固体氧化物燃料电池电解质制备方法的研究

固体氧化物燃料电池(SOFC)作为一种绿色能源得到了广泛关注,SOFC中关键材料是电解质,LaGaO_3基固体电解质(LSGM)不仅离子电导率高,而且在电池工作时稳定性好,因此成为了研究焦点。本文综述了制备中低温固体氧化物燃料电池电解质LSGM的三种方法,包括传统的固相反应法、高温高压法和溶胶凝胶法;介绍了各种方法的流程以及它们各自的优缺点。     

氧化锆基固体电解质研究

电解质是固体氧化物燃料电池（SOFC）的核心部件,其性能的优良直接决定燃料电池的应用前景。氧化锆基陶瓷具有较高的离子电导率、良好的结构和化学稳定性,是理想的固体电解质材料。本文综合介绍了各种掺杂元素对氧化锆基固体电解质性能的影响,电解质薄膜制备方法和研究现状。并对氧化锆基固体电解质的研究方向进行了展望。     

固体氧化物燃料电池氧化锆基电解质薄膜制备技术研究进展

固体氧化物燃料电池(SOFC)具有高能量转化效率、环境友好性等特征,是全球能源环境问题的重要解决方案。电解质作为SOFC的关键组件,决定了电池的工作温度与输出性能。首先,以典型的氧化锆基电解质材料为例,介绍了其导电机理和导电性能的影响因素。为促进SOFC的商业化,电解质材料需在较低的工作温度下有较低的欧姆阻抗,电解质薄膜化是降低电池工作温度的有效方法。而后,从固相粉体成型、液相成型、气相成型3个方面综述了氧化锆基电解质薄膜的常见制备方法,并分析各种方法的优劣势。最后,对电解质薄膜的制备方法做简要展望。     

微管式固体氧化物燃料电池制备技术及电堆组装工艺

微管式固体氧化物燃料电池(MT-SOFC)能显著减小固体氧化物燃料电池(SOFC)的体积,微型化结构使其传质、传热和反应效率明显提高,可实现快速启动与关闭,易于移动和携带。本文概述了微管式固体氧化物燃料电池的结构、关键制备工艺、研究现状、存在问题和应用前景。对电解质支撑型、阳极支撑型及阴极支撑型MT-SOFC结构和性能进行了分析比较,介绍了等静压成型、挤出成型和相转化纺丝法制备陶瓷中空纤维的技术,综述了微管负载型电解质膜技术和微管电池堆组装技术,并对MT-SOFC发展方向及在便携电源、汽车动力电源和微反应器领域的应用进行了展望。     

不同黏结剂体系对水基流延成型Y2O3稳定ZrO2的影响

分别采用聚乙烯醇(potyvinyl alcohol,PVA)、乳胶B1070和PVA B1070复合黏结剂体系,水系流延成型法制备固体氧化物燃料电池(solid oxidefuel cell,SOFC)电解质8%(摩尔分数)Y2O3稳定的ZrO2(8YSZ)薄膜.研究了不同黏结剂对流延工艺以及对流延坯片的影响.结果表明:不同黏结剂加入后浆料的黏度和剪切变稀程度随PVA加入量的增加而增大.相反,浆料的黏度和剪切变稀程度随B1070加入量的增大而减小.发现使用不同黏结剂对流延坯片的生坯密度和干燥收缩具有重要的影响.8YSZ坯片的烧结密度随着生坯密度增大而增大,以300(质量分数,下同)PVA 70?070为复合黏结剂,8YSZ与黏合剂的质量比为0.93,流延成型的坯体在1 400℃保温2 h烧结能获得相对密度达98.5%的SOFC电解质8YSZ薄膜.     

