Sulfated zirconia–Nafion composite membranes for higher temperature direct methanol fuel cells

A sulfated zirconia/Nafion^®115 nanocomposite membrane is prepared by ion-exchange of zirconium ions into the Nafion followed by precipitation of sulphated ZrO₂ by treatment in 5 M H₂SO₄ at 80 °C. The incorporation of sulfated zirconia increases water uptake by the Nafion membrane, and importantly, more water is absorbed than by an unmodified membrane at high temperatures. The proton conductivity of the composite membrane is evaluated and compared with that of an unmodified Nafion^®115 membrane. The nanocomposite membrane experiences a smaller decrease in proton conductivity than the Nafion^®115 membrane at high temperatures.     

Sulfated zirconia nanoparticles as a proton conductor for fuel cell electrodes

Sulfated zirconia nanoparticles are evaluated as a possible alternative for a solid proton conductor in a fuel-cell catalyst layer. Two methods are applied for the synthesis of the nanoparticles, i.e.: (i) a conventional method treating ZrO₂ particles in sulfuric acid, and (ii) a solvent-free method directly synthesizing sulfated zirconia nanoparticles through the thermal decomposition of a mixture of ZrOCl₂ and (NH₄)₂SO₄. The nanoparticles synthesized by the solvent-free method have a size of 5–10 nm and an amorphous structure, and moreover their properties are promising in view of the application. In particular, the proton conductivity of the nanoparticles is high enough, i.e. of the 10⁻² S cm⁻¹ order, to be comparable to that of Nafion. Even though they possibly reduce the activity of Pt catalyst, layers containing sulfated zirconia as a proton conductor prove to be active as catalyst in fuel cell prototypes. Compared with conventional, Nafion-based cells, the maximum power density of the cells using sulfated zirconia is about one third. We believe that improvement in the preparation procedures for catalyst layers and membrane electrode assemblies will improve the cell performance. Therefore sulfated zirconia can be a valid proton conductor for fuel cell application.     

Investigation on sulfuric acid sulfonation of in-situ sol-gel derived Nafion/SiO2 composite membrane

In this paper, an effective method to cover the conductivity loss of Nafion/SiO₂ through sulfonation and its mechanism are studied. Nafion/SiO₂ composite membranes are prepared via an in-situ sol-gel route, and then sulfonated with concentrated sulfuric acid (marked as Nafion/S-SiO₂). The effects of the sulfonation on properties of the Nafion/SiO₂ composite membrane are investigated. The results show that sulfonation can improve the proton conductivity of the Nafion/SiO₂ effectively, though it brings water-uptake loss to the composite membrane to some extent simultaneously. According to the results of FT-IR, UV resonance Raman spectroscopy, ²⁹Si solid-state MAS NMR and XRD, it’s proved that higher conductivity of Nafion/S-SiO₂ should be relevant to hydrogen bonds & chemical bonds between SiO₂ nano particles and sulfuric acid molecules. While, lower water uptake & swelling ratio should be caused by hydroxyl-elimination on the surface of SiO₂ nano-particles during sulfonation. Single cell tests show that the performance of Nafion/S-SiO₂ composite membranes substantially exceeds Nafion/SiO₂ at 110 °C and 59%RH, and in the initial testing stage no performance reduction is observed.     

Preparation and performance of nano silica/Nafion composite membrane for proton exchange membrane fuel cells

Composite membranes made from Nafion ionomer with nano phosphonic acid-functionalised silica and colloidal silica were prepared and evaluated for proton exchange membrane fuel cells (PEMFCs) operating at elevated temperature and low relative humidity (RH). The phosphonic acid-functionalised silica additive obtained from a sol–gel process was well incorporated into Nafion membrane. The particle size determined using transmission electron microscope (TEM) had a narrow distribution with an average value of approximately 11 nm and a standard deviation of ±4 nm. The phosphonic acid-functionalised silica additive enhanced proton conductivity and water retention by introducing both acidic groups and porous silica. The proton conductivity of the composite membrane with the acid-functionalised silica was 0.026 S cm⁻¹, 24% higher than that of the unmodified Nafion membrane at 85 °C and 50% RH. Compared with the Nafion membrane, the phosphonic acid-functionalised silica (10% loading level) composite membrane exhibited 60 mV higher fuel cell performance at 1 A cm⁻², 95 °C and 35% RH, and 80 mV higher at 0.8 A cm⁻², 120 °C and 35% RH. The fuel cell performance of composite membrane made with 6% colloidal silica without acidic group was also higher than unmodified Nafion membrane, however, its performance was lower than the acid-functionalised silica additive composite membrane.     

