Low methanol-permeable polyaniline/Nafion composite membrane for direct methanol fuel cells

Protonated polyaniline (PANI) is directly polymerized on Nafion 117 (N117), forming a composite membrane, to act as a methanol-blocking layer to reduce the methanol crossover in the direct methanol fuel cell (DMFC), which is beneficial for the DMFC operating at high methanol concentration. The PANI layer grown on the N117 with a thickness of 100 nm has an electrical conductivity of 13.2 S cm⁻¹. The methanol permeability of the PANI/N117 membrane is reduced to 59% of that of the N117 alone, suggesting that the PANI/N117 can effectively reduce the methanol crossover in the DMFC. Comparison of membrane-electrode-assemblies (MEA) using the conventional N117 and the newly developed PANI/N117 composite shows that the PANI/N117-based MEA outputs higher power at high methanol concentration, while the output power of the N117-based MEA is reduced at high methanol concentration due to the methanol crossover. The maximum power density of the PANI/N117-based MEA at 60 °C is 70 mW cm⁻² at 6 M methanol solution, which is double the N117-based MEA at the same methanol concentration. The resistance of PANI/N117 composite membrane is reduced at elevated methanol concentration, due to the hydrogen bonding between methanol and PANI pushes the polymer chains apart. It is concluded that the PANI/N117-based MEA performs well at elevated methanol concentration, which is suitable for the long-term operation of the DMFC.     

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.     

Methanol and water crossover in a passive liquid-feed direct methanol fuel cell

Methanol crossover, water crossover, and fuel efficiency for a passive liquid-feed direct methanol fuel cell (DMFC) were all experimentally determined based on the mass balance of the cell discharged under different current loads. The effects of different operating conditions such as current density and methanol concentration, as well as the addition of a hydrophobic water management layer, on the methanol and water crossover were investigated. Different from the active DMFC, the cell temperature of the passive DMFC increased with the current density, and the changes of methanol and water crossover with current density were inherently coupled with the temperature rise. When feeding with 2–4 M methanol solution, with an increase in current density, both the methanol crossover and the water crossover increased, while the fuel efficiency first increased but then decreased slightly. The results also showed that a reduction of water crossover from the anode to the cathode was always accompanied with a reduction of methanol crossover. Not only did the water management layer result in lower water crossover or achieve neutral or reverse water transport, but it also lowered the methanol crossover and increased the fuel efficiency.     

Effects on the electrochemical performance of surface-modified mordenite in a PTFE Nafion composite membrane for direct methanol fuel cells

Mordenite (MOR)/PTFE Nafion composite membranes were produced by impregnating Nafion solutions in a PTFE porous support with a modified form of MOR. A 3-mercaptopropyl triethoxysilane (MPTES) - MOR mixture is used as a filler in the PTFE Nafion membrane to block methanol crossover and increase water uptake. An experiment was conducted with a membrane without M-MOR (PTFE Nafion membrane) and a membrane with M-MOR at 2, 4, and 10 wt% (2-, 4-, and 10-M-MOR/PTFE Nafion membranes, respectively). In order to improve the interfacial properties, surface modification of the zeolite was conducted with a silane coupling reaction. The MOR samples were analyzed by SEM, SEM-EDS, and BET surface area analysis. The Nafion membrane was analyzed by SEM, according to the water uptake, and by an electrochemical analysis. The 10-M-MOR/PTFE Nafion membrane showed greater water uptake of 75% compared to the PTFE Nafion membrane without M-MOR (28%). It was found that the addition of MOR had a positive effect on the reduction of the methanol permeability of the MOR/PTFE Nafion membrane. The DMFC (Direct Methanol Fuel Cell) power density of MEA with the 4-M-MOR/PTFE Nafion membrane (4-M-MOR MEA) was found to be 71% higher than that of the PTFE Nafion membrane (0-M-MOR MEA).     

