A review of the main mechanisms of catalyst layer degradation in polymer electrolyte membrane fuel cell (PEMFC) and different performance recovery methods

Document Type : Research Paper

Authors

1 Malek Ashtar University of Technology, Tehran, Iran

2 Malek Ashtar University of technology, Tehran, Iran

Abstract

This paper reviewed over 100 articles on the subject of the mechanism of catalyst layer (CL) degradation and the effect of various contaminations in the polymer electrolyte membrane fuel cell (PEMFC). Also the recovery of PEMFC via different types of methods, the causes and fundamental mechanisms of cell degradation and their influence on long- term performance of PEM fuel cell were discussed in this review paper. The most important mechanism of CL degradation in PEMFC includes the effect of different contaminations  such as carbon monoxide, carbon dioxide, hydrogen sulphide, sulfur dioxide, ,  (NO, ), (SO, ), and ammonia, agglomeration of catalyst, reactant gas starvation, and oxide and hydroxide formation are investigated. Afterward, as some of these CL degradations procedures are reversible, different recovery methods for retrieving the catalyst electrochemical active surface area (ECSA) are presented. Some recovery methods including recovery by H2 purge, direct and indirect zone, short circuit method, water steam, and the reduction method are presented in this review article. The review results show that the high and effective performance of the PEMFC was achieved by applying ozone method, water steam, and reduction method. However, only H2 purge and reduction methods are applicable to the stack of fuel cells. Therefore, in light of the facts outlined above, it is safe to illustrate that the reduction method is one of the most effective methods for the recovery of reversible CL degradations. Finally, the flowchart of studying cell degradation and its recovery is also presented at the end of the paper. This review was focused on the degradation mechanism of catalyst layer in different research aspects such as contamination impacts on the performance of fuel cell, various mechanism approaches and mitigation development. As the result, we hope that this brief overview provides good perspective of the important issues that should be addressed to extend the lifetime and durability of next-generation of fuel cells for the engineers and researchers in this field.

Keywords

Main Subjects


[1] X. Zhou, J. Qiao, L. Yang, J. Zhang, A review of graphene‐based nanostructural materials for both catalyst supports and metal‐free catalysts in PEM fuel cell oxygen reduction reactions, Advanced Energy Materials, 2014, 1301523.
 
[2] M.K. Debe, Electrocatalyst approaches and challenges for automotive fuel cells, Nature, 2012, 486: 43.
 
[3] I.E.L. Stephens, J. Rossmeisl, I. Chorkendorff, Toward sustainable fuel cells, Science (New York, N.Y.) 2016, 354: 1378.
 
[4] G. Wang, Y. Yu, H. Liu, C. Gong, S. Wen, X. Wang, Z. Tu, Progress on design and development of polymer electrolyte membrane fuel cell systems for vehicle applications: A review, Fuel Processing Technology, 2018, 179: 203.
 
[5] A. Abaspour, N.T. Parsa, M. Sadeghi, A new feedback Linearization-NSGA-II based control design for PEM fuel cell, International Journal of Computer Applications, 2014, 97.
 
[6] W. Schmittinger, A. Vahidi, A review of the main parameters influencing long-term performance and durability of PEM fuel cells, Journal of power sources, 2008, 180: 1.
 
[7] H.S. Choo, D.K. Chun, J.H. Lee, H.S. Shin, S.K. Lee, Y.S. Park, B.K. Ahn, Performance Recovery of Fuel Cell Stack for FCEV, SAE Technical Paper, 2015.
 
[8] T. Patterson, Effect of potential cycling on loss of electrochemical surface area of platinum catalyst in polymer electrolyte membrane fuel cell,  AIChE Spring National Meeting Proceedings, 2002.
 
[9] S. Motupally, T. Jarvi, The Electrochem. Soc,  208th Meeting, Abstract, Los Angeles, CA, 2005.
 
[10] P. Ascarelli, V. Contini, R. Giorgi, Formation process of nanocrystalline materials from x-ray diffraction profileanalysis: Application to platinum catalysts, Journal of applied physics, 2002, 91: 4556.
 
[11] G. Hinds, NPL Report DEPC-MPE 002, National Physical Laboratory, Teddington, UK 2004.
 
