Fe-based catalysts for oxygen reduction in proton exchange membrane fuel cells with cyanamide as nitrogen precursor and/or pore-filler

Fe/N/C catalysts for oxygen reduction reaction were synthesized via impregnation or ballmilling. The role of cyanamide (CM) as nitrogen precursor and/or pore-filler for a highly microporous carbon (Black Pearls 2000) was investigated. The use of CM in this work resulted in two main differences compared with phenanthroline from our previous work; (i) ballmilling the precursors did not result in improved activity of the resulting catalysts, and (ii) the activity after the first pyrolysis in argon was relatively high, but did not increase after a second pyrolysis in NH₃. These differences may be explained by TGA measurements of both pore-fillers, where complete gasification of CM is observed at temperatures above 750 °C in Ar, while pyrolysis of phenanthroline in Ar results in 20 wt% residual carbon-based material. Consequently, when using CM as pore-filler with a highly microporous carbon support, the maximum microporous surface area and nitrogen content is reached after only a single pyrolysis in Ar. The most active catalyst prepared with CM was obtained by pyrolysing in Ar at 950 °C a catalyst precursor containing 1 wt% Fe, 80 wt% CM and Black Pearls 2000. This catalyst possessed about 1/6th the catalytic activity of best reported using phenanthroline as a pore-filler. Changing the carbon support had effects on the activity and stability of the catalysts. The catalysts made with a non-porous furnace black (N330) or carbon nanotubes as a carbon support were more stable but less performing than those using carbon supports having high microporous surface area like Black Pearls 2000 or Ketjenblack. The desirable properties for a pore-filler molecule used in the synthesis of Fe/N/C-catalysts by the pore-filling method are discussed.     

Cobalt based non-precious electrocatalysts for oxygen reduction reaction in proton exchange membrane fuel cells

Cobalt based non-precious metal catalysts were synthesized using chelation of cobalt (II) by imidazole followed by heat-treatment process and investigated as a promising alternative of platinum (Pt)-based electrocatalysts in proton exchange membrane fuel cells (PEMFCs). Transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) measurements were used to characterize the synthesized CoN_x/C catalysts. The activities of the catalysts towards oxygen reduction reaction (ORR) were investigated by electrochemical measurements and single cell tests, respectively. Optimization of the heat-treatment temperature was also explored. The results indicate that the as-prepared catalyst presents a promising electrochemical activity for the ORR with an approximate four-electron process. The maximum power density obtained in a H₂/O₂ PEMFC is as high as 200 mW cm⁻² with CoN_x/C loading of 2.0 mg cm⁻².     

Studies of oxygen reduction reaction active sites and stability of nitrogen-modified carbon composite catalysts for PEM fuel cells

A non-precious nitrogen-modified carbon composite (NMCC) catalyst is synthesized by the pyrolysis of cobalt, iron-ethylenediamine-chelate complexes on silica followed by chemical and pyrolysis treatments. Pyrolysis temperature and time have a remarkable impact on the content and the type of the nitrogen-containing functional groups in the NMCC catalysts, which affect their catalytic activity and stability. Based on the analysis of the nitrogen functional groups before and after the stability tests, the ORR active sites of the NMCC catalysts are proposed to be pyridinic-N and quaternary-N functional groups. However the pyridinic-N group is not stable in the acidic environment due to the protonation reaction.     

Enhanced performance of CO poisoned proton exchange membrane fuel cells via triode operation

The effect of triode operation on the performance of CO poisoned PEM fuel cells was investigated. In this mode of operation a third, auxiliary, electrode is introduced in addition to the anode and the cathode. Application of electrolytic current in the auxiliary circuit, comprising the cathode and the auxiliary electrode was found to significantly enhance the time-averaged power output of a state-of-the-art PEMFC unit operating with a 70 ppm CO in H₂ atmospheric pressure mixture. Both normal and triode operation were found to lead to self-sustained current and potential oscillations in the fuel cell circuit over wide ranges of external resistive load. The time averaged increase in power output was found to be typically a factor of three higher than the power output in conventional fuel cell operation and up to a factor of 1.32 larger than the power sacrificed in the auxiliary circuit. The mechanism of the enhanced anodic electrocatalysis was investigated via the use of two reference electrodes and the results are discussed together with a possible design for application of the triode concept in stacks.     

