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SPEES/PEI-based highly selective polymer electrolyte membranes for DMFC application

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Abstract

Polymer composite membranes based on sulfonated poly(phenylene ether ether sulfone) (SPEES) membrane with varying concentrations of poly(ether imide) (PEI) were prepared. The sulfonation of PEES was carried out with concentrated sulfuric acid at 10 °C, and the sulfonation degree was maintained as 70 %. The introduction of PEI into the hydrophilic SPEES matrix provided good chemical stability to the membrane. The water uptake, ion exchange capacity, and proton conductivity decrease with increasing PEI content. Scanning electron microscopy (SEM) indicates that PEI particles are homogeneously dispersed into the composite membrane. Thermogravimetric analysis (TGA) showed that all the composite membranes exhibited good thermal stability. On the other hand, the methanol permeability of the composite membranes gradually decreases from 4.23 × 10−7 cm2 s−1 to 8.84 × 10−8 cm2 s−1, which is lower than that of the Nafion 117 membrane. The relative selectivity of the PEI-incorporated SPEES membranes was higher than that of the Nafion membranes. From the observed results, the prepared SPEES/PEI-15 composite membrane can be considered as apposite polymer electrolyte membranes for the application of direct methanol fuel cells (DMFCs).

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References

  1. Lim Y, Lee H, Lee S, Jang H, Hossain MA, Cho Y, Kim T, Hong Y, Kim W (2014) Synthesis and properties of sulfonated poly (phenylene sulfone)s without ether linkage by Diels–Alder reaction for PEMFC application. Electrochim Acta 119:16–23

    Article  CAS  Google Scholar 

  2. Thanganathan U, Ghatty SL (2014) Effects of humidity and temperature on the electrochemical activities of H2/O2 PEMFCs using hybrid membrane electrolytes. J Solid State Electrochem 18:285–290

    Article  CAS  Google Scholar 

  3. Martemianov S, Ilie VR, Coutanceau C (2014) Improvement of the proton exchange membrane fuel cell performances by optimization of the hot pressing process for membrane electrode assembly. J Solid State Electrochem 18:1261–1269

    Article  CAS  Google Scholar 

  4. Thanganathan U, Nogami M (2014) Proton conductivity and structural properties of precursors mixed PVA/PWA-based hybrid composite membranes. J Solid State Electrochem 18:97–104

    Article  CAS  Google Scholar 

  5. Tohidian M, Ghaffarian SR, Shakeri SE, Dashtimoghadam E, Hasani-Sadrabadi MM (2013) Organically modified montmorillonite and chitosan–phosphotungstic acid complex nanocomposites as high performance membranes for fuel cell applications. J Solid State Electrochem 17:2123–2137

    Article  CAS  Google Scholar 

  6. Higashihara T, Matsumoto K, Ueda M (2009) Sulfonated aromatic hydrocarbon polymers as proton exchange membranes for fuel cells. Polymer 50:5341–5357

    Article  CAS  Google Scholar 

  7. Wei Z, He S, Liu X, Qiao J, Lin J, Zhang L (2013) A novel environment-friendly route to prepare proton exchange membranes for direct methanol fuel cells. Polymer 54:1243–1250

    Article  CAS  Google Scholar 

  8. Mukherjee R, Mohanty AK, Banerjee S, Komber H, Voit B (2013) Phthalimidine based fluorinated sulfonated poly(arylene ether sulfone)s copolymer proton exchange membranes. J Membr Sci 435:145–154

    Article  CAS  Google Scholar 

  9. Muthumeenal A, Neelakandan S, Rana D, Matsuura T, Kanagaraj P, Nagendran A (2014) Sulfonated polyethersulfone (SPES)-charged surface modifying macromolecules (cSMMs) blends as a cation selective membrane for fuel cells. Fuel Cells 14:853–861

    Article  CAS  Google Scholar 

  10. He XH, Zheng Y, Yao HL, Chen YW, Chen DF (2014) Hybrid network sulfonated polynorbornene/silica membranes with enhanced proton conductivity by doped phosphotungstic acid. Fuel Cells 14:26–34

