PEMFC碳纸气体扩散层内气液两相流格子Boltzmann模拟

为了提高质子交换膜燃料电池（PEMFC）水管理,本文借助多相流格子Boltzmann模型（LBM）模拟分析了PEMFC碳纸气体扩散层（GDL）内的气液两相输运过程,主要研究了GDL疏水性对气液两相流的影响。结果表明：液态水流路径不仅受到GDL结构形态的影响,而且受到材料疏水性影响。液态水在疏水性弱的GDL中不仅容易沁入,而且容易在孔隙中达到饱和;相反,在疏水性较强的GDL中,液态水很难突破沁入小尺寸孔隙,而从孔径较大的孔隙流通,从而形成毛细力主导的指进流动。     

Pore-network simulations of two-phase flow in a thin porous layer of mixed wettability: Application to water transport in gas diffusion layers of proton exchange membrane fuel cells

Pore network simulations are performed to study water transport in a model gas diffusion layer (GDL) of polymer electrolyte membrane fuel cells (PEMFCs) in relation with the change in hydrophobicity that might be due to aging or temperature effect. The change in hydrophobicity is taken into account by changing randomly the fraction of hydrophilic elements, pores or throats, in the network. The transport and equilibrium properties of the model GDL are computed as a function of liquid saturation as well as at breakthrough varying the fraction of hydrophilic elements. The results indicate that the hydrophilic element percolation threshold marks the transition between two domains. The system is found to be weakly dependent on the fraction of hydrophilic elements as long as this fraction is below the percolation threshold whereas an increase in wettability above the percolation threshold favours a greater blockage of the pore space by the water and therefore a diminished access of gas to the catalyst layer. This model may help assess the effect of a change in wettability on the fuel cell performance and may also help suggest better GDL designs in relation with the water management problem in PEMFCs.     

Fabrication of a carbon nanofiber sheet as a micro-porous layer for proton exchange membrane fuel cells

A carbon nanofiber sheet (CNFS) has been prepared by electrospinning, stabilisation and subsequent carbonisation processes. Imaging with scanning electron microscope (SEM) indicates that the CNFS is formed by nonwoven nanofibers with diameters between 400 and 700 nm. The CNFS, with its three-dimensional pores, shows excellent electrical conductivity and hydrophobicity. In addition, it is found that the CNFS can be successfully applied as a micro-porous layer (MPL) in the cathode gas diffusion layer (GDL) of a proton exchange membrane fuel cell (PEMFC). The GDL with the CNFS as a MPL has higher gas permeability than a conventional GDL. Moreover, the resultant cathode GDL exhibits excellent fuel cell performance with a higher peak power density than that of a cathode GDL fabricated with a conventional MPL under the same test condition.     

Pore network modeling of fibrous gas diffusion layers for polymer electrolyte membrane fuel cells

A pore network model of the gas diffusion layer (GDL) in a polymer electrolyte membrane fuel cell is developed and validated. The model idealizes the GDL as a regular cubic network of pore bodies and pore throats following respective size distributions. Geometric parameters of the pore network model are calibrated with respect to porosimetry and gas permeability measurements for two common GDL materials and the model is subsequently used to compute the pore-scale distribution of water and gas under drainage conditions using an invasion percolation algorithm. From this information, the relative permeability of water and gas and the effective gas diffusivity are computed as functions of water saturation using resistor-network theory. Comparison of the model predictions with those obtained from constitutive relationships commonly used in current PEMFC models indicates that the latter may significantly overestimate the gas phase transport properties. Alternative relationships are suggested that better match the pore network model results. The pore network model is also used to calculate the limiting current in a PEMFC under operating conditions for which transport through the GDL dominates mass transfer resistance. The results suggest that a dry GDL does not limit the performance of a PEMFC, but it may become a significant source of concentration polarization as the GDL becomes increasingly saturated with water.     

