含噻吩的光电转换有机功能半导体的合成与表征
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摘要
金属钌配合物染料在染料敏化太阳能电池中已经取得了超过11%的转换效率,但是由于其成本较高,会对环境造成污染,因此不能大规模应用。而纯有机染料由于具有高摩尔消光系数、低成本等优点,有望应用到染料敏化太阳能电池中,成为目前研究的重点和热点,代表了今后染料的发展方向。
参照染料敏化太阳能电池对染料的要求以及最新的发展趋势,我们设计出了具有D-π-A结构的纯有机染料C201和C203,并且通过Suzuki Coupling、Vilsmeier-Haak反应和Knoevenagel Condensation反应合成所设计的染料,并利用紫外吸收、方波伏安、核磁等测试手段对其结构及性能进行了表征与测试。结果表明,这两种染料具有高摩尔消光系数,合适的氧化还原电位。标准模拟太阳光下进行测试,在以1.0 mol/L DMⅡ,30 mmol/L I_2,0.1 mol/LGNCS,0.5 mol/L TBPY作电解质的器件中C201和C203分别获得了7.8%、8.0%的电池效率,在以DMⅡ/EMⅡ/EMITCB/I_2,NBB/GNCS(12/12/16/1.67/3.33/0.67)作电解质的器件中均获得了7.0%的转换效率。经过1000h测试,器件各项参数几乎不变,染料显示了良好的热稳定性、光稳定性。在全固态器件中,C201获得了4.7%的电池效率,这是纯有机染料在全固态电池中取得的较高效率。C203分子中的并三噻吩结构,使其在以乙腈体系做电解质的器件中,溶剂化效应较小,在器件中有良好的稳定性,不容易脱附。
此外,为了研究D-π-A结构的纯有机染料中给电子体(D)对吸收光谱的影响,我们设计并合成出了染料C202和C206。将C201、C202和C206的紫外吸收光谱进行比较,结果表明,在给电子体上引入强推电子基团,可以有效的促使染料的吸收光谱红移,而电子给体上的支链对吸收光谱几乎不产生任何影响,仅仅能增大染料分子的溶解性。
Although,the cells employ ruthenium polypyridyl complexes as charge-transfer sensitizers,yielding over 11%solar-to-electric power conversion efficiencies under AM1.5 G sunlight,the ruthenium polypyridyl complex can not be used widely due to its high-cost and pollution.Organic dyes are promising for application in DSC in that they have much higher molar extinction coefficients and lower cost than those for ruthenium polypyridyl complexes,which are becoming more and more polular and chart a new direction.
According to the demand of dye-sensitized solar cells and the tendency of development,we designed two organic dyes coded C201 and C203 which have the D-π-A structure.These sensitizers were synthesized in three steps:Suzuki Coupling,Vilsmeier-Haak reaction and Knoevenagel Condensation.The performance and structure of the two dyes were investigated by UV-Vis, square-wave voltammetry and NMR,and the data show that C201 and C203 have high molar extinction coefficients and suitable redox potentials.These dyes have achieved 8.0%,7.8%power-conversion efficiency(η) respectively,with 1.0 M DMⅡ,30 mMⅠ_2,0.1 M GNCS,0.5 M TBPY in AN/VN(85/15,v/v) as electrolyte under AM1.5 G full sunlight,and 7.0%with DMⅡ/ EMⅡ/ EMITCB /Ⅰ_2/NBB / GNCS(12 / 12 / 16 / 1.67 / 3.33 / 0.67) as electrolyte.After a 1000 h aging test, the data of devices performance only changed a little,it is impressive that the high efficiency DSC with all-organic sensitizers have showed an excellent stability measured under the dual stress of thermal stress and light-soaking.Furthermore, for the first time we have achieved 4.7%efficiency for all-solid-state dye-sensitized solar cells based on a metal-free organic dye C201.C203 has a low free energy of salvation due to its fused dithionothiophene,eliminating the dye-desorption during the long-term device operation.