Novel Nafion composite membranes with mesoporous silica nanospheres as inorganic fillers

Novel Nafion composite proton exchange membranes are prepared using mesoporous MCM-41 silica nanospheres as inorganic fillers. The novelty of this study lies in the structural design of inorganic silica fillers: the nanosized and monodisperse spherical morphology of fillers facilitates the preparation of homogenous composite membranes, whilst the superior water adsorption of the mesostructure in fillers consigns enhanced water retention properties to the polymer membranes. Scanning electron microscopy images of the composite membranes indicate that well-dispersed silica nanospheres are embedded in the Nafion matrix, but a large amount of added fillers (3 wt.%) causes some agglomeration of the nanospheres. Compared with the Nafion cast membrane, the composite membranes offer improved thermal stability, enhanced water retention properties, and reduced methanol crossover. Despite the enhancement of water retention, the composite membranes still exhibit a proton conductivity reduction of 10–40% compared with pristine Nafion. This is likely due to the incorporation of much less conductive silica fillers than Nafion. The composite membrane containing 1 wt.% of fillers displays the best cell performance in direct methanol fuel cell tests; it gives a maximum power density of 21.8 mW cm⁻², i.e., ∼20% higher than the Nafion cast membrane. This is attributed to its similar conductivity to Nafion, and its markedly reduced methanol crossover, namely, ∼1.2 times lower.     

An enhanced proton conductivity and reduced methanol permeability composite membrane prepared by sulfonated covalent organic nanosheets/Nafion

Sulfonated covalent organic nanosheets (SCONs) with a functional group (−SO₃H) are effective at reducing ion channels length and facilitating proton diffusion, indicating the potential advantage of SCONs in application for proton exchange membranes (PEMs). In this study, Nafion-SCONs composite membranes were prepared by introducing SCONs into a Nafion membrane. The incorporation of SCONs not only improved proton conductivity, but also suppressed methanol permeability. This was due to the even distribution of ion channels, formed by strong electrostatic interaction between the well dispersed SCONs and Nafion polymer molecules. Notably, Nafion-SCONs-0.6 was the best choice of composite membranes. It exhibited enhanced performance, such as high conductivity and low methanol permeability. The direct methanol fuel cell (DMFC) with Nafion-SCONs-0.6 membrane also showed higher power density (118.2 mW cm⁻²), which was 44% higher than the cell comprised of Nafion membrane (81.9 mW cm⁻²) in 2 M methanol at 60 °C. These results enabled us to work on building composite membranes with enhanced properties, made from nanomaterials and polymer molecules.     

Nafion/polyaniline composite membranes specifically designed to allow proton exchange membrane fuel cells operation at low humidity

A Nafion and polyaniline composite membrane (designated Nafion/PANI) was fabricated using an in situ chemical polymerization method. The composite membrane showed a proton conductivity that was superior to that obtained with Nafion^® 112 at low humidity (e.g. RH = 60%). Water uptake measurements revealed similarities between the Nafion^® 112 and Nafion/PANI membranes at different humidities. The high conductivity of the Nafion/PANI membrane at low humidity is hypothesized to be due to the existence of the extended conjugated bonds in the polyaniline; proton transfer is facilitated via the conjugated bonds in lower humidity environments allowing retention of the relatively high conductivity. Correspondingly, the performance of a single cell fuel cell containing the Nafion/PANI composite membrane is improved compared to a Nafion^® 112-containing cell under low humidity conditions. This is important for portable fuel cells, which are required to operate without external humidification.     