Lattice Boltzmann simulations of water transport in gas diffusion layer of a polymer electrolyte membrane fuel cell

The effect of wettability on water transport dynamics in gas diffusion layer (GDL) is investigated by simulating water invasion in an initially gas-filled GDL using the multiphase free-energy lattice Boltzmann method (LBM). The results show that wettability plays a significant role on water saturation distribution in two-phase flow in the uniform wetting GDL. For highly hydrophobicity, the water transport falls in the regime of capillary fingering, while for neutral wettability, water transport exhibits the characteristic of stable displacement, although both processes are capillary force dominated flow with same capillary numbers. In addition, the introduction of hydrophilic paths in the GDL leads the water to flow through the hydrophilic pores preferentially. The resulting water saturation distributions show that the saturation in the GDL has little change after water breaks through the GDL, and further confirm that the selective introduction of hydrophilic passages in the GDL would facilitate the removal of liquid water more effectively, thus alleviating the flooding in catalyst layer (CL) and GDL. The LBM approach presented in this study provides an effective tool to investigate water transport phenomenon in the GDL at pore-scale level with wettability distribution taken into consideration.     

Study on the performance of a proton exchange membrane fuel cell related to the structure design of a gas diffusion layer substrate

Although characteristics of the gas diffusion layer (GDL) affect the performance of a proton exchange membrane fuel cell (PEMFC), mass transfer mechanisms inside the GDL and the performance of the PEMFC have not been directly correlated. To determine the design parameters of the GDL, the effects of substrate design of the GDL on performance of a PEMFC are investigated. By adding an active carbon fiber (ACF), which has a high surface area, the substrate is designed to have a different pore size structure. The results show that steady-state and transient responses are determined by capillary pressure gradient characteristics of the GDL made by pore size distribution of the substrate. The small macro-pore functions as water-retaining passage and the large macro-pore functions as water-removal passage. It is concluded that both small and large macro-pore must be present on the substrate to facilitate its function in a wide range of operating conditions.     

Impacts of the mixed wettability on liquid water and reactant gas transport through the gas diffusion layer of proton exchange membrane fuel cells

In this paper, we develop a pore network model for liquid water and reactant gas transport through the porous gas diffusion layer (GDL) of mixed wettability. We first consider the case of uniform distribution of hydrophilic fraction along the GDL thickness. It is revealed that the addition of hydrophilic pores has a negligible impact on liquid saturation profile when the hydrophilic fraction is low (?0.2), whereas in the case of higher hydrophilic fraction (?0.4), a flat shape of liquid saturation profile is observed along the GDL thickness. The total liquid saturation in the GDL is found to first decrease and then increase with the increase of hydrophilic pores; and an optimum hydrophilic fraction exists leading to the maximum limiting current density. Also, we investigate the transport process in the GDL of non-uniform wettability (i.e., the hydrophilic fraction is 0.4 near the network inlet, while at the downstream region it is 0.3). As compared to the uniform case, the liquid saturation level at the downstream region is drastically decreased in the non-uniform system, thereby leading to a higher limiting current density. These findings suggest that the fuel cell performance can be improved by designing the GDL with appropriate wettability distribution.     

Numerical simulations of two-phase flow in a proton-exchange membrane fuel cell based on the generalized design method

The water management of proton-exchange membrane fuel cell (PEMFC) has a major impact on the performance of the cell system. In order to investigate the influence of air velocity and wettability on the whole process during penetration of liquid water, a generalized two-dimensional model in conjunction with the volume of fluid (VOF) method was used to simulate the whole processes from gas diffusion layer (GDL) to gas channel (GC). The results show that the wettability of the medium plays a significant role than flow rate for the penetration of liquid water in the GDL. It is shown that favorable hydrophobicity and high air velocity in GC is helpful to remove liquid droplets on the GDL surface. By contrast, the stable droplets spacing on GDL surface is more concentrated and the percentage of liquid area is more extensive under the hydrophilic and low-velocity case, which would aggravate the liquid water and hard to remove from the GDL surface.     

Preparation of microporous layer for proton exchange membrane fuel cell by using polyvinylpyrrolidone aqueous solution

A new method of preparing microporous layer (MPL) for proton exchange membrane fuel cell (PEMFC) was presented in this paper. Considering the bad dispersion of PTFE aqueous suspension in the carbon slurry based on ethanol, polyvinylpyrrolidone (PVP) aqueous solution was used to prepare carbon slurry for microporous layer. The prepared gas diffusion layers (GDLs) were characterized by scanning electron microscopy, contact angle system and pore size distribution analyzer. It was found that the GDL prepared with PVP aqueous solution had higher gas permeability, as well as more homogeneous hydrophobicity. Moreover, the prepared GDLs were used in the cathode of fuel cell and evaluated with fuel cell performance and EIS analysis, and the GDL prepared with PVP aqueous solution indicated better fuel cell performance and lower ohmic resistance and mass transfer resistance.     

