Numerical study for in-plane gradient effects of cathode gas diffusion layer on PEMFC under low humidity condition

A numerical study about in-plane porosity and contact angle gradient effects of cathode gas diffusion layer (GDL) on polymer electrolyte membrane fuel cell (PEMFC) under low humidity condition below 50% relative humidity is performed in this work. Firstly, a numerical model for a fuel cell is developed, which considers mass transfer, electrochemical reaction, and water saturation in cathode GDL. For water saturation in cathode GDL, porosity and contact angle of GDL are also considered in developing the model. Secondly, current density distribution in PEMFC with uniform cathode GDL is scrutinized to design the gradient cathode GDL. Finally, current density distributions in PEMFC with gradient cathode GDL and uniform cathode GDL are compared. At the gas inlet side, the current density is higher in GDL with a gradient than GDL with high porosity and large contact angle. At the outlet side, the current density is higher in GDL with a gradient than GDL with low porosity and small contact angle. As a result, gradient cathode GDL increases the maximum power by 9% than GDL with low porosity and small contact angle. Moreover, gradient cathode GDL uniformizes the current density distribution by 4% than GDL with high porosity and large contact angle.     

Oxygen starvation analysis during air feeding faults in PEMFC

A new analysis of performance degradation during oxygen starvation of PEMFC (Proton Exchange Membrane Fuel Cell) is proposed in this paper. Oxygen starvation happens for several reasons like compressor delay, fault during peak power demand or water management issues. The consequences on fuel cell performance degradation are not still well understood. This paper proposes a complete study with experimental tests and modeling. Impacts on performance were investigated under oxygen starvation and effects on the local conditions in the MEA (Membrane Electrode Assembly) were measured and modeled. In particular, current density measurements during oxygen starvation have been made with a specific bi-cell stack. Voltage oscillations were also found. Durability test have been realized on a PEMFC stack. Samples from the degraded MEA were analyzed by TEM (Transmission Electron Microscopy). Degradation mechanisms are proposed and the local conditions during oxygen starvation are identified.     

Inhomogeneous compression of PEMFC gas diffusion layer: Part II. Modeling the effect

The effect of inhomogeneous compression of GDL on the mass and charge transfer in PEMFC is studied. The model utilizes experimentally evaluated GDL parameters as a function of thickness. The modeling results are compared with a conventional model that excludes the effects. As a result, it is shown that the inhomogeneous compression has a significant effect on the current density distribution because of the varying contact resistance between GDL and electrode. This also implies that there are possible hot spots occurring inside the electrode, and thus inhomogeneous compression can have significant effects on the lifetime and local performance of the cell. According to the achieved results, the inhomogeneous compression of GDL cannot be neglected.     

Studies of sulfonated polyphenylene membranes containing benzophenone moiety for PEMFC

The sulfonated polyphenylenes containing benzophenone structure (sulfonated Parmax 1200, S-Parmax) were prepared by sulfonation reaction of Parmax 1200 with 30% fuming sulfuric acid, and degree of sulfonation was controlled by sulfonation reaction time. These polymers have all carbon structure without ether linkages that have the possibility of attack by nucleophiles (made by PEMFC operating system). The polyphenylene structure of Parmax provides a stiff and resistant backbone, whereas the pendant benzoyl group enables the solubility of the material, and also provides sites for chemical modifications. The structure properties of the synthesized polymers were investigated by ¹H NMR spectroscopy. The membranes were studied by ion exchange capacity (IEC), water uptake, and proton conductivity. These membranes deterioration test was performed by Fenton reagent, and compared with normal sulfonated poly(ether sulfone)s and Nafion. The power densities of membranes were performed by single cell.     

