双层复合衬砌隧洞运行安全预警监控指标研究

双层复合衬砌结构是一种新型隧洞衬砌结构型式,其外衬承受外部水土压力,内衬承受内水压力,体现了"结构联合、功能独立"的新型输水隧洞设计理念,目前该衬砌型式已成功应用到我国北方某输水工程中,如何确定双层复合衬砌隧洞安全预警监控指标是工程运行管理的重点和难点。本文基于以往研究成果,提出了工程结构监控指标及监控阈值确定的统一技术路径;根据双层复合衬砌结构受力特点,开展可能破坏模式分析;基于破坏模式与监测量的敏感性分析,提出层间渗压作为双层复合衬砌隧洞结构核心监控指标,内衬处的钢筋计测值以及外衬处的测缝计测值作为辅助监控指标,为双层复合衬砌隧洞安全运行提供借鉴和参考。     

Validating the efficiency of γ-Al2O3/La0.6Sr0.4Co0.2Fe0.8O3-δ double-layer electrolyte for low temperature solid oxide fuel cell

Perovskite La_0.6Sr_0.4Co_0.2Fe_0.8O_3+δ (LSCF) as a promising cathode material possessed overwhelming electronic conduction along with certain ionic conductivity. Its strong electron conduction capability hinder the application of pure-phase LSCF as electrolyte in semiconductor membrane fuel cell (SMFC). In order to constrain the electron transport and take advantage of the decent ion conduction of LSCF, a thin layer of γ-Al₂O₃ with insulating property was added as an electron barrier layer and combine with LSCF to form a two-layer structure electrolyte. Through adjusting the weight ratio of LSCF/γ-Al₂O₃ to optimize the thickness of double layers, an open circuit voltage of 0.98 V and a maximum power density of 690 mW/cm² was received at 550 °C. At the same time, SEM, EIS and other characterization technology had proven that the LSCF/γ-Al₂O₃ bi-layer electrolyte can work efficiently at low temperature. The advantage of this work is the application of double-layer (γ-Al₂O₃/LSCF) structure electrolyte to instead of mixed material electrolyte in low-temperature solid oxide fuel cells. Structural innovation and the using of insulating materials provided clues for the further development of SMFC.     

Compressive cyclic response of PEM fuel cell gas diffusion media

The fuel cell gas diffusion media (GDM) is a highly porous carbon-fiber-reinforced thin composite layer. The experimental response of these materials is observed to be highly nonlinear at low-stress levels. The cyclic mechanical response of GDM is investigated in terms of stiffness and damage parameters. The prediction of the state of deformation in GDM is vital in relating GDM's properties to ohmic and transport losses. To this end, a compressible form of the phenomenological model is proposed to capture the experimental cyclic response accurately. The model is constituent dependent; that is, the cumulative cyclic stress-strain response of GDM is a function of individual constituent phases present in the material. These individual constituents are porous matrix and reinforced fibers. The model hence derived for a typical GDM material, can predict residual strain, hysteresis, and damage quotient associated with the stress softening. This advanced model is implemented in the numerical domain to evaluate the response of the polymer electrolyte fuel cell (PEFC) unit cell. The stress-strain distribution fields are analyzed and compared with those of conventional GDM models. The results point to a remarkable deviation from the conventional notion of structural analysis.     

Compression properties of gas diffusion layers and its constitutive model under cyclic loading

The compressive deformation of gas diffusion layer (GDL), which is highly nonlinear and related to the loading history, affects the performance of PEM fuel cell stacks. However, linear elastic models are widely used. In this study, a new nonlinear constitutive model is proposed to describe the compression properties. Macroscopic studies reveal that GDL has different mechanical properties during the first and repeated compression stages. Besides, the tangent modulus has a significant linear relationship with stress. The constitutive model can be rebuilt using the micro-mechanical theory of fiber assemblies by considering the bending of carbon fibers. Furthermore, a prediction method is proposed to describe cyclic compression behavior. The prediction results fit well with the test results with an average and maximum relative error of less than 5.30% and 18.13%, respectively. These conclusions are beneficial to the design of GDL with specific mechanical properties and the real-time analysis of PEM fuel cell.     

Tailoring the hydrophilic and hydrophobic reaction fields of the electrode interface on single crystal Pt electrodes for hydrogen evolution/oxidation reactions

Interfacial hydrophobic/hydrophilic reaction fields significantly affect various reactions at the electrode surface. The hydrogen evolution reaction (HER) and the hydrogen oxidation reaction (HOR) have been investigated on single crystal Pt electrodes modified with hydrophobic/hydrophilic cations and anion-exchange copolymers in alkaline solutions. In alkali metal hydroxide solutions, Pt (110) exhibits the highest HER/HOR activity in the low-index planes of Pt. On the low-index planes of Pt, the hydrophilicity of the alkali metal cation in the supporting electrolyte activates the HER/HOR depending on its hydration energy. Hydrophilic cations at the interface facilitate the extraction of hydrogen from the hydrated water. The modification of anion-exchange copolymers with a hydrophobic skeleton on Pt (110) further enhanced the HER/HOR activity. The hydrogen bonding network formed around the hydrophobic species facilitated the mobility of water molecules and the OH⁻ as the reactant/product of the HER/HOR. Appropriately forming hydrophilic and hydrophobic reaction fields at the interface improved the HER/HOR activity.     

