Skip to main content
SpringerLink
Log in

Fabrication and characterization of graphene/sulfonated polyether sulfone octyl sulfonamide hybrid film with improved proton conductivity performance

  • Original Paper
  • Published:
Journal of Solid State Electrochemistry Aims and scope Submit manuscript

Abstract

In this study, graphene (G) was blended with sulfonated polyether sulfone octyl sulfonamide (SPESOS) in different ratios (1, 1.5, and 2 wt.%) to enhance the proton conductivity of SPESOS. The results of the water absorption analysis and current impedance spectroscopy of a G/SPESOS hybrid film showed that the proton conductivity improved due to the hydrophilic-hydrophobic nature of the hybrid. Further analysis showed that the synthesized hybrid film had a desirable contact angle and good ion exchange capacity, water absorption, and thermal stability. The hybrid film with 2 wt.% graphene showed better proton conductivity (92 mS/cm) than the pristine SPESOS film (34 mS/cm) at 100% relative humidity. These results suggested that the synthesized hybrid films offered superior proton conductivity, ion exchange capacity, and hydrophilicity compared to pristine SPESOS.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6

Similar content being viewed by others

References

  1. Sahu AK, Ketpang K, Shanmugam S, Kwon O, Lee SC, Kim H (2016) Sulfonated graphene-Nafion hybrid films for polymer electrolyte fuel cells operating under reduced relative humidity. J Phys Chem C120(29):15855–15866. https://doi.org/10.1021/acs.jpcc.5b11674

  2. Vinothkannan M, Kim AR, Nahm KS, Yoo DJ (2016) Ternary hybrid (SPEEK/SPVdF-HFP/GO) based film electrolyte for the applications of fuel cells: profile of improved mechanical strength, thermal stability and proton conductivity. RSC Adv 6(110):108851–108863. https://doi.org/10.1039/C6RA22295A

  3. Kim AR, Vinothkannan M,Yoo DJ (2018) Sulfonated fluorinated multi-block copolymer hybrid containing sulfonated(poly ether ether ketone) and graphene oxide: a ternary hybrid film architecture for electrolyte applications in proton exchange film fuel cells. J Energy Chem 27(4):1247–1260. https://doi.org/10.1016/j.jechem.2018.02.020

  4. Wu H, Peng T, Kou Z, Cheng K, Zhang J, Zhang J, Meng T, Mu S (2017) In situ constructing of ultrastableceramic@graphene core-shell architectures as advanced metal catalyst supports toward oxygen reduction. J Energy Chem 26(6):1160–1167. https://doi.org/10.1016/j.jechem.2017.08.012

    Article  Google Scholar 

  5. Tian XL, Wang L, Deng P, Chen Y, Xia BY (2017) Research advances in unsupported Pt-based catalysts for electrochemical methanol oxidation. J Energy Chem 26(6):1067–1076. https://doi.org/10.1016/j.jechem.2017.10.009

  6. Neelakandan S, Kaleekkal NJ, Kanagaraj P, Sabarathinam RM, Muthumeenal A, Nagendran A (2016) Effect of sulfonated graphene oxide on the performance enhancement of acid-base hybrid films for direct methanol fuel cells. RSC Adv 6(57):51599–51608. https://doi.org/10.1039/C5RA27655A

    Article  CAS  Google Scholar 

  7. Kim AR, Vinothkannan M, Yoo DJ (2017) Sulfonated-fluorinated copolymer blending films containing SPEEK for use as the electrolyte in polymer electrolyte fuel cell (PEFC). Int J Hydrogen Energy 42(7):4349–4365. https://doi.org/10.1016/j.ijhydene.2016.11.161

    Article  CAS  Google Scholar 

  8. Park CK, Lee CH, Guiver MD, Lee YM (2011) Sulfonated hydrocarbon films for medium-temperature and low-humidity proton exchange film fuel cells (PEMFCs). Prog Polymer Sci 36(11):1443–1498. https://doi.org/10.1016/j.progpolymsci.2011.06.001

    Article  CAS  Google Scholar 

  9. Kreuer KD (2001) On the development of proton conducting polymer films for hydrogen and methanol fuel cells. J Membrane Sci 185(1):29–39. https://doi.org/10.1016/S0376-7388(00)00632-3

