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Phosphonated mesoporous silica based composite membranes for high temperature proton exchange membrane fuel cells

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Abstract

Mesoporous Santa Barbara Amorphous (SBA-15) was synthesized, and it was grafted with phosphonate functionality using a simple two-step process involving chloromethylation and subsequent phosphonation. The phosphonated SBA-15 (PSBA-15) was characterized using Fourier transform infra-red (FTIR) spectroscopy, solid-state 13C nuclear magnetic resonance (NMR), 29Si NMR, and 31P NMR for confirming successful modification. Morphology features were verified by small angle X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy TEM analyses. Poly(styrene-ethylene-butylene-styrene) (PSEBS) was chosen as the base polymer and phosphonic acid functional groups were grafted onto the polymer using the aforementioned approach, where chloromethyl (-CH2Cl) groups were attached to the main chain using Friedel Craft’s alkylation, followed by the phosphonation of the chloromethylated polymer by the Michaels-Arbuzov reaction resulting in phosphonated PSEBS (PPSEBS). The functionalization was confirmed using NMR and FTIR spectroscopy studies. Composite PPSEBS/PSBA-15 membranes were fabricated with different filler concentrations (2, 4, 6, and 8%) of PSBA-15. Various studies such as water uptake, ion exchange capacity, and the proton conductivity of the composite membranes were undertaken with respect to fuel cell applications. From the studies, it was found that the PPSEBS/PSBA-15 membrane with 6 wt% of filler exhibited maximum proton conductivity of 8.62 mS/cm at 140 °C. Finally, membrane electrode assembly (MEA) was fabricated using PPSEBS/6% PSBA composite membrane, platinium (Pt) anode, and Pt cathode, and was tested in an in-house built fuel cell setup. A maximum power density of 226 mW/cm2 and an open circuit voltage of 0.89 V were achieved at 140 °C under un-humidified condition.

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References

  1. Chandan A, Hattenberger M, El-kharouf A, Du S, Dhir A, Self V (2013) High temperature (HT) polymer electrolyte membrane fuel cells (PEMFC) a review. J Power Sources 231:264–278

    Article  CAS  Google Scholar 

  2. Zhang L, Chae S-R, Hendren Z, Park J-S, Wiesner MR (2012) Recent advances in proton exchange membranes for fuel cell applications. Chem Eng J 206:87–97

    Article  CAS  Google Scholar 

  3. Zhengbang W, Haolin T, Mu P (2011) Self-assembly of durable Nafion / TiO 2 nanowire electrolyte membranes for elevated-temperature PEM fuel cells. J Membr Sci 369:250–257

    Article  CAS  Google Scholar 

  4. Li Q, Jensen JO, Savinell RF, Bjerrum NJ (2009) High temperature proton exchange membranes based on polybenzimidazoles for fuel cells. Prog Polym Sci 34:449–477

    Article  CAS  Google Scholar 

  5. Bose S, Kuila T, Nguyen TXH, Kim NH, Lau K, Lee JH (2011) Polymer membranes for high temperature proton exchange membrane fuel cell: recent advances and challenges. Prog Polym Sci 36:813–843

    Article  CAS  Google Scholar 

  6. Nunes S, Ruffmann B, Rikowski E, Vetter S, Richau K (2002) Inorganic modification of proton conductive polymer membranes for direct methanol fuel cells. J Membr Sci 203:215–225

    Article  CAS  Google Scholar 

  7. Jin Y, Qiao S, Zhang L, Xu ZP, Smart S, da Costa JCD, Lu GQ (2008) Novel Nafion composite membranes with mesoporous silica nanospheres as inorganic fillers. J Power Sources 185:664–669

    Article  CAS  Google Scholar 

  8. Erog I (2009) Preparation and characterization of sulfonated polysulfone / titanium dioxide composite membranes for proton exchange membrane fuel cells. Int J Hydrogen Energy 34:3467–3475

    Article  CAS  Google Scholar 

  9. Amjadi M, Rowshanzamir S, Peighambardoust SJ, Hosseini MG, Eikani MH (2010) Investigation of physical properties and cell performance of Nafion/TiO2 nanocomposite membranes for high temperature PEM fuel cells. Int J Hydrog Energy 35:9252–9260

    Article  CAS  Google Scholar 

  10. Alberti G, Casciola M (2003) Composite membranes for medium temperature pem fuel cells. Annu Rev Mater Res 33:129–154

    Article  CAS  Google Scholar 

  11. Yamada M, Honma I (2004) Anhydrous protonic conductivity of a Self-assembled acid - base composite material. J Phys Chem B 108:5522–5526, 18

