Oxygen mass transport limitations at the cathode of polymer electrolyte membrane fuel cells

Oxygen transport across the cathode gas diffusion layer (GDL) in polymer electrolyte membrane (PEM) fuel cells was examined by varying the O₂/N₂ ratio and by varying the area of the GDL extending laterally from the gas flow channel under the bipolar plate (under the land). As the cathode is depleted of oxygen, the current density becomes limited by oxygen transport across the GDL. Oxygen depletion from O₂/N₂ mixtures limits catalyst utilization, especially under the land.The local current density with air fed PEM fuel cells falls to practically zero at lateral distances under the land more than 3 times the GDL thickness; on the other hand, catalyst utilization was not limited when the fuel cell cathode was fed with 100% oxygen. The ratio of GDL thickness to the extent of the land is thus critical to the effective utilization of the catalyst in an air fed PEM fuel cell. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

Two-phase transport and the role of micro-porous layer in polymer electrolyte fuel cells

Two-phase transport of reactants and products constitutes an important limit in performance of polymer electrolyte fuel cells (PEFC). Particularly, at high current densities and/or low gas flow rates, product water condenses in open pores of the cathode gas diffusion layer (GDL) and limits the effective oxygen transport to the active catalyst sites. Furthermore, liquid water covers some of the active catalytic surface, rendering them inactive for electrochemical reaction. Traditionally, these two-phase transport processes in the GDL are modeled using so-called unsaturated flow theory (UFT), in which a uniform gas-phase pressure is assumed across the entire porous layer, thereby ignoring the gas-phase flow counter to capillarity-induced liquid motion. In this work, using multi-phase mixture (M²) formalism, the constant gas pressure assumption is relaxed and the effects of counter gas-flow are studied and found to be a new oxygen transport mechanism. Further, we analyze the multi-layer diffusion media, composed of two or more layers of porous materials having different pore sizes and/or wetting characteristics. Particularly, the effects of porosity, thickness and wettability of a micro-porous layer (MPL) on the two-phase transport in PEFC are elucidated.     

Investigation of Channel‐to‐Channel Cross Convection in Serpentine Flow Fields

Channel‐to‐channel cross convection in serpentine flow fields of polymer electrolyte fuel cells (PEFC) can influence the overall cell performance. The effect strongly depends on the gas transport properties of the gas diffusion layer (GDL). For the first time measured anisotropic, compression dependent permeability and effective diffusivity of GDLs are used to quantify the influence of cross convection on the local current distribution and performance. A model was developed to examine different channel‐rib geometries and GDL characteristics. The results show that cross convection can significantly increase the current density and consequently the power density of PEFCs. A strong sensitivity to GDL compression, flow velocity and rib width was found. As an optimised case the GDL thickness under the rib was increased resulting in about 20% higher current densities. Precise knowledge of the GDL characteristics and its compression are key to understand channel‐to‐channel cross convection and optimise perfomance.     

PEM燃料电池阴极中的液态水及其影响因素

阴极多孔介质中液态水的含量对PEM燃料电池阴极中的传质及其性能具有极其重要的影响。提出了一个二维、两相、稳态数学模型,研究PEM燃料电池阴极中两相水的传递及其对电池性能的影响。模型耦合了连续方程、动量方程和组分守恒方程,并将质子膜中的净水迁移通量作为边界条件之一来处理。通过实验的方法和数值模拟的方法,研究了电池操作压力和温度对电池性能的影响,同时验证了模型的有效性。模拟发现:提高操作压力和升高阴极加湿温度使电池阴极催化剂层(CTL)和扩散层(GDL)界面上的液态水含量大幅提高;升高阳极加湿温度,电池阴极CTL和GDL界面上的液态水含量变化不明显;而升高燃料电池的操作温度,阴极CTL和GDL界面上液态水的含量降低。     

PEMFC带沟槽气体扩散层内传输特性孔隙网络模拟

采用三维孔隙网络模型计算了不同沟槽参数下气体扩散层(GDL)的液态水突破压力、毛细压力分布、气体扩散率和液相相对渗透率随饱和度变化,并从孔隙尺度角度探究了沟槽的作用机制。研究结果表明:沟槽改变了GDL的毛细压力分布,提供了液态水直接传输路径并优化了GDL内氧气和液态水的分布,从而提高了氧气有效扩散率。沟槽位置对氧气传输有明显影响,对液相传输的影响取决于是否形成贯穿GDL的传输路径;沟槽加深,氧气和液态水传输性能增强,沟槽穿透GDL时传输性能达到最佳;沟槽变宽,液相传输性能增强,氧气传输性能在低饱和度范围内先增强后减弱。综合各因素,给出了氧气和液态水传输性能最优时的沟槽参数。     

