Abstract
Copolymers with cross-linkable pendant carboxylic acid moieties were successfully synthesized via direct copolymerization. Two types of copolymers were prepared. In the first type of copolymers, sulfonic groups were introduced on the biphenol monomers. The second type consisted of a series of copolymers having sulfonic groups on the sulfone monomers. Cross-linking of these copolymers was carried out with the prepared hexafluoro-bisphenol-A epoxy resin (HFB) and membranes were cast on glass plates. Cross-linking caused reduction in excessive fuel cross over, water and methanol uptake without compromising much on the basic membrane properties such as proton conductivity, ion exchange capacity, and selectivity ratio. The proton conductivity increased with the rise in temperature but decreased with further rise in epoxy content. The stability of the cross-linked membranes toward radical oxidation in fuel cell ambiance was revealed from Fenton’s test as cr-6FB-SP-HFB membranes exhibited highest oxidative stability. The improvement in the performance of the cross-linked membranes was found by comparing them with pristine membranes. Atomic force microscopy (AFM) and X-ray diffraction (XRD) analyses confirmed phase separation and amorphous behavior of these membranes. Mechanical properties were determined with the help of a Universal testing machine (UTM). Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) analyses revealed excellent thermal stability of these membranes.
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References
Kirubakaran A, Shailendra J, Nema RK (2009) A review on fuel cell technologies and power electronic interface. Renew Sustain Energy Rev 13:2430–2440. https://doi.org/10.1016/j.rser.2009.04.004
Kim AR, Vinothkannan M, Song MH, Lee J-Y, Lee H-K, Yoo DJ (2020) Amine functionalized carbon nanotube (ACNT) filled in sulfonated poly(ether ether ketone) membrane: effects of ACNT in improving polymer electrolyte fuel cell performance under reduced relative humidity. Compos B Eng 188:107890. https://doi.org/10.1016/j.compositesb.2020.107890
Sharaf OZ, Orphan MF (2014) An overview of fuel cell technology: fundamentals and applications. Renew Sustain Energy Rev 32:810–853. https://doi.org/10.1016/j.rser.2014.01.012
Nasirinezhad M, Ghaffarian SR, Tohidian M (2021) Eco-friendly polyelectrolyte nanocomposite membranes based on chitosan and sulfonated chitin nanowhiskers for fuel cell applications. Iran Polym J 30:355–367. https://doi.org/10.1007/s13726-020-00895-5
Yin Y, Li Z, Yang X, Cao L, Wang C, Zhang B, Wu H, Jiang Z (2016) Enhanced proton conductivity of Nafion composite membrane by incorporating phosphoric acid-loaded covalent organic framework. J Power Sources 332:265–273. https://doi.org/10.1016/j.jpowsour.2016.09.135
Gómez EER, Hernández JHM, Astaiza JED (2020) Development of a chitosan/PVA/TiO2 nanocomposite for application as a solid polymeric electrolyte in fuel cells. Polymers 12:1691. https://doi.org/10.3390/polym12081691
Eisenberg A, Yeager HL (1982) Perfluorinated ionomer membranes. ACS Symp Ser Am Chem Soc. https://doi.org/10.1021/bk-1982-0180.fw001
Hickner MA, Ghassemi H, Kim YS, Einsla BR, McGrath JE (2004) Alternate polymer systems for proton exchange membranes (PEMs). Chem Rev 104:4587–4612. https://doi.org/10.1021/cr020711a
Wee J-H (2007) Applications of proton exchange membrane fuel cell systems. Renew Sustain Energy Rev 11:1720–1738. https://doi.org/10.1016/j.rser.2006.01.005
Mauritz KA, Moore RB (2004) State of understanding of Nafion. Chem Rev 104:4535–4586. https://doi.org/10.1021/cr0207123
