固体氧化物燃料电池模式阳极内传输与电化学反应耦合机理

模式电极因其结构可控、电化学/化学反应活性位和物质传输路径明确等优势,被广泛应用于固体氧化物燃料电池新型电极研究.现有研究多采用模式电极研究新材料电化学特性、表界面催化反应机理等,尚未涉及几何结构对其内部传输与电化学反应耦合机理的影响,限制了模式电极的应用.本文建立了固体氧化物燃料电池阳极内电荷传输与电化学反应过程的格子玻尔兹曼模拟方法,明确了控制电极过程的关键无量纲参数及其对电极性能的影响规律,研究了模式阳极几何结构的影响机理.根据电极性能对无量纲参数的敏感程度,绘制了指导模式阳极设计与运行的相图,指出相图过渡区(电极性能随操作参数显著变化区域)为进行反应机理研究的最佳操作参数取值范围.同时,研究发现模式阳极电子导体内电子的快速迁移虽不限制阳极性能,其几何结构显著影响过渡区范围;离子导体内离子迁移为影响阳极性能的限速步骤,但其几何结构几乎不影响过渡区范围.本文的数值方法与机理研究结果可为固体氧化物燃料电池模式电极的设计提供重要理论依据.     

梯度孔隙阳极固体氧化物燃料电池传质与电性能研究

本文通过建立梯度孔隙阳极固体氧化物燃料电池(Solid Oxide Fuel Cell,SOFC)的三维数学模型,模拟了SOFC内部气体传输现象及电性能,通过对比梯度孔隙阳极SOFC与均匀孔隙阳极SOFC的能质传递特性,揭示了梯度孔隙阳极的优越性。研究发现,梯度孔隙阳极设计在保证传质特性不降低的同时,有效调整了电极与其他部件特别是电解质热膨胀系数的匹配。在本文的参数设置下,梯度孔隙阳极设计的SOFC最大输出功率可达到1.005W·cm~(-2),相比于均匀孔隙阳极SOFC,至少可提高8.78%。因此,梯度孔隙阳极设计的SOFC可以显著提高电池的电性能。     

多孔介质内反应气的化学和热质非同性传递过程特性

针对集成板式固体氧化物燃料电池,建立了数学物理模型,分析阳极侧多孔支撑层内富氢气体的内重整反应传递过程特性.讨论了操作温度、入口处H2O:CH4比值以及多孔材料的孔隙率对甲烷蒸汽重整转换率和氢气的生成量的影响,得到了在电池的一定运行工况范围内比较有利的反应条件.     

固体氧化物燃料电池阳极微结构三维数值模拟

固体氧化物燃料电池(SOFC)是一种清洁高效的发电设备,其电极微结构直接影响电池的电化学性能。本文通过X-ray技术获取了SOFC阳极微结构,将电荷和物质传导定义在体相材料,将电化学反应定义在三相边界线上,建立了SOFC阳极电化学–传质耦合的三维微观模型,对比了两个微结构在80?C条件下的极化特性。研究表明微结构对电极内部物理场分布有极大影响,越靠近电极电解质界面,活化极化和离子电势波动越强烈。电极孔隙相细小的喉附近存在较大传质阻力,形成明显浓度极化跳跃。活化极化和欧姆极化大小相当,各占据总损失的45%以上。本文模型可用于研究微结构改变引起的电池退化和电极的优化设计。     

梯度颗粒阳极固体氧化物燃料电池电性能的数值研究

本文通过建立梯度颗粒阳极固体氧化物燃料电池(Solid Oxide Fuel Cell,SOFC)的三维数学模型,系统地研究了梯度颗粒阳极SOFC的电性能,深入分析了梯度颗粒阳极对SOFC电性能的影响机理。研究发现,梯度颗粒阳极设计可以有效降低阳极内的活化极化、浓度极化和欧姆极化。在本文的参数设置下,梯度颗粒阳极设计的SOFC最大输出功率密度可达到0.90 W·cm~(-2),相比于颗粒尺寸为0.5μm、1.0μm和1.5μm的阳极SOFC,增幅分别为2.59%、10.30%和16.26%。因此,梯度颗粒阳极设计的SOFC可以显著提高电池的电性能。     

