Nafion/nitrated sulfonated poly(ether ether ketone) membranes for direct methanol fuel cells

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^®.     

Crosslinked SPEEK/AMPS blend membranes with high proton conductivity and low methanol diffusion coefficient for DMFC applications

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.     

Modification of sulfonated poly(ether ether ketone) proton exchange membrane for reducing methanol crossover

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.     

Preparation and properties of crosslinked sulphonated poly(arylene ether sulphone) blend s for direct methanol fuel cell applications

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).     

Performance of composite Nafion/PVA membranes for direct methanol fuel cells

This work has been focused on the characterization of the methanol permeability and fuel cell performance of composite Nafion/PVA membranes in function of their thickness, which ranged from 19 to 97 μm. The composite membranes were made up of Nafion^® polymer deposited between polyvinyl alcohol (PVA) nanofibers. The resistance to methanol permeation of the Nafion/PVA membranes shows a linear variation with the thickness. The separation between apparent and true permeability permits to give an estimated value of 4.0 × 10⁻⁷ cm² s⁻¹ for the intrinsic or true permeability of the bulk phase at the composite membranes. The incorporation of PVA nanofibers causes a remarkable reduction of one order of magnitude in the methanol permeability as compared with pristine Nafion^® membranes. The DMFC performances of membrane-electrode assemblies prepared from Nafion/PVA and pristine Nafion^® membranes were tested at 45, 70 and 95 °C under various methanol concentrations, i.e., 1, 2 and 3 M. The nanocomposite membranes with thicknesses of 19 μm and 47 μm reached power densities of 211 mW cm⁻² and 184 mW cm⁻² at 95 °C and 2 M methanol concentration. These results are comparable to those found for Nafion^® membranes with similar thickness at the same conditions, which were 210 mW cm⁻² and 204 mW cm⁻² respectively. Due to the lower amount of Nafion^® polymer present within the composite membranes, it is suggested a high degree of utilization of Nafion^® as proton conductive material within the Nafion/PVA membranes, and therefore, significant savings in the consumed amount of Nafion^® are potentially able to be achieved. In addition, the reinforcement effect caused by the PVA nanofibers offers the possibility of preparing membranes with very low thickness and good mechanical properties, while on the other hand, pristine Nafion^® membranes are unpractical below a thickness of 50 μm.     

Preparation of nitrated sulfonated poly(ether ether ketone) membranes for reducing methanol permeability in direct methanol fuel cell applications

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.     

Sulfonated poly(ether ether ketone)/polybenzimidazole oligomer/epoxy resin composite membranes in situ polymerization for direct methanol fuel cell usages

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.     

Semi-interpenetrating polymer network electrolyte membranes composed of sulfonated poly(ether ether ketone) and organosiloxane-based hybrid network

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.     

Sol–gel derived sulfonated-silica/Nafion composite membrane for direct methanol fuel cell

Sulfonated-silica/Nafion^® composite membranes were prepared in a sol–gel reaction of (3-Mercaptopropyl)trimethoxysilane (SH-silane) followed by solution casting, and then oxidated using 10 wt% H₂O₂ solution. The chemical and physical properties of the composite membranes were characterized by using FT-IR, XPS, ²⁹Si NMR and SEM analyses. Experimental results indicated that the optimum oxidation condition was 60 °C for 1 h. The performance of the silica–SO₃H/Nafion^® composite membranes was evaluated in terms of methanol permeability, proton conductivity and cell performance. The silica–SO₃H/Nafion^® composite membranes have a higher selectivity (C/P ratio = 26,653) than that of pristine Nafion^® (22,795), perhaps because of their higher proton conductivity and lower methanol permeability. The composite membrane with 0.6 wt% silica–SO₃H/Nafion^® performed better than pristine Nafion^®. The current densities were measured as 62.5 and 70 mA cm⁻² at a potential of 0.2 V with a composite membrane that contained 0 and 0.6 wt% silica–SO₃H, respectively. The cell performance of the DMFC was improved by introducing silica–SO₃H. The composite membrane with 0.6 wt% of silica–SO₃H yielded the maximum power density of 15.18 mW cm⁻². The composite membranes are suitable for DMFC applications with high selectivity.     

Sulfonated poly(ether ether ketone) membranes with sulfonated graphene oxide fillers for direct methanol fuel cells

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.     

Use of in situ polymerized phenol-formaldehyde resin to modify a Nafion membrane for the direct methanol fuel cell

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.     

