Fabrication of Function‐Graded Proton Exchange Membranes for Direct Methanol Fuel Cells Using Electron Beam‐Grafting

Function‐graded proton exchange membranes (G‐PEMs) based on poly(tetrafluoroethylene‐co‐hexafluoropropylene) were fabricated for direct methanol fuel cells (DMFCs) via electron beam‐grafting using the heterogeneous energy deposition technique. The G‐PEMs had a water uptake gradient in the proton transfer direction, originating from the sulfonic acid group gradient. The distribution of sulfonic acid groups in the various G‐PEMs was evaluated using X‐ray photoelectron spectroscopy. Four types of PEMs (flat‐type, strong‐gradient, meso‐gradient, and weak‐gradient types) were fabricated. By varying the direction of the G‐PEMs, the methanol permeation test and DMFC operation were performed with two orientations of the sulfonic acid group gradient, decreasing from the methanol injection (anode) side (decrease‐type) or the other (cathode) side (increase‐type). The methanol permeability of the strong‐gradient, meso‐gradient, and weak‐gradient G‐PEMs was lower than that of Nafion®117 and the flat‐type PEM. The “increase‐type” orientation of the strong‐gradient G‐PEM resulted in the lowest methanol permeability. The DMFC performance of the G‐PEMs was influenced by the thickness direction, such as “decrease‐type” and “increase‐type.” The performance of the “decrease‐type” assembly was higher than that of the “increase‐type.” The “decrease‐type” assembly with P‐200 k (weak‐gradient G‐PEM) exhibited the highest performance of the fabricated PEMs, comparable to that of Nafion®117.     

Effect of Porosity in Catalyst Layers on Direct Methanol Fuel Cell Performances

Effects of porosity of catalyst layers (CLs) on direct methanol fuel cell (DMFC) performances are investigated using silicon dioxide (SiO₂) particles as a pore former. The pore size and volume of CLs are controlled by changing the size and content of SiO₂. As the size of pore formed by removal of SiO₂ increases, DMFC performances are enhanced. The augmentation in performances can be explained by facilitation of fuel transport to catalyst particles, increase of utilization efficiency of catalysts, diminishment in methanol crossover, reduction in activation loss and facilitation of water discharging out of CLs of cathode due to the controlled porosity in CLs. The enhanced fuel transport, accessibility of fuels to Pt catalyst surface, is proved by the active areas of Pt catalyst. In addition to the active area of Pt catalyst, porous CLs exhibit a decline in methanol crossover, leading to increase of open circuit voltage (OCV). The porous CLs also show improvements in activation loss due to high porosity, causing enhancement in DMFC performances. In aspect of pore volume contribution to cathode performance, the SiO₂ content is optimized. Based on the DMFC performances, it can be suggested that the optimum conditions of SiO₂ are 500 nm in size and 20 wt.% in content. The porosity effect on both electrodes appears as follows: the pores in cathode are more effective on DMFC performances (55.5%) than those of anodes (44.5%) based on the maximum power of DMFC, indicating that the pores in CLs facilitate removal of water from electrodes.     

Operation Characteristic Analysis of a Direct Methanol Fuel Cell System Using the Methanol Sensor‐less Control Method

The application of methanol sensor‐less control in a direct methanol fuel cell (DMFC) system eliminates most of the problems encountered when using a methanol sensor and is one of the major solutions currently used in commercial DMFCs. This study focuses on analyzing the effect of the operating characteristics of a DMFC system on its performance under the methanol sensor‐less control as developed by Institute of Nuclear Energy Research (INER). Notably, the influence of the dispersion of the methanol injected on the behavior of the system is investigated systematically. In addition, the mechanism of the methanol sensor‐less control is investigated by varying factors such as the timing of the injection of methanol, the cathode flow rate, and the anode inlet temperature. These results not only provide insight into the mechanism of methanol sensor‐less control but can also aid in the improvement and application of DMFC systems in portable and low‐power transportation.     