金属陶瓷阳极材料的高效固体氧化物燃料电池研究

固体氧化物燃料电池(SOFC)利用金属陶瓷作阳极材料,具有能量转换效率高、燃料适用性强和无腐蚀等优点,是当今一种先进的能量转换装置。本文分析了固体氧化物燃料电池在电解质和电极材料方面的性能和特点,研究了金属陶瓷阳极材料及SOFC单电池的伏安特性和性能,探讨了固体氧化物燃料电池的应用和发展前景。     

具有复合电解质的低温固体氧化物燃料电池研究进展

高温固体氧化物燃料电池(SOFC)的低温化对于解决材料的稳定性、提高系统运行寿命和降低电池成本具有重要的意义,已成为近几年的研发热点。在实现SOFC低温化方面,目前国内外研究学者提出了不同的解决策略。综述了低温固体氧化物燃料电池(LT-SOFC)中复合电解质的研究进展,其包括引入碳酸盐材料作为第二相进行复合,构建类熔融碳酸盐固体氧化物燃料电池;引入过渡金属氧化物材料作为第二相进行复合,制备单组分燃料电池消除电极与电解质界面电阻提高电池性能,尤其是全氧化物复合电解质提高电池稳定性策略;引入半导体材料复合进一步提升LT-SOFC的电化学性能等几个方面。最后阐述了通过制备新型纳米复合材料进一步提升电解质离子电导率,改善界面接触问题以及探索新的电极材料对LT-SOFC电化学性能的影响。     

对流-扩散法制备多孔衬底支撑梯度结构电解质薄膜

以多孔氧化铝(porous alumina,p-Al2O3)为模型多孔电极衬底材料,利用对流-扩散效应成功制备得到了具有梯度结构的8%(以摩尔计)钇稳定氧化锆(yttria-stabilized zirconia,YSZ)电解质薄膜.该方法新颖、经济简单、适合于制备大尺寸平板型固体氧化物燃料电池中多孔电极支撑的电解质薄膜.利用扫描电镜和X射线角散分析技术对所制备电解质薄膜/p-Al2O3样品进行了微结构测试和表征.结果表明:由该方法在多孔衬底上实现的YSZ电解质薄膜由生长于衬底表面上的均匀致密层(≈10μm)和衬底表面下孔道中均匀填充层(≈50μm)与弥散填充层(≈250μm)构成,且各层厚度可通过改变对流-扩散沉积条件得到调节.     

硫化氢固体氧化物燃料电池研究进展

综述了H2 S固体氧化物燃料电池 (SOFC)的发展历史和研制现状 ,包括固体电解质薄膜如质子传导膜和氧离子传导膜的开发、电极催化材料尤其是阳极催化材料的研制、以及整个电池系统的性能研究。指出H2 SSOFC在工业化过程中所面临和必须解决的关键技术问题是 :电解质薄膜材料的研制及其制备 ,尤其是薄膜化的制备技术 ;电极材料的开发及制备 ,特别是阳极催化材料的选择与制备技术 ;膜 -电极三合一制备技术。并对H2 SSOFC的开发及工业应用前景作了展望     

金属支撑固体氧化物燃料电池研究进展

与传统全陶瓷结构的燃料电池不同,金属支撑固体氧化物燃料电池利用多孔金属来支撑功能阳极层–电解质层–阴极层,具有结构稳定性高、抗热快速热循环能力强,电堆组装简单,材料成本低等优势。本文分析了金属支撑固体氧化物燃料电池(SOFC)材料的选择和电池制备过程中的关键问题,并概述了金属支撑SOFC技术的研究进展。     

燃料电池固体氧化物电解质研究进展

本文对当前燃料电池用固体电解质材料的研究进展进行了综述.首先介绍了固体氧化物燃料电池的发展趋势及其与电解质材料性能的关系,然后分别对Y2O3稳定ZrO2(YSZ)、Sc2O3稳定ZrO2(ScSZ)、Ce基材料和其他一些电解质材料如Bi2O3、LaGaO3的制备、掺杂和电导率性能等方面进行了总结.最后,提出了今后电解质材料研的几个重要方向.     

Predictions on conductivity and mechanical property evolutions of yttria-stabilized zirconia in solid oxide fuel cells based on phase-field modeling of cubic-tetragonal phase transformation

Solid oxide fuel cell (SOFC) recently emerges as a promising power production technology with high efficiency. However, the degradation of yttria-stabilized zirconia (YSZ) electrolyte, brought by the cubic-tetragonal (c-t) phase transformation, remains a critical issue. Here, the c-t phase transformation of YSZ and its influences on the SOFC are quantitively investigated. First, micro-Raman spectroscopy characterization validates the occurrence of the c-t phase transformation during long-term operation. A microelasticity phase-field model is then built to simulate the phase transformation. The effects of variant nuclei and the misorientation angle between adjacent grains are investigated first based on both single-crystal and double-crystal systems. Subsequently, the phase-field model is applied on the 3D reconstructed real microstructure of polycrystalline YSZ. The results indicate that larger misorientation angles between adjacent grains suppress the development of the variants, and thus benefit in maintaining the ionic conductivity of the electrolyte and the mechanical strength of SOFCs.     

