直接甲醇燃料电池阳极通道内气泡行为

阳极催化层表面反应生成的CO2气体能否及时通过扩散层和阳极通道排出直接甲醇燃料电池(DMFC),对DMFC的性能及寿命具有重要影响,因此揭示气泡行为机理对DMFC的优化具有重要的意义。本文将DMFC阳极通道内气泡形成过程简化为气体垂直注入恒流液体中形成气泡的过程,利用可视化实验研究了气体垂直注入恒流液体中形成气泡以及气泡脱离的过程,考察了气体流量、液体流量以及浮力对气泡形成、生长及脱离过程的影响。结果表明:气泡的形成由气体的压力和表面张力产生的毛细压力共同作用,气泡生长和脱离过程相对于孕育过程较快;随着气体流量的增加,产生气泡的时间间隔变短,气泡间聚并的位置逐渐向前推移,气泡的脱离时间先减小后增大;随着液体流量的增加,气泡由弹状流向泡状流渐变,气泡的脱离时间先急剧变小,后趋于平缓;浮力对竖直向下形成气泡的影响较为明显,浮力的作用使竖直向下不易形成气泡且难于脱离孔道口。     

被动式DMFC气泡行为的实验研究和数值模拟

在被动式直接甲醇燃料电池（DMFC）中,阳极催化层表面电化学反应生成的二氧化碳（CO2）通过扩散层及时排出阳极通道,对提高直接甲醇燃料电池的性能具有重要意义,因此研究阳极通道内的气液两相流对电池性能的优化具有非常重要的意义。利用计算流体力学模拟软件Fluent,采用VOF（volume of fluid）两相流模型追踪气液界面的方法对静止甲醇溶液中CO2气泡形成的过程进行模拟,利用可视化实验对部分结果进行验证,结果表明：气泡在浮力和表面张力作用下被拉长,受尾部液体剪切力作用脱离,倾斜的扩散层表面有利于气泡尽快的离开孔口,气速较大时气泡在脱离前会出现多次融合,气泡在高浓度甲醇溶液中以气泡链的方式产生。研究结果为扩散层的制备和优化提供了参考。     

Bubbles in the anode channel and performance of a DMFC: Asymptotic solutions

Our recent 1D + 1D model of DMFC, which takes into account gaseous bubbles in the anode channel is analyzed. In this work, we derive asymptotic solution to model equations for the case of small rate of bubbles formation. The formula for the change in the mean current density of the cell due to bubbles is obtained and the effect of bubbles on the limiting current density is rationalized. Physically, the bubbles (i) decrease time-average methanol concentration in the anode channel, which reduces cell performance and (ii) decrease methanol crossover, which improves it. The resulting effect is controlled by parameter γ, which is proportional to the ratio of inlet oxygen and methanol concentrations. If oxygen is in excess, the bubbles strongly decrease cell performance close to the limiting current and have marginal positive effect at small and medium currents. Under lack of oxygen the bubbles almost always dramatically improve performance. Furthermore, in that case there exists optimal stoichiometry of the flows, which provides maximal performance. The origin of these effects is discussed.     

壁面亲水性对DMFC阳极通道内气液两相流影响的数值模拟

采用计算流体力学软件FLUENT对DMFC阳极通道内的气液两相流进行数值模拟,考察了阳极通道壁面的亲水性质对通道内气液两相流的影响.模拟结果表明:当流道侧壁面为憎水性时,CO2气体排出速度较快,但不利于反应物向扩散层方向迁移;当流道侧壁面和扩散层(GDL)表面均为亲水性时,有利于反应物向GDL方向迁移,但CO2气体排出阳极通道的速度较慢;当流道侧壁面为亲水性、GDL表面为憎水性时,既有利于反应物向GDL方向迁移,又有利于CO2气体排出通道.     

