摘要 染料敏化太阳能电池（DSSC）因其高效率、低成本、环境友好、组装简单、可柔 性化等优点而备受关注。传统的DSSC 由染料敏化光阳极、电解液、对电极三部分组成。 但电解液存在易挥发、流动性大、易泄漏的问题。传统的铂对电极存在成本高、不利于 大规模生产的问题。鉴于此，本论文拟用凝胶态电解质代替液态电解质，共轭聚合物电 极代替Pt 电极，与自制的TiO2 光阳极组装成准固态DSSC。并对凝胶态电解质、共轭聚 合物膜电极的制备工艺、结构与性能进行了系统研究，并对组装的DSSC 进行了光电转 化性能的研究，对光生电荷在DSSC 的界面传输进行了分析。主要研究结果下： （1）以PVDF 为胶凝剂，NMP 为溶剂，I2/NaI 为氧化还原电对，EC、PC 为增塑剂， 制得有良好离子电导率的凝胶态聚合物电解质，最佳配方为：NaI 浓度0.6mol/L，I2 浓 度0.05mol/L，EC/PC 质量配比为2/1，PC/EC 与PVDF 的用量均为NMP 的15wt%。该 凝胶态电解质膜具有较多、较大的便于电解质离子迁移的丰富的孔道，PC、EC 与PVDF 间较强的氢键结合提高了I−/I3 −在其中迁移的自由度，它还具有较小的Rct 和较高的电导 率，电导率达到2.63mS/cm。用PC/EC 增塑的凝胶态电解质组装的DSSC 的光电转化效 率达到1.316%，比未加增塑剂的凝胶态电解质高了50.74%。 （2）采用电化学法制备了聚苯胺(PANI)、聚吡咯(PPY)、聚噻吩（PTh）三种共轭聚 合物对电极，三者的Rct 依次增大。其中，PANI 电极具有高的催化活性、低的面电阻、 良好的电导率，PANI 和PPY 电极对电解质表现出更好的还原性。PANI 对电极具有最低 的本体电阻，为47.12Ω，与Pt 电极接近。这主要是PANI 表面的微孔结构，为电极的表 面离子的迁移提供了很好的通道，为其良好的光电性能提供了保障。PANI、PPY、PTh 对电极组装的准固态DSSC 的光电装换效率依次减小，分别为0.113%、0.046%、0.001%。 PANI 对电极的最佳制备工艺为，单体浓度为0.2mol/L，电位扫描范围为-0.20~0.85V， 扫描速率为10mV/s，扫描10 圈制备所得PANI 具有最高的光电转化效率为0.113%。PPY 对电极的最佳制备工艺为，单体浓度为0.1mol/L，扫描电压为0.8V，电沉积15min 制备 的PPY 膜组装的准固态DSSC 光电转化效率为0.063%。 （3）电沉积法比热分解法制备的Pt 电极，表面分散更均匀，表面颗粒间有一定的间隙， 更方便离子的迁移，表现出更高的光催化性能。其本体电阻Rct 为42.47Ω，低于热解法 制备的Pt 电极的；JSC 达到6.63 mA·cm−2，η 达到1.79%，均高于热解法制备的Pt 电极 的。 （4）采用溶胶凝胶法成功制备出形状较规则、粒径在20nm 左右、较大光吸收发生在 200~350nm 的锐钛矿型TiO2 纳米粉体。其原料配比为：钛酸四丁酯/无水乙醇/冰醋酸/ 二次蒸馏水体积比为1.00/3.30/0.30/0.26，煅烧温度控制在450~550℃。

ABSTRACT Dye-sensitized solar cells (DSSC) have attracted wide interest due to their high efficiency, low cost, environment friendly, simple preparation procedure and flexiblity. Conventional DSSC contain three parts which are photoanode (need dye-sensitized), electrolyte and electrode. However, the liquid electrolyte has its disadvantages, such as volatility, fluidity and easy leakage.The traditional Pt counter electrode is relatively expensive and is not good for the large scale production. In view of the above question, this paper used the gel electrolyte instead of liquid electrolyte, conjugated polymer electrode instead of Pt electrode. And a homemade TiO2 anode was assembled into the quasi-solid DSSC. The preparation, structure and properties of gel electrolytes and conjugated polymer film electrode were systematically research. We studied photoelectric transformation performance of assembly DSSC and analyzed light-generated charge transmission at the interface of DSSC. The main researches are listed as follows: (1)The gel polymer electrolyte with high ionic conductivity was obtained using PVDF, NMP, I2/NaI and EC/PC as the gelling agent, solvent, redox and plasticizer, respectively. The best formula is: NaI with concentration of 0.6mol/L, I2 with concentration of 0.05mol/L, EC/PC with mass ratio of 2/1, 15wt% of PC/EC and PVDF in NMP. The gel state electrolyte membrane has abundant and large channels for electrolyte ion migration. Strong hydrogen banding among EC, PC and PVDF raised the freedom of I−/I3 − migration. It also has smaller Rct(charge transportation resistance) and higher conductivity (2.63mS/cm). With PC/EC plasticizing gel electrolyte, the DSSC photoelectric conversion efficiency reached 1.316%, which increased by 50.74% than the gel electrolyte without plasticizer. (2) The Rct of electrochemical prepared polyaniline (PANI), polyprrole (PPY) and polythiophene (PTh) followed a gradual increase sequence. Wherein, PANI electrode has higher catalytic activity, lower surface resistance and better conductivity. PANI and PPY electrode showed better reducibility. PANI electrode has the lowest body resistance of 47.12Ω that is closed to the Pt electrode. It is attributed to the microparous structure of PANI surface, which provides plenty of channels for the ion migration of electrolyte and guarantees for good photoelectric properties. The photovoltaic conversion efficiency of quasi-solid-state DSSC are 0.113%, 0.046% and 0.001% for PANI, PPy and PTh as the courter electrodes, respectively. The best preparation technology of PANI electrode is monomer concentration of 0.2mol/L, potential scan range of -0.2~0.85V, scan rate of 10mV/s and scan circles of 10.Under this condition, the photovoltaic conversion efficiency can be reached to 0.113%. The best preparation technology of PPY electrode is monomer concentration of 0.1mol/L, scan voltage of 0.8V and electrodeposition 15min and the assembed quasi-solid-state DSSC photovoltaic conversion efficiency is 0.063%. (3) Electrodeposition preparation of Pt electrode has more uniform surface, more convenient ion migration as comparison with that obtained by thermal decomposition approach. It has a certain gap on particles surface that showed good photocataiytic properties. The body resistance is 42.47Ω, lower than Pt electrode by thermal decomposition. Its Jsc is 6.63 mA·cm−2 and η has reached 1.79%, which was all higher than Pt electrode prepared by pyrolysis. (4) Prepared the rules of shape, particle size in about 20nm and light absorption occurred in 200~350nm anatase TiO2 nanopowders by sol-gel method successfully. Its raw material ratio: Tetrabutyltitanate/Ethanol/Acetic acid/Distilled water is 1.00/3.30/0.30/0.26 by volume. Calcination temperature control at 450~550℃.