吡啶、三倍司类非对称半菁染料及有机氧化还原电对在染料敏化太阳能电池中的应用研究

发布时间：2018-04-25 09:04

本文选题：染料敏化太阳能电池 + 纯有机光敏染料　；参考：《大连理工大学》2014年博士论文

【摘要】：光敏染料和电解质作为染料敏化太阳能电池的核心组成部分,对电池的光电转换性能起着决定性的作用。设计开发高效、稳定、廉价的光敏染料和电解质能够有效降低电池成本,进而推进染料敏化太阳能电池的产业化进程。将吡啶摀离子基团作为电子受体,设计合成了11个非对称半菁染料。研究发现,与普遍采用的电子受体-氰基丙烯酸基团相比,以吡啶摀离子基团为电子受体构建的光敏染料吸收谱带发生明显红移,对太阳光光谱具有更宽的响应。将此类光敏染料应用于染料敏化太阳能电池中,染料CM104获得了7.0%(Jsc=13.4mA·cm-2,Voc=704mV,FF=74.8%)的光电转换效率；相同条件下参比染料CMR104获得了3.4%(Jsc=6.2mA·cm-2,Voc=730mV,FF=74.8%)的光电转换效率。将吡啶摀离子基团做为桥基与电子受体氰基丙烯酸基团直接相连,设计合成了3个D-A-A型半菁染料。在吡啶摀离子基团和氰基丙烯酸基团的共同吸电子作用下,此类光敏染料吸附于TiO2表面仅发生2-6nm的蓝移。将此类光敏染料应用于染料敏化太阳能电池中,以CM203为光敏染料,使用碘/硫多组分杂合电解质制备的电池获得了8.8%(Jsc=15.0mA·cm-2,Voc=820mV,FF=72.5%)的光电转换效率。将三倍司摀离子基团作为电子受体构建的光敏染料CM301-CM304在可见光区域吸收较强,但吸收光谱较窄。应用于染料敏化太阳能电池中,仅在500-650nm区域对太阳光具有较高转化效率。以CM303为光敏剂的电池获得了5.0%的光电转换效率。选用与CM303光谱互补的纯有机光敏染料CMR103和HY113共同用于制备共敏化太阳能电池,获得了8.2%的光电转换效率。共敏化电池在整个可见光区域(400-700nm)内IPCE值保持在85%以上。将L-半胱氨酸/L-胱氨酸氧化还原电对应用于染料敏化太阳能电池电解质,以N719为光敏染料,获得了7.7%的光电转换效率。此类电解质制备简单、成本低廉、腐蚀性较小,更适用于规模化生产；同时电解质对光的吸收性能较弱,有利于光敏染料对光的吸收转换。以对苯二酚/苯醌为氧化还原电对的多组分杂合电解质近乎无色,有利于光敏染料对太阳光的捕获,将此电对应用于染料敏化太阳能电池中,获得了8.4%(Jsc=17.2mA·cm-2,Voc=750mV,FF=66.3%)的光电转换效率,这一效率优于使用I-/I3-电解质封装的电池。
[Abstract]:Guang Min dyes and electrolytes, as the core components of dye sensitized solar cells, play a decisive role in the photoelectric conversion performance of the cells. The design and development of efficient, stable and cheap Guang Min dyes and electrolytes can effectively reduce the cost of solar cells and promote the industrialization of dye sensitized solar cells. Eleven asymmetric hemocyanine dyes were designed and synthesized by using pyridine group as electron acceptor. It is found that compared with the commonly used electron acceptor-cyanoacrylic group, the absorption band of Guang Min dye constructed by using pyridine as the electron acceptor has a red shift and a wider response to the solar spectrum. Using this kind of Guang Min dye in dye sensitized solar cells, the photoelectricity conversion efficiency of 7.0%(Jsc=13.4mA cm-2vocn 704mV FFU 74.8 was obtained by dye CM104, and the optoelectronic conversion efficiency of 3.4%(Jsc=6.2mA cm-2Voc730mV FFFFFF74.8g was obtained by reference dye CMR104 under the same conditions. Three D-A-A semicyanine dyes were designed and synthesized by using pyridine as the bridge group and the electron acceptor cyanoacrylic acid group as the bridge group. Under the combined action of pyridine ion group and cyanoacrylic group, only the blue shift of 2-6nm occurs on the surface of TiO2 adsorbed by this kind of Guang Min dye. This kind of Guang Min dye was used in dye sensitized solar cell. The photovoltaic conversion efficiency of 8.8%(Jsc=15.0mA cm-2v Vocn 820mV FF72.5) was obtained by using CM203 as Guang Min dye and using iodine / sulfur multicomponent hybrid electrolyte. Guang Min dye CM301-CM304, which was constructed by using the triple sieve group as the electron acceptor, had a strong absorption in the visible region, but a narrower absorption spectrum. When used in dye sensitized solar cells, the conversion efficiency of solar light is higher only in 500-650nm region. The photovoltaic conversion efficiency of the battery with CM303 as Guang Min was 5.0%. A pure organic Guang Min dye, CMR103 and HY113, complementary to CM303 spectra, was used to prepare co-sensitized solar cells. The photovoltaic conversion efficiency of 8.2% was obtained. The IPCE value of the co-sensitized cells remained above 85% in the whole visible region of 400-700 nm. L- cysteine / L- cysteine redox pair was applied to dye sensitized solar cell electrolyte. Using N719 as Guang Min dye, the photoelectric conversion efficiency of 7. 7% was obtained. This kind of electrolyte is simple in preparation, low in cost, less corrosive, and more suitable for large-scale production, and the absorption property of the electrolyte to light is weak, which is beneficial to the absorption and conversion of Guang Min dyes. The multicomponent hybrid electrolyte with hydroquinone / benzoquinone as redox electric pair is nearly colorless, which is advantageous to the capture of solar light by Guang Min dye. The photoelectricity conversion efficiency of 8.4%(Jsc=17.2mA cm-2Voct750mVFFN 66.3) is obtained by applying this pair to dye sensitized solar cells. This efficiency is superior to that of batteries packaged with I-P-I 3-electrolyte.
【学位授予单位】：大连理工大学
【学位级别】：博士
【学位授予年份】：2014
【分类号】：O621.13;TM914.4

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