Influence of the phosphoric acid-doping level in a polybenzimidazole membrane on the cell performance of high-temperature proton exchange membrane fuel cells

The acid migration in phosphoric acid-doped polybenzimidazole (PBI) membrane high-temperature proton exchange membrane fuel cells (HT-PEMFC) during operation is experimentally evaluated to clarify the influence of the acid balance between the membrane and electrodes on cell performance. A method for controlling the amount of phosphoric acid doped in PBI membranes is investigated, and PBI membranes with various amounts of phosphoric acid are prepared. Cell operation tests and AC impedance spectroscopy of cells fabricated with these membranes are conducted. It was found that the amount of phosphoric acid doped in the membranes can be controlled by changing the solution temperature and the immersion time in phosphoric acid solution. It was also found that the HT-PEMFC performance can be improved by optimizing the amount of phosphoric acid doped in the membrane and by diffusion of phosphoric acid into the catalyst layer during the initial stage of cell operation.     

Experimental and numerical investigations of the effects of PBI loading and operating temperature on a high-temperature PEMFC

In this paper, experimental and numerical investigations of the effects of polybenzimidazole (PBI) loading and operating temperature on a high-temperature proton exchange membrane fuel cell (PEMFC) performance are carried out. Experiments related to a PBI-based PEMFC are performed and a two-dimensional (2-D) simulation model is developed to numerically predict the cell characteristics. Variations of 5–30 wt% in PBI amount in the catalyst layer (CL) and 160–200 °C in cell temperature are considered. On the basis of the experimental and numerical results, the negative effect of PBI content and positive effect of operating temperature on the cell performance can be precisely captured. These effects can also be shown by measurements of the impedance spectrum and predictions of O₂ concentration and current density distributions. In addition, non-uniform distributions in the O₂ concentration and the current density in the cathode compartment are also shown in the model simulation results. Cell performance curves predicted by the present model correspond well with those obtained from experimental measurements, showing the applicability of this model in a PBI-based PEMFC.     

High CO tolerance of new SiO2 doped phosphoric acid/polybenzimidazole polymer electrolyte membrane fuel cells at high temperatures of 200–250 °C

The high CO tolerance or resistance is critical for the practical application of proton exchange membrane fuel cells (PEMFCs) coupled with on board reformers for transportation applications due to the presence of high level of CO in the reformats. Increasing the operating temperature is most effective to enhance the CO tolerance of PEMFCs and therefore is of high technological significance. Here, we report a new PEMFC based on SiO₂ nanoparticles doped phosphoric acid/polybenzimidazole (PA/PBI/SiO₂) composite membranes for operation at temperatures higher than 200 °C. The phosphoric acid within the polymer matrix is stabilized by PA/phosphosilicate nanoclusters formed via prior polarization treatment of the membrane cells at 250 °C at a cell voltage of 0.6 V for 24 h, achieving a high proton conductivity and excellent stability at temperatures beyond that of conventional PA/PBI membranes. The proton conductivity of PA/PBI/SiO₂ composite membranes is in the range of 0.029–0.041 S cm^?1 and is stable at 250 °C. The PA/PBI/SiO₂ composite membrane cell displays an exceptional CO tolerance with a negligible loss in performance at CO contents as high as 11.7% at 240 °C. The cell delivers a peak power density of 283 mW cm^?2 and is stable at 240 °C for 100 h under a cell voltage of 0.6 V in 6.3% CO-contained H₂ fuel under anhydrous conditions.     

Composite membrane by incorporating sulfonated graphene oxide in polybenzimidazole for high temperature proton exchange membrane fuel cells