[12] R.L. Borup, J.R. Davey, F.H. Garzon, D.L. Wood, M.A. Inbody, PEM fuel cell electrocatalyst durability measurements, Journal of Power Sources, 2006, 163: 76.
 
[13] W. Li, M. Ruthkosky, M. Balogh, R. Makharia, S. Oh, Proceedings of the Fuel Cells Durability, first ed., Washington, DC, 2006, 101.
 
[14] G. Escobedo, K. Schwiebert, K. Raiford, G. Nagarajan, F. Principe, Proceedings of the Fuel Cells Durability, first ed., Washington, DC, 2006, 83.
 
[15] X. Cheng, Z. Shi, N. Glass, L. Zhang, J. Zhang, D. Song, Z.-S. Liu, H. Wang, J. Shen, A review of PEM hydrogen fuel cell contamination: Impacts, mechanisms, and mitigation, Journal of Power Sources 2007, 165: 739.
 
[16] S.-Y. Ahn, S.-J. Shin, H. Ha, S.-A. Hong, Y.-C. Lee, T. Lim, I.-H. Oh, Performance and lifetime analysis of the kW-class PEMFC stack, Journal of Power Sources, 2002, 106: 295.
 
[17] J. St-Pierre, D. Wilkinsor, S. Knights, M. Bos, Relationships between water management, contamination and lifetime degradation in PEFC, Journal of New Materials for Electrochemical Systems, 2000, 3: 99.
 
[18] J. Zhang, H. Wang, D.P. Wilkinson, D. Song, J. Shen, Z.-S. Liu, Model for the contamination of fuel cell anode catalyst in the presence of fuel stream impurities, Journal of Power Sources, 2005, 147: 58.
 
[19] A. Collier, H. Wang, X.Z. Yuan, J. Zhang, D.P. Wilkinson, Degradation of polymer electrolyte membranes, International Journal of Hydrogen Energy, 2006, 31: 1838.
 
[20] J. Baschuk, X. Li, Carbon monoxide poisoningof proton exchange membrane fuel cells, International Journal of Energy Research, 2001, 25: 695.
 
[21] P. Stonehart, P.N. Ross, The commonality of surface processes in electrocatalysis and gas-phase heterogeneous catalysis, Catalysis Reviews ,1975, 12: 1.
 
[22] M. Watanabe, S. Motoo, Chemisorbed CO on a polycrystalline platinum electrode The effect of conditioning of the surface and of partial pressure of CO, Journal of electroanalytical chemistry and interfacial electrochemistry, 1986, 206:197.
 
[23] H. Igarashi, T. Fujino, M. Watanabe, Hydrogen electro-oxidation on platinum catalysts in the presence of trace carbon monoxide, Journal of Electroanalytical Chemistry, 1995, 391: 119.
 
[24] K. Jambunathan, B.C. Shah, J.L. Hudson, A.C. Hillier, Scanning electrochemical microscopy of hydrogen electro-oxidation. Rate constant measurements and carbon monoxide poisoning on platinum, Journal of Electroanalytical Chemistry, 2001, 500: 279.
 
[25] A. Rodrigues, J.C. Amphlett, R.F. Mann, B.A. Peppley, P.R. Roberge, Carbon monoxide poisoning of proton-exchange membrane fuel cells,  IECEC-97 Proceedings of the Thirty-Second Intersociety Energy Conversion Engineering Conference (Cat. No. 97CH6203), IEEE, 1997, 768.
 
[26] N. Rajalakshmi, T. Jayanth, K. Dhathathreyan, Effect of carbon dioxide and ammonia on polymer electrolyte membrane fuel cell stack performance, Fuel cells, 2003, 3:177.
 
[27] F. De Bruijn, D. Papageorgopoulos, E. Sitters, G. Janssen, The influence of carbon dioxide on PEM fuel cell anodes, Journal of Power Sources, 2002, 110: 117.
 
[28] M. Arévalo, C. Gomis-Bas, F. Hahn, B. Beden, A. Arévalo, A. Arvia, A contribution to the mechanism of “reduced” CO2 adsorbates electro-oxidation from combined spectroelectrochemical and voltammetric data,
Electrochimica acta 1994, 39:793.
 
