臺灣博碩士論文加值系統

在過去的幾十年研究當中，Ni/YSZ (Yttria Stabilized Zirconia)主
要是作為高溫型(>1000℃)固態氧化物燃料電池之陽極材料。然而，
由於Ni/YSZ 在中溫(500~700℃)的環境下使用時，其所具有的導電率
已不足。因此，為了尋求能代替Ni/YSZ 作為中溫固態氧化物燃料電
池(IT-SOFC)之陽極的話，Ni/CGO 複合陽極是一個相當適合的選擇。
本次研究的目的是以靜電輔助超音波霧化沉積法(electrostatic
assisted ultrasonic spray pyrolysis, EAUSP)來製備Ni/CGO 複合陽極。
希望其可以藉由適當的沉積參數，而沉積出其所需要的結晶相以及高
孔隙度之微觀結構，使其獲得較小的電極阻抗。從研究結果可以清楚
發現，沉積溫度與加速電壓是主導整個薄膜表面型貌的發展，進而影
響到電極與電解質之介面極化阻抗。
因此，最佳之微結構沉積條件為溫度450℃，加速電壓為12 kV，
Ni/CGO 莫耳比為6：4 時，其所沉積之Ni/CGO 薄膜其表面形貌類似
於花菜形貌，因而具有相當好的孔隙性。使得其電極介面極化阻抗值
在550℃時為0.09 Ωcm2，會比傳統利用浸漬塗覆法(550℃、0.14 Ωcm2)
或是機械混合法(550℃、0.12 Ωcm2)方式製作陽極來的低。

For the past few decades, Ni-YSZ (yttria-stabilized zirconia) has been the dominate anode material of high temperature (>1000℃) solid oxide fuel cells (SOFCs). However, the conductivity of Ni/YSZ is not enough when the operation temperature is in the intermediate rage of 500~700℃. Instead, Ni/CGO is a good candidate as the anode material of intermediate temperature SOFCs (IT-SOFC), due to its enhanced conductivity.
This work was aimed at the preparation of Ni/CGO composite anodes using the electrostatic assisted ultrasonic spray pyrolysis (EAUSP) method. By properly adjusting the deposition parameters, highly porous composite films with desired phases and microstructure rendering low electrode impedances were obtained. The results indicated that deposition temperature and the applied voltage dictated the evolution of film morphology and hence the interface impedance between the electrode and the electrolyte.
Therefore, the optimum deposition parameters for the best microstructure and hence minimum interface impedance were 12 kV for the applied voltage, 6 : 4 for the Ni-CGO mole ratio, 450℃ for the deposition temperature. The microstructure thus obtained possessed a cauliflower-like structure with high porosity. The resultant interface impedance at 550℃ was 0.09 Ωcm2, lower than that obtained from the conventional anode preparation routes of dip-casting (0.14 Ωcm2) or mechanical mixing (0.12 Ωcm2).

中文摘要............................................................................................ I
英文摘要............................................................................................ II
目錄.................................................................................................... IV
圖索引................................................................................................ VIII
表索引................................................................................................ XIII
第一章、緒論...................................................................................... 1
1-1 前言........................................................................................... 1
1-2 研究動機及目的....................................................................... 2
第二章、文獻回顧.............................................................................. 7
2-1 燃料電池簡介........................................................................... 7
2-1-1 燃料電池工作原理............................................................ 7
2-1-2 燃料電池的優點................................................................ 9
2-1-3 燃料電池之分類................................................................ 10
2-2 固態氧化物燃料電池............................................................... 11
2-2-1 固態氧化物燃料電池構造................................................ 11
2-2-2 固態氧化物燃料電池工作原理........................................ 12
2-3 CGO (gadolinia-doped ceria)……………………………… 15
2-3-1 化學計量型二氧化鈰 (stoichiometric ceria)………… 15
2-3-2 非化學計量型二氧化鈰 (non-stoichiometric
Ceria,CeO2-X)……………………………………………16
2-4 超音波霧化之原理................................................................... 20
2-5 傳統Ni/YSZ 複合陽極的導電機制......................................... 21
2-6 電池反應之極化現象............................................................... 23
2-7 電極動力學............................................................................... 24
2-7-1 活性極化機制.................................................................... 25
2-7-2 濃度極化機制.................................................................... 26
2-8 電化學量測原理....................................................................... 28
2-8-1 交流阻抗分析.................................................................... 28
第三章、實驗方法及步驟................................................................. 32
3-1 實驗藥品................................................................................... 32
3-2 實驗流程................................................................................... 33
3-3 電解質基材製備....................................................................... 34
3-4 配製溶液先驅物....................................................................... 34
3-5 靜電輔助超音波霧化沉積法................................................... 34
3-5-1 靜電輔助超音波霧化沉積設備........................................ 34
3-5-2 靜電輔助超音波霧化沉積................................................ 35
3-6 鍍膜參數設定........................................................................... 36
3-6-1 鍍膜之溫度系列................................................................ 37
3-6-2 鍍膜之電壓系列................................................................ 37
3-6-3 鍍膜之成份系列................................................................ 38
3-7 XRD 分析................................................................................... 38
3-8 SEM 觀察................................................................................... 39
3-8-1 橫截面(Cross-section)觀察試片之製作........................... 39
3-8-2 表面(Top-view) 觀察試片之製作................................... 42
3-9 陽極與電解質(Ni/CGO)介面之電化學分析........................... 42
3-9-1 Ni/CGO//CGO//Ni/CGO 對稱電池製作............................ 42
3-9-2 交流阻抗分析(Frequency Response Analyzer)………… 43
第四章、實驗結果與討論................................................................. 44
4-1 溫度系列................................................................................... 44
4-1-1 XRD 結果........................................................................... 44
4-1-2 SEM 微結構觀察................................................................ 46
4-1-3 交流阻抗分析.................................................................... 51
4-2 電壓系列................................................................................... 57
4-2-1 XRD結果............................................................................ 57
4-2-2 SEM 微結構觀察................................................................ 59
4-2-3 交流阻抗分析.................................................................... 66
4-3 成份系列................................................................................... 72
4-3-1 XRD結果............................................................................ 72
4-3-2 SEM 微結構觀察................................................................ 74
4-3-3 交流阻抗分析.................................................................... 78
4-4 活化能之探討與介面極化阻抗值之比較................................ 83
第五章、結論..................................................................................... 88
第六章、參考文獻............................................................................. 90
附錄.................................................................................................... 95
附錄一 Ce0.9Gd0.1O1.95 之JCPDS 卡................................................. 95
附錄二 NiO 之JCPDS 卡................................................................. 96
附錄三 Ni 之JCPDS 卡.................................................................... 97

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