    Article  CAS  Google Scholar 

  12. Wu D, Xu T, Wu L, Wu Y (2009) Hybrid acid – base polymer membranes prepared for application in fuel cells. J Power Sources 186:286–292

    Article  CAS  Google Scholar 

  13. Schuster M, Rager T, Noda A, Kreuer KD, Maier J (2005) About the choice of the protogenic group in PEM separator materials for intermediate temperature, low humidity operation: a critical comparison of sulfonic acid, phosphonic acid and imidazole functionalized model compounds. Fuel Cells 5:355–365

    Article  CAS  Google Scholar 

  14. Lafitte B, Jannasch P (2007) On the prospects for Phosphonated polymers as proton-exchange fuel cell membranes. Adv Fuel Cells 1:119–185

    Article  CAS  Google Scholar 

  15. Jun Y, Zarrin H, Fowler M, Chen Z (2011) Functionalized titania nanotube composite membranes for high temperature proton exchange membrane fuel cells. Int J Hydrog Energy 36:6073–6081

    Article  CAS  Google Scholar 

  16. Nurhan U, Yagmur O, Yılser D (2017) Polybenzimidazole based nanocomposite membranes with enhanced proton conductivity for high temperature PEM fuel cells. Int J Hydrog Energy 42:2648–2657

    Article  CAS  Google Scholar 

  17. Tripathi BP, Shahi VK (2011) Organic – inorganic nanocomposite polymer electrolyte membranes for fuel cell applications. Prog Polym Sci 36:945–979

    Article  CAS  Google Scholar 

  18. Hong L, Oh S, Matsuda A, Lee C, Kim D (2011) Hydrophilic and mesoporous SiO 2 – TiO 2 – SO 3 H system for fuel cell membrane applications. Electro chimica Acta 56:3108–3114

    Article  CAS  Google Scholar 

  19. Meenakshi S, Sahu AK, Bhat SD, Sridhar P, Pitchumani S, Shukla AK (2013) Mesostructured-aluminosilicate-Nafion hybrid membranes for direct methanol fuel cells. Electrochim Acta 89:35–44

    Article  CAS  Google Scholar 

  20. Jiang SP (2014) Functionalized mesoporous structured inorganic materials as high temperature proton exchange membranes for fuel cells. Jour Mat Chem A 2:7637–7655

    Article  CAS  Google Scholar 

  21. Park SJ, Lee DH, Kang YS (2010) High temperature proton exchange membranes based on triazoles attached onto SBA-15 type mesoporous silica. J Membr Sci 357:1–5

    Article  CAS  Google Scholar 

  22. Wu J, Cui Z, Zhao C, Li H, Zhang Y, Fu T (2009) High proton conductive advanced hybrid membrane based on sulfonated Si-SBA-15. Int J Hydrog Energy 34:6740–6748

    Article  CAS  Google Scholar 

  23. Won J, Lee H, Yoon K, Taik Y, Lee S (2012) Sulfonated SBA-15 mesoporous silica-incorporated sulfonated poly (phenylsulfone) composite membranes for low-humidity proton exchange membrane fuel cells : anomalous behavior of humidity-dependent proton conductivity. Int J Hydrog Energy 37:9202–9921

    Article  CAS  Google Scholar 

  24. Jiang B, Haolin T, Mu P (2011) Well-ordered sulfonated silica electrolyte with high proton conductivity and enhanced selectivity at elevated temperature for DMFC. Intl J Hyd energy 37:4612–4618

    Google Scholar 

  25. Lafitte B, Jannasch P (2005) Phosphonation of polysulfones via lithiation and reaction with chlorophosphonic acid esters. J Polym Sci Part A Polym Chem 43:273–286

    Article  CAS  Google Scholar 

  26. Allcock HR, Hofmann MA, Ambler CM, Morford R V (2012) Phenylphosphonic acid functionalized poly [aryloxyphosphazenes]. Macromolecules 35:3484–3489

  27. Abu-thabit NY, Ali SA, Zaidi SMJ (2010) New highly phosphonated polysulfone membranes for PEM fuel cells. J Membr Sci 360:26–33

    Article  CAS  Google Scholar 

  28. Parvole J, Jannasch P (2008) Poly(arylene ether sulfone)s with phosphonic acid and bis(phosphonic acid) on short alkyl side chains for proton-exchange membranes. J Mater Chem 18:5547–5556