固体氧化物燃料电池温升模拟中入口异常高温度梯度研究

针对固体氧化物燃料电池热循环失效问题,建立了固体氧化物燃料电池热气体预热动态模型,研究了电池内最大温度梯度分布规律和入口异常高温度梯度形成的原因,结果表明:在热气体参数和预热方式变化时,电池内最大温度梯度始终处于电池入口边缘处的电极表面;电池入口处存在异常高的温度梯度,且在入口一小段区域内,温度梯度沿流动方向迅速下降;其原因是模型中入口采用均一的平均速度和温度,“入口效应”强化气体与电池换热;采用入口段延长的方式可使入口速度充分发展,降低电池内最大温度梯度,但由于均一温度入口并未优化,入口处仍然存在很大的温度梯度和温度梯度变化;因此采用数值模拟研究电池预热升温安全性时,仅采用最大温度梯度作为安全性判据会高估电池内热应力.     

拉曼光谱法研究连接体氧化层应力变化及其进展

合金连接体是固体氧化物燃料电池重要组件,它的服役状况很大程度上决定着电池的工作寿命。高温氧化过程或者热循环过程中金属氧化层应力的变化是造成氧化层破坏的重要原因,这也是导致合金连接体失效的主要因素。利用拉曼光谱对氧化层应力的在线监测和实验研究可以为改善合金连接体服役年限提供重要依据。本文首先总结了近年来的连接体氧化层应力实验研究工作,分析了氧化层应力产生的原因。并且本文在比较了氧化层应力的测试方法的基础上讨论拉曼光谱法在测试氧化层应力方面的研究方法进展。     

基于高氢气利用率的质子交换膜燃料电池运行特性研究

为了提高氢气利用率本文对氢氧燃料电池在不同的阳极进口压力、阴极过量系数以及工作温度下进行阳极长时间闭口运行,考察阳极闭口对电池性能的影响。在每个操作条件运行期间阳极电池阀均未中途打开(单个操作条件最长运行时间26 h),氢气利用率达100%。结果表明:氢氧燃料电池除了在低阴极过量系数且高电流密度之外在其它各工况下阳极闭口能长时间稳定运行。膜电极分区域断面SEM测试表明出口处附近区域阳极和阴极催化层均有所减薄而其它区域膜电极催化层均没有受到影响。这表明电池出口附近碳腐蚀造成的催化层减薄与电池出口附近处水淹是有必然联系的。     

非晶硅界面缓冲层对非晶硅锗电池性能的影响

针对非晶硅锗电池本征层高锗含量时界面带隙失配以及高界面缺陷密度造成电池开路电压和填充因子下降的问题,通过在PI界面插入具有合适带隙的非晶硅缓冲层,不仅有效缓和了带隙失配,降低界面复合,同时也通过降低界面缺陷密度改善内建电场分布,从而提高了电池的收集效率. 进一步引入IN界面缓冲层以及对非晶硅锗本征层进行能带梯度设计,在仅采用Al背电极时,单结非晶硅锗电池转换效率达8.72%. 关键词： 非晶硅缓冲层 非晶硅锗薄膜太阳电池 带隙 界面     

多孔介质孔隙率对SOFC阳极管道化学/电化学反应与传递过程影响

固体氧化物燃料电池复合阳极管道由多孔层、燃料气体通道以及固体平板组成。在多孔层内部,存在着传热、多组分对流/扩散等多种传递过程,它们与CH_4的重整反应,CO、H_2的电化学反应耦合在一起,既受到设计参数,如孔隙率等的影响,同时对电池性能以及稳定性产生重要影响。编制了三维模拟程序,对阳极复合管道的化学反应以及气体流动、传热过程等进行了研究。研究结果显示,随着孔隙率的增大,在多孔层的较深区域内,重整与变换反应速度明显增加,受它的影响,H_2浓度与多孔层温度也相应提高。因此,在一定范围内提高多孔介质的孔隙率对阳极的各种传递过程与化学/电化学反应具有积极影响。     