The objective of this work is to examine the polybenzimidazole (PBI)/sulfonated graphene oxide (sGO) membranes as alternative materials for high-temperature proton exchange membrane fuel cell (HT-PEMFC). PBI/sGO composite membranes were characterized by TGA, FTIR, SEM analysis, acid doping&acid leaching tests, mechanical analysis, and proton conductivity measurements. The proton conductivity of composite membranes was considerably enhanced by the existence of sGO filler. The enhancement of these properties is related to the increased content of –SO₃H groups in the PBI/sGO composite membrane, increasing the channel availability required for the proton transport. The PBI/sGO membranes were tested in a single HT-PEMFC to evaluate high-temperature fuel cell performance. Amongst the PBI/sGO composite membranes, the membrane containing 5 wt. % GO (PBI/sGO-2) showed the highest HT-PEMFC performance. The maximum power density of 364 mW/cm² was yielded by PBI/sGO-2 membrane when operating the cell at 160 °C under non humidified conditions. In comparison, a maximum power density of 235 mW/cm² was determined by the PBI membrane under the same operating conditions. To investigate the HT-PEMFC stability, long-term stability tests were performed in comparison with the PBI membrane. After a long-term performance test for 200 h, the HT-PEMFC performance loss was obtained as 9% and 13% for PBI/sGO-2 and PBI membranes, respectively. The improved HT-PEMFC performance of PBI/sGO composite membranes suggests that PBI/sGO composites are feasible candidates for HT-PEMFC applications.     

Analytical correlations for intermediate temperature PEM fuel cells

This paper presents analytical correlations, which predict the polarization performance and thermal effects in an intermediate temperature proton exchange membrane fuel cell (PEMFC). Such correlations are useful for engineers and designers of fuel cells to expedite calculations without depending on complex computational models. Analytical results compare well with published experimental polarization data. They also indicate the temperature variations and dominant modes of heat transfer in a unit cell.     

Durability study of HTPEMFC through current distribution measurements and the application of a model

In this work, a life study of a single 50 cm² high temperature proton exchange membrane fuel cell (HTPEMFC) has been carried out and experimental results are used to assess the causes of performance degradation in PBI HTPEMFC. Current distribution measurements, electrochemical characterization and physicochemical post-mortem analyses are combined with a CFD model that uses local parameters to determine that coalescence of catalyst particles (catalyst agglomeration) can be considered one of the main reasons responsible for the PBI fuel cell short life, according to electrochemically active area (ESA) and charge transfer resistance measurements. According to the current density distribution information, this agglomeration apparently occurs over the whole electrode surface. Increase of membrane resistance also contributes to the loss of fuel cell performance, but the significance is not as large as the effect of the catalyst. The model has been demonstrated to be a suitable diagnostic tool to identify degradation causes.     

Effects of mesoporous fillers on properties of polybenzimidazole composite membranes for high-temperature polymer fuel cells

In this study, we elucidated the effects of the addition of various mesoporous silicates (0–20 wt%) to the membranes used for high-temperature proton exchange membrane fuel cells (HT-PEMFCs) on cell performance. Two types of polybenzimidazole (PBI)-based hybrid membranes were prepared by homogeneously dispersing a predetermined amount of MCM-41 or SBA-15 within the PBI matrix. Compared to the pure PBI membrane, those with MCM-41 and SBA-15 exhibited significantly enhanced phosphoric acid doping and better mechanical properties, leading to improved HT-PEMFC performance and reduced acid migration. However, the membranes with 20 wt% silicate showed inferior performance compared to those with 10 wt% silicate. In addition, the membranes with SBA-15 exhibited noticeable aggregation, lower phosphoric acid doping, and greater phosphoric acid migration during the leaching test than did the membranes with MCM-41. Finally, during the short-term durability test, the PBI/MCM-41 (10 wt%) membrane showed the best performance (maximum power density of 310  mW cm^?2).     

Operation of a proton exchange membrane fuel cell under non-humidified conditions using a membrane–electrode assemblies with composite membrane and electrode

Composite membranes with hydrophilic substances can retain water and allow the operation of proton exchange membrane fuel cells (PEMFCs) under non-humidified conditions. In this work, thin Nafion composite membranes with silica are prepared to operate a PEMFC with dry fuel and oxidant. In addition, the role of silica in the catalyst layer as a water retainer is studied. In particular, the anode and the cathode are modified separately to elucidate the effect of silica. The incorporation of silica in the membrane and the catalyst layer enhances single-cell performance under non-humidified operation. The cell performance of membrane–electrode assemblies using the composite membrane and electrode is higher than that of a MEA using commercial Nafion 111 membrane under non-humidified conditions.     

