碱金属碘化物与冠醚或穴醚的配合物中I3-和I-的氧化还原行为及其在染料敏化纳米薄膜太阳电池中的应用研究

本文利用超微铂电极和循环伏安法研究了在碱金属碘化物与冠醚或穴醚配合物的3-甲氧基丙腈(MePN)溶液中I₃^-和I^-的氧化还原行为。发现I₃^-和I^-在其中的表观扩散系数与阳离子有关，且I₃^-的表观扩散系数符合以下规律：1,2-二甲基-3-丙基咪唑阳离子(DMPI⁺)> Na(¯¯15-C-5]⁺ > K(¯¯18-C-6]⁺ > Na(¯¯2.2.1-cryptand]⁺，I^-的表观扩散系数则为：Na(¯¯2.2.1-cryptand]⁺> Na(¯¯15-C-5]⁺ ≈K(¯¯18-C-6]⁺> DMPI⁺。比较了由上述配合物和1,2-二甲基-3-丙基咪唑碘(DMPII)组成的染料敏化纳米薄膜太阳电池(DSC)的光伏性能，结果表明由上述配合物组成的DSC，其短路电流略高于DMPII，填充因子略低于DMPII，这与I^-和I₃^-在其中的表观扩散系数的大小是相一致的。此外，电解质溶液中的溶剂对DSC的光电转换效率也有较大影响，以MePN为溶剂，含DMPII的DSC的光电转换效率要高于K(¯¯18-C-6]I，而以乙腈为溶剂，两者的光电转换效率并没有明显的差别。

I−3/I− Redox Behavior of Alkali‐metal Iodide Complexes with Crown Ether/Cryptand Macrocycles and Their Applications to Dye‐sensitized Solar Cells

In this article, the I^?₃/I^? redox behavior in 3‐methoxypropionitrile (MePN) containing alkali‐metal iodide com‐plexes with crown ether and cryptand macrocycles was studied by cyclic voltammetry. It was found that the apparent diffusion coefficient D values of triiodide and iodide ions correlate with cations. D values of triiodide follow the order: 1,2‐dimethyl‐3‐propylimidazolium cation (DMPI⁺)>Na?15‐C‐5]⁺ (the mathematical symbol of inclusion, ?, was used to indicate Na⁺ included in 15‐C‐5)>K?18‐C‐6]⁺>Na?2.2.1‐cryptand]⁺ and those of iodide ions follow the order: Na?2.2.1‐cryptand]⁺>Na?15‐C‐5]⁺ ≈K?18‐C‐6]⁺ >DMPI⁺. The photovoltaic performances of dye‐sensitized solar cells (DSC) with these complexes were compared with those containing 1,2‐dimethyl‐3‐propylimidazolium iodide (DMPII) in MePN. It shows that DSC with these complexes gave a little higher short photocurrent intensity and lower fill factor than those with DMPII, which is consistent with D values of triiodide and iodide ions. Moreover, solvents played an important role for the photo‐electric conversion efficiency of DSC. The photo‐electric conversion efficiency of DSC with DMPII is higher than that with K?18‐C‐6]I in MePN, while in ACN, it shows a little difference.