Hydrophobic properties of carbon fabric with Teflon AF 2400 fluoropolymer coating deposited from solutions in supercritical carbon dioxide

A method for uniform deposition of a hydrophobizing polymer from a solution in supercritical carbon dioxide (SC-CO₂) onto the surface of carbon fabric used for manufacturing gas diffusion layers of fuel cells is developed. This approach, based on using Teflon AF 2400, a SC-CO₂-soluble copolymer, is compared to the traditional method for hydrophobization of the gas diffusion layer of a fuel cell, based on the use of an aqueous dispersion of Teflon 30N. Hydrophobizing polymers were deposited on the surface of a highly rough carbon fabric (Saati), an electrically conductive gas diffusion layer material with good mechanical and resource characteristics. In one of the versions of the method of deposition from SC-CO₂, the hydrophobic film was subjected to additional annealing at a temperature above the glass transition temperature of Teflon AF 2400 amorphous copolymer. It is shown that this approach makes it possible to form a uniform thin fluoropolymer film on carbon fibers, which imparts the most stable superhydrophobic properties to the surface of the gas diffusion layer at very low amounts of deposited polymer. In this case, the contact angle reaches a value much greater than that previously reported in the literature for similar methods. Prolonged immersion in water (for 1000 h) or wash in the presence of detergent does not impair the superhydrophobicity of the gas diffusion layer. The developed gas-diffusion layer was used to prepare an electrode for phosphoric fuel cell, the current-voltage characteristic of which indicates a satisfactory performance. The results obtained show that adopted approach is promising for developing gas diffusion layers for fuel cell electrodes.     

微流燃料电池空气阴极物质传输孔隙尺度模拟

采用格子Boltzmann方法研究了微流燃料电池空气阴极多孔扩散层内多组分物质传输特性。随机重构了扩散层,获得渗透率及有效扩散系数。建立了耦合边界电化学反应的二维模型,研究了过电位、孔隙率对氧气、水蒸气浓度分布及局部反应速率的影响。结果表明,常用的Bruggeman经验关联式会高估氧气有效扩散系数;扩散层孔隙结构对物质传输有重要影响,孔隙率减小使得传质阻力增大,导致局部氧气浓度降低,局部反应速率降低,而水蒸气浓度增大,当孔隙率从0.83降至0.7,催化界面平均氧气浓度从8.472降至8.466 mol·m^-3。     

XPS investigation of the PTFE induced hydrophobic properties of electrodes for low temperature fuel cells

In electrodes of low temperature fuel cells like polymer electrolyte membrane fuel cells (PEFC) or alkaline fuel cells (AFC) the reactants and the water must be transported. For this purpose the pore system in the electrodes needs a hydrophilic character for the transport of the water and a hydrophobic character for the transport of the gases. The degree of the hydrophobicity determines whether the pore system will be flooded by the reaction water. In the case of PEFC, this is also determined by the degree of the required humidification of the reaction gases. In AFC hydrophobicity determines the extension of the three-phase reaction zone. Caused by the strong influence of hydrophobicity on the transport processes, the electrochemical performance and the optimized operation conditions are also affected by hydrophobicity.Typically polytetrafluoro-ethylene (PTFE) is used to make the electrodes hydrophobic, because PTFE has a high chemical stability. Hydrophobicity depends on the concentration of PTFE on the electrode surface. The PTFE concentration, which is related to the hydrophobic character, can be determined by XPS. The changes in the PTFE content and structure of the electrode of a PEFC was investigated by cyclic voltammetry and XPS and correlated with the performance of the cell in long-term operation. With both methods an initial significant increase in free and electrochemically active surface platinum area is observed. This activation is associated with a degradation of the PTFE in the electrode which is responsible for the hydrophobic properties of the electrode. With further operation the performance of the cell decreases because the water management becomes more critical. Generally, it is shown that XPS can be used for the investigation of the hydrophobicity of electrodes prepared by various manufacturing techniques as well as of changes in their hydrophobicity induced by the electrochemical operation.     

A domain decomposition method for two-phase transport model in the cathode of a polymer electrolyte fuel cell

Using Kirchhoff transformation, we develop a Dirichlet–Neumann alternating iterative domain decomposition method for a 2D steady-state two-phase model for the cathode of a polymer electrolyte fuel cell (PEFC) which contains a channel and a gas diffusion layer (GDL). This two-phase PEFC model is represented by a nonlinear coupled system which typically includes a modified Navier–Stokes equation with Darcy’s drag as an additional source term of the momentum equation, and a convection–diffusion equation for the water concentration with discontinuous and degenerate diffusivity. For both cases of dry and wet gas channel, we employ Kirchhoff transformation and Dirichlet–Neumann alternating iteration with appropriate interfacial conditions on the GDL/channel interface to treat the jump nonlinearities in the water equation. Numerical experiments demonstrate that fast convergence as well as accurate numerical solutions are obtained simultaneously owing to the implementation of the above-described numerical techniques along with a combined finite element-upwind finite volume discretization to automatically control the dominant convection terms arising in the gas channel.     

