, Volume 25, Issue 11, pp 5163–5175 | Cite as

Improved performance and durability of sulfonated polyether ether ketone/cerium phosphate composite membrane for proton exchange membrane fuel cells

  • Alpay SahinEmail author
  • H. Mehmet Tasdemir
  • İrfan Ar
Original Paper


In this study, a new cerium phosphate (CePO4)-doped sulfonated polyether ether ketone (SPEEK) composite membranes were synthesized by using solution casting method with different CePO4 loading. Their performance and durability were investigated for proton exchange membranes fuel cells. Different techniques, namely Fourier transform infrared spectroscopy (FT-IR), X-ray powder diffraction (XRD), scanning electron microscopy (SEM), dynamic mechanical tests (DMA), and electrochemical impedance spectroscopy (EIS) analyses were used to characterize the synthesized membranes. Water uptake (WU) and swelling properties as well as ion exchange capacities (IEC) of synthesized membranes were also determined. Fuel cell performance, durability, and Fenton tests for oxidative stability of the synthesized membranes were also investigated. Experimental results showed that addition of CePO4 up to 10% by weight improved the membrane properties. 10 wt% CePO4-doped membrane possessed a good proton conductivity of 0.242 S/cm at 80 °C. Current and power densities of this membrane were obtained as 790 mA/cm2 and 474 mW/cm2, respectively, at 0.6 V cell potential and 80 °C fuel cell temperature. OCV decrement value of this membrane was 5.93%. When the performance and durability properties of 10% CePO4-doped membrane is compared to commercial Nafion membrane, it could be a good alternative for proton exchange membrane fuel cells.


Composite membrane Durability Long-term steady-state test PEMFC OCV variation Sulfonated polyether ether ketone 



This study is supported by Gazi University Scientific Research Fund as BAP 06/2018-02 and BAP 06/2018-06 projects.


  1. 1.
    Cheng J, He G, Zhang F (2015) A mini-review on anion exchange membranes for fuel cell applications: stability issue and addressing strategies. Int J Hydrogen Energ 40:7348–7360Google Scholar
  2. 2.
    Xing Y, Liu L, Wang C, Li N (2018) Side-chain-type anion exchange membranes for vanadium flow battery: properties and degradation mechanism. J Mater Chem A 6:22778–22789Google Scholar
  3. 3.
    Şengül E, Erdener H, Akay GR, Yücel H, Baç N, Eroğlu İ (2009) Effects of sulfonated polyether-etherketone (SPEEK) and composite membranes on the proton exchange membrane fuel cell (PEMFC) performance. Int J Hydrogen Energ 34:4645–4652Google Scholar
  4. 4.
    Devrim Y, Devrim H, Eroğlu İ (2016) Polybenzimidazole/SiO2 hybrid membranes for high temperature proton exchange membrane fuel cells. Int J Hydrogen Energ 41:10444–10052Google Scholar
  5. 5.
    Şahin A, Ar İ (2015) Synthesis, characterization and fuel cell performance tests of boric acid and boron phosphate doped, sulphonated and phosphonated poly(vinyl alcohol) based composite membranes. J Power Sources 288:426–433Google Scholar
  6. 6.
    Zakil FA, Kamarudin SK (2016) Modified Nafion membranes for direct alcohol fuel cells: an overview. Renew Sust Energ Rev 65:841–852Google Scholar
  7. 7.
    Sun P, Li Z, Wang S, Yin X (2018) Performance enhancement of polybenzimidazole based high temperature proton exchange membranes with multifunctional crosslinker and highly sulfonated polyaniline. J Membrane Sci 549:660–669Google Scholar
  8. 8.
    Wang S, Sun P, Li Z, Liu G, Yin X (2018) Comprehensive performance enhancement of polybenzimidazole based high temperature proton exchange membranes by doping with a novel intercalated proton conductor. Int J Hydrogen Energ 43:9994–10003Google Scholar
  9. 9.