Nanostructured Pt-M/C (M = Fe and Co) catalysts prepared by a microemulsion method for oxygen reduction in proton exchange membrane fuel cells

Nanostructured Pt-M/C (M = Fe and Co) catalysts have been synthesized by a microemulsion method and a high-temperature route. They have been characterized by cyclic voltammetry in 1 M H₂SO₄ and for oxygen reduction in proton exchange membrane fuel cells (PEMFC). The Pt-M alloy catalysts synthesized by the microemulsion method show higher electrochemical active surface area than those prepared by the high-temperature route, and some of them exhibit improved catalytic activity towards oxygen reduction compared to pure Pt. Among the various alloy catalysts investigated, the Pt-Co/C catalyst prepared by the microemulsion method shows the best performance with the maximum catalytic activity and minimum polarization loss. Mild heat treatment of the catalysts prepared by the microemulsion method at moderate temperatures (200 °C) in reducing atmosphere is found to improve the catalytic activity due to a cleaning of the surface and an increase in the electrochemical surface area.     

Development of gas diffusion layer using water based carbon slurry for proton exchange membrane fuel cells

The micro-porous layer of gas diffusion layers (GDLs) was fabricated with the carbon slurry dispersed in water containing sodium dodecyl sulfate (SDS), by wire rod coating process. The aqueous carbon slurry with micelle-encapsulation was highly consistent and stable without losing any homogeneity even after adding polytetrafluoroethylene (PTFE) binder for hundreds of hours. The surface morphology, contact angle and pore size distribution of the GDLs were examined using SEM, Goniometer and Hg Porosimeter, respectively. GDLs fabricated with various SDS concentrations were assembled into MEAs and evaluated in a single cell PEMFC under diverse operating relative humidity (RH) conditions using H₂/O₂ and H₂/air as reactants. The peak power density of the single cell using the GDLs with optimum SDS concentration was 1400 and 500 mW cm⁻² with H₂/O₂ and H₂/air at 90% RH, respectively. GDLs were also fabricated with isopropyl alcohol (IPA) based carbon slurry for fuel cell performance comparison. It was found that the composition of the carbon slurry, specifically SDS concentration played a critical role in controlling the pore diameter as well as the corresponding pore volumes of the GDLs.     

Numerical optimization of proton exchange membrane fuel cell cathodes

A fuel cell gradient-based optimization framework based on adaptive mesh refinement and analytical sensitivities is presented. The proposed approach allows for efficient and reliable multivariable optimization of fuel cell designs. A two-dimensional single-phase cathode electrode model that accounts for voltage losses across the electrolyte and solid phases and water and oxygen concentrations is implemented using an adaptive finite element formulation. Using this model, a multivariable optimization problem is formulated in order to maximize the current density at a given electrode voltage with respect to electrode composition parameters, and the optimization problem is solved using a gradient-based optimization algorithm. In order to solve the optimization problem effectively using gradient-based optimization algorithms, the analytical sensitivity equations of the model with respect to the design variables are obtained. This approach reduces the necessary computational time to obtain the gradients and improves significantly their accuracy when compared to gradients obtained using numerical sensitivities. Optimization results show a substantial increase in the fuel cell performance achieved by increasing platinum loading and reaching a Nafion mass fraction around 20-30 wt.% in the catalyst layer.     

The effect of nitrogen oxides in air on the performance of proton exchange membrane fuel cell

The effects of NO_x on the performance of proton exchange membrane (PEM) fuel cell were investigated through the introduction of a mixture containing NO and NO₂, in a ratio of 9:1, into the cathode stream of a single PEM fuel cell. The NO_x concentrations used in the experiments were 1480 ppm, 140 ppm and 10 ppm, which cover a range of three orders. The experimental results obtained from the tests of durability, polarization, reversibility and electrochemical impedance spectroscopy (EIS) showed a detrimental effect of NO_x on the cell performance. The electrochemical measurements results suggested that the impacts of NO_x are mainly resulted from the superposition of the oxygen reduction reaction (ORR), NO and HNO₂ oxidation reactions, and the increased cathodic impedance. Complete recovery of the cell performance was reached after operating the cell with clean air and then purging with N₂ for hours.     