Sulfonated titania submicrospheres-doped sulfonated poly(ether ether ketone) hybrid membranes with enhanced proton conductivity and reduced methanol permeability

Sulfonated titania submicrospheres (TiO₂-SO₃H) prepared through a facile chelation method are incorporated into sulfonated poly(ether ether ketone) (SPEEK) to fabricate organic-inorganic hybrid membranes with enhanced proton conductivity and reduced methanol permeability for potential use in direct methanol fuel cells (DMFCs). The pristine titania submicrospheres (TiO₂) with a uniform particle size are synthesized through a modified sol-gel method and sulfonated using 4,5-dihydroxy-1,3-benzenedisulfonic acid disodium salt as the sulfonation reagent. The sulfonation process is confirmed by Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectra (XPS). The hybrid membranes are systematically characterized in terms of thermal property, mechanical property, ionic exchange capacity (IEC), swelling behavior, and microstructural features. The methanol barrier property and the proton conductivity of the SPEEK/TiO₂-SO₃H hybrid membranes are evaluated. The presence of the fillers reduces methanol crossover through the membrane. Compared with the unsulfonated TiO₂-doped membranes, the TiO₂-SO₃H-doped ones exhibit higher proton conductivity due to the additional sulfonic acid groups on the surface of TiO₂. The hybrid membrane doped with 15 wt.% TiO₂-SO₃H submicrospheres exhibits an acceptable proton conductivity of 0.053 S cm⁻¹ and a reduced methanol permeability of 4.19 × 10⁻⁷ cm² s⁻¹.     

Novel hybrid polymer electrolyte membranes prepared by a silane-cross-linking technique for direct methanol fuel cells

To prepare a cross-linked hybrid proton exchange membrane with high mechanical and oxidative stability, a silane monomer, namely 3-glycidoxypropyltrimethoxysilane (KH-560), is first grafted to sulfonated poly(arylene ether ether ketone)s bearing carboxyl groups (SPAEK-C) and hydrolysis-condensation is then performed on the grafted membranes to make them cross-link. ¹H NMR measurements and Fourier transform infrared spectroscopy are used to characterize and confirm the structures of SPAEK-Cs and hybrid polymer electrolyte membranes, respectively. The Si-O-Si cross-linking structure enhances the stability of the PEM greatly. The proton conductivities of the hybrid membranes with 5% KH-560 in weight reach 0.155 S cm⁻¹ at 80 °C which is comparable to that of Nafion^® membranes. The ion-exchange capacity, water uptake and swelling, methanol permeability, mechanical properties are investigated to confirm their applicability in fuel cells.     

Effects and properties of various molecular weights of poly(propylene oxide) oligomers/Nafion acid–base blend membranes for direct methanol fuel cells

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.     

Highly conductive, methanol resistant fuel cell membranes fabricated by layer-by-layer self-assembly of inorganic heteropolyacid

Layer-by-layer (LBL) self-assembly is a simple and elegant method of constructing organic-inorganic composite thin films from environmentally benign aqueous solutions. In this paper, we utilize this method to develop proton-exchange membranes for fuel cells. The multilayer film is constructed onto the surface of sulfonated poly(arylene ether ketone) (SPAEK-COOH) membrane by LBL self-assembly of polycation chitosan (CTS) and negatively charged inorganic particle phosphotungstic acid (PTA). The highly conductive inorganic nanoparticles ensure SPAEK-COOH-(CTS/PTA)_n membranes to maintain high proton conductivity values up to 0.086 S cm⁻¹ at 25 °C and 0.24 S cm⁻¹ at 80 °C, which are superior than previous LBL assembled electrolyte systems. These multilayer systems also exhibit extremely low water swelling ratio and methanol permeability. The selectivity of SPAEK-COOH-(CTS/PTA)₈ is 2 orders of more than Nafion^® 117, which is attractive in direct methanol fuel cells (DMFCs).     

Synthesis and properties of novel HMS-based sulfonated poly(arylene ether sulfone)/silica nano-composite membranes for DMFC applications

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).     

A study on fabrication of sulfonated poly(ether ether ketone)-based membrane-electrode assemblies for polymer electrolyte membrane fuel cells

The porosity effect of catalyst electrodes in membrane-electrode assemblies (MEAs) using a hydrocarbon-based polymer as electrolyte and ionomer was investigated on physical and electrochemical properties by varying the content of ionomer binder (dry condition) in the catalyst electrodes. The MEAs were compared with the Nafion^®-based MEA using Nafion^® 112 and 5 wt.% ionomer solution (EW = 1100) in terms of porosity values, scanning electron microscopic images, Nyquist plots, dielectric spectra and I–V polarization curves. In this study, sulfonated poly(ether ether ketone) (SPEEK) membranes with 25 ± 5 μm of thickness and 5 wt.% ionomer solutions have been prepared. The prepared membranes were characterized in terms of FT-IR, DSC and proton conductivity. Proton conductivity of the SPEEK membranes was compared with one of the Nafion^® membranes with relative humidity. The porosity of the catalyst electrodes was calculated using the properties of catalyst, ionomer solution and solvent. As a result, the performance of the new type polymer (i.e., SPEEK in this study)-based MEA with the similar membrane conductivity and porosity of the catalyst electrode in the Nafion^® MEA was similar to that of the Nafion^® MEA.     