Effect of methanol crossover on the cathode behavior of a DMFC: A half-cell investigation

A half-cell consisting of a normal direct methanol fuel cell (DMFC) cathode and a membrane that contacts with an electrolyte solution was developed to investigate the effect of methanol crossover on the cathode behavior. Open circuit potentials, cyclic voltammetry profiles, polarization curves and electrochemical impedance spectroscopy (EIS), resulting from the oxygen reduction reaction (ORR) with/without the effect of methanol oxidation reaction (MOR), were measured. The transient measurements indicated that both current and open circuit potential of the electrode exhibited significant oscillations when the anodic MOR was superposed on the cathodic ORR, which explain the instabilities that may be encountered in the practical DMFC operation. The steady-state results confirmed that the presence of methanol at the cathode led to a significant poisoning effect on the ORR, especially when the DMFC operates at higher methanol concentrations and discharges at lower potentials. More importantly, the half-cell was proved to be ideal for the EIS study of DMFC electrodes because the system not only facilitates an accurate potential control but also reflects the actual mass transport process that occurs in practical DMFCs.     

Investigation of passive DMFC mini-stacks at ambient temperature

Two designs of flow fields/current collectors for a passive direct methanol fuel cell (DMFC) monopolar three-cell stack were investigated. The first one (A) consisted of two plastic plates covered by thin gold film current collectors in the area of electrodes with a distribution of holes through which methanol (from a reservoir) and air (from ambient) could diffuse into the electrodes. The second design (B) consisted of thin gold film deposited on the external borders of the fuel and oxidant apertures where the electrodes were placed in contact. A big central hole allowed a direct exposure of electrodes to ambient air (for the cathodes) and methanol solution (for the anodes). An investigation of the performance and discharge behaviour of the two designs was carried out. The advantages and disadvantages of each configuration were analysed. Similar performances in terms of maximum power were recorded; whereas, better mass transport characteristics were obtained with the design B. On the contrary, open circuit voltage (OCV) and stack voltage at low current were higher for the design A as a consequence of lower methanol cross-over. A longer discharge time (17 h) with a unique MeOH charge was recorded with design B at 250 mA compared to the design A (5 h). This was attributed to an easier CO₂ removal from the anode and better mass transport properties.     

Role of hydrophobic anode MPL in controlling water crossover in DMFC

The importance of reducing water crossover from anode to cathode in a direct methanol fuel cell (DMFC) has been well documented, especially if highly concentrated methanol fuel is to be used. A low-α membrane electrode assembly (MEA) with thin membrane is key to achieving this goal. The low water crossover from anode to cathode for these types of MEAs has traditionally been attributed to the use of a hydrophobic cathode micro-porous layer (MPL). However, it has recently been discovered that a hydrophobic anode MPL also reduces the water crossover, possibly even more significantly than a hydrophobic cathode MPL. In this work, we develop and use a 1D, two-phase transport model that accounts for capillary-induced liquid flow in porous media to explain how a hydrophobic anode MPL controls the water crossover from anode to cathode. We further show that a lower water crossover can lead to a lower methanol crossover via dilution of methanol in the anode catalyst layer. Finally, we perform a parametric study and show that a thicker anode MPL with greater hydrophobicity and lower permeability is more effective in reducing the water crossover.     

The effect of hydrophobicity in alkaline electrodes for passive DMFC

The effect of hydrophobicity in alkaline electrodes has been investigated in an effort to improve their performance in passive direct methanol fuel cells. Two approaches have been used to increase the hydrophobicity within the electrodes. One is using a more hydrophobic ionomer, and the other is introducing polytetrafluoroethylene (PTFE) into the catalyst layer. Two types of anion exchange ionomers with different hydrophobicity have been synthesized for this study. The effect of ion exchange capacity, ionic conductivity, and water uptake of the ionomers on the electrode performance has been studied using a half-cell test. The use of a hydrophobic ionomer resulted in enhanced cathode performance even though the ionic conductivity was lower than the more hydrophilic ionomer. Also, the addition of PTFE improved both the cathode and anode performance. The improved alkaline electrode performance was compared to a traditional acid electrode using Nafion as the ionomer. The performance increased threefold as a result of higher hydrophobicity in alkaline electrode.     

