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以作者查詢圖書館館藏 、以作者查詢臺灣博碩士 、以作者查詢全國書目 、勘誤回報 、線上人數：28 、訪客IP：3.147.67.166
姓名 賴泊叡(Bo-Ruei Lai) 查詢紙本館藏 畢業系所 材料科學與工程研究所 論文名稱 自分層電解質之形成於固態氧化物燃料電池之應用研究
(Research on the self-formed BCZY electrolyte for proton-conducting solid oxide fuel cells)相關論文 檔案 [Endnote RIS 格式]
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至系統瀏覽論文 ( 永不開放)
摘要(中) 本研究中，我們透過改變電解質之組成比例，以及透過優化製備電解質粉末等方法，對電解質進行改良。首先，我們改變電解質中BCZY與NiO之重量比，然後採用奈米球磨技術細化用於旋轉塗布漿料中之粉末粒徑。而後，在燒結過程中，細化之BCZY粉末將擴散至電解質之最表層，形成緻密薄膜，我們稱此現象為自分層現象。
最後，我們測試電池的性能。並根據性能曲線、電化學阻抗譜（EIS）和SEM圖像分析，我們可以了解電池的結構情況，並加以推測電池性能優劣的原因。經過分析，我們發現塗布2層奈米自分層電解質（35 wt% NiO-BCZY）之電池具有最佳性能。在800℃工作溫度下，此電池之最大功率密度為446.2 mW/cm2，並且其歐姆阻抗和極化阻抗值均低於標準奈米電解質（3 wt% NiO-BCZY）電池之值。 美中不足的是，經過24小時長期穩定性測試，電池之衰減率為17.43%。在之後的工作中，降低自分層電解質電池之衰減率是一個可行的目標。摘要(英) In this study, we improve the electrolyte by changing the composition ratio of the powder and optimizing the preparation of the electrolyte powder. First, we varied the weight ratio of BCZY to NiO in the electrolyte, and then used nano-ball-milling method to refine the particle size of the powder in the the spin-coating slurry. Continuously, during the sintering process, the refined BCZY particles in the improved electrolyte will diffuse to the outermost layer and form a dense film, which is called self-formed electrolyte.
Finally, we test the performance of the cell. According to the analysis on the performance curve, electrochemical impedance spectroscopy (EIS), and SEM images, we can understand the structure of the fuel cells and speculate the reasons for the performance of the cells. After we analyze the experimental results, we observed that the cell with 2 layers of self-formed electrolyte (35 wt% NiO-BCZY) film whose powder is refined by nano-ball-milling has the best performance. At the operating temperature of 800 ℃, the cell has the maximum power density of 446.2 mW/cm2, and it has lower value of the ohmic impedance and polarization impedance than the cell with standard electrolyte(3 wt% NiO-BCZY). Imperfectly, after 24-hour long-term stability test, the decay rate of the cell is 17.43 %. In the future work, it is a great goal to decreasing the decay rate of cell with self-layered electrolyte.關鍵字(中) ★ 自分層電解質
★ 表面能
★ 奈米球磨技術
★ 長時間穩定性關鍵字(英) ★ self-formed electrolyte
★ surface energy
★ nano-ball-milling technology
★ long-term stability論文目次 目錄
摘要………………..………………..……..…………..………………..…...v
Abstract………..………………..………………..………………..…..........vi
致謝………..………………..………………..………………..…...............vii
目錄…..……..………………..………………..………………..................viii
圖目錄……..………………..………………..………………......................xi
表目錄…..………………..………………..………………..…..................xiii
前言…..………………..………………..………………..….........................1
第一章、實驗原理與文獻回顧……..………………..…...............................2
1.1. 固態氧化物燃料電池(SOFC) ..………………..…...............................2
1.1.1. SOFC之原理..…………………………...…...............................2
1.1.2. SOFC之優點..…………………………...…...............................4
1.1.3. SOFC之結構..…………………………...…...............................5
1.2. SOFC之電解質材料..…………………………..…...............................7
1.2.1. 鈣鈦礦(Perovskite)結構………………..…................................7
1.2.2. 質子傳輸型電解質…………………..……................................8
1.2.3. 質子傳輸機制………………….…….……..............................10
1.3. SOFC粉末之合成方法……………….…….……...............................11
1.3.1. 固態反應法(Solid-state reaction) ….……................................11
1.3.2. 水熱法(Hydrothermal method) .…….……...............................12
1.3.3. 溶膠-凝膠法(Sol-gel method) .…….……................................12
1.3.4. 燃燒法(Combustion) .…….…….......…..…..............................12
1.4. SOFC之電池製程…………….….…….......…..…..............................13
1.4.1. 乾壓成型技術(Die-pressing technique) ..….............................13
1.4.2. 刮刀成型技術(Tape-casting technique) ..….............................13
1.4.3. 旋轉塗佈技術(Spin-coating technique) ..….............................14
1.4.4. 雷射脈衝沉積技術(Pulsed-laser deposition, PLD) .................14
1.5. 粉末燒結理論…………….……...…….......…..…..............................15
1.5.1. 燒結過程………….……...…….......…..…...............................15
1.6. 自分層電解質之擴散機制……...…….......…..…...............................16
1.6.1. 自分層電解質粉末之成分及擴散機制………........................16
1.7. 電化學分析原理………….……...…….......…..…..............................18
1.7.1. 極化曲線(I-V curve)之原理…….......…..….............................18
1.7.2. 電化學交流阻抗原理…….......…..….......................................21
1.7.3. 擬合等效電路簡介………….….......…..…..............................22
第二章、實驗方法………….….......…..…...................................................23
2.1. 實驗藥品………….……………………......…..…..............................23
2.2. 實驗方法與流程….……………………......…..…..............................24
2.2.1. BaCe0.6Zr0.2Y0.2O3-δ (BCZY622)陶瓷粉末之製備.....................24 2.2.2. 乾壓成型技術製備陽極粉末與基板…..…..............................24
