摘要
固体氧化物燃料电池(Solid Oxide Fuel Cell, SOFC)是一种不需要经过热循环过程将化学能直接转化成电能的高效、环保的能量转换系统,具有高能量转换效率、全固态结构、无污染和多种燃料气体广泛适应性等优点。SOFC的构型和电极微结构可以极大地影响SOFC系统的性能和可靠性；固体电解质及电极的性能也对SOFC将化石能源的能量直接转化为电能的效率有很大影响。本论文在第一章介绍了SOFC的基本原理,目前国内外的研发现状和发展趋势,着重综述了管式SOFC制备技术和质子导体材料问题。从SOFC产业化角度,探索研制了在中低温下适宜YSZ基的管式SOFC(第三章)；发展了适于规模化生产的低成本制备技术——浆料浸渍法,成功实现了YSZ及质子导体电解质薄膜化制备(第三章,第五章),有效的改善了质子导体材料的性质(第四章)；特别是采用浸渍成型-共烧结方法制备了基于BZCYYb电解质的质子导体SOFC,在中温下取得了目前国际文献报道的最高功率输出性能(第五章)。论文所取得的主要成果和创新点可归纳如下：
1.采用相转换(Phase inversion)方法制备了阳极支撑的Ni-YSZ|YSZ|LSM-SDC管式SOFC,较好的控制了电池的微观结构；对浸渍工艺与阳极厚度的线性关系,造孔剂含量与阳极孔隙率及电导率的关系进行了系统研究；对全电池的电化学性能在实际燃料电池的工作条件下进行了评估。以3 vo1%湿度的氢气为燃料,空气为氧化剂,在800,750,700,650,600,550和500℃下,最大输出功率密度为0.752,0.646,0.522,0.395,0.277,0.180和0.105 W cm-2；欧姆电阻为0.22,0.24,0.27,0.33,0.40,0.84和1.76Ωcm2,界面极化电阻为0.37,0.51,0.70,0.92,1.14,1.86和3.34Ωcm2(均在电池在开路下测得)。高的输出功率和低的欧姆电阻及界面极化电阻表明相转换方法非常适于YSZ基管式SOFC的制备,这种设备简单的工艺在进一步降低SOFC的造价方面也具有实际应用的潜力。
2.采用固相反应(Solid State Reaction)方法制备了BaZr0.1Ce0.7Y0.1Yb0.1O3-δ(BZCYYb)质子导体材料,并对氧化铈(CeO2)和氧化锆(ZrO2)颗粒尺度、烧结次数、烧结温度等对BZCYYb材料的性质进行了系统研究。X射线衍射(XRD)表明微米尺度氧化铈和纳米尺度氧化锆制备的BZCYYb质子导体材料具有典型的钙钛矿结构,拉曼(Raman)光谱表明BZCYYb质子导体材料为正交晶体结构；BZCYYb质子导体材料经机械压片,在1500℃烧结处理5小时之后具有致密的微结构,扫描电子显微镜(SEM)表明只有封闭的针孔存在;阿基米德方法(Archimedes method)表明致密度为96.6%,收缩率为24.0%；四探针法测试表明BZCYYb质子导体材料具有很高的质子电导率,并且,质子电导率与测试温度具有很好的线性关系。X射线衍射及拉曼光谱表明BZCYYb质子导体材料在1100℃烧结2次后,可以使固相反应更加完全,BZCYYb材料的质子电导率相比在1100℃烧结1次的材料的质子电导率提高了～15%。BZCYYb质子导体材料的制备温度以1100℃最佳,在1000℃制备过程中BaCO3未反应完全,在1200℃制备后有过烧结现象,在1100℃制备的BZCYYb材料质子电导率比制备温度为1000和1200℃的提高～30%和～35%。
3.采用浸渍成型(Dip Coating)方法制备了Ni-BZCYYb|BZCYYb管式SOFC,分别采用纯氧离子导体材料、氧离子和质子导体混合材料为阴极测试了电池性能,电池在中温区域的输出功率密度都为国际文献报道最高值,欧姆电阻及界面极化电阻都为国际文献报道最小值,在中低温高功率管式SOFC领域具有很好的实际应用前景。开路电压接近理论值能斯特方程计算值,表明BZCYYb电解质非常致密,没有任何裂纹、缺陷和开孔；非常低的欧姆电阻,表明BZCYYb电解质薄膜厚度在满足致密度的同时,有效地提高了质子和氧离子传导；很低的界面极化电阻,表明BZCYYb电解质薄膜和多孔电极之间的结合非常好,没有明显的分层、裂纹和缺陷,从而有效地增加了三相界面(Three Phase Boundaries, TPBs)区域；非常高的输出功率密度,表明电池在中温高功率领域具有很好的实际应用前景；纯氧离子导体阴极和氧离子和质子导体混合阴极的电池,阻抗谱及输出功率密度相似,表明阴极材料组成不是氧离子和质子在电池中传输的的主要限制条件。
Solid oxide fuel cell (SOFC) is an efficient, green energy conversion device. It can convert the fossil energy directly into electrical power without any thermal cycling. SOFC has attraeted wide spread attention due to its high energy conversion efficiency, solid-state structure, clean pollution-free, and awide range of adaptability of fuel gases, etc. The efficiency of SOFC convert chemical energy to electrical energy mainly depends on the electrolyte and electrode performance. The design of cell architecture and electrode microstructure may greatly influence the performance and reliability of SOFC systems. This thesis focuses on fabrieation, improvement and characterization of tubular SOFC. The optimization of electrolyte and electrode are both studied. In the first chapter, this paper introduces the fundamental principles of SOFC, the present researeh status and developing trend. On the base of analyzing the development of SOFC, we fabrieate and investigate a new process forYSZ-based cells for intermediate temperature application (in Chapter 3); developed a cost effeetive and mass produetion proeess to fabrieate YSZ and high temperature proton Conduetor membranes (in Chapter 3 and Chapter 5); effectively improved the nature of the proton conductor material (Chapter 4); particularly, the proton conductors were prepared by sintering of SOFC membrane, the maximum power output performance were achieved at the intermediate temperature of the international literature of (in Chapter 5); and new proton conducting materials have been studied (in Chapter 6). The main achievements and innovations in this paper are summarized as follows:
