, Z., Zhang, H., Zhong, H., Lu, Q., Wang, Y., and Su, D., 2012, “Effect of Particle Size on the Activity and Durability of the Pt/C Electrocatalyst for Proton Exchange Membrane Fuel Cells,” Appl. Catal. B: Environ., 111–112, pp. 264–270. [CrossRef]
Ferreira, P. J., la O’, G. J., Shao-Horn, Y., Morgan, D., Makharia, R., Kocha, S., and Gasteiger, H. A., 2005, “Instability of Pt/C Electrocatalysts in Proton Exchange Membrane Fuel Cells: A Mechanistic Investigation,” J. Electrochem. Soc., 152(11), pp. A2256–A2271. [CrossRef]
Li, H., Sun, G., Jiang, Q., Zhu, M., Sun, S., and Xin, Q., 2007, “Synthesis of Highly Dispersed Pd/C Electro-Catalyst With High Activity for Formic Acid Oxidation,” Electrochem. Comm., 9(6), pp. 1410–1415. [CrossRef]
Tang, Y., Zhang, H., Zhong, H., Xu, T., and Jin, H., 2011, “Carbon-Supported Pd–Pt Cathode Electrocatalysts for Proton Exchange Membrane Fuel Cells,” J. Power Sources, 196(7), pp. 3523–3529. [CrossRef]
Czerwiński, A., Marassi, R., and Zamponi, S., 1991, “The Absorption of Hydrogen and Deuterium in Thin Palladium Electrodes: Part I. Acidic Solutions,” J. Electroanal. Chem., 316(1–2), pp. 211–214. [CrossRef]
Łukaszewskil, M., Grdeńl, M., and Czerwiński, A., 2006, “Comparative Study on Hydrogen Electrosorption in Palladium and Palladium-Noble Metal Alloys,” J. New Mater. Electrochem. Sys., 9(4), pp. 409–417.
Birry, L., and Lasia, A., 2006, “Effect of Crystal Violet on the Kinetics of H Sorption Into Pd,” Electrochim. Acta, 51(16), pp. 3356–3364. [CrossRef]
Duncan, H., and Lasia, A., 2008, “Separation of Hydrogen Adsorption and Absorption on Pd Thin Films,” Electrochim. Acta, 53(23), pp. 6845–6850. [CrossRef]
Ohyagi, S., Matsuda, T., Iseki, Y., Sasaki, T., and Kaito, C., 2011, “Effects of Operating Conditions on Durability of Polymer Electrolyte Membrane Fuel Cell Pt Cathode Catalyst Layer,” J. Power Sources, 196(8), pp. 3743–3749. [CrossRef]
Łukaszewski, M., and Czerwinski, A., 2006, “Dissolution of Noble Metals and Their Alloys Studied by Electrochemical Quartz Crystal Microbalance,” J. Electroanal. Chem., 589(1), pp. 38–45. [CrossRef]
Liu, X., Chen, J., Liu, G., Zhang, L., Zhang, H., and Yi, B., 2010, “Enhanced Long-Term Durability of Proton Exchange Membrane Fuel Cell Cathode by Employing Pt/TiO2/C Catalysts,” J. Power Sources, 195(13), pp. 4098–4103. [CrossRef]
Jiang, R., and Anson, F. C., 1991, “The Origin of Inclined Plateau Currents in Steady-State Voltammograms for Electrode Processes Involving Electrocatalysis,” J. Electroanal. Chem., 305(2), pp. 171–184. [CrossRef]
Ma, Y., Zhang, H., Zhong, H., Xu, T., Jin, H., Tang, Y., and Xu, Z., 2010, “Cobalt Based Non-Precious Electrocatalysts for Oxygen Reduction Reaction in Proton Exchange Membrane Fuel Cells,” Electrochim. Acta, 55(27), pp. 7945–7950. [CrossRef]
Peng, Z., and Yang, H., 2009, “Synthesis of Pd-Pt Bimetallic Nanocrystals With a Concave Structure Through a Bromide-Induced Galvanic Replacement Reaction,” J. Am. Chem. Soc., 131(15), pp. 7542–7543. [CrossRef] [PubMed]
Charreteur, F., Ruggeri, S., Jaouen, F., and Dodelet, J. P., 2008, “Increasing the Activity of Fe/N/C Catalysts in PEM Fuel Cell Cathodes Using Carbon Blacks With a High-Disordered Carbon Content,” Electrochim. Acta, 53(23), pp. 6881–6889. [CrossRef]
Xu, T., Zhang, H., Zhong, H., Ma, Y., Jin, H., Zhang, Y., and Tang, Y., 2010, “Improved Stability of TiO2 Modified Ru85Se15/C Electrocatalyst for Proton Exchange Membrane Fuel Cells,” J. Power Sources, 195(24), pp. 8075–8079. [CrossRef]
Du, S., Millington, B., and Pollet, B. G., 2011, “The Effect of Nafion Ionomer Loading Coated on Gas Diffusion Electrodes With In-Situ Grown Pt Nanowires and Their Durability in Proton Exchange Membrane Fuel Cells,” Int. J. Hydrogen Energy, 36(7), pp. 4386–4393. [CrossRef]
Lin, G., and Nguyen, T. V., 2005, “Effect of Thickness and Hydrophobic Polymer Content of the Gas Diffusion Layer on Electrode Flooding Level in a PEMFC,” J. Electrochem. Soc., 152(10), pp. A1942–A1948. [CrossRef]
Eikerling, M., and Kornyshev, A. A., 1999, “Electrochemical Impedance of the Cathode Catalyst Layer in Polymer Electrolyte Fuel Cells,” J. Electroanal. Chem., 475(2), pp. 107–123. [CrossRef]
Antoine, O., Bultel, Y., and Durand, R., “Oxygen Reduction Reaction Kinetics and Mechanism on Platinum Nanoparticles Inside Nafion®,” J. Electroanal. Chem., 499(1), pp. 85–94. [CrossRef]
Roy, S. K., Orazem, M. E., and Tribollet, B., 2007, “Interpretation of Low-Frequency Inductive Loops in PEM Fuel Cells,” J. Electrochem. Soc., 154(12), pp. B1378–B1388. [CrossRef]
Kim, J. H., Jo, Y. Y., Cho, E. A., Jang, J. H., Kim, H. J., Lim, T. H., Oh, I. H., Ko, J. J., and Son, I. J., 2010, “Effects of Cathode Inlet Relative Humidity on PEMFC Durability During Startup-Shutdown Cycling II. Diagnostic Study,” J. Electrochem. Soc., 157(5), pp. B633–B642. [CrossRef]
Hong, J., Zhang, H., Ma, Y., Xu, T., Zhong, H., and Wang, M., 2010, “Stable Support Based on Highly Graphitic Carbon Xerogel for Proton Exchange Membrane Fuel Cells,” J. Power Sources, 195(19), pp. 6323–6328. [CrossRef]
Wagner, N., and Gülzow, E., 2004, “Change of Electrochemical Impedance Spectra (EIS) With Time During CO-Poisoning of the Pt-Anode in a Membrane Fuel Cell,” J. Power Sources, 127(1–2), pp. 341–347. [CrossRef]

