微管式固体氧化物燃料电池电解质膜的制备

基于聚合物溶液相分离诱导原理提出了一种新的微管式固体氧化物燃料电池（SOFC）电解质膜制备方法,应用该方法制得了YSZ电解质微管膜,该膜由致密电解质薄层和可制成电极的多孔层组成,其中YSZ致密电解质膜和多孔层厚度分别为3～5μm和70-90μm,而多孔层内表面孔隙率高于28．1％,电解质层和多孔层之间结合紧密,可避免电解质膜开裂或剥落等导致的电池性能降低等问题．该方法具有工艺简单、成本低、可靠性好等优点,为微管式SOFC电解质膜及电池的制备提供了一条新的途径．     

Matrimid5218/PSf双层非对称中空纤维膜的制备及其气体分离性能研究

以商业化聚酰亚胺Matrimid5218作为功能层材料,聚砜作为支撑层材料,采用共挤出法制备双层非对称中空纤维气体分离膜.所制备的双层非对称中空纤维膜具有致密无缺陷的超薄皮层,致密皮层厚度约为0.21μm.在25℃,0.5 MPa下,CO2/CH4的选择性系数达51.39,CO2的渗透系数为46.29 GPU,O2/N2的选择性系数达到7.13,O2的渗透速率为6.38 GPU.考察了温度和压力对膜的渗透系数和选择性系数的影响,并考察了物理老化对膜性能的影响.     

Matrimid®5218/PSf双层非对称中空纤维膜的制备及其气体分离性能研究

以商业化聚酰亚胺Matrimid®5218作为功能层材料, 聚砜作为支撑层材料, 采用共挤出法制备双层非对称中空纤维气体分离膜. 所制备的双层非对称中空纤维膜具有致密无缺陷的超薄皮层, 致密皮层厚度约为0.21 μm. 在25 ℃, 0.5 MPa下, CO2/CH4的选择性系数达51.39, CO2的渗透系数为46.29 GPU, O2/N2的选择性系数达到7.13, O2的渗透速率为6.38 GPU. 考察了温度和压力对膜的渗透系数和选择性系数的影响, 并考察了物理老化对膜性能的影响.     

真空注浆法制备YSZ电解质膜管及其在固体氧化物燃料电池中的应用

以吡啶为分散剂,采用真空注浆法制备出膜厚为0.2mm、长度为140mm的致密YSZ电解质膜管。研究了烧结温度对样品致密度和离子导电率的影响.用1650℃烧结2h制备的致密YSZ电解质膜管组装成固体氧化物燃料电池,以氢气和煤气为燃料,研究了电池在500～900℃的电化学性能.实验结果表明,用真空注浆法可制备出高质量和高密度的YSZ电解质膜管,在1600℃烧结后,其相对密度已达到理论密度的98.1%,接近理论密度.单电池的开路电压最大值为1.213V,最大输出功率为0.48W.以氢气为燃料的燃料电池性能明显高于以煤气为燃料的电池性能.     

直接氨固体氧化物燃料电池

塑性挤压成型阳极支撑管,采用真空浸涂法在阳极表面制备了均一、致密的氧化钇稳定的氧化锆电解质层,然后在电解质表面刷涂上阴极层,成功制备了阳极支撑型管状固体氧化物燃料电池.分别以氢气和氨气为燃料,考察了该管状固体氧化物燃料电池的电池性能.在800℃操作时,以氢气和氨气为燃料的电池最大输出功率密度分别为202和200 mW/cm2.表明氨气可以作为固体氧化物燃料电池的替代燃料.     

低温制备掺杂氧化锆/氧化铈电解质

固体氧化物燃料电池(SOFC)及其组元的低温制备有利于材料和电池性能的优化,降低制备成本.立方相的全致密氧化钇稳定氧化锆(YSZ)电解质是SOFC中最通用的电解质.传统的烧结工艺需要在1 400-1 450℃才能实现YSZ电解质的致密,而使用纳米粉体和三步烧结工艺可以在1 200-1 300℃得到致密电解质.氧化钪稳定...     

PEBAX®2533/PSf中空纤维复合膜制备及阻力性能

采用浸渍涂层法制备了聚醚共聚酰胺(PEBAX®2533)/聚砜(PSf)中空纤维复合膜. 考察了涂层液浓度、 温度和基膜预处理对复合膜结构、 阻力及渗透性能的影响, 并考察了操作压力对膜渗透性能的影响. 实验结果表明, 随着涂层液浓度的增加, 复合膜致密层厚度及阻力增大, 复合膜总阻力及支撑层阻力先增大后减小, CO2渗透速率先减小后增大, 分离系数增大. 随着涂层温度升高, 复合膜致密层厚度及阻力减小, 支撑层阻力增大, 复合膜总阻力先减小后增大, 分离系数和渗透速率先增大后减小. 经过预处理, 复合膜致密层厚度减小、 阻力大幅度减小, CO2渗透速率增大58%, 分离系数略有下降. 复合膜支撑层阻力过大, 尤其是支撑层的致密结构影响复合膜的塑化行为.     

