Preparation of brush-like crystals of poly[2,6-(1,4-phenylene)-benzobisimidazole]

Poly[2,6-(1,4-phenylene)-benzobisimidazole] (PPBI) crystals were prepared by using reaction-induced crystallization of oligomers during solution polymerization of 1,2,4,5-tetraaminobenzene and diphenyl terephthalate. Polymerizations were carried out at a monomer concentration of 4.3 × 10⁻² mol L⁻¹ at 350 °C for 6 h. Brush-like PPBI crystals were obtained in a mixture of structural isomers of dibenzyltoluene, in which many needle-like crystals came out vertically from the surface of the ribbon-like crystals. Average width and thickness of the ribbon-like crystals were 0.75 μm and 0.11 μm, respectively. And average length and diameter of the needle-like crystals were 0.36 μm and 50 nm, respectively. The brush-like crystals possessed high crystallinity and exhibited good thermal resistance. The ribbon-like crystals were formed by the crystallization of imidazole oligomers at an initial stage of polymerization, and then the needle-like crystals grew from the surface of the ribbon-like crystals. Polymerization occurred on the crystals when the oligomers were crystallized, leading to the high molecular weight PPBI crystals.     

Water and phosphoric acid uptake of poly [2,5-benzimidazole] (ABPBI) membranes prepared by low and high temperature casting

Phosphoric acid-doped membranes based in poly[2,5-benzimidazole] (ABPBI) were obtained by a new low temperature casting procedure and by the classical high temperature casting from methanesulfonic acid. These membranes, which can be suitable for application in direct methanol proton exchange membrane (PEM) fuel cells, were studied in relation with their phosphoric acid doping level by measuring the free and bonded acid. The water isotherms were also determined for the low and high temperature casted ABPBI membranes. Both, acid and water sorption properties, were compared with those determined in poly [2-2′-(m-fenylene)-5-5′ bibenzimidazole] (PBI) membranes. The water sorption of the ABPBI membranes over the range of all water activity is described by the modified BET equation, commonly known as Guggenheim–Anderson–de Boer (GAB) and a two-parameters empirical isotherm. The acid uptake behaviour of the membranes prepared by low and high temperature casting are related with differences in their supramolecular structure.     

Organic/inorganic composite membranes based on polybenzimidazole and nano-SiO2

Organic/inorganic composite membranes based on polybenzimidazole (PBI) and nano-SiO₂ were prepared in this work. However, the preparation of PBI/SiO₂ composite membrane is not easy since PBI is insoluble in water, while nano-SiO₂ is hydrophilic due to the hydrophilicity of nano-SiO₂ and water-insolubility of PBI. Thus, a solvent-exchange method was employed to prepare the composite membrane. The morphology of the composite membranes was studied by scanning electron microscopy (SEM). It was revealed that inorganic particles were dispersed homogenously in the PBI matrix. The thermal stability of the composite membrane is higher than that of pure PBI, both for doped and undoped membranes. PBI/SiO₂ composite membranes with up to 15 wt% SiO₂ exhibited improved mechanical properties compared with PBI membranes. The proton conductivity of the composite membranes containing phosphoric acid was studied. The nano-SiO₂ in the composite membranes enhanced the ability to trap phosphoric acid, which improved the proton conductivity of the composite membranes. The membrane with 15 wt% of inorganic material is oxidatively stable and has a proton conductivity of 3.9 × 10⁻³ S/cm at 180 °C.     

A Three‐Dimensional Non‐isothermal Model of High Temperature Proton Exchange Membrane Fuel Cells with Phosphoric Acid Doped Polybenzimidazole Membranes

High temperature proton exchange membrane fuel cells (HT‐PEMFCs) with phosphoric acid doped polybenzimidazole (PBI) membranes have gained tremendous attentions due to its attractive advantages over conventional PEMFCs such as faster electrochemical kinetics, simpler water management, higher carbon monoxide (CO) tolerance and easier cell cooling and waste heat recovery. In this study, a three‐dimensional non‐isothermal model is developed for HT‐PEMFCs with phosphoric acid doped PBI membranes. A good agreement is obtained by comparing the numerical results with the published experimental data. Numerical simulations have been carried out to investigate the effects of operating temperature, phosphoric acid doping level of the PBI membrane, inlet relative humidity (RH), stoichiometry ratios of the feed gases, operating pressure and air/oxygen on the cell performance. Numerical results indicate that increasing both the operating temperature and phosphoric acid doping level are favourable for improving the cell performance. Humidifying the feed gases at room temperature has negligible improvement on the cell performance, and further humidification is needed for a meaningful performance enhancement. Pressurising the cell and using oxygen instead of air all have significant improvements on the cell performance, and increasing the stoichiometry ratios only helps prevent the concentration loss at high current densities.     

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.     

