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.     

Power generation using a mesoscale fuel cell integrated with a microscale fuel processor

An integrated fuel reformer and fuel cell system for microscale (10–500 mW) power generation is being developed and demonstrated as an alternative to conventional batteries. In this system, thermal energy is transformed to electricity by stripping the hydrogen from the hydrocarbon fuel (reforming) and converting the hydrogen to electricity in a proton exchange membrane (PEM) fuel cell. The fabrication and operation of a mesoscale fuel cell based on phosphoric acid doped polybenzimidazole (PBI) technology is discussed, along with tests integrating the methanol processor with the fuel cell. The PBI membrane had high ionic conductivity at high temperatures (>150 °C), and sustained the high conductivity at low relative humidity at these temperatures. This high-temperature stability and high ionic conductivity enabled the membrane to tolerate extremely high levels of carbon monoxide up to 10% without significant degradation in performance. The combined fuel cell/reformer system was successfully operated to enable the production of 23 mW of electrical power.     

Planar array stack design aided by rapid prototyping in development of air-breathing PEMFC

The polymer electrolyte membrane fuel cell (PEMFC) is one of the most important research topics in the new and clean energy area. The middle or high power PEMFCs can be applied to the transportation or the distributed power system. But for the small power application, it is needed to match the power requirement of the product generally. On the other hand, the direct methanol fuel cell (DMFC) is one of the most common type that researchers are interested in, but recently the miniature or the micro-PEMFCs attract more attention due to their advantages of high open circuit voltage and high power density.     

An overview of proton exchange membranes for fuel cells: Materials and manufacturing

Due to their efficient and cleaner operation nature, proton exchange membrane fuel cells are considered energy conversion devices for various applications including transportation. However, the high manufacturing cost of the fuel cell system components remains the main barrier to their general acceptance and commercialization. The main strategy for lowering the cost of fuel cells which is critical for their general acceptance as alternative energy sources in a variety of applications is to lower the cost of the electrolyte and catalyst. An electrolyte is one of the most important components in the fuel cell and a major contributor to the cost (>$500/m² for commercial Nafion® series). Nafion is widely used as an electrolyte in PEMs, but it has some limitations in addition to high costs such as low proton conductivity, high-temperature performance degradation, and high fuel crossover. Therefore, the development and manufacturing of low-cost and high-performance electrolyte membranes with higher conductivity (～0.1 S·cm ^?1) at a wider temperature range is a top priority in the scientific community. Recent years have seen extensive research on the preparation, modification, and properties of PEMs such as non-Nafion membranes (SPI, PBI, polystyrene, polyphosphazene, SPAEK, SPEEK, SPAS, SPEN), and their composites by incorporating functionalized CNTs, GO as fillers to overcome their drawbacks. This paper provides a comprehensive review of membrane materials and manufacturing with a focus on PEMs. In particular, the review brings out the basic mechanism involved in proton conduction, important requirements, historical background, contending technologies, types, advantages and disadvantages, current developments, future goals, and directions design aspects related to thermodynamic and electrochemical principles, system assessment parameters, and the prospects and outlook.     

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.     

A review on anion exchange membranes for fuel cells: Anion-exchange polyelectrolytes and synthesis strategies

The energy distribution of the world is in a critical transition from traditional fossil fuel to new clean energy. Actually, the fuel cell is favored by researchers as an efficient and clean energy conversion equipment. The anion exchange membranes (AEMs) with excellent performance and long service life will become the development trend of alkaline fuel cells in the future. Compared with proton exchange membrane fuel cells (PEMFCs), its advantages of affordable price, work safety, and non-precious metal participation are widely favored by researchers. This paper reviews the performance of characteristics, synthesis methods, modification methods, and alkaline stability protection of anion-exchange polyelectrolytes (AEPs), and the current research and development status of AEPs used in AEMs are summarized. The evaluation and comparison of different types of AEPs and AEMs based on different AEPs are put forward. This review is expected to further deepen the understanding of AEPs in AEMFC.     