The influence of electrode morphology on the performance of a DMFC anode

For low concentrations of methanol, mass transfer in the electrode is a limiting parameter for the direct methanol fuel cell (DMFC). To improve mass transfer, it is possible to induce convection in the gas backing layer or even in the porous electrode. In this study electrodes with different amounts of PTFE were compared to observe the influence of morphology on the anode performance. The hypothesis was that adding PTFE to the anode may make the morphology more favourable for carbon dioxide to evolve as a gas by creating the necessary pore sizes. Electrode performance was characterized electrochemically and the anode layer structure was studied using SEM, Hg-porosimetry and the van der Pauw method for measuring electric conductivity. Pores smaller than 0.04 m were unaffected by adding PTFE while the volume fraction of pores of 0.04–1.0 m diameter increased. Electrodes with 50% PTFE also performed as nonhydrophobized, despite the much higher ohmic losses and thickness. This implies that, above a certain amount, adding PTFE has a positive effect and that optimizing the electrode with PTFE may give better performance than electrodes without PTFE. The results suggest that gas evolves within the electrode, giving improved mass transfer in the liquid phase.     

Review of non-platinum anode catalysts for DMFC and PEMFC application

Articles devoted to non-platinum anode catalysts for DMFC and PEMFC application, operated in acidic media were reviewed. Several classes of possible platinum substitutes based on transition metal carbides, oxides, alloys and new exotic catalysts were described, with focus on synthetic methods, corrosion stability and activity in reactions of methanol/hydrogen oxidation. Directions for future research in field of non-platinum anode materials were discussed.     

Experimental investigation of a pilot-scale jet bubbling reactor for wet flue gas desulphurisation

In the present work, an experimental parameter study was conducted in a pilot-scale jet bubbling reactor for wet flue gas desulphurisation (FGD). The pilot plant is downscaled from a limestone-based, gypsum producing full-scale wet FGD plant. Important process parameters, such as slurry pH, inlet flue gas concentration of SO₂, reactor temperature, and slurry concentration of Cl⁻ have been varied. The degree of desulphurisation, residual limestone content of the gypsum, liquid phase concentrations, and solids content of the slurry were measured during the experimental series.The SO₂ removal efficiency increased from 66.1% to 71.5% when the reactor slurry pH was changed from 3.5 to 5.5. Addition of Cl⁻ (in the form of CaCl₂·2H₂O) to the slurry increased the degree of desulphurisation to above 99%, due to the onset of extensive foaming, which substantially increased the gas-liquid contact area. An increase in the inlet flue gas SO₂ concentration from 502 to led to a decrease in the SO₂ removal efficiency from 80.1% to 69.4%. A temperature increase from 296 to caused a reduction in the degree of desulphurisation from 69.4% to 68.1%, but this result is almost within the experimental uncertainty. The residual limestone level in the gypsum formed increased with increasing values of reactor slurry pH, inlet flue gas SO₂ concentration, and slurry concentration of Cl⁻.     

DMFC多孔Pt-Ru阳极甲醇氧化宏观动力学模型化

本文旨在建立和求解DMFC多孔阳极甲醇氧化宏观动力学理论数模。根据Pt-Ru催化剂上双位机理,得到包含CO和OH覆盖率的甲醇水解本征动力学表达式;通过对该多孔阳极微元体积中的物料和电（荷）量衡算,导出了描述电极中浓度和超电势分布的两个耦联的模型方程。经量纲1化后,获得以量纲1变量和准数表示的普遍化宏观动力学数模。该模型包括催化层厚度l、比表面积a、有效扩散系数D_e和有效液相电导率κ_e等工程参数,特别是包括了与动力学参数相关且作为厚度变量函数的CO和OH覆盖率。进而,文中还给出了DMFC多孔阳极效率因子和极化曲线的计算公式。该数模为一非线性二阶微分方程组边值问题,经解耦,可得到两个同解的微分方程。用Newman的BAND（J）程序对方程进行数值求解,并在每一节点计算中嵌入一个计算CO和OH覆盖率的子程序。将模型预测值与甲醇氧化多孔阳极的极化实验数据进行对比发现：当宏观电流密度较低时二者能很好相符;当宏观电流密度较高、CO₂形成气泡的影响变大时,实验值有规律地偏低于预测值。详细的宏观动力学分析表明：提高催化剂Pt位甲醇电分解活性以减少功率损失、优化多孔电极微观和宏观结构以削弱两相流影响,应是改善该阳极性能的重要课题。本工作也可为直接乙醇燃料电池（DEFC）、直接硼氢化物燃料电池（DBFC）阳极的理论分析提供参考。     

