【作者】 秦琦；

【导师】 陶杰；

【作者基本信息】 南京航空航天大学 ， 材料加工工程， 2010， 博士

【摘要】 染料敏化太阳能电池（DSSCs）的研究对解决我国能源紧缺局面和新能源材料的研究开发有着重要的现实意义。然而,常用的液态电解质,由于其易挥发,流动性大,导致电解质易泄漏,影响电池的使用寿命。而传统的对电极是导电玻璃基的镀铂电极,其制造成本昂贵,玻璃基体易碎,限制了染料敏化太阳能电池的生产应用。针对上述问题,本论文工作采用导电聚苯胺（PANI）制备染料敏化太阳能电池用固态电解质和对电极,对于液态电解质的封装难问题和对电极的生产成本的降低提供了新的解决方案。利用扫描电镜、红外光谱分析和电导率测试等手段分别对聚苯胺电解质和对电极的微观形貌、分子结构和导电性能进行了表征,分析了不同基体材料上聚苯胺生长速度和形貌对该对电极结构和性能的影响,最后初步探讨了聚苯胺的生长机理。主要研究内容如下:（1）采用化学氧化法在染料敏化的TiO₂光阳极表面原位合成聚苯胺固态电解质,并对组装的固态染料敏化太阳能电池进行光电性能测试。结果表明,樟脑磺酸掺杂、0℃聚合2h的聚苯胺电解质电导率最高,掺杂效果最佳,具有理想的开路电压,其电池的光电转换效率达到液态DSSC的33%。并且该电解质可充分填充到TiO₂光阳极中,有效增加了电解质与光阳极的接触性。（2）制备一种新型聚苯胺/乙炔黑复合电解质,以进一步提高聚苯胺电解质与对电极的接触性。研究表明,通过加入乙炔黑粒子,不仅可以提高固态电解质的空穴迁移率,而且改善了电解质的浸润性,加强了电解质与两电极间的界面接触,从而获得更高的固态染料敏化太阳能电池的光电转换效率。当加入50wt%乙炔黑时,聚苯胺复合电解质DSSC电池的光电转换效率最优,达到了液态DSSC的47%,为固态电解质的制备提供了一条新途径。（3）分别研究以恒电位法在ITO导电玻璃、导电PET塑料和不锈钢（SS）基体表面合成聚苯胺对电极。结果表明,在不同基体表面电化学聚合聚苯胺的最佳工艺参数均为1.0V恒电位下聚合500s,可获得一层与基体结合紧密的聚苯胺致密膜,其导电性和电催化性能最佳。随着聚合电位的升高和聚合时间的延长,聚苯胺逐步形成大的颗粒球和一维纳米棒的疏松膜,其导电性及电池光电性能也明显下降。（4）基体材料的性质不同,影响了聚苯胺的生长速度和电极的界面接触电阻,导致电池光电转换效率各不相同。以导电PET塑料为基体可制备透光性较好的聚苯胺柔性对电极,但是基体电阻较大,组装的DSSC电池光电转换效率不高,仅为传统铂电极效率的78%。而不锈钢材料成本低、柔性好、面电阻小,以不锈钢为基体的聚苯胺对电极不但可以降低生产成本,而且获得了比铂电极（4.51%）更好的光电转换效率,最高达6.08%。因此,聚苯胺/不锈钢对电极有望在未来的染料敏化电池产业中,取代传统铂电极,成为最具发展潜力的低成本、柔性对电极。更多还原

【Abstract】 Dye sensitized solar cells （DSSCs） has a great practical significance to solve the energy shortage problem and develop new energy materials. However, the use of conventional liquid electrolyte in DSSCs owing to the disadvantages of fluidity and volatility results in the leakage of electrolyte, which limits the long-term performance of devices. In addition, the traditional counter electrode is composed of a platinum thin film formed on a transparent conductive glass substrate, which is relatively expensive and frangible. Considering these problems, the preparation of conducting polyaniline （PANI） used as a solid electrolyte and counter electrode for DSSCs was studied in this work. Then, the morphology, molecule structure and conductive properties of PANI were characterized respectively by Scanning Electron Microscopy, Fourier Transform Infrared spectroscopy, and four probe instrument. The growth rate of PANI synthesized on different substrate materials, and the effect of PANI morphology on the performance of the counter electrode were also analyzed. Finally, the growth mechanism of polyaniline film was preliminarily discussed. The main results are as follows:（1） A conductive polyaniline solid electrolyte was in-situ synthesized on the surface of sensitized TiO₂ anode by means of chemical oxidation polymerization. Then the photoelectrical property of solid DSSC with this PANI electrolyte was also measured. The results showed that PANI film with the best conductivity and doping effect was synthesized at 0℃for 2 hours with camphor sulfonic acid doping. Moreover, the DSSC using PANI solid electrolyte had an ideal open-circuit voltage, and 33% photo-electric conversion efficiency of the liquid DSSC. The PANI electrolyte was fully filled in TiO₂ anode, which can improve the interface contact between the electrolyte and photo anode.（2） A new PANI/acetylene black composite was fabricated as a solid electrolyte in order to enhance the interface contact between the electrolyte and counter electrode. The results showed that the incorporation of acetylene black into the polymer electrolyte improved the photovoltaic behavior of solid-state DSSC significantly, owing to the increase of the hole mobility of PANI electrolyte, the improvement of the wetting quality of the composite electrolyte, and the reinforcement of interface contact between both electrodes and the electrolyte. Finally, the DSSC with PANI-50wt% acetylene black electrolyte had 47% of the overall energy conversion efficiency of liquid DSSC. Therefore, the PANI-acetylene black composition provides one new approach for the preparation of solid electrolyte.（3） PANI counter electrodes were synthetized by potentiostatic technique on the surface of ITO conductive glasses, conductive PET, and stainless steel （SS） substrate, respectively. The results showed that the optimum processing parameters of PANI film electrodeposited on these substrates were at 1.0V for 500s, and the PANI formed a compact layer on the substrate, obtaining the highest conductivity and electrocatalytic activity. As the polymerization potential and time increasing, PANI gradually formed a loose film with the large particles or one dimension nanorods, and the conductivity and photoelectric property of PANI counter electrode were significantly decreased.（4） Owing to the intrinsic diversity of substrates, the growth rate of PANI and the contact resistance on the interface of substrates were different, which had an effect on the energy conversion efficiencies of DSSCs. The PANI flexible counter electrode with a good transparence was prepared on conductive PET plastic substrate. However, owing to the large resistance of PET substrate, the conversion efficiency of DSSC was low, which was 78% efficiency of traditional Pt electrode. And the PANI counter electrode based on the SS substrate with the advantages of low material cost, excellent flexibility and low resistance, not only reduced greatly the production cost, but also increased the efficiency of DSSC. The photoelectric measure results indicated the efficiency of DSSC with PANI/SS electrode reached 6.08%, which was higher than that with Pt electrode （4.51%）. Therefore, the PANI/SS counter electrode will be a potential substitute for platinized electrode to develop a low cost, flexible counter electrode of DSSC in the future.更多还原