Vicious cycle during chemical degradation of sulfonated aromatic proton exchange membranes in the fuel cell application
Aida Karimi
School of Chemical Engineering, Iran University of Science and Technology, Tehran, Iran
Search for more papers by this authorSeyed Hesam Mirfarsi
School of Chemical Engineering, Iran University of Science and Technology, Tehran, Iran
Fuel Cell Laboratory, Green Research Center, Iran University of Science and Technology, Tehran, Iran
Search for more papers by this authorCorresponding Author
Soosan Rowshanzamir
School of Chemical Engineering, Iran University of Science and Technology, Tehran, Iran
Fuel Cell Laboratory, Green Research Center, Iran University of Science and Technology, Tehran, Iran
Center of Excellence for Membrane Science and Technology, Iran University of Science & Technology Narmak, Tehran, Iran
Correspondence
Soosan Rowshanzamir, Iran University of Science and Technology, P.O. Box: 16846-13114, Tehran, Iran.
Email: [email protected]
Search for more papers by this authorFatemeh Beyraghi
School of Chemical Engineering, Iran University of Science and Technology, Tehran, Iran
Search for more papers by this authorDaniel Lester
Polymer Characterization Research Technology Platform, University of Warwick, Coventry, UK
Search for more papers by this authorAida Karimi
School of Chemical Engineering, Iran University of Science and Technology, Tehran, Iran
Search for more papers by this authorSeyed Hesam Mirfarsi
School of Chemical Engineering, Iran University of Science and Technology, Tehran, Iran
Fuel Cell Laboratory, Green Research Center, Iran University of Science and Technology, Tehran, Iran
Search for more papers by this authorCorresponding Author
Soosan Rowshanzamir
School of Chemical Engineering, Iran University of Science and Technology, Tehran, Iran
Fuel Cell Laboratory, Green Research Center, Iran University of Science and Technology, Tehran, Iran
Center of Excellence for Membrane Science and Technology, Iran University of Science & Technology Narmak, Tehran, Iran
Correspondence
Soosan Rowshanzamir, Iran University of Science and Technology, P.O. Box: 16846-13114, Tehran, Iran.
Email: [email protected]
Search for more papers by this authorFatemeh Beyraghi
School of Chemical Engineering, Iran University of Science and Technology, Tehran, Iran
Search for more papers by this authorDaniel Lester
Polymer Characterization Research Technology Platform, University of Warwick, Coventry, UK
Search for more papers by this authorSummary
Weak phase separation and vulnerable linking groups between aromatic units are common setbacks of sulfonated aromatic proton exchange membranes (PEMs) from durability point of view. In this study, sulfonated poly(ether ether ketone) (SPEEK) membranes were exposed to Fenton's solution for a specific time, ranging from 10 to 60 minutes. Chemical structure and morphology evolution, decay in mechanical and thermal stability, and H2 permeability of SPEEK membranes were evaluated during the chemical degradation. Less-entangled polymeric chains with lower average molecular weight of degraded SPEEK samples diminished mechanical rigidity. In addition, reduction of aromatic rings in each repeat unit led to higher thermal decomposition rate. Furthermore, randomly distributed micro-defects in the SPEEK morphology and an increase in water sorption can reduce the fatigue strength of membranes in the wet-dry cycles. Eventually, hydrogen cross-over rate was gradually increased, and henceforth, accelerated destructive radical formation and degradation can be predicted.
REFERENCES
- 1Acar C, Dincer I. The potential role of hydrogen as a sustainable transportation fuel to combat global warming. Int J Hydrogen Energy. 2020; 45(5): 3396-3406.
- 2Ahmadi P, Kjeang E. Realistic simulation of fuel economy and life cycle metrics for hydrogen fuel cell vehicles. Int J Energy Res. 2017; 41(5): 714-727.
- 3Luo L, Huang B, Cheng Z, Jian Q. Rapid degradation characteristics of an air-cooled PEMFC stack. Int J Energy Res. 2020; 44(6): 4784-4799.
- 4Peighambardoust SJ, Rowshanzamir S, Amjadi M. Review of the proton exchange membranes for fuel cell applications. Int J Hydrogen Energy. 2010; 35(17): 9349-9384.
