Investigation of mass transport in gas diffusion layer at the air cathode of a PEMFC

In a polymer electrolyte membrane fuel cell (PEMFC), slow diffusion in the gas diffusion electrode may induce oxygen depletion when using air at the cathode. This work focuses on the behavior of a single PEMFC built with a Nafion^® based MEA and an E-TEK gas diffusion layer and fed at the cathode with nitrogen containing 5, 10 and 20% of oxygen and working at different cell temperatures and relative humidities. The purpose is to apply the experimental impedance technique to cells wherein transport limitations at the cathode are significant. In parallel, a model is proposed to interpret the polarization curves and the impedance diagrams of a single PEMFC. The model accounts for mass transport through the gas diffusion electrode. It allows us to qualitatively analyze the experimental polarization curves and the corresponding impedance spectra and highlights the intra-electrode processes and the influence of the gas diffusion layer.     

PEMFC流道横截面二维两相流数学模型(Ⅰ)模型建立

建立了质子交换膜燃料电池（PEMFC）流道和脊横截面的二维两相流数学模型（across-the-channel model）。模型描述了PEMFC主要的传递和反应过程,包括阴、阳两极反应气的质量传递、动量传递、电子和质子的传递以及电化学反应等。模型细致地描述了水（液态和气态）在扩散层、催化层以及质子交换膜中的传递过程。模型可以用来研究流场、扩散层、催化层以及膜等对电池性能的影响,进而达到优化电池结构的目的。     

A three-dimensional numerical simulation of the transport phenomena in the cathodic side of a PEMFC

A three-dimensional numerical model is developed to simulate the transport phenomena on the cathodic side of a polymer electrolyte membrane fuel cell (PEMFC) that is in contact with parallel and interdigitated gas distributors. The computational domain consists of a flow channel together with a gas diffusion layer on the cathode of a PEMFC. The effective diffusivities according to the Bruggman correlation and Darcy's law for porous media are used for the gas diffusion layer. In addition, the Tafel equation is used to describe the oxygen reduction reaction (ORR) on the catalyst layer surface. Three-dimensional transport equations for the channel flow and the gas diffusion layer are solved numerically using a finite-volume-based numerical technique. The nature of the multi-dimensional transport in the cathode side of a PEMFC is illustrated by the fluid flow, mass fraction and current density distribution. The interdigitated gas distributor gives a higher average current density on the catalyst layer surface than that with the parallel gas distributor under the same mass flow rate and cathode overpotential. Moreover, the limiting current density increased by 40% by using the interdigitated flow field design instead of the parallel one.     

One‐dimensional Model of Oxygen Transport Impedance Accounting for Convection Perpendicular to the Electrode

A one‐dimensional (1D) model of oxygen transport in the diffusion media of proton exchange membrane fuel cells (PEMFC) is presented, which considers convection perpendicular to the electrode in addition to diffusion. The resulting analytical expression of the convecto‐diffusive impedance is obtained using a convection–diffusion equation instead of a diffusion equation in the case of classical Warburg impedance. The main hypothesis of the model is that the convective flux is generated by the evacuation of water produced at the cathode which flows through the porous media in vapor phase. This allows the expression of the convective flux velocity as a function of the current density and of the water transport coefficient α (the fraction of water being evacuated at the cathode outlet). The resulting 1D oxygen transport impedance neglects processes occurring in the direction parallel to the electrode that could have a significant impact on the cell impedance, like gas consumption or concentration oscillations induced by the measuring signal. However, it enables us to estimate the impact of convection perpendicular to the electrode on PEMFC impedance spectra and to determine in which conditions the approximation of a purely diffusive oxygen transport is valid. Experimental observations confirm the numerical results.     

Reduction of metal ions in dilute solutions using a GBC-reactor Part II: Theoretical model for the hydrogen oxidation in a gas diffusion electrode at relatively low current densities

The GBC-reactor is based on the combination of a gas diffusion anode and a porous cathode. A theoretical model for gas diffusion electrode, valid at relatively low current densities, is derived. This is based on the pseudohomogeneous film model including an approximation of the Volmer–Tafel mechanism for the hydrogen oxidation kinetics. Results show a severe mass transfer limitation of the hydrogen oxidation reaction inside the active layer of the gas diffusion electrode, even at low current densities. Empirical formulae are given to estimate whether leakage of dissolved hydrogen gas into the bulk electrolyte occurs at specific process conditions. A simplified version of the model, the reactive plane approximation, is presented.     

