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研究生:蔡宜臻
研究生(外文):Yi-Chen Tsai
論文名稱:改質二氧化鈦奈米管之特性研究及其於染料敏化太陽能電池之應用
論文名稱(外文):Synthesis and Characterization of Modified Titanium Dioxide Nanotubes and Application to Dye-Sensitized Solar Cells
指導教授:鄭紀民
指導教授(外文):Jih-Mirn Jehng
學位類別:碩士
校院名稱:國立中興大學
系所名稱:化學工程學系所
學門:工程學門
學類:化學工程學類
論文種類:學術論文
畢業學年度:97
語文別:中文
論文頁數:128
中文關鍵詞:二氧化鈦奈米管擔持鉻染料敏化太陽能電池
外文關鍵詞:TiO2 nanotubeschromium-dopeddye-sensitized solar cell
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本研究將商業化之二氧化鈦奈米顆粒(Degussa P25)於強鹼環境下水熱處理後,成功地製備出二氧化鈦奈米管,獲得比Degussa P25 更大的比表面積(SBET ≈ 400 m2/g),於450°C 煅燒30 分鐘後得到比表面積為160m2/g,奈米管內徑約為8 ~ 10 nm。以直接水熱法及初濕含浸法對二氧化鈦奈米管進行改質, 使用Cr(NO3)3•9H2O 作為金屬前驅物來源,以二氧化鈦奈米管為擔體,分別擔持鉻含量為0.5 wt% ~ 5 wt%於二氧化鈦奈米管中。
使用的分析儀器包括XRD、BET、SEM、TEM、EDS、XPS、UV-vis
光譜儀及Raman 光譜儀,對改質前後之二氧化鈦奈米管做特性的分析。SEM 與TEM 可觀察到奈米管狀物的結構;XRD 探討晶型的變化;由BET測得奈米管的比表面積及孔徑分佈;利用UV-vis 光譜儀觀察改質二氧化鈦奈米管前後的吸光範圍;EDS 測得鈦奈米管之組成及元素含量;XPS 得到表面元素的組成;Raman 光譜對表面活性相物質進行分析,以了解表面金屬氧化物之動態變化。
將所製備的二氧化鈦奈米管應用於染料敏化太陽能電池之薄膜電極,並探討使用二氧化鈦奈米管擔持鉻於薄膜電極,探討對染料敏化太陽能電池效能的影響。使用染料為N719,入射光強度為100 mW/cm2情況下,二氧化鈦奈米管為薄膜電極,測得短路電流密度為4.59 mA/cm2,轉換效率為1.66% ; 改質二氧化鈦奈米管為薄膜電極, 測得短路電流密度為4.23mA/cm2,光電轉換效率為1.69%。
  Commercial nanocrystalline TiO2 (Degussa P25) was used for preparing titanium dioxide nanotubes (TiNT) by hydrothermal method. Nanocrystalline TiO2 nanotubes have a high specific surface areas (SBET 400 m2/g) compared to the original Degussa P25. After being calcined at 450°C for 30 minutes, it have a tube structure with SBET 160 m2/g and the tube dimeter is approximately 8 nm to 10 nm.
  Chromium-doped titanium dioxide nanotubes containing 0.5 wt% ~ 5 wt% Cr using Cr(NO3)3•9H2O as a precursor were prepared by direct hydrothermal mothod and incipient-wetness impregnation.
  The characteristic analysis of the TiNT and the Chromium-doped TiNT were performed by XRD, BET, SEM, TEM, EDS, XPS, UV-vis and Raman spectrometer. From the SEM and TEM images, the tube-like materials were observed. X-ray diffraction patterns confirm the crystal lattice. From the BET measurements, the specific surface area and the pore size distribution were determined. From the UV-vis spectra, the extent of UV-vis absorption between the samples was compared. The EDS obtained the composition of the titanium nanotubes and the element-doped amount. The XPS spectra obtained surface elemental composition. Raman results confirm that the molecular arrangements of the active surface metal oxide have been achieved.
  The TiNT and the chromium-doped TiNT were applied in thin film electrode on the dye-sensitized solar cell. By sensitizing the anode with N719 dye and exposing under a light which light intensity is 100 mW/cm2, the electrode made of TiNT obtained short-circuit photocurrent density was 4.59 mA/cm2, and the light-to-electric conversion efficiency was 1.66%; the electrode made of chromium-doped TiNT obtained short-circuit photocurrent density was 4.23 mA/cm2, and the light-to-electric conversion efficiency was 1.69%.