Analysis of GDL flooding effects on PEMFC performance

One of the major concerns of the gas diffusion layer (GDL) inside a proton exchange membrane fuel cell (PEMFC) is water management. Treatment of the pores of the GDL can affect the PEMFC performance due to the degree of water flooding inside the GDL. In this work, GDL flooding was investigated using a simplified approach in an established numerical model. The predictions are compared with experimental data of GDLs with different treatments. Local distributions inside the cell are given and the effect of homogenous GDL flooding on these is discussed.     

质子交换膜燃料电池两维、两相流动模型

提出了考虑电池内部两相流动的质子交换膜燃料电池数学模型,模拟了阳极、阴极两侧的流道和扩散层中同时发生两相流动时电池内部的各种传递特性,并用实验数据验证了该模型的准确性。模拟结果显示,当电池阴极扩散层中有液态水存在时会大大降低膜中的局部电流密度;质子交换膜中水的净通量方向可正、可负,因此电池的增湿策略应根据不同的运行工况而不断变化。     

Effects of GDL Structure with an Efficient Approach to the Management of Liquid water in PEM Fuel Cells

A model fuel cell with a single transparent straight flow channel and segmented anode was constructed to measure the direct correlation of liquid water movement with the local currents along the flow channel. Water drops emerge through the largest pores of the GDL with the size of the droplets that emerge on the surface determined by the size of the pore and its location under the gas flow channel or under the land. Gravity, surface tension, and the shearing force from the gas flow control the movement of liquid in the gas flow channel. By creating a single large diameter pore in the GDL, liquid water flow emergent from the GDL was forced to be in specific locations along the length of the channel and either under the land or under the channel. The effects of gravity were amplified when the large pore was under the channel, but diminished with the large pore under the land. Current fluctuations were minimised when the dominant water transport from the GDL pore was near the cathode outlet. The results show that it is possible to engineer the water distribution in PEM fuel cells by modifying the pore sizes in the GDL.     

Effect of hydrophobicity and pore geometry in cathode GDL on PEM fuel cell performance

The effect of hydrophobic and structural properties of a single/dual-layer cathode gas diffusion layer on mass transport in PEM fuel cells was studied using an analytical expression. The simulations indicated that liquid water transport at the cathode is controlled by the fraction of hydrophilic surface and the average pore diameter in the cathode gas diffusion layer. Deposition of a hydrophobic microporous layer reduces the average pore diameter in the macroporous substrate. It also increases the hydrophobic surface, which improves the mass transport of the reactant. The optimized hydrophobicity and pore geometry in a dual-layer cathode GDL leads to an effective water management, and enhances the oxygen diffusion kinetics.     

A Two‐dimensional Network Study on Oxygen Transport in Porous Gas Diffusion Layer

Oxygen transport in the porous gas diffusion layer (GDL), which is generally characterised by the oxygen effective diffusivity, is of great importance for the performance of proton exchange membrane fuel cells (PEMFCs). The determination of the oxygen effective diffusivity is challenging due to the complex structure of the porous GDL samples. In the present study, a two‐dimensional network consisting of arms and nodes is adopted to illustrate how oxygen effective diffusivity is affected by the GDL structure under the condition with/without water invasion. Water permeation in the network is simulated using the invasion percolation algorithm and oxygen transport in the arms is described by Fick's law. The simulation results reveal that oxygen effective diffusivity under dry condition decreases with increase in the network heterogeneity. With water permeation, the oxygen effective diffusivity goes to zero even though water saturation is rather less than unity. The critical water saturation, above which the oxygen effective diffusivity becomes zero, is found to decrease with increasing heterogeneity. To enhance oxygen transport, four different modified networks are introduced in the present study. It is found that the network with large arms in oxygen transport direction has the best oxygen and water transport properties.     

