Membrane electrode assemblies for high-temperature polymer electrolyte fuel cells based on poly(2,5-benzimidazole) membranes with phosphoric acid impregnation via the catalyst layers

A novel strategy for introducing phosphoric acid as the electrolyte into high-temperature polymer electrolyte fuel cells by using acid impregnated catalyst layers instead of pre-doped membranes is presented in this paper. This experimental approach is used for the development of membrane electrode assemblies based on poly(2,5-benzimidazole) (ABPBI) as the membrane polymer. The acid uptake of free-standing ABPBI used for this work amounts to ABPBI × 3.1 H₃PO₄ which has a specific conductivity of ∼80 mS cm⁻¹ at 140 °C. Rather thick catalyst layers (20% Pt/C, 1 mg Pt cm⁻², 40% PTFE as binder, d = 100-150 μm) are prepared on gas diffusion layers with a dense hydrophobic microlayer. After impregnation of the catalyst layers with phosphoric acid and assembling them with a mechanically robust undoped ABPBI membrane a fast redistribution of the electrolyte occurs during cell start-up. Power densities of about 250 mW cm⁻² are achieved at 160 °C and ambient pressure with hydrogen and air as reactants. Details of membrane properties, preparation and optimization of gas diffusion electrodes and fuel cell characterization are discussed. We consider our novel approach to be especially suitable for an easy and reproducible fabrication of MEAs with large active areas.     

Highly fluorinated comb-shaped copolymer as proton exchange membranes (PEMs): Fuel cell performance

The fuel cell performance (DMFC and H₂/air) of highly fluorinated comb-shaped copolymer is reported. The initial performance of membrane electrode assemblies (MEAs) fabricated from comb-shaped copolymer containing a side-chain weight fraction of 22% are compared with those derived from Nafion and sulfonated polysulfone (BPSH-35) under DMFC conditions. The low water uptake of comb copolymer enabled an increase in proton exchange site concentrations in the hydrated polymer, which is a desirable membrane property for DMFC application. The comb-shaped copolymer architecture induces phase separated morphology between the hydrophobic fluoroaromatic backbone and the polysulfonic acid side chains. The initial performance of the MEAs using BPSH-35 and Comb 22 copolymer were comparable and higher than that of the Nafion MEA at all methanol concentrations. For example, the power density of the MEA using Comb 22 copolymer at 350 mA cm⁻² and 0.5 M methanol was 145 mW cm⁻², whereas the power densities of MEAs using BPSH-35 were 136 mW cm⁻². The power density of the MEA using Comb 22 copolymer at 350 mA cm⁻² and 2.0 M methanol was 144.5 mW cm⁻², whereas the power densities of MEAs using BPSH-35 were 143 mW cm⁻².     

A fuel cell operating between room temperature and 250 °C based on a new phosphoric acid based composite electrolyte

A phosphoric acid based composite material with core-shell microstructure has been developed to be used as a new electrolyte for fuel cells. A fuel cell based on this electrolyte can operate at room temperature indicating leaching of H₃PO₄ with liquid water is insignificant at room temperature. This will help to improve the thermal cyclability of phosphoric acid based electrolyte to make it easier for practical use. The conductivity of this H₃PO₄-based electrolyte is stable at 250 °C with addition of the hydrophilic inorganic compound BPO₄ forming a core-shell microstructure which makes it possible to run a PAFC at a temperature above 200 °C. The core-shell microstructure retains after the fuel cell measurements. A power density of 350 mW/cm² for a H₂/O₂ fuel cell has been achieved at 200 °C. The increase in operating temperature does not have significant benefit to the performance of a H₂/O₂ fuel cell. For the first time, a composite electrolyte material for phosphoric acid fuel cells which can operate in a wide range of temperature has been evaluated but certainly further investigation is required.     