Development of a novel hydrophobic/hydrophilic double micro porous layer for use in a cathode gas diffusion layer in PEMFC

In this study, a gas diffusion layer (GDL) was modified to improve the water management ability of a proton exchange membrane fuel cell (PEMFC). We developed a novel hydrophobic/hydrophilic double micro porous layer (MPL) that was coated on a gas diffusion backing layer (GDBL). The water management properties, vapor and water permeability, of the GDL were measured and the performance of single cells was evaluated under two different humidification conditions, R.H. 100% and 50%. The modified GDL, which contained a hydrophilic MPL in the middle of the GDL and a hydrophobic MPL on the surface, performed better than the conventional GDL, which contained only a single hydrophobic MPL, regardless of humidity, where the performance of the single cell was significantly improved under the low humidification condition. The hydrophilic MPL, which was in the middle of the modified GDL, was shown to act as an internal humidifier due to its water absorption ability as assessed by measuring the vapor and water permeability of this layer.     

Effects of needle orientation and gas velocity on water transport and removal in a modified PEMFC gas flow channel having a hydrophilic needle

Water management is critical to the performance and operation of the proton exchange membrane fuel cell (PEMFC). Effective water removal from the gas diffusion layer (GDL) surface exposed to the gas flow channel in PEMFC mitigates the water flooding of and improves the reactants transport into the GDL, hence benefiting the PEMFC performance. In this study, a 3D numerical investigation of water removal from the GDL surface in a modified PEMFC gas flow channel having a hydrophilic needle is carried out. The effects of the needle orientation (inclination angle) and gas velocity on the water transport and removal are investigated. The results show that the water is removed from the GDL surface in the channel for a large range of the needle inclination angle and gas velocity. The water is removed more effectively, and the pressure drop for the flow in the channel is smaller for a smaller needle inclination angle. It is also found that the modified channel is more effective and viable for water removal in fuel cells operated at smaller gas velocity.     

An approach to modeling two-phase transport in the gas diffusion layer of a proton exchange membrane fuel cell

A series of analysis methods is proposed to simulate the liquid–gas two-phase and multi-component transport phenomena in the gas diffusion layer (GDL) of a proton exchange membrane fuel cell (PEMFC). These methods involve measuring and predicting the two-phase flow properties of a GDL, and simulating the two-phase multi-component transport in the GDL. The capillary pressure is measured by the porous diaphragm method and predicted by the pore network model. The relative permeability is measured by the steady-state method and predicted by a combination of the single-phase and the two-phase lattice Boltzmann method. And the simulation of the liquid–gas two-phase transport is done using the multi-phase mixture model. The methods are applied to a carbon-fiber paper GDL to identify the two-phase multi-component transport in the GDL.     

Three-dimensional numerical simulations of water droplet dynamics in a PEMFC gas channel

The dynamic behavior of liquid water emerging from the gas diffusion layer (GDL) into the gas flow channel of a polymer electrolyte membrane fuel cell (PEMFC) is modeled by considering a 1000 μm long air flow microchannel with a 250 μm × 250 μm square cross section and having a pore on the GDL surface through which water emerges with prescribed flow rates. The transient three-dimensional two-phase flow is solved using Computational fluid dynamics in conjunction with a volume of fluid method. Simulations of the processes of water droplet emergence, growth, deformation and detachment are performed to explicitly track the evolution of the liquid–gas interface, and to characterize the dynamics of a water droplet subjected to air flow in the bulk of the gas channel in terms of departure diameter, flow resistance coefficient, water saturation, and water coverage ratio. Parametric simulations including the effects of air flow velocity, water injection velocity, and dimensions of the pore are performed with a particular focus on the effect of the hydrophobicity of the GDL surface while the static contact angles of the other channel walls are set to 45°. The wettability of the microchannel surface is shown to have a major impact on the dynamics of the water droplet, with a droplet splitting more readily and convecting rapidly on a hydrophobic surface, while for a hydrophilic surface there is a tendency for spreading and film flow formation. The hydrophilic side walls of the microchannel appear to provide some benefit by lifting the attached water from the GDL surface, thus freeing the GDL-flow channel interface for improved mass transfer of the reactant. Higher air inlet velocities are shown to reduce water coverage of the GDL surface. Lower water injection velocities as well as smaller pore sizes result in earlier departure of water droplets and lower water volume fraction in the microchannel.     