界面预湿处理对异质增强型PVDF中空纤维膜结构与性能的影响

以熔融纺丝聚氯乙烯(PVC)中空纤维多孔膜为增强体,聚偏氟乙烯(PVDF)为成膜聚合物,聚乙烯吡咯烷酮(PVP)为添加剂,N,N-二甲基乙酰胺(DMAc)为溶剂,配置铸膜液,采用同心圆牵引-涂覆法制备了异质增强型PVDF中空纤维膜.制备过程中,采用预湿溶液对增强体基膜表面进行预处理,研究了预湿溶液组成及含量对异质增强型PVDF中空纤维膜结构与性能的影响.结果表明,未经预湿处理的异质增强型PVDF中空纤维膜具有较厚的致密界面层;预湿溶液可对基膜表面孔起到保护作用,使异质增强型PVDF中空纤维膜的界面层变薄或形成多孔界面层,有益于改善增强型PVDF中空纤维膜的通透性能;与二甲基乙酰胺(DMAc)水溶液相比,以乙醇水溶液为预湿溶液所得异质增强型PVDF中空纤维膜的性能较优;当预湿液中乙醇含量为60 wt%时,所得增强型PVDF中空纤维膜的渗透性能较优,拉伸强度可达8.61 MPa.     

Ce_(0.8)Sm_(0.2)O_(1.9)固体电解质的电子电导性研究

应用溶胶-凝胶法制备了Ce_(0.8)Sm_(0.2)O_(1.9)固体电解质粉体,通过X射线衍射对所制备的电解质粉体进行了物相分析。研究表明,Sm2O3已经固溶到CeO_2中形成了具有萤石结构CeO_2基固溶体。经成型并在1450℃下烧结2 h获得致密的Ce_(0.8)Sm_(0.2)O_(1.9)固体电解质。通过组装含有氧离子阻塞电极电池(-)致密Al2O3,Pt|Ce_(0.8)Sm_(0.2)O_(1.9)(SDC)固态电解质|Pt,O2(+)测试空气中不同温度下的电子电导。应用扫描电子显微镜观察所制备试样的微观组织形貌,结果表明:制备的电解质组织致密,高温粘合剂、电解质及刚玉坩埚结合紧密,保证了阻塞电极的气密性。采用Hebb-Wagner离子阻塞电极法测定了Ce_(0.8)Sm_(0.2)O_(1.9)在空气气氛下的电子导电性。结果显示:在测量温度范围内Ce_(0.8)Sm_(0.2)O_(1.9)固体电解质的电子电导率在1×10-8~1×10-6m S·cm-1之间,经计算得出活化能的平均值为0.9885 e V。     

聚偏氟乙烯电纺膜及其电化学性能的研究

用电纺的方法制备了聚偏氟乙烯纳米纤维膜,它们具有多微孔结构,能够作为锂电池聚合物电解质.电纺中聚合物溶液的浓度对制备的电纺膜的结构形态有很大的影响,低浓度(10 wt%)时得到珠丝结构的膜,浓度15 wt%时则为纤维结构,而高浓度(18 wt%)时,电纺膜为交联的网状结构.用电纺法制备的聚偏氟乙烯纳米纤维微孔膜具有较高的孔隙率,而且它们与锂金属电极具有良好的界面稳定性;在25℃时吸液率最高可达340%,以这种膜制备的聚合物电解质室温电导率可达到1.57×10-3S.cm-1;由该电解质组装的扣式电池以0.5 mA.cm-2恒流充放电,25℃时50次循环后几乎无容量损失,具有良好的循环性能;即使60℃时,电池仍能保持良好的工作稳定性.     

Preparation of microtubular solid oxide fuel cells based on highly asymmetric structured electrolyte hollow fibers

A simple and cost-effective method has been developed for the fabrication of microtubular solid oxide fuel cells (MT-SOFCs). Highly asymmetric electrolyte hollow fibers composed of a thin dense skin layer and a thick porous substrate are first prepared by a modified phase inversion/sintering technique. The porous substrate is then formed into the anode by deposition of a Ni catalyst via an electroless plating method inside the pores while the thin dense skin layer serves directly as the electrolyte film of ...     

