Properties and morphology of Nafion/polytetrafluoroethylene composite membrane fabricated by a solution-spray process

The Nafion/polytetrafluoroethylene (Nafion/PTFE) composite membrane is fabricated by a solution-spray process. The performance and morphology of the composite membrane are studied in terms of the mechanical properties, conductivity, and permeability. The results of TEM and X-ray studies show that the morphologies of crystalline and ion cluster of the perfluorosulfonated acid (PFSA) in composite membrane are apparently similar to that of Nafion^® NR211 membrane. The composite membrane has higher stiffness and strength and lower swelling than that of Nafion^® NR211. The conductivity at 85 °C of 0.375 S cm⁻¹ is relatively high in comparison to that of 0.300 S cm⁻¹ for Nafion^® NR211. The 20 kW stack with the composite membranes is evaluated. The mean single cell voltage is 0.67 V @1000 mA cm⁻². The stack has behaved performance uniformity and steadily operated under low humidifying condition. In consideration of the integration of complex structure and perfect morphology, the solution-spray process is feasible for composite proton exchange membrane manufacture.     

Sulfonic acid functionalized graphene oxide paper sandwiched in sulfonated poly(ether ether ketone): A proton exchange membrane with high performance for semi-passive direct methanol fuel cells

Sulfonated poly(ether ether ketone) (SPEEK) membranes have been deposited on the both sides of a sulfonic acid functionalized graphene oxide (SGO) paper to form a proton exchange membrane (PEM) with a sandwiched structure. The obtained SPEEK/SGO/SPEEK membrane could exhibit proton conductivity close to Nafion^® 112 and lower methanol permeability. The use of this SPEEK/SGO/SPEEK membrane greatly improves the performance of the semi-passive direct methanol fuel cell (DMFC). The semi-passive DMFC with the SPEEK/SGO/SPEEK membrane is found to be capable of delivering the peak power density 60% higher than that with the commercial Nafion^® 112. This, along with its comparable durability to Nafion^® 112, strongly suggests the great promise of using the SPEEK/SGO/SPEEK membrane as the PEM.     

Evaluation of composite membranes for direct methanol fuel cells

The performance of direct methanol fuel cells (DMFCs) can be significantly affected by the transport of methanol through the membrane, depolarising the cathode. In this paper, the literature on composite membranes that have been developed for reduction of methanol crossover in DMFCs is reviewed. While such membranes can be effective in reducing methanol permeability, this is usually combined with a reduction in proton conductivity. Measurements of methanol permeability and proton conductivity are relatively straightforward, and these parameters (or a membrane ‘selectivity’ based on the ratio between them) are often used to characterize DMFC membranes. However, we have carried out one-dimensional simulations of DMFC performance for a wide range of membrane properties, and the results indicate that DMFC performance is normally either limited by methanol permeability or proton conductivity. Thus use of a ‘selectivity’ is not appropriate for comparison of membrane materials, and results from the model can be used to compare different membranes. The results also show that Nafion^® 117 has an optimum thickness, where DMFC performance is equally limited by both methanol permeability and proton conductivity. The model also indicates that new composite membranes based on Nafion^® can only offer significant improvement in DMFC performance by enabling operation with increased methanol concentration in the fuel. A number of composite membrane materials that have been reported in the literature are shown to deliver significant reduction in DMFC performance due to reduced proton conductivity, although improved performance at high methanol concentration may be possible.     

Effect of solvents on the characteristics of Nafion®/PTFE composite membranes for fuel cell applications

Composite membranes were prepared by impregnation of porous PTFE membrane with 2.5% Nafion^® solution prepared in various solvents. The solvents chosen were based on their solubility parameters to effectively wet the substrate for obtaining membranes with lower resistances. Earlier studies on composite membrane preparation did not take the solubility parameter of the solvent to wet the substrate into account. Membrane conductivity was dependent on the solvent type and its solubility parameter. Solvents with solubility parameter close to Nafion^® backbone/PTFE showed lower charge transfer resistance and the solvents with solubility parameter close to ionic groups showed higher conductivity. The effect of other parameters like compaction pressure, humidity and incorporation of Pt particles on the membrane resistance have also been investigated.     

