Fabrication of Dense Zirconia Electrolyte Films for Tubular Solid Oxide Fuel Cells by Electrophoretic Deposition

Electrophoretic deposition (EPD) is used to produce zirconia electrolyte films for tubular solid oxide fuel cells. A simple suspension chemistry (8-mol%-yttria-stabilized zirconia particles in acetic acid) yields films of similar quality to those from conventional approaches (such as electrochemical vapor deposition), but at potentially much less expense. A key factor in obtaining high-density, adherent films via the EPD approach is the application of a thin fugitive phase (carbon in this study) on the porous, doped lanthanum manganite cathode tubes prior to zirconia deposition.     

流延法制备Ni-YSZ/YSZ复合基膜及性能测试

采用传统有机流延法制备NiO-YSZ/YSZ复合基膜,其中包括流延浆料配制及流延工艺过程.采用共烧结方式制备均匀平整的SOFC多孔阳极支撑的致密电解质膜,阳极支撑层厚度1000 μm、阳极功能层20 μm、致密电解质层40 μm左右.并对阳极孔隙率和电解质气体渗透率、显微结构及膨胀系数等进行测试.结果表明通过复合流延的方式可以制备出具有良好组织结构和性能的SOFC阳极支撑系统.     

固体氧化物燃料电池阳极研究

作为固体氧化物燃料电池(SOFC)的关键部件之一,阳极性能对SOFC性能有着十分重要的影响.本文主要对阳极研究进展进行综述,重点对阳极组织和性能方面的研究情况进行了阐述,合理选择阳极材料和制备工艺条件,优化阳极微观组织结构是获得高性能阳极的重要方面.对阳极材料选择和制备方法进行了简单的介绍.     

支撑体材料对NaA型沸石分子筛膜形成的影响

采用水热合成法制备NaA型沸石分子筛膜,实验比较了α-AI2O3、ZrO2及TiO2三种支撑体对NaA型沸石分子筛膜形成的影响。XRD测定所合成的沸石分子筛膜是NaA型。SEM和渗透实验结果表明,沸石分子筛膜的性能与支撑体有关,TiO2优于ZrO2和α-AI2O3。TiO2支撑体上合成沸石分子筛膜的H2、N2渗透系数大小基本与膜两侧平均压力无关,理想分离系数约为8,高于Kundsen扩散分离因子3．74,表现有一定的分子筛分效应。     

Synthesis of Highly Porous Yttria-Stabilized Zirconia by Tape-Casting Methods

Porous ceramics of Y₂O₃-stabilized ZrO₂ (YSZ) were prepared by tape-casting methods using both pyrolyzable pore formers and NiO followed by acid leaching. The porosity of YSZ wafers increased in a regular manner with the mass of graphite or polymethyl methacrylate (PMMA) to between 60% and 75% porosity. SEM indicated that the shape of the pores in the final ceramic was related to the shape of the pore formers, so that the pore size and microstructure of YSZ wafers could be controlled by the choice of pore former. Dilatometry measurements showed that measurable shrinkage started at 1300 K, and a total shrinkage of 26% was observed, independent of the amount or type of pore former used. Temperature-programmed oxidation (TPO) measurements on the green tapes demonstrated that the binders and dispersants were combusted between 550 and 750 K, that PMMA decomposed to methyl methacrylate between 500 and 700 K, and that graphite combusted above 900 K. The porosity of YSZ ceramics prepared by acid leaching of nickel from NiO–YSZ, with 50 wt% NiO, was studied as a function of NiO and YSZ particle size. Significant changes in pore dimension were found when NiO particle size was changed.     

Low-Temperature Fabrication of Oxide Composites for Solid-Oxide Fuel Cells

Composites of yttria-stabilized zirconia (YSZ) with Sr-doped LaCrO₃ (LSC) and Sr-doped LaMnO₃ (LSM) were prepared by impregnation of a porous YSZ matrix with aqueous solutions of the appropriate metal salts, followed by sintering to various temperatures. XRD measurements showed that perovskite phases formed after sintering at 1073 K, a temperature well below that at which solid-state reactions with YSZ occur. The conductivities of the LSC–YSZ and LSM–YSZ composites prepared in this way were maximized at a sintering temperature of 1373 K for LSC–YSZ and 1523 K for LSM–YSZ, although reasonable conductivities were achieved at much lower temperatures. The conductivities of the two composites increased much more rapidly with the content of the conductive oxide than has been found with conventional composites formed by mixing and sintering the oxide powders. The implications for using this approach to develop novel electrodes for SOFC applications are discussed.     

