联级供电子光敏染料用于染料敏化太阳能电池的研究
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摘要
本论文设计合成了以二甲胺-三苯胺和咔唑(三苯胺)-咔唑为联级供电子基的两类光敏染料应用于染料敏化纳米晶太阳能电池(DSSC)中,利用质谱、核磁共振氢谱对这些化合物结构进行表征,并对染料的光物理、电化学性能及其在纳米TiO_2电极上的光电转换性能方面进行了测试研究。
将二甲胺-三苯胺类联级光敏染料应用于DSSC中进行光敏化性能研究。在AM1.5(100 mW cm-2)模拟太阳光的照射下,引入一个二甲胺的联级染料N-TPA1的敏化电池效率(η)为2.06%,与单级三苯胺染料相比降低0.13%,以罗丹宁乙酸为吸电子基的染料N-TPA2电池效率为1.60%。在优化试验中发现二甲胺的引入使得染料在TiO_2表面发生聚集作用。对染料结构的密度泛函理论计算(DFT)证明了N-TPA1的LUMO电子集中在氰基乙酸基团上,N-TPA2的LUMO电子集中在罗丹宁构架内。由于罗丹宁乙酸基团的羰基与五元环构架间隔一个亚甲基,使得LUMO电子分布距离吸附基团(-COOH)远,阻碍电子经由羰基注入TiO_2导带,这是N-TPA2的敏化电池效率比N-TPA1低的原因之一。
将咔唑(三苯胺)-咔唑类联级光敏染料应用于DSSC中进行光敏化性能研究。在AM 1.5(100 mW cm-2)模拟太阳光的照射下,引入一个三苯胺基团的联级染料TCB的敏化电池单色光光电转换效率(IPCE)在460 nm处最大值达到60%,在400～500 nm区域IPCE值超过50%,电池效率达到2.47%,达到相同条件下N719染料敏化电池效率的一半。对染料结构的密度泛函理论计算(DFT)证明了染料的LUMO电子分布距离吸附基团(-COOH)近,能够实现染料分子的LUMO与TiO_2的3d轨道(导带)发生电子云重叠,促进电子的注入。将CCB染料应用于Br_3~-/Br~-电解质敏化电池,开路电压可达1.03 V,是目前已知的最高开路电压,相同条件下,应用于I_3~-/I~-电解质的开路电压为0.65 V。该类化合物紫外-可见吸收谱带在350～500 nm范围内,未能充分利用太阳光,这是此类染料的光电性能低于N719染料的一个重要原因。
In this thesis,two series of the linking donor dyes have been designed and synthesized as sensitizers for the application in the dye-sensitized nanocrystalline solar cell(DSSC).The linking donor are dimethylamine-triphenylamine and carbazole(triphenylamine)-carbazole. The structures of the dyes have been characterized by mass spectra(MS)and proton nuclear magnetic resonance(1H NMR)technology.The photophysical,photoelectrocheimical properties and the performance on DSSC of the dyes are studied.
Dimethylamine-triphenylamine dyes are used in DSSC.Under simulated AM 1.5 (100mW cm-2)irradiation,a solar energy-to-electricity conversion efficiency(η)of 2.06%is obtained based on N-TPA1 with introducing a dimethylamine moiety,which has an decrease 0.13%inη,compared with triphenylamine dye.Under the same experimental conditions, N-TPA2 givesηof 1.60%with introducing rhodanine-3-acetic acid as electron-withdrawing part.Dimethylamine will enhance aggregation of a dye on TiO_2 surface.Density functional theory(DFT)calculations are performed for geometry optimization.The LUMO electron density geometry distribution of N-TPA1 is located on the cyanoacrylic group which favour electron injection,but for N-TPA2 it is mainly concentrated on the rhodanine framework,and resulting in the position of LUMO isolated from the -COOH anchoring group due to the presence of the -CH_2- group.Consequently,the N-TPA2 dye prevents electrons from effectively injecting into the TiO_2 conduction band via the carboxyl group.This is an important reason for the photoelectro peoperties of N-TPA2 inferior to N-TPA1.
Carbazole(triphenylamine)-carbazole dyes are used in DSSC.Under simulated AM 1.5 (100mW cm-2)irradiation,the highest IPCE value for DSSC based on TCB with introducing a triphenylamine moiety is 60%at 460 nm and the IPCE value is over 50%from 400 to 500 nm.TCB givesηof 2.47%,which is up to half of N719 measured in the similar condition. Density functional theory(DFT)calculations are conducted and prove that the position of the LUMO is close to the anchoring groups(-COOH)which can enhance the orbital overlap with the 3d orbitals of TiO_2 and favour electron injection.Compared to 0.65 V with I_3~-/I~-,an open-circuit voltage(V_(oc))of 1.03 V is obtained for CCB dye-sensitized solar cell with Br_3~-/ Br~- electrolyte under the same conditions,which is the highest open-circuit voltage known currently.This series of dyes have narrow absorption spectra in the visible region,from 350 to 500 nm,resulting in the weak use of solar energy,which is an important reason for the photoelectro peoperties of the dyes inferior to N719.
