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標題: | 噴射大氣電漿快速製程於染料敏化太陽能電池之應用 Rapid Atmospheric Pressure Plasma Jet Process for Dye-sensitized Solar Cell Fabrication |
作者: | Hao-Ming Chang 張浩銘 |
指導教授: | 陳建彰(Jian-Zhang Chen) |
關鍵字: | 染料敏化太陽能電池,大氣電漿,快速燒結,二氧化鈦,噴霧熱解法,散射層, Dye-sensitized solar cell,Atmospheric pressure plasma jet,Rapid sintering,Titanium dioxide,Spray pyrolysis method,Scattering layer, |
出版年 : | 2013 |
學位: | 碩士 |
摘要: | 本論文研究利用噴射大氣電漿(Atmospheric pressure plasma jet, APPJ)快速製程染料敏化太陽能電池(Dye-sensitized solar cell, DSSC)。論文內文包含三部分,分別為大氣電漿快速燒結二氧化鈦光電極染料敏化太陽能電池、大氣電漿噴霧熱解製備二氧化鈦散射層於染料敏化太陽能電池、大氣電漿快速低溫燒結二氧化鈦光電極染料敏化太陽能電池。
實驗一為利用大氣噴射電漿快速燒結染料敏化太陽能電池氧化鈦光電極,並研究不同電漿燒結時間對電池效率的影響。大氣電漿燒結30秒因殘留有機物質在光電極上而在頻譜上有較高的吸收峰,較長時間電漿處理光電極則和傳統退火光電極呈現相同的特性。從掃描式電子顯微鏡、X光繞射儀和化學分析電子頻譜的分析結果可知,傳統退火和電漿燒結的氧化鈦膜並無顯著差異。當電漿燒結時間大於一分鐘,可得到和傳統熱退火相同的效率;而電漿燒結30秒因有機物質殘留而有較低的電池效率,同時由電化學阻抗頻譜得知電子有較大的電子傳輸阻抗和較短的電子生命週期。實驗結果證實使用電漿燒結一分鐘可以完全取代傳統的燒結方式,並應用在染料敏化太陽能電池。 實驗二為研究調變大氣電漿鍍膜時間和前驅物載流氣體流量來製備二氧化鈦散射層,並應用在染料敏化太陽能電池上。前驅物載流氣體有無經過前置加熱器對於所沉積的顆粒有很大的影響。散射層的添加使得光電轉換效率提升,當前驅物載流氣體有經過前置加熱器,則所形成的顆粒為均勻圓球但是和網印二氧化鈦層的附著較差;當前驅物載流氣體不經過前置加熱器,則所形成顆粒為破碎不規則的形狀但是和網印二氧化鈦層的附著較佳。不加裝前置加熱器下通以前驅物載流氣體0.5slm沉積120秒的散射層對電池效率的提升最為顯著,電池效率可從沒有散射層光電極的6.9%提升至7.6%。 實驗三為利用氮氣、氧氣和空氣電漿燒結網印二氧化鈦漿料以得到孔隙二氧化鈦薄膜,並研究不同電漿燒結時間對電池效率的影響。實驗結果顯示,氮氣電漿本身的高反應性分子和氧氣的引入是快速移除有機物的重要關鍵。因此空氣電漿(有無側孔引入空氣中的氧氣均可)以及側孔石英管氮氣電漿具備快速燒結二氧化鈦漿料的條件,其中以具側孔石英管的條件燒結下可進一步將燒結溫度從~500℃降低至~300℃。另一方面,氧氣載流電漿會和不銹鋼電極反應,形成顆粒污染試片,因此不適合使用於材料製程。本實驗和實驗一相比,我們可以用更短的時間(~30 s)和更低的溫度(~300℃)達到一樣的電池效率。未來可將此低溫燒結的技術應用在塑膠基板染料敏化太陽能電池,並搭配上捲軸式製程發展出一套快速且低成本電池製程技術。這技術同時可以降低太陽能電池製作過程所需的能源和熱預算。 Dye-sensitized solar cells with nanoporous TiO2 photoanodes processed by atmospheric pressure plasma jets (APPJs) are investigated. First part is the rapid preparation of nanoporous TiO2 films for DSSCs by a rapid atmospheric pressure plasma jet sintering process. The second part is TiO2 particulate scattering layer deposition process for dye-sensitized solar cell using APPJs. In the third part, we investigate the influence of carrier gas on the rapid APPJ sintering process of TiO2 for DSSCs. In the first experiment, we investigate DSSCs with rapidly APPJ-sintered TiO2 photoanodes. From absorption spectra, a 30-s APPJ-sintered TiO2 layer presents extra absorption band between 400 and 500 nm due to the incomplete removal of organic solvents in the pastes. As the sintering time reaches 60 s and beyond, the absorption spectra of APPJ-sintered TiO2 are almost identical to that of the furnace-sintered one. The crystallinity, surface morphology and surface element composition of APPJ-sintered TiO2 are similar to that of furnace-sintered sample, confirmed by SEM and XRD experiments. The efficiency for DSSC with APPJ-sintered TiO2 becomes comparable to that with conventional furnace-sintered photoanode when APPJ treatment time reaches 60 s and beyond. Furthermore, TiO2 photoanode with 30 s treatment exhibits poor power conversion efficiency, attributing to organic residues in the film. Electrochemical impedance spectroscopy (EIS) also shows that the DSSC with 30 s APPJ-sintered TiO2 photoanode has an extremely large TiO2/dye/electrolyte electron transport interfacial resistance and a short carrier lifetime. Our experimental results demonstrate that a 60-s APPJ sintering process is sufficient to replace the conventional 15 min, 510oC furnace-sintering process for TiO2 photoanodes of DSSCs. The second experiment is about the APPJ-deposited particulate TiO2 scattering layer for dye-sensitized solar cells (DSSCs). The usage of a preheater prior to the injection of nebulized precursors into the plasma jets strongly modifies the morphology of the APPJ deposited TiO2 nanoparticles. In all cases, the cell efficiency is improved by the administration of scattering layer. With a preheater, the APPJ TiO2 particles reveal a well-constructed spherical shape, but the adhesion to the screen-printed nanoporous TiO2 is poorer. On the other hand, when TiO2 are deposited without a preheater, the shape of TiO2 particles is irregular but the adhesion to the main TiO2 layer is better. The DSSC with particulate TiO2 layer deposited for 120 s with a carrier gas of 0.5 slm flow rate exhibits the best cell efficiency of 7.61 %, in comparison to 6.91 % for the reference counterpart without a scattering layer. In the third experiment, we investigate the influence of carrier gases on the APPJ-sintered TiO2 for DSSCs. The experimental results indicate that the presence of both excited nitrogen plasma and oxygen gas is critical to the rapid sintering process of nanoporous TiO2 photoanodes. The TiO2 photoanodes sintered by APPJ with air carrier gas (either the tube with hole or not) and nitrogen carrier gas (tube with hole) show the ultrafast removal of organic solvents in the pastes. The rapid sintering temperature can be further reduced from ~500 oC to ~300 oC in this fashion. The film sintered by oxygen plasma is not appropriate for this fabrication process due to its contamination caused by the reaction between oxygen excited molecules and the stainless steel electrode. In this part of experiment, the cell efficiencies are identical to the first experiment, but both the processing time and temperature are greatly reduced. This rapid low-temperature TiO2 sintering technique can be beneficial for roll to roll fabrication process. The thermal budget and energy required for DSSC fabrication process are also lowered. |
URI: | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/60709 |
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顯示於系所單位: | 應用力學研究所 |
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