釹摻雜鑭鍶鈷鐵奈米纖維應用於質子傳輸型陶瓷電化學電池空氣電極

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黃婉瑜(Wan-Yu Huang) 查詢紙本館藏

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材料科學與工程研究所

論文名稱

釹摻雜鑭鍶鈷鐵奈米纖維應用於質子傳輸型陶瓷電化學電池空氣電極
(Nd Doped LSCF Nanofiber as Air Electrode for Protonic Ceramic Electrochemical Cells)

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摘要(中)

質子傳輸型陶瓷燃料電池(Protonic ceramic fuel cells, PCFCs)材料在500-800 ℃之操作溫度範圍內具有優良傳導性以及提高材料的穩定性且密封性較佳，但降低操作溫度會影響空氣電極的氧還原反應(Oxygen reduction reaction, ORR)速率。當空氣電極端使用Nd-based材料比La-based材料具有更高的氧交換率。由於Nd-based材料優異的氧交換速率，在空氣電極側可產生更快速的氧離子傳輸和氧擴散速率，藉此有效降低電化學阻抗並提升電化學性能。
在本研究中，使用NdxLa0.6-xSr0.4Co0.2Fe0.8O3-δ (x=0, 0.1, 0.2, 0.3, 0.6)奈米纖維作為PCFC的空氣電極。結果顯示，Nd摻雜LSCF電池可以有效提升性能，因Nd3+的離子半徑小於La 3+的離子半徑，導致平均A-site離子半徑改變，降低了氧遷移至空位的阻礙，使氧跳躍到氧空位所受到晶格應力減弱。
Nd0.1-LSCF電池在800°C 時的最高功率密度約為579.16 mW/cm2，比LSCF電池高 43%。歐姆電阻和極化電阻分別降低了約29% 和32%。使用Nd0.1-LSCF電池進行電解模式，空氣電極側電解水氣並於氫氣電極側產生氫氣。其法拉第電流效率達87%，能量轉換效率達85%，而產氫速率可達10.17 ml/min。
本研究結果可知，Nd0.1-LSCF奈米纖維在PCFC可以有效提升氧擴散速率與氧離子傳輸，且在800 ℃操作溫度PCFC之電化學性能表現良好具有最高功率密度579.16 mW/cm2。Nd0.1-LSCF電池成功應用於PCEC電池模式。Nd0.1-LSCF奈米纖維空氣電極提供於質子傳導型陶瓷電化學電池裝置未來發展之潛力。

摘要(英)

Operation of PCFCs in the range of 500-800 °C range would enhance the durability of materials but reduce the rate of oxygen reduction reaction (ORR) at air electrode. Nd-based cathode material has higher oxygen exchange rate than La-based ones. Due to the excellent oxygen exchange rate, rapid oxygen anion transport and oxygen surface exchange can decrease electrochemical impedance when the Nd-based cathode material is used as an air electrode.
In this research, the NdxLa0.6-xSr0.4Co0.2Fe0.8O3-δ (x=0, 0.1, 0.2, 0.3, 0.6) nanofiber is used as the air electrode for PCFCs. The cell with Nd doped LSCF can effectively promote the performance. The smaller cation radius of Nd3+ than that of La3+ causes a difference in the average A-site ion radii that has a relationship with lattice strain during oxygen hopping to oxygen vacancy.
The peak power density of Nd0.1-LSCF cell under PCFC mode at 800 °C is about 579.16 mW/cm2, 43% higher than that of LSCF cell. The ohmic resistance and polarization resistance are decreased by about 29% and 32%, respectively.
When PCFC is operated under protonic ceramic electrolysis cells (PCEC) mode, water vapor is supplied to the oxygen electrode side and thus pure H2 is generated at the hydrogen electrode side. The Faraday’s efficiency (FE) of Nd0.1-LSCF cell is 87% and the energy conversion efficiency (ECE) is 85%. The hydrogen evolution rate can achieve 10.17 ml/min.
From the results of this study, the Nd0.1-LSCF nanofiber m can enhance the transmission of oxygen ions and the diffusion of oxygen in air electrode, also keeping the outstanding performance of PCFC, with a peak power density of 579.16 mW/cm2 at 800 °C. Nd0.1-LSCF cell can be successfully operated under PCEC mode. The N0.1-LSCF nanofiber air electrode provided great potential for the future development of protonic ceramic electrochemical cell device.

