Electrospinning preparation of a graphene oxide nanohybrid proton‐exchange membrane for fuel cells

Proton‐exchange membrane (PEM) is a core component of fuel cells that provides a channel for proton migration and transport. Prevailing PEMs fabricated using well‐established casting techniques have several limitations such as low proton conductivity, high fuel permeability, and poor stability. To overcome these shortcomings, this article introduces a graphene oxide (GO)‐based nanohybrid Nafion nanofiber membrane prepared using a facile electrospinning technique. On the one hand, electrospinning nanofibers provide efficient transport paths for protons, which tremendously enhance the proton conductivity. On the other hand, GO doping in PEM improves the self‐humidification, stabilities (mechanical, thermal, and chemical), and proton conductivity and reduces the fuel permeability. In this research, nanofiber membranes were obtained from Nafion solutions containing 0, 0.1, and 0.2 wt % GO via electrospinning. The morphology, structure, mechanical properties, proton conductivity, water uptake, and swelling properties of the membranes were studied. The results demonstrated that the comprehensive performance of PEM was significantly improved. The new findings may promote the wide application of PEM fuel cells. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46443.     

Anion exchange membranes based on poly(vinyl alcohol) and quaternized polyethyleneimine for direct methanol fuel cells

The semi‐interpenetrating polymer network technique was applied in the preparation of anion exchange membranes for direct methanol fuel cells (DMFCs). Poly(vinyl alcohol) was chosen as the polymer matrix and quaternized polyethyleneimine was used as the cationic polyelectrolyte. To modify the polymer membranes for achieving desirable properties, 1,2‐bis(triethoxysilyl) ethane was used as a precursor to fabricate a set of organic–inorganic hybrid membranes. The hybrid membranes were characterized using X‐ray diffraction, scanning electron microscopy, and thermogravimetric analysis. The ionic conductivity, methanol permeability and stability under oxidative and alkaline conditions were measured to evaluate the applicability in DMFCs. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Novel grafted nafion membranes for proton‐exchange membrane fuel cell applications

Novel poly(glycidyl methacrylate)‐grafted Nafion–phosphoric acid membranes for direct‐oxidation methanol fuel cells were prepared with a potassium persulfate chemical initiation system for the first time. The introduced epoxy groups were converted to amine groups through a reaction with ethylenediamine, which consequently doped with phosphoric acid ( PO₃H) groups. The latter significantly contributed to enhancing the ion‐exchange capacity, mechanical properties, and thermal stability. Factors affecting the modification steps were studied. Changes in the chemical and morphological structure were verified through Fourier transform infrared spectroscopy, TGA, and scanning electron microscopy characterization. Various grafting percentages (GP%'s) up to 32.31% were obtained. As a result, the thickness of the grafted membranes increased. Furthermore, the methanol permeability of the modified membranes was reduced with increasing grafted polymer content compared with that of the Nafion membrane. An 83.64% reduction in the methanol permeability was obtained with a polymer grafted content of 18.27%. Finally, the efficiency factor for all of the modified Nafion membranes was enhanced compared with that of Nafion. A fourfold improvement was obtained with membranes with a GP% of 18.27% as a maximum value. Such promising results nominate the used technique as a one for the improvement of Nafion membrane efficiency. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Comparative study of composite membranes from nano‐metal‐oxide‐incorporated polymer electrolytes for direct methanol alkaline membrane fuel cells

A series of six composite membranes was prepared with two polymer electrolytes and three inorganic fillers, namely, silica, titania, and zirconia by a solution casting method. Two polymer electrolytes, that is, anion‐exchange membranes, were prepared from polystyrene‐block‐poly(ethylene‐ran‐butylene)‐block‐polystyrene (PSEBS) and polysulfone by chloromethylation and quaternization. A preliminary characterization of the ionic conductivity, methanol permeability, and selectivity ratio was done for all of the prepared composite membranes to check their suitability to work in direct methanol alkaline membrane fuel cells (DMAMFCs). The DMAMFC performance was analyzed with an in‐house fabricated single cell unit with a 25‐cm² area. Maximum performance was achieved for the composite membrane quaternized PSEBS/7.5% TiO₂ and was 74.5 mW/cm² at 60°C. For the comparison purposes, a commercially available anion‐exchange membrane (Anion Membrane International‐7001) was also investigated throughout the study. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Quaternized poly(phenylene oxide) anion exchange membrane for alkaline direct methanol fuel cells in KOH‐free media