Sulphonated Tetramethyl Poly(ether ether ketone)/Epoxy/Sulphonated Phenol Novolac Semi‐IPN Membranes for Direct Methanol Fuel Cells

The sulphonated phenol novolac (PNBS) which was used as a curing agent of epoxy was synthesised from phenol novolac (PN) and 1, 4‐butane sultone and confirmed by FTIR and ¹H NMR. The degree of sulphonation (DS) in PNBS was calculated by ¹H NMR. The semi‐IPN membranes composed of sulphonated tetramethyl poly(ether ether ketone) (STMPEEK) (the value of ion exchange capacity is 2.01 meq g^–1), epoxy (TMBP) and PNBS were successfully prepared. The semi‐IPN membranes showed high thermal properties which were measured by differential scanning calorimeter (DSC) and thermogravimetric analyses (TGA). With the introduction of the cross‐linked TMBP/PNBS, the mechanical properties, dimensional stability, methanol resistance and oxidative stability of the membranes were improved in comparison to the pristine STMPEEK membrane. Although the proton conductivities of the semi‐IPN membranes were lower than those of the pristine STMPEEK membrane, the higher selectivity defined as the ratio of the proton conductivity to methanol permeability was obtained from the STMPEEK/TMBP/PNBS‐14 semi‐IPN membrane. The results indicated that the semi‐IPN membranes could be promising candidates for usage as proton exchange membranes in direct methanol fuel cells (DMFCs).     

Influence of Methanol Crossover on the Fuel Utilization of Passive Direct Methanol Fuel Cell

The effect of methanol crossover on the fuel utilization of a passive direct methanol fuel cell (DMFC) was reported. The results revealed that the Faradaic efficiency decreased from 46.9 to 17.4% when methanol concentration increased from 1.0 to 8.0 mol L^–1 at the lower current density 11.1 mA cm^–2. However, the Faradaic efficiency increased from 14.7 to 31.3% when methanol concentration increased from 1.0 to 8.0 mol L^–1 at a higher current density of 44.4 mA cm^–2. On the other hand, although the amount of methanol was increased, the Faradaic efficiency did not change, obviously due to the uniform methanol crossover and methanol diffusion at the same methanol concentration and constant current.     

Model for the Degradation Performance of a Single‐Cell Direct Methanol Fuel Cell under Varying Operational Conditions

The effect of varying operating parameters on the degradation of a single‐cell direct methanol fuel cell (DMFC) with serpentine flow channels was investigated. Fuel cell internal temperature, methanol concentration, and air and methanol flow rates were varied in experimental tests and fuel cell performance was chronologically recorded. A DMFC semi‐empirical performance model was developed to predict the polarization curves of the DMFC and validated at different operating conditions. Performance degradation was observed and modeled over time by a linear regression model. Unlike previous studies, the cumulative exposure of the operating factors to the fuel cell was considered in the degradation analysis. The degradation model shows the cell voltage generation capacity does not significantly degrade. However, the Tafel slope of the cell changes with cumulative exposure to methanol concentration and air flow, and the ohmic resistance changes with cumulative exposure to temperature, methanol and air flow.     

Operation of the Alkaline Direct Formate Fuel Cell in the Absence of Added Hydroxide

The direct formate fuel cell (DFFC) has recently been demonstrated as a viable alkaline direct liquid fuel cell (DLFC) that does not require addition of hydroxide to the fuel stream for operation. In this work, we report that the DFFC can produce significant power at low temperatures without added hydroxide, especially when compared with other alkaline DLFCs powered by alcohols. Using oxygen at the cathode, the DFFC powered by 1 M HCOOK achieves a maximum power density of 106 mW cm^–2 at 50 °C and 64 mW cm^–2 at 23 °C. Using air at the cathode, the same DFFC achieves a maximum power density of 76 mW cm^–2 at 50 °C and 27 mW cm^–2 at 23 °C. These power densities were achieved without addition of hydroxide to the fuel stream. Constant current operation demonstrates that the maximum power density can be maintained at least for several hours of operation. Finally, we use electrochemical analysis to demonstrate that the formate oxidation reaction is not dependent on pH between 9 and 14, which permits the use of formate fuel without added hydroxide in the DFFC. An alkaline DLFC that does not require added hydroxide is promising for safe and practical operation.     