Proton exchange membranes with ultra-low vanadium ions permeability improved by sulfated zirconia for all vanadium redox flow battery

Suppressing vanadium ions crossover is a top priority in the development of membranes for vanadium redox flow battery (VRFB). One method is to dope inorganic fillers into polymer matrix, which usually decreases membrane's ion conductivity. In this work, sulfated zirconia (SZrO₂) is synthesized as a novel additive doped in sulfated poly (ether sulfone) (SPES) to simultaneously enhance the proton conduction and inhibit vanadium migration of the membranes. Membrane characterizations including battery test are carried out to reveal the effects of SZrO₂ on the membrane performance. The SPES/SZrO₂ composite membranes show vanadium permeability one order of magnitude lower than that of Nafion 212 and enhanced proton conductivity, which lead to superior cell performance. The columbic efficiency and energy efficiency of the VRFB reach 98.89% and 86.78%, respectively, at 100 mA cm⁻². Cycling test is carried out to evaluate the chemical and electrochemical stability of the membrane. Energy efficiency above 86% is maintained after70 charge-discharge cycles at 100 mA cm⁻².     

Functionalized titania nanotube composite membranes for high temperature proton exchange membrane fuel cells

In this study, functionalized titania nanotubes (F-TiO₂-NT) were synthesized by using 3-mercaptopropyl-tri-methoxysilane (MPTMS) as a sulfonic acid functionalization agent. These F-TiO₂-NT were investigated for potential application in high temperature hydrogen polymer electrolyte membrane fuel cells (PEMFCs), specifically as an additive to the proton exchange membrane. Fourier transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS) results confirmed that the sulfonic acid groups were successfully grafted onto the titania nanotubes (TiO₂-NT). F-TiO₂-NT showed a much higher conductivity than non-functionalized titania nanotubes. At 80 °C, the conductivity of F-TiO₂-NT was 0.08 S/cm, superior to that of 0.0011 S/cm for the non-functionalized TiO₂-NT. The F-TiO₂-NT/Nafion composite membrane shows good proton conductivity at high temperature and low humidity, where at 120 °C and 30% relative humidity, the proton conductivity of the composite membrane is 0.067 S/cm, a great improvement over 0.012 S/cm for a recast Nafion membrane. Based on the results of this study, F-TiO₂-NT has great potential for membrane applications in high temperature PEMFCs.     

Methanol crossover through PtRu/Nafion composite membrane for a direct methanol fuel cell

This study examined methanol crossover through PtRu/Nafion composite membranes for the direct methanol fuel cell. For this purpose, 0.03, 0.05 and 0.10 wt% PtRu/Nafion composite membranes were fabricated using a solution impregnation method. The composite membrane was characterized by inductively coupled plasma-mass spectroscopy and thermo-gravimetric analysis. The methanol permeability and proton conductivity of the composite membranes were measured by gas chromatography and impedance spectroscopy, respectively. In addition, the composite membrane performance was evaluated using a single cell test. The proton conductivity of the composite membrane decreased with increasing number of PtRu particles embedded in the pure Nafion membrane, while the level of methanol permeation was retarded. From the results of the single cell test, the maximum performance of the composite membrane was approximately 27% and 31% higher than that of the pure Nafion membrane at an operating temperature of 30 and 45 °C, respectively. The optimum loading of PtRu was determined to be 0.05 wt% PtRu/Nafion composite membrane.The PtRu particles embedded in the Nafion membrane act as a barrier against methanol crossover by the chemical oxidation of methanol on embedded PtRu particles and by reducing the proton conduction pathway.     