将二甲胺-三苯胺类联级光敏染料应用于DSSC中进行光敏化性能研究。在AM1.5(100 mW cm-2)模拟太阳光的照射下,引入一个二甲胺的联级染料N-TPA1的敏化电池效率(η)为2.06%,与单级三苯胺染料相比降低0.13%,以罗丹宁乙酸为吸电子基的染料N-TPA2电池效率为1.60%。在优化试验中发现二甲胺的引入使得染料在TiO_2表面发生聚集作用。对染料结构的密度泛函理论计算(DFT)证明了N-TPA1的LUMO电子集中在氰基乙酸基团上,N-TPA2的LUMO电子集中在罗丹宁构架内。由于罗丹宁乙酸基团的羰基与五元环构架间隔一个亚甲基,使得LUMO电子分布距离吸附基团(-COOH)远,阻碍电子经由羰基注入TiO_2导带,这是N-TPA2的敏化电池效率比N-TPA1低的原因之一。
将咔唑(三苯胺)-咔唑类联级光敏染料应用于DSSC中进行光敏化性能研究。在AM 1.5(100 mW cm-2)模拟太阳光的照射下,引入一个三苯胺基团的联级染料TCB的敏化电池单色光光电转换效率(IPCE)在460 nm处最大值达到60%,在400～500 nm区域IPCE值超过50%,电池效率达到2.47%,达到相同条件下N719染料敏化电池效率的一半。对染料结构的密度泛函理论计算(DFT)证明了染料的LUMO电子分布距离吸附基团(-COOH)近,能够实现染料分子的LUMO与TiO_2的3d轨道(导带)发生电子云重叠,促进电子的注入。将CCB染料应用于Br_3~-/Br~-电解质敏化电池,开路电压可达1.03 V,是目前已知的最高开路电压,相同条件下,应用于I_3~-/I~-电解质的开路电压为0.65 V。该类化合物紫外-可见吸收谱带在350～500 nm范围内,未能充分利用太阳光,这是此类染料的光电性能低于N719染料的一个重要原因。
In this thesis,two series of the linking donor dyes have been designed and synthesized as sensitizers for the application in the dye-sensitized nanocrystalline solar cell(DSSC).The linking donor are dimethylamine-triphenylamine and carbazole(triphenylamine)-carbazole. The structures of the dyes have been characterized by mass spectra(MS)and proton nuclear magnetic resonance(1H NMR)technology.The photophysical,photoelectrocheimical properties and the performance on DSSC of the dyes are studied.
Dimethylamine-triphenylamine dyes are used in DSSC.Under simulated AM 1.5 (100mW cm-2)irradiation,a solar energy-to-electricity conversion efficiency(η)of 2.06%is obtained based on N-TPA1 with introducing a dimethylamine moiety,which has an decrease 0.13%inη,compared with triphenylamine dye.Under the same experimental conditions, N-TPA2 givesηof 1.60%with introducing rhodanine-3-acetic acid as electron-withdrawing part.Dimethylamine will enhance aggregation of a dye on TiO_2 surface.Density functional theory(DFT)calculations are performed for geometry optimization.The LUMO electron density geometry distribution of N-TPA1 is located on the cyanoacrylic group which favour electron injection,but for N-TPA2 it is mainly concentrated on the rhodanine framework,and resulting in the position of LUMO isolated from the -COOH anchoring group due to the presence of the -CH_2- group.Consequently,the N-TPA2 dye prevents electrons from effectively injecting into the TiO_2 conduction band via the carboxyl group.This is an important reason for the photoelectro peoperties of N-TPA2 inferior to N-TPA1.
Carbazole(triphenylamine)-carbazole dyes are used in DSSC.Under simulated AM 1.5 (100mW cm-2)irradiation,the highest IPCE value for DSSC based on TCB with introducing a triphenylamine moiety is 60%at 460 nm and the IPCE value is over 50%from 400 to 500 nm.TCB givesηof 2.47%,which is up to half of N719 measured in the similar condition. Density functional theory(DFT)calculations are conducted and prove that the position of the LUMO is close to the anchoring groups(-COOH)which can enhance the orbital overlap with the 3d orbitals of TiO_2 and favour electron injection.Compared to 0.65 V with I_3~-/I~-,an open-circuit voltage(V_(oc))of 1.03 V is obtained for CCB dye-sensitized solar cell with Br_3~-/ Br~- electrolyte under the same conditions,which is the highest open-circuit voltage known currently.This series of dyes have narrow absorption spectra in the visible region,from 350 to 500 nm,resulting in the weak use of solar energy,which is an important reason for the photoelectro peoperties of the dyes inferior to N719.
引文
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