  10. Xing P, Robertson GP, Guiver MD, Mikhailenko SD, Kaliaguine S (2005) Synthesis and characterization of poly(aryl ether ketone) copolymers containing (hexafluoroisopropylidene)-diphenol moiety as proton exchange film materials. Polymer 46(10):3257–3263. https://doi.org/10.1016/j.polymer.2005.03.003

  11. Xing P, Robertson GP, Guiver MD, Mikhailenko SD, Wang K, Kaliaguine S (2004) Synthesis and characterization of sulfonated poly(ether ether ketone)forproton exchange films. J Film Sci 229(2):95–106. https://doi.org/10.1016/j.memsci.2003.09.019

    Article  CAS  Google Scholar 

  12. Kim YS, Einsla B, Sankir M, Harrison W, Pivovar BS (2006) Structure–property–performance relationships of sulfonated poly(arylene ether sulfone)s as apolymer electrolyte for fuel cell applications. Polymer 47(11):4026–4035. https://doi.org/10.1016/j.polymer.2006.02.032

  13. Mabrouk W, Ogier L, Matoussi F, Sollogoub C, Vidal S, Dachraoui M, Fauvarque JF (2011) Preparation of new proton exchange films using sulfonated poly (ether sulfone) modified by octylamine (SPESOS). Mater Chem Phys 128(3):456–463. https://doi.org/10.1016/j.matchemphys.2011.03.031

  14. Ahmed Z, Charradi K, Alsulami QA, Keshk SMAS, Chtourou R (2021) Physicochemical characterization of low sulfonated polyether ether ketone/smectite clay hybrid for proton exchange film fuel cells. J Appl Polym Sci 138(1):e49634. https://doi.org/10.1002/app.49634

  15. Charradi K, Ahmed Z, Thmaini N, Aranda P, Al-Ghamdi YO, Ocon P, Keshk SAMS, Chtourou R (2021) Incorporation of layered double hydroxide/sepiolite to improve the performance of sulfonated poly(ether ether ketone) hybridfilms for proton exchange film fuel cells. J Appl Polym Sci 138(19):e50364. https://doi.org/10.1002/app.50364

  16. Mabrouk W, Charradi K, Lafi R, AlSalem HS, Meherzi HM, Keshk SAMS (2022) Incorporation of sepiolite clay within sulfonated polyether sulfone octyl sulfonamide for the augmentation of proton conductivity. J Mater Sci 57(140):15331–15339. https://doi.org/10.1007/s10853-022-07627-5

  17. Mabrouk W, Charradi K, Meherzi HM, Alhussein A, Keshk SAMS (2022) Proton conductivity amelioration of sulfonated poly ether sulfone octyl sulfonamide via the incorporation of Montmorillonite. J Electron Mater 51(139):6369–6378. https://doi.org/10.1007/s11664-022-09862-7

    Article  CAS  Google Scholar 

  18. Pushparaj VL, Shaijumon MM, Kumar A, Murugesan S, Ci L, Vajtai R, Linhardt RJ, Nalamasu O, Ajayan PM (2007) Flexible energy storage devices based on nanohybrid paper. Proc Natl Acad Sci 104(39):13574–13577. https://doi.org/10.1073/pnas.070650810

  19. Chen J, Minett AI, Liu Y, Lynam C, Sherrell P, Wang C, Wallace GG (2008) Direct growth of flexible carbon nanotube electrodes. Adv Mater 20(3):566–570. https://doi.org/10.1002/adma.200701146

    Article  CAS  Google Scholar 

  20. Chou SL, Wang JZ, Chew SY, Liu HK, Dou SX (2008) Electrodeposition of MnO2 nanowires on carbon nanotube paper as free-standing, flexible electrode for supercapacitors. Electrochem Commun 10(11):1724–1727. https://doi.org/10.1016/j.elecom.2008.08.051

  21. Mathew E, Manoj B (2022) Disorders in graphene: types, effects and control techniques-a review. Carbon Lett 32(240):431–450. https://doi.org/10.1007/s42823-021-00289-4

  22. Yoo E, Kim J, Hosono E, Zhou H, Kudo T, Honma I (2008) Large reversible Li storage of graphene nanosheet families for use in rechargeable lithium ion batteries. Nano Lett 8(8):2277–2282. https://doi.org/10.1021/nl800957b

