Optimization of gas diffusion electrode for polybenzimidazole-based high temperature proton exchange membrane fuel cell: Evaluation of polymer binders in catalyst layer

Gas diffusion electrodes (GDEs) prepared with various polymer binders in their catalyst layers (CLs) were investigated to optimize the performance of phosphoric acid doped polybenzimidazole (PBI)-based high temperature proton exchange membrane fuel cells (HT-PEMFCs). The properties of these binders in the CLs were evaluated by structure characterization, electrochemical analysis, single cell polarization and durability test. The results showed that polytetrafluoroethylene (PTFE) and polyvinylidene difluoride (PVDF) are more attractive as CL binders than conventional PBI or Nafion binder. At ambient pressure and 160 °C, the maximum power density can reach ∼ 0.61 W cm⁻² (PTFE GDE), and the current density at 0.6 V is up to ca. 0.52 A cm⁻² (PVDF GDE), with H₂/air and a platinum loading of 0.5 mg cm⁻² on these electrodes. Also, both GDEs showed good stability for fuel cell operation in a short term durability test.     

High performance proton exchange membrane fuel cell electrode assemblies

The conventional 5-layer membrane electrode assembly (MEA) consists of a proton exchange membrane (PEM) locating at its center, two layers of Pt-C-40 (Pt content 40 wt%) locating next on both surfaces of PEM, and two gas diffusion layers (GDL) locating next on the outer surfaces of Pt-C layers (structure-a MEA). In this paper, we report three modified MEAs consisting of Pt-C-40 (Pt content 40 wt%) and Pt-C-80 (Pt content 80 wt%) catalysts. These are: (1) 7-layer structure-b MEA with a thin Pt-C-80 layer locating between Pt-C-40 layer and PEM; (2) 7-layer structure-c MEA with a thin Pt-C-80 layer locating between Pt-C-40 layer and GDL; and (3) 5-layer structure-d MEA with Pt-C-40 and Pt-C-80 mixing homogeneously and locating between PEM and GDL. Under a fixed Pt loading, we find structure-b, -c, and -d MEAs with 20-40 wt% Pt contributed from Pt-C-80 have better fuel cell performance than structure-a MEA consisting only of Pt-C-40. The reasons for the better fuel cell performance of these modified MEAs are attributed to the better feasibility for O₂ gas to reach cathode Pt particles and lower proton transport resistance in catalyst layers of the modified MEAs than structure-a MEA.     

A facile method of asymmetric ether-containing polybenzimidazole membrane for high temperature proton exchange membrane fuel cell

A facile method has been suggested for the preparation of poly [2,2′-(p-oxydiphenylene)-5,5′-benzimidazole] (OPBI) membrane that comprises of dense and porous layers for high temperature proton exchange membrane fuel cells (HT-PEMFCs). The porosity as well as the asymmetry of the membrane is formed by the use of component solvent at steadily increasing temperatures. This approach needs not to use any porogen, whereas the resultant asymmetric OPBI membrane indicates an improved phosphoric acid (PA) doping level together with mechanical strength. For instance, the PA doping level of the asymmetric OPBI membrane is almost twice as much as that of the homogenous dense OPBI membrane. The conductivity of asymmetric OPBI arrived at 0.072 S cm^?1 at 180 °C. The membrane electrode assembly (MEA) based on the asymmetric OPBI demonstrated an exceptional fuel cell functionality with a peak power density of 393 mW cm^?2 at 160 °C under anhydrous conditions.     

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.     

Investigation of membrane electrode assembly (MEA) hot-pressing parameters for proton exchange membrane fuel cell