基于润湿阶跃的水下大尺度气膜封存方法

超疏水表面水下减阻效果通常与其微结构上封存气膜的厚度和面积正相关,且气膜尺寸越大封存越困难.构造亲疏水相间表面,能在壁面形成润湿阶跃,产生约束固-气-液三相接触线移动的束缚力.通过监测切向水流作用下,润湿阶跃为54.8?,84.7?,103.6?和144.0?的亲疏水相间表面上不同面积和厚度气膜的形态发现,厘米尺度气膜可被长时间稳定封存,且气膜破坏的临界流速随润湿阶跃和气膜厚度的增加而升高,随气膜迎流宽度增加而降低.同时,该方法封存的气膜上能产生显著滑移量,尺寸0.6 cm×0.5 cm×0.15 cm的气膜上即可产生约占主流速度25%的稳定滑移速度.期待该气膜封存方法能进一步提升超疏水表面水下减阻技术性能.     

直流道PEMFC两相流数学模型

建立直流道质子交换膜燃料电池(PEMFC)三维非等温两相流数学模型,基于质子交换膜与气体之间的水分传递特征,综合考虑电渗、浓度扩散及电化学反应作用的影响,发展了膜电极水分传递的非平衡扩散模型.并自主开发程序代码对电池内复杂的多物理场耦合传递过程进行数值模拟,研究PEMFC电极内气态水、液态水分布、质子膜含水量分布和水迁移特性等,分析单电池内部的温度分布特征,并获得电池极化性能曲线.     

Effect of gas diffusion layer and membrane properties in an annular proton exchange membrane fuel cell

A complete three-dimensional and single phase computational dynamics model for annular proton exchange membrane (PEM) fuel cell is used to investigate the effect of changing gas diffusion layer and membrane properties on the performances, current density and gas concentration. The proposed model is a full cell model, which includes all the parts of the PEM fuel cell, flow channels, gas diffusion electrodes, catalyst layers and the membrane. Coupled transport and electrochemical kinetics equations are solved in a single domain; therefore no interfacial boundary condition is required at the internal boundaries between cell components. This computational fluid dynamics code is used as the direct problem solver, which is used to simulate the two-dimensional mass, momentum and species transport phenomena as well as the electron- and proton-transfer process taking place in a PEMFC that cannot be investigated experimentally. The results show that by increasing the thickness and decreasing the porosity of GDL the performance of the cell enhances that it is different with planner PEM fuel cell. Also the results show that by decreasing the thickness of the membrane the performance of the cell increases.     

PEMFC电极表面液态水生成的可视化研究

本文设计了一个可视化直流道单片电池,通过高倍高速数字摄影装置观察记录了阴极流道壁面和气体扩散层表面的凝结水出现和成长过程,并分析了电池运行温度,阴极气体压力,气体化学当量比以及气体加湿度等参数对阴极流道内液态水的生成和排出的影响。     

In situ observation of water distribution and behaviour in a polymer electrolyte fuel cell by synchrotron X‐ray imaging

In situ visualization of the distribution and behaviour of water in a polymer electrolyte fuel cell during power generation has been demonstrated using a synchrotron X‐ray imaging technique. Images were recorded using a CCD detector combined with a scintillator (Gd₂O₂S:Tb) and relay lens system, which were placed at 2.0 m or 2.5 m from the fuel cell. The images were measured continuously before and during power generation, and data on cell performance was recorded. The change of water distribution during power generation was obtained from X‐ray images normalized with the initial state of the fuel cell. Compared with other techniques for visualizing the water in fuel cells, this technique enables the water distribution and behaviour in the fuel cell to be visualized during power generation with high spatial resolution. In particular, the effects of the specifications of the gas diffusion layer on the cathode side of the fuel cell on the distribution of water were efficiently identified. This is a very powerful technique for investigating the mechanism of water flow within the fuel cell and the relationship between water behaviour and cell performance.     