Achieving breakthrough performance caused by optimized metal foam flow field in fuel cells

Enhanced mass transport in polymer electrolyte membrane fuel cells (PEMFCs) is required for achieving high performance because concentration losses dominate cell performance. In particular, the flow field is crucial for mass transport. Recently, metal foam has been proposed as an alternative flow field owing to its three-dimensional pores, high porosity, and enhanced electrical conductivity. Here, we inspect the microstructure of various copper foams and investigate its effect as a flow field on PEMFCs. The PEMFCs with the optimized foam flow field deliver the highest performance reported to date. A large contact area and small ribs of the optimized foam flow field are advantageous for mass transfer and ohmic resistance. In addition, the internally generated pressure increases the partial pressure of the reactant, which leads to increased performance. This foam flow field has a significant potential for achieving high cell performance by enhancing the electrochemical reaction of the catalyst.     

Temperature-dependent performance of the polymer electrolyte membrane fuel cell using short-side-chain perfluorosulfonic acid ionomer

We report on polymer electrolyte membrane fuel cells (PEMFCs) that function at high temperature and low humidity conditions based on short-side-chain perfluorosulfonic acid ionomer (SSC-PFSA). The PEMFCs fabricated with both SSC-PFSA membrane and ionomer exhibit higher performances than those with long-side-chain (LSC) PFSA at temperatures higher than 100 °C. The SSC-PFSA cell delivers 2.43 times higher current density (0.524 A cm⁻¹) at a potential of 0.6 V than LSC-PFSA cell at 140 °C and 20% relative humidity (RH). Such a higher performance at the elevated temperature is confirmed from the better membrane properties that are effective for an operation of high temperature fuel cell. From the characterization technique of TGA, XRD, FT-IR, water uptake and tensile test, we found that the SSC-PFSA membrane shows thermal stability by higher crystallinity, and chemical/mechanical stability than the LSC-PFSA membrane at high temperature. These fine properties are found to be the factor for applying Aquivion™ E87-05S membrane rather than Nafion^® 212 membrane for a high temperature fuel cell.     

Electrolytes for solid oxide fuel cells

The high operating temperature of solid oxide fuel cells (SOFCs), as compared to polymer electrolyte membrane fuel cells (PEMFCs), improves tolerance to impurities in the fuel, but also creates challenges in the development of suitable materials for the various fuel cell components. In response to these challenges, intermediate temperature solid oxide fuel cells (IT-SOFCs) are being developed to reduce high-temperature material requirements, which will extend useful lifetime, improve durability and reduce cost, while maintaining good fuel flexibility. A major challenge in reducing the operating temperature of SOFCs is the development of solid electrolyte materials with sufficient conductivity to maintain acceptably low ohmic losses during operation. In this paper, solid electrolytes being developed for solid oxide fuel cells, including zirconia-, ceria- and lanthanum gallate-based materials, are reviewed and compared. The focus is on the conductivity, but other issues, such as compatibility with electrode materials, are also discussed.     

Correlation between performance of polymer electrolyte membrane fuel cell and degradation of the carbon support in the membrane electrode assembly using image processing method

Long-time operation and various conditions cause the membrane electrode assembly (MEA) of polymer electrolyte membrane fuel cells (PEMFCs) to degrade, which results in decreased performance. The degradation of the MEA appears as various symptoms, such as the loss of carbon support and agglomeration of the Pt catalyst. In this paper, damage on the surface of the MEA by long-time operation and various conditions is induced intentionally by high-temperature conditions in a thermostat chamber. The MEA surface damage is photographed by scanning electron microscopy (SEM), and the loss of the carbon support that fixes the platinum catalyst is judged. Image processing is used to analyze damage on the MEA surface, and binarization processing is applied to the image processing method. SEM imagery is taken at magnifications of 100 × and the trends in quantified surface damage on the MEA according to the degradation temperature are analyzed. The correlation between the quantitative damage on the MEA surface and the performance of the PEMFC is checked. As a result, the tendency of decreasing PEMFC performance is derived from increasing quantified damage on the MEA surface.     

