SOFC之La0.6Sr0.4Co0.8Fe0.2O3-δ陰極經浸潤 La0.6-xSr0.4BaxCo0.8Fe0.2O3-δ(x=0.13、0.26、0.39)表面改質後對其效能之影響

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研究生：	孫葳 Sun Wei
論文名稱：	SOFC之La0.6Sr0.4Co0.8Fe0.2O3-δ陰極經浸潤 La0.6-xSr0.4BaxCo0.8Fe0.2O3-δ(x=0.13、0.26、0.39)表面改質後對其效能之影響 Improved efficiency of the La0.6Sr0.4Co0.8Fe0.2O3-δ cathode of SOFC by infiltration with La0.6-xSr0.4BaxCo0.8Fe0.2O3-δ (x=0.13、0.26、0.39)
指導教授：	林景崎 Jing-Chie Lin
口試委員:
學位類別：	碩士 Master
系所名稱：	工學院 - 機械工程學系 Department of Mechanical Engineering
論文出版年：	2018
畢業學年度：	106
語文別：	中文
論文頁數：	138
中文關鍵詞：	固態氧化物燃料電池、鑭鍶鈷鐵氧化物、鋇摻雜、浸潤法
外文關鍵詞：	Solid oxide fuel cell, Lanthanum-strontium-cobalt-ferrite oxide, Barium doping, infiltration
相關次數：	點閱：8 下載：0
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本研究使用甘胺酸-硝酸鹽燃燒合成法製備奈米級粒徑之鈣鈦礦結晶結構La0.6Sr0.4Co0.8Fe0.2O3 (LSCF)、La0.6-xSr0.4BaxCo0.8Fe0.2O3 (標示為x=0.13；LSB1CF、0.26；LSB2CF、0.39；LSB3CF)陰極粉末。經由調整LSCF前驅硝酸鹽水溶液之酸鹼值(pH值: 2、3、4、5)與甘胺酸-硝酸根比值(G/N比: 0.50、0.75、1.00、1.25)，觀察煆燒後粉末之結晶結構與表面形貌，並對其材料熱性質、電化學性質進行探討；再以最佳燃燒法合成參數(pH值、G/N比)進行LSBxCF之合成，並分析其電化學性質。最後評估LSCF作為陰極骨架、LSBxCF作為浸潤材料，將兩者經由浸潤法製成複合式陰極應用於質子傳導型固態氧化物燃料電池陰極之可行性。在LSCF實驗結果所示，LSCF1.00/、LSCF1.00/4、LSCF1.25/3與LSCF1.25/4等樣品為所有燃燒法合成參數中，結晶結構與表面形貌最符合作為SOFC陰極之結果，其中LSCF1.25/3由雷射粒徑分析其平均粒徑為300nm；由熱膨脹(TMA)之分析可發現LSCF1.25/3與電解質BCZY之熱膨脹係數最為相近；由四點式直流電量測導電度，LSCF1.00/4之導電度可達3690 S/cm；而LSBxCF之實驗結果，在熱重損失(TGA)分析中可發現， LSB2CF有最高之氧空缺變化量；其半電池之電子傳導阻抗與氧離子轉移阻抗分別為0.24 Ωcm2與0.30 Ωcm2。LSCF1.25/3作為陰極骨架、LSB2CF作為浸潤材料將兩者結合製成陰極進行極化曲線測試，在700°C時浸潤之陰極最高功率密度為39.5 mW/cm2，未浸潤之陰極最高功率密度為23.7 mW/cm2，效率提升將近66.67 %，而浸潤之陰極其極化阻抗為1.06 Ωcm2，未浸潤之陰極其極化阻抗為3.21 Ωcm2，阻抗降低約66.9 %。