Fabrication and Performance of Different Structural Cathode Catalyst Layers by EHDA Deposition for DMFC

In this work, electrohydrodynamic atomization Layer‐by‐Layer deposition was used to deposit cathode catalyst layers (CLs) at different working distances of 3, 5, and 7 mm. The influence of working distance on the structural characteristics of cathode CLs was analyzed. The cyclic voltammograms of the cathode electrodes with different structures and the performance of the assembled membrane‐electrode assemblies (MEAs) were examined. It was observed that the cathode CLs presented well‐packed and porous features. The dispersity of the deposited catalyst and the thickness of cathode CL increased with higher working distance, which resulted in larger electrochemical active surface area (ESA), higher performance of the assembled MEAs and higher catalyst utilization. The ESA increased by approximately 70% when the cathode CL produced at the working distance of 7 mm compared with that at 3 mm. The peak power density of 56.1 mW cm^–2 and the peak cathode catalyst specific power of 140.3 mW mg^–1 Pt were obtained when the cathode CLs produced at the working distance of 7 mm.     

Fluorenyl‐containing Quaternary Ammonium Poly(arylene ether sulfone)s for Anion Exchange Membrane Applications

A series of anion exchange membranes (AEM) based on block quaternary ammonium poly(arylene ether sulfone) (QA‐bPAES) were successfully synthesized from 9,9′‐bis(4‐hydroxyphenyl) fluorene, 4,4′‐(hexafluoroisopropylidene) diphenol and 4,4′‐difluorodiphenyl sulfone via block polymerization, chloromethylation, quaternization, alkalization and solution casting. Properties of the obtained QA‐bPAES membranes, including ion exchange capacity (IEC), water uptake, swelling ratios, methanol permeability and ion conductivity were investigated. The obtained QA‐bPAES membranes showed low water uptakes, high ion conductivities and good physical and chemical stability. For example, the membrane of QA‐bPAES(20/10)‐1.34 with IEC of 1.34 mmol g⁻¹ exhibited swelling ratios of 5.0% and 5.1% in in‐plane and through‐plane direction, respectively, and ion conductivity of 15.6 mS cm⁻¹ in water at 60 °C with low methanol permeability of 1.06 × 10⁻⁷ cm² s⁻¹ (25 °C). All the results indicated that this type of block membranes had good potentials for alkaline anion exchange membrane fuel cell applications.     

Enhancement of the Passive Direct Methanol Fuel Cells Performance by Modification of the Cathode Microporous Layer Using Carbon Nanofibers

Mass transfer is a key parameter affecting the performance of the passive direct methanol fuel cells (DMFCs), which work under natural convection. In this study, effect of carbon nanofibers (CNFs) addition to the cathode microporous layer (MPL) on the performance of the passive DMFCs was investigated. The results indicated that CNFs content has a significant influence on both of the mass transport and the electrochemical surface area (ECSA). Interestingly, addition of the CNFs (20 wt.%) leads to increase the power density of the passive DMFC to 160% compared to pristine carbon black MPL. At low current density, the CNFs content has no influence on the performance, while at high current density the maximum performance can be obtained at 20 wt.% CNFs then the performance decreases with further increase in the CNFs content. Although the highest catalyst utilization is observed at 40 wt.% CNFs, a maximum power density of 36 mW cm^–2 can be obtained at 20 wt.% CNFs and this is related to the significant effect of the mass transfer resistance under the passive operation conditions. Overall, addition of CNFs to the MPL can be considered an effective strategy to modify the passive DMFCs performance.     

Comparative Study of On‐Line Membrane Electrode Assembly Activation Procedures in Proton Exchange Membrane Fuel Cell

The major objectives of this study are to identify the best activation procedure between commonly used procedures that can significantly reduce the conditioning duration and to understand the change in interfacial properties during conditioning. In order to do that, three on‐line activation procedures were employed for activating of identical MEAs in PEMFC and studied by polarization curve and electrochemical impedance spectroscopy (EIS). These methods are constant current (0.25 A cm^–2) for 19 h, constant voltage (0.6 V) for 9 h, and USFCC protocol. The best performance was achieved by USFCC protocol within 15 h, but by constant voltage procedure, 96% of mentioned protocol was obtained during 6 h. So constant voltage activation proceeded remarkably fast, and most of the activation process was achieved in the first few hours. Obtained results from Nyquist plots during/after MEA conditioning indicate mentioned process are irreversible and interfacial structures of MEAs are different even after finishing of MEA break‐in. It could be affected the MEA performance and even its durability. These results are consistence with the obtained performance of activated MEAs either in H₂/air or H₂/O₂ PEMFC. We found the mentioned constant current procedure consume long time without reaching to expectable performance even after 19 h.     