    Song M, Lu X, Li Z, Liu G, Yin X, Wang Y (2016) Compatible ionic crosslinking composite membranes based on SPEEK and PBI for high temperature proton exchange membranes. Int J Hydrogen Energ 41:12069–12081Google Scholar
  10. 10.
    Ozden A, Ercelik M, Devrim Y, Colpan CO, Hamdullahpur F (2017) Evaluation of sulfonated polysulfone/zirconium hydrogen phosphate composite membranes for direct methanol fuel cells. Electrochim Acta 256:196–210Google Scholar
  11. 11.
    Jheng LC, Chang WJY, Hsu SLC (2016) Durability of symmetrically and asymmetrically porous polybenzimidazole membranes for high temperature proton exchange membrane fuel cells. J Power Sources 323:57–66Google Scholar
  12. 12.
    Haque MA, Sulong AB, Loh KS, Majlan EH, Husaini T, Rosli ER (2017) Acid doped polybenzimidazoles based membrane electrode assembly for high temperature proton exchange membrane fuel cell: a review. Int J Hydrogen Energ 42:9156–9179Google Scholar
  13. 13.
    Pinar FJ, Canizares P, Rodrigo MA, Úbeda D, Lobato J (2015) Long-term testing of a high-temperature proton exchange membrane fuel cell short stack operated with improved polybenzimidazole-based composite membranes. J Power Sources 274:177–185Google Scholar
  14. 14.
    Parnian MJ, Rowshanzamir S, Gashoul F (2017) Comprehensive investigation of physicochemical and electrochemical properties of sulfonated poly (ether ether ketone) membranes with different degrees of sulfonation for proton exchange membrane fuel cell applications. Energy 125:614–628Google Scholar
  15. 15.
    Lee SY, Woo HS, Song JM, Sohn JY, Shin J (2018) Preparation of crosslinked SPEEK-zirconium phosphate hybrid membranes by electron beam irradiation. Polym Compos 39:1905–1912Google Scholar
  16. 16.
    Kim DJ, Lee BN, Nam SY (2017) Characterization of highly sulfonated PEEK based membrane for the fuel cell application. Int J Hydrogen Energ 42:23768–23775Google Scholar
  17. 17.
    Şahin A (2018) The development of Speek/Pva/Teos blend membrane for proton exchange membrane fuel cells. Electrochim Acta 271:127–136Google Scholar
  18. 18.
    Wang C, Zhou Y, Shen B, Zhou X, Li J, Ren Q (2018) Proton-conducting poly(ether sulfone ketone)s containing a high density of pendant sulfonic groups by a convenient and mild post-sulfonation. Polym Chem 9:4984–4993Google Scholar
  19. 19.
    Erkartal M, Usta H, Citir M, Sen U (2016) Proton conducting poly(vinyl alcohol) (PVA)/poly(2-acrylamido-2-methylpropane sulfonic acid) (PAMPS)/zeolitic imidazolate framework (ZIF) ternary composite membrane. J Membrane Sci 499:156–163Google Scholar
  20. 20.
    Thanganathan U, Nogami M (2015) Investigations on effects of the incorporation of various ionic liquids on PVA based hybrid membranes for proton exchange membrane fuel cells. Int J Hydrogen Energ 40:1935–1944Google Scholar
  21. 21.
    Pandit S, Khilar S, Bera K, Pradhan D, Das D (2014) Application of PVA–PDDA polymer electrolyte composite anion exchange membrane separator for improved bioelectricity production in a single chambered microbial fuel cell. Chem Engineer J 257:138–1347Google Scholar
  22. 22.
    Ebenezer D, Deshpande AP, Haridoss P (2016) Cross-linked poly (vinyl alcohol)/sulfosuccinic acid polymer as an electrolyte/electrode material for H2–O2 proton exchange membrane fuel cells. J Power Sources 304:282–292Google Scholar
  23. 23.
    Boaretti C, Pasquini L, Sood R, Giancola S, Donnadio A, Roso M, Modesti M, Cavaliere S (2018) Mechanically stable nanofibrous sPEEK/Aquivion® composite membranes for fuel cell applications. J Membrane Sci 545:66–74Google Scholar
  24. 24.