A series of anion exchange membrane (AEM) electrolytes with quaternary ammonium moiety are fabricated from poly (phenylene oxide) for its application in alkaline direct methanol fuel cells (ADMFCs). In the first step, poly(phenylene oxide) (PPO) is successfully chloromethylated by substituting chloromethyl groups in the aryl position of polymer. In the second step, the chloromethylated PPO (CPPO) is further homogeneously quaternized and ion‐exchanged to form an AEM. From the second step, series of AEMs are prepared by changing the mole ratio of amine in relation to CPPO. The presence of quaternary ammonium group in the membrane was confirmed by elemental analysis. The fabricated membranes are subjected to cell polarization studies in ADMFCs, wherein quaternized poly(2,6‐dimethyl‐1,4‐phenylene oxide) (CPPO:amine of 1:8) membrane exhibits higher peak power density of 3.5 mW cm^?2 when compared with the other ratios of CPPO:amine in the absence of KOH solution. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43693.     

Poly(vinyl alcohol)/Cu(II) complex anion exchange membranes prepared using chemical fiber for direct methanol fuel cells

PVA/Cu (II) complex anion exchange membranes (AEMs) were prepared for direct methanol fuel cells. The complex was for the first time used as membrane material of AEMs. Glutaraldehyde as a crosslinking agent was introduced to control water uptake and swelling of the membranes. The membranes with thickness of 1 μm were fabricated using chemical fibers based on the solution surface tension. The complex membranes show good ionic conductivity and low methanol permeability in the magnitude of 10^?2 S · cm^?1 and 10^?7 cm^?2 · S^?1, respectively. This is a facile, efficient, green, and fast way to prepare new AEMs for direct methanol fuel cells. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1172‐1178, 2013     

Synthesis and characterization of a novel proton‐exchange membrane for fuel cells operating at high temperatures and low humidities

The synthesis of a p‐toluidine/formaldehyde (PTF) resin was performed, and the effects of the molar ratio of the individual monomers and the polymerization conditions on the structure of the PTF resin were studied. Fourier transform infrared and ¹³C‐NMR spectra were used to characterize the PTF. Wide‐angle X‐ray diffraction patterns revealed the crystalline structures of various PTFs. Polarized optical microscopy revealed that the molar ratio of the monomers had a strong effect on the crystalline morphologies. A longer polymerization time turned out a polymer with a higher intrinsic viscosity and molecular weight, which led to differences in the proton conductivity. All of the PTFs showed a higher proton conductivity than a commercial Nafion membrane at 90–100°C and 0% relative humidity. The proton conductivity of the PTF series could be improved by sulfonation with sulfuric acid and could be maintained after blending with polyurethane. Pure methanol could be used as a fuel source because of the insolubility and nonwetting properties of PTF in methanol to increase the output current density for a PTF membrane electrode assembly. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Synthesis and characterization of poly(vinyl alcohol)‐based membranes for direct methanol fuel cell

Membranes made of poly(vinyl alcohol) (PVA) and its ionic blends with sodium alginate (SA) and chitosan were synthesized and characterized for their ion-exchange capacity (IEC) and swelling index values to investigate their applicability in direct methanol fuel cells (DMFCs). These membranes were assessed for their intermolecular interactions, thermal stabilities, and mechanical strengths with Fourier transform infrared spectroscopy, X-ray diffraction methods, differential scanning calorimetry, thermogravimetric analysis, and tensile testing, respectively. Methanol permeability and proton conductivity were also estimated and compared to that of Nafion 117. In addition to being effective methanol barriers, the membranes had a considerably high IEC and thermal and mechanical stabilities. The addition of small amounts of anionic polymer was particularly instrumental in the significant reduction of methanol permeability from 8.1 × 10⁻⁸ cm²/s for PVA to 6.9 × 10⁻⁸ cm²/s for the PVA–SA blend, which rendered the blend more suitable for a DMFC. Low methanol permeability, excellent physicomechanical properties, and above all, cost effectiveness could make the use of these blends in DMFCs quite attractive. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1154–1163, 2005     

