Phosphoric acid doped polymer electrolyte membrane based on radiation grafted poly(1-vinylimidazole-co-1-vinyl-2-pyrrolidone)-g-poly(ethylene/tetrafluoroethylene) copolymer and investigation of grafting kinetics

A novel composite membrane containing Phosphoric Acid (PA) for possible application in high temperature Proton Exchange Membrane Fuel Cell (HT-PEMFC) was prepared by radiation-induced copolymerization of 1-vinylimidazole (1-Vlm) and 1-vinyl-2-pyrrolidone (1-V-2-P) onto poly (ethylene-alt-tetrafluoro...

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Main Authors: Saidi, H., Uthman, H.
Format: Article
Published: Elsevier Ltd 2017
Subjects:
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author Saidi, H.
Uthman, H.
author_facet Saidi, H.
Uthman, H.
author_sort Saidi, H.
collection ePrints
description A novel composite membrane containing Phosphoric Acid (PA) for possible application in high temperature Proton Exchange Membrane Fuel Cell (HT-PEMFC) was prepared by radiation-induced copolymerization of 1-vinylimidazole (1-Vlm) and 1-vinyl-2-pyrrolidone (1-V-2-P) onto poly (ethylene-alt-tetrafluoroethylene), ETFE films (ETFE-g-P(1-Vlm-co-1-V-2-P)) followed by protonation through PA doping. The preparation procedure involved three steps: i) Irradiation of ETFE films by an electron beam (EB) accelerator, ii) copolymerization of 1-Vlm-co-1-V-2-P onto the EB-preirradiated ETFE films under selected conditions and iii) acid doping of the grafted ETFE films with PA. The physiochemical properties of the resulted membranes were analysed in terms of degree of grafting (DG), grafting compositions, ionic conductivity, thermal properties and thermal stability using Fourier transform infrared spectroscopy (FTIR) fitted with attenuated total reflectance (ATR) and X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), and Differential scanning calorimetry (DSC), respectively. The results showed that the physiochemical properties of the membranes are comparable to Nafion 117 especially their thermal stability. At 120��C and 0% relative humidity the membrane remained stable at 76% DG and 7.6�mmol repeat polymer unit−1 with ionic conductivity of 53�mS�cm−1. Overall the characterization tests indicated that the membrane displayed impressive thermos-chemical and physical properties with less water dependency. At 200��C the membrane remained thermally stable which enhances the membrane's potential application in high temperature proton exchange membrane fuel cell (HT-PEMFC) operating at 100 �C and above. Grafting kinetics of nitrogenous and heterocyclic 1-Vim-co-1-V-2-P onto EB-preirradiated ETFE films were also investigated in conjunction with reaction parameters namely: monomer concentration (M), reaction temperature (RT), and absorbed dose (D). This was achieved by the determination of three kinetic parameters namely: the initial polymerization rate (rp0), characteristics radical recombination rate (γ) and delay time (t0) respectively. The variation of rp0 with D and M allows the determination of the order of dependence of grafting rate (Rg) on D and M which are 2.23 and 3.39 respectively. Activation energy (Ea) was also determined followed by temperature effect investigation in the range of 50–70��C.
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spelling utm.eprints-771432018-04-30T14:45:00Z http://eprints.utm.my/77143/ Phosphoric acid doped polymer electrolyte membrane based on radiation grafted poly(1-vinylimidazole-co-1-vinyl-2-pyrrolidone)-g-poly(ethylene/tetrafluoroethylene) copolymer and investigation of grafting kinetics Saidi, H. Uthman, H. T Technology (General) A novel composite membrane containing Phosphoric Acid (PA) for possible application in high temperature Proton Exchange Membrane Fuel Cell (HT-PEMFC) was prepared by radiation-induced copolymerization of 1-vinylimidazole (1-Vlm) and 1-vinyl-2-pyrrolidone (1-V-2-P) onto poly (ethylene-alt-tetrafluoroethylene), ETFE films (ETFE-g-P(1-Vlm-co-1-V-2-P)) followed by protonation through PA doping. The preparation procedure involved three steps: i) Irradiation of ETFE films by an electron beam (EB) accelerator, ii) copolymerization of 1-Vlm-co-1-V-2-P onto the EB-preirradiated ETFE films under selected conditions and iii) acid doping of the grafted ETFE films with PA. The physiochemical