Analysis of sulfur poisoning on a PEM fuel cell electrode

The extent of irreversible deactivation of Pt towards hydrogen oxidation reaction (HOR) due to sulfur adsorption and subsequent electrochemical oxidation is quantified in a functional polymer electrolyte membrane (PEM) fuel cell. At 70 °C, sequential hydrogen sulfide (H₂S) exposure and electrochemical oxidation experiments indicate that as much as 6% of total Pt sites are deactivated per monolayer sulfur adsorption at open-circuit potential of a PEM fuel cell followed by its removal. The extent of such deactivation is much higher when the electrode is exposed to H₂S while the fuel cell is operating at a finite load, and is dependent on the local overpotential as well as the duration of exposure. Regardless of this deactivation, the H₂/O₂ polarization curves obtained on post-recovery electrodes do not show performance losses suggesting that such performance curves alone cannot be used to assess the extent of recovery due to sulfur poisoning. A concise mechanism for the adsorption and electro-oxidation of H₂S on Pt anode is presented. H₂S dissociatively adsorbs onto Pt as two different sulfur species and at intermediate oxidation potentials, undergoes electro-oxidation to sulfur and then to sulfur dioxide. This mechanism is validated by charge balances between hydrogen desorption and sulfur electro-oxidation on Pt. The ignition potential for sulfur oxidation decreases with increase in temperature, which coupled with faster electro-oxidation kinetics result in the easier removal of adsorbed sulfur at higher temperatures. Furthermore, the adsorption potential is found to influence sulfur coverage of an electrode exposed to H₂S. As an implication, the local potential of a PEM fuel cell anode exposed to H₂S contaminated fuel should be kept below the equilibrium potential for sulfur oxidation to prevent irreversible loss of Pt sites.     

Transient carbon monoxide poisoning of a polymer electrolyte fuel cell operating on diluted hydrogen feed

The transient behavior of a 50 cm² PEM fuel cell fed on simulated reformate containing diluted hydrogen and trace quantities of carbon monoxide (CO) was experimentally investigated. It was found that the overall cell performance throughout the CO poisoning process can be described with a lumped model of hydrogen and CO adsorption, desorption, and electro-oxidation coupled with a current-voltage relationship for fuel cell performance. It was shown that while hydrogen dilution alone does not have an appreciable effect on cell polarization, in the presence of trace amounts of CO, hydrogen dilution amplifies the problem of CO poisoning. This is a result of the diluent reducing the partial pressure of reactants in the anode fed stream, thus retarding the already CO-impaired hydrogen adsorption onto the catalyst surface. In a diluted hydrogen stream, even low CO concentrations (i.e. 10 ppm), which are traditionally considered safe for PEM fuel cell operation, were found to be harmful to cell performance.     

Low-cost light weight high power density PEM fuel cell stack

A new approach to PEM fuel cell stack fabrication has been demonstrated. This approach is based on the use of light weight metal conductive elements together with nonconductive elements fabricated from engineering thermoplastics to yield a lightweight stack that can be manufactured from flat sheets of stock materials using inexpensive mass production techniques. The stack described here has a power output of over 520 W from a volume of 616 mL and a mass of 539 g for a power density of 967 W/kg and 846 W/L while operating at a pressure of 103 kPa with a 53% conversion efficiency. It is projected that with further refinement, PEM fuel cell stacks with power densities over 1,500 W/kg and 1,200 W/L can be produced.     

Electrochemical promotion of CO conversion to CO2 in PEM fuel cell PROX reactor

The possibility of electrochemically promoting the water–gas-shift reaction and the CO oxidation reaction in a PEM fuel cell reactor supplied with a methanol reformate mixture was investigated in PEM fuel cells with Pt or Au state-of-the-art E-TEK anodes, in order to explore the use of PEMFC units as preferential oxidation of CO (PROX) reactors. The electropromotion of CO removal was investigated both with air or H₂ fed to the cathode side and also by O₂ bleeding to the anode during normal PEMFC operation. It was found that the catalytic activity of the anode for CO conversion to CO₂ can be modified significantly by varying the catalyst potential. The magnitude of the electrochemical promotion depends strongly on the anodic electrocatalyst (Pt or Au), on the CO concentration of the fuel mixture, on the operating temperature and on the presence of oxygen. The electropromotion effect and the Faradaic efficiency were found to be much higher in CO-rich anode environments.     