    Article  Google Scholar 

  11. Verma A, Scott K (2010) Development of high-temperature PEMFC based on heteropolyacids and polybenzimidazole. J Solid State Electrochem 14:213–219

    Article  CAS  Google Scholar 

  12. Woo JY, Lee KM, Jee BC, Ryu CH, Yoon CH, Chung JH, Kim YR, Moon SB, Kang AS (2010) Electrocatalytic characteristics of Pt–Ru–Co and Pt–Ru–Ni based on covalently cross-linked sulfonated poly (ether ether ketone)/heteropolyacids composite membranes for water electrolysis. J Ind Eng Chem 16:688–697

    Article  CAS  Google Scholar 

  13. Kim DJ, Lee HJ, Nam SY (2013) Sulfonated poly (arylene ether sulfone) membranes blended with hydrophobic polymers for direct methanol fuel cell applications. Int J Hydrog Energy. doi:10.1016/j.ijhydene.2013.09.030

    Google Scholar 

  14. Mikhailenko SD, Zaidi SMJ, Kaliaguine S (2000) Electrical properties of sulfonated polyether ether ketone/polyetherimide blend membranes doped with inorganic acids. J Polym Sci Pol Phys 38:1386–1395

    Article  CAS  Google Scholar 

  15. Swier S, Shaw MT, Weiss RA (2006) Morphology control of sulfonated poly(ether ketone ketone) poly(ether imide) blends and their use in proton-exchange membranes. J Membr Sci 270:22–31

    Article  CAS  Google Scholar 

  16. Zhao C, Wang Z, Bi D, Lin H, Shao K, Fu T, Zhong S, Na H (2007) Blend membranes based on disulfonated poly(aryl ether ether ketone)s (SPEEK) and poly (amide imide) (PAI) for direct methanol fuel cell usages. Polymer 48:3090–3097

    Article  CAS  Google Scholar 

  17. Neelakandan S, Kanagaraj P, Rana D, Matsuura T, Muthumeenal A, Nagendran A (2015) Enhancing proton conduction of sulfonated poly (phenylene ether ether sulfone) membrane by charged surface modifying macromolecules for H2/O2 fuel cells. Renew Energy 78:306–313

  18. Wang G, Yao Y, Xiao G, Yan D (2013) Novel sulfonated polybenzothiazoles with outstanding dimensional stability for proton exchange membranes. J Membr Sci 425:200–207

    Article  Google Scholar 

  19. Dashtimoghadam E, Hasani‐Sadrabadi MM, Moaddel H (2010) Structural modification of chitosan biopolymer as a novel polyelectrolyte membrane for green power generation. Polym Adv Technol 21:726–734

    Article  CAS  Google Scholar 

  20. Meenakshi S, Bhat SD, Sahu AK, Alwin S, Sridhar P, Pitchumani S (2012) Natural and synthetic solid polymer hybrid dual network membranes as electrolytes for direct methanol fuel cells. J Solid State Electrochem 16:1709–1721

    Article  CAS  Google Scholar 

  21. Neelakandan S, Rana D, Matsuura T, Muthumeenal A, Kanagaraj P, Nagendran A (2014) Fabrication and electrochemical properties of surface modified sulfonated polyvinylidenefluoride-co-hexafluoropropylene membranes for DMFC application. Solid State Ionics 268:35–41

    Article  CAS  Google Scholar 

  22. Liang YF, Pan HY, Zhu XL, Zhang YX, Jian XG (2007) Studies on synthesis and property of novel acid–base proton exchange membranes. Chin Chem Lett 18:609–612

    Article  CAS  Google Scholar 

  23. Choi JM, Patel R, Han JY, Min Byoung RM (2010) Proton conducting composite membranes comprising sulfonated poly(1,4-phenylene sulfide) and zeolite for fuel cell. Ionics 16:403–408

