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1.
Sulfonated poly(ether ether ketone) has been investigated as an ionomer in the catalyst layer for direct methanol fuel cells (DMFC). The performance in DMFC, electrochemical active area (by cyclic voltammetry), and limiting capacitance (by impedance spectroscopy) have been evaluated as a function of the ion exchange capacity (IEC) and content (wt.%) of the SPEEK ionomer in the catalyst layer. The optimum IEC value and SPEEK ionomer content in the electrodes are found to be, respectively, 1.33 meq. g−1 and 20 wt.%. The membrane-electrode assemblies (MEA) fabricated with SPEEK membrane and SPEEK ionomer in the electrodes are found to exhibit superior performance in DMFC compared to that fabricated with Nafion ionomer due to lower interfacial resistance in the MEA as well as larger electrochemical active area. The MEAs with SPEEK membrane and SPEEK ionomer also exhibit better performance than that with Nafion 115 membrane and Nafion ionomer due to lower methanol crossover and better electrode kinetics.  相似文献   

2.
Sulfonated poly(ether ether ketone)s (SPEEKs) are substituted on the main chain of the polymer by nitro groups and blended with Nafion® to attain composite membranes. The sulfonation, nitration and blending are achieved with a simple, inexpensive process, and the blended membranes containing the nitrated SPEEKs reveal a liquid-liquid phase separation. The blended membranes have a lower water uptake compared to recast Nafion®, and the methanol permeability is reduced significantly to 4.29 × 10−7-5.34 × 10−7 cm2 s−1 for various contents of nitrated SPEEK for S63N17, and 4.72 × 10−7-7.11 × 10−7 cm2 s−1 for S63N38, with a maximum proton conductivity of ∼0.085 S cm−1. This study examines the single-cell performance at 80 °C of Nafion®/nitrated SPEEK membranes with various contents of nitrated SPEEK and a degree of nitration of 23-25 mW cm−2 for S63N17 and 24-29 mW cm−2 for S63N38. Both the power density and open circuit voltage are higher than those of Nafion® 115 and recast Nafion®.  相似文献   

3.
For PEMFC operation, water management is very important to provide both sufficient proton conductivity and mass transport. Therefore, in this study, the effect of the relative humidity (38–87%) on cell performance is examined for PEMFC MEAs with various Nafion® ionomer contents. The MEAs were fabricated using a CCM (catalyst-coated membrane) spraying method. As the relative humidity of the cathodes (RHC) increases, the cell voltages at 0.4 and 1.2 A/cm2 increased for a MEA with 20 wt% ionomer. This can be explained in terms of the expansion of active sites with enhanced ionic conductivity (activation overpotential). In contrast, with a higher RHC value, the cell voltages for 35 wt% ionomer (more hydrophilic) gradually decreased as a result of slower gas transport (concentration overpotential). For MEAs with intermediate ionomer contents, 25 and 30 wt%, the cell voltages at 0.4 A/cm2 showed maximum values at a RHC of 67%, at which point the mass transport begins to be the more dominant factor. The highest unit cell performance was observed in a MEA with an ionomer content of 25 wt% at a RHC of 59% and in a MEA at 20 wt% ionomer content at a higher humidity of 87%.  相似文献   

4.
A drawback of sulfonated aromatic main-chain polymers such as sulfonated poly(ether ether ketone)s (SPEEKs) is their high methanol crossover when the proton conductivity is sufficient for direct methanol fuel cell (DMFC) applications. To overcome this disadvantage, in this paper, the SPEEK substrate was coated with the crosslinked chitosan (CS) barrier layer to form the two-layer composite membranes. Scanning electron microscope (SEM) micrographs showed that the CS layer was tightly adhered on the SPEEK substrate and the thickness of CS layer could be adjusted by varying the concentration of CS solution. It was noticed that with the increment of thickness of CS layer, the methanol diffusion coefficient of the composite membranes significantly dropped from 3.15 × 10−6 to 2.81 × 10−7 cm2 s−1 at 25 °C which was about one order of magnitude lower than those of the pure SPEEK and Nafion® 117 membranes. In addition to the effective methanol barrier, the composite membranes possessed adequate thermal stability (the 5% weight lose temperature exceeded 240 °C) and good proton conductivity. The proton conductivity of all composite membranes was in the order of 10−2 S cm−1 and increased with the elevation of temperature. Furthermore, the composite membranes exhibited much higher selectivity (conductivity/methanol diffusion coefficient) compared with the pure SPEEK and Nafion® 117 membranes. These results indicated that introducing the crosslinked CS layer onto the SPEEK surface was an effective method for improving the performance of the SPEEK membrane, especially for reducing the methanol crossover.  相似文献   