直接甲醇燃料电池技术及应用

本文回顾了直接甲醇燃料电池（ＤＭＦＣ）的研究开发历史,系统阐述了ＤＭＦＣ系统中电催化剂选择与设计基本原则、电解质膜材料与甲醇渗透的关系。分析了电池工作温度、工作压力和甲醇进料方式对ＤＭＦＣ电化学性能的影响。     

Experimental Evaluation of Effective Parameters for the Synthesis of Polysulfone‐Based Anion Exchange Membrane

Experimental evaluation using screening design is employed to determine the significant parameters in preparation of anion exchange membranes applicable in solid alkaline fuel cell. Anion exchange membranes are prepared based on quaternized polysulfone using trimethylamine and N,N,N′,N′‐tetramethyl‐1,6‐hexanediamine as amination agents. Plackett Burman and Fractional Factorial designs are used to model variable factors and responses. Chloromethylation time and temperature, amination time and temperature and molar ratio of amines to chloromethylated sites on the polymer chain are studied as the model variables. Moreover, ex situ ionic conductivity (at 25 and 60 °C) and swelling ratio (at 25 °C) of the prepared anion exchange membranes are considered as the responses. Finally, based on analysis of variance using statistical software, the chloromethylation time, the amination temperature and the molar ratio of amines are defined as the dominant parameters which significantly affect the performance of the anion exchange membranes.     

Effect of Ionomer Content in Anode and Cathode Catalyst Layers on Direct Methanol Fuel Cell Performance

The influence of ionomer content on the performance of direct methanol fuel cells (DMFC) is studied. The performance is studied as a function of the (nafion/carbon, N/C) ratio on the anode and cathode. The performance of the DMFC has been found to increase as a function of the N/C ratio. The ionomer content seems to influence the catalyst layer resistance in the anode and cathode and also the methanol oxidation potential on the anode. On the cathode, catalyst utilisation is seen to be affected by the ionomer content. Cyclic voltammetry (CV) is used to study the effect of ionomer content on Platinum (Pt) utilisation on the cathode. Theoretical calculations are used to study the catalyst layer resistance on the anode and cathode as a function of ionomer content. Findings indicate that ionomer content plays only a partial role in characterising the performance of a DMFC.     

Proton Exchange Membrane Fuel Cell Operation and Degradation in Short‐Circuit

Hybridization of proton exchange membrane fuel cells (PEMFC) and ultra capacitors (UC) are considered as an alternative way to implement high autonomy, high dynamic, and reversible energy sources. PEMFC allow high efficiency and high autonomy, however their dynamic response is limited and this source does not allow recovering energy. UC appears to be a complementary source to fuel cell systems (FCS) due to their high power density, fast dynamics, and reversibility. A direct hybridization of these sources could allow reducing the number of power converters and then the total cost of the hybridized system. Simulations show the behavior of the hybrid source when the fuel cell and ultra capacitors are interconnected and the natural energy management when a charge is connected. The results show that the magnitude of the transient current supplied by the fuel cell to charge the UC can be much higher than its nominal value. An experimental setup is implemented to study the effects of these high currents in a PEMFC. This is done by imposing a controlled short‐circuit between the electrodes. The PEMFC degradation is quantified by using electrochemical impedance spectroscopy.     

A Membraneless Direct Borohydride Fuel Cell Using LaNiO3‐Catalysed Cathode

Direct borohydride fuel cell (DBFC) is one of the most exciting energy technologies that solve the hydrogen storage and safety issues by using aqueous solution of KBH₄ or NaBH₄. Here, we present a membraneless DBFC with perovskite‐type oxide LaNiO₃/C‐catalysed cathode. A significant finding from the electrochemical experiments is that it obviously shows that the existence of ions has almost no negative influence on the discharge performances of the LaNiO₃‐catalysed cathode. Therefore, the DBFC is designed without using an ion exchange membrane. The maximal power density of 127 mW cm^–2 is obtained at 65 °C under atmospheric pressure. A 500 h life test shows that the DBFC has good stability.     