Sulfonated poly(ether sulfone)‐based catalyst binder for a proton‐exchange membrane fuel cell

Sulfonated poly(ether sulfone) copolymer (PES 60) and its partially fluorinated analogue (F‐PES 60) were synthesized via the nucleophilic aromatic polycondensation of commercially available monomers to make a polymer electrolyte membrane and a binding material in the electrodes of a membrane–electrode assembly (MEA). PES 60 and F‐PES 60 showed proton conductivities of 0.091 and 0.094 S/cm, respectively, in water at room temperature. The copolymer was dissolved in the mixture of alcohol and water to get a 1 wt % binder solution. A catalyst slurry was prepared with the copolymer solution and sprayed on the copolymer (PES 60 or F‐PES 60) membrane to obtain a MEA. Both PES 60 and F‐PES 60 based MEAs were fabricated with different amounts of their binder in the electrodes to examine the effect of the copolymer binder in the catalyst layer on the fuel cell performance. The MEA with 2 wt % copolymer binder in the electrodes showed the best fuel cell performance. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Montmorillonite‐reinforced sulfonated poly(phthalazinone ether sulfone ketone) nanocomposite proton exchange membranes for direct methanol fuel cells

To produce a composite membrane with high conductivity and low permeability, SPPESK with a degree of sulfonation of 101% was carefully selected for the preparation of montmorillonite (MMT)‐reinforced SPPESK using solution intercalation. The fundamental characteristics such as water uptake, swelling ratio, proton conductivity, methanol permeability, and mechanical properties of the composite membranes were studied. Water uptake is improved when organic MMT (OMMT) loading increase. The composite membranes with CTAB‐MMT loading of 4–0.5% show 0.143–0.150 S cm^?1 proton conductivity at 80°C, which approaches the value of Nafion112. In addition, methanol permeability was decreased to 6.29 × 10^?8 cm² s^?1 by the addition of 6 wt % OMMT. As a result, the SPPESK‐MMT composite membrane is a good candidate for use in direct methanol fuel cells. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39852.     

Antibacterial antiadhesion membranes from silver‐nanoparticle‐doped electrospun poly(L‐lactide) nanofibers

Electrospun fibrous membranes have been used frequently in biomedical applications, but their simultaneous use as antibacterial agents and in the prevention of cell adhesion on repaired tendons after injury has not been investigated. In this study, silver‐nanoparticle (SN)‐loaded poly(L ‐lactide) (PLLA) fibrous membranes were prepared by the electrospinning of SNs into PLLA fibers. Micrograph results showed that these membranes were composed of electrospun fibers and that the fibers were incorporated with SNs. From the results of X‐ray diffraction and thermogravimetry, we concluded that the SNs were physically mixed into the fibers at the desired content. The mechanical properties were not significantly changed. The preliminary antibacterial effects on Staphylococcus epidermidis and Staphylococcus aureus and the synergistic antiproliferative effects of the SN‐loaded PLLA fibrous membranes were observed. Taken together, these results demonstrate that SNs can be directly loaded onto a biodegradable PLLA fibrous membrane via electrospinning to achieve proper material properties with preliminary potential as antibacterial antiadhesion barriers for tendon injury. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Highly selective sulfonated poly(vinylidene fluoride‐co‐hexafluoropropylene)/poly(ether sulfone) blend proton exchange membranes for direct methanol fuel cells

Proton exchange membranes (PEMs) based on blends of poly(ether sulfone) (PES) and sulfonated poly(vinylidene fluoride‐co‐hexafluoropropylene) (sPVdF‐co‐HFP) were prepared successfully. Fabricated blend membranes showed favorable PEM characteristics such as reduced methanol permeability, high selectivity, and improved mechanical integrity. Additionally, these membranes afford comparable proton conductivity, good oxidative stability, moderate ion exchange capacity, and reasonable water uptake. To appraise PEM performance, blend membranes were characterized using techniques such as Fourier transform infrared spectroscopy, AC impedance spectroscopy; atomic force microscopy, and thermogravimetry. Addition of hydrophobic PES confines the swelling of the PEM and increases the ultimate tensile strength of the membrane. Proton conductivities of the blend membranes are about 10^?3 S cm^?1. Methanol permeability of 1.22 × 10^?7cm² s^?1 exhibited by the sPVdF‐co‐HFP/PES10 blend membrane is much lower than that of Nafion‐117. AFM studies divulged that the sPVdF‐co‐HFP/PES blend membranes have nodule like structure, which confirms the presence of hydrophilic domain. The observed results demonstrated that the sPVdF‐co‐HFP/PES blend membranes have promise for possible usage as a PEM in direct methanol fuel cells. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43907.     

