Graphene based catalyst supports for high temperature PEM fuel cell application

In this study, the effect of graphene nanoplatelet (GNP) and graphene oxide (GO) based carbon supports on polybenzimidazole (PBI) based high temperature proton exchange membrane fuel cells (HT-PEMFCs) performances were investigated. Pt/GNP and Pt/GO catalysts were synthesized by microwave assisted chemical reduction support. X-ray diffraction (XRD), Thermogravimetric analysis (TGA), Brauner, Emmet and Teller (BET) analysis and high resolution transmission electron microscopy (HRTEM) were used to investigate the microstructure and morphology of the as-prepared catalysts. The electrochemical surface area (ESA) was studied by cyclic voltammetry (CV). The results showed deposition of smaller Pt nanoparticles with uniform distribution and higher ECSA for Pt/GNP compared to Pt/GO. The Pt/GNP and Pt/GO catalysts were tested in 25 cm² active area single HT-PEMFC with H₂/air at 160 °C without humidification. Performance evaluation in HT-PEMFC shows current densities of 0.28, 0.17 and 0.22 A/cm² for the Pt/GNP, Pt/C and Pt/GO catalysts based MEAs at 160 °C, respectively. The maximum power density was obtained for MEA prepared by Pt/GNP catalyst with H₂/Air dry reactant gases as 0.34, 0.40 and 0.46 W/cm² at 160 °C, 175 °C and 190 °C, respectively. Graphene based catalyst supports exhibits an enhanced HT-PEMFC performance in both low and high current density regions. The results indicate the graphene catalyst support could be utilized as the catalyst support for HT-PEMFC application.     

Chemically synthesized reduced graphene oxide-carbon black based hybrid catalysts for PEM fuel cells

In this study, hybrid (synthesized rGO and commercial carbon black (CB) in various weight ratios) supported Pt catalysts were synthesized by using the supercritical carbon dioxide deposition (scCO₂) technique for PEM fuel cells. In hybrid materials, rGO to CB weight ratios were changed in between 90:10 to 50:50 which were compared to their plain materials. The physicochemical and the electrochemical characteristics of the materials were examined by using BET, XRD, TGA, TEM, contact angle and roughness measurements, CV and PEM fuel cell performance tests. All these characterizations showed that the hybrid supported Pt catalysts were successfully synthesized. TEM images of the catalysts confirmed the highly dispersed and small nanoparticle formation (1.9–2.9 nm) via scCO₂ deposition technique. Among the hybrid supported catalysts, catalyst having rGO:CB ratio of 70:30 showed the best PEM fuel cell performance. Electrochemical characterization either fuel cell performance test or CV results indicated significantly enhancement in activity with an increase in CB amount in the support.     

An effective electrocatalyst based on platinum nanoparticles supported with graphene nanoplatelets and carbon black hybrid for PEM fuel cells

A facile synthesis at room temperature and at solid-state directly on the support yielded small, homogeneous and well-dispersed Pt nanoparticles (NPs) on CB-carbon black, GNP-graphene nanoplatelets, and CB-GNP-50:50 hybrid support. Synthesized Pt/CB, Pt/GNP and Pt/CB:GNP NPs were used as electrocatalysts for polymer electrolyte membrane fuel cell (PEMFC) reactions. HRTEM results displayed very small, homogeneous and well-dispersed NPs with 1.7, 2.0 and 4.2 nm mean-diameters for the Pt/CB-GNP, Pt/GNP and Pt/CB electrocatalysts, respectively. Electrocatalysts were also characterized by RAMAN, XRD, BET and CV techniques. ECSA values indicated better activity for graphene-based supports with 19 m² g⁻¹_Pt for Pt/GNP and 55 m² g⁻¹_Pt for Pt/CB-GNP compared to 10 m² g⁻¹_Pt for Pt/CB. Oxygen reduction reaction (ORR) studies and fuel cell tests were in parallel with these results where highest maximum power density of 377 mW cm⁻² was achieved with Pt/CB-GNP hybrid electrocatalyst. Both fuel cell and ORR studies for Pt/CB-GNP indicated better dispersion of NPs on the support and efficient fuel cell performance that is believed to be due to the prevention of restacking of GNP by CB. To the best of our knowledge, Pt/GNP and Pt/CB-GNP electrocatalysts are the first in literature to be synthesized with the organometallic mild synthesis method using Pt(dba)₃ precursor for the PEMFC applications.     