A poly(R1R2R3)–N/H3PO4 composite membrane for phosphoric acid polymer electrolyte membrane fuel cells

A poly(R₁R₂R₃)–N⁺/H₃PO₄ composite membrane has been developed for use in a polymer electrolyte fuel cell (PEMFC). The quaternized polysulfone (QNPSU) membrane doped with H₃PO₄ showed high proton conductivity (0.12 S cm⁻¹) at 160 °C and gave good performance in a single fuel cell tests. The peak power density with the QNPSU/H₃PO₄ composite membrane (at 150 °C, with dry H₂/O₂) was greater than 0.7 W cm⁻². The effect of the phosphoric acid doping level on fuel cell performances with the QNPSU membrane was investigated. The data show that the QNPSU/H₃PO₄ composite membrane is promising for higher temperature PEMFC applications. The study demonstrated that the poly(R₁R₂R₃)–N⁺/H₃PO₄ composite system produced an effective method to connect phosphoric acid to a non-conducting polymer structure, to produce a promising membrane for phosphoric acid polymer electrolyte membrane fuel cells.     

The stability of MEA in SPE water electrolysis for hydrogen production

Membrane electrode assemblies (MEAs) for water electrolysis were prepared by decal transferring an Ir black anode and a Pt black cathode on the two sides of a perfluorosulfonate solid polymer electrolyte (SPE) Nafion112 membrane. Performance stability of an MEA with 4 cm² effective electrode area was tested for 208 h in a single cell water electrolysis setup. The catalysts of both electrodes on the MEAs were characterized by means of XPS and XRD. Samples of feed water were analyzed by using conductivity meter, inductance coupling plasma optical emission spectroscopy (ICP-OES), ionic chromatography and total organic carbon (TOC) analyzer. Surface oxidation of the anodic Ir catalyst was evidenced, from the original metal Ir to 71.5% Ir₂O₃ and 28.5% IrO₂ after 208 h of electrolysis. While the metallic state of Pt on the cathode did not change during the same period of operation, the crystallite size of the Pt catalyst increased from 9.1 nm to 9.8 nm. Water analysis shows there is significant accumulation of impurities in the feed water, which can contaminate the MEA. Fortunately, the MEA restored more than 98% of its original performance after a simple treatment with 1 mol/L H₂SO₄ solution. This indicates the short period performance decline of the MEA is mainly caused by a recoverable contamination.     

Kinetic characterization of a Pt–Ni/C catalyst with a phosphoric acid doped PBI membrane in a proton exchange membrane fuel cell

The performance of a phosphoric acid doped polybenzimidazole (PBI) membrane, with Pt and Pt–Ni/C catalysts on the anode and cathode, respectively, was experimentally determined at 160 °C using neat H₂ and O₂. The resulting current voltage relation was then compared to a performance curve calculated from previously established values for the exchange current density and activation energy of the oxygen reduction reaction (ORR) on Pt–Ni/C. An overall voltage loss >200 mV, regardless of current density, was observed for the MEA relative to the predicted performance, implying about two orders of magnitude decrease in the exchange current density for the ORR. The reduction in exchange current density was attributed to anion (H₂PO₄⁻) adsorption.     

A study on fabrication of sulfonated poly(ether ether ketone)-based membrane-electrode assemblies for polymer electrolyte membrane fuel cells

The porosity effect of catalyst electrodes in membrane-electrode assemblies (MEAs) using a hydrocarbon-based polymer as electrolyte and ionomer was investigated on physical and electrochemical properties by varying the content of ionomer binder (dry condition) in the catalyst electrodes. The MEAs were compared with the Nafion^®-based MEA using Nafion^® 112 and 5 wt.% ionomer solution (EW = 1100) in terms of porosity values, scanning electron microscopic images, Nyquist plots, dielectric spectra and I–V polarization curves. In this study, sulfonated poly(ether ether ketone) (SPEEK) membranes with 25 ± 5 μm of thickness and 5 wt.% ionomer solutions have been prepared. The prepared membranes were characterized in terms of FT-IR, DSC and proton conductivity. Proton conductivity of the SPEEK membranes was compared with one of the Nafion^® membranes with relative humidity. The porosity of the catalyst electrodes was calculated using the properties of catalyst, ionomer solution and solvent. As a result, the performance of the new type polymer (i.e., SPEEK in this study)-based MEA with the similar membrane conductivity and porosity of the catalyst electrode in the Nafion^® MEA was similar to that of the Nafion^® MEA.     

