Semi-interpenetrating network based on cross-linked poly(vinyl alcohol) and poly(styrene sulfonic acid-co-maleic anhydride) as proton exchange fuel cell membranes

A series of promising proton conducting membranes have been synthesized by using poly(vinyl alcohol), with sulfosuccinic acid (SSA) as a cross-linking agent and poly(styrene sulfonic acid-co-maleic acid) (PSSA-MA) as proton source, which form a semi-interpenetrating network (semi-IPN) PVA/SSA/PSSA-MA membrane. A bridge of SSA between PVA molecules not only reinforces the network but also provides extra proton conducting paths. PSSA-MA chains trapped in the network were the major sources of protons in the membrane. FT-IR spectra confirmed the success of the cross-linking reaction and molecular interactions between PVA and PSSA-MA. Associated characteristics of a proton conducting membrane including ion-exchange capacity (IEC), proton conductivity and water uptake were investigated. The measured IECs of the membranes increased with increase of PSSA-MA content varying from 20 to 80% and correlated well with the measured uptake water and proton conductivity. The semi-IPN membranes with PSSA-MA over 60% exhibited a higher proton conductivity than Nafion-115 and also a reasonable level of water uptake. Fuel cell performance of membrane electrode assemblies (MEA) was evaluated at various temperatures with H₂/air as well as H₂/O₂ gases under ambient pressure. A power density of 0.7 W cm⁻² was obtained for the MEA using PVA/SSA20/PSSA-MA80 membrane using H₂/O₂ at 50 °C.     

Proton-conducting membranes with high selectivity from cross-linked poly(vinyl alcohol) and poly(vinyl pyrrolidone) for direct methanol fuel cell applications

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.     

Fabrication and characterization of poly(vinyl alcohol)/montmorillonite/poly(styrene sulfonic acid) proton-conducting composite membranes for direct methanol fuel cells

A high performance poly(vinyl alcohol)/montmorillonite/poly(styrene sulfonic acid) (PVA/MMT/PSSA) proton-conducting composite membrane was fabricated by a solution casting method. The characteristic properties of these blend composite membranes were investigated by using thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy, methanol permeability measurement, and the AC impedance method. The ionic conductivities for the composite membranes are in the order of 10⁻³ S cm⁻¹ at ambient temperature. There are two proton sources used on this novel composite membrane: the modified MMT fillers and PSSA polymer, both materials all contain the -SO₃H group. Therefore, the ionic conductivity was greatly enhanced. The methanol permeabilities of PVA/MMT/PSSA composite membranes is of the order of 10⁻⁷ cm² s⁻¹. It is due to the excellent methanol barrier properties of the PVA polymer. The peak power densities of the air-breathing direct methanol fuel cells (DMFCs) with 1M, 2M, 4M CH₃OH fuels were 14.22, 20.00, and 13.09 mW cm⁻², respectively, at ambient conditions. The direct methanol fuel cell with this composite polymer membrane exhibited good electrochemical performance. The proposed PVA/MMT/PSSA composite membrane is therefore a potential candidate for future applications in DMFC.     

Poly(styrene sulfonic acid)/poly(vinyl alcohol) copolymers with semi-interpenetrating networks as highly sulfonated proton-conducting membranes

Poly(styrene sulfonic acid)/poly(vinyl alcohol) proton-conducting membranes with semi-interpenetrating networks (semi-IPNs) were prepared using a modified two-step crosslinking strategy. We previously employed sulfosuccinic acid (SSA) and glutaraldehyde (GA) as crosslinking agents to form a dense hydrophobic layer at the outer membrane surface. Although the proton conductivity of the resulting membrane increased with the content of SSA, the methanol permeability also increased. In this study it was found that the introduction of a sufonating agent, with a high molecular weight, i.e. poly(styrene sulfonic acid) (PSSA), at a PSSA/poly(vinyl alcohol) (g g⁻¹) ratio greater than 0.72, increased the density of the tangled IPN structures that effectively impede the membrane's permeability to MeOH, while enhancing its proton conductivity. The synthesized semi-IPN membranes exhibited high proton conductivities (up to 5.88 × 10⁻² S cm⁻¹ at room temperature, i.e. greater than those of Nafion membranes) and high resistances to MeOH permeation (ca. 1 × 10⁻⁷ cm² S⁻¹, that is approximately one order of magnitude lower than that of Nafion membranes).     

