Anhydrous proton-conducting electrolyte membranes based on hyperbranched polymer with phosphonic acid groups for high-temperature fuel cells

The two different molecular weight hyperbranched polymers (HBP(L)-PA-Ac and HBP(H)-PA-Ac) with both phosphonic acid group as a functional group and acryloyl group as a cross-linker at the chain ends were successfully synthesized as a new thermally stable proton-conducting electrolyte. The cross-linked electrolyte membranes (CL-HBP-PA) were prepared by their thermal polymerizations using benzoyl peroxide and their ionic conductivities under dry condition and thermal properties were investigated. The ionic conductivities of the low molecular weight CL-HBP(L)-PA membrane and the high molecular weight CL-HBP(H)-PA membrane were found to be 1.2 × 10⁻⁵ and 2.6 × 10⁻⁶ S cm⁻¹, respectively, at 150 °C under dry condition, and showed the Vogel–Tamman–Fulcher (VTF) type temperature dependence. Both membranes were thermally stable up to 300 °C, and they had suitable thermal stability as electrolyte membranes for the high-temperature fuel cells under dry condition. Fuel cell measurements using a single membrane electrode assembly cell with both cross-linked membranes were successfully performed.     

Sulfonated polyimide hybrid membranes for polymer electrolyte fuel cell applications

Sulfonated Si-MCM-41 (SMCM) with an ion exchange capacity (IEC) of 2.3 mequiv. g⁻¹ was used as a hydrophilic and proton-conductive inorganic component. Sulfonated polyimide (SPI) based on 1,4,5,8-naphthalene tetracarboxylic dianhydride and 2,2′-bis(3-sulfophenoxy) benzidine was used as a host membrane component. The SMCM/SPI hybrid membrane (H1) with 20 wt% loading of SMCM and an IEC of 1.90 mequiv. g⁻¹ showed the high mechanical tensile strength and the slightly higher water vapor sorption than the host SPI membrane (M1) with an IEC of 1.86 mequiv. g⁻¹. H1 and M1 showed anisotropic membrane swelling with about 10 times larger swelling in thickness direction than in plane one. The proton conductivity at 60 °C of H1 was lower in water than that of M1, but comparable at 30% RH. At 90 °C, H1 showed the rather lower performance of polymer electrolyte fuel cell (PEFC) at 82% RH than M1 and fairly better performance at 30% RH. On the other hand, at 110 °C and low humidity less than 50% RH, H1 showed the much better PEFC performance than M1 and Nafion 112. This was due to the promoted back diffusion of produced water by the superior water-holding capacity of SMCM. The SMCM/SPI hybrid membranes have high potential for PEFCs at higher temperatures and lower humidities.     

Proton conducting composite membranes for fuel cell application

Composites were fabricated by blending SPSEBS (Sulfonated Poly Styrene Ethylene Butylene Poly Styrene) with Boron phosphate (BPO₄) for proton conducting applications in fuel cells. The effects of boron phosphate and its relative loading were analyzed in terms of IEC and proton conductivity. Water and methanol uptake of these membranes were also studied.The membranes were characterized by IR spectroscopy. Thermal stability was studied by TGA and DSC analyses. Surface morphology was done by Scanning Electron Microscopy (SEM). The XRD studies indicated the existence of a certain level of crystallinity in the SPSEBS, and the composite membranes. Mechanical strength of the membranes was measured by Universal Testing Machine (UTM). This paper presents the result of recent investigations to develop an optimised in-house membrane electrode assembly (MEA) preparation technique combining catalyst ink spraying and assembly hot pressing. Easy steps were chosen in this preparation technique aiming at simplification and cost reduction.     