properties of the resulted membranes were analysed in terms of degree of grafting (DG), grafting compositions, ionic conductivity, thermal properties and thermal stability using Fourier transform infrared spectroscopy (FTIR) fitted with attenuated total reflectance (ATR) and X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), and Differential scanning calorimetry (DSC), respectively. The results showed that the physiochemical properties of the membranes are comparable to Nafion 117 especially their thermal stability. At 120��C and 0% relative humidity the membrane remained stable at 76% DG and 7.6�mmol repeat polymer unit−1 with ionic conductivity of 53�mS�cm−1. Overall the characterization tests indicated that the membrane displayed impressive thermos-chemical and physical properties with less water dependency. At 200��C the membrane remained thermally stable which enhances the membrane's potential application in high temperature proton exchange membrane fuel cell (HT-PEMFC) operating at 100 �C and above. Grafting kinetics of nitrogenous and heterocyclic 1-Vim-co-1-V-2-P onto EB-preirradiated ETFE films were also investigated in conjunction with reaction parameters namely: monomer concentration (M), reaction temperature (RT), and absorbed dose (D). This was achieved by the determination of three kinetic parameters namely: the initial polymerization rate (rp0), characteristics radical recombination rate (γ) and delay time (t0) respectively. The variation of rp0 with D and M allows the determination of the order of dependence of grafting rate (Rg) on D and M which are 2.23 and 3.39 respectively. Activation energy (Ea) was also determined followed by temperature effect investigation in the range of 50–70��C. Elsevier Ltd 2017 Article PeerReviewed Saidi, H. and Uthman, H. (2017) Phosphoric acid doped polymer electrolyte membrane based on radiation grafted poly(1-vinylimidazole-co-1-vinyl-2-pyrrolidone)-g-poly(ethylene/tetrafluoroethylene) copolymer and investigation of grafting kinetics. International Journal of Hydrogen Energy, 42 (14). pp. 9315-9332. ISSN 0360-3199 https://www.scopus.com/inward/record.uri?eid=2-s2.0-84995388897&doi=10.1016%2fj.ijhydene.2016.06.187&partnerID=40&md5=7165385d2b4f5e6e3add07eabe4683b1 DOI:10.1016/j.ijhydene.2016.06.187
spellingShingle T Technology (General)
Saidi, H.
Uthman, H.
Phosphoric acid doped polymer electrolyte membrane based on radiation grafted poly(1-vinylimidazole-co-1-vinyl-2-pyrrolidone)-g-poly(ethylene/tetrafluoroethylene) copolymer and investigation of grafting kinetics
title Phosphoric acid doped polymer electrolyte membrane based on radiation grafted poly(1-vinylimidazole-co-1-vinyl-2-pyrrolidone)-g-poly(ethylene/tetrafluoroethylene) copolymer and investigation of grafting kinetics
title_full Phosphoric acid doped polymer electrolyte membrane based on radiation grafted poly(1-vinylimidazole-co-1-vinyl-2-pyrrolidone)-g-poly(ethylene/tetrafluoroethylene) copolymer and investigation of grafting kinetics
title_fullStr Phosphoric acid doped polymer electrolyte membrane based on radiation grafted poly(1-vinylimidazole-co-1-vinyl-2-pyrrolidone)-g-poly(ethylene/tetrafluoroethylene) copolymer and investigation of grafting kinetics
title_full_unstemmed Phosphoric acid doped polymer electrolyte membrane based on radiation grafted poly(1-vinylimidazole-co-1-vinyl-2-pyrrolidone)-g-poly(ethylene/tetrafluoroethylene) copolymer and investigation of grafting kinetics
title_short Phosphoric acid doped polymer electrolyte membrane based on radiation grafted poly(1-vinylimidazole-co-1-vinyl-2-pyrrolidone)-g-poly(ethylene/tetrafluoroethylene) copolymer and investigation of grafting kinetics
title_sort phosphoric acid doped polymer electrolyte membrane based on radiation grafted poly 1 vinylimidazole co 1 vinyl 2 pyrrolidone g poly ethylene tetrafluoroethylene copolymer and investigation of grafting kinetics
topic T Technology (General)
work_keys_str_mv AT saidih phosphoricaciddopedpolymerelectrolytemembranebasedonradiationgraftedpoly1vinylimidazoleco1vinyl2pyrrolidonegpolyethylenetetrafluoroethylenecopolymerandinvestigationofgraftingkinetics
AT uthmanh phosphoricaciddopedpolymerelectrolytemembranebasedonradiationgraftedpoly1vinylimidazoleco1vinyl2pyrrolidonegpolyethylenetetrafluoroethylenecopolymerandinvestigationofgraftingkinetics