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Improved properties of sulfonated octaphenyl polyhedral silsequioxane cross-link with highly sulfonated polyphenylsulfone as proton exchange membrane

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Abstract

This study explored the concept of improving the properties of the cross-linked membrane using a 1.5-nm closed cage octaphenyl polyhedral silsesquioxane (POSS) form of nanosilica carrying the sulfonic acid group. POSS functioned with SO3H groups (SPOSS) at 0, 1, 2, and 5 wt% were cross-linked with water-soluble sulfonated polyphenylsulfone (SPPSU) polymer. The cross-linking between SPPSU and SPOSS was accomplished through the interchain condensation of sulfonic acid functionalities initiated by thermal curing treatment. In this study, a covalently cross-linked membrane was obtained under stepwise thermal curing from 80 to 180 °C. Upon curing at 180 °C, the SPPSU-SPOSS showed considerable improvement on the membrane proton conductivity under low and high RH (%) conditions compared with the pristine SPPSU membrane. The membrane proton conductivity shows similar patterns with the membrane water uptake as the presence of water greatly influences the cross-linked membrane. The proton conductivity of the SPPSU cross-linked with 1 wt% SPOSS that was conducted under low RH (%) and at elevated temperature exhibited about six times higher proton conductivity as compared with pristine SPPSU membrane. However, increasing the loading of SPOSS beyond 1 wt% significantly dropped the membrane water uptake and proton conductivity due to SPOSS aggregation, blocking the hydrophilic domains in the polymer matrix. The results indicated that the incorporation of SPOSS in the SPPSU membrane by curing at 180 °C exhibit improvement on membrane water management and proton conductivity as compared with the pristine SPPSU membrane.

Schematic diagram of proton transportation mechanisms in the SPPSU-SPOSS composite membranes

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References

  1. Kirubakaran A, Jain S, Nema RK (2009) A review on fuel cell technologies and power electronic interface. Renew Sust Energ Rev 13(9):2430–2440

    Article  CAS  Google Scholar 

  2. Miyake J, Taki R, Mochizuki T, Shimizu R, Akiyama R, Uchida M, Miyatake K (2017) Design of flexible polyphenylene proton conducting membrane for next generation fuel cells. Sci Adv 3:1–8

    Article  Google Scholar 

  3. Muhmed SA, Nor NAM, Jaafar J, Ismail AF, Othman MHD, Rahman MA, Aziz F, Yusof N (2019) Emerging chitosan and cellulose green materials for ion exchange membrane fuel cell: a review. Energy Ecol Environ 2019:1–23

    Google Scholar 

  4. Tada M, Uruga T, Iwasawa Y (2015) Key factors affecting the performance and durability of cathode electrocatalysts in polymer electrolyte fuel cells characterized by in situ real time and spatially resolved XAFS techniques. Catal Lett 145(1):58–70

    Article  CAS  Google Scholar 

  5. Kyu T, Nazir NA (2013) Supramolecules impregnated proton electrolyte membranes. Curr Opin Chem Eng 2(1):132–138

    Article  Google Scholar 

  6. Park JW, Wycisk R, Pintauro PN, Yarlagadda V, Nguyen TV (2016) Electrospun nafion®/polyphenylsulfone composite membranes for regenerative hydrogen bromine fuel cells. Materials 9:1–15

    Google Scholar 

  7. Urena N, Perez-Prior MT, Rio CD, Varez A, Sanchez JY, Iojoiu C, Levenfeld B (2019) Multiblock copolymers of sulfonated PSU/PPSU poly (ether sulfone) s as solid electrolytes for proton exchange membrane fuel cells. Electrochim Acta 302:428–440

    Article  CAS  Google Scholar 

  8. Kim YS, Pivovar BS (2010) Moving beyond mass-based parameters for conductivity analysis of sulfonated polymers. Annu Rev Chem Biomol Eng 1(1):123–148