5.
Sulfonated organosilane functionalized graphene oxides (SSi-GO) synthesized through the grafting of graphene oxide (GO) with 3-mercaptopropyl trimethoxysilane and subsequent oxidation have been used as a filler in sulfonated poly(ether ether ketone) (SPEEK) membranes. The incorporation of SSi-GOs greatly increases the ion-exchange capacity (IEC), water uptake, and proton conductivity of the membrane. With well-controlled contents of SSi-GOs, the composite membranes exhibit higher proton conductivity and lower methanol permeability than Nafion® 112 and Nafion® 115, making them particularly attractive as proton exchange membranes (PEMs) for direct methanol fuel cells (DMFC). The composite membrane with optimal SSi-GOs content exhibit over 38 and 17% higher power densities, respectively, than Nafion® 112 and Nafion® 115 membranes in DMFCs, offering the possibilities to reduce the DMFC membrane cost significantly while keeping high-performance.  相似文献   

6.
Sulfonated poly(ether ether ketone)s (SPEEKs) were substituted on a polymer main chain that had previously been prepared by sulfonation of poly(ether ether ketone)s in concentrated sulfuric acid for a specified time. The product was then blended with Nafion® to create composite membranes. The blended SPEEK-containing membranes featured flaky domains dispersed in the Nafion® matrix. These blends possessed a high thermal decomposition temperature. Additionally, owing to the more crystalline, the blended membranes had a lower water uptake compared to recast Nafion®, the methanol permeability was reduced to 1.70 × 10−6 to 9.09 × 10−7 cm2 s−1 for various SPEEK concentrations, and a maximum proton conductivity of ∼0.050 S cm−1 was observed at 30 °C. The single-cell performances of the Nafion®/SPEEK membranes, with various SPEEK concentrations and a certain degree of sulfonation, were 15–25 mW cm−2 for SPEEK53 and 19–27 mW cm−2 for SPEEK63, at 80 °C. The power density and open circuit voltage were higher than those of Nafion® 115 (power density = 22 mW cm−2). The blended membranes satisfy the requirements of proton exchange membranes for direct methanol fuel cell (DMFC) applications.  相似文献   

7.
The crosslinked sulfonated poly (ether ether ketone)/2-acrylamido-2-methyl-1-propanesulfonic acid (SPEEK/AMPS) blend membranres were prepared and evaluated as proton exchange membranes for direct methanol fuel cell (DMFC) applications. The structure and morphology of SPEEK/AMPS membranes were characterized by FTIR and SEM, respectively. The effects of crosslinking and AMPS content on the performance of membranes were studied and discussed in detail. The proton conductivity and methanol diffusion coefficient of SPEEK/AMPS membranes increased gradually with the increase of AMPS content. Most SPEEK/AMPS membranes exhibited higher proton conductivity than Nafion® 117 (0.05 S cm−1 at 25 °C). However, all the membranes possessed much lower methanol diffusion coefficient compared with Nafion® 117 (2.38 × 10−6 cm2 s−1) under the same measuring conditions. Even the methanol diffusion coefficient (8.89 × 10−7 cm2 s−1) of SPEEK/AMPS 30 sample with the highest proton conductivity (0.084 S cm−1 at 25 °C) was only about one third of that of Nafion® 117. The selectivity of all the SPEEK/AMPS membranes was much higher in comparison with Nafion® 117 (2.8 × 104 S s cm−3). In addition, the SPEEK/AMPS membranes possessed relatively good thermal and hydrolytic stability. These results suggested that the SPEEK/AMPS membranes were particularly promising to be used as proton exchange membranes in DMFCs, and the high proton conductivity, low methanol diffusion coefficient and high selectivity were their primary advantages for DMFC applications.  相似文献   