1. We reported our findings in fabrication of anode-supported SOFCs with well controlled microstructures using a simple phase-inversion with dip-coating process. The effect of dip-coating on anode support thickness and the amount of pore former on the porosity and electrical conductivity of the anode supports were systematically studied. Furthermore, anode-supported full cells were fabricated and their electrochemical performances were evaluated under practical fuel cell operating conditions. When the pore former was increased to 6 wt%, the porosity of the anode was increased to～46.9%, while the conductivity was reduced to～578-462 S cm-1 in the temperature range studied. The electrochemical performance was evaluated in a single cell with a configuration of～240μm Ni-YSZ|10μ.m YSZ|20μm LSM-SDC. Peak power density reached 752,646,522,395,277,180 and 277 mW cm-2 at 800, 750,700,650,600,550 and 500℃, respectively, when hydrogen was used as fuel and ambient air as oxidant, which reached to the industry's level of Acumenirics Corporation. The Ohmic resistance (RΩ) was 0.22,0.24,0.27,0.33,0.40,0.84 and 1.76 Qcm2, while the interfacial polarization resistance (Rp) was 0.37,0.51,0.27, 0.70,0.92,1.14 and 3.34Ωm2, respectively, at 800,750,700,650,600,550 and 500℃. The high performance and low resistance of the cells indicate that the tubular SOFC has a good potential for practical applications.
2. The BaZr0.1Ce0.7Y0.1Yb0.1O3-δ(BZCYYb) proton conductor materials were prepared by solid-state reaction method, showing very high proton conductivity under 750℃, indicating the application of the high-power output SOFC at low temperature. The particle sizes of ceria and zirconia, sintering times and sintering temperature on the BZCYYb performance have been systematically studied. X-ray diffraction (XRD) show that the micrometer scale and nanoscale cerium oxide zirconia prepared BZCYYb proton conductor material has a typical perovskite structure; Raman spectra show that BZCYYb proton conductor material orthogonal crystal structure; BZCYYb proton conductor pellets were dense by mechanical pressure and sintered at 1500℃for 5 hours; scanning electron microscopy (SEM) show that there is only closed pinhole in the pellets; Archimedes method showed that the density was 96.6%, and shrinkage ratio was 24.0%; four-probe method showed that the BZCYYb proton conductor has a high proton conductivity. In addition, the proton conductivity which measured under different atmosphere has a good linear relationship with the test temperatures. XRD and Raman spectroscopy showed that BZCYYb proton conductor was pure due to complete solid state reaction when sintered at 1100℃for two times; the proton conductivity of BZCYYb which sintered at 1100℃for two times were increased～15% than those which sintered for once. The best sinter temperatue is 1100℃for BZCYYb, the reaction of BaCO3 was not completely at 1000℃; the over sintering phenomena was exist at 1200℃; the proton conductivities of BZCYYb which sintered at 1100℃were increased～30% and～35% than those which the sinter temperature was 1000 and 1200℃.
3. We reported a simple and cost-effective process for fabrication of tubular SOFCs with different cathodes, achieving much higher performance than those previously reported. The combination of dip coating and co-firing has produced tubular proton-conducting SOFCs with unique microstructure and superior cell performance. The precursors of tubular cells were with the configuration of～200nm Ni-BZCYYb|～10 nmBZCYYb. The high OCV values indicate that the gas leakage through the electrolyte was negligible and the prepared electrolyte is very dense without any cracks or pinholes. It is expected that optimization of the anode-electrolyte interface microstructure will decrease the anode polarization by increasing the three phase boundaries (TPBs) length. The high performances indicating that the tubular SOFCs based on proton and oxide ion mixed conductor electrolyte have a great potential for practical applications. The impedance spectra and output power density of the tubular SOFC which brushed with pure oxygen ion conductor cathode and oxygen ions proton conductor cathode were similar, demonstrating that the cathode material composition is not the main constraints for oxygen ions and protons transmission.
引文
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