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.     

Tungsten oxide nanowires grown on carbon paper as Pt electrocatalyst support for high performance proton exchange membrane fuel cells

Tungsten oxide nanowires (W₁₈O₄₉ NWs) were directly grown on carbon paper by chemical vapor deposition. Well-dispersed Pt nanoparticles, with a size distribution from 2 to 4 nm, were deposited on the surface of W₁₈O₄₉ NWs through a simple reductive process. The resulting Pt/W₁₈O₄₉ NW/carbon paper composites formed a three-dimensional electrode structure. In comparison to conventional Pt/C electrocatalyst, the Pt/W₁₈O₄₉ NW/carbon paper composite exhibited higher electrocatalytic activity toward the oxygen reduction reaction and better CO tolerance in a single cell polymer electrolyte membrane fuel cell.     

Preparation and characterization of sulfonated polysulfone/titanium dioxide composite membranes for proton exchange membrane fuel cells

In the present study, sulfonated polysulfone (sPS)/titanium dioxide (TiO₂) composite membranes for use in proton exchange membrane fuel cells (PEMFCs) were investigated. Polysulfone (PS) was sulfonated with trimethylsilyl chlorosulfonate in 1,2 dichloroethane at ambient temperatures. It was shown that the degree of sulfonation is increased with the molar ratio of the sulfonating agent to PS repeat unit. The degree of sulfonation was determined by elemental analysis and ¹H NMR was performed to verify the sulfonation reaction on the PS. Sulfonation levels from 15 to 40% were easily achieved by varying the content of the sulfonating agent. Composite membranes were prepared by blending TiO₂ with sPS solution in DMAC (5 wt.%) by the solution casting procedure. The membranes have been characterized by thermal analysis, water uptake, proton conductivity measurements and single cell performance. The addition of TiO₂ increased the thermal stability but high filler concentrations decreased the miscibility of the composite component, and resulted in brittle membranes. The conductivity values in the range of 10⁻³–10⁻² S/cm were obtained for composite membranes. The conductivities of the membranes show similar increasing trend as a function of operating temperature. The membranes were tested in a single cell operating at 60–85 °C in humidified H₂/O₂. Single fuel cell tests performed at different operating temperatures indicated that sPS/TiO₂ composite membrane is more hydrodynamically stable and also performed better than sPS membranes. The highest performance of 300 mA/cm² was obtained for sPS/TiO₂ membrane at 0.6 V for an H₂–O₂/PEMFC working at 1 atm and 85 °C. The results show that sPS/TiO₂ is a promising membrane material for possible use in proton exchange membrane fuel cells.     

Performance and stability of Pd-Pt-Ni nanoalloy electrocatalysts in proton exchange membrane fuel cells

Pd-Pt-Ni nanoalloy catalysts have been synthesized by a polyol reduction method and characterized for the oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs). The performance of the membrane-electrode assembly (MEA) fabricated with the Pd-Pt-Ni catalysts is found to increase continuously in the entire current density range with the operation time in the PEMFC until it becomes comparable to that of commercial Pt. The Pt-based mass activity of Pd-Pt-Ni exceeds that of commercial Pt by a factor of 2, and its long-term durability is comparable to that of commercial Pt within the 200 h of operation. Compositional characterizations by energy dispersive spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS) suggest a dealloyed active catalyst phase consisting of Pd-rich core and Pt-rich shell, formed by dissolution of Pd and Ni under the testing conditions. The surface catalytic activity of nanoparticles can be modified by the strain effect caused by lattice mismatch between the surface and core components. Transmission electron microscopy (TEM) observation of the MEA cross-section reveals that the Pd ions move into the Nafion membrane and even to the anode side and redeposit on reduction by hydrogen crossover. The deposition of Pd-rich PdPt particles mainly forms a band at the center of the membrane and along the cathode/membrane interface. On the other hand, the Ni ions ion-exchange with the protons in the Nafion membrane.     

Characteristics of proton exchange membrane fuel cells cold start with silica in cathode catalyst layers

In this study, a novel strategy is reported to improve the cold start performance of proton exchange membrane (PEM) fuel cells at subzero temperatures. Hydrophilic nano-oxide such as SiO₂ is added into the catalyst layer (CL) of the cathode to increase its water storing capacity. To investigate the effect of nanosized SiO₂ addition, the catalyst coated membranes (CCMs) with 5 wt.% and without nanosized SiO₂ are fabricated. Although at normal operation conditions the cell performance with nanosized SiO₂ was not so good as that without SiO₂, cold start experiments at −8 °C showed that the former could start and run even at 100 mA cm⁻² for about 25 min and latter failed very shortly. Even at −10 °C, the addition of SiO₂ dramatically increased the running time before the cell voltage dropped to zero. These results further experimentally proved the cold start process was strongly related with the cathode water storage capacity. Also, the performance degradation during 8 cold start cycles was evaluated through polarization curves, cyclic voltammetry (CV) and electrochemical impedance spetra (EIS). Compared with the cell without SiO₂ addition, the cell with 5 wt.% SiO₂ indicated no obvious degradation on cell performance, electrochemical active surface area and charge transfer resistance after experiencing cold start cycles at −8 °C.     