Performance of passive direct methanol fuel cell with poly(vinyl alcohol)-based polymer electrolyte membranes

Polymer electrolyte membranes (PEMs) were prepared from poly(vinyl alcohol) (PVA) and a modified PVA polyanion containing 2 mol% of 2-methyl-1-propanesulfonic acid (AMPS) groups as a copolymer. The effect of the AMPS content and the crosslinking conditions on the properties of the membranes was investigated in PEMs with various AMPS contents prepared under various crosslinking conditions. The proton conductivity and the permeability of methanol through the PEMs increased with increasing AMPS content, C_AMPS, and with decreasing annealing temperature, T_a, because of the increase in the degree of swelling. The permeability coefficient of methanol through the PEM prepared under the conditions of C_AMPS = 2.0 mol% and T_a 190 °C was approximately 30 times lower than that of Nafion^® 117 under the same measurement conditions. A maximum proton permselectivity of 96 × 10³ S cm⁻³ s, which is defined as the ratio of the proton conductivity to the permeability of methanol, was obtained for this PEM. The permselectivity value is about three times higher than that of Nafion^® 117. A passive air-breathing-type DMFC test cell constructed using the PEM delivered 2.4 mW cm⁻² of maximum power density, P_max, at 2 M methanol concentration, which is smaller than the value obtained with Nafion^® 117. However, at high methanol concentrations (>10 M), the P_max of the PEM decreases slightly to 1.6 mW cm⁻² (at a methanol concentration of 20 M), whereas the P_max of Nafion^® 117 falls to almost zero.     

A novel crosslinking strategy for preparing poly(vinyl alcohol)-based proton-conducting membranes with high sulfonation

This study synthesizes poly(vinyl alcohol) (PVA)-based polymer electrolyte membranes by a two-step crosslinking process involving esterization and acetal ring formation reactions. This work also uses sulfosuccinic acid (SSA) as the first crosslinking agent to form an inter-crosslinked structure and a promoting sulfonating agent. Glutaraldehyde (GA) as the second crosslinking agent, reacts with the spare OH group of PVA and forms, not only a dense structure at the outer membrane surface, but also a hydrophobic protective layer. Compared with membranes prepared by a traditional one-step crosslinking process, membranes prepared by the two-step crosslinking process exhibit excellent dissolution resistance in water. The membranes become water-insoluble even at a molar ratio of SO₃H/PVA-OH as high as 0.45. Moreover, the synthesized membranes also exhibit high proton conductivities and high methanol permeability resistance. The current study measures highest proton conductivity of 5.3 × 10⁻² S cm⁻¹ at room temperature from one of the synthesized membranes, higher than that of the Nafion^® membrane. Methanol permeability of the synthesized membranes measures about 1 × 10⁻⁷ cm² S⁻¹, about one order of magnitude lower than that of the Nafion^® membrane.     

Poly(vinyl alcohol)/sulfated β-cyclodextrin for direct methanol fuel cell applications

We report a composite membrane based on poly(vinyl alcohol) and sulfated β-cyclodextrin in this paper. TGA and SEM tests provide direct evidence of the thermal stability and the uniform structure of the composite membranes. The performances of the composite membranes are investigated in terms of swelling behavior, methanol permeability and proton conductivity as function of sulfated β-cyclodextrin content. We find that the introduction of sulfated β-cyclodextrin can reduce water uptake. The temperature dependence of proton conductivity reveals that the proton conducting activation energy of the composite membranes is similar to that of Nafion 115, in other words, both the vehicle and Grotthus mechanisms are assumed to be responsible for the composite membranes’ proton transfer. Methanol permeability decreases as the methanol feed concentration increases from 2 M to 20 M. Both proton conductivity and methanol permeability increases with increasing sulfated β-cyclodextrin. The selectivity of the composite membranes defined as the ratio of proton conductivity to methanol permeability obtains the maximum of 1.710 × 10⁴ S s cm⁻³ at the composition of 17 wt.% sulfated β-cyclodextrin. The MEAs fabricate with these membranes are tested, no distinct change occurred to the composite membranes after the MEAs operating for 288 h. These data indicates the chemical and electrochemical stability of the membranes and their potential application in direct methanol fuel cells.     