Quantitative analysis of oxygen-containing species adsorbed on the Pt surface of a polymer electrolyte fuel cell membrane electrode assembly electrode using stripping voltammetry

The quantity of oxygen-containing species adsorbed on Pt surface of a single-cell polymer electrolyte fuel cell membrane electrode assembly (PEFC MEA) in the gas-phase system was measured by stripping voltammetry (SV), of which the adsorbed amount is considered in terms of the quantity of electric charge required for stripping. The effect of different experimental parameters on the adsorption quantity was analyzed and an optimum condition for applying SV to a PEFC MEA electrode was then suggested. The electric charge required for stripping was observed to be linearly proportional to the potential and arose from 0.7 V vs. RHE. The adsorption amount of oxygen-containing species for the PEFC MEA at a cell temperature of 60 °C was 384 μC cm⁻²-Pt at a potential of 1.0 V vs. RHE. More importantly, considering the effect of O₂ partial pressure on the adsorption in the gas-phase PEFC MEAs, water is suggested to be the main source of the oxygen in adsorbed oxygen-containing species. The present method is well applicable to quantitative studies of the oxygen-containing species adsorbed on electrodes of PEFC MEAs.     

Performance enhancement of membrane electrode assemblies with plasma etched polymer electrolyte membrane in PEM fuel cell

In this work, a surface modified Nafion 212 membrane was fabricated by plasma etching in order to enhance the performance of a membrane electrode assembly (MEA) in a polymer electrolyte membrane fuel cell. Single-cell performance of MEA at 0.7 V was increased by about 19% with membrane that was etched for 10 min compared to that with untreated Nafion 212 membrane. The MEA with membrane etched for 20 min exhibited a current density of 1700 mA cm⁻² at 0.35 V, which was 8% higher than that of MEA with untreated membrane (1580 mA cm⁻²). The performances of MEAs containing etched membranes were affected by complex factors such as the thickness and surface morphology of the membrane related to etching time. The structural changes and electrochemical properties of the MEAs with etched membranes were characterized by field emission scanning electron microscopy, Fourier transform-infrared spectrometry, electrochemical impedance spectroscopy, and cyclic voltammetry.     

Evaluation of assemblies based on carbon materials modified with dendrimers containing platinum nanoparticles for PEM-fuel cells

Polyamidoamine (PAMAM) dendrimer-encapsulated Pt nanoparticles (G4OHPt) are synthesized by chemical reduction and characterized by transmission electronic microscopy. An H₂–O₂ fuel cell has been constructed with porous carbon electrodes modified with the dendrimer nanocomposites. Electrochemical and physical impregnation methods of electrocatalyst immobilization are compared. The modified surfaces are used as electrodes and gas-diffusion layers in the construction of three different membrane-electrode assemblies (MEAs). The MEAs have been tested in a single polymer-electrolyte membrane-fuel cell at 30 °C and 20 psig. The fuel cell is, then characterized by electrochemical impedance spectroscopy and cyclic voltammetry, and its performance evaluated in terms of polarization curves and power profiles. The highest fuel cell performance is reached in the MEA constructed by physical impregnation method. The results are compared with a 32 cm² prototype cell using commercial electrocatalyst operated at 80 °C, obtaining encouraging results.     

Effects of hot pressing conditions on the performances of MEAs for direct methanol fuel cells

The effects of hot pressing conditions (hot pressing temperature, pressure and time) on the performances of membrane electrode assemblies for direct methanol fuel cells were investigated. The performances of membrane electrode assemblies (MEAs) were characterized by the polarization curves and electrochemical impedance spectra (EIS). The surface morphologies of the electrodes were observed by scanning electron microscopy (SEM). The compression ratios of electrodes were determined by testing the thicknesses of the anodes and the cathodes before and after the hot pressing process. The MEA which was hot pressed at 135 °C under 80 kg cm⁻² for 90 s, showed the highest power density of 46.0 mW cm⁻² at 80 °C and ambient pressure. As the hot pressing temperature, pressure and time increased, the compression ratios of the anodes and cathodes increased, and the activating time required for MEA to reach optimum performance increased, too. The cell resistances of the MEAs hot pressed at higher hot pressing temperature (135 °C) and pressure (120 kg cm⁻²), or for longer time (90 s), decreased because of the good contact between the membrane and electrodes. The MEAs that were hot pressed under higher temperature (135 °C) and higher pressure (120 kg cm⁻²) benefited for long-time cell operating.     