Preparation of electrolyte membranes for micro tubular solid oxide fuel cells

Yttria-stabilized zirconia (YSZ) micro tubular electrolyte membranes for solid oxide fuel cells (SOFCs) were prepared via the combined wet phase inversion and sintering technique. The as-derived YSZ mi- cro tubes consist of a thin dense skin layer and a thick porous layer that can serve as the electrode of fuel cells. The dense and the porous electrolyte layers have the thickness of 3-5 μm and 70-90 μm, respectively, while the inner surface porosity of the porous layer is higher than 28.1%. The two layers are perfectly integrated together to preclude the crack or flake of electrolyte film from the electrode. The presented method possesses distinct advantages such as technological simplicity, low cost and high reliability, and thus provides a new route for the preparation of micro tubular SOFCs.     

Single-step fabrication of asymmetric dual-phase composite membranes for oxygen separation

Asymmetric dual-phase composite membranes for oxygen separation were conveniently fabricated by an acid leaching technique. A thin dense layer of Ce_0.85Sm_0.15O_1.925/Sm_0.6Sr_0.4FeO_3−δ was left by controlling the degree of acid leaching, and a porous substrate of Ce_0.85Sm_0.15O_1.925 with a fluorite structure was formed after dissolution of Sm_0.6Sr_0.4FeO_3−δ with a perovskite structure in HCl. Thus, a thin dense layer and a porous substrate can be fabricated in a single step in which traditional shrinkage mismatch and chemical reaction between thin dense layers and porous substrates can be avoided. The thickness of the dense layer can be controlled by varying the acid leaching time. Hence, dual-phase composite membranes with high oxygen flux can be obtained.     

Preparation of Doped Ceria Electrolyte Films for SOFCs by Spray Coating Method

Spray coating method is a cost-effective technique suitable for the preparation of uniform and large-area thin films. This article presents findings on the preparation of dense electrolyte thin films by spray coating method. Dense, crack-free Gd-doped CeO₂ (GDC) thin films with a thickness of approximately 2 µm were successfully prepared on porous NiO-GDC substrates. The influence of the dispersion of GDC nanopowders in susupension on the microstructure of the thin films was investigated. Results show that agglomeration of GDC nanopowders in suspension resulted in a porous microstructure and a densely packed microstructure was obtained for the film prepared from a well-dispersed suspension.     

Wetting properties of polystyrene/divinylbenzene crosslinked porous polymers obtained using W/O highly concentrated emulsions as templates

Macroporous polystyrene/divinylbenzene (PS‐DVB) monoliths were obtained using highly concentrated W/O emulsions as templates. These monoliths are of interest due to the high potential applications for catalysis, scaffolds for tissue engineering, filters, membranes, or drug delivery systems. Dynamic wetting behavior through the polymer monolith is directly related to contact angle. For this reason, in this paper we investigate the relationship between contact angle, morphology, and chemical composition of the dense skin layer and the highly porous interior surface of PS‐DVB porous monoliths. Whereas the dense skin layer exhibits a Wenzel regime using water as wetting liquid, the highly porous interior surface exhibits a Cassie–Baxter regime. This behavior is correlated with the roughness observed by scanning electron microscopy (SEM). However, the observed contact angle hysteresis seems to indicate that factors other than surface roughness should be taken into account. For this reason, chemical composition was also studied by elemental microanalysis and X‐ray photoelectron spectroscopy (XPS). The differences in chemical composition observed between the dense skin layer and the highly porous interior surface, according to the wetting model for a heterogeneous surface proposed by Johnson and Dettre, seems also to contribute to the wetting hysteresis. The different wetting between the dense skin layer and the highly porous interior surface results in a dual wettability phenomenon, in which a liquid wets the dense skin layer and does not penetrate into the highly porous interior of the PS‐DVB monoliths. This phenomenon can be of relevance in absorption or desorption processes such as in drug delivery processes. Copyright © 2009 John Wiley & Sons, Ltd.     

Mass transfer characteristics for VOC permeation through flat sheet porous and composite membranes: The impact of the different membrane layers on the overall membrane resistance

In this paper, the mass transfer coefficients for trichloroethylene (TCE), toluene (TOL) and dimethyl sulfide (DMS) are experimentally determined for different porous and composite membranes. For polypropylene/polyvinylidenedifluoride porous layer/thin film polydimethylsiloxane dense layer composite membranes, membrane mass transfer coefficients are 2.55E−03, 2.82E−03 and 2.90E−03 m/s for TCE, TOL and DMS in N₂ at 30.0 ± 0.1 °C, respectively. For polyester/polyacrylonitrile porous layer/thin film polydimethylsiloxane dense layer composite membranes, they are higher, namely 4.28E−03, 4.55E−03 and 4.81E−03 m/s for TCE, TOL and DMS in N₂ at 30.0 ± 0.1 °C, respectively. Analysis of the contribution of the dense layer of both composite membranes to the total membrane resistance for mass transfer, showed that this contribution was small for both composite membranes. The higher mass transfer coefficients of the thin film polydimethylsiloxane composite membranes from this study in comparison to others from the literature are primarily due to improvement of the mass transfer characteristics of the porous layer. Analysis of the mass transfer characteristics of the different porous layers of which the total porous layer is composed, showed that the contribution of the porous “backing” layer for mechanical support can be substantial in comparison to the porous layer in contact with the dense layer.     

