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| DC 欄位 | 值 | 語言 |
|---|---|---|
| dc.contributor.advisor | 簡淑華(Shu-Hua Chien) | |
| dc.contributor.author | Chih-Kuei Ke | en |
| dc.contributor.author | 葛智逵 | zh_TW |
| dc.date.accessioned | 2021-06-13T00:44:34Z | - |
| dc.date.available | 2013-08-05 | |
| dc.date.copyright | 2011-08-05 | |
| dc.date.issued | 2011 | |
| dc.date.submitted | 2011-08-04 | |
| dc.identifier.citation | 參考文獻
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| dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/29173 | - |
| dc.description.abstract | 在本研究中我們利用兩步溶劑熱的方式合成具有空心結構的二氧化鈦微米球。在第一步的溶劑熱反應，我們加入硫酸氧鈦、乙醇、甘油及乙醚在110oC下反應四小時，此時會生成實心結構的有機鈦體前驅物。在第二步的溶劑熱反應中，我們調整酒精濃度及反應時間，最後可以得到具有完整結構的空心二氧化鈦球體。藉由X光粉末繞射儀、氮氣等溫吸脫附、場發射掃描式電子顯微鏡及高解析度穿透式電子顯微鏡等鑑定方法，我們可以知道此兩步溶劑熱的方式合成之二氧化鈦球體具有銳鈦礦的晶相、310 m2/g的表面積、1-2微米的直徑及空心的內部結構。我們將製備好的二氧化鈦空心微米球應用於染料敏化太陽能電池及光電催化水分解。
我們先以二氧化鈦空心微米球應用於染料敏化太陽能電池光陽極，分別塗佈6微米及10微米兩種厚度進行測試，在使用N719染料作為敏化劑及AM 1.5模擬太陽光照射下(100 mW/cm2)，其光電轉換效率分別為4.37%及5.61%。 在染料敏化太陽能電池系統中，二氧化鈦奈米顆粒扮演著吸附染料及傳遞電子的角色。近年來研究學者指出適當地摻入次微米二氧化鈦粒子可增加入射光的散射，進而提升光利用率。近期的研究更顯示添加具高表面積之二氧化鈦大尺寸粒子除了可增加入射光散射及光利用率外，亦可提高染料的吸附量，以更進一步提升染料敏化太陽能電池的光電轉換效率。因此我們將溶膠凝膠法所製備的二氧化鈦奈米顆粒(SG)應用於染料敏化太陽能電池光陽極，在使用N719染料作為敏化劑及AM 1.5模擬太陽光照射下(100 mW/cm2)，得到光電轉換效率為7.14%；並於SG層上方塗佈上一層約250nm大小之次微米二氧化鈦粒子Merck Anatase (MA)或二氧化鈦空心微米球兩種具較大尺寸的二氧化鈦作為散射層，以組合成具雙層結構的染料敏化太陽能電池光陽極，可得到光電轉換效率分別為7.71%及8.20%。二氧化鈦空心微米球相較於次微米二氧化鈦粒子MA作為散射層可得到較高的光電轉換效率，高表面積的特性使其能吸附更多染料是主要的原因。 我們將二氧化鈦空心微米球應用於光電催化水分解之工作電極，並利用連續離子層吸附反應法(SILAR)將硫化鎘及硫化硒組裝至二氧化鈦上，以作為吸收可見光之光敏化劑。在硫化鎘的系統中，分別塗佈6微米及10微米兩種厚度二氧化鈦空心微米球層進行測試，我們發現塗佈6微米厚度的整體效率較高，並以進行五次SILAR過程之工作電極可得到最高之光電催化水分解效率3.86%；在硫化硒的系統中，則直接以塗佈6微米厚度二氧化鈦空心微米球層進行測試，以進行三次SILAR過程之工作電極可得到光電催化水分解效率4.55%。此外，我們於6微米厚度二氧化鈦空心微米球層上先進行五次SILAR過程鍍上硫化鎘，再進行一次SILAR過程鍍上硫化硒，可得到最高光電催化水分解效率5.13%。 | zh_TW |
| dc.description.abstract | Titania hollow microspheres (THMS) were prepared by a two-step solvothermal process. The solid titania precursor was formed in a solution containing TiOSO4, ethanol, glycerol and ethyl ether at 110oC for 4 h in the first step. In the second solvothermal step, it was found that the morphological integrity of the hollow microspheres could be controlled by varying the concentration of ethanol. We obtained uniform THMS in pure anatase phase, with 1∼2 μm diameter and 310 m2/g of surface area. All the samples were characterized by XRD, UV-Vis, N2 sorption isotherms, FESEM and HRTEM.
