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研究生： 成昕
Hsin Cheng
論文名稱： 鉍摻雜至La0.6Sr0.4Co0.2Fe0.8O3 作為質子傳導型SOFC陰極之可行性研究
Bismuth doped La0.6Sr0.4Co0.2Fe0.8O3 as cathode for proton-conducting solid oxide fuel cells
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： 2022
畢業學年度： 110
語文別： 中文
論文頁數： 106
中文關鍵詞： 固態氧化物燃料電池 、鑭鍶鈷鐵氧化物 、陰極材料 、鉍摻雜 、質子傳導型陰極
外文關鍵詞： Solid oxide fuel cell, Lanthanum-strontium-cobalt-ferrite oxide, cathode material, Bismuth doping, Proton-conducting cathode
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    • 本研究透過在以燃燒合成法製作之鈣鈦礦結構La0.6-xSr0.4Co0.2Fe0.8O3陰極材料中摻雜鉍，形成La0.6-xSr0.4BixCo0.2Fe0.8O3-δ(X=0、0.1、0.2、0.3、0.4、0.5；分別標示為LSB1CF、LSB2CF、LSB3CF、LSB4CF、LSB5CF) ，以探討其作為質子傳導型固態燃料電池陰極材料的可行性。燃燒過程中經由調整LSCF前驅硝酸鹽水溶液之酸鹼值(pH值: 1、2、3、4)與甘胺酸-硝酸根比值(G/N比: 0.75、1.00、1.25、1.50)，觀察經1000 °C、2 h煆燒後粉末之結晶結構，再以最佳燃燒法合成參數(G/N比、pH值)進行LSBxCF之合成，並分析其電化學性質。在LSCF實驗結果所示，在LSCF1.25/3、LSCF1.25/4、LSCF1.50/3與LSCF1.50/4等樣品中，LSCF1.50/3為所有燃燒法合成參數中結晶結構最符合作為SOFC陰極之結果，故以此參數作為後續LSBxCF合成之燃燒參數。經X光晶體繞射分析LSBxCF陰極粉末可發現，因摻雜離子半徑較小之Bi3+進入A-site，所以出現整體特徵峰的 2θ 有變大之趨勢，並且在LSB4CF、LSB5CF中出現些微雜項，其餘之參數接並未出現雜項。由四點式直流電量測導電度，LSCF雖隨著Bi的摻雜會導致電子導電度下降，但同時質子導電度會從原本無法導通質子，而隨Bi摻雜量上升而有些微提升。LSB3CF之單電池在800°C時擁有最高功率密度358.4 mW cm-2，比LSCF單電池140.6 mW cm-2高了155%，以及最低極化阻抗0.09 Ω cm2，比LSCF單電池降低25%；並且分別在700°C和600°C下皆具有最高功率密度183.5 mW cm-2、134.3 mW cm-2。
    本研究結果可知，LSB3CF陰極材料可有效提升質子在陰極中之傳導，在800 ℃操作溫度之電化學性能表現良好具有最高功率密度358.4 mW/cm2，並且在700°C及600°C下皆有最佳之電化學性能表現。