A “proton pump” concept for the investigation of proton transport and anode kinetics in proton exchange membrane fuel cells

A novel concept for the measurement of proton transport properties and electrode kinetics in proton exchange membrane fuel cells (PEMFC) is presented. The “proton pump” is essentially a fuel cell operated with pure nitrogen or very low hydrogen partial pressure instead of oxygen-containing gas on the cathode side, avoiding the complicated electrode kinetics of oxygen reduction. In this first study using this concept, we investigated the proton transport in high temperature PEMFC based on polybenzimidazole (PBI)/phosphoric acid membranes. The impedance spectra of the proton pump allow the clear distinction between anode and cathode kinetics and proton transport in the membrane. Identifying and analyzing the contribution of the anodic processes in the impedance spectra enabled the quantitative investigation of anode kinetics based on the Butler-Volmer equation. The proton transport was investigated in more detail in the current saturation region, where proton transport turned out to be the limiting process in case of sufficient H₂ supply at the anode. The maximum proton transport capacity of the PBI/phosphoric acid membrane was found to be comparable to those of Nafion^® membranes.     

质子交换膜燃料电池膜中气态水管理模型

分析质子交换膜燃料电池的膜水含量与运行参数的关系,从工程方法的角度建立水传输模型.模型分析得到,要提高膜的水合程度,需要通过增湿反应气体.过高的增湿反应气体又会引起阴极扩散层水的泛滥,需通过调节反应气体流量来缓解水的泛滥.为保证膜的高水合程度和低的阴极扩散层水的泛滥,建立了膜水含量的神经网络控制模型,为电池水管理奠定了基础.     

Optimization of cathode catalyst layer for direct methanol fuel cells: Part II: Computational modeling and design

The cathode catalyst layer in direct methanol fuel cells (DMFCs) features a large thickness and mass transport loss due to higher Pt loading, and therefore must be carefully designed to increase the performance. In this work, the effects of Nafion loading, porosity distribution, and macro-pores on electrochemical characteristics of a DMFC cathode CL have been studied with a macro-homogeneous model, to theoretically interpret the related experimental results. Transport properties in the cathode catalyst layers are correlated to both the composition and microstructure. The optimized ionomer weight fraction (22%) is found to be much smaller than that in H₂ polymer electrolyte fuel cells, as a result of an optimum balance of proton transport and oxygen diffusion. Different porosity distributions in the cathode CLs are investigated and a stepwise distribution is found to give the best performance and oxygen concentration profile. Influence of pore defects in the CLs is discussed and the location of macro-pores is found to play a dual role in affecting both oxygen transport and proton conduction, hence the performance. The reaction zone is extended toward the membrane side and the proton conduction is facilitated when the macro-pores are near the gas diffusion layer.     

Diagnosis of specific surface area in fuel cell air electrodes

A model of the air electrode used in fuel cells was developed which accounts for the diffusion of oxygen in the gas-filled pores as well as diffusion into the liquid-filled pores, and electrochemical reaction. The model was applied to the air electrode in the phosphoric acid fuel cell (PAFC) to simulate the cathode performance under a variety of conditions. Two parameters AB and AI were introduced into the model. They reflect, respectively, the effects of the interfacial surface area between the gas and liquid phases and those of the interfacial surface area between the liquid and solid phases, on the air electrode performance. AB and AI can be determined with the aid of the operating conditions and potential–current density curves of the air electrode. The main interface parameters of the air electrode can be predicted following the determination of AB and AI. The reaction rate throughout the catalyst layer was calculated by means of the model.     

Determination of overall mass transport coefficients in gas diffusion electrodes

Gas diffusion electrodes are used for many purposes, for example in fuel cells, in synthesis and as anodes in electrodeposition processes. The behaviour of gas diffusion electrodes has been the subject of many studies. In this work the transport of gas in the gas diffusion electrode, characterized by the overall mass transport coefficient, has been investigated using hydrogen-nitrogen mixtures. A reactor model for the gas compartment of the gas diffusion electrode test cell is proposed to calculate the concentration of hydrogen in the gas compartment as a function of the input concentration of hydrogen and the total volumetric gas flow rate. The mass transport coefficient is found to be independent of variations in hydrogen concentration and volumetric gas flow rate. The temperature dependence of the mass transport coefficient has been determined. A maximum was found at 40°C.Notation Agd geometric electrode surface area (m²) - C _in concentration of reactive component at the inlet of the gas compartment (mol m^–3) - c _out concentration of reactive component at the outlet of the gas compartment (mol m^–3) - E potential (V) - E _e equilibrium potential (V) - E _t upper limit potential (V) - F _v volumetric flow rate (m^–3 s^–1) - F _v,H volumetric flow rate of hydrogen (m^–3 s^–1) - F _v,N volumetric flow rate of nitrogen (m^–3 s^–1) - F _vin volumetric flow rate at the inlet of the gas compartment (m^–3 s^–1) - F _v,out volumetric flow rate at the outlet of the gas compartment (in ^–3 s^–1) - F _v,reaction volumetric flow rate of reactive component into the gas diffusion electrode (m^–3 s^–1) - Faraday constant (A s mo^–1) - I _gd current for gas diffusion electrode (A) - i _gd current density for gas diffusion electrode (A m^–2) - I _gd,1 diffusion limited current for gas diffusion electrode (A) - i _gd,1 diffusion limited current density for gas diffusion electrode (A m^–2) - I _gd,1,calc calculated diffusion limited current for gas diffusion electrode (A) - i _gd,1,calc calculated diffusion limited current density for gas diffusion electrode (A m^–2) - I _hp current for hydrogen production (A) - k _s mass transport coefficient calculated from c _out (m s^–1) - n number of electrons involved in electrode reaction - T temperature (°C) - V _m molar volume of gas (m³ mol^–1) - overpotential (V)     