Modeling, simulation and experimental validation of a PEM fuel cell system

The aim of this work is the development and experimental validation of a detailed dynamic fuel cell model using the gPROMS modeling environment. The model is oriented towards optimization and control and it relies on material and energy balances as well as electrochemical equations including semi-empirical equations. For the experimental validation of the model a fully automated and integrated hydrogen fuel cell testing unit was used. The predictive power of the model has been compared with the data obtained during load change experiments. A sensitivity analysis has been employed to reveal the most critical empirical model parameters that should be estimated using a systematic estimation procedure. Model predictions are in good agreement with experimental data under a wide range of operating conditions.     

Ignition waves in a stirred PEM fuel cell

A mathematical model of slow transient behavior in an autohumidified stirred tank reactor (STR) polymer electrolyte membrane (PEM) fuel cell is developed. The key feature of the model is the positive feedback between current, water production, and membrane resistance which leads to two stable “ignited” states, corresponding to either a uniform current distribution or a partially ignited cell with localized current production. The switching between the two regimes is accompanied by hysteresis and transient behavior on the order of 2-4 h in a small cell. We compare the numerical results to experimental data gathered by [Benziger et al. 2005. Chemical Engineering Science 60 (6), 1743-1759] and show that the lateral diffusion of water within the ionomer membrane is a possible mechanism behind the hysteresis and slow transient behavior they observed.     

Reforming methanol to electricity in a high temperature PEM fuel cell

In this paper we demonstrate for the first time a compact power unit, where a methanol reforming catalyst is incorporated into the anode of a PEMFC. The proposed internal reforming methanol fuel cell (IRMFC) mainly comprises: (i) a H₃PO₄-imbibed polymer electrolyte based on aromatic polyethers bearing pyridine units, able to operate at 200 °C and (ii) a 200 °C active and with zero CO emissions Cu–Mn–O methanol reforming catalyst supported on copper foam. Methanol is being reformed inside the anode compartment of the fuel cell at 200 °C producing H₂, which is readily oxidized at the anode to produce electricity. The IRMFC showed promising electrochemical behavior and no signs of performance degradation for more than 72 h.     

PEM fuel cell current regulation by fuel feed control

We demonstrate that the power output from a PEM fuel cell can be directly regulated by limiting the hydrogen feed to the fuel cell. Regulation is accomplished by varying the internal resistance of the membrane-electrode assembly in a self-draining fuel cell with the effluents connected to water reservoirs. The fuel cell functionally operates as a dead-end design where no gas flows out of the cell and water is permitted to flow in and out of the gas flow channel. The variable water level in the flow channel regulates the internal resistance of the fuel cell. The hydrogen and oxygen (or air) feeds are set directly to stoichiometrically match the current, which then control the water level internal to the fuel cell. Standard PID feedback control of the reactant feeds has been incorporated to speed up the system response to changes in load. With dry feeds of hydrogen and oxygen, 100% hydrogen utilization is achieved with 130% stoichiometric feed on the oxygen. When air was substituted for oxygen, 100% hydrogen utilization was achieved with stoichiometric air feed. Current regulation is limited by the size of the fuel cell (which sets a minimum internal impedance), and the dynamic range of the mass flow controllers. This type of regulation could be beneficial for small fuel cell systems where recycling unreacted hydrogen may be impractical.     

Improved performance of PEM fuel cell using carbon paper electrode prepared with CNT coated carbon fibers

Porous conducting carbon paper has been identified as the most suitable material to be used as a backing material for the fuel cell electrode. The surface of carbon fiber, the major constituent of the carbon paper was modified by: (1) removing the functional groups by heat cleaning process and (2) coating the non-functionalized carbon fiber with multi-walled carbon nanotubes (MWCNTs). This has a marked influence on the fiber–matrix interactions during later stages of processing of carbon paper that helped in controlling its various characteristic properties. Using the carbon paper formed with CNT coated carbon fiber as electrode, the maximum power density achieved from a unit fuel cell was found to be 783 mW/cm² as compared to 630 mW/cm² when the paper was formed with normal fiber.     