The hot-pressing conditions for fabricating the membrane electrode assembly (MEA) of a proton exchange membrane fuel cell (PEMFC) was investigated by using a 2ⁿ full factorial design. Time, temperature and pressure were key parameters that were varied from 500 to 1500 psi, 1 to 5 min and 100 to 160 °C, respectively. The results from the full factorial analysis indicated that the order of significance of the main MEA fabricating effects was temperature, pressure, time–temperature interaction and pressure–time–temperature interaction. By examining the cell performance curves, the lower fabrication conditions of temperature and pressure were suitable for MEA preparation. The conductive layer between the membrane and the catalyst layer became thin at high pressure and high temperature, as seen from scanning electron microscopy (SEM) images. In the ranges of condition studied, the most suitable hot-pressing condition for MEA fabrication was at 100 °C, 1000 psi and 2 min. This condition provided the highest maximum power density from the MEA and the best contact at the interfaces between the gas diffusion layer, the active layer and the electrolyte membrane. The experimental results were verified by testing with a commercial MEA in the same operating condition and with the same equipment. The performance of the fabricated MEA was better than that of the commercial one.     

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%.     

A review of high-temperature proton exchange membrane fuel cell (HT-PEMFC) system

This paper provides information encompassing the recent discovery of the High Temperature Proton Exchange Membrane Fuel Cell (HT-PEMFC) focusing on systems requirement. To have a reliable power production and higher durability level, a proper system must be applied in both normal and especially in transient operations. To date many issues of HT-PEMFC especially in durability and performance still unsolved. This article is written to provide clear information about the research undergo and must be the focus in order to produce an efficient performance. Information about the advantages towards Low Temperature Proton Exchange Membrane Fuel Cell (LT-PEMFC), the main components, and the mode of operation also discussed. In-depth research needs to be conducted into the innovative design and development of HT-PEMFC components and its system since these are the key factors for optimum performance.     

Membrane electrode assemblies doped with H3PO4 for high temperature proton exchange membrane fuel cells

H₃PO₄ content plays a critical role in high temperature proton exchange membrane fuel cells (HT-PEMFC), as it is responsible for the majority of the conductivity of the key components under high temperature operation. The conductivities of commercial AB-PBI membranes doped by immersing in 85 wt.% H₃PO₄ for different times and temperatures are investigated. The effect of H₃PO₄ loading in electrodes, including the AB-PBI polymer and a Pt/C catalyst, is also studied. The as-prepared electrodes and membranes are combined to fabricate a membrane electrode assembly for HT-PEMFCs. The results reveal that AB-PBI membranes doped with 85 wt.% H₃PO₄ at 90 °C for 9 h display a maximum conductivity of 33 mS cm⁻¹. This membrane was selected and combined with electrodes including 15 wt.% AB-PBI and 0.75 mg cm⁻² Pt with different H₃PO₄ loadings. A maximum current density of 260 mA cm⁻² was achieved in the as-prepared MEA (with 5 mg cm⁻² H₃PO₄ in electrodes) operating at 0.6 V and 160 °C, using oxygen and hydrogen.     

The effect of materials on proton exchange membrane fuel cell electrode performance

This paper describes the optimisation in the fabrication materials and techniques used in proton exchange membrane fuel cell (PEMFC) electrodes. The effect on the performance of membrane electrode assemblies (MEAs) from the solvents used in producing catalyst inks is reported. Comparison in MEA performances between various gas diffusion layers (GDLs) and the importance of microporous layers (MPLs) in gas diffusion electrodes (GDEs) are also shown. It was found that the best performances were achieved for GDEs using tetrahydrofuran (THF) as the solvent in the catalyst ink formulation and Sigracet 10BC as the GDL. The results also showed that our in-house painted GDEs were comparable to commercial ones (using Johnson Matthey HiSpec™ and E-TEK catalysts).     

Influence of operating temperature on cell performance and endurance of high temperature proton exchange membrane fuel cells

The relation between high temperature proton exchange membrane fuel cell (HT-PEMFC) operation temperature and cell durability was investigated in terms of the deterioration mechanism. Long-term durability tests were conducted at operational temperatures of 150, 170, and 190 °C for a HT-PEMFC with phosphoric acid-doped polybenzimidazole electrolyte membranes. Higher cell temperatures were found to result in a higher cell voltage, but decrease cell life. The reduction in cell voltage of approximately 20 mV during the long-term tests was considered to be caused both by aggregation of the electrode catalyst particles in the early stage of power generation, in addition to the effects of crossover due to the depletion of phosphoric acid in the terminal stage, which occurs regardless of cell temperature. It is expected that enhanced long-term durability for practical applications can be achieved through effective management of phosphoric acid transfer.     