[29] B. Nikolic, H. Huang, D. Gervasio, A. Lin, C. Fierro, R. Adzic, E. Yeager, Electroreduction of carbon dioxide on platinum single crystal electrodes: electrochemical and in situ FTIR studies, Journal of electroanalytical chemistry and interfacial electrochemistry, 1990, 295:415.
 
[30] T. Iwasita, F. Nart, B. Lopez, W. Vielstich, On the study of adsorbed species at platinum from methanol, formic acid and reduced carbon dioxide via in situ FT-ir spectroscopy, Electrochimica acta, 1992, 37: 2361.
 
[31] J. Giner, Electrochemical reduction of CO2 on platinum electrodes in acid solutions, Electrochimica Acta, 1963, 8: 857.
 
[32] J. Sobkowski, A. Czerwiński, Kinetics of carbon dioxide adsorption on a platinum electrode, Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, 1974, 55: 391.
 
[33] J. Sobkowski, A. Czerwinski, Voltammetric study of carbon monoxide and carbon dioxide adsorption on smooth and platinized platinum electrodes, The Journal of Physical Chemistry, 1985, 89: 365.
 
[34] S. Gilman, The mechanism of electrochemical oxidation of carbon monoxide and methanol on platinum. II. The “Reactant-Pair” mechanism for electrochemical oxidation of carbon monoxide and Methanol1, The Journal of Physical Chemistry, 1964, 68: 70.
 
[35] M. Murthy, M. Esayian, W.-k. Lee, J. Van Zee, The effect of temperature and pressure on the performance of a PEMFC exposed to transient CO concentrations, Journal of The Electrochemical Society,  2003, 150: A29.
 
[36] R. Mohtadi, W.-K. Lee, J. Van Zee, The effect of temperature on the adsorption rate of hydrogen sulfide on Pt anodes in a PEMFC, Applied Catalysis B: Environmental, 56:2005, 37.
 
[37] R. Mohtadi, W.-K. Lee, S. Cowan, J. Van Zee, M. Murthy, Effects of hydrogen sulfide on the performance of a PEMFC, Electrochemical and solid-state letters, 2003, 6:A272.
 
[38] S. Knights, N. Jia, C. Chuy, J. Zhang, Fuel Cell Seminar 2005: Fuel Cell Progress, Challenges and Markets, Palm Springs, California, 2005.
 
[39] N. Ramasubramanian, Anodic behavior of platinum electrodes in sulfide solutions and the formation of platinum sulfide, Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, 1975, 64: 21.
 
[40] A. Contractor, H. Lal, Two forms of chemisorbed sulfur on platinum and related studies, Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, 1979, 96: 175.
 
[41] R. Halseid, P.J. Vie, R. Tunold, Effect of ammonia on the performance of polymer electrolyte membrane fuel cells, Journal of Power Sources, 2006, 154: 343.
 
[42] H.J. Soto, W.-k. Lee, J. Van Zee, M. Murthy, Effect of transient ammonia concentrations on PEMFC performance, Electrochemical and solid-state letters, 2003, 6: A133.
 
[43] F.A. Uribe, S. Gottesfeld, T.A. Zawodzinski, Effect of ammonia as potential fuel impurity on proton exchange membrane fuel cell performance, Journal of the Electrochemical Society, 2002, 149: A293.
 
[44] R. Halseid, P.J. Vie, R. Tunold, Influence of ammonium on conductivity and water content of Nafion 117 membranes, Journal of the electrochemical society, 2004, 151: A381.
 
[45] R.L. Borup, J.R. Davey, F.H. Garzon, D.L. Wood, M.A. Inbody, Proceedings of the Fuel Cells Durability, first ed., Washington, DC, 2006, 21.
 
[46] A. Taniguchi, T. Akita, K. Yasuda, Y. Miyazaki, Analysis of electrocatalyst degradation in PEMFC caused by cell reversal during fuel starvation, Journal of PowerSources, 2004, 130: 42.
 
[47] D. Natarajan, T. Van Nguyen, Current distribution in PEM fuel cells. Part 1: Oxygen and fuel flow rate effects, AIChE Journal, 2005, 51: 2587.
 