Porous Ceramic Membranes: Preparation, Transport Properties and Applications

The preparation and characterization of porous ceramic membranes is presented. These membranes consist of a macroporous support system, with or without a mesoporous intermediate layer, and a microporous top layer. For the macroporous support membranes two manufacturing routes are described: a conventional and a RBAO (Reaction Bonded Aluminium Oxide) route. The mesoporous -Al₂O₃ layer is obtained by means of a sol-gel dipcoating technique. Three microporous top layers are considered: SiO₂, Al₂O₃-pillared montmorillonite and Laponite. These top layers have different pore structures which results in different gas transport properties. A SiO₂ membrane can be used for H₂ removal from a gas mixture. Al₂O₃-pillared montmorillonite and Laponite membranes do not show specific gas separation properties. Dehydration of water/2-propanol mixtures by means of pervaporation also proved a different behavior for these microporous membranes.     

Preparation of Yttria-Stabilized Zirconia Thin Films on Strontium-Doped LaMnO3 Cathode Substrates via Electrophoretic Deposition for Solid Oxide Fuel Cells

A yttria-stabilized zirconia (YSZ) thin film on an La_0.8Sr_0.2MnO₃ porous cathode substrate was prepared, using electrophoretic deposition (EPD) to fabricate a solid oxide fuel cell (SOFC). The electrical conductivity of an La_0.8Sr_0.2MnO₃ substrate is satisfactorily high at room temperature; therefore, YSZ powder could be deposited electrophoretically onto an La_0.8Sr_0.2MnO₃ substrate without any extra surface treatment, such as a metal coating. Successive repetition of EPD and sintering was required to obtain a film without gas leakage, because of the thermal expansion coefficient mismatch between the YSZ and the La_0.8Sr_0.2MnO₃ substrate. On the other hand, the electromotive force of the oxygen concentration in the cell that used YSZ film prepared via EPD increased and attained the theoretical value when the number of deposition and calcination cycles was increased. Six or more successive repetitions were required to obtain a YSZ film without gas leakage. A planar-type SOFC was fabricated, using nickel as the anode and YSZ film (∼10 μm thick) that had been deposited onto the La_0.8Sr_0.2MnO₃ substrate as the electrolyte and cathode. The cell exhibited an open circuit voltage of 1.0 V and a maximum power density of 1.5 W/cm². Thus, the EPD method could be used as a colloidal process to prepare YSZ thin-film electrolytes for SOFCs.     

燃料电池用有机-无机杂化质子交换膜的研究进展

质子交换膜燃料电池具有能量转化效率高、寿命长、比功率和比能量高、以及对环境友好等优点。质子交换膜则是关键部件之一,它起到分隔燃料和氧化剂、传导质子和绝缘电子的作用,其性能和寿命直接决定电池的性能和寿命。本文主要介绍了有机无机杂化质子交换膜的特点,并对近几年的发展状况进行了综述,就其设计原理、制备方法及优缺点作了简要评述。     

Fabrication,characterization, and performance of YbDSB ternary compounds for IT‐SOFC applications

(Yb₂O₃)_x(Dy₂O₃)_y(Bi₂O₃)_1?x?y (0.04≤x+y≤0.20) powders (xYbyDSB) were synthesized by modified sol‐gel Pecchini method. The powders were characterized for structural, surface morphological, thermal, and electrical properties and power density measurements by means of X‐ray diffraction (XRD), scanning electron microscopy (SEM), differential thermal analysis/thermal gravimetry (DTA/TG), and impedance spectroscopy, respectively. Lattice parameters and crystalline size of δ‐phase of Yb₂O₃‐ and Dy₂O₃‐doped Bi₂O₃ samples were calculated from the X‐ray diffraction data. Surface and grain properties of the related phases were determined by SEM analysis. In the investigated system, the maximum electrical conductivity was observed as σ=0.954 S cm^?1 for 6% mol Yb₂O₃ and 6% mol Dy₂O₃ at 800°C among all δ‐YbDSB systems. Cathode supported electrochemical cell was fabricated and 6Yb6DSB was used as the electrolyte. Maximum power density of single cell with an active area of 1.5 cm² is 72.50 mW/cm² at 700°C.     