    Hou H, Polini R, Vona MLD, Liu X, Sgreccia E, Chailan JF, Knauth P (2013) Thermal crosslinked and nanodiamond reinforced SPEEK composite membrane for PEMFC. Int J Hydrogen Energ 38:3346–3351Google Scholar
  25. 25.
    Bano S, Negi YS, Illathvalappil R, Kurungot S, Ramya K (2019) Studies on nano composites of SPEEK/ethylene glycol/cellulose nanocrystals as promising proton exchange membranes. Electrochim Acta 293:260–272Google Scholar
  26. 26.
    Kim SW, Choi SY, Rhee HW (2018) Sulfonated poly(etheretherketone) based nanocomposite membranes containing POSS-SA for polymer electrolyte membrane fuel cells (PEMFC). J Membrane Sci 566:69–76Google Scholar
  27. 27.
    Ghosh P, Dhole CK, Ganguly S, Banerjee D, Kargupta K (2018) Phosphosilicate gel-sulfonated poly(ether ether ketone) nanocomposite membrane for polymer electrolyte membrane fuel cell. Mater Today: Proceedings 5:2186–2192Google Scholar
  28. 28.
    Karimi A, Kalfati MS, Rowshanzamir S (2019) Investigation, modeling, and optimization of parameters affecting sulfonated polyether ether ketone membrane-electrode assembly. J Hydrogen Energ 44:1096–1109Google Scholar
  29. 29.
    Yang C, Srinivasan S, Bocarsly AB, Tulyani S, Benziger JB (2004) A comparison of physical properties and fuel cell performance of Nafion and zirconium phosphate/Nafion composite membranes. J Membrane Sci 237:144–1461Google Scholar
  30. 30.
    Hou H, Sun G, Wu Z, Jin W, Xin Q (2008) Zirconium phosphate/Nafion115 composite membrane for high-concentration DMFC. Int J Hydrogen Energ 33:3402–3409Google Scholar
  31. 31.
    Mosa J, Larramona G, Duran A, Aparicio M (2008) Synthesis and characterization of P2O5–ZrO2–SiO2 membranes doped with tungstophosphoric acid (PWA) for applications in PEMFC. J Membrane Sci 307:21–27Google Scholar
  32. 32.
    Park KT, Jung UH, Choi DW, Chun K, Lee HM, Kim SH (2008) ZrO2–SiO2/Nafion® composite membrane for polymer electrolyte membrane fuel cells operation at high temperature and low humidity. J Power Sources 177:247–253Google Scholar
  33. 33.
    Uma T, Nogami M (2009) The preparation and characterization of TiO2/ZrO2 composites doped with PMA/PWA. J Ceram Soc Jpn 117:411–414Google Scholar
  34. 34.
    Attaran AM, Javanbakht M, Hooshyari K, Enhessari M (2015) New proton conducting nanocomposite membranes based on poly vinyl alcohol/poly vinyl pyrrolidone/BaZrO3 for proton exchange membrane fuel cells. Solid State Ionics 269:98–105Google Scholar
  35. 35.
    Mohammadi G, Jahanshahi M, Rahimpour A (2013) Fabrication and evaluation of Nafion nanocomposite membrane based on ZrO2-TiO2 binary nanoparticles as fuel cell MEA. Int J Hydrogen Energ 38:9387–9394Google Scholar
  36. 36.
    Yang C (2007) Synthesis and characterization of the cross-linked PVA/TiO2 composite polymer membrane for alkaline DMFC. J Membrane Sci 288:51–60Google Scholar
  37. 37.
    Lobato J, Canizares P, Rodrigo MA, Ubeda D, Pinar FJ (2011) A novel titanium PBI-based composite membrane for high temperature PEMFCs. J Membrane Sci 369:105–111Google Scholar
  38. 38.