Multi-pass serpentine flow-fields to enhance under-rib convection in polymer electrolyte membrane fuel cells: Design and geometrical characterization

The flow-field for reactant distribution is an important design factor that influences the performance of polymer electrolyte membrane fuel cells (PEMFCs). Under-rib convection between neighboring channels has been recognized to enhance the performance of PEMFCs with serpentine flow-fields. This study presents a simple design method to generate multi-pass serpentine flow-fields (MPSFFs) that can maximize under-rib convection in a given cell area. Geometrical characterization indicates that MPSFFs lead to significantly higher under-rib convection intensities and more uniform conditions, such as reactant concentrations, temperature, and liquid water saturation, compared with conventional serpentine flow-fields. The implications of the enhanced under-rib convection due to MPSFFs on the performance of PEMFCs are discussed.     

High temperature operation of PEMFC: A novel approach using MEA with silica in catalyst layer

Composite membranes with inorganic substances can retain water and allow the operation of polymer electrolyte membrane fuel cells (PEMFCs) at high temperature under low humidity. In this work, the single cell was operated at high temperature using silica–Nafion composite membrane in addition with silica in catalyst layer. The cell was operated at various temperatures under different relative humidity conditions. We observed that the single cell performance decreased steeply as the cell temperature increased. The role of silica in the catalyst layer at high temperature operation was studied by varying the silica content in the catalyst layers. There was a gradual decrease in cell performance when the silica content increased in catalyst layer. The single cell performance of membrane electrode assemblies (MEAs) with composite membrane and electrode was higher than that of MEA with commercial Nafion 112 membrane for high temperature operation.     

Polybenzimidazole composite membranes containing imidazole functionalized graphene oxide showing high proton conductivity and improved physicochemical properties

Polymer composite membranes are fabricated using poly[2,2'-(m-phenylene)-5,5′-bibenzimidazole] (PBI) as a polymer matrix and imidazole functionalized graphene oxide (ImGO) as a filler material for high temperature proton exchange membrane fuel cell applications. ImGO is prepared by the reaction of o-phenylenediamine with graphene oxide (GO). The compatibility of ImGO with PBI matrix is found to be better than that of GO, and as a result PBI composite membrane having ImGO exhibits improved physicochemical properties and larger proton conductivity compared with pure PBI and PBI composite membrane having GO. For example, PBI composite membrane having 0.5 wt% of ImGO shows enhanced tensile strength (219.2 MPa) with minimal decrease of elongation at break value (28.8%) compared with PBI composite membrane having 0.5 wt% of GO (215.5 MPa, 15.4%) and pure PBI membrane without any filler (181.0 MPa, 34.8%). The proton conductivity of this membrane, at 150 °C under anhydrous condition, is 77.52 mS cm^?1.     

Effect of the fabrication condition of membrane electrode assemblies with carbon-supported ordered PtCo electrocatalyst on the durability of polymer electrolyte membrane fuel cells

Electrode structure improvement is one of the most promising paths for improving the durability of polymer electrolyte membrane fuel cells (PEMFCs). As strategies to prevent structural deformation and enhance the durability of membrane electrode assemblies (MEAs) with structurally ordered PtCo/C-based cathodes, we evaluated the effect of hot pressing and reinforcing the electrode's structure by increasing the ionomer content. Even though the initial performances of the hot-pressed MEA (HP) and the MEA with extra cathode ionomer (EI) were lower than that of the conventional MEA (CE) by 13.6% and 19.1%, respectively, CE degraded much more significantly than HP and EI after an accelerated degradation test. Therefore, HP and EI could deliver significantly higher single cell performances than CE (22.7% and 43.7%, respectively). The improvements in the durability of HP and EI could be correlated with the structural stability which could be evaluated by structure and electrochemical analysis including electrochemical impedance spectroscopy.     

Increasing the efficiency of a portable PEM fuel cell by altering the cathode channel geometry: A numerical and experimental study

Portable fuel cells are receiving great attention today mainly because their energy density is higher than any portable battery solution. Among other types, portable polymer electrolyte membrane (PEM) fuel cells are an established technology where research on increasing their efficiency is leading product development and manufacturing. The objective of this work was to study and evaluate the redesign of a commercial portable fuel cell, improving its efficiency. A three-dimensional model of the original PEM fuel cell with parallel plus a transversal flow channel design was developed using Comsol Multiphysics, including the effects of liquid water formation and electric current production. Using this model, the effects of different channel geometries and respective cathode flow rates on the cell’s performance, including the local transport characteristics, were studied. Laboratory tests with various fuel cell stacks using the new channels structure were effectuated for an evaluation of the fuel cell’s performance, showing improvements in its efficiency of up to 26.4%.     