Effect of mesoporous carbon on oxygen reduction reaction activity as cathode catalyst support for proton exchange membrane fuel cell

In this paper, a new carbon support with a large number of mesoporous-structures is selected to prepare Pt/C catalysts. Transmission electron microscope (TEM) results show that the Pt/3# catalyst presents a sponge-like morphology, Pt particles are not only evenly distributed on the surface of carbon support, but also the smaller Pt particles are deposited in the mesoporous inside the support. The average diameter of Pt particles is only 2.8 nm. The membrane electrode assembly (MEA) based on Pt/3# catalyst also shows excellent performance. In conclusion, the 3# support is an idea carbon support for PEMFC, which helps to improve the oxygen reduction reaction (ORR) activity of the catalyst. Based on the “internal-Pt” structure of the support mesoporous, the efficient three-phase boundaries (TPBs) are construct to avoid the poisoning effect of ionomer on the nano-metal particles, reduce the activation impedance and oxygen mass transfer impedance, and improve the reaction efficiency.     

On the mesoporous TiN catalyst support for proton exchange membrane fuel cell

A mesoporous TiN structure with high surface area and excellent electrical conductivity was fabricated for application as a catalyst support in proton exchange membrane fuel cell (PEMFC). Pt nanoparticles were then uniformly deposited on the TiN porous support by wet chemical reduction. The performances of PEMFC using Pt@TiN electrodes were evaluated by a single cell test station. The membrane electrode assembly using Pt@TiN for both anode and cathode exhibited 70%–120% higher specific power densities than that of commercial E-Tek due to higher electrical conductivity and porosity of the catalyst support and higher Pt utilization efficiency.     

Effect and siting of Nafion in a Pt/C proton exchange membrane fuel cell catalyst

This paper explores the effect and siting (location) of Nafion on Pt/C as exists in a PEM fuel cell catalyst layer. The addition of 30 wt% Nafion on Pt/C (Nfn-Pt/C) resulted in a severe loss of BET surface area by filling/blocking the smaller pore structures in the carbon support. Surprisingly, the presence of this much Nafion appeared to have only a minimal effect on the adsorption capability of either hydrogen or CO on Pt. However, the presence of Nafion doubled the amount of time required to purge most of the gas-phase and weakly-adsorbed hydrogen molecules away from the catalyst during hydrogen surface concentration measurements. This strongly chemisorbed surface hydrogen was determined by a H₂/D₂ switch and exchange procedure. Nafion had an even more pronounced effect on the reaction of a larger molecule like cyclopropane. Results from the modeling of cyclopropane hydrogenolysis in an idealized pores suggest that partial blockage of only the pore openings by the Nafion for the meso-macropores is sufficient to induce diffusion limitations on the reaction. The facts suggest that most of the Pt particles are in the meso-macropores of the C support, whereas Nafion is present primarily on the external surface of the C where it blocks significantly the micropores but only partially the meso-macropores.     

Functionalizing carbon nanotubes for proton exchange membrane fuel cells electrode

In recent years, carbon nanotubes (CNTs) have been increasingly considered as an advanced metal catalyst support for proton exchange membrane fuel cells (PEMFCs), owing to their outstanding physical and mechanical characteristics. However, the effective attachment of metal catalysts, uniformly dispersed onto the CNT surface, remains a formidable challenge because of the inertness of the CNT walls. Therefore, the surface functionalization of CNTs seems necessary in most cases in order to enable a homogeneous metal deposition. This review presents the different surface functionalization approaches that provide efficient avenues for the deposition of metal nanoparticles on CNTs, for the application of catalyst supports in PEMFCs with improved reactivity.     