2.2.3. 旋轉塗布所需粉末之製備……......…..…................................25
2.2.4. 陽極支撐半電池之製備…………......…..…............................25
2.2.5. 陰極與極電層之製備…………......…..……............................27
2.3. 材料性質分析……….................................…..……............................27
2.3.1. X-ray粉末繞射分析儀(X-ray diffraction, XRD) ......................27
2.3.2. 掃描式電子顯微鏡 (Scanning electron microscopy, SEM) ....28
2.4. 單電池I-V性能量測................................…..……..............................29
2.5. 電化學交流阻抗分析..................................…….................................29第三章、結果與討論................................…..…….......................................30
3.1. 全電池材料之相分析......................…..…….......................................30
3.1.1. 煆燒電解質粉末(BCZY622)之相分析.....................................30
3.1.2.電池材料之相分析.................…..…….......................................31
3.2. 微結構分析.................…..…………………........................................33
3.2.1自分層電解質半電池表面之微結構分析..................................33
3.2.2自分層電解質半電池截面之微結構分析..................................35
3.3. 全電池I-V性能曲線測量與分析…………........................................37
3.4. 全電池之EIS測量與分析…………....................................................39
3.5. 全電池之穩定性分析………………...................................................41
第四章、結論………………………..……...................................................43
參考文獻…………..………………..……...................................................44
圖目錄
圖1.1：P-SOFC操作原理。……….............................................................4
圖1.2：O-SOFC操作原理。……….............................................................4
圖1.3：鈣鈦礦晶體結構圖(ABO3) [14]。...................................................7
圖1.4：鈣鈦礦氧化物質子傳導率比較圖[18]。.......................................10
圖1.5：質子於鈣鈦礦結構中傳導之示意圖[23]。...................................11
圖1.6：乾壓成型技術示意圖。……...........................................................13
圖1.7：刮刀成型技術示意圖。……..........................................................14
圖1.8：旋轉塗佈技術之示意圖。…..........................................................14
圖1.9：雷射脈衝沉積技術示意圖。..........................................................15
圖1.10：燒結過程(a)初期階段；(b)中期階段；(c)末期階段。..............16
圖1.11：理想與實際之燃料電池極化曲線圖[41]。.................................20
圖1.12：電化學阻抗複數平面示意圖(a)奈奎斯特圖(Nyquist plot);(b)Bode
plot;(c)相角圖(phase angle plot) [43]。.........................................22
圖2.1：BCZY622粉末合成流程。............................................................24
圖2.2：旋轉塗布所需粉末之合成流程。..................................................25
圖2.3：旋轉塗布薄膜技術示意圖。..........................................................26
圖2.4：陰極與集電層之製備流程圖。......................................................27
圖2.5：布拉格繞射原理及示意圖。..........................................................28
圖2.6：燃料電池測試平台示意圖。..........................................................29
圖3.1：電解質BCZY粉末經1250 ℃煆燒後之XRD圖。....................30
圖3.2：自分層電解質(35wt%NiO-BCZY)粉末之XRD圖。..................32
圖3.2：自分層電解質(35wt%NiO-BCZY)半電池之XRD圖。..............32
圖3.4：不同成份之奈米球磨電解質，經1400 ℃或1480 ℃燒結之SEM
表面圖。..........................................................................................34
圖3.5：不同成份之奈米球磨電解質，經1400 ℃或1480 ℃燒結之SEM
表面圖。..........................................................................................36
圖3.6：奈米球磨電解質電池I-V性能曲線圖。......................................38
圖3.7：全電池電化學阻抗分析結果。......................................................40
圖3.8：3層標準奈米球磨電解質1400 ℃燒結電池之24小時長時間性能
分析。................................................................................................42
圖3.9：2層自分層奈米球磨電解質1400 ℃燒結電池之24小時長時間性
能分析。.............................................................................................42
表目錄
表1.1：NiO之表面能。..............................................................................17
表1.2：BaCeO3之表面能。.........................................................................17
表1.3：BaZrO3之表面能。.........................................................................17
表1.4：BCZ31經計算之之表面能。..........................................................18
表1.5：常見等效電路元件。......................................................................22
表2.1：實驗藥品表。..................................................................................23
表2.2：3種旋轉塗布所需粉末。...............................................................25
表2.3：本實驗旋轉塗布漿料所需粉末。..................................................26
表3.1：半電池之結構參數。......................................................................33參考文獻 參考文獻
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[48] E. Povoden-Karadeniz, “Thermodynamic Database of the La-Sr-Mn -Cr-O Oxide System and Applications to Solid Oxide Fuel Cells”, Swiss Federal Institute of Technology Zurich, 2008.指導教授 李勝偉(Sheng-Wei Lee) 審核日期 2023-8-19 推文 plurk
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