    In this study, the perovskite structure La0.6-xSr0.4Co0.2Fe0.8O3 cathode material made by the combustion synthesis method was doped with bismuth to form La0.6-xSr0.4BixCo0.2Fe0.8O3-δ(X=0 , 0.1, 0.2, 0.3, 0.4, 0.5; respectively marked as LSB1CF, LSB2CF, LSB3CF, LSB4CF) to explore its feasibility as a proton-conducting solid fuel cell cathode material. During the combustion process, the pH value (pH value: 1, 2, 3, 4) and the ratio of glycine-nitrate (G/N ratio: 0.75, 1.00, 1.25, 1.50) of the LSCF precursor nitrate aqueous solution were adjusted to observe After sintering at 1000°C for 2h, the crystalline structure of the powder is then synthesized with the best combustion method synthesis parameters (G/N ratio, pH value), and its electrochemical properties are analyzed. According to the LSCF experimental results, in the samples of LSCF 1.25/3, LSCF 1.25/4, LSCF 1.50/3 and LSCF 1.50/4, LSCF 1.50/3 is the most crystalline structure among all the combustion synthesis parameters. It conforms to the result of SOFC cathode, so this parameter is used as the combustion parameter for subsequent LSBxCF synthesis. Through X-ray crystal diffraction analysis of LSBxCF cathode powder, it can be found that the 2θ of the overall characteristic peak tends to become larger due to the smaller Bi3+ doped ion radius entering the A-site, and there are some minor miscellaneous items in LSB4CF and LSB5CF. The other parameter connections did not appear miscellaneous. The conductivity is measured by the four-point direct current electric quantity, LSCF will cause the electronic conductivity to decrease with the doping of Bi, but at the same time, the proton conductivity will never be able to conduct protons, and will slightly increase with the increase of the doping amount.. The LSB3CF single cell has the highest power density of 358.4 mW cm-2 at 800°C, which is 155% higher than the LSCF single cell 140.6 mW cm-2, and the lowest polarization impedance of 0.09 Ω cm2, which is 25% lower than the LSCF single cell; And it has the highest power density of 183.5 mW cm-2 and 134.3 mW cm-2 at 700°C and 600°C, respectively. The results of this study show that the LSB3CF cathode material can effectively enhance the conduction of protons in the cathode, and the electrochemical performance is good at the operating temperature of 800 ℃. It has the highest power density of 358.4 mW/cm2, and it has the highest power density at 700°C and 600°C. The best electrochemical performance.

    摘要 i Abstract iii 致謝 iv 目錄 v 圖目錄 ix 表目錄 xiv 第一章 緒論 1 1-1 前言 1 1-2 問題所在 2 1-3 解決方法 3 1-4論文大綱 3 第二章 理論基礎與文獻回顧 5 2-1固態氧化物燃料電池(SOFC) 5 2-1-1固態氧化物燃料電池原理與簡介 5 2-1-2固態氧化物燃料電池元件 7 2-1-3 固態氧化物燃料電池支撐類型[29] 9 2-2 電化學分析原理 10 2-2-1 直流電極化曲線(I-V Curve)原理 11 2-2-2 電化學交流阻抗頻譜(EIS)原理 13 2-3陰極元件 16 2-3-1 陰極傳導機制 17 2-3-2 陰極晶體結構 18 2-3-3 容忍因子之計算 20 2-3-4 陰極材料製備方式 21 2-4 文獻回顧 23 2-4-1 LSCF陰極的摻雜研究 24 2-4-2 提升LSCF陰極性能之相關研究 25 第三章 實驗方法 27 3-1 實驗藥品與原料 27 3-2樣品製備、條件與實驗流程 27 3-2-1 電解質粉末製備流程 27 3-2-2 陽極基板製備流程 28 3-2-3 陰極粉末製備流程 28 3-2-4 陰極樣品製備流程 29 3-2-5 陰極膏製備流程 29 3-2-6 單電池製備 30 3-3 分析及測試儀器與設備 30 3-3-1 X光晶體繞射儀(X-Ray diffraction; XRD) 30 3-3-2 掃描式電子顯微鏡(Scanning Electron Microscope; SEM) 32 3-3-3 導電性量測 32 3-3-4 直流極化曲線測試平台 33 3-3-5 電化學交流阻抗頻譜儀 33 第四章 實驗結果 35 4-1 X光晶體繞射分析 35 4-1-1 LSCF之X光繞射圖譜 35 4-1-2 LSBxCF之X光繞射圖譜 35 4-2陰極材料導電性量測 36 4-2-1 電子導電度 36 4-2-2 質子導電度 36 4-3 單電池I-V 性能曲線測量與分析 37 4-4 電化學交流阻抗頻譜分析 37 4-5掃描式電子顯微鏡之形貌觀察 38 4-5-1 低倍率形貌(10000 x) 38 4-5-2 高倍率形貌(30000x) 38 第五章 實驗結果討論 39 5-1燃燒合成法製備LSCF與LSBxCF粉末之探討 39 5-1-1 LSCF 39 5-2-2 LSBxCF 39 5-2陰極樣品特性分析之探討 40 5-3全電池性能分析 40 第六章 結論與未來工作 42 6-1 結論 42 6-2 未來工作 43 參考文獻 44 圖片 49 表目錄 83

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