[48] Z. Liu, L. Yang, Z. Mao, W. Zhuge, Y. Zhang, L. Wang, Behavior of PEMFC in starvation, Journal of power sources, 2006,157: 166.
 
[49] T.W. Patterson, R.M. Darling, Damage to the cathode catalyst of a PEM fuel cell caused by localized fuel starvation, Electrochemical and Solid-State Letters, 2006, 9: A183.
 
[50] W.R. Baumgartner, P. Parz, S. Fraser, E. Wallnöfer, V. Hacker, Polarization study of a PEMFC with four reference electrodes at hydrogen starvation conditions, Journal of Power Sources,2008, 182: 413.
 
[51] H. Tang, Z. Qi, M. Ramani, J.F. Elter, PEM fuel cell cathode carbon corrosion due to the formation of air/fuel boundary at the anode, Journal of Power Sources, 2006, 158:1306.
 
[52] J.P. Meyers, R.M. Darling, Model of carbon corrosion in PEM fuel cells, Journal of the Electrochemical Society, 2006, 153: A1432.
 
[53] S.S. Kocha, J. Deliang Yang, J.S. Yi, Characterization of gas crossover and its implications in PEM fuel cells, AIChE Journal, 2006, 52: 1916.
 
[54] A. Hernandez, D. Hissel, R. Outbib, Fuel cell fault diagnosis: A stochastic approach,  Industrial Electronics, 2006 IEEE International Symposium on, IEEE, 2006, 1984.
 
[55] N. Yousfi-Steiner, P. Moçotéguy, D. Candusso, D. Hissel, A review on polymer electrolyte membrane fuel cell catalyst degradation and starvation issues: Causes, consequences and diagnostic for mitigation, Journal of Power Sources, 2009, 194: 130.
 
[56] A. LaConti, M. Hamdan, R. McDonald, Handbook of Fuel Cells–Fundamentals, Technology and Applications, Vol. 3, W. Vielstich, HA Gasteiger, and A. Lamm, Editors, John Wiley & Sons, 2003.
 
[57] T. Van Nguyen, M.W. Knobbe, A liquid water management strategy for PEM fuel cell stacks, Journal of Power Sources, 2003,114: 70.
 
[58] M. Saito, K. Hayamizu, T. Okada, Temperature dependence of ion and water transport in perfluorinated ionomer membranes for fuel cells, The Journal of Physical Chemistry B, 2005,109: 3112.
 
[59] S. Feldberg, C. Enke, C. Bricker, Formation and dissolution of platinum oxide film: Mechanism and kinetics, Journal of The Electrochemical Society, 1963, 110: 826.
 
[60] D. Rand, R. Woods, A study of the dissolution of platinum, palladium, rhodium and gold electrodes in 1 M sulphuric acid by cyclic voltammetry, Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, 1972, 35: 209.
 
[61] L. Tang, B. Han, K. Persson, C. Friesen, T. He, K. Sieradzki, G. Ceder, Electrochemical stability of nanometer-scale Pt particles in acidic environments, Journal of the American Chemical Society, 2009, 132: 596.
 
[62] A. Lindsey, Pourbaix, M-Atlas of electrochemical equilibria in aqueous solutions, SOC CHEMICAL INDUSTRY 14 BELGRAVE SQUARE, LONDON SW1X 8PS, ENGLAND, 1966.
 
[63] H.A. Hansen, J. Rossmeisl, J.K. Nørskov, Surface Pourbaix diagrams and oxygen reduction activity of Pt, Ag and Ni (111) surfaces studied by DFT, Physical Chemistry Chemical Physics, 2008,10: 3722.
 
[64] K. Kodama, R. Jinnouchi, T. Suzuki, H. Murata, T. Hatanaka, Y. Morimoto, Increase in adsorptivity of sulfonate anions on Pt (111) surface with drying of ionomer, Electrochemistry Communications, 2013, 36: 26.
[65] B.K. Kakati, A. Unnikrishnan, N. Rajalakshmi, R. Jafri, K. Dhathathreyan, A.R. Kucernak, Recovery of Polymer Electrolyte Fuel Cell exposed to sulphur dioxide, International Journal of Hydrogen Energy, 2016, 41: 5598.
 