流化床垃圾焚烧炉飞灰沉积实验

在自行搭建的小型流化床积灰试验台上选用流化床垃圾焚烧炉对流管束浮灰,模拟焚烧炉烟气环境下开展飞灰沉积实验。首先分析浮灰理化特性,结果表明：随着粒径增大,浮灰中CaO和SO₃含量逐渐降低,而SiO₂和Al₂O₃的含量逐渐增加;碱金属Na和K以及卤素Cl的含量在粒径较小的浮灰中含量最高。其次重点研究了浮灰粒径、烟气温度和换热管表面温度对飞灰沉积特性的影响规律,结果表明：积灰中主要富含Ca、S、Si和Al等元素,积灰中CaO和SO₃含量比浮灰高,而Al₂O₃和SiO₂含量比浮灰低;积灰量随着烟气温度升高而增加;粒径对灰沉积影响作用显著,大粒径灰颗粒难沉积而小粒径灰粒易沉积;管壁温度在600℃时,积灰量最小。积灰中CaO和SO₃的含量随着管壁温度升高而减少,而难熔Al₂O₃和SiO₂的含量随着管壁温度升高而增加。     

三面加热窄矩形通道内饱和沸腾起始点的实验研究

以去离子水为实验介质,对截面为3 mm×43 mm的三面加热窄矩形通道内饱和沸腾（FDB）起始点进行了实验研究。分析了部分热工参数对饱和沸腾起始点的影响,对三面加热窄矩形通道内饱和沸腾起始点的数据进行非线性回归分析,得到适用于三面加热窄矩形通道饱和沸腾起始点热通量的经验关系式。结果表明：新拟合得到的关系式能较准确地预测三面加热窄矩形通道内饱和沸腾起始点的热通量,其预测值的相对误差为15.17%。将新关系式计算结果与现有实验数据进行比较,源于单面加热窄矩形通道的实验数据与新关系式符合程度较好,表明新关系式可适用于单面加热窄矩形通道。     

浓海水鼓泡过程中的气泡行为

鼓泡操作可强化浓海水蒸发过程,其气泡的大小及运动行为对浓海水蒸发过程有显著影响。实验通过搭建两种不同尺寸的鼓泡池,针对单鼓泡口、双鼓泡口及鼓泡阵列,在不同气量、鼓泡口深度与鼓泡口间距条件下,考察大气泡群与小气泡群在不同运动过程的行为。结果表明,在气体流量更低的情况下,液面上的小气泡群比大气泡群具有更高的表面覆盖度,更易于增加液相扰动,并能迸射出更多的小液滴,提出小气泡更适合于鼓泡浓缩晒盐过程。通过单因素实验优化后,小气泡群的覆盖率可以达到90%,蒸发速率可比传统滩晒过程增加1～1.5倍。优化后操作参数为：单鼓泡口气流量为0.4 L·min^-1、鼓泡口深度为8 cm、鼓泡口间距为12 cm。     

Experimental and numerical investigation on flexural behavior of acrylonitrile-butadiene-styrene polymer

Acrylonitrile-butadiene-styrene (ABS) is an extensively utilized rubber-toughened amorphous thermoplastic in industry. Compared to other amorphous thermoplastics, the most promising mechanical quantity of ABS is its high impact resistance. Thus, understanding the mechanical response of ABS to multiaxial loads is of the great industrial concern. The primary objective of this study was to characterize the flexural response of ABS by conducting three-point bending tests at two distinct deformation rates of 5 and 10 mm/s to figure out the deformation rate effect on the flexural response of ABS. It was observed that the ABS act stiffer with an increased deformation rate. Numerical implementation of three-point bending tests for each deformation rate was performed using the semi-analytical material model (SAMP-1) available in Ls-Dyna finite element code. The simulations for each deformation rate were run depending on SAMP-1 and Von-Misses yield surface formulations to figure out the effect of nonidentical material behavior of ABS in tension, compression, and shear on flexural response. The percentage error in the predicted peak force values considering the compression and shear test data (SAMP-1) and without it (Von Misses) was 3% and 7% for deformation rate of 5 mm/s and 5% and 12% for deformation rate of 10 mm/s. Hence, predicting the flexural behavior of ABS accurately, dissimilar material behavior needs to be taken into consideration. Moreover, associated and nonassociated flow rule effects on the flexural response of ABS were numerically investigated and there was no significant influence observed on the flexural response of ABS.     

