臺灣博碩士論文加值系統

本論文中討論的光電化學電池主要可分為吸收光子產生電子的太陽能電池與將光能轉變為化學能的光電水分解兩大類。在實驗上主要製備光電化學電池的電極，藉由不同的光電極製備方式與裝置組成來提升光電化學轉換之效率。
在量子點敏化太陽能電池的光陽極研究上，本論文中以水熱法直接在導電玻璃上生成一維結構的單晶二氧化鈦奈米柱陣列，並進一步在二氧化鈦奈米柱陣列的表面以離子吸附反應法沈積了窄能階的半導體硫化鎘作為敏化層，以硫化鋅作為保護層。且探討硫化鋅沈積量對於光電轉換效率的影響，發現在適當的硫化鋅沈積量的情況下光電流會增加、光電轉換效率也會提升。接著藉由改變二氧化鈦奈米柱陣列長度與硫化鎘沈積量來最佳化敏化電池的光電轉換效率，其最佳效率達到1.84%，此時光電流密度為4.19 mA cm-2、開環電流為0.82 V和填充因子為54%。
為了探討二氧化鈦奈米柱的生成機制，我們先合成了二氧化錫空心微米球，合成出的空心微米球是由粒徑約20到40奈米球組成；再進一步將此材料上生長了二氧化鈦奈米柱，使成二氧化鈦奈米柱-二氧化錫空心微米球的複合材料，並利用此系列材料作為染料敏化太陽能電池散射層，探討反射率與結構不同的樣品對光電轉換效率的影響。沒有塗佈上散射層的二氧化鈦奈米粒子之電極其光電轉換效率為6.5%，而以二氧化鈦奈米柱-二氧化錫空心微米球的複合材料與二氧化鈦奈米顆粒摻雜所得之混合材料作為染料敏化太陽能電池的散射層的光電轉換效率提升至7.4%。
另外，我們首次嘗試以微波輔助水熱法成功合成二氧化鈦奈米柱陣列，此方法之操作方式簡單容易且反應時間較短，並且改變反應物的濃度獲得的不同柱長與柱徑的二氧化鈦奈米柱陣列，並利用過氧化氫蝕刻的方式增加二氧化鈦奈米柱陣列的表面積，當二氧化鈦奈米柱陣列的染料吸附度與二氧化鈦奈米顆粒一樣好的情況下，光電流密度較二氧化鈦奈米顆粒所組成的電極高，因為一維結構提供直接的電子傳導路徑而使電子電洞對再結合率降低，其5 μm長度的二氧化鈦奈米柱陣列樣品可達光電效率為3.83%。
在光電水分解的研究中，我們利用溶劑熱法合成了四元硫屬化合物硫化銅錫鋅，並將其塗佈於導電玻璃上作為陰極；加上以用二氧化鈦奈米顆粒沈積硫化鎘作為陽極與銀/氯化銀作為參考電極，發展出雙光電極系統應用於光電水分解中。實驗中發現將陽極與陰極同時照光的情形下，光電流高達2.39 mA，其光電流的表現較以鉑片當陰極的實驗 (1.88 mA) 高。由於硫化銅錫鋅具經濟潛力並擁有優良的光電特性應可替代鉑成為極具潛力的陰極材料。

Photoelectrochemical cells are the devices that can convert light to the other energies such as electricity and fuels. Solar-to-electricity cells, which are called solar cells, and solar-to-fuel cells, which are focused on the solar water splitting, have been intensely researched in the past decade because of their potential applications for the alternate energy. In this thesis, we have prepared photoelectrodes of photoelectrochemical cells and improved the solar-to-electrical conversion efficiency by optimizing photoelectrodes and developing device configuration.
For quantum dots sensitized solar cells, phuotoanodes consisting of CdS sensitized titania nanorods with ZnS passivation layer are applied for solar cells. Single crystal TiO2 nanorods (TiNR) have been directly grown vertically on transparent conducting glass by a facile hydrothermal method and deposited with CdS and then a ZnS layer on the TiO2 surface via a successive ionic layer adsorption and reaction (SILAR) method. The effect of ZnS amount is studied in this system. Electrochemical results indicate that the photocurrent density (Jsc) is greatly improved by increasing the amount of ZnS. By optimizing the length of titania nanorods and the amount of CdS and ZnS, the best efficiency of 1.8% was achieved for solar cell under AM 1.5 G illumination with Jsc = 4.19 mA cm-2, Voc = 0.82 V and FF = 54%.
To study the growth mechanism of TiO2 nanorods, we have prepared tin oxide hollow microspheres (SnHMs). The SnMHs, which is consisting of SnO2 nanoparticles with 20 – 40 nm of diameter, shows hirerarichical morphology. We subsequently have synthesized TiO2 nanorods on the SnMHs by the hydrothermal method as above paragraph. The TiNR-SnMHs composite materials are obtained and used as scattering layer materials for dye-sensitized solar cells. The solar-to-electricity conversion efficiency of 7.4% in the cells with TiNR-SnMHs scaterring layer is better than that of 6.5% without the scattering layer.
We have also prepared TiNR by the microwave-assisted hydrothermal method. It costs only two hours to directly grow the TiO2 nanorods on the FTO substrate. Furthermore, we have obtained the TiO2 nanods possess different lengths and diameters by adjusting reactant concetraction. In order to enhance the dye adsorption, the TiO2 nanorods are etched by dipping in the H2O2 solution. The dye adsorption of the etched TiNR is similar to TiO2 nanoparticles (TiNP). The current densisty of the etched TiNR is even better than that of TiNP owing to the outstanding one-dimentioal structure that not only provides the direct electron pathway also reduces the recombination of electrons and holes.
In the study of solar water splitting, Cu2ZnSnS4 (CZTS) has been fabricated via a solvothermal method and deposited on a fluorine-doped tin oxide glass to form a photocathode for highly efficient solar photoelectrochemical (PEC) water splitting. The photocurrents for solar PEC water splitting are measured by a system consisting CdS/TiO2 photoanode, CZTS photocathode, and Ag/AgCl reference electrode is nominated as two-photoelectrode system. A maximum current of 2.39 mA is achieved for the device with two-photoelectrode system, under AM 1.5G with 100 mW cm-2, which is larger than that of the device with a Pt cathode (1.88 mA). The low cost and outstanding optoelectronic properties of CZTS make it a promising cathode substitute for platinum in solar PEC water splitting.

