請用此 Handle URI 來引用此文件:
http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/63792
標題: | 多色系普魯士藍類似物塗膜研發與節能變色窗戶應用 Development of Multi-color Prussian Blue Analogue Coatings and Its Application to Energy-Saving Electrochromic Windows |
作者: | Tzu-Chien Liao 廖子頡 |
指導教授: | 陳林祈(Lin-Chi Chen) |
關鍵字: | 電致色變,普魯士藍,鐵氰化鈷,鐵氰化鎳,鐵氰化銅, electrochromic,smart window,Prussian blue,cobalt hexacyanoferrate,nickel hexacyanoferrate,copper hexacyanoferrate, |
出版年 : | 2012 |
學位: | 碩士 |
摘要: | 現今已經商業化的節能窗戶中,多以三氧化鎢作為工作電極。然而,鎢金屬在地球中的蘊藏量相對地低(1.25 mg/kg in earth’s crust),因此三氧化鎢製之電致色變元件將不可避免地有較高的成本。由於普魯士藍及其衍生物其主要構成元素為蘊藏量較為豐富的鐵(5.63×104 mg/kg in earth’s crust),故其較鎢更易於取得且具備低成本之優勢。另外,藉由置換錯合物中的金屬,我們還可以獲得不同色系之類似物,而本研究則選擇開發普魯士藍、鈷、鎳及銅三種錯合物。因此,在本研究中,我們將發展一系列之鐵系錯合物,如廣為人知的普魯士藍,以期能取代成本較高之鎢系材料。本研究首先針對不可分散之普魯士藍鹽類(普魯士藍、鐵氰化鎳),以黃血鹽對其粒子表面進行修飾,使粒子表面因帶負電而避免不可分散於水溶液之聚集現象。在成功配製出普魯士藍鹽類之印墨(ink),搭配迴旋塗佈(spin-coating)將一系列普魯士藍類似物固定於導電玻璃上,可以得到紅(鐵氰化鈷、鐵氰化鎳)、藍(普魯士藍)、黃(鐵氰化鎳)三種顏色之塗膜(coatings)。在電化學及光譜性質之分析,將可分別得到普魯士藍、鐵氰化鈷、鐵氰化鎳、及鐵氰化銅之反應電位及著色效率分別為30.0(@690 nm)、11.1(@574 nm)、16.3(@412 nm)、及12.7(@370 nm) cm2/C。同時,也藉由循環伏安法對薄膜進行短期的材料穩定性測試。在經過100圈掃描後,四種薄膜皆能維持95%以上的電化學活性。在元素分析的部分,可得到四種薄膜的主要組成元素皆含有鐵、碳、氮,及相對應之過渡金屬元素,與普魯士藍類似物之主要組成元素相同,顯示製備之產物為普魯士藍類似物之可能性。而從SEM微結構的分析中,四種薄膜之表面皆由奈米粒子堆疊而成,粒徑則由10~70 nm不等。值得一提的是,鐵氰化銅之粒子呈現方塊狀的型態,與其餘三種薄膜的球狀粒子有明顯差異。另外,本研究也使用層疊法(Layer-by-layer)製備普魯士藍-鐵氰化鎳之複合膜。此複合膜成功延伸普魯士藍在300-500 nm波段之穿透度變化調控光譜,可達到40%,且可展現四色態之變色效應。最後,我們利用不同色系的普魯士藍類似物薄膜,彼此搭配為兩組不同的互補式元件。其一為普魯士藍-鐵氰化鉬元件(Prussian blue-MoHCF ECD, PMECD),透過紅色系之鐵氰化鉬,成功彌補藍光區域。元件之全光譜穿透度(300~900nm)得以在60%到20%之間調節,其節能表現可達到196 W/m2。而以普魯士藍-鐵氰化鎳複合膜,與鐵氰化銅所組合之元件(Prussian blue-NiPBA/CuHCF ECD, PNCECD),其全光譜調控穿透度則在55%到30%之間,節能表現可達到125.0 W/m2。此元件總共可以展現出四種不同的色態。兩種互補式元件其可做為未來應用於節能及多色態建築裝式玻璃之智慧型窗戶原型。 Currently, most of the commercial electrochromic windows(ECWs) are based on WO3 working electrodes. However, Tungsten is a relatively low-abundance metal on earth(1.25 mg/kg in earth’s crust), so WO3 will have inevitably high production cost. Prussian blue and its analogue(PBA) are composed of high-abundance metal, iron, which is easily acquired and low cost (5.63×104 mg/kg in earth’s crust). Also, replacement of the iron atom complexed to ferricyanide by different metals results in different color PB analogues, and we developed Prussian blue, cobalt. nickel, and copper-based analogues in this study. Thus, in this research, we try to replace WO3-based ECWs by a series of iron-based complexes electrochromic materials, which features the well-known Prussian blue (PB). First, we use ferrocyanide ions to modify the surface of un-dispersible Prussian blue analogue salt, so the particle will cover negative charge to prevent from the un-dispersible aggregation. After the modification, the Prussian blue salt can disperse in water and be prepared as print ink. These inks can be coated on the ITO glass and formed blue(Prussian blue), red(CoPBA and CuPBA), and yellow(NiPBA) color films with spin-coating process. In the electrochemical and spectrum analysis, the coloration efficiency of the PB, CoPBA, NiPBA, and CuPBA were 29.9(@ 690 nm), 11.1(@ 574 nm), 16.3(@ 412 nm), and 12.7(@ 370 nm) cm2/C, respectively. Meanwhile, the short–term stability was tested by CV method. After 100 CV scan, these PBA films can retain ca. 95% electrochemical activity. The element analysis result showed that the PB, CoPBA, NiPBA, and CuPBA films were composed of Fe, C, and N elements, which corresponds to the compositions of Prussian blue family. The SEM result showed that these films were constructed by nano-particles which were 10 ~ 70 nm in a diameter. It is worth to note that the morphology of CuPBA particle is cubic-shape, and the other PBA particle are ball-shape. Besides, we also fabricated the Prussian blue- NiHCF composite film with layer-by-layer strategy. The composite film can extend the range of controllable spectrum from 300 nm to 500 nm. Also, it can show 4-color-state-chromism. Finally, we build two kind of complementary electrochromic device with different Prussian blue analogues. The Prussian blue-MoHCF ECD can control the blue light filed spectrum by red-like electrochromic film, MHCF. The PMECD can control the transmittance of full spectrum (300-900 nm) from 60% to 20%, and the energy-saving performance can reach to 196 W/m2. The device assembled with Prussian blue-NiPBA composite film and CuPBA(PNCECD) can controlled the transmittance of full spectrum from 55% to 30%, and the energy-saving performance is 125.0 W/m2. Also, PNCECD can show four color states in different operating voltage. To sum up, this study developed a series of Prussian blue analogues and built two kind of promising smart window prototypes with the PBAs. |
URI: | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/63792 |
全文授權: | 有償授權 |
顯示於系所單位: | 生物機電工程學系 |
文件中的檔案:
檔案 | 大小 | 格式 | |
---|---|---|---|
ntu-101-1.pdf 目前未授權公開取用 | 6.08 MB | Adobe PDF |
系統中的文件,除了特別指名其著作權條款之外,均受到著作權保護,並且保留所有的權利。