过渡金属离子掺杂和表面活性剂修饰聚苯胺的合成及其在染料敏化太阳能电池中的应用

发布时间：2018-07-03 03:44

本文选题：染料敏化太阳能电池 + 对电极　；参考：《河北师范大学》2017年硕士论文

【摘要】：对电极是染料敏化太阳能电池(DSSCs)的重要组成部分,起着传递外电路电子和催化再生氧化还原电对的作用。铂(Pt)是常用的高效对电极催化材料。然而,Pt价格昂贵且储量有限,限制了其在DSSCs中的大规模使用。由此各种非Pt对电极材料成为研究热点。如碳材料、过渡金属化合物、有机导电聚合物。其中导电聚合物具有合成过程简单,原料丰富、可塑性强等特点,有利于降低DSSCs成本,适宜工业化生产。1)本论文采用电化学和化学法合成导电聚合物聚苯胺(PANI)。探讨了过渡金属离子掺杂和表面活性剂修饰对其催化性能的影响。研究发现采用电化学方法合成的PANI对电极的DSSCs效率为3.87%,Ni~(2+)、Co~(2+)、Mn~(2+)三种离子修饰的PANI电极的催化活性明显提高,DSSCs的效率分别为4.70%、4.57%和3.94%。然而,Cu~(2+)离子掺杂则会降低PANI的催化活性。催化活性的差异是由于金属离子与PANI不同的配位构型所造成。采用化学法合成的PANI的催化活性较低,电池效率仅为1.94%。Mn~(2+)、Ni~(2+)和Co~(2+),掺杂同样可提高PANI的催化活性,电池效率分别达到4.41%、2.36%、2.10%。Cu~(2+)掺杂则使电池效率下降为1.41%。为了提高电极的导电性,制备了MWCNT PANI以及Graphene-PANI复合型对电极。研究证明复合了MWCNT或Graphene的电极的催化活性明显升高。基于Ni~(2+),Co~(2+)掺杂MWCNT PANI对电极的电池效率提高到6.00%和5.75%;基于Mn~(2+),Co~(2+)掺杂Graphene PANI对电极提高到5.38%和4.65%;2)本文还考察了乙二胺四乙酸二钠、灵芝多糖和十二烷基硫酸钠等表面活性剂修饰对化学方法合成的PANI催化性能的影响。实验结果显示,表面活性剂修饰可明显改变PANI的电极形貌。乙二胺四乙酸二钠修饰的PANI电极表面微观结构为珊瑚状;灵芝多糖修饰的PANI电极表面则由微小颗粒堆积而成;十二烷基硫酸钠修饰PANI电极表面呈典型的棒状结构。不同的电极形貌导致了PANI催化活性的不同,以乙二胺四乙酸二钠、灵芝多糖和十二烷基硫酸修饰的PANI为对电极的电池效率分别为2.51%、2.69%和4.25%,均高于以不经修饰的PANI为对电极的电池效率(2.29%)。综上所述,Ni~(2+)、Co~(2+)和Mn~(2+)掺杂能不同程度的提高PANI对电极的催化活性。通过MWCNT、Graphene复合或表面活性剂修饰均可进一步提高PANI的催化性能。本文研究的导电聚合物非Pt电极材料有利于降低DSSCs的成本,提高其在各种光伏器件中的竞争力。
[Abstract]:Pair electrode is an important component of dye sensitized solar cells (DSSCs), which plays the role of external circuit electron transfer and catalytic regeneration redox pair. Platinum (Pt) is one of the most effective catalytic materials for electrode. Therefore, all kinds of non-Pt electrode materials have become the focus of research. Such as carbon materials, transition metal compounds, organic conductive polymers. Conductive polymers have the advantages of simple synthesis, abundant raw materials, strong plasticity, which is beneficial to reduce the cost of DSSCs, and is suitable for industrial production of .1) in this paper, the electrochemistry and chemical methods are used to synthesize conductive polymer Polyaniline (pani). The effects of transition metal ion doping and surfactant modification on their catalytic properties were investigated. It was found that the catalytic activity of pani electrode modified with Ni ~ (2) Co ~ (2) O ~ (2) O ~ (2) and Ni ~ (2) O ~ (2) mn ~ (2) was 4.70% and 3.94%, respectively. However, doping with Cu2 ions will decrease the catalytic activity of pani. The difference in catalytic activity is due to the different coordination configurations of metal ions and pani. The catalytic activity of pani synthesized by chemical method is relatively low, and the efficiency of the battery is only 1.94. Mn2 + Ni2 and Co2. Doping can also improve the catalytic activity of pani. The efficiency of the battery reached 4.41% 2.36% 2.10%. Cu2 doping decreased the efficiency of the battery to 1.41l. In order to improve the conductivity of the electrode, MWCNT and Graphene-PANI composite counter electrodes were prepared. The results showed that the catalytic activity of the electrode with MWCNT or Graphene was significantly increased. The battery efficiency of electrode was increased to 6.00% and 5.75 based on Ni ~ (2) Co ~ (2) doped MWCNT / pani and Mn2 / Co ~ (2) doped Graphene / pani pair electrode to 5.38% and 4.65% respectively. Effects of modified surfactants such as Ganoderma lucidum polysaccharides and sodium dodecyl sulfate on the catalytic properties of pani synthesized by chemical method. The experimental results show that surfactant modification can obviously change the morphology of pani electrode. The surface microstructure of pani electrode modified by ethylenediamine tetraacetate disodium acetate was coral, the surface of pani electrode modified by Ganoderma lucidum polysaccharide was piled up by tiny particles, and the surface of pani electrode modified by sodium dodecyl sulfate showed typical rod-like structure. Different electrode morphology resulted in different catalytic activity of pani, and disodium ethylenediamine tetraacetate, The cell efficiency of pani modified with Ganoderma lucidum polysaccharide and dodecyl sulphuric acid was 2.51% and 4.25%, respectively, which was higher than that of unmodified pani (2.29%). In conclusion, the doping of Ni ~ (2) Co ~ (2) and mn ~ (2) can improve the catalytic activity of pani to different extent. The catalytic performance of pani can be further improved by MWCNT- Graphene composite or surfactant modification. The conductive polymer non-Pt electrode materials studied in this paper can reduce the cost of DSSCs and improve their competitiveness in various photovoltaic devices.
【学位授予单位】：河北师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TM914.4

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