Fabrication and evaluation of Nafion nanocomposite membrane based on ZrO2–TiO2 binary nanoparticles as fuel cell MEA

Synthesis and characterization of nanocomposite membranes for proton exchange membrane fuel cell (PEMFC) operating at different temperatures and humidity were investigated in this study. Recast Nafion composite membrane with ZrO₂ and TiO₂ nanoparticles with 75 nm in mean size diameter, prepared for PEM fuel cells. Nafion/TiO₂ composite membranes have been also fabricated by in-situ sol–gel method. However, fine particles of the ZrO₂ were synthesized and Nafion/ZrO₂ composite membrane were produced by blending a 5% (w/w) Nafion-water dispersion with the inorganic compound. All nanocomposite membranes demonstrated higher water retention in comparison with unmodified membranes. Proton conductivity increased with increasing ZrO₂ content while TiO₂ additive (with mean size of 25 nm) enhanced water retention. Subsequently, structures of the membranes were investigated by Atomic Force Microscopy (AFM), Scanning Electron Microscopy (SEM) as well as X-Ray Diffraction (XRD). In addition, water uptake and proton conductivity of the modified membranes were also measured. The nanocomposite membrane was tested in a 25 cm² commercial single cell at the temperature range of 80–110 °C and in humidified H₂/O₂ under different relative humidity (RH) conditions. The membrane electrode assembly (MEA) prepared from Nafion/TiO₂, ZrO₂ presented highest PEM fuel cell performance in respect of I–V polarization under condition of 110 °C, 0.6 V and 30% RH and 1 atm.     

Self-assembly of highly charged polyelectrolyte complexes with superior proton conductivity and methanol barrier properties for fuel cells

The paper is concerned with the formation of Layer-by-Layer (LbL) self-assembly of highly charged polyvinyl sulfate potassium salt (PVS) and polyallylamine hydrochloride (PAH) on Nafion membrane to obtain the multilayered composite membranes with both high proton conductivity and methanol blocking properties. Also, the influences of the salt addition to the polyelectrolyte solutions on membrane selectivity (proton conductivity/methanol permeability) are discussed in terms of controlled layer thickness and charge density.The deposition of the self-assembly of PAH/PVS is confirmed by SEM analysis and it is observed that the polyelectrolyte layers growth on each side of Nafion membrane regularly. (PAH/PVS)₁₀-Na⁺ and (PAH/PVS)₁₀-H⁺ with 1.0 M NaCl provide 55.1 and 43.0% reduction in lower methanol permittivity in comparison to pristine Nafion, respectively, while the proton conductivities are 12.4 and 78.3 mS cm⁻¹. Promisingly, it is found that the membrane selectivity values (Φ) of all multilayered composite membranes in H⁺ form are much higher than those of Na⁺ form and perfluorosulfonated ionomers reported in the literature. These encouraging results indicate that composite membranes having both superior proton conductivity and improved methanol barrier properties can be prepared from highly charged polyelectrolytes including salt for fuel cell applications.     

Stabilizing phosphotungstic acid in Nafion membrane via targeted silica fixation for high-temperature fuel cell application

With PWA as proton transfer and silica as water retainer, stable phosphotungstic acid/silica/Nafion (PWA/Si–N) composite membrane is non-destructively fabricated and exhibits excellent stability and high temperature proton conductivity. Compared with pristine Nafion, high temperature proton conductivity is significantly enhanced due to the collaboration between –SO₃H ionic clusters and the in-situ filled silica embedded PWA nanoparticles. PWA is stabilized in the ionic clusters via in-situ catalyzing the hydrolysis silica precursor targeted filled into the –SO₃H ionic clusters. Stable proton conductivity of the PWA/Si–N membrane at 110 °C and 60% RH is high to 0.058 S/cm, which is 2.4 folds of that of Nafion. At the same time, the composite membrane still maintains good mechanical and thermal stability. As a result, high temperature fuel cell performance of the composite membrane is improved by 41% compared with the pristine Nafion membrane. The in-situ coating method proved to be an effective method to solve the stability of PWA in Nafion membrane, especially the inorganic oxide with good hygroscopicity as the modifier.     