目錄
摘要 I
Abstract III
目錄 V

第一章 緒論 1
1.1 光電化學的歷史沿革 1
1.2 太陽能電池 5
1.3 光電水分解 18
1.4 材料製備方法介紹 24
1.4.1 水熱法與溶劑熱法合成 27
1.4.2 微波輔助水熱法合成 29
第二章 實驗 32
2.1 藥品 32
2.2 樣品製備 34
2.2.1量子點敏化太陽能電池樣品 34
2.2.2 二氧化鈦奈米柱-二氧化錫空心球複合材料製備 38
2.2.3 微波輔助水熱法製備二氧化鈦奈米柱陣列 40
2.2.4 光電水分解材料製備 41
2.3 研究設備 42
2.3.1 實驗室基本儀器 42
2.3.2 場發射掃描式電子顯微鏡 43
2.3.3 高解析穿透式電子顯微鏡 43
2.3.4 紫外光-可見光光譜儀 44
2.3.5 X光繞射儀 44
2.3.6 X光電子能譜 45
2.3.7 模擬光源 45
2.3.8 敏化太陽能電池組裝以及數據測試 47
2.3.9 光電水分解系統設置以及數據量測 62
第三章 結果與討論 67
3.1 量子點敏化太陽能電池效能最佳化 67
3.2 TiNR-SnHMs複合材料之應用 87
3.3 微波輔助水熱法合成二氧化鈦奈米柱陣列並應用於染料
敏化太陽能電池 97
3.4 CZTS光陰極材料之應用於光電水分解系統之探討 107
第四章 結論 116