Porosity-graded micro-porous layers for polymer electrolyte membrane fuel cells

In this paper, the effect of porosity-graded micro-porous layer (GMPL) on the performance of polymer electrolyte membrane fuel cells (PEMFCs) was studied in detail. The GMPL was prepared by printing micro-porous layers (MPL) with different content of NH₄Cl pore-former and the porosity of the GMPL decreased from the inner layer of the MPLs at the membrane/MPL interface to the outer layer of the MPLs at the gas diffusion electrode/MPL interface. The morphology and porosity of the GMPLs were characterized and the performance of the cell with GMPLs was compared with those having conventional homogeneous MPLs. The result demonstrates that the fuel cells consisting of GMPL have better performance than those consisting of conventional homogeneous MPLs, especially at high current densities. Micro-porous layer with graded porosity is beneficial for the electrode process of fuel cell reaction probably by facilitating the liquid water transportation through large pores and gas diffusion via small pores in the GMPLs.     

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.     

Synthesis and characterization of polyvinyl alcohol copolymer/phosphomolybdic acid-based crosslinked composite polymer electrolyte membranes

Polymer electrolyte membrane fuel cells (PEMFCs) are very promising as future energy source due to their high-energy conversion efficiency and will help to solve the environmental concerns of energy production. Polymer electrolyte membrane (PEM) is recognised as the key element for an efficient PEMFC. Chemically crosslinked composite membranes consisting of a poly(vinyl alcohol-co-vinyl acetate-co-itaconic acid) (PVACO) and phosphomolybdic acid (PMA) have been prepared by solution casting and evaluated as proton conducting polymer electrolytes. The proton conductivity of the membranes is investigated as a function of PMA composition, crosslinking density and temperature. The membranes have also been characterized by FTIR spectroscopy, TGA, AFM and TEM. The proton conductivity of the composite membranes is of the order of 10⁻³ S cm⁻¹ and shows better resistance to methanol permeability than Nafion 117 under similar measurement conditions.     

Potential of hydrolyzed oxymethylene dimethyl ether for the suppression of fuel crossover in polymer electrolyte fuel cells

Fuel crossover is a crucial issue for polymer electrolyte fuel cells (PEFCs) supplied directly with liquid fuels. Therefore, finding a type of fuel with a low fuel crossover rate is required. In this study, we investigated fuel crossover characteristics for oxymethylene dimethyl ether (OME), which has attracted attention for use in engines, and compared it with methanol. Cell performance tests and exhaust gas analyses showed that fully hydrolyzed OME (h-OME), which consisted of methanol and formaldehyde, yields high cell performance at high fuel concentrations, due to the low fuel crossover rate, compared with a direct methanol fuel cell (DMFC). To clarify a factor suppressing fuel crossover, h-OME's effective diffusion coefficient in the membrane was measured. Although an effective diffusion coefficient for fuels like methanol commonly increases with increased fuel's concentration, h-OME's effective diffusion coefficient decreased with increased fuel concentration, leading to a low fuel crossover rate at high h-OME concentrations.     

Modification of hydrocarbon structure for polymer electrolyte membrane fuel cell binder application

The development of novel hydrocarbon polymer membranes needs to be accompanied by catalyst layer hydrocarbon binder research so that the resultant membrane electrode assembly (MEA) can be durable. Hydrocarbon polymers which show high performance levels as membranes, however, are inadequate as catalyst layer binders as they are designed for low fuel penetration. Modification to the hydrocarbon polymer structure of high performing hydrocarbon polymers such as Sulfonated poly(arylene ether sulfone) (SPAES) can take advantage of its high conductivity while increasing gas permeability and maintaining interfacial compatibility with the membrane. The incorporation of a biphenyl fluorene group into the polymer backbone of SPAES successfully increased d-spacing which led to an increase in gas crossover. In the catalyst layer, the modified polymer ionomer showed higher penetration into primary pore volume thus increasing ESA. Higher catalyst utilization due to easier fuel access and ionomer coverage led to higher fuel cell performance. Durability tests revealed that structural modification did not hinder interfacial compatibility as well as performance.