π桥中不同吸电子基团对三苯胺-氰基丙烯酸类染料敏化太阳能电池性能影响的理论研究

doi:10.7503/cjcu20150094

摘要/Abstract

摘要：

采用密度泛函理论和含时密度泛函理论计算了染料的紫外-可见吸收光谱、电子注入驱动力、半导体导带能级移动量以及染料与碘的相互作用能等一系列评价电池性能的理论参数, 以解释在π桥上引入不同吸电子基团导致三苯胺-氰基丙烯酸基染料敏化太阳能电池光电转换效率降低的原因. 结果表明, 在染料π桥上引入吸电子基团虽可以在一定程度上改善吸收光谱, 但同时也引入了额外的与电解质中碘相互作用的位点, 加快了与电解质之间的复合速率, 影响了电子注入驱动力, 最终导致电池光电转换效率降低. 因此, 在设计高效光敏染料时除了考虑吸收光谱外, 也应考虑染料与电解质之间的复合以及电子注入驱动力这2个影响电池性能的关键因素.

关键词: 染料敏化太阳能电池, 密度泛函理论, 吸电子基团, 电子复合, 电子注入驱动力

Abstract:

We performed this work in order to rationalize the negative effect of introducing different electron-withdrawing groups in phenylene-based π-spacers on the performance of dye-sensitized solar cells based on five organic dyes consisting of triphenylamine as donor and cyanoacrylic acid as acceptor. UV-absorption spectrum, the electron injection driving force, the shift of the conduction band energy level and the interaction energy of dye-I₂ and so on, were carried out with density functional theory(DFT) and time-dependent DFT, which are associated with the performance of cell. The results reveal that charge recombination between injected electrons and iodine as well as the electron injection driving force limit the open-circuit photovoltage and the short-circuit current density, respectively, eventually led to the reduce of conversion efficiency. Therefore, in design and development more efficient dyes in future, except for considering the absorption spectrum, the interaction between dyes and I₂and the electron injection efficiency should be taken into account as the critical factors for the efficiency of dye-sensitized solar cell(DSSC).

Key words: Dye-sensitized solar cell, Density functional theory, Electron-withdrawing group, Charge recombination, Electron injection driving force

中图分类号:

O641

TrendMD:

顾冬梅, 张建钊, 张吉, 李海斌, 耿允, 苏忠民. π桥中不同吸电子基团对三苯胺-氰基丙烯酸类染料敏化太阳能电池性能影响的理论研究. 高等学校化学学报, 2015, 36(7): 1344.

GU Dongmei, ZHANG Jianzhao, ZHANG Ji, LI Haibin, GENG Yun, SU Zhongmin. Different Electron-withdrawing Groups in π Spacers Effect on the Performance of Dye-sensitized Solar Cells Based on Triphenylamine-cyanoacrylic Acid Dyes^†. Chem. J. Chinese Universities, 2015, 36(7): 1344.

图/表 6

Fig.1 Molecular structures of dyes 1—5

Fig.2 Total(a) and Partial(b) density of state(DOS) for dye 1 adsorbed on (TiO2)38 clusterThe dash line intercepts with the energy axis correspond to calculated ECB edges.

Fig.3 Optimized molecular structures of the dye-I2 adducts with the corresponding interaction energies and the distances to TiO2 surface

Table 1 Computed maximum absorption wavelengths(λmax), the molar absorption coefficient(ε), and the nature of the transitions of dyes 1—5 corresponding to S0 →S1 in CH2Cl2 solution by TD-PCM-CAM-B3LYP/6-31G* method based on B3LYP/6-31G* geometries, and the electron injection driving force(ΔGinj)

Dye	State	Main configuration^a	λ_max/nm(eV)	ε^b/ (L·mol^-1·cm^-1)	λ_max/ nm(eV)^[36]	ΔG_inj/eV
1	S₀→S₁	HOMO→LUMO(76%), HOMO-1→LUMO(14%)	426(2.91)	137506	438(2.33)	1.20
2	S₀→S₁	HOMO→LUMO(78%), HOMO-1→LUMO(12%)	451(2.75)	128008	441(2.29)	0.96
3	S₀→S₁	HOMO→LUMO(78%), HOMO-1→LUMO(12%)	451(2.75)	129357	444(2.28)	0.95
4	S₀→S₁	HOMO→LUMO(71%), HOMO-1→LUMO(13%)	417(2.97)	108957	425(2.34)	1.23
5	S₀→S₁	HOMO→LUMO(82%), HOMO-1→LUMO(10%)	480(2.58)	122658	500(2.11)	0.73

Fig.4 Calculated absorption spectra of the dyes 1—5(a—e) in CH2Cl2 solution at TD-CAM-B3LYP/6-31G*/PCM level of theory

Fig.5 Schematic representation of calculated the ground state oxidation potentials(Edye) and the excited(Edye*) state oxidation potential values of dyes 1—5

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