An integrated model of the water transport in nonuniform compressed gas diffusion layers for PEMFC

Water transport in gas diffusion layer (GDL) is a very important issue for high power density Proton Exchange Membrane Fuel Cell (PEMFC). During the GDL and bipolar plate (BPP) assembly process, the water transport behavior is greatly influenced by the nonuniform compression on the GDL, which leads to uneven distribution of the internal mass transport pores. In this study, an integrated model is developed to predict the water transport in nonuniform compressed GDL. Firstly, a GDL compression deformation model is built to obtain the relationship between the GDL deformation and assembly clamping force based on energy method. Then, a water transport model is established by considering the probability density function (PDF) of the pore size for the compressed GDL. The accuracy of the integrated model has been verified by comparing with the finite element method (FEM) and the computational fluid dynamics (CFD) simulation results. The influence of assembly clamping force, GDL thickness and channel geometry are analyzed based on the integrated model. Drainage pressure increases monotonically with the assembly clamping force and is divided into three stages. For the baseline case, 0.2 mm of GDL thickness and small rib-channel ratio is conducive to improving drainage capacity. It provides the guidance for matching of GDL/BPP assembly condition and performance prediction of PEMFC.     

Analysis of surface and interior degradation of gas diffusion layer with accelerated stress tests for polymer electrolyte membrane fuel cell

The effects of surface and interior degradation of the gas diffusion layer (GDL) on the performance and durability of polymer electrolyte membrane fuel cells (PEMFCs) have been investigated using three freeze-thaw accelerated stress tests (ASTs). Three ASTs (ex-situ, in-situ, and new methods) are designed from freezing ?30 °C to thawing 80 °C by immersing, supplying, and bubbling, respectively. The ex-situ method is designed for surface degradation of the GDL. Change of surface morphology from hydrophobic to hydrophilic by surface degradation of GDL causes low capillary pressure which decreased PEMFC performance. The in-situ method is designed for the interior degradation of the GDL. A decrease in the ratio of the porosity to tortuosity by interior degradation of the GDL deteriorates PEMFC performance. Moreover, the new method showed combined effects for both surface and interior degradation of the GDL. It was identified that the main factor that deteriorated the fuel cell performance was the increase in mass transport resistance by interior degradation of GDL. In conclusion, this study aims to investigate the causes of degraded GDL on the PEMFC performance into the surface and interior degradation and provide the design guideline of high-durability GDL for the PEMFC.     

Three dimensional numerical simulation of gas-liquid two-phase flow patterns in a polymer-electrolyte membrane fuel cells gas flow channel

Water management in polymer-electrolyte membrane fuel cells (PEMFCs) has a major impact on fuel cell performance and durability. To investigate the two-phase flow patterns in PEMFC gas flow channels, the volume of fluid (VOF) method was employed to simulate the air-water flow in a 3D cuboid channel with a 1.0 mm × 1.0 mm square cross section and a 100 mm in length. The microstructure of gas diffusion layers (GDLs) was simplified by a number of representative opening pores on the 2D GDL surface. Water was injected from those pores to simulate water generation by the electrochemical reaction at the cathode side. Operating conditions and material properties were selected according to realistic fuel cell operating conditions. The water injection rate was also amplified 10 times, 100 times and 1000 times to study the flow pattern formation and transition in the channel. Simulation results show that, as the flow develops, the flow pattern evolves from corner droplet flow to top wall film flow, then annular flow, and finally slug flow. The total pressure drop increases exponentially with the increase in water volume fraction, which suggests that water accumulation should be avoided to reduce parasitic energy loss. The effect of material wettability was also studied by changing the contact angle of the GDL surface and channel walls, separately. It is shown that using a more hydrophobic GDL surface is helpful to expel water from the GDL surface, but increases the pressure drop. Using a more hydrophilic channel wall reduces the pressure drop, but increases the water residence time and water coverage of the GDL surface.     

