Composites of Proton-Conducting Polymer Electrolyte Membrane in Direct Methanol Fuel Cells

Fuel cells are a replacement for the conventional energy resources. As early as 1839, William Grove discovered the basic operating principle of fuel cells by reversing water electrolysis to generate electricity from hydrogen and oxygen. A Direct Methanol Fuel Cell (DMFC) operates on liquid fuel, which is one of the exciting varieties of fuel cells. There are many problems with DMFCs such as the high cost of electrolyte membranes, high platinum loading, CO poisoning, fuel cross-over, and so on. In this review, research regarding the solution of these problems will be cited and discussed. The electrical performance (in respect to power density) of the composites for the Nafion® and other perfluorinated membranes in DMFC are evaluated. The effect of these modifications on various aspects, such as mobility of protons through the membrane, permeation of hydronium ions, and cross-over of methanol through the membrane leading to the negative potential, have previously been discussed. Therefore, the main focus of this review is on the effect of composites of Nafion® and non-fluorinated membranes on the DMFC performance.     

Polyelectrolyte Nanocomposite Membranes with Imidazole-Functionalized Multi-Walled Carbon Nanotubes for Use in Fuel Cell Applications

The preparation and characterization of a new type of nanocomposite polyelectrolyte membrane (PEM), based on Nafion® and imidazole modified multi-walled carbon nanotubes (MWCNT-Im), for direct methanol fuel cell (DMFC) applications is described. Related to the interactions between the protonated imidazole groups, grafted on the surface of multi-walled carbon nanotubes (MWCNT), and the negatively charged sulfonic acid groups of Nafion®, new electrostatic interactions can be formed in the interface of the Nafion® and MWCNT-Im which result in both lower methanol permeability and also higher proton conductivity. The physical characteristics of these manufactured nanocomposite membranes were investigated by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), water uptake, methanol permeability and ion exchange capacity, as well as proton conductivity. The Nafion®/MWCNT-Im membranes showed higher proton conductivity, lower methanol permeability and, as a consequence, a higher selectivity parameter in comparison to neat Nafion® or Nafion® containing –OH functionalized multi-walled carbon nanotubes (MWCNT-OH) membranes. The obtained results indicated that the Nafion®/MWCNT-Im membranes could be utilized as efficient polyelectrolyte membranes for direct methanol fuel cell applications.     

Polyelectrolyte Nanocomposite Membranes Using Surface Modified Nanosilica for Fuel Cell Applications

The preparation and characterization of a new type of nanocomposite polyelectrolyte membrane (PEM), based on Nafion® (E. I. du Pont de Nemours and Co., Ltd., for its copolymer of tetrafluoroethylene and perfluorinated vinyl ether) and sulfonic acid (-SO₃H) or phosphotungstic acid (PWA) modified nanosilica (Si-SO₃H or Si-PWA, respectively), for direct methanol fuel cell (DMFC) applications are described. Physical characteristics of these manufactured nanocomposite membranes were investigated by scanning electron microscopy (SEM), water uptake, methanol permeability and ion exchange capacity, as well as proton conductivity. The Nafion®/Si-PWA and Nafion®/Si-SO₃H membranes showed higher proton conductivity, lower methanol permeability and, as a consequence, a higher selectivity parameter, in comparison to the neat Nafion® or Nafion®/pristine nanosilica membranes. The obtained results indicated that both the Nafion®/Si-PWA and Nafion®/Si-SO₃H membranes could be utilized as promising polyelectrolyte membranes for direct methanol fuel cell applications.     