    Jian-hua T, Peng-fei G, Zhi-yuan Z, Wen-hui L, Zhong-qiang S (2008) Preparation and performance evaluation of a Nafion-TiO2 composite membrane for PEMFCs. Int J Hydrogen Energ 33:5686–5690Google Scholar
  39. 39.
    Santiago EI, Isidoro RA, Dresch MA, Matos BR, Linardi M, Fonseca FC (2009) Nafion–TiO2 hybrid electrolytes for stable operation of PEM fuel cells at high temperature. Electrochimi Acta 54:4111–4117Google Scholar
  40. 40.
    Gandhi K, Dixit BK, Dixit DK (2012) Effect of addition of zirconium tungstate, lead tungstate and titanium dioxide on the proton conductivity of polystyrene porous membrane. Int J Hydrogen Energ 37:3922–3930Google Scholar
  41. 41.
    Kumar KS, Rajendran S, Prabhu MR (2017) A study of influence on sulfonated TiO2-poly (vinylidene fluoride-co-hexafluoropropylene) nano composite membranes for PEM fuel cell application. Appl Surf Sci 418:64–71Google Scholar
  42. 42.
    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 Hydrogen Energ 35:9250–9260Google Scholar
  43. 43.
    Kim DS, Park HB, Rhim JW, Lee YM (2004) Preparation and characterization of crosslinked PVA/SiO2 hybrid membranes containing sulfonic acid groups for direct methanol fuel cell applications. J Membrane Sci 240:37–48Google Scholar
  44. 44.
    Lavorgna M, Mascia L, Mensitieri G, Gilbert M, Sherillo G, Palomba B (2007) Hybridization of Nafion membranes by the infusion of functionalized siloxane precursors. J Membrane Sci 294:159–168Google Scholar
  45. 45.
    Le MV, Tsai DS, Yang CY, Chung WH, Lee HY (2011) Proton conductors of cerium pyrophosphate for intermediate temperature fuel cell. Electrochimi Acta 56:6654–6660Google Scholar
  46. 46.
    Sun P, Li Z, Dong F, Wang S, Yin X, Wang Y (2017) High temperature proton exchange membranes based on cerium sulfophenyl phosphate doped polybenzimidazole by end-group protection and hot-pressing method. Int J Hydrogen Energ 42:486–495Google Scholar
  47. 47.
    Jiang Y, Matthieu T, Lan R, Xu X, Cowin PI, Tao S (2011) A stable NH4PO3-glass proton conductor for intermediate temperature fuel cells. Solid State Ionics 192:108–112Google Scholar
  48. 48.
    Sun C, Stimming U (2008) Synthesis and characterization of NH4PO3 based composite with superior proton conductivity for intermediate temperature fuel cells. Electrochimi Acta 53:6417–6422Google Scholar
  49. 49.
    Jin Y, Shen Y, Hibino T (2010) Proton conduction in metal pyrophosphates (MP2O7) at intermediate temperatures. J Mater Chem 20:6214–6217Google Scholar
  50. 50.
    Hogarth WHJ, Muir SS, Whittaker AJ, Costa JCD, Drennan J, Lu GQ (2007) Proton conduction mechanism and the stability of sol–gel titanium phosphates Warren. Solid State Ionics 177:3389–3394Google Scholar
  51. 51.
    Al-Othmana A, Tremblaya AY, Pell W, Letaief S, Burchell TJ, Peppley BA, Ternane M (2010) Zirconium phosphate as the proton conducting material in direct hydrocarbon polymer electrolyte membrane fuel cells operating above the boiling point of water. J Power Sources 195:2520–2525Google Scholar
  52. 52.
    Dong F, Li Z, Wang S, Wang Z (2011) Synthesis and characteristics of proton-conducting membranes based on cerium sulfophenyl phosphate and poly (2,5-benzimidazole) by hot-pressing method. Int J Hydrogen Energ 26:11068–11074Google Scholar
  53. 53.
