臺灣博碩士論文加值系統

氧化鎢電致變色元件可藉由外加電壓調節UVA紫外光、可見光和部份近紅外光，由於具有高穿透率變化、高著色效率及良好的化學穩定性，因此被認為具有潛力發展人性化智慧節能玻璃帷幕。然而其性質容易受到薄膜之結晶性、表面形貌、微結構與成分等影響，目前電致變色領域主要挑戰為可大面積化的多孔電極。本研究利用界面活性劑輔助溶膠凝膠法，製備具有奈米多孔的氧化鎢電致變色薄膜，分別從表面形貌的改變、結晶性的影響以及微結構的變化著手，探討其對電致變色性質的影響，最後以全溶液法組成全固態電致變色元件，並測量其熱遮蔽能力。
第一部份利用界面活性劑作為模板，引導氧化鎢薄膜形成多孔結構，而藉由界面活性劑的添加濃度改變，因為溶液中分子表面能的緣故，使得氧化鎢與有機物混合物會形成不同的微相結構，經過熱處理移除有機物後，最後形成具有不同多孔結構的氧化鎢薄膜。研究結果顯示，添加少於0.06 g/ml界面活性劑的氧化鎢薄膜具有約10 nm大小的奈米微孔，其穿透率變化量為60 %，而添加0.10 g/ml界面活性劑的氧化鎢薄膜具有數十奈米的球狀孔洞，其穿透率變化量為67.6 %。
承接第一部份的研究，第二部份以不同的溫度對奈米多孔氧化鎢進行熱處理，獲得具有不同結晶性的奈米多孔氧化鎢。以界面活性劑F-127作為模板使得孔洞結構足以承受400 ℃的熱處理溫度而不至於崩塌，透過循環伏安法和即時著/去色穿透率變化分光光譜途的分析，可以得知結晶奈米多孔氧化鎢薄膜雖然具有較佳的穩定性，然而較為緻密的晶體結構讓鋰離子在遷入或遷出時需要克服更大的應變能，而非晶質奈米多孔氧化鎢薄膜具有較佳的可逆性與反應速率，其著色與去色響應時間不到15秒，且經過千次循環仍舊保持穩定。
於第三部份將非晶質奈米多孔氧化鎢薄膜以不同的濕度進行時效處理，嘗試在氧化鎢結構中形成結晶水，研究結果顯示，在高濕度下進行時效處理之氧化鎢薄膜，其穿透率變化量相較於低濕度時效處理之氧化薄膜提升近兩成，而著/去色響應時間更縮短至10秒以內，著色效率也提升到60 cm2C-1，由Raman分析中可以發現OH拉伸散射峰變強，表示結晶水在氧化鎢結構中形成一快速質子交換通道，有助於電致變色反應。
最後一部份將前述氧化鎢薄膜和以溶膠凝膠法製備的氧化鉭薄膜，以化學浴成長的氧化鎳薄膜結合，組裝成全固態電致變色元件，透過紫外光-可見光-紅外光分光光譜儀的分析，以中華民國國家標準CNS 12381-R3161進行計算，可得到其可見光穿透率在去色和著色狀態下分別約為55 % 和36 %，而日光輻射熱穿透率在去色和著色狀態分別約為38 %和20 %，符合我國奈米隔熱膜產品規範。而實際以太陽燈照射量測照度的測試，可得其熱遮斷係數在著色和去色狀態分別為0.16和0.36，分別可阻擋84 %到64 %的能量穿透，具有調整日光輻射熱能穿透的能力與大面積化的潛力。

Electrochromic device have the ability to change the transmittance to block the solar radiation by controlling the applied voltage and have the application for energy-saving windows. State-of-the art, the challenges of the device are nanostructured electrodes and large-scale fabricating. In this research, porous tungsten oxide is synthesized by the surfactant-assisted sol-gel method. Porous structure, crystallinity, and composition can be modified by the concentration of surfactant, annealing temperature, and curing condition. The effects of different morphology and structure are studied by chronoampermetry and cyclic voltammetry. Transmittance modulation and coloration efficiencies are 67.6 % and ~60 cm2C-1. It needs less than 10 s to switch from colored state to beach state. All solid electrochromic devices are fabricated by all-solution method. Thermal shielding ability is measured by UV-Vis-IR spectroscopy and illuminating meter. Visible light transmittances and solar heat transmittances are 55.2/35.9 % and 38.2/20.1 % in colored/bleach state respectively. The transmitted illumination can be modulated from 36 % to 16 %. The transmittance in visible light region is higher than 50 % and the ability of blocking infrared is enough to use as energy-saving smart window.

總目錄
摘要 .....................................................I
Extended Abstract III
致謝 ..................................................XIII
總目錄 ...................................................XIV
圖目錄 ..................................................XVII
第一章 緒論 1
1-1. 前言 1
1-2. 研究動機 9
第二章 文獻回顧 11
2-1. 電致色變材料簡介 11
2-2. 氧化鎢材料簡介 14
2-3. 氧化鎢變色機制簡介 16
2-3-1. 非晶氧化鎢的電致變色機制 16
2-3-2. 結晶氧化鎢的電致變色機制 17
2-4. 電致變色元件 18
2-5. 電致變色性質評估 22
2-5-1. 穿透率變化量 22
2-5-2. 著色效率 22
2-5-3. 循環穩定性 22
2-5-4. 響應時間 23
2-5-5. 可逆性 23
2-6. 氧化鎢奈米結構簡介 23
2-7. 氧化鎢之製備方法 26
第三章 研究方法與實驗步驟 28
3-1. 實驗藥品與基材 28
3-2. 實驗步驟 29
3-3. 實驗設備 32
3-3-1. 旋轉塗佈機 32
3-3-2. 手套箱 32
3-3-3. 高溫爐 34
3-4. 分析儀器與方法 34
3-4-1. 結構與形貌分析 34
3-4-2. 成份和化學鍵結分析 38
3-4-3. 光學性質量測 39
3-4-4. 電致變色性質分析 39
第四章 界面活性劑F-127濃度對多孔氧化鎢薄膜之影響 42
4-1. 前言 42
4-2. 實驗步驟 42
4-3. 結果與討論 45
4-3-1. 結構分析 45
4-3-2. 電致變色性質 51
4-3-3. 電化學循環分析 54
4-4. 小結 58
第五章 熱處理溫度對多孔氧化鎢薄膜及其特性之研究 59
5-1. 前言 59
5-2. 實驗步驟 59
5-3. 結果與討論 60
5-3-1. 熱重分析 60
5-3-2. 微結構分析 62
5-3-3. 電致變色性質 66
5-4. 小結 72
第六章 時效處理對奈米氧化鎢結構影響與電致變色性質之改善 73
6-1. 前言 73
6-2. 實驗步驟 73
6-3. 結果與討論 74
6-3-1. 微結構分析 74
6-3-2. 電化學分析與電致變色性質 78
6-4. 小結 86
第七章 電致變色元件熱遮蔽效益測試 87
7-1. 前言 87
7-2. 實驗步驟 87
7-2-1. 電致變色元件組裝 88
7-2-2. 熱隔絕效益量測 88
7-3. 結果與討論 91
7-3-1. 表面形貌分析 91
7-3-2. 分光光譜儀分析 91
7-3-3. 元件可見光穿透率、太陽熱能穿透率試驗法 95
7-3-4. ISO制物質與皮膚抗陽光系數和太陽可見光穿透率試驗法 101
7-3-5. 熱遮蔽試驗測試 104
7-4. 小結 107
第八章 總結 108
參考文獻 110

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