In the present study, we have applied the prepared THMS to use in dye sensitized solar cells(DSSCs) and solar water splitting. In DSSCs, the THMS was used as a scattering layer atop the conventional TiO2 nanoparticle film. The solar energy conversion efficiency was significantly enhanced by nearly 15% as compared to that without THMS layer sensitized with N719 dye under AM 1.5 solar irradiation (100 mW/cm2). The improved light harvesting characteristics were due to dye adsorption capacity of the THMS and its high diffusion reflectance property which attest to the superior light scattering property. In the solar photoelectrocatalytic water splitting, considerably high photoconversion efficiencies of 3.86% was attained by the CdS quantum dots sensitized THMS and of 4.55% was reached by the CdSe quantum dots sensitized THMS that were prepared by SILAR process. By CdS and CdSe cosensitization of THMS, the highest efficiency of 5.13% was achieved. Accordingly, the titania hollow microspheres can be beneficial for application in solar energy conversion. | en |
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| dc.description.tableofcontents | 目錄
摘要 Ⅰ Abstract Ⅲ 謝誌.................................................................................................................................Ⅳ 目錄 Ⅴ 圖目錄 Ⅶ 表目錄.............................................................................................................................XI 第一章 緒論 1 1.1 前言 1 1.2 太陽能電池簡介 2 1.3 染料敏化太陽能電池 (dye-sensitized solar cell, DSSC) 5 1.3.1 染料敏化太陽能電池工作原理 6 1.3.2 影響染料敏化太陽能電池光電轉換效率之因素 8 1.4 光電催化水分解 25 1.5 量子點.................................................................................................................29 1.5.1 量子點的特性.............................................................................................29 1.5.2 量子點合成及組裝技術.............................................................................33 1.6 二氧化鈦空心微米球的文獻回顧及合成方法................................................34 1.6.1 硬性模板法.................................................................................................34 1.6.2 軟性模板法.................................................................................................37 1.6.3 無模板法.....................................................................................................41 1.7 研究動機............................................................................................................43 第二章 實驗方法 44 2.1 藥品及儀器 44 2.2 二氧化鈦空心微米球THMS之製備 46 2.3 二氧化鈦奈米粒子醬料之製備...……………………………………………………….47 2.4 染料敏化太陽能電池光陽極之製備 47 2.5 光電催化水分解工作電極之製備 54 2.6 材料特性分析.....................................................................................................54 2.6.1 場發射掃描式電子顯微鏡 (Field Emission Scanning Electron Microscopy) 54 2.6.2 高解析穿透式電子顯微鏡 (High Resolution Transmission Electron Microscopy) 54 2.6.3 能量分散式X光光譜儀 (Energy Dispersive X-ray Spectrometers)...............54 2.6.4 X-射線繞射光譜 (X-ray Diffraction Spectroscopy) 55 2.6.5 紫外光-可見光吸收光譜儀（UV-Visible Spectrophotometer） 56 2.6.6 氮氣等溫吸附與脫附 (N2 Sorption) 57 2.7 染料敏化太陽能電池組裝及測試 .......................59 2.8 染料吸附量測試.................................................................................................69 2.9 光電催化水分解反應.........................................................................................71 第三章 結果與討論 73 3.1 二氧化鈦空心微米球THMS 74 3.1.1 第二步溶劑熱法中酒精濃度對形成二氧化鈦空心微米球的影響.........74 3.1.2 第二步溶劑熱法中反應時間對二氧化鈦微米球內部結構的影響.........79 3.2 