  23. Yin H, Zhang C, Liu F, Hou Y (2014) Hybrid of iron nitride and nitrogen-doped graphene aerogel as synergistic catalyst for oxygen reduction reaction. Adv Funct Mater 24(20):2930–2937. https://doi.org/10.1002/adfm.201303902

    Article  CAS  Google Scholar 

  24. Ye YS, Cheng MY, Xie XL, Rick J, Huang YJ, Chang FC, Hwang BJ (2013) Alkali doped polyvinyl alcohol/graphene electrolyte for direct methanol alkaline fuel cells. J Power Sources 239:424–432. https://doi.org/10.1016/j.jpowsour.2013.03.021

    Article  CAS  Google Scholar 

  25. Wang S, Yu D, Dai L, Chang DW, Baek JB (2011) Polyelectrolyte-functionalizedgraphene as metal-free electrocatalysts for oxygen reduction. ACS Nano 5(8):6202–6209. https://doi.org/10.1021/nn200879h

  26. Yong YC, Dong XC, Chan-Park MB, Song H, Chen P (2012) Macroporous and monolithic-anode based on polyaniline hybridized three-dimensional graphene for high-performance microbial fuel cells. ACS Nano 6(3):2394–2400. https://doi.org/10.1021/nn204656d

    Article  CAS  PubMed  Google Scholar 

  27. Dai W, Yu L, Li Z, Yan J, Liu L, Xi J, Qiu X (2014) Sulfonated poly(ether ether ketone)/graphene hybrid film for vanadium redox flow battery. Electrochi Acta 132:200–207. https://doi.org/10.1016/j.electacta.2014.03.156

  28. Xiaobing H, Hao K, Tao C, Jie G, Yuan Z, Sang Y, Guowen H (2021) Effect of π–π stacking interfacial interaction on the properties of graphene/poly(styrene-b-isoprene-b-styrene) hybrids. Nanomaterials 11(9):2158. https://doi.org/10.3390/nano11092158

    Article  CAS  Google Scholar 

  29. Choi E, Han TH, Hong J, Kim J, Lee SH, Kima HW (2010) Noncovalent functionalization of graphene with end-functional polymers. J Mater Chem 20(9):1907–1912. https://doi.org/10.1039/B919074K

    Article  CAS  Google Scholar 

  30. Mabrouk W, Lafi R, Charradi K, Ogier L, Hafiane A, Fauvarque JF, Sollogoub C (2020) Synthesis and characterization of new proton exchange film deriving sulfonated polyether sulfone using ionic crosslinking electrodialysis applications. Polym Eng Sci 60(12):3149–3158. https://doi.org/10.1002/pen.25543

  31. Charradi K, Ahmed Z, Moussa M, Beji Z, Brahmia A, Othman I, Abu-Haija M, Chtourou R, Keshk SM (2022) A facile approach for the synthesis of zinc ferrite/cellulose as an effective magnetic photocatalyst for the degradation of methylene blue in aqueous solution. Cellulose 29(466):2565–2576‏. https://doi.org/10.1007/s10570-021-04334-3

  32. Bagheri A, Javanbakht M, Beydaghi H, Salarizadeh P, Shabanikiac A, Amoli HS (2016) Sulfonated poly(ether ether ketone) and sulfonated polyvinylidene fluoride-co-hexafluoropropylene based blend proton exchange films for direct methanol fuel cell applications. RSC Adv 6(45):39500–39510. https://doi.org/10.1039/C6RA00038J

  33. Liang L, Shi Z, Tan X, Sun S, Chen M, Dastan D, Dong B, Cao L (2021) Largely improved breakdown strength and discharge efficiency of layer-structured nanocomposites by filling with a small loading fraction of 2D zirconium phosphate nanosheets. Adv Mater Interfaces 9:2101646. https://doi.org/10.1002/admi.202101646

    Article  CAS  Google Scholar 

  34. Zhang M, Shi Z, Zhang J, Zhang K, Lei L, Dastan D, Dong B, Cao L (2021) Greatly enhanced dielectric charge storage capabilities of layered polymer composites incorporated with low loading fractions of ultrathin amorphous iron phosphate nanosheets. J Mater Chem C 9:10414–10424. https://doi.org/10.1039/DITC01974K