Sulfonated graphene oxide/Nafion composite membranes for high-performance direct methanol fuel cells

An easy and effective method for producing low methanol-crossover membranes is developed by dispersing sulfonated graphene oxide (SGO) into a Nafion matrix. A SGO/Nafion mixture with low SGO content exhibits unique viscosity behavior and allows for better SGO dispersion within the Nafion. After film casting, the composite membranes show lower methanol and water uptakes, a reduced swelling ratio, improved proton conductivity in low relative humidity, and extremely high methanol selectivity, which can be implemented in direct methanol fuel cells (DMFCs). The regular backbone of the composite membrane shows a higher storage modulus, increased α-relaxation (transition temperature), and improved tolerance to pressure during membrane electrode assembly (MEA). The small angle X-ray spectra indicate the shrinkage of the ionic clusters in the composite membranes, which thus reduce methanol crossover. The hybrid membranes applied to DMFCs demonstrate performances superior to that of the commercial Nafion 115 in 1 M and 5 M methanol solutions.     

Nafion/polyaniline/silica composite membranes for direct methanol fuel cell application

This work investigates the characterization and performance of polyaniline and silica modified Nafion membranes. The aniline monomers are synthesized in situ to form a polyaniline film, whilst silica is embedded into the Nafion matrix by the polycondensation of tetraethylorthosilicate. The physicochemical properties are studied by means of X-ray diffraction and Fourier transform infrared techniques and show that the polyaniline layer is formed on the Nafion surface and improves the structural properties of Nafion in methanol solution. Nafion loses its crystallinity once exposed to water and ethanol, whilst the polyaniline modification allows crystallinity to be maintained under similar conditions. By contrast, the proton conductivities of polyaniline modified membranes are 3–5-fold lower than that of Nafion. On a positive note, methanol crossover is reduced by over two orders of magnitude, as verified by crossover limiting current analysis. The polyaniline modification allows the membrane to become less hydrophilic, which explains the lower proton conductivity. No major advantages are observed by embedding silica into the Nafion matrix. The performance of a membrane electrode assembly (MEA) using commercial catalysts and polyaniline modified membranes in a cell gives a peak power of 8 mW cm⁻² at 20 °C with 2 M methanol and air feeding. This performance correlates to half that of MEAs using Nafion, though the membrane modification leads to a robust material that may allow operation at high methanol concentration.     

Sorbitol-plasticized chitosan/zeolite hybrid membrane for direct methanol fuel cell

Organic–inorganic hybrid membranes, as promising direct methanol fuel cell membranes, have become a research focus in recent years. Wherein interfacial morphology, greatly influenced by the polymer chain flexibility and interfacial stress generated during membrane formation, is a critical determinant of efficient suppression of methanol crossover. In this study, a novel and feasible approach for rational fabrication of organic/inorganic hybrid direct methanol fuel cell (DMFC) membrane is tentatively explored. By adding plasticizer in the membrane casting solution and/or elevating solvent evaporation temperature during membrane fabrication, the glass transition temperature (T_g) and crystallinity of the chitosan/zeolite hybrid membrane are both remarkably decreased. In particular, the interface voids are substantially eliminated, generating a more desirable interfacial morphology and consequently leading to an improved performance in suppressing methanol crossover. The chitosan/mordenite/sorbitol hybrid membrane prepared with 30 wt% of sorbitol and 15 wt% of mordenite exhibits a 44% reduction in methanol permeability compared with chitosan control membrane. The variation of methanol permeability with mordenite and sorbital content is tentatively elucidated by the change of free volume cavity size in the membrane determined by positron annihilation lifetime spectroscopy (PALS) measurements.     

