【作者】 金立国；

【导师】 张显友；

【作者基本信息】 哈尔滨理工大学 ， 材料学， 2011， 博士

【摘要】 染料敏化多孔纳米晶半导体太阳能电池由于廉价高效的特点近年来得到迅猛发展,成为当前科学研究和技术开发的热点之一。这种电池作为一种多组分复合体系,目前还存在着一些制约因素,譬如液态电解质电池引起的电极腐蚀、电解液泄露、寿命短,目前常用的羧酸多吡啶钌价格昂贵等等一系列问题。针对这些问题,准固态或固态电解质被不断开发和利用,但目前,其效率无法与液态电解质相比,主要是由于这些电解质的填充性和孔隙填充较差,不能形成有效地界面结合,还有电解质中离子的迁移速度较差等原因制约了电池的效率提高。本论文基于寻找新型电解质材料和开发新型染料的考虑,采用溶胶-凝胶法制备具有血液仿生触变性电解质,得到准固态染料敏化太阳能电池。并且通过分子结构优化,合成含偶氮苯卟啉衍生物染料,并将其应用到液态染料敏化太阳能电池。本论文研究主要内容包括：通过溶胶水热法合成纳米TiO2溶胶并配合有机高分子分散剂(PVA)得到镀膜用溶胶,运用电流体动力学(electro-hydrodynamic, EHD)制备了纳米晶TiO2多孔薄膜。通过SEM、TEM及光谱等分析表明：EHD制备的纳米晶TiO2多孔薄膜中具有多级结构特征,并表现出良好的光散射性质。利用溶胶-凝胶法合成的纳米TiO2前驱体溶胶并配合离子液体电解质制备了三种不同组成的血液仿生触变性准固态电解质。通过电解质的触变性、热稳定性、离子电导率和填充性分析,结果表明,血液仿生触变性电解质具有优异热稳定性、较高的离子电导能力和在多孔薄膜孔隙填充性质。通过血液仿生触变性电解质成功组装染料敏化太阳能电池,并进行光电性能的分析。在模拟太阳光强度为100mW/cm2下,电解质TPNE1、TPNE2及TPNE3分别获得了总体光电能量转换效率为6.45%、6.36%及5.7%,并且具有较高的填充因子(≥0.70)。在未进行任何封装条件下,10天测试时间内,触变性电解质电池器件的稳定性明显好于其对应成分的离子液体电解质。电化学阻抗分析结果表明,触变性电解质表现出与离子液体电解质相比拟的电荷传输能力。通过分子结构优化,成功合成了含偶氮苯卟啉染料衍生物H2P和其锌金属离子络合衍生物ZnP。引入的偶氮苯基来增加卟啉分子的π共轭体系,偶氮苯端基连接的酚基并作为在氧化钛半导体的吸附基团。通过光谱及循环伏安法测试分析,验证了含偶氮苯卟啉衍生物染料作为染料敏化太阳能电池的光敏剂的可行性。利用偶氮苯卟啉衍生物染料敏化纳米晶TiO2多孔薄膜,配合液态电解质组装电池。结果表明,卟啉衍生物染料ZnP表现出较为优异的敏化能力,在模拟太阳光强度为100mW/cm2下,获得了光电能量转换效率为4.37%,尤其短路光电流达到14.6mA/cm2,在已被应用的卟啉染料敏化太阳能电池所报道的最高值之一。更多还原

【Abstract】 Nowadays, dye-sensitized solar cell (DSSC) is of great interest because of its relatively low cost and reasonably high efficiency. The energy conversion efficiency of DSSCs has already reached to as high as 11.2%. However, as a complex system for DSSCs, there are still many important unsolved issues, such as device sealing and stability caused by liquid electrolytes and expensive sensitizers. Recently, many efforts are more focusing on new type dye and quasi-solid or solid electrolyte research. However, the photoelectric conversion efficiency of DSSCs based on quasi-solid or solid electrolyte are relatively low because these electrolytes can not full into porous films with leading to the interfacial bonding was poor and its ionic mobility is relatively low. In this dissertation, based on the idea of seeking new type electrolyte and developing new type dye, we prepared blood mimetic thixotropy electrolyte by sol-gel method, and applied it into quasi-solid DSSC. Porphyrin derivatives with containing azobenzene functional group were also synthetized and applied into liquid state DSSC. The main work is concentrated on the following aspects:Nanometer TiO2 sol for coating film was prepared by cooperating hydrothermal colloidal sol with organic polymer dispersing agent (PVA). Nanocrystalline TiO2 porous films were prepared by using electro-hydrodynamic technique (EHD), and the characteristics of the films are investigated by using TEM, SEM and optical spectrum.etc. The results show the films prepared by EHD technique have multilevel hierarchical structure, therefore, better optical scattering properties.Three different constituent quasi-solid electrolytes with blood mimetic thixotropy were prepared by cooperating ionic liquid electrolyte with nanometer TiO2 colloidal sol synthetized by sol-gel method. The new type electrolytes were measured in thixotropy, thermostability, ionic conductivity and wetting property, etc. The results indicated the blood mimetic thixotropy electrolytes show the better thermostability, higher ionic conductivity and higher fill property in porous films.Blood mimetic thixotropy electrolytes are adopted in DSSCs and their photophysical and electrochemical properties are studied. Under under an AM-1.5 illumination at 100 mW/cm2, the overall energy conversion efficiency of 6.45%, 6.36% and 5.7% are obtained for the DSSC devices of TPNE1, TPNE2 and TPNE3, respectively, and the higher fill factors (≥0.70) are obtained. Measured in 10 days, the DSSC devices of TPNE1, TPNE2 and TPNE3 show higher stability than that of device with ionic liquid electrolyte without any sealing. The results of electrochemistry impedance analysis indicate these thixotropy electrolytes show the equal charge transmittablity relative to ionic liquid electrolyte.By molecular structure optimizing, we successfully synthetized H2P and ZnP porphyrin derivatives with containing azobenzene fuctional group. Introducing of azobenzene group can enhanceπ-conjugated system of porphyrin derivatives, and phenolic group in the terminal group of azobenzene acts as the anchoring group of TiO2 surface. We also verified two prophyrin derivatives can serve as the photosensitizer for DSSC by optical spectrum and cyclic voltammetry measurements.Two porphyrin derivatives are applied as photosensitizers for fabrication of liquid DSSCs based on TiO2 photoelectrode, and the performances of cells are explored. Under illumination of simulated AM-1.5 solar light (100mW/cm2), the short-circuit current density of 14.6 mA/cm2 and the overall energy conversion efficiency of 4.37% are obtained with the maximum IPCE value of 75% for the device of ZnP. Especially, the high short-circuit current density is the highest one reported to our knowledge.更多还原