The degree and effect of methanol crossover in the direct methanol fuel cell

A simple model is presented to describe the permeation of methanol from the anode to the cathode in direct methanol fuel cell (DMFC). Measured permeation rates of water and methanol through Nafion^® 117 under varied pressure differentials across the membrane are used to determine key parameters in the model. This model is able to explain the effect of oxygen pressure at the cathode and methanol concentration at the anode on the measured cell voltage-current response of the DMFC.     

Novel non-alloy Ru/Pd composite membrane fabricated by electroless plating for hydrogen separation

This study presents a new non-alloy Ru/Pd composite membrane fabricated by electroless plating for hydrogen separation. It shows that palladium and ruthenium can be deposited on an aluminum-oxide-modified porous Hastalloy by using our new EDTA-free plating bath at room temperature and 358 K, respectively. A 6.8 μm thick non-alloy Ru/Pd membrane film could be plated and helium leak test confirmed that the membrane was free of defects. Hydrogen permeation test showed that the membrane had a hydrogen permeation flux of 4.5 × 10⁻¹ mol m⁻² s⁻¹ at a temperature of 773 K and a pressure difference of 100 kPa. The hydrogen permeability normalized value with thickness of the membrane was 1.4 times higher than our pure Pd membrane having similar structure. The EDX profiles of the front and back side membrane, cross-sectional EDX line scanning and XRD profile show that there was no alloying progress between the palladium and ruthenium layer after hydrogen permeation test at 773 K.     

A novel membrane for DMFC - Na2Ti3O7 nanotubes/Nafion composite membrane

In this study, novel sodium titanate (Na₂Ti₃O₇) nanotube/Nafion^® composite membranes were prepared by a solution casting method. The properties of these composite membranes were studied using Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). Additionally, the water uptake, methanol permeability, proton conductivity, and selectivity of the composite membranes were measured to evaluate the applicability of these membranes in DMFCs. It was found that the addition of Na₂Ti₃O₇ nanotubes enhanced the water uptake and reduced the methanol permeability of the composite membranes. The proton conductivity and methanol permeability depend on the Na₂Ti₃O₇ nanotube content. Using the selectivity, the optimal nanotube contents was found to be 5 wt%. The new composite membrane was found to have significantly higher selectivity than a pure Nafion^® membrane and thus has good potential to outperform Nafion^® in DMFCs.     

Coolant induced variable temperature flow field for improved performance of proton exchange membrane fuel cells

The objective of the coolant induced variable temperature flow field concept is to maintain high membrane water content along the entire flow field without external humidification and without occurrence of liquid water inside the cell at higher currents. This is achieved by imposing a temperature gradient in the cathode downstream direction in such manner that the product water is just sufficient to maintain close to 100% relative humidity along the entire flow field. The concept must be feasible for stack applications and flexible to enable efficient operation under significantly different operating conditions. The concept is investigated via interactive combination of computational fluid dynamics modeling and experimental validation for two membranes, namely Nafion^® 212 and Nafion^® 115. Additional calculations are also carried out for a five-cell stack with Nafion^® 212 membranes. The results of the computational fluid dynamics model are compared with the experimental data. Calculated and measured current density and relative humidity distributions along the cell give insight in the membrane water content and membrane water flux. With the coolant induced variable temperature flow field concept it is possible to achieve close to 100% relative humidity along the entire flow field without the requirement for external humidification, and to minimize the occurrence of liquid water inside the cell, resulting in improved performance of the cell in comparison with commonly used isothermal operation.     