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摘要··········································································································ii
Abstract ····································································································iii
目次········································································································· iv
表目次···································································································· vii
圖目次··································································································· viii
第一章 緒論···························································································· 1
第一節 前言···················································································· 1
第二節 太陽能電池概述·································································· 3
一、結晶矽太陽電池·································································· 4
二、Ⅲ-Ⅴ族砷化鎵(GaAs)太陽電池··········································· 5
三、Ⅱ-Ⅵ族碲化鎘(CdTe)太陽電池············································ 5
四、硒化銦銅(Copper Indium Diselenide, CuInSe2)太陽電池······· 6
五、銅銦鎵硒(Copper Indium Gallium Diselenide, CIGS)太陽電池
····························································································· 7
第二章 文獻回顧與理論說明·································································· 8
第一節 二氧化鈦光觸媒·································································· 8
一、二氧化鈦············································································· 8
二、光催化反應······································································· 10
第二節 二氧化鈦奈米管································································ 12
一、二氧化鈦奈米管製備方法·················································· 12
二、二氧化鈦奈米管生成機制·················································· 14
三、二氧化鈦奈米管結構························································· 16
第三節 觸媒改質··········································································· 17
一、觸媒改質製備方法···························································· 17
二、二氧化鈦改質···································································· 18
第四節 染料敏化太陽能電池························································· 22
一、染料敏化TiO2 太陽電池基本結構及工作原理··················· 22
二、光敏化劑-染料·································································· 24
三、電解質··············································································· 26
四、相對電極··········································································· 27
五、太陽能電池電流-電壓輸出特性········································· 27
第三章 研究動機·················································································· 29
第四章 實驗技術與方法······································································· 30
第一節 實驗藥品及儀器設備························································· 30
一、實驗藥品··········································································· 30
二、實驗儀器設備···································································· 32
第二節 實驗步驟··········································································· 34
一、水熱合成法製備二氧化鈦奈米管······································· 34
二、二氧化鈦奈米管擔持金屬·················································· 34
三、染料敏化太陽能電池元件製作及組裝······························· 35
第三節 分析儀器應用與原理························································· 38
一、廣角X 光繞射儀······························································· 38
二、氮氣恆溫吸/脫附儀··························································· 39
三、場發射掃描式電子顯微鏡·················································· 40
四、能量散佈光譜儀································································ 41
五、穿透式電子顯微鏡···························································· 42
六、拉曼光譜儀······································································· 44
七、X 光光電子能譜儀····························································· 45
八、原子力顯微鏡···································································· 46
九、紫外光/可見光吸收光譜儀················································· 48
十、太陽能電池I-V 曲線量測儀器··········································· 49
第五章 結果與討論··············································································· 50
第一節 水熱法製備二氧化鈦奈米管之特性分析···························· 50
一、粉末X-ray 繞射分析(XRD) ··············································· 50
二、氮氣吸脫附比表面積分析與孔徑分佈(BET) ······················ 52
三、SEM 表面型態分析···························································· 58
四、EDS 能量分散光譜分析····················································· 60
五、TEM 微結構分析······························································· 61
六、拉曼光譜(Raman Spectroscopy)分析·································· 63
七、X 光光電子能譜儀(XPS)···················································· 65
第二節 擔持鉻氧化物之二氧化鈦奈米管之特性分析···················· 68
一、粉末X-ray 繞射分析(XRD) ··············································· 68
二、氮氣吸脫附比表面積分析與孔徑分佈(BET) ······················ 70
三、SEM 表面型態分析···························································· 76
四、EDS 能量分散光譜分析····················································· 79
五、TEM 微結構分析······························································· 81
六、拉曼光譜(Raman Spectroscopy)分析·································· 84
第三節 光電極特性分析─鉑對電極·············································· 86
一、原子力顯微鏡分析(AFM) ·················································· 86
二、SEM 表面型態分析···························································· 90
第四節 光電極特性分析─二氧化鈦薄膜電極······························· 92
一、SEM 表面型態分析···························································· 92
二、紫外光/可見光(UV-vis)吸收光譜分析································ 95
三、薄膜X-ray 繞射分析(XRD) ··············································· 98
第五節 染料敏化太陽能電池電壓-電流特性分析························ 99
第六章 結論························································································ 110
第七章 未來方向與建議····································································· 112
參考文獻······························································································· 113
附錄一 Brunauer-Emmett-Teller 理論·················································· 121
附錄二 Barrett-Joyner-Halenda 理論···················································· 122
附錄三 等溫吸附曲線········································································· 124
附錄四 等溫吸附曲線之遲滯現象······················································· 126
附錄五 JCPDS 資料庫········································································· 127
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