Fabrication and performance of PEN SOFCs with proton-conducting electrolyte

A positive-electrolyte-negative (PEN) assembly solid oxide fuel cell (SOFC) with a thin electrolyte film for intermediate temperature operation was fabricated. Instead of the traditional screen-printing method, both anode and cathode catalysts were pressed simultaneously and formed with the fabrication of nano-composite electrolyte by press method. This design offered some advantageous configurations that diminished ohmic resistance between electrolyte and electrodes. It also increased the proton-conducting rate and improved the performance of SOFCs due to the reduction of membrane thickness and good contact between electrolyte and electrodes. The fabricated PEN cell generated electricity between 600°C and 680°C using H₂S as fuel feed and air as oxidant. Maximum power densities 40 mW·cm⁻² and 130 mW·cm⁻² for the PEN configuration with a Mo-Ni-S-based composite anode, nano-composite electrolyte (Li₂SO₄+Al₂O₃) film and a NiO-based composite cathode were achieved at 600°C and 680°C, respectively.     

多孔壳聚糖膜的制备表征及其吸附性能研究

以琼胶固体颗粒为致孔剂,通过热致相转移法制备了的多孔壳聚糖膜,并通过FT-IR和SEM对其进行了表征,也考察了其对有机染料二甲苯蓝FF的吸附性能。结果表明,以琼胶作为制孔剂可以制备出性能良好的多孔壳聚糖膜,在吸附有机染料方面,多孔壳聚糖膜PCS-2对二甲苯蓝FF的吸附量是壳聚糖膜的1.3倍。另外,作为对比,本文也制备和表征了琼胶-壳聚糖共混薄膜。     

Vapor Phase Fabrication of Hydrophilic and Hydrophobic Asymmetric Polymer Membranes

The fabrication of asymmetric polymer membranes via vapor phase deposition is demonstrated. In this solventless process, the dense layer is deposited first and then the porous layer is subsequently deposited onto the dense layer. A variety of functional polymer membranes can be produced by varying the precursor molecules. The functionality of the dense and porous layers can be independently tailored to be either hydrophobic or hydrophilic, resulting in membranes that are fully hydrophilic, fully hydrophobic, or asymmetric in both structure and chemical functionality. The thickness of both the porous and dense layers can be separately tuned by controlling the deposition time.

     

复合陶瓷膜的研究现状及发展前景

在简要介绍复合陶瓷膜这一概念的基础上,对非对称性无机复合相顶层分离膜的研究现状进行了综述,概述了近期国内对以Al2O3,SiO2,ZrO2,TiO2为基础的不同材质的复合陶瓷膜的研究进展,提出了研究中存在的问题及复合膜的发展前景。     

Fabrication and operation of flow‐through tubular SOFCs for electric power and synthesis gas cogeneration from methane

Flow‐through type tubular solid oxide fuel cells were successfully fabricated and operated with a single‐chamber configuration for realizing the simultaneous generation of electric power and synthesis gas from methane by integrating a downstream catalyst into the fuel cell reactor. A new operation mode, which completely eliminated the gas diffusion between cathode side and anode side, is proposed. The cell showed high open‐circuit voltages of 1.02–1.08 V at the furnace temperature range of 650–800°C when operating on CH₄‐O₂ gas mixture at a molar ratio of 2:1. A peak power density of approximately 300 mW cm^?2 and a maximum power output of 1.5 W were achieved for a single cell with an effective cathode geometric surface area of 5.4 cm² at the furnace temperature of 750°C. The in‐situ initialization of the cell using CH₄‐O₂ gas mixture was also realized via applying an effective catalyst into the tubular cell. © 2013 American Institute of Chemical Engineers AIChE J, 60: 1036–1044, 2014     

Effects of Thermal Treatment on Gas Transport Through Porous Silica Membranes

Abstract

The effects of thermal treatment from 180°C to 1150°C on the gas transport properties of porous silica membranes were systematically studied for various gases. The permeance of all gases, except for CO₂, has a maximum at 800°C. The CO₂ permeance was constant from 180°C to 600°C and then decreased monotonically. Membranes thermally treated at 1150°C did not exhibit any gas permeation because of pore collapse. The gas transport behavior follows a combination of Knudsen diffusion and surface diffusion for all gases tested except for carbon dioxide. The permeation of carbon dioxide is strongly affected by capillary condensation. We propose a new transport model composed of two components; that is, the Knudsen diffusion factor, α, and the surface diffusion factor, β. A transition was observed for α and β at around 800–900°C, which is close to the strain point of the membrane. This transition treatment temperature can be correlated with the changes in gas permeance. The model allows qualitative evaluation of gas transport through porous membranes regardless of their actual microporous structures.     