Use of cellulose-based carbon aerogels as catalyst support for PEM fuel cell electrodes: Electrochemical characterization

New nanostructured carbons have been developed through pyrolysis of organic aerogels, based on supercritical drying of cellulose acetate gels. These cellulose acetate-based carbon aerogels (CA) are activated by CO₂ at 800 °C and impregnated by PtCl₆²⁻; the platinum salt is then chemically or electrochemically reduced. The resulting platinized carbon aerogels (Pt/CA) are characterized with transmission electron microscopy (TEM) and electrochemistry. The active area of platinum is estimated from hydrogen adsorption/desorption or CO-stripping voltammetry: it is possible to deposit platinum nanoparticles onto the cellulose acetate-based carbon aerogel surface in significant proportions. The oxygen reduction reaction (ORR) kinetic parameters of the Pt/CA materials, determined from quasi-steady-state voltammetry, are comparable with that of Pt/Vulcan XC72R. These cellulose acetate-based carbon aerogels are thus promising electrocatalyst support for PEM application.     

Effect of carbon black additive in Pt black cathode catalyst layer on direct methanol fuel cell performance

Vulcan XC-72R, Ketjen Black EC 300J and Black Pearls 2000 carbon blacks were used as the additive in Pt black cathode catalyst layer to investigate the effect on direct methanol fuel cell (DMFC) performance. The carbon blacks, Pt black catalyst and catalyst inks were characterized by N₂ adsorption and scanning transmission electron microscopy (STEM) with Energy dispersive X-ray (EDX) spectroscopy. The cathode catalyst layers without and with carbon black additive were characterized by scanning electron microscopy, EDX, cyclic voltammetry and current-voltage curve measurements. Compared with Vulcan XC-72R and Black Pearls 2000, Ketjen Black EC 300J was more beneficial to increase the electrochemical surface area and DMFC performance of the cathode catalyst layer. The cathode catalyst layer with Ketjen Black EC 300J additive was kept intimately binding with the Nafion membrane after 360 h stability test of air-breathing DMFC.     

Modeling of PEM fuel cell Pt/C catalyst degradation

Pt/C catalyst degradation remains as one of the primary limitations for practical applications of proton exchange membrane (PEM) fuel cells. Pt catalyst degradation mechanisms with the typically observed Pt nanoparticle growth behaviors have not been completely understood and predicted. In this work, a physics-based Pt/C catalyst degradation model is proposed with a simplified bi-modal particle size distribution. The following catalyst degradation processes were considered: (1) dissolution of Pt and subsequent electrochemical deposition on Pt nanoparticles in cathode; (2) diffusion of Pt ions in the membrane electrode assembly (MEA); and (3) Pt ion chemical reduction in membrane by hydrogen permeating through the membrane from the negative electrode. Catalyst coarsening with Pt nanoparticle growth was clearly demonstrated by Pt mass exchange between small and large particles through Pt dissolution and Pt ion deposition. However, the model is not adequate to predict well the catalyst degradation rates including Pt nanoparticle growth, catalyst surface area loss and cathode Pt mass loss. Additional catalyst degradation processes such as new Pt cluster formation on carbon support and neighboring Pt clusters coarsening was proposed for further simulative investigation.     

Experimental verification for simulation study of Pt/CNT nanostructured cathode catalyst layer for PEM fuel cells

In this study, parametric study on the cathode catalyst layer in a Proton Exchange Membrane (PEM) fuel cell was conducted. Steady-state, two dimensional (2D) and nonisothermal conditions were proposed as critical hypotheses of work in essence. Multi-component mass diffusion along with convection mechanism in a single cell, conduction changes of proton and electron with experimental data and Knudsen diffusion which has a crucial impact on the simulation task in nanoscale, were considered in our study. Moreover, carbon nanotube (CNT), platinum (Pt) and Nafion loading effects as well as the porosity characteristics in a single-phase flow at different catalyst layer (CL) thicknesses were thoroughly investigated. The results presented herein, revealed that the amount of Pt and CNT has more profound effect than catalyst porosity. Based on the results derived, the model presented could be a promising mean to develop and construct a nanostructured catalyst layer. Meanwhile, our modified agglomerate model predicts the performance of fuel cell systems in different experimental conditions.     