Study on hydrogen permeation of Ni‐BaZr0.1Ce0.7Y0.2O3−δ asymmetric cermet membrane

Early on, we had reported the preparation process of Ni‐BaZr_0.1Ce_0.7Y_0.2O_3?δ asymmetric cermet membrane (Ni‐BZCY ACM). In this work, we further optimized the sintering procedure and investigated the effect of water vapor in feed gas, operating time, H₂ concentration difference across the membrane, and dense layer thickness of Ni‐BZCY ACM on hydrogen permeation behaviors. Adding the water vapor into feed gas can effectively improve the hydrogen permeability due to the appearance of a new proton hydration path. An almost unchanged hydrogen permeation output during 100‐hour testing confirms the membrane stability under operating condition. More important, the rate‐limiting step for hydrogen permeation process was elucidated according to the relationship between dense membrane thicknesses and hydrogen permeation fluxes. The surface exchange kinetics predominated permeation performance when the thickness is down to 50 μm, especially at a lower temperature, which was found for the first time for Ni‐BZCY cermet membrane. This result indicated that enhancing exchange kinetics of membrane surface became significant and indispensable for higher hydrogen separation efficiency.     

Understanding of temperature-dependent performance of short-side-chain perfluorosulfonic acid electrolyte and reinforced composite membrane

The short-side-chain (SSC) perfluorosulfonic acid (PFSA) membranes are important candidates as membrane electrolytes applied for high temperature or low relative humidity (RH) proton exchange membrane fuel cells. In this paper, the fuel cell performance, proton conductivity, proton mobility, and water vapor absorption of SSC PFSA electrolytes and the reinforced SSC PFSA/PTFE composite membrane are investigated with respect to temperature. The pristine SSC PFSA membrane and reinforced SSC composite membrane show better fuel cell performance and proton conductivity, especially at high temperature and low relative humidity conditions, compared to the long-side-chain (LSC) Nafion membrane. Under the same condition, the proton mobility of SSC PFSA membranes is lower than that of the LSC PFSA membrane. The water vapor uptake values for Nafion 211 membrane, pristine SSC PFSA membrane and SSC PFSA/PTFE composite membrane are 9.62, 11.13, and 11.53 respectively at 40 °C and they increase to 9.89, 12.55 and 13.09 respectively at 120 °C. The high water content of SSC PFSA membrane makes it maintain high performance even at elevated temperatures.     

Nanocomposite membranes of surface-sulfonated titanate and Nafion® for direct methanol fuel cells

Various thiol and sultone groups were grafted onto the surface of titanate nanosheets to render organic sulfonic acid (HSO₃–) functionality. The nanocomposite membranes were cast together with Nafion^® using these materials as inorganic fillers. Nanocomposite membranes containing surface-sulfonated titanates showed higher proton conductivity than composite membranes containing untreated TiO₂ P25 particles. They showed better mechanical and thermal stability than Nafion alone. The methanol permeability of nanocomposite membranes decreased with increasing the content of the sulfonated titanate in the nanocomposite membranes. The relative permeability of methanol through these composite membranes with 2 and 5 M methanol solutions was reduced by up to 38 and 26%, respectively, relative to pristine Nafion 115 membranes. The membrane electrode assembly using Nafion/sulfonated titanate nanocomposite membranes exhibited up to 57% higher power density than the assembly containing a pristine Nafion membrane under typical operating conditions of direct methanol fuel cells.     

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.     

Experimental study on water transport in membrane humidifiers for polymer electrolyte membrane fuel cells

This paper presents an experimental setup for the measurement of water transfer in membrane humidifiers for automotive polymer electrolyte membrane (PEM) fuel cells at different process conditions. This setup was used to determine steady-state water permeation through perfluorinated sulfonic acid (PFSA)-based polymer membranes. The process conditions were varied within a relative humidity in the feed stream of RH = 30–90 %, absolute pressures of p = 1.25–2.5 bar, and temperatures of T = 320–360 K. The examined membranes are Nafion® membranes of different thicknesses (Nafion® 211, 212 and 115) and an experimental composite membrane manufactured by W. L. Gore & Associates. It was found that the overall water permeance is affected by both the mass transfer resistance of the membrane and the resistances in the boundary layers of the adjacent gas streams. The overall permeance is a strong function of water activity, with high levels of relative humidity showing the highest overall permeance. The absolute pressure only affects the overall permeance by affecting the diffusion in the boundary layers. Lower pressures are preferable for high overall water permeances. Increasing temperatures favor diffusion in the membrane and the boundary layers but lead to lower sorption into the membrane. The thicker Nafion® membranes show lower overall permeance at higher temperatures, while the overall permeance of the composite membrane shows no dependency on the temperature. Investigation of membrane humidifiers in counter-, co-, and cross-flow shows that the flow configuration in our setup has very little impact on the water flux in the humidifier.     