Nafion-impregnated electrospun polyvinylidene fluoride composite membranes for direct methanol fuel cells

Composite membranes consisting of polyvinylidene fluoride (PVdF) and Nafion have been prepared by impregnating various amounts of Nafion (0.3–0.5 g) into the pores of electrospun PVdF (5 cm × 5 cm) and characterized by scanning electron microscopy, differential scanning calorimetry, X-ray diffraction, and proton conductivity measurements. The characterization data suggest that the unique three-dimensional network structure of the electrospun PVdF membrane with fully interconnected fibers is maintained in the composite membranes, offering adequate mechanical properties. Although the composite membranes exhibit lower proton conductivity than Nafion 115, the composite membrane with 0.4 g Nafion exhibits better performance than Nafion 115 in direct methanol fuel cell (DMFC) due to smaller thickness and suppressed methanol crossover from the anode to the cathode through the membrane. With the composite membranes, the cell performance increases on going from 0.3 to 0.4 g Nafion and then decreases on going to 0.5 g Nafion due to the changes in proton conductivity.     

Pt/CNTs-Nafion reinforced and self-humidifying composite membrane for PEMFC applications

A novel thin three-layer reinforced and self-humidifying composite membrane has been developed for PEMFCs. The membrane has two outer layers of plain Nafion and a middle layer of Pt/carbon nanotubes (Pt/CNTs) dispersed Nafion. The Pt/CNTs present in the membrane provides the sites for the catalytic recombination of H₂ and O₂ permeating through the membrane from the anode and cathode to produce water and improve the mechanical properties of the composite membrane at the same time. The water produced directly humidifies the membrane and allows the operation of PEMFCs with dry reactants. The electrochemical performance and mechanical properties of the composite membranes are compared with those of a commercial Nafion^® membrane. The self-humidifying composite membrane could minimize membrane conductivity loss under dry conditions and improve mechanical strength due to the presence of the Pt/CNTs.     

Investigation of physical properties and cell performance of Nafion/TiO2 nanocomposite membranes for high temperature PEM fuel cells

Synthesis and characterization of Nafion/TiO₂ membranes for proton exchange membrane fuel cell (PEMFC) operating at high temperatures were investigated in this study. Nafion/TiO₂ nanocomposite membranes have been prepared by in-situ sol–gel and casting methods. In the sol–gel method, preformed Nafion membranes were soaked in tetrabutylortotitanate (TBT) and methanol solution. In order to compare synthesis methods, a Nafion/TiO₂ composite membrane was fabricated with 3 wt.% of TiO₂ particles by the solution casting method. The structures of membranes were investigated by Differential Scanning Calorimetry (DSC), Scanning Electron Microscopy (SEM), and Energy Dispersive X-Ray Analysis (EDXA). Also, water uptake and proton conductivity of modified membranes were measured. Furthermore, the membranes were tested in a real PEMFC. X-Ray spectra of the composite membranes indicate the presence of TiO₂ in the modified membranes. In case of the same doping level, sol–gel method produces more uniform distribution of Ti particles in Nafion/TiO₂ composite membrane than the ones produced by casting method. Water uptake of Nafion/TiO₂ membrane with 3 wt.% of doping level was found to be 51% higher than that of the pure Nafion membrane. EIS measurements showed that the conductivity of modified membranes decreases with increasing the amount of doped TiO₂. Finally, the membrane electrode assembly (MEA) prepared from Nafion/Titania nanocomposite membrane shows the highest PEMFC performance in terms of voltage vs. current density (V–I) at high temperature (110 °C) which is the main goal of this study.     

Methanol crossover reduction by Nafion modification with palladium composite nanoparticles: Application to direct methanol fuel cells

Modified Nafion membranes by self-assembling of palladium composite nanoparticles were successfully synthesized and used for the reduction of methanol crossover in Direct Methanol Fuel Cells (DMFC). The positively charged polydiallyldimethylammonium (PDDA) was used for stabilizing the palladium nanoparticles. Modified and unmodified membranes were tested in a DMFC at 30 °C and 50 °C. The performance of the DMFC using modified membranes with different composite nanoparticles (i.e., Pd/PDAA ratios) and self-assembling times was compared with that using an unmodified membrane. The modified Nafion membranes proved to reduce the methanol crossover in ca. 10% – 35%, depending on the self-assembling time, nanoparticles composition and test temperature. However, a decrease in the performance was observed mainly for the modified membrane with the higher PDDA content due to a decrease in the proton conductivity. On the other hand, the membrane modified with nanoparticles containing less PDDA and tested at 50 °C showed similar performance as the unmodified one. Additionally, the fuel cell efficiencies obtained for all the modified membranes at both temperatures were similar or higher than the unmodified one.     