Influence of carbon nanofiber properties as electrocatalyst support on the electrochemical performance for PEM fuel cells

Novel carbonaceous supports for electrocatalysts are being investigated to improve the performance of polymer electrolyte fuel cells. Within several supports, carbon nanofibers blend two properties that rarely coexist in a material: a high mesoporosity and a high electrical conductivity, due to their particular structure. Carbon nanofibers have been obtained by catalytic decomposition of methane, optimizing growth conditions to obtain carbon supports with different properties. Subsequently, the surface chemistry has been modified by an oxidation treatment, in order to create oxygen surface groups of different nature that have been observed to be necessary to obtain a higher performance of the electrocatalyst.     

Utilization of the graphene aerogel as PEM fuel cell catalyst support: Effect of polypyrrole (PPy) and polydimethylsiloxane (PDMS) addition

In this study, three-dimensional (3D) graphene aerogel (GA) was synthesized by a self-assembly hydrothermal process as a PEM fuel cell catalyst support. The synthesized GA was also modified with the polypyrrole (PPy) by in-situ chemical oxidative polymerization of the pyrrole monomer (PPy-GA). The electrocatalytic performance of the platinum (Pt) nanoparticles (NPs) supported with both GA and PPy-GA materials towards oxygen reduction reaction (ORR) was investigated. In addition, the hydrophobic polydimethylsiloxane (PDMS) polymer was added to the catalyst ink media in order to enhance the hydrophobic property and durability of the synthesized GA and PPy-GA supported Pt catalysts. Pt NPs were decorated over the support materials with the microwave irradiation technique. Various characterization techniques such as FTIR, Raman Spectroscopy, BET, SEM, EDX, TEM, TGA, contact angle measurements, 3D topography images and four-point probe electrical conductivity measurements were performed in order to analyze the GA based support materials. Electrochemical characterizations were also carried out with cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) measurements. It was observed that PDMS addition to the catalyst ink media increased the electrocatalytic activity and durability of the GA supported Pt catalyst. Otherwise, the performance of the PPy modified GA supported Pt catalyst was negatively affected by the addition of PDMS to the catalyst media.     

Innovative catalyst supports to address fuel cell stack durability

To successfully penetrate the automotive market, cost-efficient and durable fuel cell technologies are necessary to compete with existing mature technologies.     

Improvement of proton-exchange membrane fuel cell performance using platinum-loaded carbon black entrapped in crosslinked chitosan

To improve the performance of proton-exchange membrane fuel cells which use hydrogen and oxygen as fuels, the application of small proton-conducting polymer to extend the three-phase boundary into the primary pores of catalyst-loaded carbon black agglomerates is of interest. An alternative and simple crosslinking method is proposed in place of the complicated polymer-grafting methods. Platinum-loaded carbon black is entrapped in epichlorohydrin-crosslinked chitosan of low molecular weight. Morphology and pore analyses of carbon black prior and post treatment are assessed, as well as performances of fuel cells fabricated with the treated and the untreated carbon black at 40 °C and 100% humidity. Results indicate the existence of chitosan chains in the primary pores of the carbon black agglomerates, corresponding to a decline in the activation overvoltage and resulting in significantly better cell performance. An increase in chitosan amount, however, does not necessarily enhance the cell performance because effects of ohmic and concentration losses may become more dominant than that of the raised exchange current density of the cell.     

Synthesis of polypyrrole (PPy) based porous N-doped carbon nanotubes (N-CNTs) as catalyst support for PEM fuel cells

In this study, it was aimed to synthesize catalytically active, high surface area carbon nanotubes (CNTs) by means of nitrogen doping (N-doping). The synthesized nitrogen doped carbon nanotubes (N-CNTs) were used as Pt catalyst support in order to improve oxygen reduction reaction (ORR) kinetics at the cathode electrode in PEM fuel cell. Polypyrrole (PPy) was served as both carbon and nitrogen source and FeCl₃ solution was used as oxidizing agent in the synthesis procedure of N-CNTs. Chemical activation of the materials was made with potassium hydroxide (KOH) solution during 12 and 18 h time periods. It was considered that activation period is of great importance on the properties of the synthesized PPy based N-CNTs. 12 h activated N-CNTs gave higher surface area (1607.2 m²/g) and smaller micropore volume (0.355 cm³/g) in comparison to 18 h activated N-CNTs having smaller surface area (1170.7 m²/g) and higher micropore volume (0.383 cm³/g). PEM fuel cell performance results showed that 12 h activated N-CNTs are better catalyst supports than 18 h activated N-CNTs for Pt nanoparticle decoration.     