Coupled mechanical stress and multi-dimensional CFD analysis for high temperature proton exchange membrane fuel cells (HT-PEMFCs)

We use a combined finite element method (FEM)/computational fluid dynamics (CFD) methodology to numerically investigate the effects of gas diffusion layer (GDL) compression/intrusion on the performance of a phosphoric acid-doped polybenzimidazole (PBI) membrane-based high temperature proton exchange membrane fuel cell (HT-PEMFC). Three-dimensional (3-D) FEM simulations are conducted under various displacement clamping conditions to analyze cell deformation characteristics. Then, a multi-dimensional HT-PEMFC CFD model is applied to the deformed cell geometries to study transport and electrochemical processes during HT-PEMFC operations. Our numerical simulation results reveal that the maximum stresses in the deformed GDLs always occur near the edge of the ribs. The combined effects of GDL compression/intrusion considerably increase spatial non-uniformity in the species and current density distributions, and reduce cell performance.     

Preparation and operation of gas diffusion electrodes for high-temperature proton exchange membrane fuel cells

Gas diffusion electrodes for high-temperature PEMFC based on acid-doped polybenzimidazole membranes were prepared by a tape-casting method. The overall porosity of the electrodes was tailored in a range from 38% to 59% by introducing porogens into the supporting and/or catalyst layers. The investigated porogens include volatile ammonium oxalate, carbonate and acetate and acid-soluble zinc oxide, among which are ammonium oxalate and ZnO more effective in improving the overall electrode porosity. Effects of the electrode porosity on the fuel cell performance were investigated in terms of the cathodic limiting current density and minimum air stoichiometry, anodic limiting current and hydrogen utilization, as well as operations under different pressures and temperatures.     

A Non‐isothermal Model of a Laboratory Intermediate Temperature Fuel Cell Using PBI Doped Phosphoric Acid Membranes

A two‐dimensional non‐isothermal model developed for a single intermediate temperature fuel cell with a phosphoric acid (PA) doped PBI membrane is developed. The model of the experimental cell incorporates the external heaters, and the body of the fuel cell. The catalyst layers were treated as spherical catalyst particles agglomerates with porous inter‐agglomerate space. The inter‐agglomerate space is filled with a mixture of electrolyte (hot PA) and PTFE. All the major transport phenomena are taken into account except the crossover of species through the membrane. This model was used to study the influence of two different geometries (along the channel direction and cross the channel direction) on performance. It became clear, through the performance analyses, that the predictions obtained by along the channel geometry did not represent the general performance trend, and therefore this geometry is not appropriate for fuel cell simulations. Results also indicate that the catalyst layer was not efficiently used, which leads to large temperature differences through the MEA.     

Preparation and Characterisation of Proton Exchange Membranes Based on Crosslinked Polybenzimidazole and Phosphoric Acid

Crosslinked polybenzimidazole (PBI) was synthesised via free radical polymerisation between N‐vinylimidazole and vinylbenzyl substituted PBI. The degree of crosslinking increases with increasing content of the crosslinker. The phosphoric acid doping behaviour, mechanical properties, proton conductivity and acid migration stability of crosslinked PBI and linear PBI are discussed. The results show that the acid doping ability decreases with increasing degree of crosslinking of PBI. The introduction of N‐vinylimidazole in PBI is beneficial to its oxidation stability. The mechanical stability of crosslinked PBI/H₃PO₄ membrane is better than that of linear PBI/H₃PO₄ membrane. The proton conductivity of the acid doped membranes can reach ∼10^–4 S cm^–1 for crosslinked PBI/H₃PO₄ composite membranes at 150 °C. The temperature dependence of proton conductivity of the acid doped membranes can be modelled by an Arrhenius relation. The proton conductivity of crosslinked PBI/H₃PO₄ composite membranes is a little lower than that of linear PBI/H₃PO₄ membranes with the same acid content. However, the migration stability of H₃PO₄ in crosslinked PBI/H₃PO₄ membranes is improved compared with that of linear PBI/H₃PO₄ membranes.     

A “proton pump” concept for the investigation of proton transport and anode kinetics in proton exchange membrane fuel cells

A novel concept for the measurement of proton transport properties and electrode kinetics in proton exchange membrane fuel cells (PEMFC) is presented. The “proton pump” is essentially a fuel cell operated with pure nitrogen or very low hydrogen partial pressure instead of oxygen-containing gas on the cathode side, avoiding the complicated electrode kinetics of oxygen reduction. In this first study using this concept, we investigated the proton transport in high temperature PEMFC based on polybenzimidazole (PBI)/phosphoric acid membranes. The impedance spectra of the proton pump allow the clear distinction between anode and cathode kinetics and proton transport in the membrane. Identifying and analyzing the contribution of the anodic processes in the impedance spectra enabled the quantitative investigation of anode kinetics based on the Butler-Volmer equation. The proton transport was investigated in more detail in the current saturation region, where proton transport turned out to be the limiting process in case of sufficient H₂ supply at the anode. The maximum proton transport capacity of the PBI/phosphoric acid membrane was found to be comparable to those of Nafion^® membranes.