8.
The role of Nafion® binder in the electrodes was evaluated by changing its content for the membrane electrode assembly (MEA) fabrication. In the study, we prepared MEAs that have two different compositions of catalyst layers in electrodes. One layer which is close to the electrolyte membrane has the higher Nafion® content. The other which is near the gas diffusion media (GDM) has the lower one. Also, we changed the thickness of two layers to find the ideal composition of the binder and Pt/C in the electrode. The dual catalyst layer coated MEA showed higher cell performance at high current density region than the pristine MEA.  相似文献   

9.
A semi-interpenetrating polymer network (semi-IPN) proton exchange membrane is prepared from the sulfonated poly(ether ether ketone) (sPEEK) and organosiloxane-based organic/inorganic hybrid network (organosiloxane network). The organosiloxane network is synthesized from 3-glycidyloxypropyltrimethoxysiane and 1-hydroxyethane-1,1-diphosphonic acid. The semi-IPN membranes prepared were stable up to 300 °C without any degradation. The methanol permeability is much lower than Nafion® 117 under addition of the organosiloxane network. The proton conductivity of semi-IPN membranes increases with an increase the organosiloxane network content; the membrane containing the 20-24 wt% organosiloxane network shows higher conductivity than Nafion® 117. The power density of the MEA fabricated with the semi-IPN membrane with 24 wt% organosiloxane network is 135 mW cm−2, much better than that of the pristine sPEEK membrane, 85 mW cm−2. Chemical synthesis of the semi-IPN membranes is identified using FTIR, and its ion cluster dimension examined using SAXS. The dimensional stability associated with water swelling and dissolution is investigated at different temperatures, and the semi IPN membranes dimensionally stable in water at elevated temperature.  相似文献   

10.
Membrane electrode assemblies (MEAs) for fuel cell applications consist of electron conductive support materials, proton conductive ionomer, and precious metal nanoparticles to enhance the catalytic activity towards H2 oxidation and O2 reduction. An optimized connection of all three phases is required to obtain a high noble metal utilization, and accordingly a good performance. Using polyaniline (PANI) as an alternative support material, the generally used ionomer Nafion® could be replaced in the catalyst layer. PANI has the advantage to be electron and proton conductive at the same time, and can be used as a catalyst support as well. In this study, a new technique building up alternating layers of PANI supported catalyst and single-walled carbon nanotubes (SWCNT) supported catalyst is introduced. Multilayers of PANI and SWCNT catalysts are used on the cathode side, whereas the anode side is composed of commercial platinum/carbon black catalyst and Nafion®, applied by an airbrush. No additional Nafion® ionomer is used for proton conductivity of the cathode. The so called spray coating method results in high power densities up to 160 mW cm−2 with a Pt loading of 0.06 mg cm−2 at the cathode, yielding a Pt utilization of 2663 mW mgPt−1. As well as PANI, supports of SWCNTs have the advantage to have a fibrous structure and additional, they provide high electron conductivity. The combination of the new technique and the fibrous 1-dimensional support materials leads to a porous 3-dimensional electrode network which could enhance the gas transport through the electrode as well as the Pt utilization. The spray coating method could be upgraded to an in-line process and is not restricted to batch production.  相似文献   