染料敏化太陽能電池 86 3.2.1 不同厚度二氧化鈦空心微米球單層結構染料化太陽能電池測試…….86 3.2.2 不同厚度SG + 10THMS雙層結構染料敏化太陽能電池測試 90 3.2.3 不同厚度SG + 6THMS雙層結構染料敏化太陽能電池測試.................94 3.2.4 8SG +10THMS與12SG +6THMS於染料敏化太陽能電池測試結果比較.................................................................................................................98 3.2.5 Sol-gel TiO2、MA及THMS二氧化鈦的比較.......................................101 3.2.6 SG + THMS及SG + MA雙層結構染料敏化太陽能電池測試比較......104 3.3 光電催化水分解反應 101 3.3.1 CdS/THMS於光電催化水分解反應測試................................................111 3.3.2 CdSe/THMS於光電催化水分解反應測試.......................................................122 3.3.3 CdSe/CdS/THMS於光電催化水分解反應測試..............................................127 第四章 結論 132 參考文獻 134 附錄A 量子點敏化太陽能電池(quantum dot sensitized solar cells,QDSSCs)........144 圖目錄 圖1-1 各類型太陽能電池效率的發展情形 4 圖1-2 染料敏化太陽能電池的基本結構 6 圖1-3 不同半導體的能隙能階圖 8 圖1-4 染料敏化太陽能電池的能階示意圖 9 圖1-5 N3系列的染料及其所對應在不同波長下的吸收光譜 10 圖1-6 N3及Black dye 染料的IPCE(incident photo to current conversion efficiency)應答曲線及其化學結構 11 圖1-7 一維奈米結構半導體幫助光電子傳遞的示意圖 14 圖1-8 次微米實心球體結構示意圖.........................................................................14 圖1-9 N719染料紫外可見光吸收光譜 15 圖1-10 添加不同比例的奈米棒得到的光散射強度圖譜，依序為(0%、5%、10%、15%的奈米棒) 17 圖1-11 六種不同奈米複合結構光陽極示意圖 19 圖1-12 六種不同奈米複合結構光陽極IPCE比較圖 20 圖1-13 不同霧度值對量子效率的影響 22 圖1-14 不同玻璃基板隨著波長改變的霧度變化以及其量子效率的差異 23 圖1-15 霧度對於IPCE值及光電流的變化 24 圖1-16 水分解製氫的實驗裝置圖.............................................................................26 圖1-17 光化學電池的能階示意圖.............................................................................27 圖1-18 太陽光光譜分佈圖.........................................................................................27 圖1-19 TiO2/CdS/CdSe階梯能階示意圖...................................................................28 圖1-20 電子能階隨粒子尺寸的變化狀況.................................................................29 圖1-21 CdS的吸、放光光譜與粒徑大小的關係，圓圈處表示激子吸收峰.........30 圖1-22 CdSe和CdS的粒徑與激子吸收峰位置之關係曲線...................................30 圖1-23 各種量子點放光波長與量子點尺寸的關係圖.............................................31 圖1-24 (a)衝擊離子化效應示意圖 (b)歐傑再結合效應示意圖..............................32 圖1-25 連續離子層吸附反應法.................................................................................33 圖1-26 硬性模板法製備空心球的製備過程.............................................................35 圖1-27 以LbL方法製備二氧化鈦空心球.................................................................35 圖1-28 利用polystyrene陣列製備二氧化鈦空心球.................................................36 圖1-29 利用TiF4一鍋合成二氧化鈦空心球............................................................37 圖1-30 利用離子液體合成二氧化鈦空心球.............................................................38 圖1-31 利用超音波噴灑熱解法製備二氧化鈦空心球.............................................38 圖1-32 利用皮克林乳膠法製備二氧化鈦空心球.....................................................39 圖1-33 利用TBAH產生氣泡製備二氧化鈦空心球.................................................39 圖1-34 利用NH4F及H2O2製備二氧化鈦空心球....................................................40 圖1-35 利用auto-orientation assembly方式製備二氧化鈦空心球...........................41 圖1-36 利用dissolution-redeposition方式製備二氧化鈦空心球.............................42 圖2-1 二氧化鈦空心微米球THMS製備流程圖 46 圖2-2 二氧化鈦奈米粒子(sol-gel TiO2)醬料製備流程圖。 47 圖2-3 雙層結構染料敏化太陽能電池之工作電極製備流程圖.............................50 圖2-4 SILAR法組裝CdS流程圖............................................................................52 圖2-5 SILAR法組裝CdSe流程圖...........................................................................53 圖2-6 Hitachi-U3410 擴散反射式紫外線-可見光光譜儀。 57 圖2-7 IUPAC制定之物理等溫吸附-脫附分類圖。 