    Article  CAS  Google Scholar 

  9. Kim JD, Ghil LJ (2016) Annealing effect of highly sulfonated polyphenylsulfone polymer. Int J Hydrog Energy 41(27):11794–11800

    Article  CAS  Google Scholar 

  10. Kamel MSA, Mohamed HFM, Abdel-Hamed MO, Abdel-Hady EE (2019) Characterization and evaluation of nafion HP jpJPs proton exchange membrane: transport properties, nanostructure, morphology, and cell performance. J Solid State Electrochem 23(9):2639–2656

    Article  CAS  Google Scholar 

  11. Zhang J, Chen F, Ma X, Guan X, Chen D, Hickner MA (2015) Sulfonated polymers containing polyhedral oligomeric silsesquioxane (POSS) core for high performance proton exchange membranes. Int J Hydrog Energy 40(22):7135–7143

    Article  CAS  Google Scholar 

  12. Zheng Y, Ash U, Pandey RP, Ozioko AG, Ponce-Gonzalez J, Handl M, Weissbach T, Varcoe JR, Holdcraft S, Liberatore MW, Hiesgen R, Dekel DR (2018) Water uptake study of anion exchange membranes. Macromolecules 51(9):3264–3278

    Article  CAS  Google Scholar 

  13. Mazzapioda L, Panero S, Navarra MA (2019) Polymer electrolyte membranes based on nafion and a superacidic inorganic additive for fuel cell application. Polymers 11(5):914 (1-10)

    Article  CAS  Google Scholar 

  14. Yen YC, Ye YS, Cheng CC, Lu CH, Tsai LD, Huang JM, Chang FC (2010) The effect of sulfonic acid groups within a polyhedral oligomeric silsesquioxane containing cross-linked proton exchange membrane. Polymer 51(1):84–91

    Article  CAS  Google Scholar 

  15. Salarizadeh P, Javanbakht M, Pourmahdian S (2017) Enhancing the performance of speek polymer electrolyte membranes using functionalized TiO2 nanoparticles with proton hopping sites. RSC Adv 7(14):8303–8313

    Article  CAS  Google Scholar 

  16. Shi S, Chen G, Wang Z, Chen X (2013) Mechanical properties of nafion 212 proton exchange membrane subjected to hygrothermal aging. J Power Sources 238:318–323

    Article  CAS  Google Scholar 

  17. Kim K, Heo P, Hwang W, Baik JH, Sung YE, Lee JC (2018) Cross-linked sulfonated poly (arylene ether sulfone) containing a flexible and hydrophobic bishydroxy perfluoropolyether cross-linker for high-performance proton exchange membrane. Appl Mater Interfaces 10(26):21788–21793

    Article  CAS  Google Scholar 

  18. Mokhtaruddin SR, Mohamad AB, Loh KS, Kadhum AAH (2016) Thermal properties and conductivity of nafion-zirconia composite membrane. Malays J Anal Sci 20(3):670–677

    Article  Google Scholar 

  19. Awang N, Jaafar J, Ismail AF (2018) Thermal stability and water content study of void free electrospun speek/cloisite membrane for direct methanol fuel cell application. Polymers 10:1–16

    Article  Google Scholar 

  20. Matsushita S, Kim JD (2018) Organic solvent-free preparation of electrolyte membranes with high proton conductivity using aromatic hydrocarbon polymers and small cross-linker molecules. Solid State Ionics 316:102–109

    Article  CAS  Google Scholar 

  21. Wu Y, Li L, Feng S, Liu H (2013) Hybrid Nanocomposite based on novolac resin and octa (phenyl) polyhedral oligomeric silsesquioxanes (POSS): miscibility, specific interactions, and thermomechanical properties. Polym Bull 70(12):3261–3277

    Article  CAS  Google Scholar 

  22. Lee CH, Park HB, Lee YM, Lee RD (2005) Importance of proton conductivity measurement in polymer electrolyte membrane for fuel cell application. Ind Eng Chem Res 44(20):7617–7626