Amelioration in physicochemical properties and single cell performance of sulfonated poly(ether ether ketone) block copolymer composite membrane using sulfonated carbon nanotubes for intermediate humidity fuel cells

A composite membrane composed of a sulfonated diblock copolymer (SDBC) based on poly(ether ether ketone) blocks copolymerized with partially fluorinated poly(arylene ether sulfone) and sulfonated carbon nanotubes (SCNTs) was fabricated by simple solution casting. Addition of the SCNT filler enhanced the water absorption and proton conductivity of membranes because of the increased per‐cluster volume of sulfonic acid groups, at the same time reinforced the membranes' thermal and mechanical properties. The SDBC/SCNT‐1.5 membrane exhibited the most improved physicochemical properties among all materials. It obtained a proton conductivity of 10.1 mS/cm at 120°C under 20% relative humidity (RH) which was 2.6 times more improved than the pristine membrane (3.9 mS/cm). Moreover, the single cell performance of the SDBC/SCNT‐1.5 membrane at 60°C and 60% RH at ambient pressure exhibited a peak power density of 171 mW/cm² at a load current density of 378 mA/cm², while the pristine membrane exhibited 119 mW/cm² at a load current density of 294 mA/cm². Overall, the composite membrane exhibited very promising characteristics to be used as polymer electrolyte membrane in fuel cells operated at intermediate RH.     

Tangential and normal conductivities of Nafion® membranes used in polymer electrolyte fuel cells

Conductivity measurements of Nafion^® 112, 115 and 117 membranes in the normal direction are reported in this paper. The measurements were made by means of impedance spectroscopy as a function of temperature. The conductivity was measured directly on hot-pressed carbon paper/membrane/carbon paper samples fully immersed in deionized water. The data show that Nafion^® membranes are really isotropic and that tangential and normal direction conductivity measurements gave the same results when the same hydration level was utilized.     

Preparation and properties of high performance nanocomposite proton exchange membrane for fuel cell

Various spatially enlarged organoclays were prepared by using poly(oxyproplene)-backboned quaternary ammonium salts of various molecular weights M_w 230, 400 and 2000 as the intercalating agents for Na⁺-montmorillonite. The modified MMT was utilized to improve the compatibility with Nafion^®. Sufficient interaction of the modified MMT with Nafion^® was studied by using X-ray diffraction (XRD) and X-ray photoelectron spectra (XPS). The performance of the Nafion^®/m-MMT composite membranes for direct methanol fuel cell (DMFCs) was evaluated in terms of water uptake, ion exchange capacity (IEC), methanol permeability, proton conductivity, and cell performance. The methanol permeability of the composite membrane decreased with the increasing of m-MMT content. The proton conductivity of the membrane was lowered slightly from that of pristine Nafion^® membrane. These results led to an essential improvement in the single-cell performance of DMFCs.     

Development of materials for mini DMFC working at room temperature for portable applications

Methanol permeability measurements and direct methanol fuel cell tests were performed at room temperature with different commercially available or recast Nafion^® membranes and sulfonated polyimide (SPI) membranes. Power densities as high as 20 mW cm⁻² could be obtained with Nafion^® 115. However, in order to meet the technological requirements for portable applications, thinner membranes have to be considered. As the MeOH crossover increases greatly (from (7 to 20) × 10⁻⁸ mol s⁻¹ cm⁻²) while Nafion^® membranes thickness decreases, non-perfluorinated polymers having high IEC are promising candidates for DMFC working at room temperature. The development catalysts tolerant to methanol is also relevant for this application. In spite of the low permeability to MeOH of SPI membranes, the obtained electrical performance with E-TEK electrodes based MEAs was lower than that obtained with Nafion^® membranes. No significant increase of performances was neither evidenced by using homemade PtCr(7:3)/C and PtRu(4:1)/C catalysts instead of E-TEK electrodes with recast Nafion^® based MEAs. However, MEAs composed with thin SPI membranes (50 μm) and homemade PtCr/C catalysts gave very promising results (18 mW cm⁻²). Based on experimental observations, a speculative explanation of this result is given.     