Determination of oxygen effective diffusivity in porous gas diffusion layer using a three-dimensional pore network model

In proton exchange membrane fuel cell (PEMFC) models, oxygen effective diffusivity is the most important parameter to characterize the oxygen transport in the gas diffusion layer (GDL). However, its determination is a challenge due to its complex dependency on GDL structure. In the present study, a three-dimensional network consisting of spherical pores and cylindrical throats is developed and used to investigate the effects of GDL structural parameters on oxygen effective diffusivity under the condition with/without water invasion process. Oxygen transport in the throat is described by Fick's law and water invasion process in the network is simulated using the invasion percolation with trapping algorithm. The simulation results reveal that oxygen effective diffusivity is slightly affected by network size but increases with decreasing the network heterogeneity and with increasing the pore connectivity. Impacts of network anisotropy on oxygen transport are also investigated in this paper. The anisotropic network is constructed by constricting the throats in the through-plane direction with a constriction factor. It is found that water invasion has a more severe negative influence on oxygen transport in an anisotropic network. Finally, two new correlations are introduced to determine the oxygen effective diffusivity for the Toray carbon paper GDLs.     

Understanding Water Transport in Polymer Electrolyte Fuel Cells Using Coupled Continuum and Pore‐Network Models

Water management remains a critical issue for polymer electrolyte fuel cell performance and durability, especially at lower temperatures and with ultrathin electrodes. To understand and explain experimental observations better, water transport in gas diffusion layers (GDLs) with macroscopically heterogeneous morphologies was simulated using a novel coupling of continuum and pore‐network models. X‐ray computed tomography was used to extract GDL material parameters for use in the pore‐network model. The simulations were conducted to explain experimental observations associated with stacking of anode GDLs, where stacking of the anode GDLs increased the limiting current density. Through imaging, it is shown that the stacked anode GDL exhibited an interfacial region of high porosity. The coupled model shows that this morphology allowed more efficient water movement through the anode and higher temperatures at the cathode compared to the single GDL case. As a result, the cathode exhibited less flooding and hence better low temperature performance with the stacked anode GDL.     

On the modeling of water transport in polymer electrolyte membrane fuel cells

Water management is a critical issue in polymer electrolyte membrane (PEM) fuel cells, and water transport through the membrane, catalyst layer and gas diffusion layer has significant impact on the cell performance and durability. In this study, the mechanism of water transport processes in PEM fuel cells has been analyzed through 3-D unsteady non-isothermal simulations, along with a comprehensive examination of various modeling approaches in literature. It is shown that the finite rates of sorption/desorption of water in membrane affect the cell current output and the cell response time. Water dissolved in the membrane should be taken as the proper mechanism of water formation in the cathode of practical PEM fuel cells. Capillary pressure and relative permeability have significant impact on the distribution of liquid water saturation and transport, implying a need for their determination under specific PEM fuel cell conditions.     

Anisotropic, effective diffusivity of porous gas diffusion layer materials for PEFC

A comparative, experimental diffusivity study of gas diffusion layer (GDL) materials for polymer electrolyte fuel cells (PEFC) is presented for the first time. The GDL plays an important role for electrochemical losses due to gas transport limitations at high current densities. Characterization and optimization of these layers is therefore essential to improve power density. A recently developed method which allows for fast diffusimetry is applied and data compared to the literature values. Measurements are made as a function of direction and compression and the effect of different binder structures and hydrophobic treatments on effective diffusivities are discussed. A better understanding of the results is gained by including novel GDL cross-section images and a meaningful unit cell model for the interpretation of the data. The diffusivity data is valuable for GDL manufacturers and future PEFC models. The study reveals that a binder-fiber ratio larger than 50% has a negative impact on the effective diffusion properties. The hydrophobic treatment which is necessary to improve the water management can impede diffusion and thus reduce the power density. Furthermore binder has an isotropic effect while compression pronounces the in-plane orientation of the fibers.     

Effects of hydrophobic polymer content in GDL on power performance of a PEM fuel cell

Effects of hydrophobic polymer content within a carbon paper, used as the cathode gas diffusion layer (GDL), on power performance of a H₂/air proton exchange membrane fuel cell (PEMFC) have been studied. Electrochemical methods are used in conjunction with morphology and wetting property characterization. Surface contact angle of wet-proof-treated GDL as a function of temperature is measured by a novel capillary rise method. It is shown that the contact angle generally decreases with the temperature, and that there is insignificant difference in contact angle on carbon papers treated with different contents of fluorinated ethylene propylene (FEP) ranging from 10 to 40 wt.%. Under all humidification conditions in this study, a membrane-electrode assembly (MEA) consisting of 10 wt.% FEP-impregnated GDL shows higher power densities than 30 wt.% FEP-impregnated one. Surface morphology of the hydrophobic polymer-treated carbon paper has been analyzed by scanning electron microscopy (SEM) and is identified as playing a crucial role in affecting the power performance of such treated GDL in the PEM fuel cell.     