亚微米晶粒氧化钇稳定氧化锆电解质的稳定性

氧化钇稳定氧化锆(yttria-stabilized zirconia,YSZ)是目前使用最多的电解质材料,YSZ结构和性能的长期稳定对固体氧化物燃料电池(solid oxide full cell,SOFC)系统的可靠性至关重要。重点研究了具有亚微米结构的YSZ在850℃环境中的长期老化性能,结果发现:在850℃空气气氛中老化处理300h后,YSZ中小于1μm的部分晶粒出现了继续生长的现象,使得小于1μm晶粒比例下降10%～20%;当这部分晶粒长大到1～2μm,呈现稳定状态,即没有出现晶粒的过分长大;老化600h和1000h后,小晶粒(小于1μm)所占比例几乎不变。伴随着晶粒尺寸分布变化,YSZ电解质的电导率也比老化处理初期(300h)有所降低;当老化处理600h后,电导率下降趋势变缓;老化处理1000h后,电导率基本稳定,且1000℃电导率仍然保持在0.15S/cm以上。电导率下降主要是由YSZ晶粒部分长大引起的。具有上述性能的YSZ用作SOFC电解质可以满足长期使用的要求。     

固体氧化物燃料电池电解质材料的研究进展

固体氧化物燃料电池(SOFC)被誉为21世纪最具有发展潜力的能源材料之一,它的热效率高、燃料的适应性强,能很好地满足区域供电、供热的需要,具有重要的经济和社会意义。本文综述了SOFC电解质的研究进展,指出在诸多的电解质材料中,尽管氧化铋系电解质拥有最高的电导率,但由于其化学稳定性很差,难以获得广泛的应用;氧化钇全稳定的氧化锆(YSZ)由于其中低温的电导率较低,只适用于高温SOFC;稀土掺杂的氧化铈和LaGaO3钙钛矿材料拥有较高的中低温电导率,性质较为稳定,是适用于中低温SOFC的电解质材料。     

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.     

Improved Electrodes/Electrolyte Interfaces for Solid Oxide Fuel Cell by Using Dual‐Sized Powders in Electrolyte Slurry

The dense electrolyte film with the rough surfaces for solid oxide fuel cell (SOFC) was fabricated on NiO/yttria‐stabilized zirconia (YSZ) anode substrate by using dual‐sized YSZ powders without additional effort to roughen electrolyte film. The dual‐sized YSZ powders consisted of the fine YSZ powder and the coarse YSZ powder at different weight ratios. Incorporation of the coarse YSZ powder into the fine YSZ powder is in order to increase the surface roughness of electrolyte film, and the surface roughness obviously increased with the increase of coarse YSZ powder. The rough surfaces resulted in an enlargement of the electrochemical active area. It was found that electrode polarization was reduced evidently and cell electrochemical performance was enhanced, as the surface roughness increased. However, the excessive coarse YSZ powder was not beneficial for densification of electrolyte film and thus the open‐circuit voltage (OCV) was declined. The cell with 17 wt.% coarse YSZ powder in the electrolyte exhibited the best performance and the maximum power density was 1,930 mW cm^–2 at 800 °C.     

Electrophoretic Deposition of Zirconia Thin Film on Nonconducting Substrate for Solid Oxide Fuel Cell Application

Electrophoretic deposition (EPD) of 8 mol% yttria‐stabilized zirconia (YSZ) electrolyte thin film has been carried out onto nonconducting porous NiO‐YSZ cermet anode substrate using a fugitive and electrically conducting polymer interlayer for solid oxide fuel cell (SOFC) application. Such polymer interlayer burnt out during the high‐temperature sintering process (1400°C for 6 h) leaving behind a well adhered, dense, and uniform ceramic YSZ electrolyte film on the top of the porous anode substrate. The EPD kinetics have been studied in depth. It is found that homogeneous and uniform film could be obtained onto the polymer‐coated substrate at an applied voltage of 15 V for 1 min. After the half‐cell (anode + electrolyte) is co‐fired at 1400°C, a suitable cathode composition (La_0.65Sr_0.3MnO₃) thick film paste is screen printed on the top of the sintered YSZ electrolyte. A second stage of sintering of such cathode thick film at 1100°C for 2 h finally yield a single cell SOFC. Such single cell produced a power output of 0.91 W/cm² at 0.7 V when measured at 800°C using hydrogen and oxygen as fuel and oxidant, respectively.     