Synthesis of Ultrafine Size Platinum Nanoparticles on Defective Graphene with Enhanced Performance Towards Methanol Electro‐Oxidation

Graphene nanosheets (GS) were formed by the thermal‐expansion method. Large micropores about 1–2 nm were produced, which might provide abundant anchor sites for fixing catalyst. Platinum nanoparticles (NPs) supported on exfoliated GS (Pt/GS) were synthesized through an improved impregnation approach and mixture gas (5% H₂ in N₂) reduction. SEM and TEM images indicated the simple and clean method can effectively synthesize Pt with uniform dispersion and small size (below 3 nm) on the 2D specific and stratiform GS. The different amounts of Pt loaded on carbon carriers have been investigated respectively to evaluate the preferable electrocatalyst. Experimental results showed that Pt/GS of 20 wt.% initiated CO oxidation at the lowest onset potential in comparison with the commercial Pt/C (JM), indicating a higher CO tolerance of Pt/GS catalysts. In addition, Pt/GS of 20 wt.% exhibited enhanced electrocatalytic activity and high durability towards methanol oxidation. The high performance is exclusively attributed to synergistic effects of exfoliated GS and ultrafine size Pt NPs. Combining a melt‐diffusion strategy with the effective reduction of Pt precursors by the hydrogen gas, this present method is easy to scale up and possesses a significant potential for synthesizing anode electro‐catalyst of direct methanol fuel cells.     

Analysis of Direct Methanol Fuel Cell (DMFC)‐Performance via FTIR Spectroscopy of Cathode Exhaust

Water and methanol flux through Nafion™ and polyaryl‐blend membranes prepared at ICVT were studied under DMFC operation. The water, methanol, and CO₂ content in the cathode exhaust were measured by FTIR spectroscopy. Both the water and methanol flux turned out to be strongly dependent on the operating temperature and thus on membrane swelling. Apart from this, water flux through the membrane is primarily affected by the gas volume flux on the cathode side. A coupling between water flux and methanol flux was observed, which leads to the conclusion that methanol is transported both by diffusion and by convection caused by the superimposed water flux. Polyaryl‐blend membranes showed a reduced diffusive methanol transport when compared to Nafion™ due to their different internal microstructure. The impact of methanol cross‐over on cathode losses at high current density needs further clarification with respect to the prevailing mechanism of methanol oxidation at the cathode.     

A Three‐Dimensional Non‐isothermal Model of High Temperature Proton Exchange Membrane Fuel Cells with Phosphoric Acid Doped Polybenzimidazole Membranes

High temperature proton exchange membrane fuel cells (HT‐PEMFCs) with phosphoric acid doped polybenzimidazole (PBI) membranes have gained tremendous attentions due to its attractive advantages over conventional PEMFCs such as faster electrochemical kinetics, simpler water management, higher carbon monoxide (CO) tolerance and easier cell cooling and waste heat recovery. In this study, a three‐dimensional non‐isothermal model is developed for HT‐PEMFCs with phosphoric acid doped PBI membranes. A good agreement is obtained by comparing the numerical results with the published experimental data. Numerical simulations have been carried out to investigate the effects of operating temperature, phosphoric acid doping level of the PBI membrane, inlet relative humidity (RH), stoichiometry ratios of the feed gases, operating pressure and air/oxygen on the cell performance. Numerical results indicate that increasing both the operating temperature and phosphoric acid doping level are favourable for improving the cell performance. Humidifying the feed gases at room temperature has negligible improvement on the cell performance, and further humidification is needed for a meaningful performance enhancement. Pressurising the cell and using oxygen instead of air all have significant improvements on the cell performance, and increasing the stoichiometry ratios only helps prevent the concentration loss at high current densities.     

Effect of pH Value on Performance of PtRu/C Catalyst Prepared by Microwave‐Assisted Polyol Process for Methanol Electrooxidation

PtRu/C catalysts with different mean particle sizes have been synthesised by microwave‐assisted polyol process at various pH values and characterised by transmission electron microscopy (TEM), energy dispersive analysis of X‐ray (EDAX) and X‐ray diffraction (XRD). Their electrochemical performances have been tested by cyclic voltammetry, amperomeric i–t, and CO‐stripping techniques. The effects of pH values on performances of the PtRu/C catalysts have been mainly investigated. It has been found that the particle size, composition and catalytic activity of the PtRu/C catalyst are very sensitive to the pH value of reducing solution, and the PtRu/C catalyst prepared at the pH value of 8 exhibits the better performance for methanol electrooxidation than the other samples. The size of the nanoparticles decreases as the pH value increases from 0.2 to 10 with the largest size of 4.4 nm and the smallest one of 2.1 nm. The two metal elements distribute uniformly in the catalyst and their metal loadings are similar to the theoretical value.