58 圖2-8 IUPAC制定之遲滯迴圈型態示意圖。 58 圖2-9 光電轉換效率測試組裝及裝置圖.................................................................59 圖2-10 光電轉換效率裝置光路徑圖.........................................................................60 圖2-11 染料敏化太陽能電池光電轉換效率測試電壓電流圖.................................60 圖2-12 Z 、 Z’、 Z”、 Ө之間的關係圖.........................................................62 圖2-13 染料敏化太陽能電池電化學阻抗圖譜.........................................................63 圖2-14 染料敏化太陽能電池等效電路圖.................................................................64 圖2-15 染料敏化太陽能電池電化學阻抗原始數據分析.........................................65 圖2-16 特定波光束輸出系統設備圖(Oriel Instruments)...........................................68 圖2-17 特定波光束輸出系統光路徑圖.....................................................................68 圖2-18 N719染料之紫外-可見光光譜.....................................................................69 圖2-19 N719染料吸收度對濃度檢量線...................................................................70 圖2-20 水分解反應之光源系統.................................................................................71 圖2-21 水分解反應槽示意圖.....................................................................................72 圖2-22 水分解反應測試電壓電流圖.........................................................................73 圖2-23 施加不同電壓下水分解反應之光電轉換效率.............................................73 圖3-1 第一步溶劑熱法所得實心有機鈦球：(a) FESEM及(b) HRTEM影像......74 圖3-2 以不同酒精濃度進行第二步溶劑熱法的in-situ XRD圖像：(a)70%酒精(b)80%酒精(c)85%酒精.................................................................................75 圖3-3 以水作為第二部水熱溶劑反應6小時後的FESEM影像..........................76 圖3-4 以不同酒精濃度進行第二步溶劑熱法反應6小時後的FESEM影像。 (a-1,a-2) THMS-30-6 (b-1,b-2) THMS-50-6 (c-1,c-2) THMS-80-6 (d-1,d-2) THMS-85-6 (e-1,e-2) THMS-90-6 (f-1,f-2) THMS-95-6................77圖3-5 改變反應時間以90%酒精進行第二步溶劑熱法的FESEM影像。 (a) THMS-90-3 (b) THMS-90-6 (c) THMS-90-12 (d) THMS-90-24。..........79圖3-6 改變反應時間以90%酒精進行第二步溶劑熱法的HRTEM影像。 (a-1,a-2) THMS-90-3 (b-1,b-2) THMS-90-6 (c-1,c-2) THMS-90-12 (d-1,d-2) THMS-90-24....................................................................................80 圖3-7 改變反應時間以90%酒精進行第二步溶劑熱法的XRD圖譜...................82 圖3-8 改變反應時間以90%酒精進行第二步溶劑熱法的氮氣等溫吸附與脫附 曲線圖以及BJH脫附孔徑分佈圖。(a) THMS-90-6 (b) THMS-90-12 (c) THMS-90-24..............................................................................................83 圖3-9 在90%酒精的條件下經歷第二步溶劑熱法不同時間後狀態示意圖.........85 圖3-10 二氧化鈦空心微米球塗佈於FTO上經450oC鍛燒及TiCl4後處理後之FESEM影像 (a)截面圖 (b)截面放大圖.......................................................86 圖3-11 不同厚度二氧化鈦空心微米球單層結構作為染料化太陽能電池光陽極 之電流電壓圖.................................................................................................87 圖3-12 不同厚度二氧化鈦空心微米球單層結構Haze factor圖譜.........................88 圖3-13 不同厚度二氧化鈦空心微米球單層結構電極之入射單色光子-電子轉 化效率圖譜.....................................................................................................89 圖3-14 SG/THMS之FESEM影像............................................................................90 圖3-15 不同厚度SG + 10THMS雙層結構作為染料敏化太陽能電池光陽極之 電流電壓圖.....................................................................................................91 圖3-16 不同厚度SG + 10THMS雙層結構Haze factor圖譜..................................92 圖3-17 不同厚度SG + 10THMS雙層結構電極之入射單色光子-電子轉化效 率圖譜.............................................................................................................93 圖3-18 不同厚度SG + 6THMS雙層結構作為染料敏化太陽能電池光陽極之 電流電壓圖.....................................................................................................94 