Effect of a GDL based on carbon paper or carbon cloth on PEM fuel cell performance

A commercially available GDL based on carbon paper or carbon cloth as a macroporous substrate was characterized by various physical and electrochemical measurements: mercury porosimetry, surface morphology analysis, contact angle measurement, water permeation measurement, polarization techniques, and ac-impedance spectroscopy. SGL 10BB based on carbon paper demonstrated dual pore size distribution and high water flow resistance owing to less permeable macroporous substrate, and more hydrophobic and compact microporous layer, as compared to ELAT-LT-1400 W based on carbon cloth. The membrane-electrode-assembly fabricated using SGL 10BB showed an improved fuel cell performance when air was used as an oxidant. The ac-impedance response indicated that a microporous layer which has high volume of micropores and more hydrophobic property allows oxygen to readily diffuse towards the catalyst layer due to effective water removal from the catalyst layer to the gas flow channel.     

Calorimetric study of the reversibility of CO pollutant adsorption on high loaded Pt/carbon catalysts used in PEM fuel cells

A major obstacle to the broader use of fuel cells is the poisoning of supported Pt catalysts by the CO present in virtually all feeds. In this paper, the microcalorimetry technique was employed to study and compare the CO adsorption properties of different commercial carbon-supported platinum catalysts with high Pt loading, aimed to be used in proton exchange membrane fuel cells (PEMFCs) applications. Combined with other techniques of characterization, such as BET, XRD, TPD-MS and TPR, adsorption microcalorimetry has permitted a better understanding of the studied systems. The pore architecture of Pt/C catalysts was found to influence the kinetics of heat release during CO adsorption. The accessibility of CO molecules to the adsorption sites increased with the mesoporosity of the catalyst. The degree of catalyst poisoning by CO upon successive air/H₂/CO cycles varied between 2 and 30% for the different studied samples. These results confirm that the surface chemistry of the catalyst, and in particular the Pt deposition method, affects the surface site energy distribution and consequently the adsorptive properties towards H₂ and CO. It was found that both H₂ and CO are chemisorbed on the investigated samples. Pt/C powders exhibit higher differential heats of carbon monoxide adsorption in comparison with hydrogen adsorption. A reaction between pre-adsorbed H₂ and CO from the gas phase takes place on Pt/C catalysts as a result of competitive adsorption.     

The role of mechanically induced defects in carbon nanotubes to modify the properties of electrodes for PEM fuel cell

The characteristics and reactivity of two anodes based on Pt supported on carbon nanotubes (CNTs) without or with defects induced by ball-milling are studied by SEM, TEM, cyclic voltammetry (CV) and single-cell measurements using a flow of pure H₂ or containing 50 ppm CO. It is evidenced that the presence of defects influences several properties and not only the dispersion of Pt particles. Therefore, the performances cannot be correlated neither with the geometrical surface area of Pt particles, neither with the electrochemical active surface area determined from CV tests. The presence of defects, enhancing the amount of surface functional groups on CNT, influences various aspects: (i) the efficiency of three-phase boundary and thus the transport of protons to or from the active metal particles, (ii) the resistance of electron transfer and (iii) the tolerance of the catalyst to CO poisoning. The latter is attributed to carbon functional groups in close contact with very small Pt particles favoring the reactivation of Pt sites poisoned by CO.     