- 5Houchins C, Kleen G, Spendelow J, et al. US DOE progress toward developing low-cost, high performance, durable polymer electrolyte membranes for fuel cell applications. Membranes. 2012; 2(4): 855-878.
- 6Rath R, Kumar P, Mohanty S, Nayak SK. Recent advances, unsolved deficiencies, and future perspectives of hydrogen fuel cells in transportation and portable sectors. Int J Energy Res. 2019; 43(15): 8931-8955.
- 7Kocha SS, Deliang Yang J, Yi JS. Characterization of gas crossover and its implications in PEM fuel cells. AIChE Journal. 2006; 52(5): 1916-1925.
- 8Shin DW, Guiver MD, Lee YM. Hydrocarbon-based polymer electrolyte membranes: importance of morphology on ion transport and membrane stability. Chem Rev. 2017; 117(6): 4759-4805.
- 9Zuo H, Chen L, Kong M, et al. Toxic effects of fluoride on organisms. Life Sci. 2018; 198: 18-24.
- 10Wei H, Chen R, Li G. Effect of chemical structure on the performance of sulfonated poly (arylene ether sulfone) as proton exchange membrane. Int J Hydrogen Energy. 2015; 40(41):14392–14397.
- 11Lee KH, Chu JY, Kim AR, Yoo DJ. Effect of functionalized SiO2 toward proton conductivity of composite membranes for PEMFC application. Int J Energy Res. 2019; 43(10): 5333-5345.
- 12Wang C, Lee SY, Shin DW, Kang NR, Lee YM, Guiver MD. Proton-conducting membranes from poly (ether sulfone) s grafted with sulfoalkylamine. J Membr Sci. 2013; 427: 443-450.
- 13Shimizu R, Otsuji K, Masuda A, et al. Durability of newly developed Polyphenylene-based ionomer membranes in polymer electrolyte fuel cells: accelerated stress evaluation. J Electrochem Soc. 2019; 166(7):F3105–F3110.
- 14Sarirchi S, Rowshanzamir S, Mehri F. Simultaneous improvement of ionic conductivity and oxidative stability of sulfonated poly (ether ether ketone) nanocomposite proton exchange membrane for fuel cell application. Int J Energy Res. 2020; 44(4): 2783-2800.
- 15Beyraghi F, Mirfarsi SH, Rowshanzamir S, Karimi A, Parnian MJ. Optimal thermal treatment conditions for durability improvement of highly sulfonated poly (ether ether ketone) membrane for polymer electrolyte fuel cell applications. Int J Hydrogen Energy. 2020; 45(24):13441–13458.
- 16Gubler L, Nauser T, Coms FD, Lai Y-H, Gittleman CS. Perspective—prospects for durable hydrocarbon-based fuel cell membranes. J Electrochem Soc. 2018; 165(6):F3100–F3103.
- 17Banerjee S, Kar KK. Impact of degree of sulfonation on microstructure, thermal, thermomechanical and physicochemical properties of sulfonated poly ether ether ketone. Polymer. 2017; 109: 176-186.
- 18Kim AR, Gabunada JC, Yoo DJ. Amelioration in physicochemical properties and single cell performance of sulfonated poly (ether ether ketone) block copolymer composite membrane using sulfonated carbon nanotubes for intermediate humidity fuel cells. Int J Energy Res. 2019; 43(7): 2974-2989.
- 19Ohira A, Kuroda S. Differences in the oxygen permeation behavior of perfluorinated and hydrocarbon-type polymer electrolyte membranes at elevated temperatures. Eur Polym J. 2015; 67: 78-87.
- 20Sayadi P, Rowshanzamir S, Parnian MJ. Study of hydrogen crossover and proton conductivity of self-humidifying nanocomposite proton exchange membrane based on sulfonated poly(ether ether ketone). Energy. 2016; 94: 292-303.
- 21Parnian MJ, Rowshanzamir S, Gashoul F. Comprehensive investigation of physicochemical and electrochemical properties of sulfonated poly(ether ether ketone) membranes with different degrees of sulfonation for proton exchange membrane fuel cell applications. Energy. 2017; 125: 614-628.
