臺灣博碩士論文加值系統

非再生能源的枯竭以及負面影響對於人類文明發展有重大之影響，其中電力是發展的重要關鍵。為達到滿足發展需求亦不造成環境汙染，綠色能源之發展越趨於重要，但因其供電不穩使其成為應用上之一大限制。大型儲能系統的誕生，不但能達到削峰填谷之效亦能達到穩定電網之用途，隨未來綠色能源蓬勃發展同時擔任重要角色。全釩氧化液流電池，具有循環壽命長、可深度放電、零交叉汙染以及設計靈活之優點，但其於能量密度及電極上仍有改善空間。本研究中針對石墨氈電極進行表面改質並使用與活性物質相同之釩氧化物進行改質，使其即便殘留於電極表面，也不會對電池性能造成影響。
藉由熱重分析儀之幫助下，可得知處理溫度約在350oC左右，且藉由場發式電子顯微鏡觀察表面形貌，發現電極表面於活化後具有蝕刻之痕跡。在比表面積之量測下，發現濃度為10mM時比表面積提升了約三倍之多，配合表面分析組成後，在該濃度活化對其表面帶有最多含氧量，因此可證明其表面具有較大之反應面積及活性位點。在經由循環伏安法之分析後，V10-EGF之極化現象明顯降低並在阻抗分析下得知其電荷轉移阻抗縮小了約2.5倍，在單電池充放電後，其活化後之石墨氈電極之電容量較TGF高，且達理論電容使用量約70%。V10-EGF在長時間循環下電容量衰退率僅10%相對於TGF(23%)，具有較高之電化學活性。其結果與材料表面分析之結果相呼應並確認此法可有效改善電極之電化學性質，進而提高電池效能。

Large-scale electrical energy storage (ESS) also has attracted attention because wind and sunlight generate energy intermittently. Redox flow batteries are considered one of various large-scale ESS systems because of their advanced characteristics, including extended life, safety, design flexibility, rapid response, low maintenance cost, and decoupled scaling of power and energy.
In this work, a simple and environment friendly method to prepared activated graphite felt for vanadium redox flow battery (VRFB) by deposited the vanadium precursor on the surface of graphite felt and calcined to vanadium oxide. The intermediate material, VO2, will lead to the oxidation of carbon during the calcination. Compared with the normal etching method, this method was simple and without pickling process. The surface of activated graphite felt exists lots of pores and rough after suitable calcination temperature between 350°C and 400oC and the surface area of activated graphite felt reached to 17.11 m2/g. In addition, the polarization of activated graphite felt was decreased and the resistance of charge transfer was reduced (0.27Ω). Per-forming the single cell test at current density of 150 mA/cm2, the utilization of capacity reached to 70% and the capacity retention was 84% after 50 cycles. The above results illustrate the activated graphite felt has potential as electrode for VRFB.

摘要 I
Abstract II
致謝 III
目錄 IV
圖目錄 VII
表目錄 X
第1章、 前言 1
1-1 緒論 1
1-2 液流電池簡介 6
第2章、 文獻回顧 7
2-1 液流電池發展歷史 7
2-1-1 The iron-chromium redox system 7
2-1-2 Zinc/bromine redox flow cells 8
2-1-3 All vanadium redox flow battery(VRB) 8
2-1-4 Bromine/polysulphide flow battery 9
2-1-5 Zinc/cerium redox flow cells 9
2-1-6 The vanadium-bromine redox system 10
2-2 全釩氧化還原液流電池工作原理 12
2-3 全釩氧化還原液流電池關鍵材料 14
2-3-1 電解液 16
2-3-2 離子交換膜 17
2-3-3 雙極板 18
2-3-4 電池電極 19
第3章、 研究動機與目的 30
3-1 研究目的 30
第4章、 實驗方法與步驟 32
4-1 實驗器材 32
4-1-1 化學藥品及材料 32
4-1-2 實驗器材及設備 33
4-2 儀器分析 34
4-2-1 熱重量分析儀(Thermal gravity Analysis, TGA) 34
4-2-2 場發射掃描式電子顯微鏡(Field emission scanning electron microscopy, FE-SEM) 34
4-2-3 比表面積分析儀(BET) 34
4-2-4 X射線光電子能譜儀(XPS) 34
4-2-5 接觸角量測儀(Contact angle) 34
4-2-6 半電池循環伏安測試(Cyclic Voltammetry) 35
4-2-7 交流阻抗分析 35
4-2-8 單電池充放電測試 35
4-3 實驗步驟前處理 36
4-3-1 熱處理 36
4-3-2 V2O5活化石墨氈電極 36
4-3-3 電解液製備 39
4-3-4 半電池測試之極片製作與組裝 39
4-3-5 全電池測試與組裝 39
第5章、 結果與討論 40
5-1-1 電極重量變化分析 40
5-1-2 電極顯微組織分析 43
5-1-3 電極比表面積變化分析 45
5-1-4 電極親水性分析 47
5-1-5 拉曼散射光譜(Raman Spectroscopy) 50
5-1-6 X射線光電子能譜(XPS) 52
5-2 電化學性能分析 57
5-2-1 半電池循環伏安測試(Cyclic Voltammetry) 57
5-2-2 交流阻抗分析(A.C. Impedance) 61
5-2-3 單電池充放電測試(Charge-Discharge) 64
5-2-4 單電池長時間循環測試(Long-term cycle charge-discharge) 71
第6章、 結論 72
第7章、 參考文獻 73
附錄 – 作者簡介及發表著作一覽表 80

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