Preparation and properties of high performance nanocomposite proton exchange membrane for fuel cell

Various spatially enlarged organoclays were prepared by using poly(oxyproplene)-backboned quaternary ammonium salts of various molecular weights M_w 230, 400 and 2000 as the intercalating agents for Na⁺-montmorillonite. The modified MMT was utilized to improve the compatibility with Nafion^®. Sufficient interaction of the modified MMT with Nafion^® was studied by using X-ray diffraction (XRD) and X-ray photoelectron spectra (XPS). The performance of the Nafion^®/m-MMT composite membranes for direct methanol fuel cell (DMFCs) was evaluated in terms of water uptake, ion exchange capacity (IEC), methanol permeability, proton conductivity, and cell performance. The methanol permeability of the composite membrane decreased with the increasing of m-MMT content. The proton conductivity of the membrane was lowered slightly from that of pristine Nafion^® membrane. These results led to an essential improvement in the single-cell performance of DMFCs.     

Polybenzimidazole containing ether units as electrolyte for high temperature proton exchange membrane fuel cells

A rapid method to synthesize poly[2,2′-(p-oxydiphenylene)-5,5′-benzimidazole] (OPBI) through a solution polycondensation under microwave irradiation is explored. Synthesis parameters affecting the molecular weight (M_w) of OPBI, including the mass ratio of solvent to P₂O₅, the monomer concentration, and reaction time, are optimized. The main characteristics of OPBI are studied, and the corresponding membrane is prepared through a solvent casting process. A series of sulfuric acid doped OPBI (H₂SO₄/OPBI) hybrid membranes with different acid doping levels (ADLs) are developed. The effects of H₂SO₄ on microstructure, ADL and electrochemical properties of these membranes are explored. Herein, the hybrid membrane shows high proton conductivity (190 mS cm⁻¹) at elevated temperature (160 °C) and anhydrous conditions, high ADL (18.73 mol of H₂SO₄ for OPBI per repeat unit, i.e., ADL = 18.73 mol PRU⁻¹) and excellent dimensional stability (40.3%). All these properties demonstrated that H₂SO₄/OPBI hybrid membrane can be used as an alternative membrane for high temperature proton exchange membrane fuel cells (HT-PEMFCs).     

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.     

Study on the membrane electrode assembly fabrication with carbon supported cobalt triethylenetetramine as cathode catalyst for proton exchange membrane fuel cell

An improved fabrication technique for conventional hot-pressed membrane electrode assemblies (MEAs) with carbon supported cobalt triethylenetetramine (CoTETA/C) as the cathode catalyst is investigated. The V-I results of PEM single cell tests show that addition of glycol to the cathode catalyst ink leads to significantly higher electrochemical performance and power density than the single cell prepared by the traditional method. SEM analysis shows that the MEAs prepared by the conventional hot-pressed method have cracks between the cathode catalyst layer and Nafion membrane, and the contact problem between cathode catalyst layer and Nafion membrane is greatly suppressed by addition of glycol to the cathode catalyst ink. Current density-voltage curve and impedance studies illuminate that the MEAs prepared by adding glycol to the cathode catalyst ink have a higher electrochemical surface area, lower cell ohmic resistance, and lower charge transfer resistance. The effects of CoTETA/C loading, Nafion content, and Pt loading are also studied. By optimizing the preparation parameters of the MEA, the as-fabricated cell with a Pt loading of 0.15 mg cm⁻² delivers a maximum power density of 181.1 mW cm⁻², and a power density of 126.2 mW cm⁻² at a voltage of 0.4 V.     