Homogeneous polymer/filler composite membrane by spraying method for enhanced direct methanol fuel cell performance

In this work, composite membranes for a direct methanol fuel cell (DMFC) were prepared using a spraying method to improve cell performance especially at a high methanol concentration. Nafion polymer and mordenite as a filler were used for the composite membrane preparation using a spraying method and a conventional solution casting method and the membranes from the two methods were compared. SEM images showed that a more homogeneous composite membrane could be obtained using the spraying method. The effect of mordenite content was also studied. The membranes were consequently characterized and tested in DMFC operation. The results were compared to those prepared using the solution casting method at 30, 50, and 70 °C with methanol concentrations of 2, 4, and 8 M. It was found that the membrane with 5 wt.% mordenite from the spraying method showed a vast improvement in DMFC performance. When the cell was operated at 70 °C, the maximum power density of 5 wt.% mordenite from the spraying method was higher than that of commercial membrane and 5 wt.% from the solution casting method. Power densities from the 5 wt.% sprayed membrane were higher by around 29%, 40%, and 60% at 2, 4, and 8 M methanol concentration, respectively.     

A novel hybrid Nafion-PBI-ZP membrane for direct methanol fuel cells

Methanol crossover through proton conducting membranes represents one of the main drawbacks in DMFCs. This study presented a novel organic-inorganic hybrid membrane with several different compositions by casting mixtures of zirconium phosphate (ZP), polybenzimidazole (PBI) and Nafion dispersion in dimethylacetamide. The presence of PBI and ZP in the membranes was demonstrated with energy dispersive X-ray (EDX) analysis. From the scanning electron microscopy (SEM) analysis, it was observed that the hybrid Nafion-PBI-ZP membrane had the finest structure. This is because the synthesized films were homogeneous and therefore formed a dense membrane. The water content was higher in the hybrid membrane: 39.91% compared with 35.52% in Nafion117. The water content is important for the ion transportation in the membrane; therefore, a higher water uptake rate will contribute to a better fuel cell performance. It was determined that the proton conductivity of the hybrid membrane was 0.020 S cm⁻¹, which was comparable with Nafion117, which had a proton-conductivity of 0.022 S cm⁻¹. The methanol permeability of the hybrid membrane was 2.34 × 10⁻⁷ cm² s⁻¹, while the value for Nafion117 was 8.91 × 10⁻⁷ cm² s⁻¹. This showed that the methanol permeability of the hybrid membrane was almost 4 times lower than that of Nafion117. The selectivity factor for the Nafion-PBI 1%-ZP 1% membrane was 8.64 × 10⁴ Scm⁻³, while that of Nafion117 was 2.48 × 10⁴ S scm⁻³. From a thermogravimetry analysis (TGA), the addition of PBI and zirconium phosphate was shown to improve the thermal durability in the temperature range from room temperature to 450 °C over that of Nafion117. This study proofed that the Nafion-PBI 1%-ZP 1% performed better than commercial Nafion117 and other type of membranes. The membrane was tested on as single cell of DMFC. It gave the highest power density as compared to other type of membrane and proofed that it has potential to be used in DMFCs.     

Reduction of methanol crossover in a flowing electrolyte-direct methanol fuel cell

The flowing electrolyte-direct methanol fuel cell (FE-DMFC) is a type of fuel cell in which a flowing liquid electrolyte is used, in addition to two solid membranes, to reduce methanol crossover. In this study, FE-DMFCs having new materials and design were manufactured and studied. In this design, the flow field plates were made of stainless steel 2205 and had a pin type flow structure. PTFE treated carbon felts were used as the backing layers as well as the flowing electrolyte channel. Nafion^® 115 or Nafion^® 212 was used as the membranes. The polarization curves and methanol crossover current densities under different methanol concentrations and flow rates of sulfuric acid were measured using fully automated DMFC test stations. The performances of the FE-DMFCs were compared with those of the DMFCs having a single or double membrane. This study is, to the authors' knowledge, the first experimental study on measuring the methanol crossover in a FE-DMFC. The results of this study demonstrate that this technology enables a significant reduction of methanol permeation. At different cell current densities, Faradaic efficiencies up to 98% were achieved. It was shown that for a fixed flow rate of sulfuric acid solution (5 ml/min), at 0.1 A/cm², the Nafion^® 115 based FE-DMFC operating at 1 M yields the highest cell voltage (0.38 V). The maximum power density of the FE-DMFC (0.0561 W/cm²) was achieved when the cell operates with 3 M methanol concentration and 10 ml/min sulfuric acid solution at 0.3 A/cm².     