Study of the influence of Nafion/C composition on electrochemical performance of PEM single cells with ultra-low platinum load

The electrochemical performance of membrane electrode assemblies (MEAs) with ultra-low platinum load (0.02 mg_Pt cm^?2) and different compositions of Nafion/C in the catalytic layer have been investigated. The electrodes were fabricated depositing the catalytic ink, prepared with commercial catalyst (HiSPEC 2000), onto the gas diffusion layers by wet powder spraying. The MEAs were electrochemically tested using current-voltage curves and electrochemical impedance spectroscopy measurements. The experiments were carried out at 70 °C in H₂/O₂ and H₂/air as reactant gases at 1 and 2 bar pressure and 100% of relative humidity. For all MEAs tested, power density increases when the gasses pressure is increased from 1 to 2 bar. On the other hand, power density also increased when oxygen is used instead of air as oxidant gas in cathode. The lower power density (34 mW cm^?2) and power per Pt loading (0.86 kW g_Pt^?1) corresponds to the MEA prepared without Nafion in anode and cathode catalytic layers working with hydrogen and air at 1 bar pressure as reactants gas. The MEA with 30% wt Nafion/C reached the highest power density (422 mW cm^?2) and power per Pt loading (10.60 kW g_Pt^?1) using hydrogen and oxygen at 2 bar pressure. Finally, electrode surface microstructure and cross sections of MEAs were analyzed by Scanning Electron Microscopy (SEM). Examination of the electrodes, revealed that the most uniform ionomer network surface corresponds to the electrode with 40 wt% Nafion/C, and MEA ionomer-free catalytic layer shows delamination, it leads to low electrochemical performance.     

Feasibility of ultra-low Pt loading electrodes for high temperature proton exchange membrane fuel cells based in phosphoric acid-doped membrane

Factors as the Pt/C ratio of the catalyst, the binder content of the electrode and the catalyst deposition method were studied within the scope of ultra-low Pt loading electrodes for high temperature proton exchange membrane fuel cells (HT-PEMFCs). The Pt/C ratio of the catalyst allowed to tune the thickness of the catalytic layer and so to minimize the detrimental effect of the phosphoric acid flooding. A membrane electrode assembly (MEA) with 0.05 mg_Ptcm⁻² at anode and 0.1 mg_Ptcm⁻² at cathode (0.150 mg_Ptcm⁻² in total) attained a peak power density of 346 mW cm⁻². It was proven that including a binder in the catalytic layer of ultra-low Pt loading electrodes lowers its performance. Electrospraying-based MEAs with ultra-low Pt loaded electrodes (0.1 mg_Ptcm⁻²) rendered the best (peak power density of 400 mW cm⁻²) compared to conventional methods (spraying or ultrasonic spraying) but with the penalty of a low catalyst deposition rate.     

Studies of performance degradation of a high temperature PEMFC based on H3PO4-doped PBI

