鑭鈣鈷鐵氧化物作為SOFC陰極之氧還原反應觸媒作用｜國立臺灣科技大學博碩士論文系統

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研究生：	金祖永 Tsu-Yung Jin
論文名稱：	鑭鈣鈷鐵氧化物作為SOFC陰極之氧還原反應觸媒作用 (La0.75Ca0.25)(CoxFe1-x)O3-δ as SOFC Cathode and its Catalytic Effect on Oxygen Reduction Reaction
指導教授：	蔡大翔 Dah-Shyang Tsai
口試委員:	許貫中 Kung-Chung Hsu 周振嘉 Chen-Chia Chou 黃鶯聲 Ying-Sheng Huang
學位類別：	碩士 Master
系所名稱：	工程學院 - 化學工程系 Department of Chemical Engineering
論文出版年：	2007
畢業學年度：	95
語文別：	中文
論文頁數：	154
中文關鍵詞：	鑭鈣鈷鐵氧化物、陰極、固態氧化物電池、氧還原反應、鑭鏑鉬鎢氧化物
外文關鍵詞：	Lanthanum calcium cobalt ferrites, Cathode, Solid oxide fuel cell, Oxygen reduction reaction, Lanthanum dysprosium tungsten molybdate
相關次數：	點閱：250 下載：3
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本研究探討以鑭鈣鈷鐵氧化物(La0.75Ca0.25)(CoxFe1-x)O3 (x=0.1~0.9)，作為匹配鑭鏑鉬鎢氧化物電解質(La1.8Dy0.2)(Mo2-xWx)O9 (x=0.4及1.0)之陰極氧還原反應電化學研究，以XRD、SEM分析材料結構，電化學交流阻抗分析圖譜儀及恆電位儀分析鑭鈣鈷鐵氧化物於鑭鏑鉬鎢氧化物電解質上之氧還原反應催化活性。
由XRD分析結果顯示，陰極材料為斜方晶相之鈣鈦礦結構，無第二相存在，隨著鈷含量的增加結構對稱性增加，但摻雜銅的量為0.1、0.15 mole%時有少量第二相三氧化四銅存在。根據熱重與熱差分析之結果，顯示陰極材料並無一階相轉變發生，且陰極與電解質間似乎無固態反應生成第二相之現象發生，然而鉬在600 ℃~800 ℃間擴散至陰極之現象嚴重影響多孔結構與晶粒大小，其對氧還原反應催化作用之影響為一重要因素。
陰極粉末膏網印於電解質上，經燒結900 ℃、2小時後，顯微結構顯示陰極層為相當多孔之結構。以交流阻抗分析三極式半電池之結果顯示，(La0.75Ca0.25)(Co0.8Fe0.2)O3-δ陰極組成在700 ℃下ASR達到最低為11.45 Ω•cm2，摻雜銅0.05 mole%於鑭之位置證明可大幅降低氧還原反應所造成之阻抗，在700 ℃下ASR達到最低為5.56 Ω•cm2，800 ℃為0.39 Ω•cm2。
利用半電池交流阻抗(impedance)所量測到的RLF以及CorrView商用軟體進行回歸計算求得之交換電流密度，在(La0.75Ca0.25) (Co0.8Fe0.2)O3-δ之陰極組成，其交換電流密度800 ℃時高達43.12 mA/cm2，(La0.7Ca0.25Cu0.05)(Co0.8Fe0.2)O3-δ之陰極組成，其交換電流密度800 ℃時高達58.7 mA/cm2。

This master thesis investigates the structures and the electrocatalytic
properties of (La0.75Ca0.25)(CoxFe1-x)O3 (x=0.1 – 0.9) cathode interfaced to
the electrolyte of (La1.8Dy0.2)(Mo2-xWx)O9 (x=0.4 and 1.0). The
microstructures of (La0.75Ca0.25)(CoxFe1-x)O3 are investigated by X-ray
diffraction (XRD), scanning electron microscopy (SEM). The
electrocatalytic properties are focused on the oxygen reduction reaction
(ORR) using impedance spectroscopy and potentiodynamic measurement
on a half-cell setup.
Analysis of XRD patterns indicates that (La0.75-xCa0.25) (CoyFe1-y)O3
(x=0.0, 0.03, 0.05; y=0.1 – 0.9) belongs to the perovskite structure of
orthorhombic cell, but a small amount of secondary phase do exist at
x=0.10 and 0.15. Thermogravimetric and differential thermal analysis
points out little reaction between (La0.75Ca0.25) (CoxFe1-x)O3 and
(La1.8Dy0.2)(Mo1.6W0.4)O9 between 30 - 950°C. However the Mo diffusion
at 600-800°C significantly influences the porous structure of cathode and
its grain size, which could be a significantly factor in catalyzing oxygen
reduction reaction.
The minimum area specific resistance of ORR on
(La0.75Ca0.25)(Co0.8Fe0.2)O3 is estimated 11.45 Ωcm2 at the targeted
operation temperature 700°C using impedance spectroscopy. If copper is
doped on the A-site of perovskite, the area specific resistance can be
further reduced to 5.56 Ωcm2 at 700°C, 0.39 Ωcm2 at 800°C. The values
of resistance measured by impedance spectroscopy are converted into the
values of exchange current density, which are similar to those obtained by
IV
potentiodynamic measurement. The exchange current density of
(La0.75Ca0.25)(Co0.8Fe0.2)O3 is 43.12 mAcm-2 at 800°C, that of
(La0.7Ca0.25Cu0.05) (Co0.8Fe0.2)O3 is 58.7 mAcm-2 at 800°C.

