臺灣博碩士論文加值系統

在本研究中，選擇了兩種固態氧化物燃料電池的內部元件及一種單電池進行其製備及分析。
首先，利用化學共沉法合成氧化釓添加氧化鈰(GDC)之纖維。由於其較高的導電性，異價離子添加的氧化鈰是取代目前常見的釔安定氧化鋯(YSZ)電解質的適當材料。合成的GDC纖維透過SEM、TEM、DTA/TG、XRD及ICP-AES等技術進行其化學，結晶動力學及微結構等性質的分析。結果顯示纖維之合成過程屬於零級反應。且所合成之析出物的微結構會因檸檬酸及氫氧化鈉濃度之添加量不同而有所影響。除了纖維之外，膠粒、柱狀及片狀之析出物亦可透過不同比例之檸檬酸及氫氧化鈉濃度產生。
其次，當做固態氧化物燃料電池的陰極材料錳酸鍶鑭(LSM)，透過兩種溶膠凝膠法合成而得。其一為Pechini法，其二則是以聚丙烯酸(PAA)做為高分子添加劑的溶膠凝膠法。除了上述的分析技術，所合成之粉末也以SEM-EDS之技術進行全定量分析以得知其化學成分之分布。同時，LSM粉體終於熱處理過程中所殘餘之碳含量則以碳硫分析儀進行分析，並以三點直流方式測定LSM與YSZ間之介面電阻。
最後，電解質支撐之固態氧化物燃料電池也於此研究中製備。透過網印技術，LSM陰極薄膜及氧化鎳/氧化鋯(NiO/YSZ)陽極薄膜成功的披覆於氧化鋯的電解質支撐上。此氧化鋯電解質之電性利用交流阻抗分析儀進行分析。最後也報導所製備的三層燃料電池之單電池微結構。

This study, two components in solid oxide fuel cell (SOFC) and one cell were fabricated and analyzed. First, fibrous Gd2O3 doped ceria (GDC), which is the alternative material for electrolyte, was synthesized by chemical co-precipitate method. The chemical, growth and microstructural properties of the GDC fibers were characterized by scanning and transmission electron microscopies (SEM and TEM), differential thermogravimetry (DTA/TG), X-ray diffraction (XRD), and inductive coupling plasma-atomic emission spectroscopy (ICP-AES) technologies. The results of fiber synthesis reaction showed zero-order kinetics. The morphologies were closely affected by the concentrations of additives, citric acid and sodium hydroxide. Three types of morphologies, including spherical colloids, fibers, stick-in-bundles, and flakes could be synthesized by control the ratio of citric acid and sodium hydroxide.
Second, LSM powders were synthesized by Pechini method and a sol-gel process with PAA as chelating agent. Besides the analysis technologies mentioned above, the powders were also characterized by quantitative energy dispersive spectroscopy (EDS) to identify their compositional homogeneity. In addition, the residual carbon content in the LSM powders and their electrical resistance of the LSM/YSZ interface were also analyzed by carbon/sulfur analyzer and 3-terminal measurement, respectively.
Finally, an electrolyte supported SOFC was fabricated by screen printing. The electrical conductivity of 8Y-YSZ electrolyte analyzed by AC impedance and the microstructure of the tri-layer single cell were prepared and characterized.

List of Figures VI
List of Tables X
Chapter 1 Introduction 1
Chapter 2 Literature Review 4
2.1 Electric Conductive Cerium Oxide 4
2.2 Synthesis of Oxide Fibers 11
2.2.1 AAO Template 11
2.2.2 Hydrothermal Precipitation 12
2.2.3 Electrospinning 13
2.2.4 Precipitation Method 16
2.3 Electrical Properties of Cerium Oxide 20
2.3.1 Theory of Oxygen Transport 20
2.3.2 Dopant Effect 22
2.3.3 Grain Boundary/Impurity Effects 27
2.3.4 Reduction Behavior of Ceria 28
2.4 Cathode Materials for SOFC 39
2.4.1 LaMnO3 Materials 40
2.4.2 Synthesis of LSM Powders 42
Chapter 3 Experimental 46
3.1 Materials 46
3.2 Synthesis of Doped/Undoped Ceria Fibers 47
3.3 Fabrication of Cathode Powders 48
3.3.1 Sol-Gel Synthesis 48
3.3.2 Pechini Method 49
3.4 Single Cell Fabrication 49
3.4.1 Fabrication of Dense YSZ Thin Plate 49
3.4.2 Anode and Cathode Thin Film Fabrication 50
3.5 Characterization 50
3.5.1 ICP-AES Analysis 50
3.5.2 Density Measurement 51
3.5.3 Thermal Analysis 52
3.5.4 BET Measurement 53
3.5.5 Residual Carbon Analysis 53
3.5.6 Microstructural Analysis and Phase Identification 54
(1) SEM Observation. 54
(2) TEM Observation 55
3.5.7 XRD Analysis 56
3.5.8 Electrical Properties Measurement 56
(1) DC Electrical Measurement 56
(2) Electrochemical Impedance Spectroscopy Measurement 58
Chapter 4 Results and Discussions 68
4.1 Synthesis of CeO2 (GDC and SDC) Fibers 68
4.1.1 Effects of Sodium Hydroxide/Citric Acid 68
4.1.2 Kinetic Analysis of Fiber Synthesis 70
4.1.3 Morphology Evolution by Thermal Treatment 74
4.2 Properties of LSM Powders 96
4.2.1 Phase Formation of LSM 96
4.2.2 Quantitative Analysis of Composition 98
4.2.3 Reduction of Surface Area 100
4.2.4 Electrical Properties of LSM Powders 101
4.3 Fabrication and Properties of Electrolyte Supported SOFC Single Cell 121
4.3.1 Sintering Behavior and Electric Properties of 8YSZ Plate 121
4.3.2 Fabrication of Anode and Cathode Layers 123
Chapter 5 Conclusions 131
References 134

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