Ion-beam formation of electrocatalysts for fuel cells with polymer membrane electrolyte

Active layers of electrocatalysts are prepared by the ion-beam assisted deposition (IBAD) of platinum onto carbon-based AVCarb® Carbon Fiber Paper P50 and Toray Carbon Fiber Paper TGP-H-060 T supports and Nafion® N 115 polymer membrane electrolyte in the mode where the deposited metal ions are used as ions assisting the deposition process. Metal deposition and mixing of the deposited layer with the substrate under an accelerating voltage of 10 kV by the same metal ions are carried out from a neutral fraction of metal vapor and the ionized plasma of a pulsed vacuum-arc discharge, respectively. The composition and microstructure of the surface layers obtained are studied by Rutherford backscattering spectrometry (RBS), scanning electron microscopy (SEM), electron-probe microanalysis (EPMA), and X-ray fluorescence (XRF) analysis. The platinum concentration in the layers is (0.5–1.5) × 10¹⁶ at/cm². The prepared electrocatalysts exhibit activity in the process of the electrochemical oxidation of methanol and ethanol, which form the basis for the principle of operation of low temperature fuel cells (direct methanol fuel cells (DMFC) and direct ethanol fuel cells (DEFC)).     

Pore-filling electrolyte membranes based on plasma-activated microporous PE matrices and sulfonated hydrogenated styrene butadiene block copolymer (SHSBS): Single cell test and impedance spectroscopy in symmetrical mode

In this research the performance of proton exchange membrane fuel cells (PEMFC's) was studied, using pore-filling electrolyte membranes based on plasma-activated microporous polyethylene (PE) matrices coated with sulfonated hydrogenated butadiene–styrene block copolymer (SHSBS). The voltage–current and power density curves were recorded under different experimental temperature and pressure conditions. In addition, an electrochemical study was completed by means of electrochemical impedance spectroscopy (EIS) in the symmetrical mode, adjusting the electrical response obtained to an equivalent circuit, which allows for isolation of the different processes occurring within the system. Two parameters were taken into account in the study: the membrane's proton transport or ion resistance (R₁) and its charge transfer resistance (R₂).The results obtained indicate that SHSBS shows a single cell behaviour which is comparable to that of the commercial membrane Nafion®. In contrast, the performance of the PE–SHSBS pore-filling electrolyte membranes was lower than that of Nafion®. Likewise it was found that the different plasma treatments applied to the microporous PE matrix have an effect on the proton exchange capacity of the pore-filling electrolyte membrane. EIS allowed to determine the ion resistance of the proton exchange membrane, and it was demonstrated that the kinetics of the cathodic reaction and the cathode itself are decisive elements in membrane performance and hence prime objectives to be optimized, when the reduction of the overvoltages is at stake, which are currently observed in the polarization curve at low and high power densities.     

Design of novel SPEEK-based proton exchange membranes by self-assembly method for fuel cells

Fuel cell represents a new energy conversion device, which promises to provide clean source of power. Fuel cell [particularly proton exchange membrane fuel cell and direct methanol fuel cell (DMFC)] is a promising candidate for transportation and portable power source applications. In DMFC, there is a problem of methanol crossover. In order to reduce such a problem, there has been an intensive research activity in the modification of Nafion. In the present investigation, self-assembled membranes were fabricated with sulfonated polyether ether ketone as the core part of the membrane. Aminated polysulfone and sulfonated polysulfone were used as the layers in order to prevent the crossover of methanol. The assembled membranes were characterized by ion exchange capacity, water and methanol absorption, and durability. The methanol permeability and selectivity ratio proved a strong influence on DMFC application. Scanning electron microscopy proved smooth surface, which established strong cohesive force for the polymer chains. Among the synthesized self-assembled membranes, the membrane with two bilayers was the best in terms of power density in DMFC. The membrane electrode assembly with two bilayers showed higher performance (~61.05 mW/cm²) than sulfonated poly(ether ether ketone) and Nafion in DMFC.     

Does power ultrasound affect Nafion® dispersions?