X‐ray tomography of morphological changes after freeze/thaw in gas diffusion layers

Liquid water produced in a polymer electrolyte membrane fuel cell experiences a freeze/thaw cycle when the cell is switched off and on while operating at ambient temperatures below freezing. This freeze/thaw cycle permanently deforms the polymer electrolyte membrane fuel cell capillary structures and reduces both the cell life and its ability to generate electric power. The X‐ray tomography facility at the Pohang Accelerator Laboratory was used to observe the freeze/thaw effects on the gas diffusion layer (GDL), which is the thickest capillary layer in the cell. Morphological changes in the GDL under a water freeze/thaw cycle were observed. A scenario in which freeze/thaw cycles affect fuel cell performance is suggested based on images from X‐ray tomography.     

Quantitative visualization of a gas diffusion layer in a polymer electrolyte fuel cell using synchrotron X‐ray imaging techniques

A gas diffusion layer (GDL) in a polymer electrolyte fuel cell (PEFC) is quantitatively visualized using synchrotron X‐ray micro‐computed tomography. For three‐dimensional reconstruction, an adaptive threshold method is used. This method is compared with the conventional method, i.e. Otsu's method. Additionally, the spatial and temporal variations of the porosity distribution of the GDL under freeze‐and‐thaw cycles are investigated experimentally. The freeze‐and‐thaw cycles are established simply using a CRYO system and light source illumination, respectively. Structural defects are found to largely affect the porosity of the GDL. In addition, a cyclic porosity variation is observed in the GDL under freeze‐and‐thaw cycles. The heterogeneous porosity is irreversibly decreased with the progress of repetitive cycles.     

PEMFC气体扩散层内各向异性传递过程数值模拟

质子交换膜燃料电池(PEMFC)气体扩散层(GDL)具有各向异性属性,常规数值模拟对GDL采取均匀模型,忽略了各向异性传递过程对PEMFC性能的影响。本文发展了一个三维非等温单相模型,在GDL平面内和GDL厚度方向采用不同的传递系数,模拟了各向异性传递系数对PEMFC整体和局部性能的影响。在本文计算条件下,GDL各向异性和均匀模型模拟得到的电池极化曲线几乎完全相同,但电池电流密度分布和温度分布等局部特性存在很大差异。该结果进一步证明了不能单独用极化曲线来验证电池数学模型的正确性。     

超疏水纳米结构表面池沸腾特性

本文通过采用物理气相沉积法于TiO2纳米管阵列表面修饰一层聚四氟乙烯(PTFE)纳米颗粒,得到超疏水表面,并研究此超疏水纳米结构表面的池沸腾特性.研究表明,超疏水纳米结构表面沸腾特性类似于膜沸腾,沸腾工质难以浸润该表面,其沸腾传热系数及临界热流密度均较低.分析表明,固液处于Cassie-Baxter接触状态,纳米结构表...     

Quantifying phosphoric acid in high‐temperature polymer electrolyte fuel cell components by X‐ray tomographic microscopy

Synchrotron‐based X‐ray tomographic microscopy is investigated for imaging the local distribution and concentration of phosphoric acid in high‐temperature polymer electrolyte fuel cells. Phosphoric acid fills the pores of the macro‐ and microporous fuel cell components. Its concentration in the fuel cell varies over a wide range (40–100 wt% H₃PO₄). This renders the quantification and concentration determination challenging. The problem is solved by using propagation‐based phase contrast imaging and a referencing method. Fuel cell components with known acid concentrations were used to correlate greyscale values and acid concentrations. Thus calibration curves were established for the gas diffusion layer, catalyst layer and membrane in a non‐operating fuel cell. The non‐destructive imaging methodology was verified by comparing image‐based values for acid content and concentration in the gas diffusion layer with those from chemical analysis.     

压缩对不同疏水性处理气体扩散层内两相流的影响

聚四氟乙烯(PTFE)常用于调节质子交换膜燃料电池(PEMFC)中气体扩散层(GDL)的疏水性。目前虽有很多关于PTFE对GDL中水传输影响的研究,但同时考虑三维GDL微孔结构和压缩影响的研究还很缺乏。本文研究了压缩对不同接触角(不同PTFE含量)的GDL微孔结构中水传输行为的影响。通过耦合有限元方法(FEM)和流体体积(VOF)模型来模拟未压缩及压缩GDL中的两相流现象。结果表明,采用不同的接触角时,压缩对GDL内水传输行为的影响不同。压缩有利于水从GDL中排出,并促进水在GDL中的不均匀分布;压缩还促进了亲水性GDL内水在脊下的堆积,以及疏水性GDL内水在流道下方的堆积。由此可见,在进行GDL中内水传输行为研究时,应同时考虑压缩和接触角的影响。     