Graphene oxide supported Pd-Fe nanohybrid as an efficient electrocatalyst for proton exchange membrane fuel cells

The experimental realization and computational validation for graphene oxide (GO) supported palladium (Pd)-iron (Fe) nanohybrids as a new generation electrocatalyst for proton-exchange membrane fuel cells (PEMFCs) has been reported. The experimental apprehension of the present catalyst system has been initiated with the graphene oxide, followed by the doping of Pd and Fe via thermal inter calation of palladium chloride and iron chloride with the in-situ downstream reduction to get nanohybrids of the GO-Pd-Fe. These nanohybrids are subsequently characterized by RAMAN, FT-IR, UV–Vis, XRD, SEM, EDS, TEM and HRTEM analysis. Furthermore, the first principle calculations based on Density Functional Theory (DFT) with semi-empirical Grimme DFT-D₂ correction has been performed to support the experimental findings. Computational results revealed the alteration of graphene electronic nature from zero-band gaped to metallic/semi-metallic on adsorption of transition metal clusters. Moreover, the defect sites of the graphene surface are more favorable than the pristine sites for transition metal adsorption owing to the strong binding energies of the former. Electrochemical studies show that GO-Pd-Fe nanohybrids catalyst (Pd: Fe = 2:1) demonstrates excellent catalytic activity as well as the higher electrochemical surface area of (58.08 m²/g Pd–Fe)⁻¹ which is higher than the commercially available Pt/C catalyst with electrochemical surface area 37.87 m²/(g Pt)⁻¹.     

Recent progress of catalyst ink for roll-to-roll manufacturing paired with slot die coating for proton exchange membrane fuel cells

Roll-to-roll (R2R) manufacturing paired with slot die coating is a promising route to realize the mass production of catalyst layers of proton exchange membrane fuel cells and achieve a sharp decrease in manufacturing costs through scale effect. Catalyst ink runs through the route and governs the ultimate structure of catalyst layer. Therefore, designing and preparing an optimal high-solid content catalyst ink and figuring out how to utilize it well in the R2R process has become a significant challenge. Herein, recent progress in catalyst ink is focused on design, preparation, rheology, slot die coating, and drying process. This review is a significant step forward in providing fundamental knowledge and understanding of the nature of advanced catalyst ink and its compatibility with the R2R process which are essential for designing and manufacturing excellent catalyst layers.     

A review of platinum-based catalyst layer degradation in proton exchange membrane fuel cells

Catalyst layer degradation has become an important issue in the development of proton exchange membrane (PEM) fuel cells. This paper reviews the most recent research on degradation and durability issues in the catalyst layers including: (1) platinum catalysts, (2) carbon supports, and (3) Nafion ionomer and interfacial degradation. The review aims to provide a clear understanding of the link between microstructural/macrostructural changes of the catalyst layer and performance degradation of the PEM fuel cell fueled with hydrogen under normal operating or accelerated stress conditions. In each section, different degradation mechanisms and their corresponding representative mitigation strategies are presented. Also, general experimental methods are classified and various investigation techniques for evaluating catalyst degradation are discussed.     

Preparation of dispersible double-walled carbon nanotubes and application as catalyst support in fuel cells

Dispersion of double-walled carbon nanotubes (DWCNTs) in ethylene glycol (EG) medium by a simple ultrasonication method is investigated. Excellent dispersion of DWCNTs in EG without addition of a surfactant is found. Surface structure and crystallinity of the DWCNTs undergo little change. The dispersion state of DWCNTs is found to be very important for deposition of Pt nanoparticles on them. The Pt particles prepared in the homogenous dispersion system has a small size and uniform distribution. As a result, the electrochemical activity of the Pt catalyst is much higher than that prepared in the nondispersible system. In terms of the good dispersion in EG medium achieved by a simple method, the DWCNT solutions could also be widely used in energy, biology, medicine and other fields.     

Sea urchin-like mesoporous carbon material grown with carbon nanotubes as a cathode catalyst support for fuel cells

A sea urchin-like carbon (UC) material with high surface area (416 m² g⁻¹), adequate electrical conductivity (59.6 S cm⁻¹) and good chemical stability was prepared by growing carbon nanotubes onto mesoporous carbon hollow spheres. A uniform dispersion of Pt nanoparticles was then anchored on the UC, where the Pt nanoparticles were prepared using benzylamine as the stabilizer. For this Pt loaded carbon, cyclic voltammogram measurements showed an exceptionally high electrochemically active surface area (EAS) (114.8 m² g⁻¹) compared to the commonly used commercial E-TEK catalyst (65.2 m² g⁻¹). The durability test demonstrates that the carbon used as a support exhibited minor loss in EAS of Pt. Compared to the E-TEK (20 wt%) cathode catalyst, this Pt loaded UC catalyst has greatly enhanced catalytic activity toward the oxygen reduction reaction, less cathode flooding and considerably improved performance, resulting in an enhancement of ca. 37% in power density compared with that of E-TEK. Based on the results obtained, the UC is an excellent support for Pt nanoparticles used as cathode catalysts in proton exchange membrane fuel cells.     