Cross-linked poly(arylene ether ketone) electrolyte membranes with enhanced proton conduction for fuel cells

A new class of covalently cross-linkable poly(arylene ether ketone)s (cPAEKs) with sulfonic acid groups on both the backbone and pedant positions were synthesized. 3-Amino-1,5-napthalene disulfonic acid salt was chosen as a strong sulfonating agent for the preparation of csPAEK membranes with high sulfonation degree (SD). The major advantage of synthesized membranes is their exceptionally high-proton conductivities but still maintaining low methanol permeability and water uptake. All csPAEK membranes exhibited higher proton conductivity than Nafion^®117 over the temperature range of 40–90 °C. For example, among these membranes, csPAEK0 with the lowest SD shows a proton conductivities of 0.071 S cm⁻¹ at 40 °C and 0.118 S cm⁻¹ at 90 °C, which are higher than those of Nafion^®117 (0.057 S cm⁻¹ at 40 °C and 0.108 S cm⁻¹ at 90 °C). More interestingly, csPAEK0 appears to have a low water uptake, with values of only 22% at 40 °C and 27% at 90 °C, indicating high dimensional stability in hot water. Moreover, in many cases, csPAEK membranes with 15% cross-linking degree (CD) exhibited low methanol permeability, good thermal stability, and showed very high strain at break. The superior proton conduction, methanol permeation, and water uptake properties of the prepared membranes are of significant interest for both PEMFCs and DMFCs applications.     

Investigation of the effects of AMPS-modified nanoclay on fuel cell performance of sulfonated aromatic proton exchange membranes

Here we describe preparation and characterization of a series of nanocomposite polyelectrolytes based on partially sulfonated poly (ether ether ketone) (SPEEK) and organically modified montmorillonite (MMT). Optimum degree of sulfonation for SPEEK is selected based on its transport properties. MMT is modified via ion exchange reaction using a 2-acrylamido-2-methylpropanesulfonic acid (AMPS) as a functional modifier. AMPS-MMT at different loadings is introduced into the SPEEK matrices via the solution intercalation technique. Also, the nanocomposite membranes are fabricated using SPEEK and commercially available nanoclays like Cloisite Na (Na-MMT) and Cloisite 15A. Transport properties, proton conductivity and methanol permeability of the fabricated composite membranes are evaluated. Presence of AMPS-MMT significantly decreases the activation energy needed for proton conductivity. A membrane based on SPEEK/AMPS-MMT-3 wt% is selected as an optimum formulation which exhibits a high selectivity and power density at the elevated methanol concentrations. Moreover, it is found that the optimum nanocomposite membrane not only provides higher power output compared to the neat SPEEK and Nafion^®117 membranes, but also exhibits a higher open circuit voltage (OCV) in comparison with pristine SPEEK and commercial Nafion^® 117 membranes. Owing to the desirable transport and electrochemical properties SPEEK/AMPS-MMT nanocomposite can be considered as an alternative membrane for direct methanol fuel cell applications.     

SPEEK/epoxy resin composite membranes in situ polymerization for direct methanol fell cell usages

Sulfonated poly(ether ether ketone) (SPEEK)/4,4′-diglycidyl(3,3′,5,5′-tetramethylbiphenyl) epoxy resin (TMBP) composite membranes in situ polymerization were prepared for the purpose of improving the methanol resistance and mechanical properties of SPEEK membranes with high ion-exchange capacities (IEC) for the usage in the direct methanol fuel cells (DMFCs). The effects of introduction of TMBP content on the properties of the composite membranes were investigated in detail. The composite membranes have good mechanical, thermal properties, lower swelling ratio, lower water diffusion coefficient (0.87 × 10⁻⁵ cm² s⁻¹ at 80 °C) and better methanol resistance (5.26 × 10⁻⁷ cm² s⁻¹ at 25 °C) than SPEEK membranes. The methanol diffusion coefficients of the composite membranes are much lower than that of SPEEK membrane (17.5 × 10⁻⁷ cm² s⁻¹ at 25 °C). Higher selectivity was been found for the composite membranes in comparison with SPEEK. Therefore, the SPEEK/TMBP composite membranes show a good potential in DMFCs usages.