Ethanol crossover and direct ethanol PEM fuel cell performance modeling and experimental validation

In the present work, a one-dimension, steady-state and single phase model is developed with the purpose of describing the mass transport within a PtRu/Nafion^®-115/Pt membrane-electrode assembly and the performance of a direct ethanol proton exchange membrane fuel cell (DE-PEMFC). The effect of the most important cell operating parameters on the ethanol crossover rate and the fuel cell performance is investigated. According to the results, in the case of low current density values and high concentrations of ethanol aqueous solutions, ethanol crossover could pose serious problems to the DEFC operation. Moreover, it was pointed out that the ethanol crossover rate dependence on the ethanol feed concentration is an almost linear function presenting a maximum at about . A further increase of the ethanol feed concentration leads to a steep decrease of ethanol crossover rate. This behavior could be attributed to the membrane swelling which is responsible for the membrane volume fraction decrement. It was also found that by the aid of the same model the performance of a direct ethanol PEM fuel cell over three different anode catalysts can be predicted. A relatively good agreement between theory and experimental results related to both ethanol crossover rates and direct ethanol fuel cell performance was found.     

Corrosion resistance and sintering effect of carbon supports in polymer electrolyte membrane fuel cells

The corrosion resistance of carbon black, carbon nanofiber and carbon nanocage used as catalyst supports in fuel cells was investigated by monitoring CO₂ emission using on-line mass spectrometry when 1.4 V was applied for 30 min. The changes associated with the carbon corrosion were assessed through electrochemical methods. In general, graphitized carbon supports were more corrosion-resistant than amorphous carbon black. However, the degree of graphitization did not directly correlate with higher resistance to corrosion. Hydrophobicity was critical in enhancing resistance to corrosion. When sintering of Pt particles was considered, carbon nanocages were more resistant than nanofibers. The present findings thus indicate that the carbon nanocage is an appropriate catalyst support in fuel cell systems.     

Importance of catalyst stability vis-à-vis hydrogen peroxide formation rates in PEM fuel cell electrodes

The role of catalyst stability on the adverse effects of hydrogen peroxide (H₂O₂) formation rates in a proton exchange membrane fuel cell (PEMFC) is investigated for Pt, Pt binary (PtX, X = Co, Ru, Rh, V, Ni) and ternary (PtCoX, X = Ir, Rh) catalysts supported on ketjen black (KB) carbon. The selectivity of these catalysts towards H₂O₂ formation in the oxygen reduction reaction (ORR) was measured on a rotating ring disc electrode. These measured values were used in conjunction with local oxygen and proton concentrations to estimate local H₂O₂ formation rates in a PEMFC anode and cathode. The effect of H₂O₂ formation rates on the most active and durable of these catalysts (PtCo and PtIrCo) on Nafion membrane durability was studied using a single-sided membrane electrode assembly (MEA) with a built-in reference electrode. Fluoride ion concentration in the effluent water was used as an indicator of the membrane degradation rate. PtIrCo had the least fluorine emission rate (FER) followed by PtCo/KB and Pt/KB. Though PtCo and PtIrCo show higher selectivity for H₂O₂ formation than unalloyed Pt, they did not contribute to membrane degradation. This result is explained in terms of catalyst stability as measured in potential cycling tests in liquid electrolyte as well as in a functional PEM fuel cell.     

Oxidation of carbon monoxide on poly-oriented and single-crystalline platinum electrodes over a wide range of pH

The oxidative stripping of pre-adsorbed carbon monoxide has been studied on poly-oriented platinum, and on Pt(1 1 1), Pt(1 0 0) and Pt(1 1 0) single-crystal electrodes in phosphate buffer solutions as a function of pH, both stripping voltammetry and chronoamperometry. It was found that the stripping peak potential has a tendency to decrease as a function of pH until a pH of ca. 10–11, which is ascribed to a weaker adsorption of phosphate on platinum with increasing pH. Above a pH of ca. 11, the stripping peak appears to stay constant or increase, depending on the surface structure. We hypothesize that this may be due to the fact that above a pH of ca. 10–11, the main product of carbon monoxide oxidation is carbonate, which may be block active sites on the surface. By comparison with the stripping on the single-crystalline Pt, the stripping voltammetry on the poly-oriented Pt electrode appears as a convolution of the oxidation on the different facets. A similar conclusion is drawn for the chronoamperometry experiments, and it is suggested that this may be the main reason for the asymmetrical transients observed on the poly-oriented Pt electrodes, as well as on other strongly heterogeneous Pt electrodes that have been studied in the literature.     