A 3D model for the free-breathing direct methanol fuel cell: Methanol crossover aspects and validations with current distribution measurements

A three-dimensional model has been developed for the free-breathing direct methanol fuel cell (DMFC) assuming steady-state isothermal and single-phase conditions. Especially the MeOH crossover phenomenon is investigated and the model validations are done using previous cathodic current distribution measurements. A free convection of air is modelled in the cathode channels and diffusion and convection of liquid (anode) and gaseous species (cathode) in the porous transport layers. The MeOH flow in the membrane is described with diffusion and protonic drag. The parameter ψ$\psi$ in the model describes the MeOH oxidation rate at the cathode and it is fitted according to the measured current distributions. The model describes the behaviour of the free-breathing DMFC, when different operating parameters such as cell temperature, MeOH concentration and flow rate are varied in a wide range. The model also predicts the existence of the experimentally observed electrolytic domains, i.e. local regions of negative current densities. Altogether, the developed model is in reasonable agreement with both the measured current distributions and polarization curves. The spatial information gained of mass transfer phenomena inside the DMFC is valuable for the optimization of the DMFC operating parameters.     

Synthesis and characterization of sulfonated polyphenylene containing DCTPE for PEMFC potential application

The synthesis of conjugated polyphenylenes containing tetraphenylethylene (PPTPE) moiety, their functionalization with sulfonic acid groups, and the measurement of apposite parameters for PEMs are described. The polymers were prepared by Ni-catalyzed carbon–carbon coupling reaction of dichlorotetraphenylethylene and 2,5-dichlorobenzophenone. These polymers have all carbon–carbon linkages without any ether linkage on polymer backbone, which were not attacked by nucleophiles (H₂O, hydrogen peroxide, hydroxide anion and radical), and the twisted structure provided good solubility in aprotic polar solvent. The sulfonic acid groups were introduced by sulfonation reaction with concentrated sulfuric acid. All these membranes were prepared from dimethylacetamide (DMAc) polymer solution. The membranes were studied by ion exchange capacity (IEC), water uptake, proton conductivity, and single cell performance. The chemical degradation test of the prepared membrane was performed by Fenton reagent, and compared with normal sulfonated poly(ether sulfone)s & Nafion.     

Modification of carbon aerogel supports for PEMFC catalysts

Nitrogen enriched carbon aerogels and Co-based non-noble metal catalysts supported on carbon aerogels have been synthesized and tested using XPS, HRTEM, XRD and RDE techniques. XPS spectra of unmodified carbon aerogels indicated a presence of two oxygen O(1s) groups and five carbon C(1s) groups in deconvoluted spectra. XPS spectra of chemically modified samples indicated nitrogen N(1s) introduced in the carbon aerogel structure by acidic (HNO₃) or basic (NH₄OH) chemical treatment.Synthesis of aerogel supported Co catalysts performed by using Co-methoxy-tetra-phenylporfirin as a macrocyclic compound incorporated into the aerogel structure, and sintered at 700 and 900 °C in N₂, revealed the presence of Co-metal nano-particles with 20 nm diameter. HRTEM and diffraction patterns show a β-Co FCC structure with many {111}<110> micro-twins in the Co nano-particles. The electrochemical properties of the synthesized catalysts in O₂-free and O₂-saturated sulfuric and perchloric acid solutions, evaluated by a rotating disc electrode (RDE) technique, demonstrated catalytic activity in hydrogen oxidation and oxygen reduction reactions.     

Sulfonated poly(ether sulfone) electrolytes structured with mesonaphthobifluorene graphene moiety for PEMFC

Sulfonated poly(ether sulfone)s containing a mixture of cis and trans mesonaphthobifluorene moiety were synthesized, and their properties were characterized. The mesonaphthobifluorene graphene moiety contained 6 phenyl rings and was conjugated together to form planar sheets of sp²-bonded carbon. Poly(arylene ether sulfone)s containing a mixture of cis and trans tetraphenyl ethylene units were synthesized by polycondensation, and converted into graphene by intramolecular Friedel–Craft cyclization with Lewis acid (FeCl₃). The sulfonation was taken selectively on mesonaphthobifluorene units with concentrated sulfuric acid. The structural properties of the sulfonated polymers were investigated by ¹H NMR spectroscopy. The membranes were studied with regard to ion exchange capacity (IEC), water uptake, and proton conductivity.     