Capillary pressures in carbon paper gas diffusion layers having hydrophilic and hydrophobic pores

Capillary pressures in a carbon paper gas diffusion layer (GDL) having hydrophilic and hydrophobic pores of a polymer electrolyte membrane fuel cell (PEMFC) are investigated by both lattice Boltzmann simulations and experimental measurements. The simulated and measured capillary pressures as a function of water saturation for water drainage and imbibition processes in the GDL are presented and compared. It is shown that the pore-scale simulated drainage and imbibition capillary pressure curves are in good agreement with that obtained by experiment, both indicating the coexistence of hydrophilic and hydrophobic properties in the polytetrafluoroethylene (PTFE) treated carbon paper GDLs. The fitted capillary pressure curves, obtained from this paper, can provide more accurate predictions of the capillary pressure in carbon paper GDLs with non-uniform porosity and wettability than the standard Leverett–Udell relationship which was obtained for soil with more uniform porosity and wettability.     

Enhanced low-humidity performance in a proton exchange membrane fuel cell by developing a novel hydrophilic gas diffusion layer

An ultrathin layer of hydrophilic titanium dioxide (TiO₂) is coated on the gas diffusion layer (GDL) to enhance the performance of a proton exchange membrane fuel cell (PEMFC) at low relative humidity (RH) and high cell temperature. Both of the modified and unmodified GDLs are characterized using contact angles, and the cell performance is evaluated at various RHs and cell temperatures. It is found that the modified GDL, which contains a hydrophilic TiO₂ layer between the microporous layer (MPL) and the gas diffusion-backing layer (GDBL), exhibits better self-humidification performance than a conventional GDL without the TiO₂ layer. At 12% RH and 65 °C cell temperature, the current density is 1190 mA cm⁻² at 0.6 V, and it maintains 95.8% of its initial performance after 50 h of continuous testing. The conventional GDL, however, exhibits 55.7% (580 mA cm⁻²) of its initial performance (1040 mA cm⁻²) within 12 h of testing. The coated hydrophilic TiO₂ layer acts as a mini humidifier retaining sufficient moisture for a PEMFC to function at low humidity conditions.     

A two dimensional partial flooding model for PEMFC

Proton exchange membrane fuel cells (PEMFCs) have attracted much attention in these years. In PEMFCs, liquid/gas two-phase flow is a common phenomenon, which has great influence on fuel cell performance. However, the liquid water transport process has not been satisfactorily modeled yet. In this work, a two dimensional partial flooding model was developed, in which the pore size distribution of the gas diffusion layer (GDL) is taken into consideration in the explanation of fuel cell flooding for the first time. Liquid water produced is considered to flood a fraction of the GDL hydrophobic pores with diameter greater than the capillary condensation threshold diameter, and the unflooded pores will serve as passageway for gas transportation and the corresponding catalyst area is available for electrochemical reaction. Use this model, it is simple to explain membrane dehydration and electrode flooding. Different operation conditions have been studied with the model and the model polarization curves show reasonable accordance with the experimental results.     

A pore network study on the role of micro-porous layer in control of liquid water distribution in gas diffusion layer

In proton exchange membrane fuel cell (PEMFC), a hydrophobic micro-porous layer (MPL) is usually placed between catalyst layer (CL) and gas diffusion layer (GDL) to reduce flooding. Recent experimental studies have demonstrated that liquid water saturation in GDL is drastically decreased in the presence of MPL. However, theoretical studies based on traditional continuum two-phase flow models suggest that MPL has no effect on liquid water distribution in GDL. In the present study, a pore network model with invasion percolation algorithm is developed and used to investigate the impacts of the presence of MPL on liquid water distribution in GDL from the viewpoint at the pore level. A uniform pressure and uniform flux boundary conditions are considered for liquid water entering the porous layer in PEMFC. The simulation results reveal that liquid water saturation in GDL is reduced in the presence of MPL, but the reduction depends on the condition of liquid water entering the porous layer in PEMFC.