    Article  CAS  Google Scholar 

  29. Matsumura S, Hlil AR, Lepiller C, Gaudet J, Guay D, Shi Z (2008) Ionomers for proton exchange membrane fuel cells with sulfonic acid groups on the end-groups: novel branched poly(ether-ketone)s. Macromolecules 41:281–284

    Article  CAS  Google Scholar 

  30. Wang Y, Zhu L, Guo B, Chen S, Wu W (2014) Mesoporous silica SBA-15 functionalized with phosphonate derivatives for uranium uptake. New J Chem 14:3853–3861

    Article  Google Scholar 

  31. Vijayakumar E, Dharmalingam S (2015) A quaternized mesoporous silica/polysulfone composite membrane for an efficient alkaline fuel cell application. RSC Adv 5:42828–42835

    Article  CAS  Google Scholar 

  32. Vijayakumar E, Raja A, Madhubala G, Dharmalingam S (2018) A synthesis study of phosphonated PSEBS for high temperature proton exchange membrane fuel cells. J Appl Polym Sci 135:45954–45959

    Article  CAS  Google Scholar 

  33. Vijayakumar E, Dharmalingam S (2016) Synthesis characterization and performance evaluation of ionic liquid immobilized SBA-15 /quaternised polysulfone composite membrane for alkaline fuel cell. Microporous Mesoporous Mater 236:260–268

  34. Vijayakumar E, Dharmalingam S (2018) Anion exchange composite membrane based on octa quaternary ammonium polyhedral oligomeric Silsesquioxane for alkaline fuel cells. J Power Sources 375:412–420

    Article  CAS  Google Scholar 

  35. Srivastava R (2007) An efficient, eco-friendly process for aldol and Michael reactions of trimethylsilyl enolate over organic base-functionalized SBA-15 catalysts. J Mol Catal A Chem 264:146–152

    Article  CAS  Google Scholar 

  36. Mistry B (2009) A handbook of spectroscopic data chemistry (UV, IR, PMR, 13CNMR and mass spectroscopy). Oxford Book Company, London

    Google Scholar 

  37. Chem JM, Chen S, Huang C, Yokoi T, Tang C, Huang S (2012) Synthesis and catalytic activity of amino-functionalized SBA-15 materials with controllable channel lengths and amino loadings. Mater Chem 22:2233–2243

    Article  Google Scholar 

  38. Ran J, Wu L, Wei B, Chen Y, Xu T (2014) Simultaneous enhancements of conductivity and stability for anion exchange membranes (AEMs) through precise structure design. Sci Rep 4:6486–6491

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  39. Zhang B, Cao Y, Jiang S, Li Z, He G, Wu H (2016) Enhanced proton conductivity of Nafion nanohybrid membrane incorporated with phosphonic acid functionalized graphene oxide at elevated temperature and low humidity. J Membr Sci 518:243–253

    Article  CAS  Google Scholar 

  40. Qian W, Shen C, Gao S, Xiang J (2017) Phosphonic acid functionalized siloxane crosslinked with 3-glycidoxyproyltrimethoxysilane grafted polybenzimidazole high temperature proton exchange membranes. J Appl Polym Sci 134:1–10

    Article  CAS  Google Scholar 

  41. Jiang Z, Zheng X, Wu H, Wang J, Wang Y (2008) Proton conducting CS/P(AA-AMPS) membrane with reduced methanol permeability for DMFCs. J Power Sources 180:143–153

    Article  CAS  Google Scholar 

Download references

Funding

This work was financially supported by the Council of Scientific and Industrial Research (CSIR), New Delhi, India (Vide letter No. 01(2452)/11/EMR-11, letter dated 16.05.2011), Science and Engineering Board (SERB), New Delhi, India (Vide file No. EMR/2016/005615), and Center for Technology Development and Transfer (CTDT) Anna University.

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  1. Department of Mechanical Engineering, Anna University, Chennai, 600 025, India

    Vijayakumar Elumalai, Saranya Rathinavel, Raja Annapooranan, Madhubala Ganapathikrishnan & Dharmalingam Sangeetha

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  1. Vijayakumar Elumalai
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  2. Saranya Rathinavel
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  3. Raja Annapooranan
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  4. Madhubala Ganapathikrishnan
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  5. Dharmalingam Sangeetha
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Correspondence to Dharmalingam Sangeetha.

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Elumalai, V., Rathinavel, S., Annapooranan, R. et al. Phosphonated mesoporous silica based composite membranes for high temperature proton exchange membrane fuel cells. J Solid State Electrochem 23, 1837–1850 (2019). https://doi.org/10.1007/s10008-019-04290-w

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