Compositional and structural study of ash deposits spatially distributed in superheaters of a large biomass-fired CFB boiler

Recognizing the nature and formation progress of the ash deposits is essential to resolve the deposition problem hindering the wide application of large-scale biomass-fired boilers. Therefore, the ash deposits in the superheaters of a 220 t/h biomass-fired CFB boiler were studied, including the platen (PS), the high-temperature (HTS), the upper and the lower low-temperature superheaters (LTS). The results showed that the deposits in the PSs and HTSs were thin (several millimeters) and compact, consisting of a yellow outer layer and snow-white inner layer near the tube surface. The deposits in the upper LTS appeared to be toughly sintered ceramic, while those in the lower LTS were composed of dispersive coarse ash particles with an unsintered surface. Detailed characterization of the cross-section and the initial layers in the deposits revealed that the dominating compositions in both the PSs and the HTSs were Cl and K (approximately 70%) in the form of KCl. Interestingly, the cross-section of the deposition in the upper LTS exhibited a unique lamellar structure with a major composition of Ca and S. The contents of Ca and Si increased from approximately 10% to approximately 60% in the deposits from the high temperature surfaces to the low temperature ones. It was concluded that the vaporized mineral matter such as KCl played the most important role in the deposition progress in the PS and the HTS. In addition, although the condensation of KCl in the LTSs also happened, the deposition of ash particles played a more important role.     

Effect of hydrophilic pipe structure of proton exchange membrane fuel cell on water removal from the gas diffusion layer surface

In a proton exchange membrane fuel cell (PEMFC), effective GDL surface water elimination is significant to water management. This paper used the volume-of-fluid method (VOF) method to carry out simulation research on transferring liquid water in the flow channel with a hydrophilic pipe. The findings indicated that compared with a straight channel, a hydrophilic pipe structure could effectively remove water from the gas diffusion surface (GDL) and reduce the surface water coverage of the GDL. With the increase in the diameter and height of the pipe structure, the GDL surface's water coverage first increased and then decreased, and it was less with the pipe structure than with the direct flow channel. The removal rate of water on the GDL surface was accelerated. The spacing of hydrophilic pipes has a significant impact on the transportation of water. As the spacing increases, the removal rate of water on the GDL surface slowed. A hydrophilic pipe structure with a diameter of 75 μm, a height of 400 μm, and spacing of 300 μm has good water removal performance on the GDL surface. This research work proposes a new internal structure design of the flow channel, which has specific implications for removing water on the GDL surface.     

Effect of transition metal doping on the sintering and electrochemical properties of GDC buffer layer in SOFCs

A dense Ce_0.9Gd_0.1O_2−d (GDC) interlayer is an essential component of the SOFCs to inhibit interfacial elemental diffusion between zirconia-based electrolytes (eg YSZ) and cathodes. However, the characteristic high sintering temperature of GDC (>1400°C) makes it challenging to fabricate an effective highly dense interlayer owing to the formation of more resistive (Zr,Ce)O₂ interfacial solid solutions with YSZ at those temperatures. To fabricate a useful GDC interlayer, we studied the influence of transition metal (TM) (Co, Cu, Fe, Mn, & Zn) doping on the sintering and electrochemical properties of GDC. Dilatometry data showed dramatic drops in the necking and final sintering temperatures for the TM-doped GDCs, improving the densification of the GDC in the order of Fe > Co > Mn > Cu > Zn. However, the electrochemical impedance data showed that among various transition metal dopants, Mn doping resulted in the best electrochemical properties. Anode supported SOFCs with Mn-doped, nano, and commercial-micron GDC interlayers were compared with regard to their performance and stability levels. Although all of the SOFCs showed stable performance, the SOFC with the Mn-doped GDC interlayer showed the highest power density of 1.14 W cm⁻² at 750°C. Hence, Mn-doped GDC is suggested for application as an effective diffusion barrier layer in SOFCs.     

α钛富氧层增厚动力学模型

为了实现在工业化生产中对α钛富氧层厚度预测和控制,通过实验研究α钛富氧层在高温空气环境中的形成及增厚过程,讨论热处理温度和时间的影响作用,建立高温(750~850℃)空气环境下关于温度、时间的富氧层增厚动力学模型。结果表明:当恒温热处理温度为750~850℃时,α钛富氧层厚度x与保温时间t0.5呈正比例关系,且升高热处理温度可显著提高富氧层增厚速度。在此温度范围内,氧原子的扩散激活能约为203473 J/mol,计算曲线与实验数据吻合性较好。结合文献中已有的扩散系数方程和实验测得的富氧层厚度数据,推导得到5个富氧层增厚动力学方程,其中3个方程的计算曲线与实验数据吻合性较好,可为实际生产中预估富氧层厚度提供理论支持。     

Lower down both ohmic and cathode polarization resistances of solid oxide fuel cell via hydrothermal modified gadolinia doped ceria barrier layer

Hydrothermal reaction in Cerium and Gadolinium solution as an optimization method is developed and first reported for the densification of gadolinia doped ceria, the barrier layer between Zirconia electrolyte and (La,Sr)(Co,Fe)O_3-δ cathode. This method is based on the hydrothermal reaction for nano particles in-situly grown on porous surface, to improve barrier layer density, alongside the sintering of cathode at 1075 °C. As a result, the ohmic resistance is prominently decreased by ～16.4 % at 750 °C for electrolyte supported symmetrical cell. Whereas, the cathode polarization resistance is decreased by as much as a factor of ～3 from 0.3702 Ω·cm² to 0.1325 Ω·cm² at 750 °C and $p_{O_2}=0.21atm$. Furthermore, the anode supported cell exhibits higher open circuit voltage, smaller area specific resistance, elevated performance output and less degradation. And this modified barrier layer shows reduced Sr migration in 300 h operation at 750 °C. The hydrothermal reaction is demonstrated to prepare denser and sintering-active barrier layer with faster oxygen ion transfer and better interface connection, with large-scale application prospects and cost-competitiveness.