Breakthrough/drainage pressures and X-ray water visualization in gas diffusion layer of PEMFC

The primary role of the gas diffusion layers (GDLs) in polymer electrolyte membrane fuel cells (PEMFC) is to maintain the delicate balance between water retention and removal in GDLs. Water management in the fuel cell is related to the breakthrough pressure at which water starts to pass through GDL, and the drainage pressure, which is maintained after the breakthrough. These pressures are both related to water management in fuel cells. Here we measured these pressures for two different GDLs and used X-ray tomography to visualize the water distributions within them. We then relate the variations in liquid pressures to the visualization and discuss water management in PEMFC.     

Phase-contrast X-ray imaging of the gas diffusion layer of fuel cells

The understanding of and in situ observation of the transport and distribution of water in carbon‐paper gas diffusion layers (GDLs) using non‐destructive imaging techniques is critical for achieving high performance in polymer electrolyte fuel cells (PEFCs). To investigate the behavior of water in GDLs of PEFCs, phase‐contrast X‐ray imaging via X‐ray interferometric imaging (XII) and diffraction‐enhanced imaging (DEI) were performed using 35 keV X‐rays. The XII technique is useful for the radiographic imaging of GDLs and in situ observations of water evolution processes in operating PEFCs. DEI provides a way for tomographic imaging of GDLs in PEFCs. Because high‐energy X‐rays are applicable to the imaging of both carbon papers and heavy materials, which make up PEFCs, phase‐contrast X‐ray imaging techniques have proven to be valuable for investigation of GDLs.     

Superhydrophobicity of polyvinylidene fluoride membrane fabricated by chemical vapor deposition from solution

Due to the chemical stability and flexibility, polyvinylidene fluoride (PVDF) membranes are widely used as the topcoat of architectural membrane structures, roof materials of vehicle, tent fabrics, and so on. Further modified PVDF membrane with superhydrophobic property may be even superior as the coating layer surface. The lotus flower is always considered to be a sacred plant, which can protect itself against water, dirt, and dust. The superhydrophobic surface of lotus leaf is rough, showing the micro- and nanometer scale morphology. In this work, the microreliefs of lotus leaf were mimicked using PVDF membrane and the nanometer scale peaks on the top of the microreliefs were obtained by the method of chemical vapor deposition from solution. The surface morphology of PVDF membrane was investigated by scanning electronic microscopy (SEM) and atomic force microscope (AFM). Elemental composition analysis by X-ray photoelectron spectroscopy (XPS) revealed that the material of the nanostructure of PVDF membrane was polymethylsiloxane. On the lotus-leaf-like PVDF membrane, the water contact angle and sliding angle were 155° and 4°, respectively, exhibiting superhydrophobic property.     

Preparation and properties of ZnS superhydrophobic surface with hierarchical structure

A novel ZnS hierarchical structure composed of nanorod arrays with branched nanosheets and nanowires grown on their upside walls, was synthesized over Au-coated silicon substrate via chemical vapor deposition technique. Contact angle and sliding angle of this hierarchical film with no surface modification were measured to be about 153.8° and 9.1° for 5 μl water droplets. Self-cleaning behavior and dynamic water-repelling performance were clearly demonstrated. In addition, electrowetting transition phenomenon from superhydrophobic to hydrophilic state happened when a critical bias ∼7.0 V was applied. Below this threshold voltage, the contact angle change is little. This work for the first time reports the creation of ZnS superhydrophobic surface and could enrich its research field as surface functional materials.     

Heat and mass transport in the photoacoustic effect on liquids

The temperature oscillation accompanying the photoacoustic effect generates a periodic variation of the vapor pressure of a liquid. The propagation of the oscillating concentration of the vapor in the inert cell gas (air) is described by a mass diffusion wave on which a convective motion of the gas is superposed. The diffusion wave characterized by the diffusion coefficient of the cell gas alone can be measured by the Mirage effect, whereas a microphone detects the total mass flux including the convective flux, which increases with temperature. On approaching the boiling temperature, the convective flow will govern the oscillating transport of mass. The photoacoustic signal is determined directly from the flux of heat and mass at the boundary between liquid and gas using the Gauss' divergence theorem. We have found that the temperature behaviour of the amplitude and phase angle of the photoacoustic signal depends on the length of the gas column in the cell. The contribution of thermal expansion to the photoacoustic signal is considered using the composite piston model. The results of the calculations agree fairly well with the experimental data.