關鍵字(中)

★ 釹摻雜鑭鍶鈷鐵
★ 奈米纖維
★ 空氣電極
★ 氧還原反應
★ 質子傳輸型陶瓷電化學電池

關鍵字(英)

★ Nd-doped LSCF
★ nanofiber
★ air electrode
★ oxygen reduction reaction
★ protonic ceramic electrochemical cell

論文目次

摘要 VI
Abstract VIII
致謝 X
目錄 XI
圖目錄 XV
表目錄 XVIII
前言 1
第一章、實驗原理與文獻回顧 3
1.1. 質子傳輸型陶瓷燃料電池 3
1.1.1. 質子傳輸型陶瓷燃料電池之原理 3
1.1.2. 質子傳輸型陶瓷燃料電池之結構 5
1.2. 質子傳輸型陶瓷電解電池 8
1.2.1. 質子傳輸型陶瓷電解電池之原理 8
1.2.2. 質子傳輸型陶瓷電解電池之結構 9
1.3. PCFC之空氣電極材料與傳輸機制 10
1.3.1. 空氣電極種類介紹 10
1.3.2. MIEC傳輸機制 12
1.3.3. 鈣鈦礦 (Perovskite)結構及性質 13
1.3.4. A-site元素摻雜與氧原子跳躍機制之關係 14
1.4. 靜電紡絲 16
1.4.1. 靜電紡絲原理 16
1.4.2. 靜電紡絲影響參數 17
1.4.3. 奈米纖維應用於燃料電池之優勢與發展困境 19
1.5. 電解質粉末合成方法與燒結機制 20
1.5.1. PCFC電解質粉末合成方法 20
1.5.2. 粉末燒結理論 20
1.5.3. 質子傳輸機制 22
1.6. PCFC電池製備方法 23
1.6.1. 乾壓成型技術 (Dry pressing technique) 23
1.6.2. 刮刀成型技術 (Tape casting technique) 23
1.6.3. 旋轉塗佈技術 (Spin coating technique) 24
1.7. 電化學分析原理 25
1.7.1. 極化曲線 (I-V curve)之原理 25
1.7.2. 電化學交流阻抗頻譜之原理 27
1.7.3. 等效電路之簡介 29
第二章、實驗方法 32
2.1. 容忍決定因子之計算 32
2.2. 實驗藥品 33
2.3. 實驗方法與流程 34
2.3.1. 粉末合成 34
2.3.2. 刮刀成型技術製備陽極基板 35
2.3.3. 奈米纖維 (Nanofiber)製備 36
2.3.4. 單電池製備 37
2.4. 材料性質分析 38
2.4.1. X光粉末繞射儀 38
2.4.2. 掃描式電子顯微鏡 (Scanning electron microscopy, SEM) 39
2.4.3. 穿透式電子顯微鏡 (Transmission Electron Microscopy, TEM)
40
2.5. 單電池 I-V 性能量測 40
2.6. 電化學交流阻抗分析 41
第三章、結果與討論
42
3.1. 材料相分析 42
3.1.1. 煆燒電解質粉末之相分析 42
3.1.2. 奈米纖維材料之相分析 43
3.2. 微結構分析 46
3.2.1. 釹摻雜鑭鍶鈷鐵奈米纖維之表面結構分析 46
3.2.2. 釹摻雜鑭鍶鈷鐵空氣電極之橫截面結構分析 49
3.3. 單電池 I-V 性能曲線測量與分析 52
3.4. 單電池之 EIS測量與分析 54
3.5. 單電池之長時間性能穩定性分析 57
3.6. 單電池之電解電流與法拉第效率 58
第四章、結論 62
參考文獻 63

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指導教授

李勝偉(Sheng-Wei Lee)

審核日期

2021-8-4

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