Preparation of Nafion-sulfonated clay nanocomposite membrane for direct menthol fuel cells via a film coating process

Nafion sulfonated clay nanocomposite membranes were successfully produced via a film coating process using a pilot coating machine. For producing the composite membranes, we optimized the solvent ratio of N-methyl-2-pyrrolidinone (NMP) to N,N′-dimethylacetamide (DMAc), the amount of sulfonated montmorillonite (S-MMT) in composite membranes and the overall concentration of composite dispersions. Based on the optimized viscosity and composition, the composite dispersions were coated on a poly(ethylene terephthalate) (PET) substrate film. The distance between a metering roll and a PET film and the ratio of metering roll speed versus coating roll speed of the pilot coating machine were varied to control membrane thickness. The film coated composite membrane exhibited enhanced properties in the swelling behavior against MeOH solution, ion conductivity and MeOH permeability, compared to the cast Nafion composite membrane due to the higher dispersion state of S-MMT in Nafion matrix and the uniform distribution of small-size ion clusters. These properties influenced a cell performance test of a direct methanol fuel cell (DMFC), showing the film coated composite membrane had a higher power density than that of Nafion 115. The power density was also related with the higher selectivity of the composite membrane than Nafion 115.     

Nafion/Pd–SiO2 nanofiber composite membranes for direct methanol fuel cell applications

One of the major challenges for direct methanol fuel cells is the problem of methanol crossover. With the aim of solving this problem without adverse effects on the membrane conductivity, Nafion/Palladium–silica nanofiber (N/Pd–SiO₂) composite membranes with various fiber loadings were prepared by a solution casting method. The silica-supported palladium nanofibers had diameters ranging from 100 nm to 200 nm and were synthesized by a facile electro-spinning method. The thermal properties, ionic exchange capacities, water uptake, proton conductivities, methanol permeabilities, chemical structures, and micro-structural morphologies were determined for the prepared membranes. It was found that the transport properties of the membranes were affected by the fiber loading. All of the composite membranes showed higher water uptake and ion exchange capacities compared to commercial Nafion 117 and proved to be thermally stable for use as proton exchange membranes. The composite membranes with optimum fiber content (3 wt%) showed an improved proton conductivity of 0.1292 S cm⁻¹ and a reduced methanol permeability of 8.36 × 10⁻⁷ cm² s⁻¹. In single cell tests, it was observed that, the maximum power density measured with composite membrane is higher than those of commercial Nafion 117.     

Fabrication and investigation of SiO2 supported sulfated zirconia/Nafion self-humidifying membrane for proton exchange membrane fuel cell applications

A self-humidifying composite membrane based on Nafion^® hybrid with SiO₂ supported sulfated zirconia particles (SiO₂–SZ) was fabricated and investigated for fuel cell applications. The bi-functional SiO₂–SZ particles, possessing hygroscopic property and high proton conductivity, were homemade and as the additive incorporated into our composite membrane. X-ray diffraction (XRD) and Fourier infrared spectrum (FT-IR) techniques were employed to characterize the structure of SiO₂–SZ particles. Scanning electronic microscopy (SEM) and energy dispersive spectroscopy (EDS) measurements were conducted to study the morphology of composite membrane. To verify the advantages of Nafion^®/SiO₂–SZ composite membrane, the IEC value, water uptake, proton conductivity, single cell performance and areal resistance were compared with Nafion^®/SiO₂ membrane and recast Nafion^® membrane. The single cell employing our Nafion^®/SiO₂–SZ membrane exhibited the highest peak power density of 0.98 W cm⁻² under dry operation condition in comparison with 0.74 W cm⁻² of Nafion^®/SiO₂ membrane and 0.64 W cm⁻² of recast Nafion^® membrane, respectively. The improved performance was attributed to the introduction of SiO₂–SZ particles, whose high proton conductivity and good water adsorbing/retaining function under dry operation condition, could facilitate proton transfer and water balance in the membrane.