Synthesis surface effects on the stress and deformation of film/substrate system

The closed-form solutions of bending curvature and stress distribution in film/substrate system with the synthesis surface effect are proposed by minimizing the total potential energy. Effects of the roughness and the residual surface stress on stress in film are addressed. Results reveal that, at a given thickness of the substrate, effects of roughness and residual surface stress on the bending curvature become significant with decreasing the film thickness. The roughing surface will enlarge the magnitudes of bending curvature and film stress. The direction change of residual surface stresses can lead to a reversed bending of film/substrate system.     

Interface Separation in Residually-Stressed Thin-Film Structures

Plasticity is a significant contributor to the interfacial fracture resistance of multilayer thin-film structures containing ductile layers. Salient parameters affecting plasticity contributions to interfacial fracture energy including the ductile layer thickness, yield strength, and the maximum cohesive stress governing interface separation, have been reported. However, the effects of residual stresses in the thin-film layers on such plasticity contributions have not been considered. We explore the effect of residual stresses on debonding with particular attention to the relationship between the stress state in both ductile and elastic layers and the resulting macroscopic debond energy. Using multiscale simulations it is shown that residual thin-film stresses can alter plasticity in the ductile layer and significantly influence the macroscopic fracture energy. A simple yield-based model to account for this behavior is proposed.     

A diagnostic study of turbulence features in wind tunnel flow over simple topographic shapes

Summary The turbulence features observed in wind tunnel experiments of flow over isolated simple-shaped two-dimensional hills and valleys are analysed in the light of transport equations of Reynolds stresses in the streamline coordinate system. The analysis has shown that near the surface the streamwise pressure gradient is the driving parameter for all the stresses. At higher levels, the effects of streamline curvature and streamwise pressure gradient act differently on the source terms of stresses, showing that the shear stress is the most sensitive to streamline curvature, whereas the streamwise stress is the most sensitive to streamwise pressure gradient. Although two of the considered topographies are specular images, the turbulence response is not so, since it depends on the sequence of curvatures to which it is subjected. The information and analysis presented will constitute a valuable resource to those seeking an understanding of atmospheric boundary layer development over complex terrain. It will also provide a support for the development and validation of more rigorous turbulence models.     

基于XRD的镀锌钝化膜残余应力试验研究

利用XRD技术测试了镀锌钝化膜结合界面的残余应力，同时通过电解抛光法检测了其厚度方向残余应力的分布规律，分析了残余应力对镀锌钝化膜结合强度的影响. 试验结果表明，镀锌钝化膜的残余应力均表现为压应力，并随着基体表面残余应力的增大而减小；钝化膜在2—10μm厚度方向的残应力为-274.5—-428.3MPa，其应力为梯度分布；镀锌钝化膜与基体的界面结合强度与其残余应力成反比，减小薄膜残余应力，有利于提高镀锌钝化膜与基体的结合强度. 关键词： X射线衍射法(XRD) 镀锌钝化膜 结合强度 残余应力     

An in situ growth method for property control of LPCVD polysilicon film

Polysilicon films deposited by low-pressure chemical vapor deposition(LPCVD)exhibit large residual stress and stress gradient,depending on the deposition condition.An in situ growth method based on multilayer concept is presented to control the property for as-deposited polysilicon.A 3-μm thick polysilicon film with nine layers structure is demonstrated under the detailed analysis of multi-layer theory and material characteristic of polysilicon.The results show that a 3-μm-thick polysilicon film with 8-MPa overall residual tensile stress and 2.125-MPa/μm stress gradient through the film thickness is fabricated successfully.     