Formation of integrally skinned asymmetric polysulfone gas separation membranes by supercritical CO2

Integrally skinned asymmetric polysulfone membranes were prepared from originally dense films inducing asymmetry by the formation of the porous layer adding to one side of the membranes chloroform and supercritical CO₂ (SCCO₂), and then allowing the SCCO₂ expansion to occur. The influence of the chloroform/polysulfone mass ratio (g CH₃Cl/g PSF), SCCO₂ density and depressurization rate over the thickness of both the porous and the dense skin layers, the morphology of the porous support and the pure O₂ and N₂ permeability and selectivity performance were studied.The results show that it is possible to induce a very-controlled asymmetry in a dense film following the procedure described in this work and as expected, the thickness of the porous layer increases while the dense skin layer decreases as the chloroform/polysulfone mass ratio increases. Images of the porous layer show that the average-pore size decreases at high SCCO₂ densities and slightly decreases with increasing the CO₂ depressurization rates. The O₂ and N₂ permeability coefficients, measured at 35 °C and 2 bar, for the polysulfone asymmetric membranes are practically the same of those determined in dense films, suggesting that the dense skins are essentially defect-free of pinholes.     

Examination of wet coating and co-sintering technologies for micro-SOFCs fabrication

Preparation conditions to obtain a dense electrolyte layer on a micro-tubular electrode support were investigated using wet coating and subsequent co-firing techniques. An anode-supported micro-tubular SOFC with 1.5 mm diameter was successfully fabricated by careful control of the co-sintering process of electrolyte/anode support laminates. The densification of the electrolyte layer deposited on the support surface was greatly affected by the shrinkage of tubular support during the co-sintering process. Support shrinkage above 15% was found to produce a fully densified electrolyte layer on the anode support. In contrast, the use of an anode support with shrinkage below 10% constrained gadolinium-doped ceria (GDC) sintering, resulting in a poorly densified GDC microstructure. Finally, we obtained a micro-tubular cell composed of a dense GDC and a porous (La,Sr)(Co,Fe)O₃–GDC multi-layered structure on a NiO–GDC micro-tubular anode support. The cell, with a dense and ≈15 μm thick GDC electrolyte layer, was electrochemically evaluated in a temperature range from 450 to 550 °C. This micro-tubular cell with an electrode length of 6.3 mm showed a power density above 0.1, 0.2 and 0.4 W/cm² at 450, 500 and 550 °C, respectively, in wet H₂ fuel flow.     

Permeation of carbon dioxide through homogeneous and asymmetric polysulfone membranes

To confirm the validity of the working assumption that a thin dense skin layer in an asymmetric membrane can be essentially replaced by a thick homogeneous dense membrane, both homogeneous and asymmetric polysulfone membranes were prepared by solvent casting, and the permeation behavior of carbon dioxide through these two types of membranes was investigated. The pressure dependence of the mean permeability coefficient through an asymmetric polysulfone membrane is apparently very similar to that through a homogeneous dense membrane, following the dual mode mobility model driven by gradients of chemical potential. The dense skin layer in the asymmetric membrane can be simulated approximately by a homogeneous dense membrane from the point of view of gas sorption and diffusion.     

In Situ Electrodeposition of an Asymmetric Sol–Gel Membrane Based on an Octadecyltrimethoxysilane Langmuir Film

The unique properties of Langmuir film formation were utilized in assembling a thin skin of an asymmetric membrane. An octadecyltrimethoxysilane (ODTMS) Langmuir monolayer was formed at the air–water interface and served as the substrate for growing a bulky sol–gel polymer in situ. The latter was based on the electrochemical deposition of tetramethoxysilane dissolved in the water subphase by means of horizontal touch electrochemistry. The resultant asymmetric layer that consisted of a thin hydrophobic ODTMS Langmuir film connected to a bulk hydrophilic sol–gel network was studied in situ and ex situ by using various techniques, such as cyclic voltammetry, electrochemical impedance spectroscopy (EIS), scanning electron microscopy, transmission electron microscopy (TEM), and goniometry. We found that a porous hydrophilic film grew on top of a hydrophobic layer as was evident from TEM, contact angle, and EIS analyses. The film thickness and film permeability could be controlled by changing the deposition conditions such as the potential window applied and its duration. Hence, this method offers an alternative approach for assembling asymmetric films for various applications