圖3-19 不同厚度SG + 6THMS雙層結構Haze factor圖譜.....................................96 圖3-20 不同厚度SG + 6THMS雙層結構電極之入射單色光子-電子轉化效率 圖譜.................................................................................................................97 圖3-21 8SG +10THMS與12SG +6THMS作為染料敏化太陽能電池光陽極之 電流電壓圖.....................................................................................................99 圖3-22 8SG +10THMS與12SG +6THMS暗電流測試圖......................................100 圖3-23 8SG +10THMS與12SG +6THMS電極之入射單色光子-電子轉化效 率圖譜...........................................................................................................100 圖3-24 XRD圖譜：(a) SG (b) MA (c) THMS.........................................................101 圖3-25 HRTEM影像：(a) SG (b) MA (c) THMS....................................................102 圖3-26 FESEM影像：(a) SG (b) MA (c) THMS.....................................................102 圖3-27 氮氣等溫吸附與脫附曲線圖：(a) SG (b) MA (c) THMS...........................103 圖3-28 12SG、12SG+6MA及12SG+6THMS作為染料敏化太陽能電池光陽 極之電流電壓圖...........................................................................................104 圖3-29 12SG、12SG+6MA及12SG+6THMS之Haze factor圖譜.......................105 圖3-30 12SG、12SG+6MA及12SG+6THMS電極之入射單色光子-電子轉化 效率圖譜.......................................................................................................107 圖3-31 12SG、12SG+6MA及12SG+6THMS電極吸附染料後的現象(Top View)107 圖3-32 12SG、12SG+6MA及12SG+6THMS電極吸附染料後的現象(Bottom View).............................................................................................................108 圖3-33 12SG、12SG+6MA及12SG+6THMS電極結構示意圖............................108 圖3-34 12SG、12SG+6MA及12SG+6THMS電極之電化學阻抗圖譜................109 圖3-35 1CdS/THMS/FTO之(a) FESEM影像側面圖 (b) FESEM影像俯視圖 (c) EDX圖像結果.........................................................................................112 圖3-36 3CdS/THMS/FTO之(a) FESEM影像側面圖 (b) FESEM影像俯視圖 (c) EDX圖像結果.........................................................................................113 圖3-37 5CdS/THMS/FTO之(a) FESEM影像側面圖 (b) FESEM影像俯視圖 (c) EDX圖像結果.........................................................................................114 圖3-38 7CdS/THMS/FTO之(a) FESEM影像側面圖 (b) FESEM影像俯視圖 (c) EDX圖像結果.........................................................................................115 圖3-39 CdS標準繞射峰圖譜....................................................................................116 圖3-40 mCdS/6THMS/FTO之XRD圖譜................................................................116 圖3-41 mCdS/6THMS/FTO之紫外-可見光光譜.....................................................117 圖3-42 mCdS/10THMS/FTO之電流電壓圖............................................................118 圖3-43 mCdS/10THMS/FTO之效率電壓圖............................................................118 圖3-44 mCdS/6THMS/FTO之電流電壓圖..............................................................120 圖3-45 mCdS/6THMS/FTO之效率電壓圖..............................................................120 圖3-46 3CdSe/6THMS/FTO之(a) FESEM影像側面圖 (b) FESEM影像俯視圖 (c) EDX圖像結果.........................................................................................122 圖3-47 CdSe標準繞射峰圖譜.................................................................................123 圖3-48 3CdSe/6THMS/FTO的XRD圖譜..............................................................123 圖3-49 nCdSe/6THMS/FTO之紫外-可見光光譜...................................................124 圖3-50 