聚合物光伏器件和染料敏化太阳能电池柔性对电极的制备与研究
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摘要
本论文介绍了本体异质结型聚合物太阳能电池(PSCs)器件和染料敏化太阳能电池(DSSCs)对电极的最新进展。本体异质结型聚合物太阳能电池的给体与受体的界面形态是影响能量转换效率的一个重要因素。因此,本论文研究了光活性层的相态结构与聚合物PSCs器件的光伏性能之间的关系,同时制备了效率相对较高的双给体聚合物太阳能电池器件。对电极是影响染料敏化太阳能电池光电转换效率以及制备成本的关键因素之一,但是昂贵的铂对电极限制了DSSCs的大规模应用,为此,本研究制备出了高效的柔性炭气凝胶对电极以取代铂对电极。其主要研究内容如下:
1.制备并优化了以(苯乙撑-三噻吩)共聚物为给体,PCBM为受体的聚合物太阳能电池器件,并研究了给体与受体在不同比例混合时的活性层的微相分离结构;以具有给电子支链的聚合物和吸电子支链的聚合物共同作为电子给体材料,用于制备PSCs器件,以提高激子的寿命和传输长度,从而提高PSCs的光电转换效率。结果表明,以单一聚合物制备的器件的能量转换效率分别为1.75%和1.49%,而以两种聚合物同时作为给体的器件,在没有经过高温退火的条件下,其能量转换效率效率达到了1.97%。
2.分别以炭气凝胶、炭黑和活性炭在不锈钢网基底上制备了柔性的染料敏化太阳能电池对电极,通过扫描电镜、比表面积、孔径分布、电化学阻抗和光伏性能测试来研究对电极的光物理与光化学性质。结果表明,具有较高比表面积的中孔炭气凝胶具有远比炭材料如炭黑、石墨等更好的催化还原活性,其催化活性甚至还超过了比表面积是两倍于炭气凝胶的活性炭制备的对电极,这说明炭气凝胶的中孔结构和高孔隙率更有利于I_3~-在电解质和对电极界面处的扩散,从而提高I_3~-在对电极上的还原速度。在相同实验条件下,以铂对电极制备的DSSCs的能量转换效率为9.14%,开路电压为0.74V,而以炭气凝胶对电极制备的DSSCs的能量转换效率为9.43%,开路电压达到了0.84V。这表明炭气凝胶柔性对电极在染料敏化太阳能电池中有着很好的潜在应用前景。
In this dissertation, the research progress in bulk-heterojunction polymer solar cell (PSCs) and the counter electrode (CE) for dye-sensitized solar cells (DSSCs) were introduced systematically. The interphase morphology of the donor and acceptor is a vital ingredient to affect the power conversion efficiency (PCE) of bulk-heterojunction polymer solar cells. In this study, the relationship between the interphase morphology of photovoltaic active layer based on a phenyleneviny-alt-trithiophene copolymer and the photovoltaic performance was studied, and a high performance PSCs device based on double donors was fabricated. As one of the indispensable components in DSSCs, CE should be low cost and high performance. However, platinum CE is not an economic way for mass production. In the study, high peformance flexible carbon aerogel CE was prepared as a low cost substitute for platinum counter electrode. The main study results are as follows:
1. PSCs devices were fabricated and optimized with a phenyleneviny-alt-trithiophene copolymer as electron donor, and PCBM as electron acceptor. The microphase separation of the photovoltaic active layer with different weigh ratio of donor and acceptor was discussed. Two conjugated polymers with electron-withdrawing side chain and electron-donating side chain were blended in the photovoltaic active layer as electron donor materials to improve exciton life time and exciton diffusion length. The result indicated that the PCE of the PSCs devices based on P2 and P3 was 1.75% and 1.49%, respectively. Whereas, the PCE of PSC device with double donors reached 1.97% without any annealed procedure.
2. High efficiency DSSCs were fabricated with carbon aerogel, carbon black and active carbon CEs on flexible stainless steel mesh, and the electrocatalytic activity of these flexible carbon CEs was investigated. The photophysical and photochemical were investigated by scanning electron photomicrograph, BET specific surface area, pore size distribution, electrochemical impedance and photovoltaic properties in detail. The results indicate that catalytic reduction activity of carbon aerogel with high specific surface area is superior to carbon black and graphite. Though the SBET of active carbon is twice larger than that of carbon aerogel, the cell with the carbon aerogel CE shows higher short-circuit photocurrent and conversion efficiency. It indicates that the mesopore structure and the large mesopore volume of carbon aerogel facilitate the diffusion of I_3~- ions at the interface of electrolyte and the CE. In the same conditions, the PCE of the DSSC based on Pt CE reached 9.14% and Voc was 0.74V. However, that based on carbon aerogel reached 9.43%, and Voc was 0.84V. It suggests that flexible carbon aerogel CE has strong potential for high performance DSSCs.