Microscale simulations of reaction and mass transport in cathode catalyst layer of polymer electrolyte fuel cell

The resistance of the cathode oxygen reduction reaction in polymer electrolyte fuel cells must be reduced for improving the performance. Therefore, it is important to thoroughly understand the relationship between the heterogeneous structures and the cell performance. However, it is difficult to obtain such an understanding using experimental approaches and typical uniform porous simulations. In this study, numerical analysis was used to simulate a three-dimensional catalyst layer (CL) with carbon black (CB) aggregate structures and ionomer coating models, and a cathode reaction and mass transport simulation model incorporating the heterogeneous structure was developed. Moreover, the relationship between the electrode structure and the cell performance, including the reaction distribution and output performance, was examined. The current density distribution depended on the CB structure and ionomer adhesion shape. From the viewpoint of enhancing both the Pt utilization and the mass transport performance, an adequate heterogeneous pore structure in the CL is necessary. These results were used to determine the optimal material properties for the high performance cell.     

Current distribution measurements with a free-breathing direct methanol fuel cell using PVDF-g-PSSA and Nafion 117 membranes

The methanol crossover and other mass transfer phenomena have been investigated in a free-breathing direct methanol fuel cell (DMFC). The current distribution profile along the MeOH flow channel was measured and information of local concentrations of the reacting species was obtained. The DMFC with a segmented cathode was found to be very useful for a detailed analysis of the interrelated parameters, which cause the local variations of the cell current. The connections between different operating parameters were clarified in detail for two different membranes. The measurements were done for both an experimental poly(vinylidene fluoride)-graft-poly(styrene sulfonic acid) (PVDF-g-PSSA) membrane and the commercial Nafion^® 117 membrane, which have different methanol permeabilities. The MeOH concentration and the flow rate were varied in a wide range in order to determine their optimum values. The deviations from an even current density distribution were observed to increase as a function of MeOH concentration and decrease as a function of temperature. The power production of a free-breathing DMFC was observed to be proportional to the local oxygen concentration at the cathode side and inadequate air convection together with the MeOH crossover phenomenon was observed to decrease the cell performance locally.     

Determination of the pore size distribution of micro porous layer in PEMFC using pore forming agents under various drying conditions

In this paper, the effect of the pore size distribution of a micro-porous layer (MPL) on the performance of polymer electrolyte membrane fuel cells (PEMFC) was investigated using self-made gas diffusion layers (GDLs) with different MPLs for which the pore size distribution was modified using pore forming agents under different drying conditions. When MPL dried at high temperature, more macro pores, approximately 1,000–20,000 nm in diameter, and less micro pores, below 100 nm, were observed relative to when MPL was dried at low temperature. Self-made GDLs were characterized by a field-emission scanning electron microscope (FE-SEM), mercury porosimetry and self-made gas permeability measurement equipment. The performance of the single cells was measured under two different humidification conditions. The results demonstrate that the optimum pore size distribution of MPL depended on the cell operating humidification condition. The MPL dried at high temperature performed better than the MPL dried at low temperature under a low humidification condition; however, MPL dried at low temperature performed better under a high humidification condition.     

Behavior of current distribution evolution under reactant starvation conditions based on a single polymer electrolyte membrane fuel cell (PEMFC) with triple-serpentine flow field: An experimental study

Reactant starvation is unfavorable to the durability and life extension of PEMFC engines. In this paper, a 25 cm² segmented PEMFC is assembled to investigate starvation phenomenon, and the contour maps of current distribution are given to analyze the reactant starvation mechanism.The experimental results prove the high-quality homogeneity of current with triple-serpentine configuration even under starvation conditions. The air starvation experiments suggest the migration of lowest current region and the variation trend of standard deviation with the increasing of stoichiometry. The survival time increases with the anode stoichiometry, and the current density of anode downstream constantly increases with the reversal of cell, reflecting severe hydrogen starvation in these local areas.It is concluded ORR dominates the specific current distribution rather than any other electrochemical reactions. This study sheds the light of improving the lifespan and potential large-scale commercialization realization of PEMFC engines.     