Characterizing membrane electrode assemblies for high temperature polymer electrolyte membrane fuel cells using design of experiments

A comparative study of four different high temperature polymer electrolyte membrane fuel cell (HT-PEFC) polybenzimidazole (PBI) based membrane electrode assemblies (MEAs) is undertaken utilizing the design of experiments (DOE) method, a very valuable statistical optimization method, much underutilized in fuel cell research. Single cell voltages are examined as a response (target variable) at two levels (high and low) of four factors (controlled variables); anode and cathode stoichiometry, operating temperature and current density. This yields a two-level, four factor (2⁴) full factorial DOE. The data is used to form a linear regression model for each MEA, which is in turn utilized to predict the cell voltage at random values within the selected ranges of the four factors for validation. The main effects and two factor interactions of each factor are compared to determine their effect on the cell voltage and the underlying physics is examined to determine the best performing MEAs. The PBI based MEA has a much higher tolerance to carbon monoxide (CO) in the fuel stream in comparison with Nafion based MEAs due to the different proton conducting mechanism as well as a higher operating temperature, thus enabling reliable operation of HT-PEFC stacks with reformate containing upto 3% CO.     

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.     

New process for high temperature polybenzimidazole membrane production and its impact on the membrane and the membrane electrode assembly

Water addition is a key step in the new process developed at BASF Fuel Cell Inc. (BFC) for polybenzimidazole (PBI) membrane production. The added water prevents further polymerization and controls the solution viscosity for easier membrane casting. For large-scale PBI membrane production, a certain amount of tension is necessary during membrane upwinding. The applied tension could affect the polymer orientation and result in anisotropic membrane mechanical properties and proton conductivity. The membrane prepared with tension shows higher elastic modulus and proton conductivity in machine direction, which might suggest some degree of polymer chain orientation. However, the membrane electrode assembly (MEA) performance is not affected by the membrane's apparent anisotropic character. However, we observed performance variation as a function of MEA break-in condition, which might be explained by the formation of a phosphate anion concentration gradient during MEA operation.     

Thin film thermocouples for in situ membrane electrode assembly temperature measurements in a polybenzimidazole-based high temperature proton exchange membrane unit cell

This paper presents Type-T thin film thermocouples (TFTCs) fabricated on Kapton (polyimide) substrate for measuring the internal temperature of PBI (polybenzimidazole)-based high temperature proton exchange membrane fuel cell (HT-PEMFC). Magnetron sputtering technique was employed to deposit a 2 μm thick layer of TFTCs on 75 μm thick Kapton foil. The Kapton foil was treated with in situ argon plasma etching to improve the adhesion between TFTCs and the Kapton substrate. The TFTCs were covered with a 7 μm liquid Kapton layer using spin coating technique to protect them from environmental degradation. This Kapton foil with deposited TFTCs was used as sealing inside a PBI (polybenzimidazole)-based single cell test rig, which enabled measurements of in situ temperature variations of the working fuel cell MEA. The performance of the TFTCs was promising with minimal interference to the operation of the fuel cell.     

Novel epoxy-based cross-linked polybenzimidazole for high temperature proton exchange membrane fuel cells

An approach has been proposed to prepare the reinforced phosphoric acid (PA) doped cross-linked polybenzimidazole membranes for high temperature proton exchange membrane fuel cells (HT-PEMFCs), using 1,3-bis(2,3-epoxypropoxy)-2,2-dimethylpropane (NGDE) as the cross-linker. FT-IR measurement and solubility test showed the successful completion of the crosslinking reaction. The resulting cross-linked membranes exhibited improved mechanical strength, making it possible to obtain higher phosphoric acid doping levels and therefore relatively high proton conductivity. Moreover, the oxidative stability of the cross-linked membranes was significantly enhanced. For instance, in Fenton’s reagent (3% H₂O₂ solution, 4 ppm Fe²⁺, 70 °C), the cross-linked PBI-NGDE-20% membrane did not break into pieces and kept its shape for more than 480 h and its remaining weight percent was approximately 65%. In addition, the thermal stability was sufficient enough within the operation temperature of PBI-based fuel cells. The cross-linked PBI-NGDE-X% (X is the weight percent of epoxy resin in the cross-linked membranes) membranes displayed relatively high proton conductivity under anhydrous conditions. For instance, PBI-NGDE-5% membrane with acid uptake of 193% exhibited a proton conductivity of 0.017 S cm⁻¹ at 200 °C. All the results indicated that it may be a suitable candidate for applications in HT-PEMFCs.