浮阀鼓泡器塔板的流体力学性能实验

分析了浮阀鼓泡器的结构特点。在1000mm×350mm规格的实验塔中,应用典型的水—空气冷模实验系统对浮阀鼓泡器塔盘进行了实验研究,测定了多种气液负荷下的塔板压降、雾沫夹带和泄漏量等流体力学性能。利用氧解吸法测定了塔板传质效率,并与F1型浮阀塔板进行了对比研究。实验结果表明,在相同条件下,浮阀鼓泡器塔板比F1型浮阀塔板的板效率提高10%～20%,板压降降低200Pa以上,雾沫夹带与泄漏与F1阀基本相当。在小气速时,由于浮阀鼓泡器存在着鼓泡口而使得泄漏量比F1阀稍大,不过在工业应用范围内,浮阀鼓泡器的泄漏量和F1浮阀基本相当。是一种综合性能优良的新型浮阀。     

Experimental analysis of platinum utilization in a DMFC cathode

An experimental analysis of platinum utilization in a DMFC cathode is performed. The chief objective of this work is to elucidate the effect of Nafion and polytetrafluoroethylene (PTFE) on platinum utilization values on the cathode. Polarization curves indicate that the performance of a DMFC is sensitive to the Carbon/Nafion (C/N) and Nafion:PTFE (N/P) ratio in the catalyst layer. Our analysis shows that supported Pt/C catalysts have a much higher platinum utilization value than unsupported catalysts. Platinum utilization is a maximum at a C/N ratio of 2.5 and at a N/P ratio of six. Platinum utilization is more sensitive to the Nafion content in the catalyst layer than the Teflon content.     

Experimental investigation of passive/active oxidation behavior of SiC based ceramic thermal protection materials exposed to high enthalpy plasma

The passive/active oxidation behavior of a CVD-SiC coated C/C-SiC thermal protection material of the hypersonic SpaceLiner vehicle is investigated experimentally. For the safety of spacecraft and its passengers, it is important to know whether the thermal protection system will experience passive/active oxidation during the vehicle's entry into Earth's atmosphere. Active oxidation can promote material loss whereas passive oxidation forms a protective film.The high enthalpy flight conditions of SpaceLiner vehicle are duplicated in VKI Plasmatron, where the samples are exposed to high enthalpy plasma and the surface temperatures increase up to 2800 K at various total pressure (2–20 kPa) conditions. Surface temperature profiles, visual characteristics, mass changes, emissivity, spectrometer and SEM/EDX data are examined to identify the oxidation transition border of the tested material. A temperature jump is observed in all active oxidation regimes. The experimental results are found to be in good agreement with correlations from the literature.     

Experimental investigation of cocurrent two-phase flow in a vertical rectangular channel

New time averaged data of two-phase flow in bubbly and slug regimes are presented. A modified dual spherical tipped optical fiber probe is used to measure local void fractions, gas velocity and bubble sizes. Hot film anemometry was used to measure the local mean liquid velocity axially. The void fraction, gas and liquid velocities values were presented as averages over the long and short dimensions respectively. Also core values of these variables are presented along the smaller dimension of 12.7 mm, near the plane of symmetry of the longer dimension, to show the most general trend of the different bubbly and slug flow runs. Bubble sizes obtained experimentally were compared with predictive models applied to circular geometries and were found to have a reasonable agreement. It was also interesting to find that local void fractions measured using hot film anemometers were comparable to those found by optical fiber probes. Frequencies of interfacial passage of bubbles and slugs are presented which show rather flat profiles across the channel. It is hoped that these data can be further used in predictive two-phase two-fluid models in the future. Lastly of interest is the fact that slip values near the boundaries were shown to be less than 1.0 for some cases in bubbly flow similar to those observed in circular geometries.