Diffusion study in a novel three-dimensional electrode for direct methanol fuel cells

A three-dimensional electrode formed by depositing Pt on polypyrrole treated polystyrene spheres (denoted as Pt/Ppy/PS) is prepared and characterized by different methods. The Pt/Ppy/PS prepared by using mixed polystyrene spheres of 200 nm-2 μm as support shows best performance for methanol oxidation due to the big and small holes or channels coexistent structure, which causes the difference in pressure inside the electrode and results in the reduction of the liquid sealing effect. The three-dimensional structure makes it easier for the liquid reactant to diffuse into the catalyst layer and the gaseous products evolve out from the catalyst layer. The diffusion behaviours of Pt/Ppy/PS and Pt/C electrodes are characterized by cyclic voltammetry. It is shown that the methanol oxidation on Pt/Ppy/PS electrode is not controlled by concentration polarization at slow scan rates, while the reaction on the traditional Pt/C electrode is diffusion controlled at all scan rates. The electrochemical impedance spectroscopic study (EIS) reveals that the three-dimensional electrode has higher active surface area.     

In situ deposition of platinum nanoparticles on bacterial cellulose membranes and evaluation of PEM fuel cell performance

In situ deposition of platinum (Pt) nanoparticles on bacterial cellulose membranes (BC) for a fuel cell application was studied. The platinum/bacterial cellulose (Pt/BC) membranes under different experimental conditions were characterized by using SEM (scanning electron microscopy), TEM (transmission electron microscopy), EDS (energy dispersive spectroscopy), XRD (X-ray diffractometry) and TG (thermo-gravimetric analysis) techniques. TEM images and XRD patterns both lead to the observation of spherical metallic platinum nanoparticles with mean diameter of 3–4 nm well impregnated into the BC fibrils. TG curves revealed these Pt/BC composite materials had the high thermal stability. The electrosorption of hydrogen was investigated by CV (cyclic voltammetry). It was found that Pt/BC catalysts have high electrocatalytic activity in the hydrogen oxidation reaction. The single cell performance of Pt/BC was tested at 20 °C, 30 °C, and 40 °C under non-humidified conditions. Preliminary tests on a single cell indicate that renewable BC is a good prospect to be explored as membrane in fuel cell field [B.R. Evans, H.M. O’Neill, V.P. Malyvanh, I. Lee, J. Woodward, Biosens. Bioelectron. 18 (2003) 917].     

Development of nano-electrocatalysts based on carbon nitride supports for the ORR processes in PEM fuel cells

This report describes the development and the optimization of new synthesis routes yielding electrocatalysts for the oxygen reduction reaction (ORR) aimed at application in proton exchange membrane fuel cells (PEMFCs). The preparation protocols consist in the synthesis of two groups of hybrid inorganic-organic precursors, characterized by a different concentration of nitrogen, which subsequently undergo a high-temperature pyrolysis in inert atmosphere, washing and activation. The resulting materials show a well-controlled stoichiometry. The nitrogen incorporated in the support transforms the matrix into a supramolecular ligand, and stabilizes the electrocatalyst by coordinating the active metal clusters. The latter are composed of an “active metal” such as Pt or Pd, combined with one or more “co-catalyst” elements such as Au, Fe, Co and Ni. An extensive characterization of the carbon nitride electrocatalysts under the chemical, structural, morphological and electrochemical points of view is described, together with their use in membrane electrode assemblies (MEAs) tested in single fuel cells under operative conditions. Results indicated that the best electrocatalysts are those characterized by a “core-shell” morphology. These systems consist of metal carbon nitride materials with a low concentration of nitrogen (shell) supported on electronically conductive graphite nanoparticles (core). Promising results were obtained both in terms of ORR overpotential (η) and of mass activity (A_m). Indeed, η resulted up to ∼30 mV lower with respect to reference Pt-based systems, and an A_m equal to 0.3-0.4 g of Pd or Pt to achieve 1 kW was reached.