壳聚糖基Semi-IPN多孔膜的制备及其吸附性能的研究

利用戊二醛在成膜时使壳聚糖交联,形成壳聚糖／聚乙二醇半互穿网络,进一步抽提制得壳聚糖基多孔膜。多孔膜在溶液中有较好的化学稳定性,孔径尺寸在亚微米级别,可以通过改变交联剂用量得到不同孔结构的多孔膜。多孔膜对甲基橙和活性橙82有较好的吸附性,染料分子的极性基团越多,壳聚糖基多孔膜对其吸附能力越强。     

Stability and Activity of (Pr1‐xNdx)2NiO4 as Cathodes for Solid Oxide Fuel Cells: I. Quantification of Phase Evolution in Pr2NiO4

Praseodymium nickelate (Pr₂NiO₄) is an active oxygen electrode for solid oxide fuel cells, but undergoes phase transition at elevated temperatures (e.g., 750°C). Quantification of this phase evolution in an operating single cell is challenging because of the overlap of X‐ray diffraction (XRD) peaks between the cathode and oxide current collector. In this work, we replace the oxide current collector with a gold metal grid, circumventing these challenges by allowing the exposure of the cathode to the X‐ray beam, while eliminating peak overlap. Quantification of the phase evolution was performed by a least‐squares fitting of the linear combination of XRD standards against the experimental patterns. Energy‐dispersive spectroscopy analysis on long‐term operated cells showed the absence of reactions between the gold grids and the cathodes. Additionally, the grids exhibited excellent mechanical stability under operating conditions and enabled similar cell performance as an oxide current collector.     

陶瓷膜过滤细微颗粒悬浮体系的数学模拟

通过对陶瓷膜过滤悬浮液过程中单颗粒的受力分析,获得了可沉积颗粒临界粒径(xcrit)的计算公式.计算的xcrit值与实验测定的沉积层内的粒径分布一致:随颗粒粒径的增大, xcrit呈先增大后减小的趋势. 在讨论xcrit与颗粒粒径(dp)、膜孔径(dm)关系的基础上,将微滤过程按dp/dm的比值分为三种类型:dp/dm≤1, 颗粒迅速阻塞膜孔;1＜dp/dm≤10 ,颗粒在膜表面形成连续滤饼;dp/dm》10,颗粒对膜孔口覆盖,在膜表面形成不连续滤饼.并以此为基础建立了预测陶瓷膜过滤不同粒径和粒径分布的颗粒悬浮液渗透通量的数学模型.计算结果与实验结果的比较表明:本模型对文献模型的改进之处是适用范围从1＜dp/dm≤10扩展到0.48≤dp/dm≤120;在操作压力对渗透通量的影响计算中,假设滤饼层孔隙率不变的计算结果与实验结果一致,说明此体系的滤饼是不可压缩的;在错流速率对渗透通量的影响计算中,假定滤饼层孔隙率随错流速率成指数变化的计算结果比假定沉积层孔隙率随错流速率不变的计算结果好,说明错流速率的变化同时影响滤饼层内颗粒的粒径分布和其形成的滤饼层的结构.     

氨燃料固体氧化物燃料电池性能研究进展与展望

氨是一种零碳燃料,也是富氢载体,具有较大储运优势。固体氧化物燃料电池(solid oxide fuel cell, SOFC)是一种清洁高效发电装置,在分布式发电、热电联供、储能调峰等领域有广阔应用前景,氨气可直接用作SOFC阳极燃料以实现高效、清洁、低成本发电。首先简介了质子传导型和氧离子传导型氨SOFC的工作原理,电解质、电极材料的选择以及氨气在阳极的分解过程。其次总结了氨SOFC的实验研究现状,以单电池最大功率密度为评价指标,综述了不同电解质/电极材料、电解质厚度、操作温度等因素下两种传导类型的氨SOFC的性能表现,并分析了造成电池性能差异的原因。之后介绍了氨SOFC当前面临的挑战,最后对氨SOFC未来研究方向、热电联供系统的应用进行了展望。