Novel ultrathin composite membranes of Nafion/PVA for PEMFCs

The electrospinning approach is an easy and useful method to fabricate porous supports with tailored properties for the preparation of impregnated membranes with enhanced characteristics. Therein, this technique was used to obtain polyvinyl alcohol (PVA) nanofiber mats in which Nafion^® polymer was infiltrated. These Nafion/PVA membranes were characterized in their mechanical properties, proton conductivity and fuel cell performance. Conductivity of the composite membranes was below the showed by pristine Nafion^® due to the non-ionic conducting behaviour of the PVA phase, although the incorporation of the PVA nanofibers strongly reinforced the mechanical properties of the membranes. Measurements carried out in a single cell fed with H₂/Air confirmed the high performance exhibited by a 19 μm thick nanofiber reinforced membrane owing to its low ionic resistance. These reasons make ultrathin (<20 μm) Nafion/PVA composite membranes promising candidates as low cost ion-exchange membranes for fuel cell applications.     

MWCNTs reinforced Nafion membrane prepared by a novel solution-cast method for PEMFC

An improved solution-cast method is presented to prepare multi-wall carbon nanotubes (MWCNTs)/Nafion^® reinforced membrane with different MWCNTs content (from 1 to 4 wt.%). MWCNTs were oxidized by H₂O₂ and sodium hydroxide (NaOH) was added into the MWCNTs/Nafion^®/N,N-dimethylacetamide (DMAC) solution. The long-term stability of the resulting dispersions was much better than the unmodified dispersions. The as-cast membrane was observed by scanning electron microscope (SEM). The MWCNTs were uniformly dispersed in the Nafion^® resin. The tensile strength and the elongation at break were greatly improved for the reinforced membranes compared to the recast Nafion^® membranes (54 and 27%, respectively). The fuel cell performance of the reinforced membranes with different MWCNTs contents was also tested at 80 °C under fully humidified conditions. By comparing the mechanical properties, proton conductivity and fuel cell performance of the reinforced membranes, we concluded that the content of MWCNTs in the reinforced membranes should not exceed 3 wt.%. The MWCNTs/Nafion^® reinforced membrane with 3 wt.% MWCNTs content showed the best mechanical characteristics and excellent fuel cell performance.     

Highly branched poly(arylene ether)/surface functionalized fullerene‐based composite membrane electrolyte for DMFC applications

Sulfonated branched polymer membranes have been gaining immense attention as the separator in energy‐related applications especially in fuel cells and flow batteries. Utilization of this branched polymer membranes in direct methanol fuel cell (DMFC) is limited because of large free volume and high methanol permeation. In the present work, sulfonated fullerene is used to improve the methanol barrier property of the highly branched sulfonated poly(ether ether ketone sulfone)s membrane without sacrificing its high proton conductivity. The existence of sulfonated fullerene with larger size and the usage of small quantity in the branched polymer matrix effectively prevent the methanol transportation channel across the membrane. The composite membrane with an optimized loading of sulfonated fullerene displays the highest proton conductivity of 0.332 S cm^?1 at 80°C. Radical scavenging property of the fullerene improves the oxidative stability of the composite membrane. Composite membrane exhibits the peak power density of 74.38 mW cm^?2 at 60°C, which is 30% larger than the commercial Nafion 212 membrane (51.78 mW cm^?2) at the same condition. From these results, it clearly depicts that sulfonated fullerene‐incorporated branched polymer electrolyte membrane emerges as a promising candidate for DMFC applications.