A three-dimensional agglomerate model for the cathode catalyst layer of PEM fuel cells

In this work, a three-dimensional, steady-state, multi-agglomerate model of cathode catalyst layer in polymer electrolyte membrane (PEM) fuel cells has been developed to assess the activation polarization and the current densities in the cathode catalyst layer. A finite element technique is used for the numerical solution to the model developed. The cathode activation overpotentials, and the membrane and solid phase current densities are calculated for different operating conditions. Three different configurations of agglomerate arrangements are considered, an in-line and two staggered arrangements. All the three arrangements are simulated for typical operating conditions inside the PEM fuel cell in order to investigate the oxygen transport process through the cathode catalyst layer, and its impact on the activation polarization. A comprehensive validation with the well-established two-dimensional “axi-symmetric model” has been performed to validate the three-dimensional numerical model results. Present results show a lowest activation overpotential when the agglomerate arrangement is in-line. For more realistic scenarios, staggered arrangements, the activation overpotentials are higher due to the slower oxygen transport and lesser passage or void region available around the individual agglomerate. The present study elucidates that the cathode overpotential reduction is possible through the changing of agglomerate arrangements. Hence, the approaches to cathode overpotential reduction through the optimization of agglomerate arrangement will be helpful for the next generation fuel cell design.     

Water balance for the design of a PEM fuel cell system

The design of a proton exchange membrane (PEM) fuel cell system is important for the optimization of the function of supporting parameters in the fuel cell. The water balance in a PEM fuel cell is investigated based on the water transport phenomena. In this investigation, the diffusion of water from the cathode side to the anode side of the cell is observed to not occur at 20% relative humidity at the cathode (RHC) and 58% relative humidity at the anode (RHA). The minimum concentration of condensed water at the cathode side is observed at a cathode gas inlet relative humidity of 40% RHC–92% RHC and at temperatures between 343 K and 363 K. RHC operating conditions that are greater than 90% and at a temperature of 363 K increased the concentration of condensed water and occurred quickly, which result in a water balance that became difficult to control. On the anode side, the condensation of water is observed at operating temperatures of 353 K and 363 K.     

Investigation of the effect of graphitized carbon nanotube catalyst support for high temperature PEM fuel cells

In this study, it is aimed to investigate the graphitization effect on the performance of the multi walled carbon nanotube catalyst support for high temperature proton exchange membrane fuel cell (HT-PEMFC) application. Microwave synthesis method was selected to load Pt nanoparticles on both CNT materials. Prepared catalyst was analyzed thermal analysis (TGA), Transmission Electron Microscopy (TEM) and corrosion tests. TEM analysis proved that a distribution of Pt nanoparticles with a size range of 2.8–3.1 nm was loaded on the Pt/CNT and Pt/GCNT catalysts. Gas diffusion electrodes (GDE) were manufactured by an ultrasonic spray method with synthesized catalyst. Polybenzimidazole (PBI) membrane based Membrane Electrode Assembly (MEA) was prepared for observe the performance of the prepared catalysts. The synthesized catalysts were also tested in a HT-PEMFC environment with a 5 cm² active area at 160 °C without humidification. This study demonstrates the feasibility of using the microwave synthesis method as a fast and effective method for preparing high performance Pt/CNT and Pt/GCNT catalyst for HT-PEMFC. The HT-PEMFC performance evaluation shows current densities of 0.36 A/cm²0.30 A/cm² and 0.20 A/cm² for the MEAs prepared with Pt/GCNT, Pt/CNT and Pt/C catalysts @ 0.6 V operating voltage, respectively. AST (Accelerated Stress Test) analyzes of MEAs prepared with Pt/GCNT and Pt/CNT catalysts were also performed and compared with Pt/C catalyst. According to current density @ 0.6 V after 10,000 potential cycles, Pt/GCNT, Pt/CNT and Pt/C catalysts can retain 61%, 67% and 60% of their performance, respectively.     

Stabilised control strategy for PEM fuel cell and supercapacitor propulsion system for a city bus

Fuel Cell (FC) buses have been developed as a long term zero emission solution for city transportation and have reached levels of maturity to supplement the coming London 2020 Ultra low emission zone implementation. This research developed a scaled laboratory Fuel Cell/Supercapacitor hybrid drivetrain implementing DC/DC converters to maintain the common busbar voltage and control the balance of power. A novel and simple hybrid control strategy based on balancing the currents on the common busbar whilst maintaining a stable FC output has been developed. It has been demonstrated that the FC power output can be controlled at a user defined value for both steady state and transient load conditions. The proposed control strategy holds the promise of extending FC life, downsizing power systems and improving the FC operating efficiency.     