Modelling and experimental validation of a high temperature polymer electrolyte fuel cell

A steady-state, isothermal, one dimensional model of a proton exchange membrane fuel cell (PEMFC), with a polybenzimidazole (PBI) membrane, was developed. The electrode kinetics were represented by the Butler–Volmer equation, mass transport was described by the multi-component Stefan–Maxwell equations and Darcy’s law and the ionic and electronic resistances described by Ohm’s law. The model incorporated the effects of temperature and pressure on the open circuit potential, the exchange current density and diffusion coefficients, together with the effect of water transport across the membrane on the conductivity of the PBI membrane. The polarisation curves predicted by the model were validated against experimental data for a PEMFC operating in the temperature range of 125–200 °C. There was good agreement between experimental and model data of the effect of temperature and oxygen/air pressure on cell performance. The model was used to simulate the effect of catalyst loading and the Pt/carbon ratio on cell performance and, in the latter case, a 40 wt.% Pt/C ratio gave the highest peak power density.     

Development and electrochemical studies of gas diffusion electrodes for polymer electrolyte fuel cells

Electrochemical studies on low catalyst loading gas diffusion electrodes for polymer electrolyte fuel cells are reported. The best performance is obtained with an electrode formed from 20 wt% Pt/C, 0.4 mg Pt cm^–2 and 1.1 mg Nafion^® cm^–2 in the catalyst layer and 15% PTFE in a diffusion layer of 50 µm thickness, for both the cathode and the anode. However, it is also observed that the platinum requirement can be diminished to values close to 0.2 mg Pt cm^–2 in the cathode and 0.1 mg pt cm^–2 in the anode, without appreciably affecting the good characteristics of the fuel cell response. The experimental fuel cell data were analysed using theoretical models of the electrode structure and of the fuel cell system. It is seen that most of the electrode systems present limiting currents and some also show linear diffusion components arising from diffusion limitations in the gas channels and/or in the thin film of electrolyte covering the catalyst particles.     

A Simple and Accurate Method for High‐Temperature PEM Fuel Cell Characterisation

A set of basic parameters for any polymer electrolyte membrane fuel cell (PEMFC) includes the Tafel slope b and the exchange current density j_* of the cathode catalyst, the oxygen diffusion coefficient D_b in the cathode gas‐diffusion layer and the cell resistivity R_cell. Based on the analytical model of a PEMFC [A. A. Kulikovsky, Electrochim. Acta (2004) 617], we propose a two‐step procedure allowing to evaluate these parameters for a high‐temperature PEMFC. The procedure requires two polarisation curves measured at different oxygen (air) stoichiometries. The method is validated using the experimental data obtained with the in‐house designed cell. High quality of fitting confirms validity and accuracy of this approach. The physical background of the method is discussed.     

A critical look into effects of electrode pore morphology in solid oxide fuel cells

Knudsen diffusion, an important form of gas transport in sub‐micro/nanoscale porous electrodes of solid oxide fuel cells (SOFCs), is evaluated typically based on the assumption of isotropic cross‐sections of electrode pores. As a consequence, errors are induced in the evaluation of gas transport and polarization loss of SOFCs with irregular, anisotropic pore morphology. Here, a numerical model is derived to investigate the impact of pore morphology on Knudsen diffusivity and effective total diffusivity in porous SOFC electrodes. Based on the model, the correlation between pore morphology and important parameters of SOFCs, including limiting current density (LCD) and concentration polarization (CP), is evaluated. As the aspect ratio of pore cross‐section increases, the gas diffusivity in SOFC electrodes decreases, and then nontrivial variations in LCD and CP are induced. This work facilitates the accurate evaluation of gas transport in SOFCs as well as the rational design of electrode microstructure of SOFCs. © 2016 American Institute of Chemical Engineers AIChE J, 63: 2312–2317, 2017     