Synthesis and characterization of Pd-Ni nanoalloy electrocatalysts for oxygen reduction reaction in fuel cells

Carbon-supported Pd-Ni nanoalloy electrocatalysts with different Pd/Ni atomic ratios have been synthesized by a modified polyol method, followed by heat treatment in a reducing atmosphere at 500-900 °C. The samples have been characterized by X-ray diffraction (XRD), energy dispersive spectroscopy (EDS), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV), rotating disk electrode (RDE) measurements, and single-cell proton exchange membrane fuel cell (PEMFC) tests for oxygen reduction reaction (ORR). XRD and TEM data reveal an increase in the degree of alloying and particle size with increasing heat-treatment temperature. XPS data indicate surface segregation with Pd enrichment on the surface of Pd₈₀Ni₂₀ after heat treatment at ≥500 °C, suggesting possible lattice strains in the outermost layers. Electrochemical data based on CV, RDE, and single-cell PEMFC measurement show that Pd₈₀Ni₂₀ heated at 500 °C has the highest mass catalytic activity for ORR among the Pd-Ni samples investigated, with stability and catalytic activity significantly higher than that found with Pd. With a lower cost, the Pd-Ni catalysts exhibit higher tolerance to methanol than Pt, offering an added advantage in direct methanol fuel cells (DMFC).     

CoPdx oxygen reduction electrocatalysts for polymer electrolyte membrane and direct methanol fuel cells

The electrochemical activity of carbon-supported cobalt-palladium alloy electrocatalysts of various compositions have been investigated for the oxygen reduction reaction in a 5 cm² single cell polymer electrolyte membrane fuel cell. The polarization experiments have been conducted at various temperatures between 30 and 60 °C and the reduction performance compared with data from a commercial Pt catalyst under identical conditions. Investigation of the catalytic activity of the CoPd_x PEMFC system with varying composition reveals that a nominal cobalt-palladium atomic ratio of 1:3, CoPd₃, exhibits the best performance of all studied catalysts, exhibiting a catalytic activity comparable to the commercial Pt catalyst. The ORR on CoPd₃ has a low activation energy, 52 kJ/mol, and a Tafel slope of approximately 60 mV/decade, indicating that the rate-determining step is a chemical step following the first electron transfer step and may involve the breaking of the oxygen bond. The CoPd₃ catalyst also exhibits excellent chemical stability, with the open circuit cell voltage decreasing by only 3% and the observed current decreasing by only 10% at 0.8 V over 25 h. The CoPd₃ catalyst also exhibits superior tolerance to methanol crossover poisoning than Pt.     

Calculation of reversible electrode heats in the proton exchange membrane fuel cell from calorimetric measurements

A calorimeter was used to measure the heat production in polymer electrolyte membrane (PEM) fuel cells operated on hydrogen and oxygen at 50 °C and 1 bar. Two cells were examined, one using a 35 μm thick Nafion membrane and a catalyst loading of 0.6/0.4 mg Pt cm⁻², for the cathode and anode layer, respectively, the other using a 180 μm thick Nafion membrane and loading of 0.4/0.4 mg Pt cm⁻². The cells investigated thus had different membranes and catalyst layers, but identical porous transport layers and micro-porous layers. The calorimeter is unique in that it provides the heat fluxes out of the cell, separately for the anode and the cathode sides. The corresponding cell potential differences, ohmic cell resistance and current densities are also reported. The heat fluxes through the current collector plates were decomposed by a thermal model to give the contributions from the ohmic and the Tafel heats to the total heat fluxes. Thus, the contributions from the reversible heat (the Peltier heats) to the current collectors were determined. The analysis suggests that the Peltier heat of the anode of these fuel cell materials is small, and that it is the cathode reaction which generates the main fraction of the total heat in a PEM fuel cell. The entropy change of the anode reaction appears to be close to zero, while the corresponding value for the cathode is near −80 J K⁻¹ mol⁻¹.     