PEMFC阴极扩散层结构特性对水淹影响的数值分析

建立质子交换膜燃料电池一维两相传递模型,通过达西定律和菲克定律的联立求解得到扩散层中的液体饱和度和氧气浓度分布。考察扩散层特性参数孔隙率、厚度、接触角、渗透率对阴极水淹的影响,结果表明扩散层表面憎水将有助于液态水移出,但当达到憎水条件后,增大接触角对液态水传输和氧气传质的影响逐渐变小。憎水条件下孔隙率和厚度对液态水传输的影响不是很明显,但孔隙率增大和扩散层厚度减小均有利于氧气传质,实际应用中孔隙率增大的同时,厚度也要适当增大,极限电流密度相差不大。模型计算结果与文献中不同PTFE含量条件下实验的Tafel斜率和极限电流密度比较,吻合较好。     

Non-isothermal effects of single or double serpentine proton exchange membrane fuel cells

Mathematical models on transport processes and reactions in proton exchange membrane (PEM) fuel cell generally assume an isothermal cell behavior for sake of simplicity. This work aims at exploring how a non-isothermal cell body affects the performance of PEM fuel cells with single and double serpentine cathode flow fields, considering the effects of flow channel cross-sectional areas. Low thermal conductivities of porous layers in the cell and low heat transfer coefficients at the surface of current collectors, as commonly adopted in cell design, increase the cell temperature. High cell temperature evaporates fast the liquid water, hence reducing the cathode flooding; however, the yielded low membrane water content reduces proton transport rate, thereby increasing ohmic resistance of membrane. An optimal cell temperature is presented to maximize the cell performance.     

The Influence of the Gas Diffusion Layer on Water Management in Polymer Electrolyte Fuel Cells

Performance losses due to flooding of gas diffusion layers (GDLs) and flow fields as well as membrane dehydration are two of the major problems in PEFC. In this investigation, the effect of GDL on the cell water management in PEFC is studied using segmented and single cell experiments. The behaviour of four different commercial GDLs was investigated at both high and low inlet humidity conditions by galvanostatic fuel cell experiments. The influence of varying reactant humidity and gas composition was studied. The results at high inlet humidity show that none of the studied GDLs are significantly flooded on the anode side. On the other hand, when some of the GDLs are used on the cathode side they are flooded, leading to increased mass transfer losses. The results at low inlet humidity conditions show that the characteristics of the GDL influence the membrane hydration. It is also shown that inlet humidity on the anode side has a major effect on flooding at the cathode.     

Mathematical Model of Proton Exchange Membrane Fuel Cell with Consideration of Water Management

One‐dimensional model on the membrane electrode assembly (MEA) of proton exchange membrane fuel cell is proposed, where the membrane hydration/dehydration and the possible water flooding of the respective cathode and anode gas diffusion layers are considered. A novel approach of phase‐equilibrium approximation is proposed to trace the water front and the detailed saturation profile once water emerges in either anode or cathode gas diffusion layer. The approach is validated by a semi‐analytical method published earlier. The novel approach is applicable to the polarization regime from open circuit voltage to the limiting current density under practical operation conditions. Oxygen diffusion is limited by water accumulation in the cathode gas diffusion layer as current increases, caused by excessive water generation at the cathode catalyst layer and the electro‐osmotic drag across the membrane. The existence of liquid water in the anode gas diffusion layer is predicted at low current densities if high degrees of humidification in both anode and cathode feeds are employed. The influences of inlet relative humidity, imposed pressure drop, and cell temperature are correlated well with the cell performance. In addition, the overpotentials attributed from individual components of the MEA are delineated against the cell current densities.     

采用不同流场的质子交换膜燃料电池内部传递现象模拟

A numerical model for proton exchange membrane (PEM) fuel cell is developed, which can simulate such basic transport phenomena as gas-liquid two-phase flow in a working fuel cell. Boundary conditions for both the conventional and the interdigitated modes of flow are presented on a three-dimensional basis. Numerical techniques for this model are discussed in detail. Validation shows good agreement between simulating results and experimental data. Furthermore, internal transport phenomena are discussed and compared for PEM fuel cells with conventional and interdigitated flows. It is found that the dead-ended structure of an interdigitated flow does increase the oxygen mass fraction and decrease the liquid water saturation in the gas diffusion layer as compared to the conventional mode of flow. However, the cathode humidification is important for an interdigitated flow to acquire better performance than a conventional flow fuel cell.