Figures

Grahic Jump Location
Fig. 5

EISs of single cell with Pd/C catalyst after different potential cycles at the current density of 100 mA cm−2 (a), 200 mA cm−2 (b), and 500 mA cm−2 (c) during the accelerated stress test. (d) The magnification of (a) (100 mA cm−2) at high frequency region.

Grahic Jump Location
Fig. 1

(a) CV curves of the Pd/C catalyst at different potential cycles during the AST test with scan rate of 50 mV s−1 and (b) ORR curves of Pd/C catalyst before and after 200 potential cycles with scan rate of 5 mV s−1 and rotation speed of 1600 rpm. The electrolytes are the in N2-saturated and O2-saturated 0.5 M H2SO4 solutions, respectively.

Grahic Jump Location
Fig. 2

Typical TEM images of the Pd/C catalyst before (a) and after (b) 200 CV potential cycles

Grahic Jump Location
Fig. 3

CV curves of the MEA with Pd/C catalyst after different potential cycles during the accelerated stress test. Potential scan rate: 20 mV s−1.

Grahic Jump Location
Fig. 4

Performances of single cell with Pd/C catalyst after different potential cycles during the accelerated stress test at cell operating temperature of 80 °C. Anode: the commercial TKK 28.4 wt.% Pt/C with the Pt loading is 0.3 mg cm−2. Total metal loading of cathode: 0.5 mg cm−2. H2/O2 pressure: 0.2 MPa/0.2 MPa. Membrane: Nafion 212. Pure hydrogen and pure oxygen were put into the anode and the cathode with saturated humidification, respectively.

Grahic Jump Location
Fig. 6

Voltage of single cell with Pd/C catalyst operating at interval constant current mode at 80 °C. Anode: the commercial TKK 28.4 wt.% Pt/C with the Pt loading is 0.3 mg cm−2. Total metal loading of cathode: 0.5 mg cm−2. H2/O2 pressure: 0.2 MPa/0.2 MPa. Membrane: Nafion 212. Pure hydrogen and pure oxygen were put into the anode and the cathode with saturated humidification, respectively.

Grahic Jump Location
Fig. 7

Performances of single cell at different discharging time during the durability test

Grahic Jump Location
Fig. 8

EISs of single cell after different times at current densities of 100 mA cm−2 (a), 200 mA cm−2 (b), and 500 cm−2 (c) during durability test according to the performance measurements

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