燃料电池用碱性膜材料的研究进展

碱性膜直接甲醇燃料电池因为结合了质子交换膜燃料电池和液体碱燃料电池的优点而产生自身独特的性质,使其可以在一定程度上弥补质子交换膜燃料电池以及液体碱燃料电池的缺点而尤其引人关注。其中碱性膜电解质为碱性膜燃料电池的核心组件,其性能直接关系到燃料电池的性能及寿命。截至目前,关于碱性膜材料的制备及应用方面的报道较多,涉及的碱性膜电解质的种类也较多。本文以燃料电池用碱性膜电解质为综述内容,对国内外关于碱性膜电解质的研究报道进行系统的梳理和介绍。     

Solution‐blown SPEEK/POSS nanofiber–nafion hybrid composite membranes for direct methanol fuel cells

This study aims to develop novel hybrid composite membranes (NHMs) by impregnating Nafion solution into the porous sulfonated poly(ether ether ketone)/polyhedral oligomeric silsesquioxanes (SPEEK/POSS) nanofibers (NFs). The composite membrane was prepared by solution blowing of a mixture of SPEEK/POSS solution. The characteristics of the SPEEK/POSS NFs and the NHMs, including morphology, thermal stability, and performance of membrane as PEMs, were investigated. The performance of NHMs was compared with that of Nafion117 and SPEEK/Nafion composite membranes. Results showed that the introduction of POSS improved the proton conductivity, water swelling, and methanol permeability of membranes. A maximum proton conductivity of 0.163 S cm^?1 was obtained when the POSS content was 6 wt % at 80°C, which was higher than that of Nafion117 and SPEEK/Nafion. NHMs could be used as proton exchange membranes (PEMs) for fuel cell applications. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42843.     

Zeolite-based composite membranes for high temperature direct methanol fuel cells

Composite Nafion membranes containing three natural zeolites (Mordenite, Chabazite and Clinoptilolite) were prepared by using a recast procedure for application in high temperature Direct Methanol Fuel Cells (DMFCs). The Nafion-zeolite membranes have shown good properties for high temperature DMFC application, due to their improved water retention characteristics. A maximum power density of 390 mW cm^–2 was achieved at 140 °C with the mordenite-based composite membranes in the presence of oxygen feed. The electrochemical behaviour of the composite membranes was interpreted in the light of surface properties and acidic characteristics of the fillers.     

Recent developments in fuel‐processing and proton‐exchange membranes for fuel cells

In recent years, great progress has been made in the development of proton‐exchange membrane fuel cells (PEMFCs) for both mobile and stationary applications. This review covers two types of new membranes: (1) carbon dioxide‐selective membranes for hydrogen purification and (2) proton‐exchange membranes; both of these are crucial to the widespread application of PEMFCs. On hydrogen purification for fuel cells, the new facilitated transport membranes synthesized from incorporating amino groups in polymer networks have shown high CO₂ permeability and selectivity versus H₂. The membranes can be used in fuel processing to produce high‐purity hydrogen (with less than 10 ppm CO and 10 ppb H₂S) for fuel cells. On proton‐exchange membranes, the new sulfonated polybenzimidazole copolymer‐based membranes can outperform Nafion^® under various conditions, particularly at high temperatures and low relative humidities. Copyright © 2010 Society of Chemical Industry     

Enhanced mechanical flexibility and performance of sodium alginate polymer electrolyte bio‐membrane for application in direct methanol fuel cell

A new membrane was synthesized containing pure alginate, crosslinking agent (CaCl₂), and plasticizer (glycerol). Characterization studies of the membrane were applied to determine the characteristics and morphology using field emission scanning electron microscope, EDX, FTIR, XRD, and atomic force microscopy analysis. The half‐cell performance test of the membrane was verified by several tests, including proton conductivity and methanol permeability. The best membrane had high proton conductivity (10.1 × 10^?3 S cm^?1) and very low methanol permeability (1.984 × 10^?7 cm² s^?1), which consequently resulted in very high selectivity (5.0907 × 10⁴ Ss cm^?3). Glycerol had a positive modification and good influence on the alginate characteristics. Furthermore, the poor mechanical properties of the alginate biopolymer were enhanced by calcium chloride and glycerol inside the polymer. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46666.     

