鈷系統氧化還原電解質因具有較正的氧化還原電位與較低的吸光競爭性，近年來被視為取代傳統碘氧化還原對，提升染敏電池光電轉換效能的有效方法。本研究之目的在開發適用於鈷錯合物電解質的碳黑對電極，以取代傳統的白金電極。首先對染料的浸泡時間、鈷錯合物氧化還原對比例、以及電解質濃度等條件進行優化。碳黑電極之製作是以市售的導電碳黑為主材料，利用乙基纖維素為分散劑、乙醇為溶劑來配製碳黑分散液，再藉由旋轉塗佈法將碳黑沉積於導電玻璃上來製備碳黑電極。由電化學阻抗頻譜、塔佛極化分析、及循環伏安法等分析結果顯示，乙基纖維素之存在會增加電極與電解質之間的電荷傳輸阻力，降低碳黑電極的效能。但碳黑電極經熱處理後不僅與白金電極有相近之電化學表現，更呈現比白金電極更低之電荷傳輸阻力。此碳黑對電極應用於電池元件中可得到7.18%的光電轉換效率，此表現與應用白金對電極之元件相當(7.14%)。此外，本研究亦藉由調控碳黑分散液中乙基纖維素及碳黑的含量來控制碳黑在電極上的沉積量，製備具高透明度的碳黑電極，並應用於製備雙面照射元件以及串級結構電池。結果顯示，具相近穿透度的碳黑與白金電極，兩者所製備之電池之轉化效率亦相近。將穿透度73% 之碳黑電極用在雙面照射元件中，太陽光自光電極側及對電極側照射所測得之元件效率值小於1%，而利用碳黑對電極所製備的串級電池，可將光電轉換效率提升至7.63%。本研究亦進一步使用高消光係數之有機染料，並搭配碳黑對電極，所製備出的元件可達到8.80%之光電轉換效率。

On account of a more positive redox potential and less competitions for light adsorption, cobalt-based redox electrolyte has been considered as a great candidate replacing the traditional iodide-based electrolyte to boost the power conversion efficiency of a dye-sensitized solar cell. The purpose of this study is to develop a carbon black counter electrode manufacturing process to replace conventional platinum electrode for dye-sensitized solar cells employing cobalt-based redox electrolyte. This research began from optimizing some parameters in fabricating solar cell devices, such as the immersion time of sensitizer, redox ratios of cobalt-based electrolyte, and electrolyte concentrations. The fabrication of carbon black utilizing commercial carbon black with high electrical conductivity. A carbon black dispersion was first prepared by mixing carbon black powders and ethyl cellulose in ethanol, and then the carbon back thin film on FTO glass could be deposited by employing the spin-coating method. From the results of electrochemical impedance spectra, Tafel polarization, and cyclic voltammetry, it showed that the existence of ethyl cellulose would hinder the catalytic activity of carbon black toward the redox reaction in cobalt-based electrolytes and increase the charge transfer resistance at electrode/electrolyte interface, thereby suppressing the cell performance. However, the heat-treated carbon black electrode not only displayed a comparable electrocatalytic performance related to platinum electrode, but also represented a lower charge transfer resistance. Besides, the solar cell device employing a heat-treated carbon black electrode possessed a power conversion efficiency of 7.18%, which was similar to that measured from a device with platinum electrode (7.14%). Furthermore, the contents of ethyl cellulose and ethanol in carbon black dispersions were adjusted to increase the transparency of carbon black electrodes. There is no obvious difference in cell performance between the cell devices prepared by using carbon black and platinum counter electrodes, which both performed a nearly identical transparency. In addition, the carbon black electrode with a 73% transmittance was further applied to fabricating cell devices for dual side illumination or with a tandem structure. It indicated that the discrepancy in power conversion efficiencies of a cell device was less than 1% as the cell was illuminated on photoelectrode and on counter electrode. Moreover, by composing a tandem structure with all carbon black counter electrodes, the power conversion efficiency could be enhance to 7.63%. At last, the highest power conversion efficieny 8.80% could be achieved by ultilizing organic sensitizer with a carbon black counter electrode.

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