金刚石层厚度对复合片(PDC)残余应力的影响

 通过X射线应力测试和有限元分析相结合的方法,研究了金刚石层厚度对聚晶金刚石复合片（PDC）残余应力的影响,并根据实验测试结果推导出了PDC表面中心与边缘的应力随金刚石层厚度变化的关系式。随着金刚石层厚度由0.5 mm增加到2.0 mm,PDC表面中心的压应力从1 800 MPa下降至700 MPa左右,而边缘部分的应力逐渐由压应力转为拉应力。金刚石层加厚虽然对边缘部分的最大拉应力影响不大,但使PDC边缘拉应力区宽度由0.76 mm增加到了2.85 mm。金刚石层厚度的增加还使得PDC边缘界面附近y方向的最大拉应力和位于界面边缘处的最大剪应力显著加大,这是金刚石层较厚的PDC界面容易产生裂纹的主要原因。     

Annealing effects on residual stress of HfO2/SiO2 multilayers

HfO2/SiO2 multilayer films were deposited on BK7 glass substrates by electron beam evaporation method.The effects of annealing at the temperature between 200 and 400℃ on residual stresses have been studied.It is found that the residual stress of as-deposited HfO2/SiO2 multilayers is compressive.It becomes tensile after annealing at 200℃,and then the value of tensile stress increases as annealing temperature increases.And cracks appear in the film because tensile stress is too large when the sample is annealed at 400℃.At the same time,the crystallite size increases and interplanar distance decreases with the increase of annealing temperature.The variation of residual stresses is corresponding with the evolution of structures.     

Residual stress of physical vapor-deposited polycrystalline multilayers

An extended one-dimensional stress model for the deposition of multilayer films is built based on the existing stress model by considering the influence of deposition conditions. Both thermal stress and intrinsic stress are considered to constitute the final residual stress in the model. The deposition process conditions such as deposition temperature, oxygen pressure, and film growth rate are correlated to the full stress model to analyze the final residual stress distribution, and thus the deformation of the deposited multilayer system under different process conditions. Also, the model is numerically realized with in-house built code. A deposition of Ag-Cu multilayer system is simulated with the as-built extended stress model, and the final residual stresses under different deposition conditions are discussed with part of the results compared with experiment from other literature.     

2024铝合金激光多次冲击诱导残余应力状态分布规律

采用高功率激光器多次冲击2024铝合金,用X射线衍射技术分析了冲击区域的残余应力,研究了冲击残余应力状态分布规律,并用其评价激光冲击强化效果。研究表明,随着冲击次数增加,塑变量及塑性应变梯度逐渐减小,测点是双向压应力状态,而4次冲击时,塑性应变梯度增大,光斑中心是单向压应力状态,其他点是双向压应力状态。当激光功率密度为2.8 GW/cm2时,3次冲击强化效果最佳,材料是二向压应力状态,残余最大主应力及应力强度的均值最大,方差最小,分布基本均匀,塑性应变梯度较小。     

The influence of compressive stress applied by hard coatings on the power loss of grain oriented electrical steel sheet

To reduce the core loss of electrical steel the vacuum arc ion plating technique has been used to deposit titanium nitride (TiN) layers on highly grain oriented electrical steel sheets. The layer thickness, the stresses of layers and coated sheets and the achieved reduction in core losses have been measured as functions of coating duration and applied bias voltage. Well adhered layers with high compressive stress up to 6.8 GPa have been produced. With increasing bias voltage the layer thickness decreases and the intrinsic stress of the layers increase. A further increase of bias voltage leads to a drop in stress due to thermal relaxation. In general, the tensile stress of the coated sheets rises with increasing layer thickness while the core loss of the coated material decreases with increasing tensile stress of the steel sheet and increasing bias voltage. The highest reduction of core loss has been found to be 28% (from P_1.7=0.86 W/kg for commercially coated HGO electrical steel sheet with glass film to 0.62 W/kg for TiN coated material) and is due to the reduction of excess loss only.