Operating characteristics of 40 W-class PEMFC stacks using reformed gas under low humidifying conditions

The small PEMFC stack to be integrated with miniaturized fuel reformer is usually operated under very poor operating conditions such as low relative humidity and reformed gas conditions including trace amounts of CO. Hence, for the stable operation of the stack under such real conditions, the effect of reactants feeding method and stack operating conditions such as stack temperature and gas humidity were experimentally investigated and the optimal operating strategy was suggested.     

Experimental study on non-uniform arrangement of 3D printed structure for cathodic flow channel in PEMFC

Enhancing mass transfer capability of flow channel is important subject to improve fuel cell performance. In this study, an experimental study about non-uniform arrangement of metallic structures in cathodic flow channel on polymer electrolyte membrane fuel cell is conducted. Metallic 3D printer is used to manufacture 3D mesh with complex geometry. Channel width and bottom-rear channel depth are selected to change the geometry of structure. Assuming that accelerating flow velocity and reinforcing flow direction to gas diffusion layer can improve fuel cell performance, eight basic arrangements are inserted into cathodic carbon bipolar plate to measure fuel cell performance. With I–V curve, the unit cells with non-uniform arrangements of width and tapered structure show performance enhancement of 12.8% in maximum power density, compared with conventional parallel flow channel. According to electrochemical impedance spectroscopy results, performance enhancement by non-uniform arrangement is mainly occur in high current density operation due to low mass transfer resistance.     

Preparation and characterization of grafted propane sulfonic acid polyphenylene membrane via superacid-catalyzed reaction

A series of polyphenylene-based polyelectrolytes were synthesized from 2,2'-biphenol, and isatin by superacid catalyzed polyhydroxyalkylation reactions. Grafted sulfonated polyphenylenes were synthesized via K₂CO₃ catalyzed condensation reaction with 3-bromopropane sulfonic acid potassium salt. These polymers have all carbon–carbon linkages without any ether linkage on polymer backbone, which were not attacked by nucleophiles (H₂O, hydrogen peroxide, hydroxide anion and radical). Particularly, chemical modification to flexible sulfoalkyl groups implanted to a biphenol unit afforded better stability due to less reactive towards nucleophilic substitution reaction, and good proton mobility because of well phase separation. The structural properties of the synthesized polymers were investigated by ¹H NMR spectroscopy. The membranes were studied by ion exchange capacity (IEC), water uptake, dimensional stability as well as proton conductivity assessment. The chemical degradation test was performed by Fenton's reagent, and compared with the usual sulfonated poly(ether sulfone)s and Nafion.     

Chelating agent assisted heat treatment of carbon supported cobalt oxide nanoparticle for use as cathode catalyst of polymer electrolyte membrane fuel cell (PEMFC)

Cobalt-based catalysts for the oxygen reduction reaction (ORR) in polymer electrolyte membrane fuel cell (PEMFC) have been successfully incorporated cobalt oxide (Co₃O₄) onto Vulcan XC-72 carbon powder by thermal decomposition of Co-ethylenediamine complex (ethylenediamine, NH₂CH₂CH₂NH₂, denoted en) at 850 °C. The catalysts were prepared by adsorbing the cobalt complexes [Co(en)(H₂O)₄]³⁺, [Co(en)₂(H₂O)₂]³⁺ and [Co(en)₃]³⁺ on commercial XC-72 carbon black supports, loading amount of Co with respect to carbon black was about 2%, the resulting materials have been pyrolyzed under nitrogen atmosphere to create CoO_x/C catalysts, donated as E1, E2, and E3, respectively. The composite materials were characterized using X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM) and X-ray photoelectron spectroscopy (XPS). Chemical compositions of prepared catalysts were determined using inductively-coupled plasma-atomic emission spectroscopy (ICP-AES). The catalytic activities for ORR have been analyzed by cyclic voltammetry (CV) and linear sweep voltammetry (LSV). The electrocatalytic activity for oxygen reduction of E2 is superior to that of E1 and E3. Membrane electrode assemblies (MEAs) containing the synthesized CoO_x/C cathode catalysts were fabricated and evaluated by single cell tests. The E2 cathode performed better than that of E1 and E3 cathode. This can be attributed to the enhanced activity for ORR, in agreement with the composition of the catalyst that CoO co-existed with Co₃O₄. The maximum power density 73 mW cm⁻² was obtained at 0.3 V with a current density of 240 mA cm⁻² for E2 and the normalized power density of E2 is larger than that that of commercial 20 wt.% Pt/C-ETEK.     