Gil-Castell O, Teruel-Juanes R, Arenga F, Salaberria AM, Baschetti MG, Labidi J, Badia JD, Ribes-Greusa A (2019) Crosslinked chitosan/poly(vinyl alcohol)-based polyelectrolytes for proton exchange membranes. React Funct Polym 142:213–222. https://doi.org/10.1016/j.reactfunctpolym.2019.06.003
Smitha B, Sridhar S, Khan AA (2005) Solid polymer electrolyte membranes for fuel cell applications-a review. J Membrane Sci 259:10–26. https://doi.org/10.1016/j.memsci.2005.01.035
Hamrock SJ, Yandrasits MA (2006) Proton exchange membranes for fuel cell applications. J Macromol Sci Polym Rev 46:219–244. https://doi.org/10.1080/15583720600796474
Li L, Zhang J, Wang YX (2003) Sulfonated poly(ether ether ketone) membranes for direct methanol fuel cell. J Membrane Sci 226:159–167. https://doi.org/10.1016/j.memsci.2003.08.018
Lufrano F, Gatto I, Staiti P, Antonucci V, Passalacqua E (2001) Sulfonated polysulfone ionomer membranes for fuel cells. Solid State Ion 145:47–51. https://doi.org/10.1016/S0167-2738(01)00912-2
Molla-Abbasi P, Janghorban K, Asgari MS (2018) A novel heteropolyacid-doped carbon nanotubes/Nafion nanocomposite membrane for high performance proton-exchange methanol fuel cell applications. Iran Polym J 27:77–86. https://doi.org/10.1007/s13726-017-0587-0
Costa ML, Pardini LC, Rezende MC (2005) Influence of aromatic amine hardeners in the cure kinetics of an epoxy resin used in advanced composites. Mater Res 8:65–70. https://doi.org/10.1590/S1516-14392005000100012
Maka H, Spychaj T, Pilawka R (2014) Epoxy resin/phosphonium ionic liquid/carbon nanofiller systems: chemorheology and properties. Express Polym Lett 8:723–732. https://doi.org/10.3144/expresspolymlett.2014.75
Kiran V, Awasthi S, Gaur B (2015) Hydroquinone based sulfonated poly(arylene ether sulfone) copolymer as proton exchange membrane for fuel cell applications. Express Polym Lett 9:1053–1067. https://doi.org/10.3144/expresspolymlett.2015.95
Boroglu MS, Cavus S, Boz I, Ata A (2011) Synthesis and characterization of poly (vinyl alcohol) proton exchange membranes modified with 4, 4-diaminodiphenylether-2,2-disulfonic acid. Express Polym Lett 5:470–478. https://doi.org/10.3144/expresspolymlett.2011.45
Han M, Zhang G, Li M, Wang S, Liu Z, Li H, Zhang Y, Xu D, Wang J, Ni J, Na H (2011) Sulfonated poly(ether ether ketone)/polybenzimidazole oligomer/epoxy resin composite membranes in situ polymerization for direct methanol fuel cell usages. J Power Sources 196:9916–9923. https://doi.org/10.1016/j.jpowsour.2011.08.049
Tong JY, Guo Q, Wang XX (2009) Properties and structure of SPEEK proton exchange membrane doped with nanometer CeO2 and treated with high magnetic field. Express Polym Lett 3:821–831. https://doi.org/10.3144/expresspolymlett.2009.10
Han S, Zhang M-S, Shin J, Lee Y-S (2014) A convenient crosslinking method for sulfonated poly (ether ether ketone) membranes via friedel-crafts reaction using 1,6-dibromohexane and aluminium trichloride. J Appl Polym Sci 131:40695. https://doi.org/10.1002/app.40695
Lee KH, Chu JY, Kim AR, Nahm KS, Yoo DJ (2013) Highly sulfonated poly (arylene biphenylsulfone ketone) block copolymers prepared via post-sulfonation for proton conducting electrolyte membranes. Bull Korean Chem Soc 34:1763–1770. https://doi.org/10.5012/bkcs.2013.34.6.1763
Matsumoto K, Higashihara T, Ueda M (2009) Locally sulfonated poly(ether sulfone)s with highly sulfonated units as proton exchange membrane. J Polym Sci A Polym Chem 47:3444–3453. https://doi.org/10.1002/pola.23403