[66] B.K. Kakati, A.R. Kucernak, Gas phase recovery of hydrogen sulfide contaminated polymer electrolyte membrane fuel cells, Journal of Power Sources, 2014, 252: 317.
 
[67] B. Kakati, A. Kucernak, K. Fahy, Using corrosion-like processes to remove poisons from electrocatalysts: a viable strategy to chemically regenerate irreversibly poisoned polymer electrolyte fuel cells, Electrochimica Acta, 2016, 222: 888.
 
[68] K. Saikia, B.K. Kakati, B. Boro, A. Verma, Current Advances and Applications of Fuel Cell Technologies,  Recent Advancements in Biofuels and Bioenergy Utilization, Springer, 2018, 303.
 
[69] K. Sehested, H. Corfitzen, J. Holcman, C.H. Fischer, E.J. Hart, The primary reaction in the decomposition of ozone in acidic aqueous solutions, Environmental Science & Technology, 1991, 25: 1589.
 
[70] K. Sehested, H. Corfitzen, J. Holcman, E.J. Hart, Decomposition of ozone in aqueous acetic acid solutions (pH 0-4), The Journal of Physical Chemistry, 1992, 96: 1005.
 
[71] G. Gupta, B. Wu, S. Mylius, G.J. Offer, A systematic study on the use of short circuiting for the improvement of proton exchange membrane fuel cell performance, International Journal of Hydrogen Energy, 2017, 42: 4320.
 
[72] Y. Zhan, Y. Guo, J. Zhu, L. Li, Current short circuit implementation for performance improvement and lifetime extension of proton exchange membrane fuel cell, Journal of Power Sources, 2014, 270: 183.
 
[73] A. Koschany, C. Lucas, T. Schwesinger, Gas diffusion electrode with reduced diffusing capacity for water and polymer electrolyte membrane fuel cells, Google Patents, 2002.
[74] M.T. Pearson, Apparatus for improving the performance of a fuel cell electric power system, Google Patents, 2009.
 
[75] M.T. Pearson, Method and apparatus for controlling voltage from a fuel cell system, Google Patents, 2005.
 
[76] J. Zhang, PEM fuel cell electrocatalysts and catalyst layers: fundamentals and applications, Springer Science & Business Media, 2008.
 
[77] N. Marković, T. Schmidt, V. Stamenković, P. Ross, Oxygen reduction reaction on Pt and Pt bimetallic surfaces: a selective review, Fuel cells, 2001, 1: 105.
 
[78] F. De Bruijn, V. Dam, G. Janssen, Durability and degradation issues of PEM fuel cell components, Fuel cells, 2008, 8: 3.
 
[79] H. Steininger, S. Lehwald, H. Ibach, Adsorption of oxygen on Pt (111), Surface Science, 1982, 123: 1.
 
[80] T. Zambelli, J. Barth, J. Wintterlin, G. Ertl, Complex pathways in dissociative adsorption of oxygen on platinum, Nature, 1997, 390: 495.
 
[81] J. Kim, D.-M. Kim, S.-Y. Kim, S.W. Nam, T. Kim, Humidification of polymer electrolyte membrane fuel cell using short circuit control for unmanned aerial vehicle applications, international journal of hydrogen energy, 2014, 39: 7925.
 
[82] C. Lombard, S. Le Doze, E. Marencak, P.-M. Marquaire, D. Le Noc, G. Bertrand, F. Lapicque, In situ regeneration of the Ni-based catalytic reformer of a 5 kW PEMFC system, International journal of hydrogen energy,  2006, 31: 437.
 
[83] J.R. Rostrup-Nielsen, Catalytic steam reforming,  Catalysis, Springer1984, 1.
 
[84] T. Van Herwijnen, W. De Jong, Kinetics and mechanism of the CO shift on CuZnO: 1. Kinetics of the forward and reverse CO shift reactions, Journal ofCatalysis, 1980, 63: 83.
 
[85] J.R. Rostrup-Nielsen, Steam reforming catalysts: an investigation of catalysts for tubular steam reforming of hydrocarbons: a contribution from the Research Laboratory of Haldor Topsøe A/S, Teknisk Forlag, 1975.
 
