本文選題：有機太陽能電池 + 光電活性聚合物　； 參考：《浙江理工大學(xué)》2017年碩士論文

【摘要】：有機太陽能電池具有質(zhì)輕、價廉以及可卷對卷大面積制備等優(yōu)點,受到了人們的廣泛關(guān)注。而在有機太陽能電池中,電荷是否能高效傳輸決定著電池的短路電流密度,而光電活性聚合物納米纖維因為擁有極高的比表面積常被用來建立高效的電荷傳輸路徑,所以在有機太陽能電池活性層中引進纖維可以提高器件的光電轉(zhuǎn)化效率。但是目前所制備的光電活性聚合物纖維耐溶劑性能差,無法進行溶液再加工處理,限制了其在有機光伏領(lǐng)域中的進一步發(fā)展。本論文工作基于靜電紡絲可便利制備核殼結(jié)構(gòu)納米纖維的技術(shù),提出一種制備結(jié)構(gòu)穩(wěn)定且可溶劑再分散的光電活性聚合物納米纖維的新策略。該策略利用可交聯(lián)的光電活性聚合物,將其置于納米纖維的核層,外面包裹鈍性的聚合物,而后經(jīng)內(nèi)部交聯(lián)和去除保護聚合物后制備獲得。在本論文第一部分工作中,我們驗證了這一策略。我們選用有機光伏領(lǐng)域典型的聚合物光伏材料PTB7,在其部分側(cè)鏈末端引入端烯鍵,合成得到可交聯(lián)的光電聚合物PTB7-Vn。性能研究發(fā)現(xiàn)在聚合物PTB7中引入一定量的末端雙鍵其熱學(xué)、光學(xué)及電化學(xué)性質(zhì)并不會明顯改變,并且聚合物PTB7-V0.05經(jīng)紫外照射8小時后交聯(lián)度高達90%以上�；诖�,我們開始制備化學(xué)穩(wěn)定的聚合物PTB7-V0.05納米纖維的研究。我們利用單針頭靜電紡絲技術(shù),在紡絲液中添加聚氧化乙烯(PEO)作為輔助聚合物增加溶液粘性,添加極性溶劑(乙酸、DMF)增加紡絲液的導(dǎo)電性,并且優(yōu)化光電活性聚合物含量、靜電紡絲電壓、推注速度等工藝參數(shù),成功制備了以PTB7-V0.05為核、PEO為殼的同軸納米纖維,經(jīng)紫外照射纖維內(nèi)部發(fā)生交聯(lián)固化,再用異丙醇洗滌去除PEO后,得到直徑在100 nm以下的具有優(yōu)異結(jié)構(gòu)穩(wěn)定性的純PTB7-V0.05纖維。經(jīng)驗證,該纖維可穩(wěn)定分散存在于其良溶劑中。在第二部分工作中,我們對PTB7-Vn的光伏性能進行了細致的表征優(yōu)化,并初步研究了它們的交聯(lián)性質(zhì)。實驗發(fā)現(xiàn)三羥甲基丙烷三(3-巰基丙酸)酯(TTMP)可以顯著提高PTB7-Vn體系的紫外交聯(lián)度,當添加體積比僅為0.01%的TTMP時,PTB7-V0.05在紫外照射30 min下就擁有63.41%的交聯(lián)度,其器件仍保留了 85%的初始效率值。而且TTMP也可以增加器件的短路電流,基于氯苯、二苯醚和0.01%的TTMP混合溶劑制備的器件效率達到6.78%,電池的穩(wěn)定性能正在進一步測試當中。在第三部分工作中,我們通過引入烷基側(cè)鏈來增加BDT-DTBT體系小分子的溶解性,并使用非氯綠色溶劑甲苯來制備器件。研究發(fā)現(xiàn)烷基鏈引入的位置對其光伏性能有著深刻的影響,烷基鏈位于內(nèi)側(cè)分子的光伏性能明顯優(yōu)于位于末端的分子。而且基于甲苯溶劑制備的電池效率與氯仿溶劑相當,這對有機太陽能電池的工業(yè)化應(yīng)用有著重大意義。
[Abstract]:Organic solar cells have attracted wide attention due to their advantages of light weight, low price and large area preparation. In organic solar cells, whether the charge can be transmitted efficiently determines the short circuit current density of the cell, and the photoactive polymer nanofibers are often used to establish an efficient charge transfer path because of their extremely high specific surface area. Therefore, the introduction of fiber into the active layer of organic solar cells can improve the photoelectric conversion efficiency of the devices. However, the photoactive polymer fibers have poor solvent resistance and can not be reprocessed in solution, which limits their further development in the field of organic photovoltaic. Based on the technology that electrostatic spinning can facilitate the preparation of core-shell nanofibers, a new strategy for preparing photoactive polymer nanofibers with stable structure and solvent dispersion is proposed. In this strategy, crosslinked photoactive polymers are placed in the nuclear layer of nanofibers and coated with blunt polymers, which are then prepared by internal crosslinking and removal of protective polymers. In the first part of this thesis, we verify this strategy. In this paper, a typical polymer photovoltaic material PTB7 in organic photovoltaic field is selected, and a crosslinked photovoltaic polymer PTB7-Vn is synthesized by introducing terminal bond at the end of some side chains of PTB7. It was found that the thermal, optical and electrochemical properties of the polymer PTB7-V0.05 could not be changed obviously by introducing a certain amount of end double bond into the polymer PTB7, and the crosslinking degree of the polymer PTB7-V0.05 was over 90% after 8 hours of ultraviolet irradiation. Based on this, we began to prepare chemically stable polymer PTB 7-V 0.05 nanofibers. Using single needle electrospinning technology, we added polyethylene oxide (PEO) as auxiliary polymer to the spinning solution to increase the viscosity of the solution, and the polar solvent (DMF) to increase the conductivity of the spinning solution and optimize the content of photoactive polymer. Coaxial nanofibers with PTB7-V0.05 as shell were successfully prepared by electrospinning voltage and injection speed. The fibers were crosslinked and solidified by UV irradiation, and then washed with isopropanol to remove PEO. Pure PTB7-V0.05 fibers with a diameter below 100 nm with excellent structural stability were obtained. It is proved that the fiber can be dispersed stably in the solvent. In the second part, we optimized the photovoltaic properties of PTB7-Vn and studied their crosslinking properties. It was found that the UV crosslinking degree of PTB7-Vn system could be significantly increased by trimethylolpropane tris (TTMP). When the volume ratio of TTMP was only 0.01%, the crosslinking degree of PTB7-V0.05 was 63.41% after 30 min of external irradiation. The device still retains an initial efficiency value of 85%. Furthermore, TTMP can increase the short-circuit current of the device. The device efficiency based on chlorobenzene, diphenyl ether and 0.01% TTMP mixed solvent is 6.78. The stability of the battery is being further tested. In the third part, we introduce alkyl side chains to increase the solubility of small molecules in BDT-DTBT system, and use non-chlorinated green solvent toluene to prepare the devices. It is found that the position of alkyl chain has a profound influence on its photovoltaic performance, and the photovoltaic performance of alkyl chain located inside molecule is obviously superior to that of the molecule located at the end of the alkyl chain. Moreover, the efficiency of the organic solar cells based on toluene solvent is equal to that of chloroform solvent, which is of great significance to the industrial application of organic solar cells.
【學(xué)位授予單位】：浙江理工大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：TQ340.64;TM914.4

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本文編號：2107390