In this paper, a 600 h life test of a high temperature PEMFC based on phosphoric acid (H₃PO₄)-doped polybenzimidazole (PBI) (H₃PO₄/PBI HT-PEMFC) at a current density of 714 mA cm⁻² (the beginning 510 h continuous test) and 300 mA cm⁻² (the last 90 h intermittent test) was carried out. After the life test, degradation of the MEA occurred. The H₂ crossover rate through the PBI membrane and the open circuit voltage (OCV) of the cell were tested with time. The results showed that, at the beginning of 510 h continuous test, the PBI membrane did not show much physical degradation, but during the last 90 h test there was a remarkable physical degradation which resulted in a higher H₂ crossover. The catalysts, PBI membranes and the membrane electrode assemblies (MEAs) before and after the life test were comprehensively examined by transmission electron microscopy (TEM), scanning electron microscopy (SEM) and energy-dispersive spectroscopy (EDS). TEM results showed that the particle size of the Pt/C catalysts in the anode and cathode increased from 3.72 to 7.40 and 8.39 nm, respectively. SEM images of MEA in cross-section revealed that the PBI membrane became thin after the life test. EDS analysis implied the leaching of H₃PO₄ from the PBI membrane had occurred. Therefore, we conclude that physical degradation of PBI membrane, agglomeration of the electrocatalysts (both anode and cathode) and the leaching of H₃PO₄ from the PBI membrane were responsible for the performance degradation of the H₃PO₄/PBI HT-PEMFC.     

Performance of an ultra-low platinum loading membrane electrode assembly prepared by a novel catalyst-sprayed membrane technique

Membrane electrode assemblies (MEAs) with ultra-low platinum loadings are attracting significant attention as one method of reducing the quantity of precious metal in polymer electrolyte membrane fuel cells (PEMFCs) and thereby decreasing their cost, one of the key obstacles to the commercialization of PEMFCs. In the present work, high-performance MEAs with ultra-low platinum loadings are developed using a novel catalyst-sprayed membrane technique. The platinum loadings of the anode and cathode are lowered to 0.04 and 0.12 mg cm⁻², respectively, but still yield a high performance of 0.7 A cm⁻² at 0.7 V. The influence of Nafion content, cell temperature, and back pressures of the reactant gases are investigated. The optimal Nafion content in the catalyst layer is ca. 25 wt.%. This is significantly lower than for low platinum loading MEAs prepared by other methods, indicating ample interfacial contact between the catalyst layer and membrane in our prepared MEAs. Scanning electron microscopy (SEM) and electrochemical impedance spectroscopy (EIS) measurements reveal that our prepared MEA has very thin anode and cathode catalyst layers that come in close contact with the membrane, resulting in a MEA with low resistance and reduced mass transport limitations.     

Enhancement of the fuel cell performance of a high temperature proton exchange membrane fuel cell running with titanium composite polybenzimidazole-based membranes

The fuel cell performance of a composite PBI-based membrane with TiO₂ has been studied. The behaviour of the membrane has been evaluated by comparison with the fuel cell performance of other PBI-based membranes, all of which were cast from the same polymer with the same molecular weight. The PBI composite membrane incorporating TiO₂ showed the best performance and reached 1000 mW cm⁻² at 175 °C. Moreover, this new titanium composite PBI-based membrane also showed the best stability during the preliminary long-term test under our operation conditions. Thus, the slope of the increase in the ohmic resistance of the composite membrane was 0.041 mΩ cm² h⁻¹ and this is five times lower than that of the standard PBI membrane. The increased stability was due to the high phosphoric acid retention capacity - as confirmed during leaching tests, in which the Ti-based composite PBI membrane retained 5 mol of H₃PO₄/PBI r.u. whereas the PBI standard membrane only retained 1 mol H₃PO₄/PBI r.u. Taking into account the results obtained in this study, the TiO₂-PBI based membranes are good candidates as electrolytes for high temperature PEMFCs.     

A novel self-humidifying membrane electrode assembly with water transfer region for proton exchange membrane fuel cells

A novel self-humidifying membrane electrode assembly (MEA) with the active electrode region surrounded by a unactive “water transfer region (WTR)” was proposed to achieve effective water management and high performance for proton exchange membrane fuel cells (PEMFCs). By this configuration, excess water in the cathode was transferred to anode through Nafion membrane to humidify hydrogen. Polarization curves and power curves of conventional and the self-humidifying MEAs were compared. The self-humidifying MEA showed power density of 85 mW cm⁻² at 0.5 V, which is two times higher than that of a conventional MEA with cathode open. The effects of anode hydrogen flow rates on the performance of the self-humidifying MEA were investigated and its best performance was obtained at a flow rate of 40 ml min⁻¹. Its performance was the best when the environmental temperature was 40 °C. The performance of the self-humidifying MEA was slightly affected by environmental humidity. The area of WTR was optimized, and feasible area ratio of the self-humidifying MEA was 28%.     