Direct methanol fuel cell based on poly(vinyl alcohol)/titanium oxide nanotubes/poly(styrene sulfonic acid) (PVA/nt-TiO2/PSSA) composite polymer membrane

The high performance poly(vinyl alcohol)/titanium oxide nanotubes/poly(styrene sulfonic acid) (PVA/nt-TiO₂/PSSA) proton-conducting composite membrane is prepared by a solution casting method. The characteristic properties of these blend composite membranes are investigated by thermal gravimetric analysis (TGA), scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDX), micro-Raman spectroscopy, dynamic mechanical analysis (DMA), methanol permeability measurement and AC impedance method. It is found that the peak power densities of the DMFC with 1, 2, and 4 M CH₃OH fuels are 12.85, 23.72, and 10.99 mW cm⁻², respectively, at room temperature and ambient air. Especially, among three methanol concentrations, the 2 M methanol shows the highest peak power density among three methanol concentrations. The results indicate that the air-breathing direct methanol fuel cell comprised of a novel PVA/nt-TiO₂/PSSA composite polymer membrane has excellent electrochemical performance and stands out as a viable candidate for applications in DMFC.     

A novel organic/inorganic polymer membrane based on poly(vinyl alcohol)/poly(2-acrylamido-2-methyl-1-propanesulfonic acid/3-glycidyloxypropyl trimethoxysilane polymer electrolyte membrane for direct methanol fuel cells

Poly(vinyl alcohol)/poly(2-acrylamido-2-methyl-1-propanesulfonic acid (PAMPS)/3-glycidyloxypropyl)trimethoxysilane (PVA/PAMPS/GPTMS) organic/inorganic proton-conducting polymer membranes are prepared by a solution casting method. PAMPS is a polymeric acid commonly used as a primary proton donor, while 3-(glycidyloxypropyl)trimethoxysilane (GPTMS) is an inorganic precursor forming a semi-interpenetrating network (SIPN). Varying amounts of sulfosuccinic acid (SSA) are used as the cross-linker and secondary proton source. The characteristic properties of PVA/PAMPS/GPTMS composite membranes are investigated by thermal gravimetric analysis (TGA), scanning electron microscopy (SEM), micro-Raman spectroscopy and the AC impedance method. Direct methanol fuel cells (DMFCs) made of PVA/PAMPS/GPTMS composite membranes are assembled and examined. Experimental results indicate that DMFCs employing an inexpensive, non-perfluorinated, organic/inorganic SIPN membrane achieve good electrochemical performance. The highest peak power density of a DMFC using PVA/PAMPS/GPTMS composite membrane with 2 M CH₃OH solution fuel at ambient temperature is 23.63 mW cm⁻². The proposed organic/inorganic proton-conducting membrane based on PVA/PAMPS/GPTMS appears to be a viable candidate for future DMFC applications.     

Improving the direct methanol fuel cell performance with poly(vinyl alcohol)/titanium dioxide nanocomposites as a novel electrolyte additive

The present investigation deals with the fabrication of new poly(vinyl alcohol)/titanium dioxide (PVA/TiO₂) nanocomposites (NCs) with different titanium dioxide (TiO₂) loading by using ultrasound irradiation. For the improvement of nanoparticles (NPs) dispersion and increasing possible interactions between NPs and PVA, the surface of TiO₂ NPs was modified by γ-aminopropyltriethoxy silane. The as-prepared NCs were characterized by spectroscopic, thermogravimetric analysis and electron microscopy methods. The results demonstrate that NPs dispersed homogeneously within the PVA matrix on nanoscale, which could be assigned to the hydrogen and covalent bonds formed between PVA and NPs. The results indicated that heat stability of NCs was improved in the presence of modified TiO₂ NPs. The mechanisms of surface modification and a possible mechanism of ultrasonic induced interaction between polymer and NPs have been analyzed.     

Crosslinked poly(vinyl alcohol) membrane as separator for domestic wastewater fed dual chambered microbial fuel cells

The use of Nafion as a proton exchange membrane in microbial fuel cells (MFCs) is expensive with operational issues like biofouling and fuel crossover limiting the practical application of the device to harvest energy from wastewaters. In this connection, a facile route is adapted to fabricate a Nafion-alternative membrane using poly(vinyl alcohol) (PVA) crosslinked with glutaraldehyde (GA) as a relatively low-cost, effective membrane for MFCs. The crosslinking of the PVA membrane resulted in a reduction in hydroxyl groups and the formation of the acetal ring and ether linkage demonstrated by controlled water uptake and swelling ratio with enhanced thermo-mechanical stability. The crosslinked membrane displayed higher power density than those typically reported for domestic wastewater fed MFCs, reaching a maximum of 158.28 mW/m² for the fabricated membrane. The PVA-GA membrane with antimicrobial activity, high power performance, and negligible fuel crossover shows its potential as a separator in future MFCs based on its performance and low cost of installation.     