Electrosynthesis of nitroso compounds from (<Emphasis Type="Italic">1</Emphasis><Emphasis Type="Bold">S</Emphasis>, <Emphasis Type="Italic">2</Emphasis><Emphasis Type="Bold">S</Emphasis>)-2-amino-l-(4-nitrophenyl)-propane-1,3-diol derivatives

Nitroso compounds were electrogenerated from (1S, 2S)-2-amino-1-(4-nitrophenyl)-propane-1,3-diol derivatives (derivatives of p-nitrophenylserinol) in a “redox” flow cell equipped with two consecutive porous electrodes of opposite polarities. In spite. of the relative instability in methanol-acetate buffer of the hydroxylamine intermediates produced at the first porous electrode (cathode), the nitroso derivatives were prepared in good yields at the second one (anode). A coupling reaction between some nitroso derivatives and p-toluenesulphinic acid led to N-sulphonylphenylhydroxylamines.     

In situ grown carbon nanotubes on carbon paper as integrated gas diffusion and catalyst layer for proton exchange membrane fuel cells

In situ grown carbon nanotubes (CNTs) on carbon paper as an integrated gas diffusion layer (GDL) and catalyst layer (CL) were developed for proton exchange membrane fuel cell (PEMFC) applications. The effect of their structure and morphology on cell performance was investigated under real PEMFC conditions. The in situ grown CNT layers on carbon paper showed a tunable structure under different growth processes. Scanning electron microscopy (SEM) and Brunauer–Emmett–Teller (BET) demonstrated that the CNT layers are able to provide extremely high surface area and porosity to serve as both the GDL and the CL simultaneously. This in situ grown CNT support layer can provide enhanced Pt utilization compared with the carbon black and free-standing CNT support layers. An optimum maximum power density of 670 mW cm⁻² was obtained from the CNT layer grown under 20 cm³ min⁻¹ C₂H₄ flow with 0.04 mg cm⁻² Pt sputter-deposited at the cathode. Furthermore, electrochemical impedance spectroscopy (EIS) results confirmed that the in situ grown CNT layer can provide both enhanced charge transfer and mass transport properties for the Pt/CNT-based electrode as an integrated GDL and CL, in comparison with previously reported Pt/CNT-based electrodes with a VXC72R-based GDL and a Pt/CNT-based CL. Therefore, this in situ grown CNT layer shows a great potential for the improvement of electrode structure and configuration for PEMFC applications.     

Electrochemical nucleation and growth of copper on chromium-plated electrodes

Nucleation and growth of copper electrodeposited on chromium plated electrodes in copper sulfate electrolytes were examined, focusing on the influence of prior Cr plating conditions on the nucleation density and growth kinetics of the copper electrodeposits. The Cr-plated electrodes were made by electrodeposition of Cr on copper sheets for 2 to 60 s at 0.1 A cm^–2 in CrO₃ 350 g L^–1 + H₂SO₄ 3.5 g L^–1. Copper was then electrodeposited onto the Cr-plated electrode under potentiostatic conditions. Copper initially nucleated and grew according to a three-dimensional diffusion controlled progressive nucleation process, and later according to an instantaneous nucleation process. The period during which copper nucleation is controlled by the diffusion controlled progressive nucleation process decreases with increasing Cr plating time. The nucleation density of copper was extremely high on the 2 s Cr-plated electrode, producing an extremely fine and uniform electrodeposit. However, on the 4 s Cr-plated electrode, the nucleation density of copper significantly reduced to one hundredth of that on the 2 s Cr-plated electrode, and then decreased slightly with increasing Cr plating time (thickness of Cr layer). These results appear to be associated with the IR drop across the Cr layer, including the surface Cr oxide/hydroxide film (termed the cathode film), which significantly reduces the driving force for the electrodeposition of copper under potentiostatic plating conditions.     

Model‐Based Ex Situ Diagnostics of Water Fluxes in Catalyst Layers of Polymer Electrolyte Fuel Cells

The ability to predict the electrochemical performance of the cathode catalyst layer in a polymer electrolyte fuel cell hinges on a precise knowledge of water distribution and fluxes. Water transport mechanisms that must be accounted for include vapor diffusion, liquid water permeation and vaporization exchange. In order to facilitate experimental efforts to this effect, we propose an ex situ model of water fluxes in catalyst layers. The model formulation is similar to transmission line models that are widely used in the analysis of electrochemical impedance spectra of porous composite electrodes. Focusing in this article on steady state and isothermal conditions, we rationalize the response function between defined environmental conditions, i.e. gas pressures, partial vapor pressures and temperature, which are defined at the boundaries of the catalyst layer, and the net water flux. This response function provides diagnostic capabilities to isolate and extract water transport parameters of catalyst layers from measurements of water fluxes through membrane electrode assemblies or half cell systems. An important asset of the model is the ability to analyze catalyst layer transport properties under partial saturation.