11.
A diamine-terminated polybenzimidazole oligomer (o-PBI) has been synthesized for introducing the benzimidazole groups (BI) into sulfonated poly(ether ether ketone) (SPEEK) membranes. SPEEK/o-PBI/4,4′-diglycidyl(3,3′,5,5′-tetramethylbiphenyl) epoxy resin (TMBP) composite membranes in situ polymerization has been prepared for the purpose of improving the performance of SPEEK with high ion-exchange capacities (IEC) for the usage in the direct methanol fuel cells (DMFCs). The composite membranes with three-dimensional network structure are obtained through a cross-linking reaction between PBI oligomer and TMBP and the acid-base interaction between sulfonic acid groups and benzimidazole groups. Resulting membranes show a significantly increasing of all of the properties, such as high proton conductivity (0.14 S cm−1 at 80 °C), low methanol permeability (2.38 × 10−8 cm2 s−1), low water uptake (25.66% at 80 °C) and swelling ratio (4.11% at 80 °C), strong thermal and oxidative stability, and mechanical properties. Higher selectivity has been found for the composite membranes in comparison with SPEEK. Therefore, the SPEEK/o-PBI/TMBP composite membranes show a good potential in DMFCs usages.  相似文献   

12.
Sulfonated poly(ether ether ketone)s (SPEEKs) were further substituted on the polymer main chain by nitration. All sulfonation and nitration were achieved with an inexpensive and simple post substitute reaction. The nitrated SPEEKs have a high glass transition temperature and thermal decomposition temperature, and a lower water uptake than SPEEK, which provides sufficient mechanical strength without swelling in the direct methanol fuel cell (DMFC) application. The methanol permeability of nitrated SPEEKS is reduced to 1.76 × 10−7 cm2 s−1 for S53N22 and 1.86 × 10−7 cm2 s−1 for S63N17 with no loss of conductivity in the DMFC application, and a proton conductivity that reached 0.026 S cm−1. The nitrated SPEEK membranes satisfy the requirements of proton-exchange membranes for the DMFC.  相似文献   

13.
Commercial Nafion®-115 (trademark registered to DuPont) membranes were modified by in situ polymerized phenol formaldehyde resin (PFR) to suppress methanol crossover, and SO3 groups were introduced to PFR by post-sulfonatation. A series of membranes with different sulfonated phenol formaldehyde resin (sPFR) loadings have been fabricated and investigated. SEM-EDX characterization shows that the PFR was well dispersed throughout the Nafion® membrane. The composite membranes have a similar or slightly lower proton conductivity compared with a native Nafion® membrane, but show a significant reduction in methanol crossover (the methanol permeability of sPFR/Nafion® composite membrane with 2.3 wt.% sPFR loading was 1.5 × 10−6 cm2 s−1, compared with the 2.5 × 10−6 cm2 s−1 for the native Nafion® membrane). In direct methanol fuel cell (DMFC) evaluation, the membrane electrode assembly (MEA) using a composite membrane with a 2.3 wt.% sPFR loading shows a higher performance than that of a native Nafion® membrane with 1 M methanol feed, and at higher methanol concentrations (5 M), the composite membrane achieved a 114 mW cm−2 maximum power density, while the maximum power density of the native Nafion® was only 78 mW cm−2.  相似文献   

14.
Various molecular weights of poly(propylene oxide) diamines oligomers/Nafion® acid–base blend membranes were prepared to improve the performance of Nafion® membranes in direct methanol fuel cells (DMFCs). The acid–base interactions were studied by Fourier transform infrared spectroscopy (FT-IR) and differential scanning calorimetry (DSC). The performance of the blend membranes was evaluated in terms of methanol permeability, proton conductivity and cell performance. The proton conductivity was slightly reduced by acid–base interaction. The methanol permeability of the blend D2000/Nafion® was 8.61 × 10−7 cm2 S−1, which was reduced 60% compared to that of pristine Nafion®. The cell performance of D2000/Nafion® blend membranes was enhanced significantly compared to pristine Nafion®. The current densities that were measured with Nafion® and 3.5 wt% D2000/Nafion® blend membranes were 62.5 and 103.5 mA cm−2, respectively, at a potential of 0.2 V. Consequently, the blend poly(propylene oxide) diamines oligomers/Nafion® membranes critically improved the single-cell performance of DMFC.  相似文献   