Performance comparison of modified poly(vinyl alcohol) based membranes in alkaline fuel cells

There are several problems which are holding back the use of fuel cells. The utilization of fuel cells depends on the start-up costs which are very high due to the use of expensive materials for their construction. In that respect, we describe a cost-effective alkaline fuel cell (AFC) that uses solid, polymer based, membrane instead of conventionaly used, highly concentrated, corrosive, liquid alkaline electrolyte. This approach to AFC is potentially the basis of a simple, low-cost system, that can solve one of the problems of the highly-efficient and environment-friendly AFC.The focus of this paper are low cost composite alkaline membranes, based on poly(vinyl alcohol) (PVA). The PVA matrix is made by solution cast method and gamma irradiation crosslinking. Three different types of membranes are obtained in this manner - plain PVA membrane, PVA membrane cross-linked using gamma irradiation (γ-PVA) and composite PVA membrane doped with Mo (PVA-Mo). These membranes are immersed in the alkaline solution and investigated as anion exchange membranes. The performance of the solid alkaline fuel cells (SAFCs) containing these PVA membranes has been studied under hydrogen and oxygen gas flow on the Pt/C catalyst. Both, γ-PVA and PVA-Mo membranes are modified to absorb larger amounts of alkaline solution than the PVA membrane, thus greatly improving the performance of the SAFC, in terms of output power. This is clearly indicated in the polarisation curves. The electrochemical impedance spectroscopy measurements during the SAFC operation were also performed to give better insight in the effect observed. Investigation presented in this paper clearly indicates that solid alkaline PVA membranes can be used for the construction of the SAFCs.     

Poly (vinyl alcohol)/3-(trimethylammonium) propyl-functionalized silica hybrid membranes for alkaline direct ethanol fuel cells

A novel hybrid membrane based on poly (vinyl alcohol)/3-(trimethylammonium) propyl-functionalized silica (PVA-TMAPS) is prepared by a simple solution-casting method. The properties of the PVA-TMAPS membranes are characterized by Fourier transform infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM), thermal gravimetric analysis (TGA), and X-ray diffraction (XRD). It is found that the thermal stability of the membranes increases with the addition of TMAPS particles. Moreover, the study of the effect of different weight ratios of PVA to TMAPS on the OH⁻ conductivity shows that the membrane with a ratio of PVA:TMAPS = 90:10 exhibited the highest OH⁻ conductivity. Finally, it is shown that the application of the alkaline membrane (PVA:TMAPS = 90:10) to an direct ethanol fuel cell can yield a peak power density of about 50 mW cm⁻² at 60 °C.     

Fabrication and properties of poly(vinyl alcohol)-based polymer electrolyte membranes for direct methanol fuel cell applications

A series of poly(vinyl alcohol) (PVA)-based organic–inorganic crosslinked polymer electrolyte membranes with PVA and poly(methacrylic acid-2-acrylamido-2-methyl-1-propanesulfonic acid-vinyltriethoxysilicone) (PMAV) are prepared for direct methanol fuel cell applications. Fourier transform infrared (FTIR) spectroscopy measurements clearly reveal the existence of crosslinking reactions and molecular interactions in PVA–PMAV membranes. The results of TGA show that the PVA–PMAV membranes possess good thermal stability. The uptake behavior, methanol diffusion coefficient, proton conductivity and selectivity of membranes also are investigated as function of PMAV content. The results indicate that the PVA-based organic–inorganic crosslinked membranes are particularly promising to be used as polymer electrolyte membranes due to their excellent methanol barrier property, suitable proton conductivity and high selectivity.     

Mass balance research for high electrochemical performance direct methanol fuel cells with reduced methanol crossover at various operating conditions

Mass balance research in direct methanol fuel cells (DMFCs) provides a more practical method in characterizing the mass transport phenomena in a membrane electrode assembly (MEA). This method can be used to measure methanol utilization efficiency, water transport coefficient (WTC), and methanol to electricity conversion rate of a MEA in DMFCs. First, the vital design parameters of a MEA are recognized for achieving high methanol utilization efficiency with increased power density. In particular, the structural adjustment of anode diffusion layer by adding microporous layer (MPL) is a very effective way to decrease WTC with reduced methanol crossover due to the mass transfer limitation in the anode. On the other hand, the cathode MPL in the MEA design can contribute in decreasing methanol crossover. The change of structure of cathode diffusion layer is also found to be a very effective way in improving power density. In contrast, the WTC of DMFC MEAs remains virtually constant in the range of 3.4 and 3.6 irrespective of the change of the cathode GDL. The influence of operating condition on the methanol utilization efficiency, WTC, and methanol to electricity conversion rate is also presented and it is found that these mass balance properties are strongly affected by temperature, current density, methanol concentration, and the stoichiometry of fuel and air.     

