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研究生(外文):Chih-Shiun Chou
論文名稱(外文):Application of Cu-Based Material on Solid Oxide Fuel Cell (SOFC) and Development of Melt-Extrusion (ME) Module
指導教授(外文):Wen-Chen Wei
口試委員(外文):Kuen-Shyang HwangAn-Bang WangI-Ming Hung
外文關鍵詞:Cubrassoxidation kineticsanodeIT-SOFCmelt-extrusion (ME)
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本研究使用銅基材料製作固態燃料電池之陽極,進行以下的研究開發工作。測試銅與銅鋅合金之基本性質,如導電性、熱膨脹係數、硬度等特性,並對此金屬之抗氧化性做深入探討,測試並比較銅與鎳金屬、鈦六鋁四釩合金在不同測試條件下之氧化行為,最後用表面氧化層之微結構與熱重分析的氧化結果相互驗證。本研究亦製備摻釤及鈷之氧化鈰(Co-SDC)電解質,並提出合成與燒結SDC粉末的方法,利用銅的高導電性和防止積碳的特性,與SDC良好的催化性和離子導電性,使此電池能在750 oC達到112 mW cm-2的最高電功率輸出。此外有鑒於銅鋅合金相較於純銅有較低的熔點和成形性,非常適合做為3D列印的金屬胚料,因此本研究亦設計與開發一熱熔擠(ME)裝置來擠製銅鋅合金,此裝置能達到1100 oC,且有優異的隔熱特性,當擠出嘴為1000 oC時,此裝置外部僅為51 oC。

This study used Cu-based materials as an anode of solid oxide fuel cells (SOFCs) and conducted the following R&D works. Properties of Cu and Cu-Zn alloy were investigated, including electrical conductivity, coefficient of thermal expansion (CTE), hardness and oxidation behavior. The oxidation-resistance of Cu, Ni and Ti-6Al-4V was investigated and compared. Moreover, the microstructure of the oxide layers was observed to verify the results of TGA test. This study also developed cobalt-doped SDC cermet as an electrolyte for intermediate temperature (IT)-SOFC. The Cu-based electrode provided good electronic conductivity and prevented carbon deposition. The SDC was used as catalyst and ionic conductor. The methods to synthesize SDC and sinter a dense SDC electrolyte were also provided in this study. Maximum power density of the Cu-based SOFC was 112 mW cm-2 at 750 oC. On the other hand, due to a low melting point and good formability of Cu-Zn alloy, it was suitably applied on 3D printing (3DP) technique. As a result, a melt-extrusion (ME) module was designed to print Cu-Zn alloy. The ME module could reach 1100 oC to extrude Cu-Zn alloy. Besides, the heat insulation of the module was excellent, which was 51 oC outside the module while the temperature in the nozzle was 1000 oC.

List of Figures-VII
List of Tables-XII
Chapter 1 Introduction-1
Chapter 2 Literature review-3
2.1 Introduction of Cu-Zn Alloy-3
2.1.1 Hardness of Cu-Zn Alloy-4
2.1.2 Other Cu-Based Alloys-5
2.2 SOFC with Cu-Based Anode-6
2.2.1 Sintering of SDC Electrolyte-8
2.2.2 Cu-Based Anode for SOFC-9
2.3 Advantages of Metallic 3D Printing-11
2.3.1 Introduction of Different 3D Printing Processes-11
2.3.2 Metal Materials for 3D Printing-13
Chapter 3 Experimental Procedure-24
3.1 Materials-24
3.2 SDC Powder Synthesis-24
3.3 Preparation of Anode Slurry-25
3.4 SOFC Assembly-26
3.5 Assembly of Melt-Extrusion Module-26
3.5.1 Assembly of Barrel-26
3.5.2 Preparation of Castable-27
3.6 Property Characterization-28
3.6.1 Sedimentation Test-28
3.6.2 Particle Size Measurement-29
3.6.3 SEM Analysis-29
3.6.4 Density Measurement-30
3.6.5 Conductivity Measurement-30
3.6.6 Thermal Expansion Analysis-31
3.6.7 XRD Analysis-32
3.6.8 Metallographic Study of Cu-Zn Alloy-32
3.6.9 Test of Oxidation-Resistance-33
3.6.10 Cell Test-35
3.6.11 Thermal Distribution Measurement-36
Chapter 4 Results and Discussion-44
4.1 Properties of Cu-Zn Alloy-44
4.1.1 Electric Property of Cu-Zn Alloy-44
4.1.2 CTE of Cu-Zn Alloy-45
4.1.3 Stability of Cu-Zn Alloy with Electrolyte Oxide-46
4.1.4 Annealing Microstructure and Hardness of Cu-Zn Alloy-47
4.2 Oxidation Kinetics of Cu-Zn Alloy and Other Metals-60
4.2.1 Mass Change during Oxidation Process-60
4.2.2 Activation Energy for Oxidation-61
4.2.3 Oxidation of Cu-Zn Alloy in Protect Atmosphere-63
4.2.4 Microstructure of Oxide Layer-65
4.3 Assembly and Properties of SOFC-81
4.3.1 Solid-State Reaction of SDC Powder-81
4.3.2 Behavior of Sintered SDC Electrolyte-83
4.3.3 Properties of CuO-SDC Slurry and Anode-84
4.3.4 Cell Test and Microstructure-85
4.3.5 Cell Test with Hydrocarbon Fuel-86
4.4 High-Temperature Melt-Extrusion Module-102
4.4.1 Assembly of Melt-Extrusion Module-102
4.4.2 Performance of Heater-103
4.4.3 Module Test-105
(1) Temperature Distribution-105
(2) Extrusion of Cu-Zn Alloy-106
(3) Extrusion Greater than 1100 oC-107
Chapter 5 Conclusions-118

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