【作者】 朱静燕；

【导师】 高延敏；

【作者基本信息】 江苏科技大学 ， 材料学， 2011， 硕士

【摘要】 染料敏化剂是DSSC的关键材料之一,目前使用的材料是稀有金属染料,价格高、有毒,影响其使用性能,为了降低金属染料DSSC的成本、避免毒性,替代材料逐渐成为研究的热点。金属酞菁及其衍生物由于光稳定性好、在红光及近红外区有强的吸收、无毒的特性,成为最有希望的替代材料之一;但是酞菁染料存在着激发寿命短、转化效率较低等缺陷,阻滞了酞菁在DSSC中的应用。为改善酞菁敏化效果,本文从分子设计入手,其基本思路是:在酞菁环上引入了可与nm-TiO₂作用的羧基,以扩大酞菁分子的吸光范围;同时合成双核金属酞菁,研究了扩大的共轭体系及不同金属离子对染料的影响;为进一步提高太阳能电池的光电转换效率,尝试将金属酞菁盐与N719染料配合协同敏化nm-TiO₂电极,并组装成电池测试了其电池效率。本文采用苯酐-尿素熔融法合成了相关酞菁化合物,通过红外光谱、紫外-可见光谱、循环伏安及热重分析对产物进行了表征,结果表明,不同金属离子的引入使得两类酞菁IR中的金属-配位-配体的振动峰以Zn>Cu>Fe的顺序向高频方向移动; UV-Vis中的Q带随着中心离子价层d电子数的增多都发生了横移,其顺序为Zn>Cu>Fe;循环伏安曲线则表明,随着中心金属的极化能力的减小,酞菁盐的氧化还原电势都呈现出Fe（Ⅱ） >Cu（Ⅱ）>Zn（Ⅱ）的次序;TG-DTA说明了两类酞菁在空气中的热稳定性顺序为Cu> Zn> Fe。相比于单核金属酞菁,双核酞菁IR中的金属-配位-配体伸缩振动频率略有增高;UV-Vis中Q带有较大的红移且在800⁹00nm出现了一较小的吸收峰;热力学稳定性方面有明显的提高。计算了合成染料的能带结构参数并与锐钛型TiO₂能带结构比较,发现合成的染料均可满足DSSC对能级匹配的要求。将合成的染料制成DSSC,测试了染料敏化太阳能电池的相关性能,研究了不同酞菁的敏化效果。结果显示单核酞菁比双核酞菁具有更高的短路电流密度及光电转化率,其中以单核锌酞菁最佳。最后将合成的酞菁染料与N719配合使用,通过紫外-可见吸收光谱及I-V曲线探讨了两种染料协同敏化电池的效果,结果表明, ZnPc（COOH）₄/ b-ZnPc（COOH）₆与N719协同敏化时,ZnPc（COOH）₄好于b-ZnPc（COOH）₆;两种染料协同敏化使电池获得了更为优异的性能,其中以ZnPc（COOH）₄与N719共同敏化的电池效率最高。更多还原

【Abstract】 Sensitized dye is an important role in DSSC. Nowadays researches are focus on rare dyes, which are high in cost as well as toxic that will effect their using. So experts are working hard to overcome these disadvantages currently. Metal phtahlocynine and its derivatives have many advantages such as non-toxic, good light stability and in red and near infrared region these dyes have strongly sorption. Therefore they can be well potential materials. However phthalocyanine dye can not exist long after excitation and this stop the charge removing, gathering on the surface of electrode.In order to get the better performance we can design and optimize the phthalocyanine molecule. The basic idea is that introducing the carboxyl which can react with nm-TiO₂ to the phtaalocyanine ring in order to expand the absorbance scope of phtahalocyanine molecules. At the same time we syntheized dinuclear metal phthalocyanine and studied the effect of expanding conjugated systems and different metal ions on dye. At last we try to complex metal phthalocyanine salt and N719 dye with sensitized nanocrystalline titanium dioxide films to make the cell and analyze its properties.In this paper, we syntheized melt phthalocyanine with phthalic anhydride - urea and all the productions would be analyzed by IR, UV-visible spectroscopy, cyclic voltammetry and thermal gravimetric analysis. The result as follow: with the introduction of different metal center icons, the vibration frequency of metal-ligand in single-core metal phthalocyanine and planar binuclear metal phthalocyanine is speeded as Zn>Cu>Fe. The Q belt of the former phthalocyanine salt in UV-Vis is traversing as the increase mount of the eletronics in central ion valence d and the order is Zn>Cu>Fe. In CV curves analysis, the redox potential order of two types of phthalocyanine salt is Fe（Ⅱ）>Cu（Ⅱ）>Zn（Ⅱ） according the reducing polarization ability of the central compounds. According TG-DTA, the stability order of the two types salt under air is Cu> Zn> Fe.Compared with single-core metal phthalocyanine, the metal stretching vibration frequency of dual-core phthalocyanine is slightly higher in IR spectra. The Q belt has a large red shift and there is a small peak appears in 800⁹00 nm. The thermodynamic stability of binuclear phthalocyanine are significantly improved. Through comparing the band structure parameters of synthetic dyes with that of TiO₂, we found that synthetic dyes can match all the requirements of energy level. DSSC were made with different synthetic dye, we tested the properties of these dye-sensitized solar cells and studied the sensitization effect of different phthalocyanine.It shows that compared with dual-core phthalocyanine, single-core phthalocyanine has higher short-circuit current density and photoelectric conversion. Zinc phthalocyanine battery which has the maximum extinction coefficient is the best choice.At last we try to complex metal phthalocyanine salt and N719 dye with sensitized nanocrystalline titanium dioxide films to make the cell and analyze its properties by ultraviolet - visible absorption spectra and I-V curves. The results show that, when ZnPc（COOH）₄/ b-ZnPc（COOH）₆ sensitized with the N719 coordination, the property of ZnPc（COOH）₄ is better than that of b-ZnPc（COOH）₆. Coordination of the two dye-sensitized is better than single phthalocyanine. The ZnPc（COOH）₄ and N719 co-sensitized has higher short-circuit current density and photoelectric conversion.更多还原