Optimization and parametric analysis of PEMFC based on an agglomerate model for catalyst layer

A one-dimensional, non-isothermal, single-phase, steady-state comprehensive model is developed to investigate the effects of different parameters of catalyst layer and operational case as relative humidity on the proton exchange membrane fuel cell (PEMFC) performance, then to optimize the design and operation of PEMFC. The agglomerate model with thin film of polymer and liquid water was employed to describe electrochemical reaction in catalyst layers. The model considers the effect of different production ratio of water vapor and liquid water in the reaction on the fuel cell performance. The effects of operational case as temperature, relative humidity of reactants and catalyst layer structure parameters as Pt loading, agglomerate radius and Pt radius on cell performance are computed and discussed in detail. The results indicate that agglomerate radius, Pt loading and Pt particle radius, operation temperature and pressure have different kinds of effects on performance, and the performance can be improved by suitable operational case and catalyst layer structure. Results can provide good reference for optimization design of the catalyst layer and the whole cell.     

Sulfonated MWNT and imidazole functionalized MWNT/polybenzimidazole composite membranes for high-temperature proton exchange membrane fuel cells

Composite membranes used for proton exchange membrane fuel cells comprising of polybenzimidazole (PBI) and carbon nanotubes with certain functional groups were studied, because they could enhance both the mechanical property and fuel cell performance at the same time. In this study, sodium poly(4-styrene sulfonate) functionalized multiwalled carbon nanotubes (MWNT-poly(NaSS))/PBI and imidazole functionalized multiwalled carbon nanotubes (MWNT-imidazole)/PBI composite membranes were prepared. The functionalization of carbon nanotubes involving non-covalent modification and covalent modification were confirmed by FITR, XPS, Raman spectroscopy, and TGA. Compared to unmodified MWNTs and MWNT-poly(NaSS), MWNT-imidazole provided more significant mechanical reinforcement due to its better compatibility with PBI. For MWNT-poly(NaSS)/PBI and MWNT-imidazole/PBI composite membranes at their saturated doping levels, the proton conductivities were up to 5.1 × 10⁻² and 4.3 × 10⁻² S/cm at 160 °C under anhydrous condition respectively, which were slightly higher than pristine PBI (2.8 × 10⁻² S/cm). Also, MWNT-poly(NaSS)/PBI and MWNT-imidazole/PBI composite membranes showed relatively improved fuel cell performance at 170 °C compared to pristine PBI.     

Numerical analysis of effects of gas crossover through membrane pinholes in high-temperature proton exchange membrane fuel cells

Durability is a major issue in the widespread commercialization of proton exchange membrane fuel cells (PEMFCs). Various failure modes have been identified over their long runtime. These mainly originate from membrane and catalyst layer failures. One of the most common failure modes in PEMFCs is due to pinhole formation in the membrane and resultant reactant gas crossover through the membrane. Gas crossover induces several critical problems in PEMFCs, including severe reactant depletion in the downstream regions, mixed potential at the electrodes, and formation of local hot spots by hydrogen/oxygen catalytic reaction, which indicates that the cell performance decreases with increasing gas crossover. In this study, we numerically investigate the effects of gas crossover on the performance of a high-temperature PEMFC based on a phosphoric-acid-doped polybenzimidazole (PBI) membrane. In contrast to previous gas-crossover studies 1 and 2 in which uniform gas crossover throughout the entire membrane has been simply assumed, our focus is on examining the impacts of localized gas crossover due to membrane pinholes. Numerical simulations are carried out via arbitrarily assuming pinholes in the membrane. The simulation results clearly show that the presence of pinholes in the membrane significantly disrupts the species, current density, and temperature distributions. Our findings may improve the fundamental and detailed understanding of localized gas-crossover phenomena through the membrane pinholes and the influence of these phenomena on high-temperature PEMFC operation.     

Sulfonated graphene oxide as an inorganic filler in promoting the properties of a polybenzimidazole membrane as a high temperature proton exchange membrane