Electrochemical performance of an air-breathing direct methanol fuel cell using poly(vinyl alcohol)/hydroxyapatite composite polymer membrane

A novel composite polymer membrane based on poly(vinyl alcohol)/hydroxyapatite (PVA/HAP) was successfully prepared by a solution casting method. The characteristic properties of the PVA/HAP composite polymer membranes were examined by thermal gravimetric analysis (TGA), X-ray diffraction (XRD), scanning electron microscopy (SEM), micro-Raman spectroscopy and AC impedance method. An air-breathing DMFC, comprised of an air cathode electrode with MnO₂/BP2000 carbon inks on Ni-foam, an anode electrode with PtRu black on Ti-mesh, and the PVA/HAP composite polymer membrane, was assembled and studied. It was found that this alkaline DMFC showed an improved electrochemical performance at ambient temperature and pressure; the maximum peak power density of an air-breathing DMFC in 8 M KOH + 2 M CH₃OH solution is about 11.48 mW cm⁻². From the application point of view, these composite polymer membranes show a high potential for the DMFC applications.     

Characterization of cation-exchange membranes prepared from poly(vinyl alcohol) and poly(vinyl alcohol-b-styrene sulfonic acid)

Block-type cation-exchange membranes (CEMs) have been prepared by blending poly(vinyl alcohol) (PVA) and the polyanion poly(vinyl alcohol-b-styrene sulfonic acid) at various molar percentages of cation-exchange groups to vinyl alcohol groups, C_pa, and by cross-linking the PVA chains with glutaraldehyde (GA) solution at various GA concentrations, C_GA. The characteristics of the block-type CEMs were compared with random-type CEMs prepared in a previous study from the random copolymer, poly(vinyl alcohol-co-2-acrylamido-2-methylpropane sulfonic acid). At equal molar percentages of the cation-exchange groups, the water content of the block-type CEMs was less than that of the random-type CEMs. The charge density of the block-type CEMs increased with increasing C_pa and reached a maximum value. Further, the maximum value of the charge density increased with increasing C_GA. The maximum charge density value of 1.3 mol/dm³ was obtained for the block-type CEM with C_pa = 3.1 mol% and C_GA = 0.10 vol.%, which is almost two thirds of the value of a commercially available CEM [CMX: ASTOM Corp. Japan]. A comparison of the block-type and random-type CEMs with almost the same membrane resistance showed that the block-type CEMs had higher dynamic transport numbers than the random-type ones. The dynamic transport number and membrane resistance of the block-type CEM with C_pa = 4.0 mol% and C_GA = 0.10 vol.% were 0.96 and 4.9 Ω cm², respectively.     

Self-crosslinked anion exchange membranes by bromination of benzylmethyl-containing poly(sulfone)s for direct methanol fuel cells

A series of novel anion exchange membranes based on poly(arylene ether sulfone) were fabricated. And the synthesized 1, 1, 2, 3, 3-pentamethylguanidine was used as a hydrophilic group. Bromination reaction rather than chloromethylation was used for the preparation of target conductive polymers. Fourier transform infrared spectroscopy (FTIR), ¹H NMR and mass spectrometry (MS) were used to characterize the as-synthesized polymers. The ratio of hydrophilic to hydrophobic monomers was varied to study the structure-property of the membranes. The performance of the membrane with both hydrophilic/hydrophobic segments was improved over the membrane with sole hydrophilic segments. The self-crosslinking structure of the as-prepared membranes is partly responsible for their very low methanol permeability with the minimum of 1.02 × 10⁻⁹ cm⁻²⋅S⁻¹ at 30 °C and insolubility in organic solvents considered. The structural dependence of water uptake is in the range of 25–87%. The as-prepared membranes did not suffer from serious membrane swelling. The ionic exchange capacity (IEC) reached a maximum of 1.21 mmol⋅g⁻¹. The ionic conductivity of the membrane in deionized water is 6.00 and 13.00 × 10⁻² S⋅cm⁻¹ at 30 and 80 °C respectively.     

Sulfonated poly(ether ether ketone) as an ionomer for direct methanol fuel cell electrodes

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.     

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^®.