The effect of low frequency power ultrasound on Nafion® ionomer used for fabricating proton exchange membrane fuel cell (PEMFC) and water electrolyzer (PEMWE) catalyst inks was investigated. In this study, a series of Nafion® dispersions having three concentrations (10, 5, and 2.5% w/v) were studied under various irradiation durations (t_us), at fixed ultrasonic frequency (f = 42 kHz) and ultrasonic power (P > 2 W), under either controlled or unregulated bulk solution temperature conditions using a laboratory ultrasonic cleaning bath. Viscosity (η), thermal degradation, and glass transition temperature (T_g) for all Nafion® dispersion samples was measured and compared to untreated Nafion® samples. In our conditions, it was found that power ultrasound lowered the viscosity of all tested Nafion® dispersion samples; whilst thermogravimetric and differential scanning calorimetry analyses showed that for all ultrasonically irradiated samples, a negligible overall polymer degradation and no obvious change in T_g was observed under controlled and unregulated bulk temperature conditions. It was found that it is possible that acoustic cavitation causes depolymerisation followed by a polymerisation initiation step during ultrasonication. By comparing the ultrasonically treated and high-shear mixed samples, it was also observed that acoustic and hydrodynamic cavitation played an important role in the reduction of dispersion viscosity.     

Effect of solvent and crystal size on the selectivity of ZSM-5/Nafion composite membranes fabricated by solution-casting method

Zeolite/Nafion composite membranes with high proton selectivity were successfully fabricated using the solution-casting method. The types of zeolites are nano-sized and large sized Na-ZSM-5, H-ZSM-5, and their ball-milled ones. Two different schemes of experiments were conducted depending on the type of solvent. In case of using as-received Nafion® ionomer dispersions, the experimental results clearly show that the proton conductivity of zeolite composite membrane using either H-type or Na-type ZSM-5 depends on the type of solvent. It is thought that when propanol and water as the solvents were used, more hydrophilic H-type ZSM-5 seems to have been more randomly dispersed into hydrophobic region rather than hydrophilic ionic clustered channels within Nafion. Therefore, H-type ZSM-5 existing near hydrophobic region seems to provide additional path for proton migration but weakening the mechanical strength. These composite membranes show higher water uptake than commercial Nafion® 115, strongly suggesting better water retention ability of zeolite. The most interesting result is that the methanol permeability has decreased with increasing zeolite contents even when the proton conductivity increased, and the proton selectivities of these composite membranes expressed as characteristic factor were higher than that of Nafion® 115. In case of using a mixture of high boiling point DMF and ethanol as the solvent, unlike the previous case where no DMF was used, the proton conductivity slightly dropped with increasing zeolite contents. These results should have been attributed to a blocking effect of zeolite particles surrounded by inversely oriented hydrophilic micelles of Nafion. However, the values of proton conductivity of most composite membranes were significantly higher than that of Nafion® 115, and methanol permeability also decreased with increasing zeolite contents. The significantly lower methanol permeability of the composite membrane fabricated with DMF as the solvent is probably due to the more effective blocking effect of H-ZSM-5 for ionic clustered channels as well as difficult transport of methanol through zeolite pores.In case of the composite membranes containing ZSM-5 with large crystal size, it is found that the methanol permeability has increased considerably with the increasing of zeolite contents due to void fractions between polymer phases and zeolite particles. In case of using ball-milled ZSM-5 with small crystal size, however, the value of characteristic factor tends to increase with increasing zeolite contents. Consequently, it is seen that the characteristic factor of Zeolite/Nafion composite membranes was much higher than Nafion® 115. The results obtained throughout this study strongly suggest that zeolites with small crystal size and high hydrophilicity are very prospective for composite membrane for direct methanol fuel cells in the future.     

Surface-modified Nafion membrane by trioctylphosphine-stabilized palladium nanoparticles for DMFC applications

Trioctylphosphine (TOP)/Pd composites have been synthesized and used as a methanol-barrier material to modify the surface of Nafion 115. The TOP/Pd composites have been applied to the surface of Nafion instead of being incorporated into the Nafion matrix, to provide the best chance of maintaining the inherent proton conductivity of Nafion. The properties of the TOP/Pd-modified membrane, in terms of its conductivity and methanol permeability, as well as the performance of the membrane electrode assembly (MEA) in direct methanol fuel cell (DMFC), have been analyzed and compared with those of bare Nafion. The DMFC performance of the TOP/Pd-modified membrane is somewhat better than that of the bare Nafion one at methanol concentration of 2 M and significantly better at a high concentration of 5 M. The TOP/Pd-modified membrane is able to operate the DMFC using a high concentration of methanol, which can satisfy the requirement to reduce the reactant volumes for portable applications as well as to achieve high performance. In contrast to bare Nafion, the TOP/Pd-modified membrane with its well-adhering and crack-free modified surface shows effect on reducing the methanol loss.     