Kim H, Kabir MDL, Choi S-J (2019) Imparting high proton conductivity to Nafion® tuned by acidic chitosan for low-temperature proton exchange membrane fuel cell applications. J Nanosci Nanotechnol 19:6625–6629. https://doi.org/10.1166/jnn.2019.17081
Ding FC, Wang SJ, Xiao M, Meng YZ (2007) Cross-linked sulfonated poly(phathalazinone ether ketone)s for PEM fuel cell application as proton-exchange membrane. J Power Sources 164:488–495. https://doi.org/10.1016/j.jpowsour.2006.11.028
Guhan S, Sangeetha D (2008) Evaluation of sulfonated poly(ether ether ketone) silicotungstic acid composite membranes for fuel cell applications. Int J Polym Mater 58:87–98. https://doi.org/10.1080/00914030802565442
Van Krevelen DW (1975) Some basic aspects of flame resistance of polymeric materials. Polymer 16:615–620. https://doi.org/10.1016/0032-3861(75)90157-3
Shahi VK (2007) Highly charged proton-exchange membrane: Sulfonated poly(ether sulfone)-silica polyelectrolyte composite membranes for fuel cells. Solid State Ion 177:3395–3404. https://doi.org/10.1016/j.ssi.2006.10.023
Hsu WY, Gierke TD (1983) Ion transport and clustering in Nafion perfluorinated membranes. J Membr Sci 13:307–326. https://doi.org/10.1016/S0376-7388(00)81563-X
Kraytsberg A, Ein-Eli Y (2014) Review of advanced materials for proton exchange membrane fuel cells. Energy Fuels 28:7303–7330. https://doi.org/10.1021/ef501977k
Wang L, Wang D, Zhu G, Li J (2011) Synthesis and properties of highly branched sulfonated poly(arylene ether)s as proton exchange membranes. Eur Polym J 47:1985–1993. https://doi.org/10.1016/j.eurpolymj.2011.07.016
Malakhov AO, Volkov AV (2020) Modification of polymer membranes for use in organic solvents. Russ J Appl Chem 93:14–24. https://doi.org/10.1134/S1070427220010024)
Nguyen MDT, Dang HS, Kim DJ (2015) Proton exchange membranes based on sulfonatedpoly(arylene ether ketone) containing triazole group for enhanced proton conductivity. J Membr Sci 496:13–20. https://doi.org/10.1016/j.memsci.2015.08.029
Sahu AK, Pitchumani S, Sridhar P, Shukla AK (2009) Nafion and modified- Nafion membranes for polymer electrolyte fuel cells: an overview. Bull Mater Sci 32:285–294. https://doi.org/10.1007/s12034-009-0042-8
d’Almeida JRM, Menezes GW, Monteiro SN (2003) Ageing of the DGEBA/TETA epoxy system with off-stoichiometric compositions. Mater Res 6:415–420. https://doi.org/10.1590/S1516-14392003000300017
Kim AR, Vinothkannan M, Lee KH, Chu JY, Ryu SK, Kim HG, Lee J-Y, Lee H-K, Yoo DJ (2020) Ameliorated performance of sulfonated poly(arylene ether sulfone) block copolymers with increased hydrophilic oligomer ratio in proton-exchange membrane fuel cells operating at 80% relative humidity. Polymers 12:1871. https://doi.org/10.3390/polym12091871
Krishnan P, Park J-S, Kim C-S (2006) Preparation of proton-conducting sulfonated poly(ether ether ketone)/boron phosphate composite membranes by an in situ sol-gel process. J Membr Sci 279:220–229. https://doi.org/10.1016/j.memsci.2005.12.010
Mokhtaruddin SR, Mohamad AB, Loh KS, Kadhum AAH (2016) Thermal properties and conductivity of nafion-zirconia composite membrane. Malaysian J Anal Sci 20:670–677. https://doi.org/10.17576/mjas-2016-2003-28670
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Dhiman, R., Kiran, V., Gaur, B. et al. Biphenol based membranes with ionic channels for fuel cell application. Iran Polym J 30, 855–872 (2021). https://doi.org/10.1007/s13726-021-00942-9
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DOI: https://doi.org/10.1007/s13726-021-00942-9