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:386 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.
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