Investigating the effect of operating parameters on the open circuit voltage of a passive DMFC

The variations of the open circuit voltages (OCVs) were studied in a passive air-breathing direct methanol fuel cell with an air-breathing cathode using Nafion 115 as the electrolyte membrane. The effects of some operating parameters such as cell temperature, cell orientation, and also methanol concentration on the OCV of fabricated fuel cell were investigated experimentally. The experimental results showed that the OCV values depend strongly on the cell orientation, cell temperature, and methanol concentration. The OCV values decrease with an increase in methanol concentration and cell temperature. Also, the OCV values in vertical orientation are lower than the OCV values in other orientations.     

Improvement of the barrier properties of Nafion® by fluoro-modified montmorillonite

Montmorillonite (MMT) was modified by two types of cationic fluorosurfactants in order to improve compatibility with and dispersion within Nafion® membranes. Perfluoropolyether-containing cationic surfactant improved efficiency, by improving the barrier properties of Nafion® towards methanol. Moreover, the fluoro-modified MMT had no deleterious impact on the ionic conductivity of the membranes in contrast to conventional organo-modified MMT. The performances of a small size fuel cell were accordingly improved.     

The effect of cell orientations and environmental conditions on the performance of a passive DMFC single cell

A single cell passive air-breathing liquid feed direct methanol fuel cell (DMFC) is designed and fabricated. Furthermore, the effects of cell orientation and environmental conditions such as temperature and relative humidity on the performance of such passive DMFC are tested experimentally. The obtained results indicate that both environmental temperature and relative humidity have significant effects on the performance of fabricated fuel cell. The experimental data contained within this work shows that under lower relative humidity and higher temperature, the passive air-breathing direct methanol fuel cell has higher power output and better performance. According to experimental results, flooding has a vital role on the cell performance in various relative humidity and temperatures. The results also show that cell orientation has a strong effect on the performance of passive DMFC. The best power output and performance were achieved under vertical orientation.     

Characterization of nanohybrid membranes for direct methanol fuel cell applications

A series of sulfonated poly(2,6-dimethyl-1,4-phenylene oxide) (S-PPO) and sulfonated poly(ether ether ketone) (S-PEEK) at various sulfonation degrees were prepared and characterized for their degree of sulfonation, water uptake, ion exchange capacity, proton conductivity and methanol permeability. Based on the obtained results, the optimum samples were determined and subsequently blended together at different compositions. A single glass transition temperature (T_g) was determined for all blend samples, which was attributed to the presence of sulfonate groups on polymer backbones resulting in the formation of electrostatic cross-linking besides phenyl–phenyl interactions. Moreover, the molecular level of mixing in blends was verified through WAXS patterns. According to the membrane selectivity and hydrolytic stability measurements, 75 wt.% of S-PPO and 25 wt.% of S-PEEK was selected as the optimum composition. Afterwards, different amounts of an organically modified montmorillonite (MMT) were incorporated into the predetermined optimum composition matrices to reduce the methanol permeability of the resulted nanocomposite proton exchange membranes. The XRD patterns of nanocomposites revealed the exfoliated microstructure of the clay nanolayers in the polymeric matrices. Transport property measurements of nanohybrid membranes showed that the maximum selectivity parameter of 75 wt.% S-PPO/25 wt.% S-PEEK composition appeared in the presence of 1.5 wt.% of MMT, which is 1.53 times higher than the corresponding value for Nafion^® 117. The DMFC single cell test of the optimum nanohybrids membrane at 5 M methanol feed showed an open circuit voltage of 0.77 V and maximum power density of 135 mW cm^? 2 in comparison with 0.67 V and 108 mW cm^? 2 for Nafion^® 117, respectively. Fabricated nanohybrid membranes, thanks to their high selectivity, desirable transport properties and tenability, could be considered as promising polyelectrolytes for direct methanol fuel cell applications.     