In this study, the nanostructured perovskite La0.6Sr0.4Co0.8Fe0.2O3 (LSCF) and La0.6-xSr0.4BaxCo0.8Fe0.2O3 (note as x=0.13; LSB1CF, 0.26; LSB2CF, 0.39; LSB3CF) prepared by the glycine-nitrate combustion synthesis method were considered as a potential candidate for use as cathode in solid oxide fuel cells (SOFC) operated at intermediate-temperature. In the present work, combustion synthesis method was investigated by adjusting the pH of LSCF nitrate solution (pH=2, 3, 4, 5) and ratio between glycine and nitrate (G/N=0.50, 0.75, 1.00, 1.25). The crystal structure and morphology of the powders after calcining were analyzed and also its thermal properties and electrochemical characteristic were discussed. The optimal combustion synthesis parameters (pH and G/N) were used to synthesize the LSBxCF. Then the crystal structure and electrochemical properties were investigated. Finally, the feasibility for using as cathode in P-SOFC though combining LSCF as cathode backbone and LSBxCF as infiltrating material together by infiltration to fabricate a composite cathode was evaluated. The results of LSCF analysis showed that LSCF1.00/3, LSCF1.00/4, LSCF1.25/3 and LSCF1.25/4 were the optimal parameters for combustion synthesis whose crystal structure and morphology were the most suitable as cathode for SOFC. Among all, LSCF1.25/3 was analyzed that its average particle size around 300nm. For the measurement of thermal expansion coefficient (TMA), the coefficient of LSCF1.25/3 was about 11.8 × 10-6 K-1 which was the closest to that of electrolyte BCZY. In the results of four-probe DC conductivity measurement, LSCF1.00/4 had the highest conductivity near 3690 S/cm@550°C. For the thermosgravimetric analysis of LSBxCF, the results showed that the weight loss of La0.34Sr0.4Ba0.26Co0.8Fe0.2O3 (LSB2CF) was the biggest which indicated that LSB2CF provided the highest amount of oxygen vacancies in LSBxCF. Also, the resistance of electron conductivity and oxygen ion transfer for half-cell of LSB2CF was 0.24 Ωcm2 and 0.30 Ωcm2 respectively. Then, results of performance tests for the cell used LSCF as cathode backbone and LSB2CF as infiltrating material showed that the maximum power density of infiltrated cell was 39.5 mW/cm2 and pristine was 23.7 mW/cm2. The power density enhanced about 66.67 %. The polarization resistance of infiltrated cell was 1.06 Ωcm2 and pristine was 3.21 Ωcm2. The resistance reduced about 66.9 %.

摘要    i
Abstract    iii
致謝    iv
表目錄    viii
圖目錄    ix
第一章 緒論    1
1-1前言    1
1-2 研究動機與目的    3
1-3 論文架構    5
第二章 實驗理論與文獻回顧    6
2-1 燃料電池簡介    6
2-1-1 固態氧化物燃料電池原理與簡介    7
2-1-2 固態氧化物燃料電池元件    8
2-1-3 固態氧化物燃料電池支撐類型[31]    11
2-2陰極元件    11
2-2-1 陰極傳導機制[32]    12
2-2-2 陰極晶體結構    13
2-2-3 陰極材料製備方式    15
2-3 電化學分析原理    18
2-3-1 直流電極化曲線(I-V Curve)原理    18
2-3-2 電化學交流阻抗頻譜(EIS)原理    21
2-4 文獻回顧    24
2-4-1 SOFC陰極材料    24
2-4-2 SOFC陰極合成法    25
2-4-3 複合陰極製程    27
第三章 實驗方法    29
3-1 實驗藥品與原料    30
3-2 樣品製備、條件與實驗流程    30
3-2-1 陰極粉末製備流程    30
3-2-2 陰極樣品製備流程    31
3-2-3 陰極膏製備流程    32
3-2-4 半電池製備    32
3-2-5 浸潤法製程    34
3-3 實驗設備    34
3-3-1 X光晶體繞射儀(X-Ray diffraction; XRD)    34
3-3-2 掃描式電子顯微鏡(Scanning Electron Microscope; SEM)    35
3-3-3 熱重損失分析儀(Thermogravity Analysis; TGA)    36
3-3-4 導電性量測    36
3-3-5直流極化曲線測試平台    37
3-3-6 電化學交流阻抗頻譜儀    37
第四章 實驗結果    39
4-1 X光晶體繞射分析    39
4-1-1 LSCF之X光繞射圖譜    39
4-1-2 LSBxCF之X光繞射圖譜    40
4-2 LSCF陰極表面形貌觀察    40
4-3 陰極粉末熱重分析    41
4-3-1 LSCF之熱重分析    41
4-3-2 LSBxCF之熱重分析    42
4-4 LSCF熱機械性質分析    42
4-5 陰極材料導電性量測    42
4-5-1 LSCF之導電度    43
4-5-2 LSBxCF之導電度    43
4-6 直流極化曲線測試分析    43
4-6-1 LSCF之直流極化曲線    44
4-6-2 LSBxCF之直流極化曲線    44
4-6-3 LSB2CF浸潤LSCF陰極骨架之直流極化曲線    44
4-7 電化學交流阻抗頻譜分析    44
4-7-1 LSCF之交流阻抗頻譜    45
4-7-2 LSBxCF之交流阻抗頻譜    45
4-7-3 LSB2CF浸潤LSCF陰極骨架之交流阻抗頻譜    46
第五章 實驗結果討論    47
5-1 燃燒合成法製備LSCF與LSBxCF粉末之探討    47
5-1-1 LSCF    47
5-1-2 LSBxCF    48
5-2 陰極樣品特性分析之探討    49
5-2-1 氧空缺    49
5-2-2 熱膨脹係數    50
5-2-3 導電性    50
5-3 全電池性能分析    51
5-3-1 LSCF陰極    51
5-3-2 LSBxCF陰極    52
5-3-3 LSB2CF浸潤LSCF陰極    52
第六章 結論與未來工作    54
6-1 結論    54
6-2 未來工作    55
參考文獻    56


                                

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