    Liu CP, Dai CA, Chao CY, Chang SJ (2014) Novel proton exchange membrane based on crosslinked poly(vinyl alcohol) for direct methanol fuel cells. J Power Sources 249:285–298Google Scholar
  54. 54.
    Pandey J, Mir FQ, Shukla A (2014) Synthesis of silica immobilized phosphotungstic acid (Si-PWA)-poly(vinyl alcohol) (PVA) composite ion-exchange membrane for direct methanol fuel cell. Int Hydrogen Energ 39:9473–9481Google Scholar
  55. 55.
    Liu Z, Yang Y, Lu W, Wang C, Chen M, Mao Z (2012) Durability test of PEMFC with Pt-PFSA composite membrane. Int J Hydrogen Energ 37:956–960Google Scholar
  56. 56.
    Wu B, Zhao M, Shi W, Liu W, Liu J, Xing D, Yao Y, Hou Z, Ming P, Gu J, Zou Z (2014) The degradation study of Nafion/PTFE composite membrane in PEM fuel cell under accelerated stress tests. Int J Hydrogen Energ 39:14381–14390Google Scholar
  57. 57.
    Xiao S, Zhang H, Li X, Mai Z (2011) Investigation of the differences between the in situ open circuit voltage test and ex situ Fenton test for PEM oxidation characterization. Int J Hydrogen Energ 3:10934–10939Google Scholar
  58. 58.
    Ghassemzadeha L, Kreuera KD, Maiera J, Müller K (2011) Evaluating chemical degradation of proton conducting perfluorosulfonic acid ionomers in a Fenton test by solid state 19F NMR spectroscopy. J Power Sources 196:2490–2497Google Scholar
  59. 59.
    Ali AF, Hanna AA, Gad AE (2008) Synthesis of α-zirconium phosphate from acetyl acetonate solution; a comparative synthesis study of α-ZrP. Phosphorus Res Bull 22:32–40Google Scholar
  60. 60.
    Salarizadeh P, Javanbakht M, Pourmahdian S, Hazer MSA, Hooshyari K, Askari MB (2019) Novel proton exchange membranes based on proton conductive sulfonated PAMPS/PSSA-TiO2 hybrid nanoparticles and sulfonated poly (ether ether ketone) for PEMFC. Int J Hydrogen Energ 44:3099–3114Google Scholar
  61. 61.
    Akay RM, Ata KC, Kadıoglu T, Celik C (2018) Evaluation of SPEEK/PBI blend membranes for possible direct borohydride fuel cell (DBFC) application. Int J Hydrogen Energ 43:18702–18711Google Scholar
  62. 62.
    Jeon S, Lee J, Rios GM, Kim HJ, Lee SY, Cho EA, Lim TH, Jang JH (2010) Effect of ionomer content and relative humidity on polymer electrolyte membrane fuel cell (PEMFC) performance of membrane-electrode assemblies (MEAs) prepared by decal transfer method. Int J Hydrogen Energ 35:9678–9686Google Scholar
  63. 63.
    Wang C, Zhou Y, Xu C, Zhao X, Li J, Ren Q (2018) Synthesis and properties of new side-chain-type poly(arylene ether sulfone)s containing triimidazole cations as anion-exchange membranes. Int J Hydrogen Energ 43:20739–20749Google Scholar
  64. 64.
    Wang C, Xu C, Shen B, Zhao X, Li J (2016) Stable poly(arylene ether sulfone)s anion exchange membranes containing imidazolium cations on pendant phenyl rings. Electrochim Acta 190:1057–1065Google Scholar
  65. 65.
    Wang C, Shen B, Dong H, Chen W, Xu C, Li J, Ren Q (2015) Sulfonated poly(arylene sulfide sulfone)s containing trisulfonated triphenylphosphine exide moieties for proton exchange membrane. Electrochim Acta 177:145–150Google Scholar
  66. 66.
    Wang C, Shen B, Xu C, Zhao X, Li J (2015) Side-chain-type poly(arylene ether sulfone)s containing multiple quaternary ammonium groups as anion exchange membranes. J Membrane Sci 492:281–288Google Scholar
  67. 67.