15.
A series of hydrocarbon membranes consisting of poly(vinyl alcohol) (PVA), sulfosuccinic acid (SSA) and poly(vinyl pyrrolidone) (PVP) were synthesized and characterized for direct methanol fuel cell (DMFC) applications. Fourier transform infrared (FT-IR) spectra confirm a semi-interpenetrating (SIPN) structure based on a cross-linked PVA/SSA network and penetrating PVP molecular chains. A SIPN membrane with 20% PVP (SIPN-20) exhibits a proton conductivity value comparable to Nafion® 115 (1.0 × 10−2 S cm−1 for SIPN-20 and 1.4 × 10−2 S cm−1 for Nafion® 115). Specifically, SIPN membranes reveal excellent methanol resistance for both sorption and transport properties. The methanol self-diffusion coefficient through a SIPN-20 membrane conducted by pulsed field-gradient nuclear magnetic resonance (PFG-NMR) technology measures 7.67 × 10−7 cm2 s−1, which is about one order of magnitude lower than that of Nafion® 115. The methanol permeability of SIPN-20 membrane is 5.57 × 10−8 cm2 s−1, which is about one and a half order of magnitude lower than Nafion® 115. The methanol transport behaviors of SIPN-20 and Nafion® 115 membranes correlate well with their sorption characteristics. Methanol uptake in a SIPN-20 membrane is only half that of Nafion® 115. An extended study shows that a membrane-electrode assembly (MEA) made of SIPN-20 membrane exhibits a power density comparable to Nafion® 115 with a significantly higher open current voltage. Accordingly, SIPN membranes with a suitable PVP content are considered good methanol barriers, and suitable for DMFC applications.  相似文献   

16.
HMS-based sulphonated poly(arylene ether sulphone) (HMSSH) is synthesised using 4,4′-dihydroxy-α-methylstilbene (HMS) monomer to introduce an interesting stilbene core as crosslinkable group. Crosslinked blend membranes are obtained by blending the BPA-based sulphonated poly(arylene ether sulphone) (BPASH) with crosslinkable HMS-based sulphonated poly(arylene ether sulphone) by UV irradiation of the blend membrane. Compared to the native BPASH with crosslinked BPASH/HMSSH blend membranes, the crosslinked blend membranes greatly reduce the water uptake and methanol permeability with only a slight reduction in proton conductivity. The crosslinked blend membrane, which has a 6% HMSSH content, has a water uptake of 59%, methanol permeability of 0.75 × 10−6 cm2 s−1, and proton conductivity of 0.08 S cm−1. A membrane-electrode assembly is used to investigate single-cell performance and durability test for DMFC applications. Both the power density and open circuit voltage are higher than those of Nafion® 117. A maximum power density of 32 mW cm−2 at 0.2 V is obtained at 80 °C, which is higher than that of Nafion® 117 (25 mW cm−2).  相似文献   

17.
Direct methanol fuel cells using an alkaline anion exchange membrane (AAEM) were prepared, studied, and optimized. The effects of fuel composition and electrode materials were investigated. Membrane electrode assemblies fabricated with Tokuyama® AAEM and commercial noble metal catalysts achieved peak power densities between 25 and 168 mW cm−2 depending on the operating temperature, fuel composition, and electrode materials used. Good electrode wettability at the anode was found to be very important for achieving high power densities. The performance of the best AAEM cells was comparable to Nafion®-based cells under similar conditions. Factors limiting the performance of AAEM MEAs were found to be different from those of Nafion® MEAs. Improved electrode kinetics for methanol oxidation in alkaline electrolyte at Pt-Ru are apparent at low current densities. At high current densities, rapid CO2 production converts the hydroxide anions, necessary for methanol oxidation, to bicarbonate and carbonate: consequently, the membrane and interfacial conductivity are drastically reduced. These phenomena necessitate the use of aqueous potassium hydroxide and wettable electrode materials for efficient hydroxide supply to the anode. However, aqueous hydroxide is not needed at the cathode. Compared to AAEM-based fuel cells, methanol fuel cells based on proton-conducting Nafion® retain better performance at high current densities by providing the benefit of carbon dioxide rejection.  相似文献   