    Article  CAS  Google Scholar 

  24. Wu H, Cao Y, Shen X, Li Z, Xu T, Jiang Z (2014) Preparation and performance of different amino acids functionalized titania-embedded sulfonated poly (ether ether ketone) hybrid membranes for direct methanol fuel cells. J Membr Sci 463:134–144

    Article  CAS  Google Scholar 

  25. Unveren EE, Inan TY, Çelebi SS (2013) Partially sulfonated poly(1,4‐phenylene ether‐ether‐sulfone) and poly(vinylidene fluoride) blend membranes for fuel cells. Fuel Cells 13:862–872

    CAS  Google Scholar 

  26. Hong YT, Lee CH, Park HS, Min KA, Kim HJ, Nam SY, Lee YM (2008) Improvement of electrochemical performances of sulfonated poly(arylene ether sulfone) via incorporation of sulfonated poly(arylene ether benzimidazole). J Power Sources 175:724–731

    Article  CAS  Google Scholar 

  27. Kumar S, Rath T, Mahaling RN, Reedy CS, Das CK, Pandey KN, Srivastava RB, Yadaw SB (2007) Study on mechanical morphological and electrical properties of carbon nanofiber/polyetherimide composites. Mat Sci Eng B-Solid 141:61–70

    Article  CAS  Google Scholar 

  28. Chen P, Chen X, An Z (2012) Covalently and ionically crosslinked sulfonated poly(arylene ether ketone)s as proton exchange membranes. Polym Bull 68:1369–1386

    Article  CAS  Google Scholar 

  29. Gohil GS, Nagarale RK, Binsu VV, Shahi VK (2006) Preparation and characterization of monovalent cation selective sulfonated poly(ether ether ketone) and poly(ether sulfone) composite membranes. J Colloid Interf Sci 29:845–853

    Article  Google Scholar 

  30. Gupta D, Choudhary V (2013) Non-fluorinated hybrid composite membranes based on polyethylene glycol functionalized polyhedral oligomeric silsesquioxane [PPOSS] and sulfonated poly(ether ether ketone) [SPEEK] for fuel cell applications. React Funct Polym 73:1268–1280

    Article  CAS  Google Scholar 

  31. Feng S, Shen K, Wang Y, Pang J, Jiang Z (2013) Concentrated sulfonated poly (ether sulfone)s as proton exchange membranes. J Power Sources 224:42–49

    Article  CAS  Google Scholar 

  32. Ilbeygi H, Ismail AF, Mayahi A, Nasef MM, Jaafar J, Jalalvandi E (2013) Transport properties and direct methanol fuel cell performance of sulfonated poly (ether ether ketone)/Cloisite/triaminopyrimidine nanocomposite polymer electrolyte membrane at moderate temperature. Sep Purif Technol 118:567–575

    Article  CAS  Google Scholar 

  33. Woo Y, Oh SY, Kang YS, Jung B (2003) Synthesis and characterization of sulfonated polyimide membranes for direct methanol fuel cell. J Membr Sci 220:31–45

    Article  CAS  Google Scholar 

  34. Madaeni SS, Amirinejad S, Amirinejad M (2011) Phosphotungstic acid doped poly (vinyl alcohol)/poly (ether sulfone) blend composite membranes for direct methanol fuel cells. J Membr Sci 380:132–137

    Article  CAS  Google Scholar 

  35. Ismail AF, Othman NH, Mustafa A (2009) Sulfonated polyether ether ketone composite membrane using tungstosilicic acid supported on silica–aluminium oxide for direct methanol fuel cell (DMFC). J Membr Sci 329:18–29

    Article  CAS  Google Scholar 

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Correspondence to A. Nagendran.

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Neelakandan, S., Kanagaraj, P., Sabarathinam, R.M. et al. SPEES/PEI-based highly selective polymer electrolyte membranes for DMFC application. J Solid State Electrochem 19, 1755–1764 (2015). https://doi.org/10.1007/s10008-015-2784-0

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  • DOI: https://doi.org/10.1007/s10008-015-2784-0

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