Novel hybrid polymer electrolyte membranes prepared by a silane-cross-linking technique for direct methanol fuel cells

To prepare a cross-linked hybrid proton exchange membrane with high mechanical and oxidative stability, a silane monomer, namely 3-glycidoxypropyltrimethoxysilane (KH-560), is first grafted to sulfonated poly(arylene ether ether ketone)s bearing carboxyl groups (SPAEK-C) and hydrolysis-condensation is then performed on the grafted membranes to make them cross-link. ¹H NMR measurements and Fourier transform infrared spectroscopy are used to characterize and confirm the structures of SPAEK-Cs and hybrid polymer electrolyte membranes, respectively. The Si-O-Si cross-linking structure enhances the stability of the PEM greatly. The proton conductivities of the hybrid membranes with 5% KH-560 in weight reach 0.155 S cm⁻¹ at 80 °C which is comparable to that of Nafion^® membranes. The ion-exchange capacity, water uptake and swelling, methanol permeability, mechanical properties are investigated to confirm their applicability in fuel cells.     

Phosphoric acid doped polybenzimidazole based polymer electrolyte membrane and functionalized SBA-15 mesoporous for elevated temperature fuel cell

Polymer electrolyte membrane as heart of a Fuel Cell electrochemical system to improve the durability of Fuel Cell performance at elevated temperatures requires the highest stability of proton conductivity, and thermal and chemical stability in long-term operations. In this research, the effect of SBA-15 mesoporous on the properties of H₃PO₄ doped polybenzimidazole/ionic liquid membranes were investigated for Fuel Cell applications under elevated temperatures. The H₃PO₄ doped polybenzimidazole based membranes were successfully fabricated by using polybenzimidazole (PBI) polymer with the same molecular weight and different amounts of 1,6-di (3-methylimidazolium) hexane dibromide dicationic ionic liquid (Mim₂⁺ Br₂⁻ DIL), pure SBA-15 mesoporous and functionalized SBA-15 mesoporous with polyamidoamine groups (PAMAM mesoporous).The H₃PO₄ doped composite membrane containing 7% w/w Mim₂⁺ Br₂⁻ DIL and 2% w/w PAMAM mesoporous with a superior mechanical strength and high thermal and chemical stability indicate a best electrochemical performance at 180 °C and 0.50 V under anhydrous conditions. The high proton conductivity stability of the composite membranes under elevated temperature and high humidity indicates that the introduction of PAMAM mesoporous with the NH₂, NH and CO groups on the inner wall of its pores significantly improves the ability to retain of Mim₂⁺ Br₂⁻ DIL and H₃PO₄. The results imply that use of PAMAM mesoporous as Mim₂⁺ Br₂⁻ DIL and H₃PO₄ protectors against their leaching from the composite membrane is a new strategy to improve the stability of elevated temperature Fuel Cells performance in long-term operation.     

Novel hybrid polymer electrolyte membranes with high proton conductivity prepared by a silane-crosslinking technique for direct methanol fuel cells

In order to prepare a hybrid proton exchange membrane with low methanol permeability and high proton conductivity, two silane monomers, namely 3-glycidoxypropyl-trimethoxysilane (GPTMS) and 3-mercaptopropyl-trimethoxysilane (MPTMS) are first blended with a sulfonated poly(arylene ether ketone) (SPAEK). Then the blended membrane is heated to induce the grafting of GPTMS onto SPAEK. Finally, a hydrolysis-condensation is performed on the grafted membrane to induce cross-linking. The -SH groups of MPTMS are oxidized to sulfonic acid groups, which are attributed to enhance the proton conductivity of hybrid membranes. Fourier transform infrared spectroscopy is used to characterize and confirm the structures of SPAEK and these cross-linked hybrid membranes. The proton conductivity of a cross-linked hybrid membrane G50M50 reaches up to 0.20 S cm⁻¹ at 80 °C, which is comparable to that of SPAEK and much higher than that of Nafion. Meanwhile, the methanol permeability is nearly three times lower than that of Nafion and two times lower than that of SPAEK. The ion-exchange capacity, water uptake, membrane swelling and thermal stability are also investigated to confirm their applicability in fuel cells.     