Interaction of a ceria‐based anode functional layer with a stabilized zirconia electrolyte: Considerations from a materials perspective

We report on the materials interaction of gadolinium‐doped ceria (GDC) and yttria‐stabilized zirconia (YSZ) in the context of high‐temperature sintering during manufacturing of anode supported solid oxide fuel cells (AS–SOFC). While ceria‐based anodes are expected to show superior electrochemical performance and enhanced sulfur and coking tolerance in comparison to zirconia‐based anodes, we demonstrate that the incorporation of a Ni–GDC anode into an ASC with YSZ electrolyte decreases the performance of the ASC by approximately 50% compared to the standard Ni–YSZ cell. The performance loss is attributed to interdiffusion of ceria and zirconia during cell fabrication, which is investigated using powder mixtures and demonstrated to be more severe in the presence of NiO. We examine the physical properties of a GDC–YSZ mixed phase under reducing conditions in detail regarding ionic and electronic conductivity as well as reducibility, and discuss the expected impact of cation intermixing between anode and electrolyte.     

Densification of plasma sprayed YSZ electrolytes by spark plasma sintering (SPS)

Solid oxide fuel cells (SOFC) are promising candidates for alternative power generation systems due to their high-energy conversion efficiencies, and low emissions of environmentally hazardous by-products. Plasma spray (PS) is an effective, and relatively inexpensive process for fabricating high performance yttria stabilized zirconia (YSZ) electrolyte for SOFC. Yet, because of the numerous inter-granular defects introduced to the electrolyte by the plasma spray process, the electrolyte is not gas tight and consequently, the energy efficiency of the cell is severely curtailed. In order to improve the performance of the SOFC, spark plasma sintering (SPS) is introduced as a post-spray treatment to enhance the density of the PS YSZ electrolyte rapidly, and effectively. In this study, spark plasma sintering (SPS) was performed at 1200, 1400 and 1500 °C. Each sintering cycle had a holding time of 3 min. Single and multiple SPS cycles (3 min at preset temperature per cycle) were used to treat the plasma sprayed yttria stabilized zirconia (PS YSZ) electrolytes. The microstructure of as-received and SPS treated electrolytes as examined by scanning electron microscopy (SEM) demonstrated a microstructure transition above 1200 °C, where the typical plasma sprayed lamella structure transformed to a granular-type structure. The porosity of as-received and SPS post-treated electrolytes, which were determined by a mercury intrusion porosimeter (MIP) revealed a significant reduction in pores at 1500 °C. Average pore size reduced from 0.2 to 0.08 μm. The ionic conductivity of the electrolytes is evaluated by AC impedance spectroscopy to characterize the effect of SPS on enhancing the ionic conductivity of the electrolytes.     

Robust and reliable solid oxide fuel cells with modified thin film YSZ electrolyte

Reduce electrolyte thickness can improve solid oxide fuel cell (SOFC) performance. However, thinner electrolyte often contains prominent defects and flaws, which may decrease the yield and increase operation risk. This work proposes a method to modify the thin film YSZ electrolyte, to improve cell reliability and durability. The as-sintered anode supported half-cell with screen printed YSZ electrolyte was immersed in precursor solution of Y(NO₃)₃·6H₂O and Zr(NO₃)₄·5H₂O, and being treated under hydrothermal condition of 150°C for 12 h. As a result, the modified cells show slight increase in the OCV values. Furthermore, the hydrothermal modification effectively promotes interface sintering between YSZ electrolyte and GDC barrier layer, yielding a smaller ohmic resistance of .142 Ω·cm² (a decrease of ∼11%) and a higher peak power density of .964 W/cm² (an increase of ∼18%) at 750°C, than pristine cell. Moreover, the modified cell operates stably over 300 h, while the pristine cell presents large and irregular voltage fluctuations. This work suggests that the hydrothermal modification is an effective and promisingly industrial applicable method for thin film electrolyte recovery in SOFCs.