A commercial perfluorinated sulfonic acid (PFSA) membrane, Nafion, shows outstanding conductivity under conditions of a fully humidified surrounding. Nevertheless, the use of Nafion membranes that operate only at low temperature (<100 °C) can lead to some disadvantages in PEMFC systems, such as a low impurity tolerance and slow kinetics. To overcome the above problems, this study introduces a highly durable composite membrane with an inorganic filler for a high-temperature proton exchange membrane fuel cell (HT-PEMFC) applications under anhydrous conditions. In this work, polybenzimidazole (PBI) is used as a polymer electrolyte membrane with the addition of a sulfonated graphene oxide (SGO) inorganic filler. The amount of SGO filler was varied (0.5–6 wt.%) to study its influence on proton conductivity at elevated temperature, mechanical stability as well as phosphoric acid doping level. In particular, PBI-SGO composite membranes exhibited higher the level of acid dopant and proton conductivities than those of the pure PBI membranes. The PBI-SGO 2 wt.% composite membrane displayed the highest proton conductivity, with a value of 9.142 mS cm⁻¹ at 25 °C, and it increased to 29.30 mS cm⁻¹ at 150 °C. The PBI-SGO 2 wt.% also displayed the maximum values in the acid doping level (11.63 mol of PA/PBI repeat unit) and mechanical stability (48.86 MPa) analyses. In the HT-PEMFC test, compared with a pristine PBI membrane, the maximum power density was increased by 40% with the use of a PBI composite membrane with 2 wt.% SGO. These results show that the PBI-SGO membrane has a great potential to be applied as an alternative membrane in HT-PEMFC applications, offering the possibility of improving impurity tolerance and kinetic reactions.     

Composite anode for CO tolerance proton exchange membrane fuel cells

Fuel of proton exchange membrane fuel cells (PEMFC) mostly comes from reformate containing CO, which will poison the fuel cell electrocatalyst. The effect of CO on the performance of PEMFC is studied in this paper. Several electrode structures are investigated for CO containing fuel. The experimental results show that thin-film catalyst electrode has higher specific catalyst activity and traditional electrode structure can stand for CO poisoning to some extent. A composite electrode structure is proposed for improving CO tolerance of PEMFCs. With the same catalyst loading, the new composite electrode has improved cell performance than traditional electrode with PtRu/C electrocatalyst for both pure hydrogen and CO/H₂. The EDX test of composite anode is also performed in this paper, the effective catalyst distribution is found in the composite anode.     

Recycling of membrane electrode assembly of PEMFC by acid processing

A simple, high efficient and environmentally friendly approach was investigated to recycle the key materials of membrane electrode assembly (MEA) applied in proton exchange membrane fuel cell (PEMFC). The catalyst coated membranes (CCMs) was dipped into sulfuric acid until the formation of transparent solution composed of Pt and perfluorosulfonic acid resin. Wherein, the membrane was dissolved, and the amorphous carbon nanoparticles as catalyst supports in catalyst layers were oxidized. Subsequently, both metal Pt and perfluorosulfonic acid resin were separated by centrifugal separation. Then the resin was recast into a membrane and the single fuel cell performance was tested. As a result, the solution to recycle the key materials of MEAs is promising for recycling MEA materials used in PEMFC.     

A high conductivity Cs2.5H0.5PMo12O40/polybenzimidazole (PBI)/H3PO4 composite membrane for proton-exchange membrane fuel cells operating at high temperature

A high conductivity composite proton-exchange membrane Cs_2.5H_0.5PMo₁₂O₄₀ (CsPOM)/polybenzimidazole (PBI) for use in hydrogen proton-exchange fuel cells has been prepared. The CsPOM composite membrane is insoluble in water. The composite membrane doped with H₃PO₄ showed high-proton conductivity (>0.15 S cm⁻¹) and good thermal stability. ³¹P NMR analysis has suggested the formation of a chemical bond between the CsPOM and PBI in the composite membrane. The performance of the membrane in a high-temperature proton-exchange membrane fuel cell (PEMFC) fueled with hydrogen was better than that with a phosphoric acid-doped PBI membrane under the same conditions and at temperatures greater than 150 °C. The CsPOM/PBI composite would appear to be a promising material for high-temperature PEMFC applications.     