    Park HY, Ryu BK (2016) Characterization and catalytic behavior od cerium oxide doped into aluminosilicophosphate glasses. J Ceram Soc Jpn 124:155–159Google Scholar
  68. 68.
    Sivasankaran AA, Sangeetha D (2005) Influence of sulfonated SiO2 in sulfonated polyether ether ketone nanocomposite membrane in microbial fuel cell. Fuel 159:689–696Google Scholar
  69. 69.
    Verma S, Bamzai KK (2014) Preparation of cerium orthophosphate nanosphere by coprecipitation route and its structural, thermal, optical, and electrical characterization. J Nanopart 2014:1–12Google Scholar
  70. 70.
    Pasquini L, Wacrenier O, Di Vona ML, Knauth P (2018) Hydration and ionic conductivity of model cation and anion-conducting ionomers in buffer solutions (phosphate, acetate, citrate). J Phys Chem B 122:12009–12016PubMedGoogle Scholar
  71. 71.
    Lin CW, Lu YS (2013) Highly ordered graphene oxide paper laminated with a Nafion membrane for direct methanol fuel cells. J Power Sources 237:187–194Google Scholar
  72. 72.
    Zhang X, liu Q, Xi L, Huang D, Fu X, Zhang R, Hu S, Zhao F, Li X, Bao X (2019) Poly(2,5-benzimidazole)/sulfonated sepiolite composite membranes with low phosphoric acid doping levels for PEMFC applications in a wide temperature range. J Membrane Sci 574:282–298Google Scholar
  73. 73.
    Subianto S, Pica M, Casciola M, Cojocaru P, Merlo L, Hards G, Jones DJ (2013) Physical and chemical modification routes leading to improved mechanical properties of perfluorosulfonic acid membranes for PEM fuel cells. J Power Sources 233:216–230Google Scholar
  74. 74.
    Pei H, Hong L, Lee JY (2006) Polymer electrolyte membrane based on 2-acrylamido-2-methyl propanesulfonic acid fabricated by embedded polymerization. J Power Sources 160:949–956Google Scholar
  75. 75.
    Wang JTS, Hsu SLC (2011) Enhanced high-temperature polymer electrolyte membrane for fuel cells based on polybenzimidazole and ionics liquids. Electrochim Acta 56:2842–2846Google Scholar
  76. 76.
    Parnian MJ, Rowshanzamir S, Prasad AK, Advani SG (2018) Effect of ceria loading on performance and durability of sulfonated poly (ether ether ketone) nanocomposite membranes for proton exchange membrane fuel cell applications. J Membrane Sci 565:342–357Google Scholar
  77. 77.
    Salleh MT, Jaafar J, Mohamed MA, Norddin MNAM, Ismail AF, Othman MHD, Rahman MA, Yusof N, Aziz F, Salleh WNW (2017) Stability of SPEEK/Cloisite®/TAP nanocomposite membrane under Fenton reagent condition for direct methanol fuel cell application. Polym Degrad Stabil 137:83–99Google Scholar
  78. 78.
    Gashoul F, Parnian MJ, Rowshanzamir S (2017) A new study on improving the physicochemical and electrochemical properties of SPEEK nanocomposite membranes for medium temperature proton exchange membrane fuel cells using different loading of zirconium oxide nanoparticles. Int J Hydrogen Energ 42:590–602Google Scholar
  79. 79.
    Park J, Kim D (2014) Effect of cerium/18-crown-6-ether coordination complex OH quencher on the properties of sulfonated poly(ether ether ketone) fuel cell electrolyte membranes. J Membrane Sci 469:238–244Google Scholar
  80. 80.
    Shin D, Han M, Shul YG, Lee H, Bae B (2018) Analysis of cerium-composite polymer-electrolyte membranes during and after accelerated oxidative-stability test. J Power Sources 378:468–474Google Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Department of Chemical Engineering of Faculty of EngineeringGazi UniversityAnkaraTurkey

Personalised recommendations