Low methanol crossover and high efficiency direct methanol fuel cell: The influence of diffusion layers

This experimental work aims to investigate the possibility to reduce methanol crossover in DMFC modifying diffusion layer characteristics. Improvements in crossover measurement are firstly proposed, permitting to conclude that in the investigated conditions carbon dioxide flow through the membrane can be neglected. The experimental results evidence that introducing appropriate anode and cathode microporous layers determines: a strong reduction in methanol crossover, approximately 45% at low current density; a considerable increment of efficiency; a moderate decrease of power density. The complete experimental analysis demonstrates that methanol transport in both liquid and vapour phases can be controlled modifying properly diffusion layer characteristics in order to increase DMFC efficiency.     

Chitosan/heteropolyacid composite membranes for direct methanol fuel cell

As inorganic proton conductors, phosphomolybdic acid (PMA), phosphotungstic acid (PWA) and silicotungstic acid (SiWA) are extremely attractive for proton-conducting composite membranes. An interesting phenomenon has been found in our previous experiments that the mixing of chitosan (CS) solution and different heteropolyacids (HPAs) leads to strong electrostatic interaction to form insoluble complexes. These complexes in the form of membrane (CS/PMA, CS/PWA and CS/SiWA composite membranes) have been prepared and evaluated as novel proton-conducting membranes for direct methanol fuel cells. Therefore, HPAs can be immobilized within the membranes through electrostatic interaction, which overcomes the leakage problem from membranes. CS/PMA, CS/PWA and CS/SiWA composite membranes were characterized for morphology, intermolecular interactions, and thermal stability by SEM, FTIR, and TGA, respectively. Among the three membranes, CS/PMA membrane was identified as ideal for DMFC as it exhibited low methanol permeability (2.7 × 10⁻⁷ cm² s⁻¹) and comparatively high proton conductivity (0.015 S cm⁻¹ at 25 °C).     

A 3D model for the free-breathing direct methanol fuel cell: Methanol crossover aspects and validations with current distribution measurements

A three-dimensional model has been developed for the free-breathing direct methanol fuel cell (DMFC) assuming steady-state isothermal and single-phase conditions. Especially the MeOH crossover phenomenon is investigated and the model validations are done using previous cathodic current distribution measurements. A free convection of air is modelled in the cathode channels and diffusion and convection of liquid (anode) and gaseous species (cathode) in the porous transport layers. The MeOH flow in the membrane is described with diffusion and protonic drag. The parameter ψ$\psi$ in the model describes the MeOH oxidation rate at the cathode and it is fitted according to the measured current distributions. The model describes the behaviour of the free-breathing DMFC, when different operating parameters such as cell temperature, MeOH concentration and flow rate are varied in a wide range. The model also predicts the existence of the experimentally observed electrolytic domains, i.e. local regions of negative current densities. Altogether, the developed model is in reasonable agreement with both the measured current distributions and polarization curves. The spatial information gained of mass transfer phenomena inside the DMFC is valuable for the optimization of the DMFC operating parameters.     

Multifunctional composite membrane based on a highly porous polyimide matrix for direct methanol fuel cells

A highly porous polyimide film with tunable pore size, porosity and thickness is synthesized and used as a matrix to construct a Nafion-infiltrated composite membrane. A very efficient way for an easy and complete infiltration of the proton-conducting polymer into this substrate is developed, which is usually a major problem for composite membranes. Due to the complete inertness to methanol and the very high mechanical strength of the polyimide matrix, the swelling of the composite membrane is greatly suppressed and the methanol crossover is also significantly reduced (80 times), where as while high proton conductivity (comparable with Nafion) and mechanical strength (4 times stronger than Nafion) is still maintained. This membrane demonstrates significantly improved cell performance compared with the Nafion membrane and is a promising candidate for use in direct methanol fuel cells.     