圖目錄
圖1-1 太陽光能譜圖 7
圖1-2 空氣質量計算示意圖 7
圖1-3 矽太陽能電池的種類 9
圖1-4 敏化太陽能電池的作用原理圖 13
圖1-5 光電化學水分解產氫的實驗裝置圖 20
圖1-6 光電水分解半導體能帶位置與水分解氧化還原位置示意圖 22
圖1-7 零維與一維材料電子傳導路徑圖 26
圖 2-1 二氧化鈦奈米柱陣列製程示意圖 35
圖 2-2 製備CdS/TiNR的實驗步驟示意圖 36
圖 2-3 製備ZnS與ZnO保護層實驗步驟示意圖 37
圖2-4 二氧化鈦奈米顆粒製備流程 39
圖2-5 光電水分解燈源組示意圖 46
圖2-6 光電轉換效率測試組裝及裝置圖。 47
圖2-7 敏化太陽電池組成示意圖 48
圖2-8 染料敏化太陽能電池的效率測試 49
圖2-9 染料敏化太陽能電池開環電壓對時間的變化 51
圖2-10 敏化太陽能電池電子生命週期對於開環電壓的變化曲線圖 53
圖2-11電子在二氧化鈦半導體中進行的三種路徑。 54
圖2-12染料敏化太陽能電池電化學阻抗圖譜 55
圖2-13染料敏化太陽能電池的等效電路圖 56
圖2-14染料敏化太陽能電池電化學阻抗原始數據分析 57
圖2-15特定波光束輸出系統設備圖 60
圖2-16特定波光束輸出系統光路徑圖 60
圖2-17光電水分解裝置圖 62
圖2-18 光電水分解電流-電壓曲線 63
圖2-19 Tafel 測量裝置組裝示意圖 64
圖2-20 Tafel極化曲線 65
圖 3-1 二氧化鈦奈米柱SEM構型 67
圖3-2 不同水熱法次數製備的二氧化鈦奈米柱XRD圖譜影像 68
圖 3-3 二氧化鈦奈米柱穿透式電子顯微鏡影像圖 69
圖3-4 在二氧化鈦奈米柱上沈積不同次數的CdS的SEM影像 71
圖3-5 CdS/TiNR、TiNR以及FTO之XRD圖譜 72
圖3-6 TiNR與xCdS/TiNR的UV-VIS圖譜 73
圖3-7 ZnS/CdS/TiNR的SEM圖 74
圖 3-8 CdS/TiNR與ZnS/CdS/TiNR的XPS光譜分析 74
圖3-9 沈積CdS次數不同光電池所表現之電流電壓性質 75
圖3-10 不同二氧化鈦柱長度光電池所表現之J-V 性質 76
圖3-11 ZnS/CdS/TiNR和ZnO/CdS/TiNR 組成太陽電池的電流密度-時間圖 78
圖3-12 ZnS/CdS/TiO2 nanorods及ZnO/CdS/TiO2 nanorods的光電子路徑示意圖 78
圖3-13 不同層數ZnS保護層之電流密度-時間圖 79
圖3-14 不同二氧化鈦柱長度光電池所表現之J-V 性質 80
圖3-15 不同層數ZnS 保護層之IPCE圖 81
圖3-16 不同ZnS保護層數的OCVD結果。 82
圖3-17 無照光之太陽能電池組抗分析圖 83
圖3-18 各電池照光情況之電化學組抗分析圖 84
圖3-19 二氧化鈦奈米顆粒的氮氣等溫吸脫附圖 85
圖3-20 FTO導電玻璃與二氧化鈦奈米柱陣列掃瞄式電子顯微鏡圖 86
圖3-21 二氧化鈦中空微米球的掃描式電子顯微鏡圖 87
圖 3-22 二氧化鈦中空微米球的穿透式電子顯微鏡圖 87
圖3-23 TiNR-SnMHs複合材料之掃瞄式電子顯微鏡圖 88
圖3-24 TiNR-SnMHs複合材料之穿透式電子顯微鏡圖 88
圖 3-25 不同散射層材料之染料敏化太陽能電池效率-電壓圖 89
圖 3-26 不同散射層材料之反射率圖 91
圖 3-27 SnMHs與TiNP不同比例摻雜之散射層 92
圖3-28 SnMHs及TiNR-SnMHs為散射層的J-V圖 94
圖3-29 微波輔助水熱法合成之二氧化鈦奈米柱陣列SEM圖 95
圖 3-30 微波輔助水熱法及水熱法之二氧化鈦奈米柱陣列XRD圖 96
圖3-31 不同濃度的TBOT進行微波輔助水熱法 98
圖3-32 不同TBOT濃度所成長二氧化鈦奈米柱陣列SEM側面圖 99
圖3-33 不同TBOT濃度之二氧化鈦奈米柱陣列之SEM正面圖 100
圖 3-34 不同TBOT濃度之二氧化鈦奈米柱之電流密度-電壓圖。 101
圖 3-35 過氧化氫蝕刻二氧化鈦奈米柱之SEM圖 103
圖3-36 不同蝕刻時間後之樣品於太陽能電池光電效率之影響 105
圖3-37 CdS/TiNP與CZTS的掃瞄式電子顯微鏡影像。 108
圖3-38 CdS/TiNP與CZTS的XRD圖譜 108
圖3-39 CdS/TiNP與CZTS的UV-Vis圖譜 109
圖3-40 三電極系統的光電水分解測試 110
圖3-41 雙光電極系統的光電水分解測試 112
圖3-42 雙光電極系統之電流-電壓圖 114
圖3-43 光電水分解半導體能階位置示意圖 115


表目錄
表2-1 研究中所使用的儀器及型號 42
表 2-2 三電極系統及雙光電極系統裝置比較 61
表 3-1 不同水熱法製備次數相對應的奈米柱陣列長度與直徑 66
表 3-2 沈積CdS次數不同光電池相對應之電池參數 76
表 3-3 不同二氧化鈦柱長度組成光電池相對應之電池參數 77
表 3-4 不同ZnS保護層組成光電池相對應之電池參數 80
表 3-5 各電池照光情況之電化學組抗分析參數 84
表 3-6 不同散射層之染料敏化太陽能電池之數據整理 90
表 3-7 散射層對染料敏化太陽電池光電轉換效率數據整理表 92
表3-8 SnMHs及TiNR-SnMHs散射層的光電轉換效率數據整理表 94
表3-9 不同TBOT濃度所成長二氧化鈦奈米柱陣列之柱直徑邊長 100
表3-10 二氧化鈦奈米柱之染料敏化電池數據 101
表3-11 不同蝕刻時間後對於染料敏化太陽能電池之影響 105
表3-12 三電極系統光電水分解系統數據整理 111
表3-13 雙光電極光電水分解系統數據整理 112
表3-14 使用Pt或是CZTS的光電水分解系統之數據整理 114

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