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系統識別號 U0026-2707201617163800
論文名稱(中文) 鍺酸鑭基磷灰石離子導體之晶體結構與電性
論文名稱(英文) Crystal Structure and Electrical Properties of La/Ge Based Apatite Ionic Conductors
校院名稱 成功大學
系所名稱(中) 資源工程學系
系所名稱(英) Department of Resources Engineering
學年度 104
學期 2
出版年 105
研究生(中文) 陳正威
研究生(英文) Zheng-Wei Chen
學號 N46034104
學位類別 碩士
語文別 中文
論文頁數 82頁
口試委員 指導教授-黃啟原
口試委員-吳毓純
口試委員-黃正亮
口試委員-李文熙
中文關鍵字 鍺酸鑭  固態氧化物燃料電池  離子導體  磷灰石 
英文關鍵字 lanthanum germanate  SOFC  apatite structure  ionic conductors 
學科別分類
中文摘要 本研究利用固態反應法製備計量比不同之鍺酸鑭 (La10-xGe6O27-1.5x,x = 0、0.25、0.5、0.75、1),探討晶體結構與電性之間的關聯,並模擬間隙氧在結構中的移動路徑。
實驗結果顯示 1200°C/3 h 的煅燒條件下,所有成分點皆可合成單一相的鍺酸鑭,透過 PDF卡號比對,LGO9、LGO9.25、LGO9.5 為六方晶系 (P63/m),而 LGO9.75、LGO10 繞射峰數目變多,經比對後屬於三斜晶系的繞射峰,透過晶格常數精算,三軸長度 (a、b、c) 與夾角 (α、β、γ) 皆不相等,結構為三斜晶系 (Pī)。透過高溫 XRD 分析,六方晶系成分點在 500°C -800°C 繞射峰無明顯變化,而三斜晶系成分點繞射峰數目有變少的趨勢,其中 LGO9.75 在 600°C - 700°C 已由三斜晶系轉為六方晶系;而 LGO10 並未發生相轉換,結構仍維持三斜晶系。本研究模擬出 5 條間隙氧移動路徑,其中 1 條繞著鍺氧四面體在結構中穿梭;另外 4 條則是繞著通道氧移動,但所有間隙氧移動路徑皆沿 c 軸以類正弦模式傳遞。六方晶系成分點之導電率、間隙氧移動空間皆大於三斜晶系成分點,且導電率與間隙氧移動空間呈正相關,代表間隙氧移動空間越大,導電率越高。
英文摘要 Apatite structures have the highest conductivity of all solid oxide fuel cell (SOFC) electrolytes because of their conduction mechanism. Among all apatite-type electrolytes, lanthanum germanates possess the highest conductivity. To observe the relationship between composition, crystal structure, and ionic conductivity, lanthanum germanates (La10-xGe6O27-1.5x, x = 0, 0.25, 0.5, 0.75, 1) were synthesized using the solid-state method. The XRD pattern showed that a single phase could be obtained for all compositions calcined at 1200°C/3 h. Crystal structure analysis using the Rietveld refinement approach indicated that x = 0.5, 0.75, 1 has a hexagonal structure (P63/m, #176) and x = 0, 0.25 has a triclinic structure (Pī, #2). These results show that five migration pathways could be established, assuming the interstitial oxygen passes the larger opening within the crystal structure. These five migration pathways are sinusoid-like three-dimensional routes along the c-axis. Since x = 0, 0.25 transforms to a triclinic phase, the migration opening becomes narrower and lowers the ionic conductivity. The Arrhenius plot of x = 0.25 demonstrated a sharp decrease in activation energy, indicating that the phase transition from triclinic to hexagonal occurred at around 650°C.
論文目次 摘要 I
Abstract II
誌謝 X
目錄 XI
圖目錄 XIV
表目錄 XVIII
第一章 緒論 1
1-1 前言 1
1-2 研究動機 3
1-3 研究目的 5
第二章 文獻回顧與理論基礎 6
2-1 燃料電池 6
2-1-1 燃料電池之原理 6
2-1-2 燃料電池之種類及優缺點 7
2-1-3 燃料電池之分類與應用 10
2-2 固態氧化物燃料電池 10
2-2-1 固態氧化物燃料電池的原理及要求 10
2-2-2 固態氧化物燃料電池之電解質種類 11
2-3 磷灰石結構固態電解質 15
2-3-1 磷灰石結構固態電解質導電載體 16
2-3-2 間隙氧離子在磷灰石結構中的傳遞情形 17
2-4 鍺酸鑭基電解質 19
2-5 矽酸鑭基與鍺酸鑭基電解質的比較 19
2-6 影響磷灰石結構電解質導電率的因素 20
第三章 實驗方法與分析 26
3-1 粉末製備 27
3-1-1 起始原料 27
3-1-2 鍺酸鑭基 (La10-xGe6O27-1.5x) 粉末製備 27
3-1-3 粉末之熱差/熱重分析 28
3-2 煅燒粉末製備 28
3-3 煅燒粉末分析 29
3-3-1 X 光繞射儀 29
3-3-2 同步輻射 XRD 31
3-3-3 掃描式電子顯微鏡 31
3-4 生胚製備 32
3-4-1 生胚燒結收縮量測 32
3-5 燒結體製備 32
3-6 燒結體分析 32
3-6-1 密度量測 32
3-6-2 X 光繞射儀 33
3-6-3 掃描式電子顯微鏡 33
3-6-4 導電率量測 33
3-6-5 活化能計算 34
第四章 結果與討論 35
4-1 起始粉末分析 35
4-1-1 氧化鑭熱重/熱差分析 35
4-1-2 粉末微結構分析 36
4-2 粉末之熱差/熱重分析 37
4-3 粉末煅燒分析 38
4-3-1 結晶相分析 38
4-3-2 Rietveld refinement 41
4-3-3 同步輻射 XRD 分析 44
4-3-4 高溫 XRD 45
4-4 晶體結構分析 49
4-4-1 間隙氧移動路徑分析 (1) 53
4-4-2 間隙氧移動路徑分析 (2) 58
4-5 煅燒粉末微結構分析 60
4-6 燒結體分析 62
4-6-1 燒結收縮量測 62
4-6-2 結晶相分析 64
4-6-3 微結構分析 65
4-6-4 電性分析 68
4-7 晶體結構與導電率綜合分析 71
4-8 與添加鎢/鎳樣品比較 72
4-8-1 晶格常數 72
4-8-2 晶體結構 73
4-8-3 導電率 74
4-8-4 活化能 76
第五章 結論 78
參考文獻 79

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