目錄
中文摘要...............................................Ⅰ
英文摘要...............................................Ⅲ
誌謝....................................................V
目錄..................................................VII
圖目錄................................................XII
表目錄..............................................XVIII

第一章  緒論............................................1
1  前言	...............................................1
第二章  文獻回顧與理論基礎..............................2
1  燃料電池簡介.......................................2
2  固態氧化物燃料電池(Solid Oxide Fuel Cell)..........7
2.1  SOFC之電池元件...................................9
2.2  SOFC之運作原理..................................10
2.3  SOFC之現況......................................12
3  陰極材料結構與製備方法............................15
3.1  鈣鈦礦結構......................................15
3.2  溶膠-凝膠法(Sol-gel process)....................16
4  鑭鉬氧化物(La2Mo2O9)..............................19
4.1  鑭鏑鉬鎢氧化物電解質配合之陰極材料選擇..........22
5  陰極/電解質間之界面電化學.........................25
5.1  SOFC之極化現象..................................26
5.2  陰極氧還原反應(ORR).............................28
6  電化學交流阻抗分析基本原理........................38
6.1  交流阻抗分析之等效電路元件......................42
6.3  等效電路模擬....................................48
7  交換電流密度......................................51
7.1  Butler-Volmer 方程式............................51
7.2  交換電流密度之計算方法..........................53
2-8  研究目的..........................................57
第三章  實驗方法及步驟.................................58
1  實驗藥品..........................................58
2  實驗流程..........................................61
3  鑭鏑鉬鎢氧化物的製備..............................62
3.1  粉末烘乾、配粉及混合程序........................62
3.2  煆燒(Calcination)...............................62
3.3  塊材成形(Forming)...............................63
3.4  塊材燒結(Sintering).............................63
4  鑭鈣銅鈷鐵氧化物的製備............................65
4.1  前驅物配製......................................65
4.2  煆燒(Calcination)...............................65
4.3  粉末膏製作(Paste preparation)...................66
3-5  材料與電化學觸媒特性分析試片製作..................68
5.1  X光繞射分析之試片...............................68
5.2  場發掃描式電子顯微鏡微結構觀察分析之試片........68
5.3  熱重及熱差分析儀之粉末製備......................69
5.4  陰極(LCaCuCoF)/電解質(LDMW)之半電池試片.........69
6  材料特性分析......................................72
6.1  X光繞射分析.....................................72
6.2  密度量測........................................72
6.3  掃描式電鏡於截面及表面微觀分析..................73
6.4  EDS元素分析.....................................73
6.5  熱重及熱差分析儀(SDT)之量測.....................73
6.6  LCaCuCoF / LDMW之半電池交流阻抗量測.............74
6.7  LCaCuCoF / LDMW之DC極化曲線量測.................75
6.8  活化能(Activation energy)計算...................76
第四章  結果與討論.....................................77
1  XRD繞射分析.......................................78
1.1  孔隙度估算......................................85
4-2  熱重與熱差分析(TG/DTA)............................86
4-3  燒結溫度對於ORR阻抗之影響.........................88
3.1  顯微結構與元素分析..............................89
3.2  電化學交流阻抗分析..............................96
4  不同鈷含量對於ORR阻抗之影響......................104
4.1  顯微結構分析...................................104
4.2  電化學交流阻抗分析.............................104
5  煆燒溫度對於ORR阻抗之影響........................109
5.1  XRD繞射分析....................................109
5.2  顯微結構分析...................................111
5.3  電化學交流阻抗分析.............................113
6  DC bias對於ORR阻抗之影響.........................116
7  不同電解質對於ORR阻抗之影響......................120
7.1  顯微結構與元素分析.............................120
7.2  電化學交流阻抗分析.............................125
8  不同鈣含量對於ORR阻抗之影響......................128
8.1  XRD繞射分析....................................128
8.2  顯微結構與交流阻抗分析.........................129
9  摻雜銅對於ORR阻抗之影響..........................132
9.1  XRD繞射分析....................................132
9.2  顯微結構分析...................................133
9.3  交流阻抗分析...................................135
4-10  交換電流密度....................................137
第五章   結論.........................................141
參考文獻..............................................144
附錄A.................................................151
附錄B.................................................152
附錄C.................................................153

                                

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