Ultrasonic radiation to enable improvement of direct methanol fuel cell

To improve DMFC (direct methanol fuel cell) performance, a new method using ultrasonic radiation is proposed and a novel DMFC structure is designed and fabricated in the present paper. Three ultrasonic transducers (piezoelectric transducer, PZT) are integrated in the flow field plate to form the ultrasonic field in the liquid fuel. Ultrasonic frequency, acoustic power, and methanol concentration have been considered as variables in the experiments. With the help of ultrasonic radiation, the maximum output power and limiting current of cell can be independently increased by 30.73% and 40.54%, respectively. The best performance of DMFC is obtained at the condition of ultrasonic radiation (30 kHz and 4 W) fed with 2 M methanol solution, because both its limiting current and output power reach their maximum value simultaneously (222 mA and 33.6 mW, respectively) under this condition. These results conclude that ultrasonic can be an alternative choice for improving the cell performance, and can facilitate a guideline for the optimization of DMFC.     

Improving the Performance of Nafion®-Based Fuel Cell Membranes by Introducing Histidine Functionalized Carbon Nanotubes

A new polymer nanocomposite membrane based on Nafion and functionalized carbon nanotubes (CNTs) was developed for proton exchange membrane fuel cell (PEMFC) applications. Histidine, an imidazole-based amino acid, was used for modifying the surface of CNTs. The modification of CNTs was characterized by means of Fourier transform infrared spectroscopy (FTIR) and their Zeta potential. The imidazole groups, due to forming and breaking of hydrogen bonding, can facilitate proton transport across the polymer matrix by the Grotthuss mechanism. The final structure of the Nafion/CNT nanocomposites was investigated by small angle X-ray scattering (SAXS). The results confirm that the transport properties of the fabricated new membranes were significantly improved in comparison with unmodified and conventional Nafion® membranes. The power density of the imidazole-CNT (Im-CNT) Nafion® composite membranes was about three times more than Nafion® membranes. Also, the experimental results showed that the proton conductivity for the conventional Nafion® membranes decreased over 100°C but the conductivity for the Nafion®/Im-CNT remained at a nearly constant value above 100°C up to 120°C. Thus, the nanocomposite based on Nafion/imidazole functionalized CNT can be considered as an anhydrous PEMFC membrane for high-temperature applications.     

Polyelectrolyte Nanocomposite Membranes,Based on Chitosan-phosphotungstic Acid Complex and Montmorillonite for Fuel Cells Applications

A polyelectrolyte complex (PEC) of chitosan and phosphotungstic acid (PWA) was prepared and characterized as a proton-conducting membrane for direct methanol fuel cell (DMFC) applications. Fourier transform infrared spectroscopy showed the presence of stable PWA in PEC. To reduce the methanol permeability, several amounts of montmorilonite (MMT) nanoclays (trade name: Cloisite Na) were introduced to the system. The X-ray diffraction patterns of nanocomposite membranes proved the nanoclay layers were exfoliated in the membranes at loading weights of MMT lower than 3 wt%. Proton conductivity and methanol permeability were measured. According to the selectivity parameter—ratio of proton conductivity to methanol permeability—PEC containing 2 wt% MMT (PEC/2 wt% MMT) was identified as the optimum composition. Finally, DMFC performance tests were investigated at 70°C and 5 M methanol feed and the optimum membrane showed higher maximum power density in comparison with Nafion 117. The results indicated the optimum nanocomposite membrane is a promising polyelectrolyte membrane (PEM) for DMFC applications.     