Synthesis and properties of fluorine‐ and siloxane‐containing polybenzimidazoles for high temperature proton exchange membrane fuel cells

In this study, new fluorine–siloxane‐containing polybenzimidazole (PBI) copolymers were synthesized by copolymerization of 3,3′‐diaminobenzidine, 2,2‐bis(4‐carboxyphenyl)‐hexafluoropropane (HFA), and 1,3 bis(carboxypropyl)tetramethyldisiloxane (BTMDS) with different molar ratios. PBI copolymer membranes were prepared by solution‐casting and then doped with phosphoric acid. The structures of PBI copolymers were characterized by FTIR and X‐ray diffraction. The solubility of the PBI copolymers was significantly increased by the introduction of the bulky HFA group and the flexible BTMDS group into the polymer backbone. The PBI copolymers still maintained good thermal stability and mechanical properties. Because of the introduction of the flexible and hydrophobic siloxane group in the polymer backbone, the methanol permeability was reduced and the proton conductivity under anhydrous condition at high temperatures was increased compared to the PBI without the siloxane group. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4107–4112, 2013     

Preparation of a crosslinked polyelectrolyte membrane for fuel cells with an allyl methacrylate based two‐step reaction

In this study, a proton‐exchange membrane for fuel cells was prepared via a two‐step reaction with an allyl methacrylate (AMA) as an asymmetric crosslinking agent. First, a linear‐chain polymer was synthesized, consisting of hydrophilic 2‐acrylamido‐2‐methylpropanesulfonic acid (AMPS), hydrophobic 2,2,2‐trifluoroethyl methacrylate (TFEMA), and AMA. Subsequently, we crosslinked the linear‐chain polymer by reacting the remaining allyl group during dry heating. The proton conductivity of the prepared membrane was 7 × 10^?2 S/cm at room temperature. The membrane was characterized by Fourier transform infrared spectroscopy, differential scanning calorimetry, and atomic force microscopy. The polymer electrolyte membrane fuel cell (PEMFC) performance was evaluated for a membrane electrode assembly composed of the crosslinked AMPS–TFEMA–AMA/ fluoroalkyl graft polymer (FGP) membrane. As a result of a power‐generation test, a maximum power density of 174 mW/cm² at a current density of 400 mA/cm² was observed for a PEMFC single cell. Consequently, it was confirmed that the AMPS–TFEMA–AMA/FGP membrane for PEMFC could easily be prepared via a two‐step reaction at a low cost and that PEMFC exhibited a cell performance and that of cells with the Nafion membrane. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Novel bilayer electrospun poly(caprolactone)/ silk fibroin/ strontium carbonate fibrous nanocomposite membrane for guided bone regeneration

In this study, a thin layer with a thickness of about 120 μm of poly(caprolactone) (PCL) was fabricated by electrospinning method. Then, a fibrous nanocomposite composed of PCL/silk fibroin/strontium carbonate (PCL/SF/SrCO₃) was electrospun on the prepared layer. Then, they were characterized. The mechanical properties, water uptake, degradation rate, wettability, porosity, and bioactivity of the electrospun membrane were scrutinized in vitro. Cytotoxicity of the samples was assessed by using osteoblast-like cells (SAOS-2) and L929 fibroblasts. Moreover, the cell adhesion, alkaline phosphatase (ALP) activity, and calcium deposition through alizarin red staining were conducted. Results revealed that the bilayer structure doubled the optimum mechanical properties and the addition of SrCO₃ up to 15%–20% increased ALP activity, calcium deposition, and bioactivity. According to the results, the nanofibrous bilayer membrane containing 20 wt% SrCO₃, 20 wt% SF, and 60 wt% PCL was chosen as the optimum sample. Therefore, this membrane could be applied in guided bone regeneration (GBR).