Abstract
Poly(ether ketone sulfone)s with functionalized benzotriazole side chains are simply designed and successfully obtained by the copolycondensation of 4,4-difluorodiphenylsulfone, 4,4’-dihydroxydiphenylamine and a benzotriazole-based difluoro compound. The resulting polymers are identified by Fourier transform infrared spectroscopy and nuclear magnetic resonance, and the results are consistent with the proposed polymer structures. Owing to the intermolecular hydrogen bonding, the phosphoric acid (PA)-doped polymer membranes show encouraging mechanical properties. Taking advantage of the flexible movement of the benzotriazole in the side chains, the resulting membranes exhibit promising proton conductivities and fuel cell performance, which makes them a strong potential material for applications in high-temperature proton exchange membrane fuel cells.
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References
Martos A, Biasizzo M, Trotta F, Río C, Várez A, Levenfeld B. Synthesis and characterization of sulfonated PEEK-WC-PES copolymers for fuel cell proton exchange membrane application. Eur Polym J. 2014;93:390–402.
Zhang H, Shen PK. Advances in the high performance polymer electrolyte membranes for fuel cells. Chem Soc Rev. 2012;41:2382–94.
Chang G, Shang Z, Yang L. Hydrogen bond cross-linked sulfonated poly(imino ether ether ketone) (PIEEK) for fuel cell membranes. J Power Sources. 2015;282:401–8.
Shin DW, Guiver M, Lee YM. Hydrocarbon-based polymer electrolyte membranes: importance of morphology on ion transport and membrane stability. Chem Rev. 2017;117:4759–805.
Bose S, Kuila T, Nguyen TXH, Kim NH, Lau K, Lee JH. Polymer membranes for high temperature proton exchange membrane fuel cell: recent advances and challenges. Prog Polym Sci. 2011;36:813–43.
Park SJ, Lee DH, Kang YS. High temperature proton exchange membranes based on triazoles attached onto SBA-15 type mesoporous silica. J Membr Sci. 2010;357:1–5.
Chandan A, Hattenberger M, El-kharouf A, Du S, Dhir A, Self V et al. High temperature (HT) polymer electrolyte membrane fuel cells (PEMFC)-a review. J Power Sources. 2013;231:364–78.
Xu X, Wang H, Lu S, Guo Z, Rao S, Xiu R et al. A novel phosphoric acid doped poly(ether sulphone)-poly(vinyl pyrrolidone) blend membrane for high-temperature proton exchange membrane fuel cells. J Power Sources. 2015;286:458–63.
Wang K, Yang L, Wei W, Zhang L, Chang G. Phosphoric acid-doped poly(ether sulfone benzotriazole) for high temperature proton exchange membrane fuel cell applications. J Membr Sci. 2018;549:23–7.
Heinzel A, Barragan VM. A review of the state-of-the-art of the methanol crossover in direct methanol fuel cells. J Power Sources. 1999;84:70–4.
Steele BCH, Heinzel A. Materials for fuel-cell technologies. Nature. 2001;414:345–52.
Chen C, Levitin G, Hess DW, Fuller TF. XPS investigation of Nafion® membrane degradation. J Power Sources. 2007;169:288–95.
Silva BBR, Soares JB, Malfatti CF, Forte MMC. Benzimidazole effect on the performance of polyelectrolyte membranes based on sulfonated hydrocarbon resin. J Membr Sci. 2011;374:12–9.
Çelik SÜ, Bozkurt A, Hosseini S. Alternatives toward proton conductive anhydrous membranes for fuel cells: heterocyclic protogenic solvents comprising polymer electrolytes. Prog Polym Sci. 2012;37:1265–91.
Ahn MK, Lee S, Min C, Yu Y, Jang J, Gim M et al. Enhanced proton conductivity at low humidity of proton exchange membranes with triazole moieties in the side chains. J Membr Sci. 2017;523:480–6.
Henkensmeier D, Duong NMH, Brela M, Dyduch K, Michalak A, Jankova K et al. Tetrazole substituted polymers for high temperature polymer electrolyte fuel cells. J Mater Chem A. 2015;3:14389–400.
Xu J, Ni H, Wang S, Wang S, Wang Z, Zhang H. Direct polymerization of a novel sulfonated poly(arylene ether ketone sulfone)/sulfonated poly(vinylalcohol) crosslinked membrane for direct methanol fuel cell applications. J Membr Sci. 2015;492:505–17.
Zhang N, Zhao C, Ma W, Wang S, Wang B, Zhang G et al. Macromolecular covalently cross-linked quaternary ammonium poly(ether ether ketone) with polybenzimidazole for anhydrous high temperature proton exchange membranes. Polym Chem. 2014;5:4939–47.
Yang J, Xu Y, Zhou L, Che Q, He R, Li Q. Hydroxyl pyridine containing polybenzimidazole membranes for proton exchange membrane fuel cells. J Membr Sci. 2013;466:318–25.
Wang S, Zhao C, Ma W, Zhang G, Liu Z, Ni J et al. Preparation and properties of epoxy-cross-linked porous polybenzimidazole for high temperature proton exchange membrane fuel cells. J Memb Sci. 2012;411:54–63.
Mader JA, Benicewicz BC. Sulfonated polybenzimidazoles for high temperature PEM fuel cells. Macromolecules. 2010;43:6706–15.
Li X, Ma H, Shen Y, Hu W, Jiang Z, Liu B et al. Dimensionally-stable phosphoric acid–doped polybenzimidazoles for high-temperature proton exchange membrane fuel cells. J Power Sources. 2016;336:391–400.
Chen JC, Chen PY, Liu YC, Chen KH. Polybenzimidazoles containing bulky substituents and ether linkages for high-temperature proton exchange membrane fuel cell applications. J Memb Sci. 2016;513:270–9.
Hubner G, Roduner E. EPR investigation of HO/ radical initiated degradation reactions of sulfonated aromatics as model compounds for fuel cell proton conducting membranes. J Mater Chem. 1999;9:409–18.
Panchenko A, Dilger H, Möller E, Sixt T, Roduner E. In situ EPR investigation of polymer electrolyte membrane degradation in fuel cell applications. J Power Sources. 2004;127:325–30.
Bu F, Zhang Y, Hong L, Zhao W, Li D, Li J et al. 1,2,4-Triazole functionalized poly(arylene ether ketone) for high temperature proton exchange membrane with enhanced oxidative stability. J Membr Sci. 2018;545:167–75.
Acknowledgements
This work was financially supported by the National Natural Science Foundation of China (21504073, 21202134, 11447215), the Fundamental Science on Nuclear Wastes and Environmental Safety Laboratory (15kffk03), the Scientific Research Fund of Sichuan Provincial Education Department (16ZA0136, 18ZA0495), and the Longshan academic talent research supporting program of SWUST (18LZX308 and 18LZX446). Li Yang and Guanjun Chang are grateful for financial support from the China Scholarship Council.
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Du, M., Yang, L., Luo, X. et al. Novel phosphoric acid (PA)-poly(ether ketone sulfone) with flexible benzotriazole side chains for high-temperature proton exchange membranes. Polym J 51, 69–75 (2019). https://doi.org/10.1038/s41428-018-0118-7
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DOI: https://doi.org/10.1038/s41428-018-0118-7
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