Low-cost graphite as durable support for Pt-based cathode electrocatalysts for proton exchange membrane based fuel cells

Proton exchange membrane fuel cell (PEMFC) technology has reached pre-commercial viability, but their insufficient durability acts as a major roadblock in its full-fledged utilization. It has been well established that the issue of durability is majorly due to the corrosion of carbon support used for Pt. Therefore, a search for low-cost and robust alternative support is highly desirable. In this paper, different graphite (and graphene) materials as durable support for Pt-based electrocatalyst are investigated. We followed the top-down approach where a fully graphitized support is mildly wet-milled and surface-treated to give a sufficient surface modification for improved Pt deposition on these supports. All the graphite-supported Pt samples showed better durability than that of state-of-the-art commercial electrocatalysts. Considering both activity and durability the best catalyst among the investigated samples showed a comparable mass specific activity (MSA) of 0.186 A/mg and significantly higher durability (70%) after 7500 stress cycles. For HiSpec9100 and BASF commercial electrocatalysts, the normalized ESA retention value after 7500 stress cycles was 40% and 47%, respectively.     

Fuzzy observer-based fault tolerant control against sensor faults for proton exchange membrane fuel cells

In this paper, robust fault diagnosis problem of Proton Exchange Membrane Fuel Cells (PEMFC) is presented based on Takagi-Sugeno (TS) Fuzzy Unknown Input Observer (FUIO). TS FUIO based on Linear Matrix Equalities (LMEs) and the Linear Matrix Inequalities (LMIs) are design. Firstly, the nonlinear PEMFC system with sensor faults and disturbance is represented by TS fuzzy model. Then, a FUIO and sensor fault estimation algorithm is developed and then a model based Fuzzy Fault Tolerant Controller design uses the concept of Parallel Distributed Compensation (PDC). Sufficient stability conditions are studied based on LMIs and LMEs. In order to verify the proposed approach, a PEMFC system with return manifold pressure and hydrogen mass sensors fault and disturbance was tested to illustrate the effectiveness of the proposed strategy.     

Dynamic conducting effect of WO3/PFSA membranes on the performance of proton exchange membrane fuel cells

The homogenous proton conducting WO₃/PFSA membranes are prepared based on a dynamic conducting concept, that is, the resistance of the membrane can be reduced during the fuel cell operation due to the formation of the conducting hydrogen tungsten bronzes. The novel membranes are characterized by different techniques. The results proved that the resistances of the WO₃-containing membranes in single fuel cells measured by in situ AC impedance spectroscopy during the operation are significantly lower than that of the single fuel cell using Nafion^® 112 membrane. It is revealed that the performances of the single fuel cells with WO₃/PFSA membranes are superior to that of the single cell with Nafion^® 112 membrane.     

Synthesis and characterization of Cu@Pt/C core-shell structured catalysts for proton exchange membrane fuel cell

A Cu@Pt/C catalyst was synthesized by a two-step reduction method using Vulcan XC-72R as the supporting material. Physical and electrochemical techniques were applied to investigate the structure and performance of the catalyst. X-ray diffraction (XRD) and transmission electron microscopy (TEM) examinations showed that the catalyst has a core-shell structure, the distribution of the catalyst particles is quite uniform, and the particle size ranges from 5 to 6 nm. Cyclic voltammetry (CV) and rotating disk electrode (RDE) tests confirmed the high performance of the Cu@Pt/C catalyst with the atom ratio Cu: Pt of 2.73: 1, making it a promising low-Pt catalyst for proton exchange membrane fuel cell (PEMFC).     

Evaluation of electrochemical performance for surface-modified carbons as catalyst support in polymer electrolyte membrane (PEM) fuel cells

The electrochemical performance of platinum (Pt) catalyst deposited on various functionalized carbon supports was investigated and compared with that of a commercial catalyst, Pt on Vulcan XC-72 carbon. The supports employed were graphitic or amorphous with a wide range of surface areas. Cyclic voltammetry (CV) and rotating disk electrode (RDE) studies on the supported catalysts indicated equivalent platinum catalyst activities. Fuel cell performance was determined for membrane electrode assemblies (MEA) fabricated from the supported catalysts. The use of high surface area supports did not necessarily translate into a higher electrochemical utilization of platinum. Electrochemical impedance spectroscopy (EIS) measurements indicated lower ohmic losses for low surface area carbon MEAs. This is explained by the supported catalyst electrode microstructures and their intrinsic resistivities. Correlation of all data indicates that for low surface carbons, nature of the support does not significantly affect the Pt catalytic activity. The influence of the support is more critical when high surface area carbons are used because of the vastly different electrode morphology and resistivity.     

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.