1.制备并优化了以(苯乙撑-三噻吩)共聚物为给体,PCBM为受体的聚合物太阳能电池器件,并研究了给体与受体在不同比例混合时的活性层的微相分离结构;以具有给电子支链的聚合物和吸电子支链的聚合物共同作为电子给体材料,用于制备PSCs器件,以提高激子的寿命和传输长度,从而提高PSCs的光电转换效率。结果表明,以单一聚合物制备的器件的能量转换效率分别为1.75%和1.49%,而以两种聚合物同时作为给体的器件,在没有经过高温退火的条件下,其能量转换效率效率达到了1.97%。
2.分别以炭气凝胶、炭黑和活性炭在不锈钢网基底上制备了柔性的染料敏化太阳能电池对电极,通过扫描电镜、比表面积、孔径分布、电化学阻抗和光伏性能测试来研究对电极的光物理与光化学性质。结果表明,具有较高比表面积的中孔炭气凝胶具有远比炭材料如炭黑、石墨等更好的催化还原活性,其催化活性甚至还超过了比表面积是两倍于炭气凝胶的活性炭制备的对电极,这说明炭气凝胶的中孔结构和高孔隙率更有利于I_3~-在电解质和对电极界面处的扩散,从而提高I_3~-在对电极上的还原速度。在相同实验条件下,以铂对电极制备的DSSCs的能量转换效率为9.14%,开路电压为0.74V,而以炭气凝胶对电极制备的DSSCs的能量转换效率为9.43%,开路电压达到了0.84V。这表明炭气凝胶柔性对电极在染料敏化太阳能电池中有着很好的潜在应用前景。
In this dissertation, the research progress in bulk-heterojunction polymer solar cell (PSCs) and the counter electrode (CE) for dye-sensitized solar cells (DSSCs) were introduced systematically. The interphase morphology of the donor and acceptor is a vital ingredient to affect the power conversion efficiency (PCE) of bulk-heterojunction polymer solar cells. In this study, the relationship between the interphase morphology of photovoltaic active layer based on a phenyleneviny-alt-trithiophene copolymer and the photovoltaic performance was studied, and a high performance PSCs device based on double donors was fabricated. As one of the indispensable components in DSSCs, CE should be low cost and high performance. However, platinum CE is not an economic way for mass production. In the study, high peformance flexible carbon aerogel CE was prepared as a low cost substitute for platinum counter electrode. The main study results are as follows:
1. PSCs devices were fabricated and optimized with a phenyleneviny-alt-trithiophene copolymer as electron donor, and PCBM as electron acceptor. The microphase separation of the photovoltaic active layer with different weigh ratio of donor and acceptor was discussed. Two conjugated polymers with electron-withdrawing side chain and electron-donating side chain were blended in the photovoltaic active layer as electron donor materials to improve exciton life time and exciton diffusion length. The result indicated that the PCE of the PSCs devices based on P2 and P3 was 1.75% and 1.49%, respectively. Whereas, the PCE of PSC device with double donors reached 1.97% without any annealed procedure.
2. High efficiency DSSCs were fabricated with carbon aerogel, carbon black and active carbon CEs on flexible stainless steel mesh, and the electrocatalytic activity of these flexible carbon CEs was investigated. The photophysical and photochemical were investigated by scanning electron photomicrograph, BET specific surface area, pore size distribution, electrochemical impedance and photovoltaic properties in detail. The results indicate that catalytic reduction activity of carbon aerogel with high specific surface area is superior to carbon black and graphite. Though the SBET of active carbon is twice larger than that of carbon aerogel, the cell with the carbon aerogel CE shows higher short-circuit photocurrent and conversion efficiency. It indicates that the mesopore structure and the large mesopore volume of carbon aerogel facilitate the diffusion of I_3~- ions at the interface of electrolyte and the CE. In the same conditions, the PCE of the DSSC based on Pt CE reached 9.14% and Voc was 0.74V. However, that based on carbon aerogel reached 9.43%, and Voc was 0.84V. It suggests that flexible carbon aerogel CE has strong potential for high performance DSSCs.
引文
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