- 22Zhang L, Mukerjee S. Investigation of durability issues of selected nonfluorinated proton exchange membranes for fuel cell application. J Electrochem Soc. 2006; 153(6):A1062–A1072.
- 23Wu J, Yuan XZ, Martin JJ, et al. A review of PEM fuel cell durability: degradation mechanisms and mitigation strategies. J Power Sources. 2008; 184(1): 104-119.
- 24Dafalla AM, Jiang F. Stresses and their impacts on proton exchange membrane fuel cells: a review. Int J Hydrogen Energy. 2018; 43(4): 2327-2348.
- 25Khorasany R, Singh Y, Alavijeh AS, Kjeang E, Wang G, Rajapakse R. Fatigue properties of catalyst coated membranes for fuel cells: ex-situ measurements supported by numerical simulations. Int J Hydrogen Energy. 2016; 41(21): 8992-9003.
- 26Lü W, Liu Z, Wang C, Mao Z, Zhang M. The effects of pinholes on proton exchange membrane fuel cell performance. Int J Energy Res. 2011; 35(1): 24-30.
- 27Alavijeh AS, Khorasany RM, Nunn Z, et al. Microstructural and mechanical characterization of catalyst coated membranes subjected to in situ hygrothermal fatigue. J Electrochem Soc. 2015; 162(14):F1461–F1469.
- 28Rodgers MP, Bonville LJ, Kunz HR, Slattery DK, Fenton JM. Fuel cell perfluorinated sulfonic acid membrane degradation correlating accelerated stress testing and lifetime. Chem Rev. 2012; 112(11): 6075-6103.
- 29Frensch SH, Serre G, Fouda-Onana F, et al. Impact of iron and hydrogen peroxide on membrane degradation for polymer electrolyte membrane water electrolysis: computational and experimental investigation on fluoride emission. J Power Sources. 2019; 420: 54-62.
- 30Gubler L, Dockheer SM, Koppenol WH. Radical (HO•, H• and HOO•) formation and ionomer degradation in polymer electrolyte fuel cells. J Electrochem Soc. 2011; 158(7):B755–B769.
- 31Kundu S, Simon LC, Fowler MW. Comparison of two accelerated Nafion degradation experiments. Polym Degrad Stab. 2008; 93(1): 214-224.
- 32Ghassemzadeh L, Kreuer KD, Maier J, Müller K. Evaluating chemical degradation of proton conducting perfluorosulfonic acid ionomers in a Fenton test by solid-state 19F NMR spectroscopy. J Power Sources. 2011; 196(5): 2490-2497.
- 33Mench MM, Kumbur EC. Polymer electrolyte fuel cell degradation. 1st ed. London, England: Academic Press; 2011.
- 34Panchenko A. DFT investigation of the polymer electrolyte membrane degradation caused by OH radicals in fuel cells. J Membr Sci. 2006; 278(1): 269-278.
- 35Holmes T, Skalski TJ, Adamski M, Holdcroft S. Stability of hydrocarbon fuel cell membranes: reaction of hydroxyl radicals with sulfonated Phenylated Polyphenylenes. Chem Mater. 2019; 31(4): 1441-1449.
- 36Salleh MT, Jaafar J, Mohamed MA, et al. Stability of SPEEK/Cloisite/TAP nanocomposite membrane under Fenton reagent condition for direct methanol fuel cell application. Polym Degrad Stab. 2017; 137: 83-99.
- 37Shimizu R, Tsuji J, Sato N, et al. Durability and degradation analysis of hydrocarbon ionomer membranes in polymer electrolyte fuel cells accelerated stress evaluation. J Power Sources. 2017; 367: 63-71.
- 38Luo X, Ghassemzadeh L, Holdcroft S. Effect of free radical-induced degradation on water permeation through PFSA ionomer membranes. Int J Hydrogen Energy. 2015; 40(46):16714–16723.
- 39Mirfarsi SH, Karimi A, Rowshanzamir S, Parnian MJ. Study of mechanical degradation of sulfonated poly (ether ether ketone) membrane using ex-situ hygrothermal cycles for polymer electrolyte fuel cell application. J Power Sources. 2018; 401: 73-84.