We designed and synthesized two organic dyes coded C202 and C206 in order to study how the donor impact the electronic absorption spectra.Through comparing the UV-absorption spectra of C201,C202 and C206,we got a conclution that the electron donating group would make the absorption red-shift, meanwhile,the long branches can improve the dissolvability of dye,having little impact to the absorption.
参照染料敏化太阳能电池对染料的要求以及最新的发展趋势,我们设计出了具有D-π-A结构的纯有机染料C201和C203,并且通过Suzuki Coupling、Vilsmeier-Haak反应和Knoevenagel Condensation反应合成所设计的染料,并利用紫外吸收、方波伏安、核磁等测试手段对其结构及性能进行了表征与测试。结果表明,这两种染料具有高摩尔消光系数,合适的氧化还原电位。标准模拟太阳光下进行测试,在以1.0 mol/L DMⅡ,30 mmol/L I_2,0.1 mol/LGNCS,0.5 mol/L TBPY作电解质的器件中C201和C203分别获得了7.8%、8.0%的电池效率,在以DMⅡ/EMⅡ/EMITCB/I_2,NBB/GNCS(12/12/16/1.67/3.33/0.67)作电解质的器件中均获得了7.0%的转换效率。经过1000h测试,器件各项参数几乎不变,染料显示了良好的热稳定性、光稳定性。在全固态器件中,C201获得了4.7%的电池效率,这是纯有机染料在全固态电池中取得的较高效率。C203分子中的并三噻吩结构,使其在以乙腈体系做电解质的器件中,溶剂化效应较小,在器件中有良好的稳定性,不容易脱附。
此外,为了研究D-π-A结构的纯有机染料中给电子体(D)对吸收光谱的影响,我们设计并合成出了染料C202和C206。将C201、C202和C206的紫外吸收光谱进行比较,结果表明,在给电子体上引入强推电子基团,可以有效的促使染料的吸收光谱红移,而电子给体上的支链对吸收光谱几乎不产生任何影响,仅仅能增大染料分子的溶解性。
Although,the cells employ ruthenium polypyridyl complexes as charge-transfer sensitizers,yielding over 11%solar-to-electric power conversion efficiencies under AM1.5 G sunlight,the ruthenium polypyridyl complex can not be used widely due to its high-cost and pollution.Organic dyes are promising for application in DSC in that they have much higher molar extinction coefficients and lower cost than those for ruthenium polypyridyl complexes,which are becoming more and more polular and chart a new direction.
According to the demand of dye-sensitized solar cells and the tendency of development,we designed two organic dyes coded C201 and C203 which have the D-π-A structure.These sensitizers were synthesized in three steps:Suzuki Coupling,Vilsmeier-Haak reaction and Knoevenagel Condensation.The performance and structure of the two dyes were investigated by UV-Vis, square-wave voltammetry and NMR,and the data show that C201 and C203 have high molar extinction coefficients and suitable redox potentials.These dyes have achieved 8.0%,7.8%power-conversion efficiency(η) respectively,with 1.0 M DMⅡ,30 mMⅠ_2,0.1 M GNCS,0.5 M TBPY in AN/VN(85/15,v/v) as electrolyte under AM1.5 G full sunlight,and 7.0%with DMⅡ/ EMⅡ/ EMITCB /Ⅰ_2/NBB / GNCS(12 / 12 / 16 / 1.67 / 3.33 / 0.67) as electrolyte.After a 1000 h aging test, the data of devices performance only changed a little,it is impressive that the high efficiency DSC with all-organic sensitizers have showed an excellent stability measured under the dual stress of thermal stress and light-soaking.Furthermore, for the first time we have achieved 4.7%efficiency for all-solid-state dye-sensitized solar cells based on a metal-free organic dye C201.C203 has a low free energy of salvation due to its fused dithionothiophene,eliminating the dye-desorption during the long-term device operation.
We designed and synthesized two organic dyes coded C202 and C206 in order to study how the donor impact the electronic absorption spectra.Through comparing the UV-absorption spectra of C201,C202 and C206,we got a conclution that the electron donating group would make the absorption red-shift, meanwhile,the long branches can improve the dissolvability of dye,having little impact to the absorption.
引文
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