Poly(1-vinylimidazole)/Pd-impregnated Nafion for direct methanol fuel cell applications

Nafion is modified by incorporating poly(1-vinylimidazole)/Pd composites into the ion cluster channels of the membrane. The poly(1-vinylimidazole)/Pd-impregnated (PVI/Pd-impregnated) membranes is characterized by means of X-ray photoelectron spectroscopy (XPS), proton conductivity and methanol permeability measurements and compared with those of the untreated Nafion. The dependence of the membrane proton conductivity and methanol permeability on the poly(1-vinylimidazole) (PVI) and palladium contents in the PVI/Pd-impregnated Nafion is studied. The performance of the cells employing the PVI/Pd-impregnated Nafion is evaluated using a direct methanol fuel cell (DMFC) unit cell. It is found that the best cell performance is obtained when Nafion is impregnated with the PVI/Pd composite solution for 20 h. This result suggests that there exists an optimum content of palladium and PVI in the modified membrane to obtain a high-proton conductivity and low-methanol permeability that result in a high-cell performance.     

A study on the overall efficiency of direct methanol fuel cell by methanol crossover current

This paper was presented to determine the methanol crossover and efficiency of a direct methanol fuel cell (DMFC) under various operating conditions such as cell temperature, methanol concentration, methanol flow rate, cathode flow rate, and cathode backpressure. The methanol crossover measurements were performed by measuring crossover current density at an open circuit using humidified nitrogen instead of air at the cathode and applied voltage with a power supply. The membrane electrode assembly (MEA) with an active area of 5 cm² was composed of a Nafion 117 membrane, a Pt–Ru (4 mg/cm²) anode catalyst, and a Pt (4 mg/cm²) cathode catalyst. It was shown that methanol crossover increased by increasing cell temperature, methanol concentration, methanol flow rate, cathode flow rate and decreasing cathode backpressure. Also, it was revealed that the efficiency of the DMFC was closely related with methanol crossover, and significantly improved as the cell temperature and cathode backpressure increased and methanol concentration decreased.     

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.     

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.     

Supported PtRu on mesoporous carbons for direct methanol fuel cells

We prepared and characterized several cryogel mesoporous carbons of different pore size distribution and report the catalytic activity of PtRu supported on mesoporous carbons of pore size >15 nm in passive and in active direct methanol fuel cells (DMFCs). At room temperature (RT), the specific maximum power of the passive DMFCs with mesoporous carbon/PtRu systems as anode was in the range 3–5 W g⁻¹. Passive DMFC assembly and RT tests limit the performance of the electrocatalytic systems and the anodes were thus tested in active DMFCs at 30, 60 and 80 °C. Their responses were also compared to those of commercial Vulcan carbon/PtRu. At 80 °C, the specific maximum power of the active DMFC with C656/PtRu was 37 W g⁻¹ and the required amount of Pt per kW estimated at 0.4 V cell voltage was 31 g kW⁻¹, a value less than half that of Vulcan carbon/PtRu.     

Synthesis of highly stable PTFE-ZrP-PVA composite membrane for high-temperature direct methanol fuel cell

A composite membrane was synthesized by functionalizing the Polytetrafluoroethylene film with inorganic Zirconium Phosphate and polyvinyl alcohol. The hybrid method of pore infiltration and layer by layer coating was adopted to obtain the membrane. Hydrophilicity of the PTFE support was increased by chemical treatment. The proton conductivity of the membrane was increased considerably by using chemically treated hydrophilic support. The composition of ZrP and PVA in the solution (sol) was optimized with respect to methanol crossover and proton conductivity. The top view of the membrane surface morphology was observed by using SEM and EDX revealed the presence of 31.9% Zirconium and 26.44% Phosphate in the synthesized membrane. The membrane top layer functional groups were analyzed by FT-IR and the spectra confirm the incidence of functional groups related to ZrP and PVA. Thermal stability of the membrane was analyzed using TGA-DTA and it was stable up to 140 °C. The membrane was mechanically stabile with a mechanical strength of 44 MPa. The membrane possessed proton conductivity of 28.1 mS cm⁻¹ and low methanol permeability (14.5 × 10-7 cm² s⁻¹) at 80 °C.