Iron porphyrin-based cathode catalysts for polymer electrolyte membrane fuel cells: Effect of NH3 and Ar mixtures as pyrolysis gases on catalytic activity and stability

Ten different catalysts were prepared by loading 66 wt% ClFeTMPP on N330, a furnace grade carbon black, and pyrolyzing this catalyst precursor for 10 min at 950 °C in a NH₃/Ar gas mixture with various NH₃ volume fractions (from 0% to 100%). The activity and stability of these catalysts were measured in a fuel cell and compared. The only stable catalyst, although the least active, among these was the one pyrolyzed in pure Ar. A notable leap in catalytic activity, but drop in stability, was observed for all catalysts pyrolyzed in gas mixtures containing NH₃, even with a mere volume fraction of 1.3% NH₃ in the pyrolysis gas mixture. Catalytic activities increased, while stability decreased with increasing volume fraction of NH₃. The physicochemical properties of these catalysts were correlated with their electrochemical behaviour observed in fuel cell tests. It was found that a volume fraction of only 1.3% NH₃ was enough to double the micropore surface area, the surface nitrogen and iron concentrations in the resulting catalyst. Since the active sites are believed to be of the Fe/N/C type, the sharp increase in catalytic activity with as little as 1.3% NH₃ is attributed to the concurrent increase in microporous surface area, N and Fe surface contents in these catalysts. The only property that apparently correlates with stability is the degree of graphitization of the catalyst, which was estimated either from either X-ray diffraction and Raman spectroscopy measurements. Lastly, it was found that the catalysts’ peroxide yield, resulting from the partial reduction of O₂, does not correlate with their degree of stability.     

基于膜电极的质子交换膜微生物燃料电池

通过采用传统电化学燃料电池的技术和材料,以寻求提高微生物燃料电池的电流密度,制作基于膜电极的微生物燃料电池。通过构建温控压力机,制作了一系列膜电极(MEA),并对作为正极的多种碳材料进行了筛选。使用定制的玻璃微生物燃料电池来放置膜电极和培养Geobacter sulfurreducens,对产生的电流进行评价。细胞的生长以乙醇为唯一碳源,因而代表了一种新型的乙醇/氧气燃料电池。相比以前的设计,基于膜电极的微生物燃料电池的电极表面每个单位会多产生出100倍的电流,并且可以被长久使用。     

Engineering model for coupling wicks and electroosmotic pumps with proton exchange membrane fuel cells for active water management

We present theoretical and experimental studies of an active water management system for proton exchange membrane (PEM) fuel cells that uses integrated wicks and electroosmotic (EO) pumps. The wicks and EO pumps act in concert to remove problematic excess liquid water from the fuel cell. In a previous paper, we showed that this system increases maximum power density by as much as 60% when operating with low air stoichiometric ratios and a parallel channel flow field. The theoretical model we develop here accounts for several key factors specific to optimizing system performance, including the wick's hydraulic resistance, the variation of water pH, and the EO pump's electrochemical reactions. We use this model to illustrate the favorable scaling of EO pumps with fuel cells for water management. In the experimental portion of this study, we prevent flooding by applying a constant voltage to the EO pump. We experimentally analyze the relationships between applied voltage, pump performance, and fuel cell performance. Further, we identify the minimum applied pump voltage necessary to prevent flooding. This study has wide applicability as it also identifies the relationship between active water removal rate and flooding prevention.     