- 40Zhao Y-y, Choe Y-K, Tsuchida E, Ikeshoji T, Ohira A. Theoretical studies of pendant effects on the properties of sulfonated hydrocarbon polymer electrolyte membranes. J Phys Chem C. 2015; 119(21):11362–11369.
- 41Zhao Y-y, Tsuchida E, Choe Y-K, Wang J, Ikeshoji T, Ohira A. Theoretical studies on the degradation of hydrocarbon copolymer ionomers used in fuel cells. J Membr Sci. 2015; 487: 229-239.
- 42Perrot C, Gonon L, Marestin C, Morin A, Gebel G. Aging mechanism of sulfonated poly(aryl ether ketone) (sPAEK) in an hydroperoxide solution and in fuel cell. J Power Sources. 2010; 195(2): 493-502.
- 43Venkatesan S v, Lim C, Holdcroft S, Kjeang E. Progression in the morphology of fuel cell membranes upon conjoint chemical and mechanical degradation. J Electrochem Soc. 2016; 163(7):F637–F643.
- 44Tang H, Peikang S, Jiang SP, Wang F, Pan M. A degradation study of Nafion proton exchange membrane of PEM fuel cells. J Power Sources. 2007; 170(1): 85-92.
- 45Mikhailenko SD, Celso F, Kaliaguine S. Properties of SPEEK based membranes modified with a free radical scavenger. J Membr Sci. 2009; 345(1–2): 315-322.
- 46Kim YS, Hickner MA, Dong L, Pivovar BS, McGrath JE. Sulfonated poly (arylene ether sulfone) copolymer proton exchange membranes: composition and morphology effects on the methanol permeability. J Membr Sci. 2004; 243(1-2): 317-326.
- 47He C, Mighri F, Guiver MD, Kaliaguine S. Tuning surface hydrophilicity/hydrophobicity of hydrocarbon proton exchange membranes (PEMs). J Colloid Interface Sci. 2016; 466: 168-177.
- 48Shaari N, Kamarudin SK. Recent advances in additive-enhanced polymer electrolyte membrane properties in fuel cell applications: an overview. Int J Energy Res. 2019; 43(7): 2756-2794.
- 49Mendil-Jakani H, López IZ, Mareau V, Gonon L. Optimization of hydrophilic/hydrophobic phase separation in sPEEK membranes by hydrothermal treatments. Phys Chem Chem Phys. 2017; 19(24):16013–16022.
- 50Peckham TJ, Holdcroft S. Structure-morphology-property relationships of nonperfluorinated proton-conducting membranes. Adv Mater. 2010; 22(42): 4667-4690.
- 51Stern C, Frick A, Weickert G. Relationship between the structure and mechanical properties of polypropylene: effects of the molecular weight and shear-induced structure. J Appl Polym Sci. 2007; 103(1): 519-533.
- 52Tang Y, Karlsson AM, Santare MH, Gilbert M, Cleghorn S, Johnson WB. An experimental investigation of humidity and temperature effects on the mechanical properties of perfluorosulfonic acid membrane. Mater Sci Eng A. 2006; 425(1–2): 297-304.
- 53Sadeghi Alavijeh A, Goulet MA, Khorasany RMH, et al. Decay in mechanical properties of catalyst coated membranes subjected to combined chemical and mechanical membrane degradation. Fuel Cells. 2015; 15(1): 204-213.
- 54Lee CH, Lee K-S, Lane O, et al. Solvent-assisted thermal annealing of disulfonated poly (arylene ether sulfone) random copolymers for low humidity polymer electrolyte membrane fuel cells. RSC Adv. 2012; 2(3): 1025-1032.
- 55Park HB, Shin H-S, Lee YM, Rhim J-W. Annealing effect of sulfonated polysulfone ionomer membranes on proton conductivity and methanol transport. J Membr Sci. 2005; 247(1–2): 103-110.
- 56Roy A, Hickner MA, Lee H-S, et al. States of water in proton exchange membranes: part A-influence of chemical structure and composition. Polymer. 2017; 111: 297-306.
- 57Ji C, Niu H, Wang S, Liang C, Li X, Yang J. Research on two-phase flow considering hydrogen crossover in the membrane for a polymer electrolyte membrane fuel cell. Int J Energy Res. 2019; 43(7): 2881-2896.