A novel electrocatalyst support with proton conductive properties for polymer electrolyte membrane fuel cell applications

The objective of this study is to graft the surface of carbon black, by chemically introducing polymeric chains (Nafion^® like) with proton-conducting properties. This procedure aims for a better interaction of the proton-conducting phase with the metallic catalyst particles, as well as hinders posterior support particle agglomeration. Also loss of active surface can be prevented. The proton conduction between the active electrocatalyst site and the Nafion^® ionomer membrane should be enhanced, thus diminishing the ohmic drop in the polymer electrolyte membrane fuel cell (PEMFC). PtRu nanoparticles were supported on different carbon materials by the impregnation method and direct reduction with ethylene glycol and characterized using amongst others FTIR, XRD and TEM. The screen printing technique was used to produce membrane electrode assemblies (MEA) for single cell tests in H₂/air (PEMFC) and methanol operation (DMFC). In the PEMFC experiments, PtRu supported on grafted carbon shows 550 mW cm⁻² gmetal⁻¹ power density, which represents at least 78% improvement in performance, compared to the power density of commercial PtRu/C ETEK. The DMFC results of the grafted electrocatalyst achieve around 100% improvement. The polarization curves results clearly show that the main cause of the observed effect is the reduction in ohmic drop, caused by the grafted polymer.     

New materials for polymer electrolyte membrane fuel cell current collectors

Polymer Electrolyte Membrane Fuel cells for automotive applications need to have high power density, and be inexpensive and robust to compete effectively with the internal combustion engine. Development of membranes and new electrodes and catalysts have increased power significantly, but further improvements may be achieved by the use of new materials and construction techniques in the manufacture of the bipolar plates. To show this, a variety of materials have been fabricated into flow field plates, both metallic and graphitic, and single fuel cell tests were conducted to determine the performance of each material. Maximum power was obtained with materials which had lowest contact resistance and good electrical conductivity. The performance of the best material was characterised as a function of cell compression and flow field geometry.     

A review of polymer electrolyte membrane fuel cell stack testing

This paper presents an overview of polymer electrolyte membrane fuel cell (PEMFC) stack testing. Stack testing is critical for evaluating and demonstrating the viability and durability required for commercial applications. Single cell performance cannot be employed alone to fully derive the expected performance of PEMFC stacks, due to the non-uniformity in potential, temperature, and reactant and product flow distributions observed in stacks. In this paper, we provide a comprehensive review of the state-of-the art in PEMFC testing. We discuss the main topics of investigation, including single cell vs. stack-level performance, cell voltage uniformity, influence of operating conditions, durability and degradation, dynamic operation, and stack demonstrations. We also present opportunities for future work, including the need to verify the impact of stack size and cell voltage uniformity on performance, determine operating conditions for achieving a balance between electrical efficiency and flooding/dry-out, meet lifetime requirements through endurance testing, and develop a stronger understanding of degradation.     

Numerical modeling of a non-flooding hybrid polymer electrolyte fuel cell

Experimental results were recently reported regarding a novel “non-flooding” hybrid fuel cell consisting of proton exchange membrane (PEM) and anion exchange membrane (AEM) half-cells on opposite sides of a water-filled, porous intermediate layer. Product water formed in the porous layer, where it could permeate to the exterior of the cell, rather than at the electrodes. Although electrode flooding was mitigated, the reported power output was low. To investigate the potential for increased power output, a physicochemical charge transport model of the porous electrolyte layer is reported here. Traditional electrochemical modeling was generalized in a novel way to consider both ion transport and reaction in the aqueous phase and electronic conduction in the graphitic scaffold using a unified Poisson–Nernst–Planck framework. Though the model used no arbitrary or fitting parameters, the ionic resistance calculated for the porous layer agreed well with the highly non-Ohmic experimental values previously reported for the entire fuel cell. Interestingly, electronic charge carriers in the scaffold were found to obviate the need for counterion presence in this unique electrolyte structure. Still, the thickness- and temperature-dependent model results offer limited prospects for improving the power output.     

