臺灣博碩士論文加值系統

釩氧化還原液流電池(Vanadium Redox Flow Battery, VRFB)之主要關鍵組件為離子交換膜、電極、電解質與流道模型之元件。各關鍵材料之性質決定電池的能量密度，彼此間層層相連亦環環相扣。因此，這些關鍵材料在不同充-放電電量狀態 (State of charge, SOC)之健康狀態(State of health, SOH)監測是研究電池最需要且最欠缺的技術。本論文開發一新的動態交流阻抗數學分析模型加以分析改變關鍵材料類型於不同SOC下，監測VRFB系統之交流阻抗變化。實驗上分別對離子交換膜、電極、電解質與流道模型進行改質，以提升電池之能量效率為目標，進行電池充放電測試。同時，進行交流阻抗動態分析測試，並將動態偵測到的阻抗值代入開發之VRFB系統動態方程式，探討改變關鍵材料對VRFB系統之影響。

The key materials of all vanadium redox flow battery (All-VRFB) system include ion exchange membrane, electrodes, electrolyte, and flow channel. The battery’s energy density not only is decided by the characteristics of these key materials, but also there are intimate relationship between each other. Therefore, these key materials of VRFB influence different charge-discharge power status (State of charge, SOC) and the state of cell’s health (SOH) is urgent to be resolved. In this study, a new performance evaluating for redox flow battery with electrochemical impedance spectroscopy (EIS) was developed. This model can be used a test tool for the SOH of VRFB with various key materials, different SOC, and charge–discharge properties. In our experiment, we also improve the performance of cell by modified key materials, and to verify the model. Simultaneously, the AC impedance changes of All-VRFB will be verified under different SOC. Using the cell impedance dynamic mathematical analysis model evaluate and analyze the SOH of the cell. From these results investigate the effect of key materials for All-VRFB system.

摘要 I
目錄 III
圖目錄 VI
表目錄 IX
第一章 緒論 1
第二章 文獻回顧 3
2-1 簡介全釩氧化-還原液流電池 (All-VRFB) 3
2-1-1 全釩氧化-還原液流電池之發展歷史 3
2-1-2 全釩氧化-還原液流電池之操作原理 3
2-1-3全釩氧化-還原液流電池之關鍵組件 5
2-2 簡介交流阻抗動態模型 10
2-2-1 交流阻抗分析(AC Impedance)之原理 10
2-2-2等效電路模型(Equivalent Circuit Models) 11
2-3 All-VRFB關鍵材料之改質製備方法 17
2-4 循環伏安法原理 20
2-4-1基本原理 20
2-4-2循環伏安法之相關係數 21
第三章 實驗與研究方法 23
3-1 前言 23
3-2 實驗架構 24
3-3 實驗藥品及耗材 25
3-4 實驗儀器 28
3-5 All-VRFB系統等效電路設計之實驗步驟 30
3-5-1 等效電路設計及數學模擬方程式推導 30
3-5-2 交流阻抗動態分析實驗 30
3-6 All-VRFB系統關鍵材料之製備與檢測分析 30
3-6-1 利用溶膠-凝膠法進行離子交換膜改質 30
3-6-2 利用無電電鍍法進行電極改質 31
3-6-3 添加有機物進行電解質改質 32
3-6-4 化學結構分析實驗 32
3-6-5 水吸收率實驗 33
3-6-6 離子交換容量實驗 33
3-7 All-VRFB系統關鍵材料之電化學性質測定 34
3-7-1 循環伏安測試 34
3-7-2 電化學係數測試 34
3-8 All-VRFB系統關鍵材料之充放電測試 35
3-8-1 All-VRFB之單電池組件結構說明 35
3-8-2 釩單電池充放電測試 37
3-8-3 釩離子動態滲透率測試 39
3-9 All-VRFB系統關鍵材料之交流阻抗分析測試 40
3-9-1 不同離子交換膜材下之交流阻抗分析測試 40
3-9-2 不同電極材料下之交流阻抗分析測試 40
3-9-3 不同電解質條件下之交流阻抗分析測試 41
3-9-4 不同流道下之交流阻抗分析測試 41
第四章 交流阻抗動態模型之測試推導對全釩液流儲能電池系統之應用 42
4-1前言 42
4-2等效電路設計及數學模擬方程式推導 43
4-2-1 All-VRFB系統之等效電路模型之建立緣起 43
4-2-2 All-VRFB系統之動態方程式的推導原理 44
4-2-3 All-VRFB系統之動態數學參數推衍 47
4-3交流阻抗動態測試結果對動態數學參數模型推導之驗證 50
4-4 結論 57
第五章 以交流阻抗動態模型實務評估分析All-VRFB關鍵材料之特性 59
5-1 前言 59
5-2 離子交換膜 60
5-2-1 Nafion離子交換膜之改質 60
5-2-2 離子交換膜之充放電測試 63
5-2-3 離子交換膜之交流阻抗分析 65
5-3 電極 68
5-3-1電極之電化學性質測試 68
5-3-2電極之充放電測試 69
5-3-3電極之交流阻抗分析 70
5-3-4 電極(C/TiO2/Pd)應用於半釩氧化還原液流電池(semi-VRFB) 72
5-4 電解質 76
5-4-1電解質之電化學性質測試 76
5-4-2電解質之充放電測試 78
5-4-3電解質之交流阻抗分析 80
5-5 流道模型 82
5-5-1蛇行型流道(Serpentine channel)之流速測試 82
5-5-2蛇行型流道(Serpentine channel)不同流速之交流阻抗分析 84
5-5-3指叉型流道(Interdigitated channel)之流速測試 85
5-5-4指叉型流道(interdigitated channel)不同流速之交流阻抗分析 87
5-6 結論 88
第六章 總結與未來展望 90
6-1交流阻抗動態模型之測試推導與VRFB之特性研究 90
6-2以交流阻抗動態模型實務評估分析對VRFB關鍵材料之特性影響 90
6-3 未來展望 91
參考文獻 92

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