    Article  CAS  Google Scholar 

  35. Liu Y, Wang J, Zhang H, Ma C, Liu J, Cao S, Zhang X (2014) Enhancement of proton conductivity of chitosan film enabled by sulfonated graphene oxide under both hydrated and anhydrous conditions. J Power Sources 269:898–911. https://doi.org/10.1016/j.jpowsour.2014.07.075

  36. Mabrouk W, Lafi R, Fauvarque JF, Hafiane A, Sollogoub C (2021) New ion exchange film derived from sulfochloratedpolyether sulfone for electrodialysis desalination of brackish water. Polym Adv Technol 32(1):304–314. https://doi.org/10.1002/pat.5086

    Article  CAS  Google Scholar 

  37. Altaf F, Ahmed S, Dastan D, Batool R, Rehman ZU, Shi Z, Hameed MU, Bocchetta P, Jacob K (2022) Novel sepiolite reinforced emerging composite polymer electrolyte membranes for high-performance direct methanol fuel cells. Mater Today Chem 24:100843. https://doi.org/10.1016/j.mtchem.2022.100843

  38. Zhu P, Dastan D, Liu L, Wu LK, Shi Z, Chu QQ, Altaf F, Mohammed MKA (2023) Surface wettability of various phases of titania thin films: atomic-scale simulation studies. J Mol Graph Model 118:108335. https://doi.org/10.1016/j.jmgm.2022.108335

Download references

Acknowledgements

The authors would like to thank Research and Technology Center of Energy, Technopark Borj Cedria for their support. The authors extend their appreciation to the manager of Eras Labo for providing the SPESOS polymer free of charge.

Author information

Authors and Affiliations

  1. CERTE, Laboratory Water, Films and Biotechnology of the Environment, Water Research and Technologies Center, Technologic Park Borj Cedria, BP 273, Soliman, 8020, Tunisia

    Walid Mabrouk & Ali Boubakri

  2. CERTE, Laboratory of Desalination and Valorization of Natural Water, Water Research and Technologies Center, Technologic Park Borj Cedria, BP 273, Soliman, 2020, Tunisia

    Sonia Jebri

  3. CRTEn, Nanomaterials and Systems for Renewable Energy Laboratory, Research and Technology Center of Energy, Technopark Borj Cedria, BP 095, Hammam Lif, Tunisia

    Khaled Charradi, Bishir Silimi & Sherif. M. A. S. Keshk

  4. KUU, Department of Chemistry, Faculty of Science and Arts, King Khalid University, Mohail Assir, Saudi Arabia

    Abdullah Y. A. Alzahrani

  5. INRAP, National Institute of Research and Physico-Chemical Analysis, Laboratory of Materials, Treatment, and Analysis (LMTA), Sidi Thabet, 2020, Tunisia

    Ouassim Ghodbane

  6. FST, Laboratory of Analytical Chemistry and Electrochemistry, LR99ES15, University of Tunis El Manar Campus, Tunis 2092, Tunisia

    Noureddine Raouafi

Authors
  1. Walid Mabrouk
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Sonia Jebri
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Khaled Charradi
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Bishir Silimi
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Abdullah Y. A. Alzahrani
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Ali Boubakri
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Ouassim Ghodbane
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Noureddine Raouafi
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Sherif. M. A. S. Keshk
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Walid Mabrouk.

Ethics declarations

Conflict of interest

The authors declare no competing interests.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Highlights

• An organic-inorganic hybrid film having potential applications in fuel cells was prepared and characterized.

• Graphene improved the contact angle, water uptake, and other physicochemical properties of hybrid films.

• Hybrid film 2% G/SPESOS exhibited proton conductivity augmentation at elevated temperatures and humidity.

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Mabrouk, W., Jebri, S., Charradi, K. et al. Fabrication and characterization of graphene/sulfonated polyether sulfone octyl sulfonamide hybrid film with improved proton conductivity performance. J Solid State Electrochem 27, 991–999 (2023). https://doi.org/10.1007/s10008-023-05411-2

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10008-023-05411-2

Keywords

Search

Navigation