Preparation, characterization and evaluation of proton-conducting hybrid membranes based on sulfonated hydrogenated styrene-butadiene and polysiloxanes for fuel cell applications

This paper describes the preparation of proton-conducting hybrid membranes (HMs) obtained by a solvent casting procedure using a solution containing sulfonated hydrogenated styrene-butadiene (HSBS-S) and an inorganic-organic mixture (polysiloxanes) previously prepared by a sol-gel route. HSBS-S copolymers with different sulfonation degrees were obtained and characterized by means of elemental analysis (EA), chemical titration and electrochemical impedance spectroscopy (EIS). HSBS-S with the best properties in terms of proton conductivity and solubility for the casting procedure was selected to prepare the HMs. The solvent casting procedure permitted the two phases to be homogeneously distributed while maintaining a relatively high proton conductivity in the membrane. HMs with different blend ratios were characterized using structural (Fourier transform infrared-attenuated total reflectance (FTIR-ATR), dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC)), electrical (EIS), physicochemical (water uptake, ion-exchange capacity) and thermal (TGA-MS) methods. Finally, the optimized HSBS-S membrane and HMs were tested in hydrogen single fuel cells to obtain the polarization and power curves at different cell temperatures and gas pressures. Results indicate that HMs show a considerable improvement in performance compared to the optimized HSBS-S membrane denoting the benefit of incorporating the inorganic-organic network in the hydrogenated styrene-butadiene matrix. A Nafion membrane was used as reference material throughout this work.     

Proton transport of porous triazole-grafted polysulfone membranes for high temperature polymer electrolyte membrane fuel cell

Introduction of porous structure to high temperature polymer electrolyte membranes is one of effective pathways to increase their proton conductivity under elevated temperature. However, the effect of the porous structure on the proton diffusion mechanism of these membranes is still unclear. In this work, the proton transport behaviour of a series of porous triazole-polysulfone (PSf) membranes under elevated temperature is comprehensively investigated. The functional triazole ring in the framework of porous triazole-PSf acts a proton acceptor to form acid-base pair with phosphoric acid (PA). In addition, the proton diffusion coefficient and proton conductivity of PA-doped porous triazole-PSf is an order of magnitude higher than that of the PA-doped dense triazole-PSf membrane. Percolation theory calculation convinces that the high proton conductivity of PA-doped porous triazole-PSf is due to the formation of continuous long-range proton diffusion channels under high pore connectivity and porosity. On the contrary, excessive pore connectivity also results in high gas permeability, leading to decrease of the open circuit voltage and cell performance of the single cell. Consequently, the optimum porosity for the PA-doped porous triazole-PSf membrane is 75% for fuel cell operating with the maximum peak power density of 550 mW·cm^?2 and great durability for 120 h under 140 °C.     

Ultrathin proton-conducting sandwich membrane with low methanol permeability based on perfluorosulfonic acid polymer and phosphosilicate

An ultra-thin, free-standing proton-conductive membrane of Nafion^®/Phosphosilicate/Nafion^® (NPN) with a sandwich structure has been prepared. The NPN membrane of thickness 960 nm shows extremely low methanol permeability of 1 × 10⁻⁸ cm² s⁻¹, and area specific resistance (ASR) smaller than 0.2 Ω cm².     

Numerical modeling of an automotive derivative polymer electrolyte membrane fuel cell cogeneration system with selective membranes

Cogeneration power plants based on fuel cells are a promising technology to produce electric and thermal energy with reduced costs and environmental impact. The most mature fuel cell technology for this kind of applications are polymer electrolyte membrane fuel cells, which require high-purity hydrogen.The most common and least expensive way to produce hydrogen within today's energy infrastructure is steam reforming of natural gas. Such a process produces a syngas rich in hydrogen that has to be purified to be properly used in low temperature fuel cells. However, the hydrogen production and purification processes strongly affect the performance, the cost, and the complexity of the energy system.Purification is usually performed through pressure swing adsorption, which is a semi-batch process that increases the plant complexity and incorporates a substantial efficiency penalty. A promising alternative option for hydrogen purification is the use of selective metal membranes that can be integrated in the reactors of the fuel processing plant. Such a membrane separation may improve the thermo-chemical performance of the energy system, while reducing the power plant complexity, and potentially its cost. Herein, we perform a technical analysis, through thermo-chemical models, to evaluate the integration of Pd-based H₂-selective membranes in different sections of the fuel processing plant: (i) steam reforming reactor, (ii) water gas shift reactor, (iii) at the outlet of the fuel processor as a separator device. The results show that a drastic fuel processing plant simplification is achievable by integrating the Pd-membranes in the water gas shift and reforming reactors. Moreover, the natural gas reforming membrane reactor yields significant efficiency improvements.     