Novel aryloxy-polybenzimidazoles as proton conducting membranes for high temperature PEMFCs

Polybenzimidazole (PBI) is the material of choice to fabricate proton exchange membranes for high temperature PEMFCs. Among the most recent trends in the design of PBI polymers, we recall the introduction of oxygen atoms in the polymer backbone. In fact, the presence of ether groups improves the polymer solubility in polar solvents and, consequently, the membrane and MEA processability. In addition, it provides reactive points for functionalization processes and further chemical modifications. Here we reported on the synthesis and characterization of new arylether-based PBIs, and namely Poly 1,4-bis-(4-(1H,1′H-2,5′-bibenzo[d]imidazol-2′-yl)phenoxy)benzene and Poly 2′,2″-(4,4′-oxybis(4,1-phenylene))bis(1H,1′H-2,5′-bibenzo[d]imidazole), labelled in the following as PBI-108 and PBI-109, respectively. The polymers differ for the number of the ether-based spacers, which are one in case of PBI-108, and two for PBI-109. The H₃PO₄-doped membranes were characterised in terms of thermal and chemical stability, proton conductivity and fuel cell performances. In particular, the MEAs properties were investigated with respect to the acid doping level of the electrodes, temperature, pressure and gas flow rates.The monomer structure does not remarkably affect the electrochemical properties of the membranes. However, the PBI-109 membrane is chemically more stable in presence of oxy- and hydroxyl-free radicals with respect to PBI-108 and oxygen-free PBI systems. Proton conductivity of 8 mS cm⁻¹ was measured at 120 °C and RH = 50% in the case of aryloxy-PBI with the shorter spacer. The power density increases with temperature, pressure and air stoichiometry. Values as high as to 400 mW cm⁻¹ were measured at 150 °C, λ_air = 6 and a backpressure of 2 bar.     

Membrane electrode assembly with doped polyaniline interlayer for proton exchange membrane fuel cells under low relative humidity conditions

A membrane electrode assembly (MEA) was designed by incorporating an interlayer between the catalyst layer and the gas diffusion layer (GDL) to improve the low relative humidity (RH) performance of proton exchange membrane fuel cells (PEMFCs). On the top of the micro-porous layer of the GDL, a thin layer of doped polyaniline (PANI) was deposited to retain moisture content in order to maintain the electrolyte moist, especially when the fuel cell is working at lower RH conditions, which is typical for automotive applications. The surface morphology and wetting angle characteristics of the GDLs coated with doped PANI samples were examined using FESEM and Goniometer, respectively. The surface modified GDLs fabricated into MEAs were evaluated in single cell PEMFC between 50 and 100% RH conditions using H₂ and O₂ as reactants at ambient pressure. It was observed that the MEA with camphor sulfonic acid doped PANI interlayer showed an excellent fuel cell performance at all RH conditions including that at 50% at 80 °C using H₂ and O_2.     

Nanoimprinted electrodes for micro-fuel cell applications

Nanoimprint lithography (NIL) was used to fabricate electrodes with high specific Pt surface areas for use in micro-fuel cell devices. The Pt catalyst structures were characterized electrochemically using cyclic voltammetry and were found to have electrochemical active surface areas (EAS) ranging from 0.8 to 1.5 m² g⁻¹ Pt. These NIL catalyst structures were tested in fuel cell membrane electrode assemblies (MEA) by directly embossing a Nafion 117 membrane. The features of the mold were successfully transferred to the Nafion and a 7.5 nm thin film of Pt was deposited at a wide angle to form the anode catalyst layer. The resulting MEA yielded a very high Pt utilization of 15,375 mW mg⁻¹ Pt compared to conventionally prepared MEAs (820 mW mg⁻¹ Pt). Embossing pattern transfer was also demonstrated for spin casted Nafion films which could be used for new applications.