[86] H.S. Bengaard, J.K. Nørskov, J. Sehested, B. Clausen, L. Nielsen, A. Molenbroek, J. Rostrup-Nielsen, Steam reforming and graphite formation on Ni catalysts, Journal of Catalysis, 2002, 209: 365.
 
[87] R.S. Treptow, Le Chatelier's principle: A reexamination and method of graphic illustration, Journal of Chemical Education, 1980, 57: 417.
 
[88] J.H. Jung, S.H. Kim, S.H. Hur, S.H. Joo, W.M. Choi, J. Kim, Polymer electrolyte membrane fuel cell performance degradation by coolant leakage and recovery, Journal of Power Sources, 2013, 226: 320.
 
[89] A.M. Abdullah, M.M. Saleh, M.I. Awad, T. Okajima, F. Kitamura, T. Ohsaka, Temperature effect on the recovery of SO 2-Poisoned GC/Nano-Pt electrode towards oxygen reduction, Journal of Solid State Electrochemistry, 2010, 14: 1727.
 
[90] I. Urdampilleta, F. Uribe, T. Rockward, E.L. Brosha, B. Pivovar, F.H. Garzon, PEMFC poisoning with H2S: dependence on operating conditions, ECS Transactions, 2007, 11: 831.
 
[91] W. Shi, B. Yi, M. Hou, F. Jing, P. Ming, Hydrogen sulfide poisoning and recovery of PEMFC Pt-anodes, Journal of power sources, 2007, 165: 814.
 
[92] C.-H. Chen, A. Halford, M. Walker, C. Brennan, S.C. Lai, D.J. Fermin, P.R. Unwin, P. Rodriguez, Electrochemical characterization and regeneration of sulfur poisoned Pt catalysts in aqueous media, Journal of Electroanalytical Chemistry, 2018, 816: 138.
 
[93] Y. Zhai, O. Baturina, D. Ramaker, E. Farquhar, J. St-Pierre, K. Swider-Lyons, Chlorobenzene poisoning andrecovery of platinum-based cathodes in proton exchange membrane fuel cells, The Journal of Physical Chemistry C, 2015, 119 20328.
 
[94] Y. Garsany, S. Dutta, K.E. Swider-Lyons, Effect of glycol-based coolants on the suppression and recovery of platinum fuel cell electrocatalysts, Journal of Power Sources, 2012, 216: 515.
 
[95] B. Gould, G. Bender, K. Bethune, S. Dorn, O. Baturina, R. Rocheleau, K. Swider-Lyons, Operational performance recovery of SO2-contaminated proton exchange membrane fuel cells, Journal of The Electrochemical Society, 2010, 157: B1569-.
 
[96] K. Franaszczuk, J. Sobkowski, The voltammetry of platinized platinum electrodes in aqueous Na2SO4, Journal of electroanalytical chemistry and interfacial electrochemistry, 1989, 261: 223.
 
[97] H.A. Gasteiger, N. Markovic, P.N. Ross Jr, E.J. Cairns, Methanol electrooxidation on well-characterized platinum-ruthenium bulk alloys, The Journal of Physical Chemistry, 1993, 97: 12020.
 
[98] P. Vanysek, Electrochemical series, CRC handbook of chemistry and physics, 2000, 8.
 
[99] J. Schüring, H.D. Schulz, W.R. Fischer, J. Böttcher, W.H. Duijnisveld, Redox: fundamentals, processes and applications, Springer Science & Business Media, 2013.
 
[100] J.P. Hoare, The normal oxygen potential on bright platinum, Journal of the Electrochemical Society, 1963, 110: 1019.
 
[101] M. Waje, W. Li, Z. Chen, P. Larsen, Y. Yan, Effect of Scan Range on Pt Surface Area Loss in Potential Cycling Experiments, ECS Transactions, 2007, 11: 1227.
 
[102] A.K.Z. Jürgen Hunger (ZSW), Ludwig Jörissen (ZSW), Test Module D-04: Stack Performance Recovery, 2015.
 
[103] M.M. Walczak, D.A. Dryer, D.D. Jacobson,
M.G. Foss, N.T. Flynn, ph dependent redox couple: An illustration of the nernst equation, Journal of chemical education,  1997, 74: 1195.