Proton exchange membrane fuel cell of polybenzimidazole electrolyte doped with phosphoric acid and antimony chloride

The proton conductivity of phosphoric acid (PA) doped polybenzimidazole (PBI) membrane is improved through imbibing antimony pentachloride before doping PA. The antimony involvement diminishes the temperature dependence of proton conductivity in the targeted temperature range 160–260 °C. Among the compositions being prepared, the most conductive one exhibits 8.08 × 10⁻² S cm⁻¹ at 180 °C, with a small temperature sensitivity 6.3 × 10⁻⁵ S cm⁻¹ °C⁻¹. Several membrane-electrode assemblies (MEAs) have been prepared with the Pt/C catalyst layers to evaluate the practicality of co-doped PBI membrane. After proper activation, the hydrogen/air cell generates substantial electric power, denoted by its peak value over 500 mW cm⁻² at 180 °C. Impedance analysis indicates carbon monoxide poisoning affects overall MEA kinetics, as evidenced in the rising resistances of electrolyte, cathode, and anode. But the poisoned performance due to 3% CO/H₂ fuel can be rejuvenated after the fuel is switched back to pure hydrogen in one or two hours.     

Comparative studies of polymer electrolyte membrane fuel cell stack and single cell

The polymer electrolyte membrane fuel cell (PEMFC) was investigated comparatively as a single cell and a 30-cell stack. Various types of Nafion membranes, such as Nafion 117, 115, 112 and 105, were tested as electrolyte within the single cell and at different temperatures, among which Nafion 112 gave the optimal result. The 30-cell stack was evaluated at different humidities and temperatures. The potential–current and power–current curves, both for single cell and the stack, were analyzed by computer simulation, whereby the kinetic and mass-transfer parameters were calculated. The long-term performance of the stack and the water production during long-term operation were also measured.     

Fast proton-conducting glass membrane based on porous phosphosilicate and perfluorosulfonic acid polymer

A proton-conducting glass membrane based on porous phosphosilicate and perfluorosulfonic acid polymer was prepared via a modified sol-gel approach. The morphology, pore structure, water uptake property, proton conductivity and fuel cell performance of the membrane were investigated in this work. The hybrid glass membrane showed extremely high proton conductivity of 0.1 S cm⁻¹ in humid atmosphere. In the H₂/O₂ fuel cell measurement, an open circuit potential (OCV) of 0.94 V and a maximum output power density of 42.6 mW cm⁻² was obtained at 25 °C.     

Prediction of local current distribution in polymer electrolyte membrane fuel cell with artificial neural network

In the development process of a fuel cell, understanding the local current distribution is essentially required to achieve better performance and durability. Therefore, many developers apply a segmented fuel cell to observe current distribution under various operating conditions. With the application, experimental data is collected. This study suggests a utilization method for this collected data to develop a local current prediction model. The details of this neural network-based prediction model are introduced, including the pretreatment of the data. In the pretreatment process, current residual values are used for better prediction performance. As a result, the model predicted local current values with a 2.98% error. With the model, the effects of pressure, temperature, cathode relative humidity, and cathode flow rate on local current distribution trends are analyzed. Since the non-uniform current distribution of a fuel cell often leads to low performances or fast local degradation, the optimal operating condition to achieve current uniformity is acquired with an additional model. This model is developed by switching inputs and outputs of the local current prediction model. With the model application, the uniform current distribution is achieved with a standard deviation of 0.039 A/cm² under the current load at 1 Acm^?2.     

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.