    Article  CAS  Google Scholar 

  23. Khabibullin A, Minteer SD, Zharov I (2014) The effect of sulfonic acid group content in pore-filled silica colloidal membranes on their proton conductivity and direct methanol fuel cell performance. J Mater Chem A 2(32):12761–12769

    Article  CAS  Google Scholar 

  24. Kim SW, Choi SY, Rhee HW (2018) A novel sPEEK nanocomposite membrane with wee-controlled sPOSS aggregation in tunable nanochannels for past proton conduction. Nanoscales 10(38):18217–18227

    Article  CAS  Google Scholar 

  25. Yameen B, Kaltbeitzel A, Glasser G, Langner A, Muller F, Gosele U, Knoll W, Azzaroni O (2010) Hybrid polymer-silicon proton conducting membranes via a pore-filing surface-initiated polymerization approach. ACS Appl Mater Interfaces 2(1):279–287

    Article  CAS  Google Scholar 

  26. Sengupta S, Lyulin AV (2018) Molecular dynamics simulations of substrate hydrophilicity and confinement effects in capped nafion films. J Phys Chem B 122(22):6107–6119

    Article  CAS  Google Scholar 

  27. Francia C, Ijeri VS, Specchia S, Spinelli P (2011) Estimation of hydrogen crossover through nafion membranes in PEMFCs. J Power Sources 196(4):1833–1839

    Article  CAS  Google Scholar 

  28. O’Hayre R, Cha S, Colella W, Prinz FB (2009) Fuel cell fundamentals, Second edn. Wiley, New York

    Google Scholar 

  29. Niya SMR, Hoorfar M (2014) Process modelling of the ohmic loss in proton exchange membrane fuel cells. Electrochim Acta 120:193–203

    Article  CAS  Google Scholar 

Download references

Acknowledgments

The authors would like to express their gratitude to the Ministry of Higher Education (MOHE), Universiti Teknologi Malaysia (UTM) and Research Management Centre (RMC), UTM, for supporting the research management activities. The authors would also like to acknowledge support by the International Cooperative Graduate School (ICGS) Fellowship under the “Universiti Teknologi Malaysia-NIMS Cooperative Graduate School Program” to conduct research in the National Institute of Materials Science (NIMS), Tsukuba, Japan.

Funding

This work was supported by Ministry of Higher Education (MOHE) under project grant MRUN (R.J130000.7851.4L880) and Universiti Teknologi Malaysia (UTMPR:Q.J130000.2851.00L22, UTM-TDR:Q.J130000.3551.06G88). This work also was supported by the MEXT Program for the Development of Environmental Technology using Nanotechnology.

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Authors and Affiliations

  1. Hydrogen Production Materials Group, Center for Green Research on Energy and Environmental Materials, National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki, 305-0044, Japan

    Nor Azureen Mohamad Nor & Je-Deok Kim

  2. Polymer Electrolyte Fuel Cell Group, Global Research Center for Environmental and Energy based on Nanomaterials Science (GREEN), National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki, 305-0044, Japan

    Nor Azureen Mohamad Nor & Je-Deok Kim

  3. Advanced Membrane Technology Research Centre (AMTEC), School of Chemical & Energy Engineering, Faculty of Engineering, Universiti Teknologi Malaysia, 81310, Skudai, Johor, Malaysia

    Nor Azureen Mohamad Nor & Juhana Jaafar

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  1. Nor Azureen Mohamad Nor
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  2. Juhana Jaafar
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Correspondence to Juhana Jaafar or Je-Deok Kim.

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Nor, N.A.M., Jaafar, J. & Kim, JD. Improved properties of sulfonated octaphenyl polyhedral silsequioxane cross-link with highly sulfonated polyphenylsulfone as proton exchange membrane. J Solid State Electrochem 24, 1185–1195 (2020). https://doi.org/10.1007/s10008-020-04594-2

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  • DOI: https://doi.org/10.1007/s10008-020-04594-2

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