nCdSe/6THMS/FTO之電流電壓圖.............................................................125 圖3-51 nCdSe/6THMS/FTO之效率電壓圖.............................................................125 圖3-52 1CdSe/5CdS/6THMS/FTO之(a) FESEM影像側面圖 (b) FESEM影像 俯視圖(c) EDX圖像結果.............................................................................127 圖3-53 1CdSe/5CdS/6THMS/FTO之XRD圖譜.....................................................128 圖3-54 nCdSe/5CdS/6THMS/FTO之紫外-可見光光譜..........................................128 圖3-55 nCdSe/5CdS/6THMS/FTO之電流電壓圖...................................................129 圖3-56 nCdSe/5CdS/6THMS/FTO之效率電壓圖...................................................129 表目錄 表1-1 各類型太陽能電池的比較.................. ...3 表1-2 利用各種奈米結構二氧化鈦製備染料敏化太陽能電池光陽極的研究 團隊及其測試出的最高光電轉換效率 13 表1-3 不同顆粒大小的二氧化鈦依不同比例配製成的塗料。 18 表1-4 六種不同奈米複合結構光陽極光伏特表現。 19 表2-1 本研究中所使用的儀器及其型號。 45 表3-1 在90%酒精的條件下經歷第二步溶劑熱法不同時間後之狀態整理..........85 表3-2 不同厚度二氧化鈦空心微米球單層結構作為染料化太陽能電池光陽極 光伏特表現.....................................................................................................89 表3-3 不同厚度SG + 10THMS雙層結構作為染料化太陽能電池光陽極光伏 特表現.............................................................................................................93 表3-4 不同厚度SG + 6THMS雙層結構作為染料化太陽能電池光陽極光伏 特表現.............................................................................................................96 表3-5 8SG +10THMS與12SG +6THMS作為染料化太陽能電池光陽極光伏 特表現.............................................................................................................99 表3-6 SG、MA及THMS各種特性比較..............................................................103 表3-7 12SG、12SG+6MA、12SG+6THMS及18SG作為染料化太陽能電池光陽極光伏特表現..............................................................................................106 表3-8 12SG、12SG+6MA及12SG+6THMS電極之電化學阻抗參數分析.......109 表3-9 1CdS/THMS/FTO之EDX數據結果............................................................112 表3-10 3CdS/THMS/FTO之EDX數據結果............................................................113 表3-11 5CdS/THMS/FTO之EDX數據結果............................................................114 表3-12 7CdS/THMS/FTO之EDX數據結果............................................................115 表3-13 mCdS/10THMS/FTO的J-0.4V、Voc、η數據整理.......................................119 表3-14 mCdS/6THMS/FTO的J-0.4V、Voc、η數據整理.........................................121 表3-15 3CdSe/6THMS/FTO之EDX數據結果........................................................122 表3-16 nCdSe/6THMS/FTO的J-0.4V、Voc、η數據整理........................................126 表3-17 1CdSe/5CdS/6THMS/FTO之EDX數據結果..............................................127 表3-18 nCdSe/5CdS/6THMS/FTO的J-0.4V、Voc、η數據整理..............................130 | |
| dc.language.iso | zh-TW | |
| dc.title | 二氧化鈦空心微米球的製備及其應用 | zh_TW |
| dc.title | Fabrication of TiO2 hollow microspheres and their applications | en |
| dc.type | Thesis | |
| dc.date.schoolyear | 99-2 | |
| dc.description.degree | 碩士 | |
| dc.contributor.oralexamcommittee | 劉如熹(Ru-Shi Liu),蘇昭瑾(Chao-Chin Su) | |
| dc.subject.keyword | 二氧化鈦空心微米球,染料敏化太陽能電池,光電催化水分解,散射,染料吸附,連續離子層吸附反應法。, | zh_TW |
| dc.subject.keyword | Titania hollow microspheres,Dye sensitized solar cells,Solar water splitting,Light-scattering,Dye adsorption,SILAR., | en |
| dc.relation.page | 148 | |
| dc.rights.note | 有償授權 | |
| dc.date.accepted | 2011-08-04 | |
| dc.contributor.author-college | 理學院 | zh_TW |
| dc.contributor.author-dept | 化學研究所 | zh_TW |
| 顯示於系所單位： | 化學系 | |
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