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Polymer electrolyte membranes (PEM) prepared by radiation-induced graft copolymerization are investigated. For this purpose, commercial poly(ethylene-alt-tetrafluoroethylene) (ETFE) films were activated by electron beam treatment and subsequently grafted with the monomers glycidyl methacrylate (GMA), hydroxyethyl methacrylate (HEMA) and N,N′-methylenebis(acrylamide) (MBAA) as crosslinker. The target is to achieve a high degree of grafting (DG) and high proton conductivity. To evaluate the electrochemical performance, the PEMs were tested in a fuel cell and in a vanadium redox-flow battery (VRFB). High power densities of 134 mW∙cm−2 and 474 mW∙cm−2 were observed, respectively.

Polymer electrolyte membranes (PEM) for potential applications in fuel cells or vanadium redox flow batteries were synthesized and characterized. ETFE (poly (ethylene-alt-tetrafluoroethylene)) and PVDF (poly (vinylidene fluoride)) serving as base materials were activated by electron beam treatment with doses ranging from 50 to 200 kGy and subsequently grafted via radical copolymerization with the functional monomers 2-acrylamido-2-methylpropane sulfonic acid and acrylic acid in aqueous phase. Since protogenic groups are already contained in the monomers, a subsequent sulfonation step is omitted. The mechanical properties were studied via tensile strength measurements. The electrochemical performance of the PEMs was evaluated by electrochemical impedance spectroscopy and fuel cell tests. The proton conductivities and ion exchange capacities are competitive with Nafion 117, the standard material used today.

Proton exchange membranes for high temperature fuel cell applications were obtained via graft copolymerizations on commercial poly(ethylene-alt-tetrafluoroethylene) (ETFE) films. ETFE was activated by electron beam treatment, and the hydrophilic monomers acrylic acid and hydroxyethyl methacrylate were grafted to ETFE. The maximum grafting level was 620%. The grafted membranes were doped with the proton carrier phosphoric acid leading to a maximum doping level of 450%. Stress-strain measurements indicate good mechanical stability of the composite membranes. The polymer-acid membranes were tested in a H 2 /O 2 fuel cell. At a current density of 200 mA Á cm À2 a stable power density of 113 mW Á cm À2 was determined at 120 8C. The results show that high phosphoric acid contents associated with high proton conductivity may be obtained with a copolymer containing acrylic acid.

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A core component of energy storage systems like vanadium redox flow batteries (VRFB) is the polymer electrolyte membrane (PEM). In this work, the frequently used perfluorosulfonic-acid (PFSA) membrane Nafion™ 117 and a novel poly (vinylidene difluoride) (PVDF)-based membrane are investigated. A well-known problem in VRFBs is the vanadium permeation through the membrane. The consequence of this so-called vanadium crossover is a severe loss of capacity. For a better understanding of vanadium transport in membranes, the uptake of vanadium ions from electrolytes containing Vdimer(IV–V) and for comparison also V(II), V(III), V(IV), and V(V) by both membranes was studied. UV/VIS spectroscopy, X-ray absorption near edge structure spectroscopy (XANES), total reflection X-ray fluorescence spectroscopy (TXRF), inductively coupled plasma optical emission spectrometry (ICP-OES), and micro X-ray fluorescence spectroscopy (microXRF) were used to determine the vanadium concentrations and the species inside the membrane. The results strongly support that Vdimer(IV–V), a dimer formed from V(IV) and V(V), enters the nanoscopic water-body of Nafion™ 117 as such. This is interesting, because as of now, only the individual ions V(IV) and V(V) were considered to be transported through the membrane. Additionally, it was found that the Vdimer(IV–V) dimer partly dissociates to the individual ions in the novel PVDF-based membrane. The Vdimer(IV–V) dimer concentration in Nafion™ was determined and compared to those of the other species. After three days of equilibration time, the concentration of the dimer is the lowest compared to the monomeric vanadium species. The concentration of vanadium in terms of the relative uptake λ = n(V)/n(SO3) are as follows: V(II) [λ = 0.155] > V(III) [λ = 0.137] > V(IV) [λ = 0.124] > V(V) [λ = 0.053] > Vdimer(IV–V) [λ = 0.039]. The results show that the Vdimer(IV–V) dimer needs to be considered in addition to the other monomeric species to properly describe the transport of vanadium through Nafion™ in VRFBs.