18.
Novel 4,4′-dihydroxy-α-methylstilbene (HMS)-based sulfonated poly(arylene ether sulfone) with sulfonic acid composition ranging from 10 to 40 mol% was synthesized via nucleophilic step polymerization of 4,4′-dihydroxy-α-methylstilbene, 4,4′-dichloro-3,3′-disulfonic acid diphenylsulfone and 4,4′-dichlorodiphenylsulfone and blended with silica sol to form organic/inorganic nano-composite membranes. The organic/inorganic nano-composite copolymers produced show a high glass transition temperature and thermal decomposition temperatures from 318 to 451 °C. The copolymers present appropriate toughness during the membrane process. The equilibrium water uptake and proton conductivity of the obtained organic/inorganic nano-composite membranes were measured as functions of temperature, degree of sulfonation and silica content. In general, the water uptake increased from 8 to 37 wt.%, and the proton conductivity of the organic/inorganic nano-composite membranes increased from 0.003 to 0.110 S cm−1 as the degree of sulfonation increased from 10 to 40 mol%, the silica content increased from 3 to 10 wt.%, and the temperature increased from 30 to 80 °C. The single cell performance of the 40 mol% organic/inorganic nano-composite membrane with various silica contents ranged from 11 to 13 mW cm−2 at 80 °C, and the power density was higher than Nafion® 117. Including the thermal properties, swelling, conductivity and single cell performance, the nano-composite membranes are able to satisfy the requirements of proton exchange membranes for direct methanol fuel cells (DMFC).  相似文献   

19.
Custom-made proton exchange membranes (PEM) are synthesized by incorporating sulfonated poly(ether ether ketone) (SPEEK) in poly(ether sulfone) (PES) for electricity generation in microbial fuel cells (MFCs). The composite PES/SPEEK membranes at various composition of SPEEK are prepared by the phase inversion method. The membranes are characterized by measuring roughness, proton conductivity, oxygen diffusion, water crossover and electrochemical impedance. The conductivity of hydrophobic PES membrane increases when a small amount (3–5%) of hydrophilic SPEEK is added. The electrochemical impedance spectra shows that the conductivity and capacitance of PES/SPEEK composite membranes during MFC operation are reduced from 6.15 × 10−7 to 6.93 × 10−5 (3197 Ω–162 Ω) and from 3.00 × 10−7 to 1.56 × 10−3 F, respectively when 5% of SPEEK added into PES membrane. The PES/SPEEK 5% membrane has the highest performance compared to other membranes with a maximum power density of 170 mW m−2 at the maximum current density of 340 mA m−2. However, the interfacial reaction between the membrane and the cathode with Pt catalyst indicates moderate reaction efficiency compared to other membranes. The COD removal efficiency of MFCs with composite membrane PES/SPEEK 5% is nearly 26-fold and 2-fold higher than that of MFCs with Nafion 112 and Nafion 117 membranes respectively. The results suggest that the PES/SPEEK composite membrane is a promising alternative to the costly perfluorosulfonate membranes presently used as separators in MFC systems.  相似文献   

20.
We investigated the effects of the compositions of catalyst layers and diffusion layers on performances of the membrane electrode assemblies (MEAs) for direct dimethyl ether fuel cell. The performances of the MEAs with different thicknesses of Nafion membranes were compared in this work. The optimal compositions in the anode are: 20 wt% Nafion content and 3.6 mg cm−2 Pt loading in the catalyst layer, and 30 wt% PTFE content and 1 mg cm−2 carbon black loading in the diffusion layer. In the cathode, MEA with 20 wt% Nafion content in the catalyst layer and 30 wt% PTFE content in the diffusion layer presented the optimal performance. The MEA with Nafion 115 membrane displayed the highest maximum power density of 46 mW cm−2 among the three MEAs with different Nafion membranes. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

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