Maximum equivalent efficiency and power output of a PEM fuel cell/refrigeration cycle hybrid system

With the help of the current models of proton exchange membrane (PEM) fuel cells and three-heat-source refrigeration cycles, the general model of a PEM fuel cell/refrigeration cycle hybrid system is originally established, so that the waste heat produced in the PEM fuel cell may be availably utilized. Based on the theory of electrochemistry and non-equilibrium thermodynamics, expressions for the efficiency and power output of the PEM fuel cell, the coefficient of performance and cooling rate of the refrigeration cycle, and the equivalent efficiency and power output of the hybrid system are derived. The curves of the equivalent efficiency and power output of the hybrid system varying with the electric current density and the equivalent power output versus efficiency curves are represented through numerical calculation. The general performance characteristics of the hybrid system are discussed. The optimal operation regions of some parameters in the hybrid system are determined. The advantages of the hybrid system are revealed.     

A parametric study of cathode catalyst layer structural parameters on the performance of a PEM fuel cell

This paper is a computational study of the cathode catalyst layer (CL) of a proton exchange membrane fuel cell (PEMFC) and how changes in its structural parameters affect performance. The underlying mathematical model assumes homogeneous and steady-state conditions, and consists of equations that include the effects of oxygen diffusion, electrochemical reaction rates, and transport of protons and electrons through the Nafion ionomer (PEM) and solid phases. Simulations are concerned with the problem of minimizing activation overpotential for a given current density. The CL consists of four phases: ionomer, solid substrate, catalyst particles and void spaces. The void spaces are assumed to be fully flooded by liquid water so that oxygen within the CL can diffuse to reaction sites via two routes: within the flooded void spaces and dissolved within the ionomer phase. The net diffusive flux of oxygen through the cathode CL is obtained by incorporating these two diffusive fluxes via a parallel resistance type model. The effect of six structural parameters on the CL performance is considered: platinum and carbon mass loadings, ionomer volume fraction, the extent to which the gas diffusion layer (GDL) extends into the CL, the GDL porosity and CL thickness. Numerical simulations demonstrate that the cathode CL performance is most strongly affected by the ionomer volume fraction, CL thickness and carbon mass loading. These results give useful guidelines for manufactures of PEMFC catalyst layers.     

Carbon support oxidation in PEM fuel cell cathodes

Oxidation of the cathode carbon catalyst support in polymer electrolyte fuel cells (PEMFC) has been examined. For this purpose platinum supported electrodes and pure carbon electrodes were fabricated and tested in membrane-electrode-assemblies (MEAs) in air and nitrogen atmosphere. The in situ experiments account for the fuel cell environment characterized by the presence of a solid electrolyte and water in the gas and liquid phases. Cell potential transients occurring during automotive fuel cell operation were simulated by dynamic measurements. Corrosion rates were calculated from CO₂ and CO concentrations in the cathode exhaust measured by non-dispersive infrared spectroscopy (NDIR). Results from these potentiodynamic measurements indicate that different potential regimes relevant for carbon oxidation can be distinguished. Carbon corrosion rates were found to be higher under dynamic operation and to strongly depend on electrode history. These characteristics make it difficult to predict corrosion rates accurately in an automotive drive cycle.     

Statistical design of experiment approach for modeling and optimization of PEM fuel cell

Polymer electrolyte membrane (PEM) fuel cell has many input factors and it is very difficult to find which input factor affects response or output factor significantly. The general method of changing one factor at a time is statistically not correct because the interaction of the factors also affects the response in most of the cases. Mathematical and simulation models are important tools for designing and analysis of fuel cell-based systems. In this paper, first, a protocol for development of a 25-cm² active area, high performance, PEM fuel cell is presented and then its simulation model is developed using the first principle in MATLAB SIMULINK. Full factorial statistical design of experiment methodology is used to develop first- and second-order Metamodels (Mathematical model of simulation model) for PEM fuel cell to find which input factors affect the response variables significantly. Validation of the Metamodels is checked by various statistical tests, viz, normality, regression analysis, analysis of variance, and lack of fit. Steepest ascent method is used to find the maximum power delivered by PEM fuel cell within the defined ranges of input factors.