Fabrication of crosslinked polybenzimidazole membranes by trifunctional crosslinkers for high temperature proton exchange membrane fuel cells

Two trifunctional bromomethyls containing crosslinkers, 1,3,5-tris(bromomethyl)benzene (B3Br) and 1,3,5-tris(bromomethyl)-2,4,6-triethylbenzene (Be3Br), are employed to covalently crosslink polybenzimidazole (PBI) membranes for the high temperature proton exchange membrane fuel cell. The presence of three bromomethyl groups in each crosslinker molecule is expected to create more free volume for acid doping while enhancing the adhesive strength of the PBI chains. In addition, the influence of the two crosslinker structures on the property of the crosslinked membranes is compared and analyzed. All the crosslinked PBI membranes exhibit longer morphology durability over the pristine PBI membrane toward the radical oxidation. Moreover, the crosslinked PBI membranes with the crosslinker Be3Br containing three ethyl groups display superior acid doping level, high conductivity and excellent mechanical strength simultaneously, over those with the crosslinker B3Br and the pristine PBI membrane. Single cell measurements based on the acid doped membrane with a crosslinking degree of 7.5% by Be3Br demonstrate the technical feasibility of the prepared membranes for high temperature proton exchange membrane fuel cells.     

Fabrication of catalyst-coated membrane-electrode assemblies by doctor blade method and their performance in fuel cells

Membrane-electrode assemblies (MEAs) have been fabricated with a direct coating of the catalyst slurry by a doctor blade method on the pre-swollen Nafion membrane for proton exchange membrane (PEMFC) and direct methanol fuel cells (DMFC). The effects of various swelling agents with different boiling points such as ethylene glycol (EG), diethylene glycol (DEG), triethylene glycol (TEG), tetraethylene glycol (TEEG), and glycerol in the swelling step of the membrane and the drying step of the coated catalyst have been investigated. Also, the use of dimethyl sulfoxide (DMSO) as a dispersing agent in the catalyst slurry has been investigated. Among the various swelling agents investigated, EG gives the best results with the dispersing agent DMSO offering further improvement. The MEAs fabricated with the EG-swollen membranes and DMSO as a dispersing agent in the catalyst layer show good performance in single fuel cells with hydrogen and methanol fuels.     

Demonstration of a 20 W class high-temperature polymer electrolyte fuel cell stack with novel fabrication of a membrane electrode assembly

Acid-doped polybenzimidazole (PBI) membrane and polytetrafluoroethylene (PTFE)-based electrodes are used for the membrane electrode assembly (MEA) in high-temperature polymer electrolyte fuel cells (HTPEFCs). To find the optimum PTFE content for the catalyst layer, the PTFE ratio in the electrodes is varied from 25 to 50 wt%. To improve the performance of the electrodes, PBI is added to the catalyst layer. With a weight ratio of PTFE to Pt/C of 45:55 (45 wt% PTFE in the catalyst layer), the fuel cell shows good performance at 150 °C under non-humidified conditions. When 5 wt% PBI is added to the electrodes, performance is further improved (250 mA cm⁻² at 0.6 V). Our 20 W class HTPEFC stack is fabricated with a novel MEA. This MEA consists of 8 layers (1 phosphoric acid-doped PBI membrane, 2 electrodes, 1 sub-gasket, 2 gas-diffusion media, 2 gas-sealing gaskets). The sub-gasket mitigates the destruction of a highly acid-doped PBI membrane and provides long-term durability to the fuel cell stack. The stack operates for 1200 h without noticeable cell degradation.     

Phosphoric acid‐doped electrodes for a PBI polymer membrane fuel cell

A study of a phosphoric acid (PA)‐doped polybenzimidazole (PBI) membrane fuel cell is reported. The fuel cell used polytetrafluoroethylene (PTFE) in the catalyst layer of the membrane electrode assembly to act as a binder and did not use PBI. The PTFE provided an amorphous phase to hold the PA added to the catalyst layers. The study investigated several parameters of the fuel cell electrode, catalyst layer including: PA loading, PTFE content and catalyst loading and wt% of Pt in the carbon supported catalysts and doping of the PBI membrane. There was a minimum amount of acid doping that gave good cell performance for oxygen reduction in the cathode layer. Good performance of the fuel cell was achieved at 120°C with air of 0.27 W cm^?2 using a 0.51 mg_Pt cm^?2 loading of catalyst. Peak power of 0.4 W cm^?2 was achieved with air at 150°C using a membrane doping of PA of 5.6 PRU (doped acid molecules per repeat polymer unit). Heat treatment of the PTFE‐bonded electrodes to increase hydrophobicity did not improve the cell performance. The effect of a perfluorinated surfactant although reported to enhance oxygen solubility in the catalyst layer led to a poorer cell performance. Copyright © 2010 John Wiley & Sons, Ltd.