Preparation and characterization of carbon-supported PtVFe electrocatalysts

This paper reports the results of an investigation of the preparation and characterization of carbon-supported ternary PtVFe electrocatalysts. The catalysts were prepared by assembly of pre-synthesized PtVFe nanoparticles onto carbon support. The size, composition, and metal loading on carbon support were controllable. The carbon-supported PtVFe nanoparticles were further processed by thermal treatment, which were optimized for achieving effective shell removal and alloy formation. The structure and morphology of the catalysts were characterized using several techniques, including TEM, DCP-AES, FT-IR, TGA, and XRD. The catalysts were also examined for their intrinsic kinetic activities towards oxygen reduction reaction (ORR). The results have shown that the ternary catalysts are highly active for electrocatalytic ORR. Implications of our findings to applications in fuel cell catalysis are also discussed.     

Recent progress in direct ethanol proton exchange membrane fuel cells (DE-PEMFCs)

Direct ethanol fuel cells (DEFCs) belong to the family of proton exchange membrane fuel cells (PEMFCs), in which ethanol is directly used as the fuel. In the present work, the main aspects related to DEFCs such as electrocatalysts, membrane electrode assembly (MEA) preparation and their corresponding effects on the total cell performance are summarized and discussed. Furthermore, the issues about the disadvantages such as ethanol crossover and the electrolyte membrane's thermal and mechanical stability, as well as the challenges for DEFC's rapid development and commercialization are addressed.     

Water flooding and pressure drop characteristics in flow channels of proton exchange membrane fuel cells

Water flooding of the flow channels is one of the critical issues to the design and operation of proton exchange membrane fuel cells (PEMFCs). The liquid water and total pressure drop characteristics both in the anode and cathode parallel flow channels of an operating PEMFC were experimentally studied. The gas/liquid two-phase flow both in the anode and cathode flow channels was observed, and the total pressure drop between the inlet and outlet of the flow field was measured. The effects of cell temperature, current density and operating time on the total pressure drop were investigated. The results indicated that the total pressure drop in the flow channels mainly depends on the resistance of the liquid water in the flow channels to the gas flow, and the different flow patterns distinguish the total pressure drops in the flow field. Clogging by water columns result in a higher pressure drop in the flow channels. The total pressure drop measurement can be considered as an in situ diagnoses method to characterize the degree of the flow channels flooding. The liquid water in the cathode flow channels was much more than that in the anode flow channels. The pressure drop in the cathode flow channels was higher than that in the anode flow channels. During the fuel cell operation, the cell performance decreased gradually and the pressure drop both in the anode and the cathode flow channels increased. The rate of flooding at the cathode side reached 49.56% under experimental conditions after 78 min of operation. However, it was zero at the anode side.     

Synthesis of Pt nanocatalyst with micelle-encapsulated multi-walled carbon nanotubes as support for proton exchange membrane fuel cells

Micelle-encapsulated multi-walled carbon nanotubes (MWCNTs) with sodium dodecyl sulfate (SDS) were used as catalyst support to deposit platinum nanoparticles. High resolution transmission electron microscopy (HRTEM) images reveal the crystalline nature of Pt nanoparticles with a diameter of ∼4 nm on the surface of MWCNTs. A single proton exchange membrane fuel cell (PEMFC) with total catalyst loading of 0.2 mg Pt cm⁻² (anode 0.1 and cathode 0.1 mg Pt cm⁻², respectively) has been evaluated at 80 °C with H₂ and O₂ gases using Nafion-212 electrolyte. Pt/MWCNTs synthesized by using modified SDS-MWCNTs with high temperature treatment (250 °C) showed a peak power density of 950 mW cm⁻². Accelerated durability evaluation was carried out by conducting 1500 potential cycles between 0.1 and 1.2 V with 50 mV s⁻¹ scan rate, H₂/N₂ at 80 °C. The membrane electrode assembly (MEA) with Pt/MWCNTs showed superior performance stability with a power density degradation of only ∼30% compared to commercial Pt/C (70%) after potential cycles.     

直接甲醇燃料电池用阻醇质子交换膜研究进展

直接甲醇燃料电池是近十年兴起的新型燃料电池,并以其独特的优点引起了人们广泛的关注。作为其重要组成部分的质子交换膜的性质是影响电池性能的关键因素。本文在介绍近两年质子交换膜研究最新进展的基础上,综述了天然聚合物用作质子交换膜材料的研究情况,并分析了其优劣势及应用前景。