Preparation of poly(vinyl phosphate-b-styrene) copolymers and its blend with PPO as proton exchange membrane for DMFC applications

Poly(vinyl phosphate-b-styrene) (poly(VPP-b-St)) block copolymers were prepared via consecutive telomerization of vinyl acetate (VAc), atom transfer radical polymerization (ATRP) with styrene, saponification, and phosphorylation with phosphorus oxychloride. The resulting block copolymers were characterized by FT-IR and pH titration. Then, the block copolymers were blended with poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) to prepare direct methanol fuel cell (DMFC) membrane. The performance of poly(VPP-b-St)/PPO blend membranes was measured in terms of proton conductivity, methanol permeability, thermal and hydrolytic stability. The proton conductivities were in the range of 10^− 4 to 10^− 2 S/cm (60 °C, RH = 95%); the methanol permeabilities were in the range of 4.14 × 10^− 8 to 9.62 × 10^− 8 cm²/s (25 °C), and quite lower than that of Nafion® 117. Also, the thermal stability of the blend membranes was characterized by TGA, and was stable up to 400 °C; the blend membranes had better hydrolytic stability.     

DMFC阳极流动阻力特性实验研究

本文借助可视化手段,针对平行流场和蛇形流场,实验研究不同放电电流密度、甲醇浓度、进料温度和入口流量对液相进料直接甲醇燃料电池阳极流场流动阻力特性的影响.结果表明:放电电流密度增加,流场压降随之增加,小电流放电,蛇型流场较平行流场压降增加慢,当超过某一值时,蛇型流场的压降增加较平行流场快;随甲醇浓度的提高,进出口压降均略有减小,且两种流场压降变化趋势一致;随进料温度升高,平行流场压降逐渐增大,蛇彤流场压降变化较小;随着甲醇溶液流量增大,平行流场和蛇行流场压降均逐渐增人,平行流场增加缓慢,蛇形流场压降增加速度远大于平行流场.     

Influence of methanol impurity in hydrogen on PEMFC performance

Proton exchange membrane fuel cells [PEMFC] have become highly attractive for stationary as well as mobile energy applications due to their good efficiency compact cell design and zero emissions. PEM fuel cells mainly consist of anode and cathode containing platinum/platinum alloy electrocatalysts and Nafion membrane as the electrolyte. They operate on hydrogen fuel, which is generally produced by reforming of hydrocarbons, alcohols such as methanol and may contain large amounts of impurities such as methanol, carbon dioxide, trace amounts of carbon monoxide, etc. The studies on the effect of methanol impurity in hydrogen on fuel cell performance and methods of mitigation of poisoning are very important for the commercialization of fuel cells and are described in a limited number of papers only. In this paper, we present the studies on the influence of methanol impurity in hydrogen for the PEM fuel cells. The effect of various parameters such as methanol concentration, cell voltage, current density, exposure time, reversibility, operating temperature, etc. on the cell performances was investigated using pure hydrogen. Various methods of methanol poisoning mitigation were also investigated.     

Electrochemical and impedance spectroscopy studies in H2/O2 and methanol/O2 proton exchange membrane fuel cells

This works report results of the structural and the electrochemical characterization of membrane electrode assemblies (MEA) for proton exchange membrane fuel cells (PEMFC) under various cell conditions using different MEA production processes. Electrochemical impedance spectroscopy (EIS) was applied “on-line” (in situ) as a tool for diagnosis concerning the cell performance. MEA with a 25-cm² surface area were prepared using Pt/C and Pt–Ru/C commercial electrocatalysts from E-TEK and Pt–Ru/C electrocatalysts produced by the alcohol reduction process. The catalytic ink was applied directly onto the carbon cloth or, alternatively, onto the Nafion® membrane. Two carbon cloth thicknesses were tested as diffusion layers in the MEA: 0.346 mm (common) and 0.424 mm (ELAT). An increase of the electrocatalytic activity can be obtained by pH control in the alcohol reduction process, possibly due to the better particle dispersion and the smaller particle sizes observed. In addition, a slower current decay in the ohmic region was observed using the thinner carbon cloth. This can be related to a lower resistance of the gas flow through the cloth to the catalytic active layer. Different types of methanol feed were employed in the experiments: by humidification and by evaporation. The results showed that the choice of suitable methods for catalyst preparation as well as for MEA production enhance PEMFC performance.