Efficient fault diagnosis method of PEMFC thermal management system for various current densities

The temperature of a fuel cell has a considerable impact on the saturation of a membrane, electrochemical reaction speed, and durability. So thermal management is considered one of the critical issues in polymer electrolyte membrane fuel cells. Therefore, the reliability of the thermal management system is also crucial for the performance and durability of a fuel cell system. In this work, a methodology for component-level fault diagnosis of polymer electrolyte membrane fuel cell thermal management system for various current densities is proposed. Specifically, this study suggests fault diagnosis using limited data, based on an experimental approach. Normal and five component-level fault states are diagnosed with a support vector machine model using temperature, pressure, and fan control signal data. The effects of training data at different operating current densities on fault diagnosis are analyzed. The effects of data preprocessing method are investigated, and the cause of misdiagnosis is analyzed. On this basis, diagnosis results show that the proposed methodology can realize efficient component-level fault diagnosis using limited data. The diagnosis accuracy is over 92% when the residual basis scaling method is used, and data at the highest operating current density is used to train the support vector machine.     

Effects of basic gas diffusion layer components on PEMFC performance with capillary pressure gradient

The gas diffusion layer (GDL) is composed of a substrate and a micro-porous layer (MPL), and is treated with polytetrafluoroethylene (PTFE) to promote water discharge. Additionally, the MPL mainly consists of carbon black and PTFE. In other words, the optimal design of these elements has a dominant effect on the polymer electrolyte membrane fuel cell (PEMFC) performance. For the GDL, it is crucial to prevent water flooding, and the water flux within the GDL is strongly affected by the capillary pressure gradient. In this study, the PEMFC performance was systematically investigated by varying the substrate PTFE content, MPL PTFE content, and MPL carbon loading per unit area. The effects of each experimental variable on the PEMFC performance and especially on the capillary pressure gradient were quantitatively analyzed when the GDLs were manufactured by the doctor blade manufacturing method. The experimental results indicated that as the PTFE content of the anode and cathode GDL increased, the PEMFC performance deteriorated due to the deformation of the porosity and tortuosity of the GDL. Additionally, the PEMFC performance improved as the MPL PTFE content of the cathode GDL increased at low relative humidity (RH), but the PEMFC performance tendency was reversed at high RH. Further, the MPL carbon loading of 2 mg/${\text{cm}}^2$ demonstrated the best performance, and the advantages and disadvantages of the MPL carbon loading were identified. In addition, the effects of each experimental variable on liquid water, water vapor, and gas permeability were investigated.     

Numerical study on PEMFC’s geometrical parameters under different humidifying conditions

Steady-state and three-dimensional simulations were carried out to study the influences of geometrical parameters on the performance of PEMFC under different hydrating conditions. Flow fields, species transport, transport of water in polymer membrane and movement of liquid water in cathode and anode porous layers were determined, in order to accomplish a complete estimation of ohmic and concentration losses of PEMFC power. The geometrical parameters were thickness of the polymer membrane, cathode catalyst layer as well as gas channel to rib width ratio. Every simulation was made under different relative humidities of inlet flows (50 and 100%) for every change of characteristic length. Results show that the influence of the geometrical parameters on ohmic and concentration losses is of considerable importance. The performance of PEMFC is seriously affected under dehydrating conditions. However, such performance may be considerably improved by using suitable geometrical parameters. Cathode and anode liquid saturation may not only affect the transport of species, but also the polymer electrolyte water content. These results show the importance of simultaneously calculating both the water absorption and desorption through the polymer electrolyte and the liquid saturation in the cathode and anode porous mediums to obtain an actual view of ohmic and concentration losses of the PEMFC performance.