【作者】 岳根田；

【导师】 吴季怀；

【作者基本信息】 华侨大学 ， 材料学， 2013， 博士

【摘要】 染料敏化太阳能电池（DSSC）由于具有制备过程简单、成本低、环境友好和光电转换效率高等优点，成为当前新型太阳能电池领域的研究热点。根据该领域研究中存在的关键科学技术问题，本文开展了基于异质结和导电聚合物对电极的染料敏化太阳能电池研究，以达到提高电池效率和降低成本的效果。主要研究内容和结果如下：第一章：较为全面地综述了太阳能电池的国内外研究进展，重点介绍了DSSC的发展、研究现状、基本原理、表征手段和DSSC目前存在的问题，阐述了本论文的研究目的和科学意义。第二章：基于掺氟导电玻璃（FTO）制备非典聚3-己基噻吩/6,6-苯基-C61丁酸甲酯（P3HT/PCBM）异质结杂化太阳能电池（HSC）。紫外-可见光谱表明作为电子给体和受体材料的P3HT和PCBM具有良好的光敏化功能；直接以P3HT/PCBM溶液代替染料和I–/I3–氧化还原电解质作为空穴传输介质，制备出高效率的HSC。在P3HT/PCBM质量比为1:2的优化条件下，获得2.97%的光电转换效率。第三章：以高导电性的聚3,4-乙基二氧噻吩:聚苯乙烯磺酸盐（PEDOT:PSS）作为电子-空穴传输介质，制备FTO/PEDOT:PSS/TiO₂/PCBM:P3HT/Pt异质结固态杂化太阳能电池。在真空环境下120℃热处理PEDOT:PSS膜及电池器件，在标准太阳光照射下获得1.90%的最佳光电性能。第四章：利用P3HT或聚3-辛基噻吩（P3OT）作为空穴传输介质，TiO₂作为紫外光吸收剂和电子导体，首次设计和制备紫外光响应的异质结杂化太阳能电池FTO/TiO₂/P3HT/Pt和FTO/TiO₂/P3OT/Pt。紫外-可见吸收光谱和单色光转换光谱表明TiO₂膜、P3HT/TiO₂膜和P3OT/TiO₂膜在300-400nm都显示了较强的紫外光响应。在100mW·cm^-2紫外光照射下，其光电转换效率分别达到1.28%和1.16%。该电池在暗条件下和紫外光辐照下均具有良好的稳定性，并通过添加无机盐在导电聚合物中优化电池的效能。第五章：热裂解法制备Pt/C60对电极，化学池沉积制备TiO₂-聚（二烯丙基二甲基氯化铵）-碲化镉（TiO₂-PDDA-（CdTe）n）光阳极，并组装CdTe量子点敏化的异质结杂化太阳能电池。对比基于I–/I3–、S2–/Sx和PCBM/P3HT的不同传输电解质制备的器件性能，发现以空穴传输材料和协助敏化剂的PCBM/P3HT制备的电池效率最高。在100mW·cm–2标准太阳光照射下，获得3.40%的光电转换效率。第六章：利用具有高电导率的导电聚合物PEDOT:PSS，制备PEDOT:PSS/C对电极导电浆料，刮涂法制备PEDOT:PSS/C对电极，80℃真空热处理组装的DSSC在100mW·cm^-2模拟太阳光辐照下获得7.61%的光电转换效率。扫描电镜表明PEDOT:PSS/C对电极具有大的比表面积；循环伏安测试、电阻率和电导率的实验证明，PEDOT:PSS/C对电极具有很小的电荷传输电阻和优良的电导率，在电解质I–/I3–体系中具有良好的电化学催化性能。第七章：循环伏安法制备具有低电化学阻抗和高电导率的导电聚合物PEDOT:PSS/聚吡咯（PPy）复合膜，并作为对电极将其应用于DSSC，在标准太阳光照射下，获得7.60%的光电转换效率。PEDOT:PSS/PPy对电极的电子扫描显微镜测试表明其具有高的电化学活性表面积和较大的粗糙面；各种电化学表征表明PEDOT:PSS/PPy对电极具有良好的电催化活性。第八章：采用水热法合成硫化钨（WS2）并成功修饰在多壁碳纳米管（MWCNT），混浆法在导电玻璃基底制备MWCNT-WS2对电极，并首次应用于DSSC。循环伏安和电化学阻抗等广泛的电化学表征表明MWCNT-WS2对电极具有良好的电催化活性和更小的电化学阻抗；研究了MWCNT对对电极电催化活性和DSSC光电性能的影响，发现当MWCNT含量为5wt.%时电催化性能最好。在100mW·cm–2标准太阳光照射下，基于MWCNT-WS2对电极组装的DSSC光电转换效率达到6.41%，开路电压、短路电流和填充因子分别为0.73V、13.51mA·cm^-2和0.65。第九章：总结本论文的主要研究内容和创新点，并对今后的工作作出展望。更多还原

【Abstract】 Dye-sensitized solar cell （DSSC） has been one of the hot-spots in the field ofsolar cells, because of its simple fabrication process, low cost, environmentallyfriendly and high efficiency. According to the problems of key scientific andtechnicol in this filed, the research in dye-sensitized solar cell based on theheterojunction and conducting polymer counter electrodes was carried out in thispaper to improve the performance and reduce the cost of device. There are somemajor works and results in the following:In chapter1, it demonstrated the research progress of DSSCs at home and abroad.The development process, current study situation, fundamentals, charccterization andproblems of the DSSC were described emphatically, and the research purpose andsignificance of the thesis were also illustrated.In chapter2, an iodine/iodide-free and poly （3-hexylthiophene）/6,6-phenyl-C61-butyric acid methyl ester （P3HT/PCBM） heterojunction hybrid solarcell （HSC） was fabricated based on the fluorine-doped tin oxide conductive glasssubstrate （FTO）. The UV-vis spetra showed that the P3HT and PCBM as the electrondonor and acceptor materials had excellent sensitization functions. A HSC with highefficient was fabricated by using P3HT/PCBM as charge carrier transferring mediumto replace dye and I/I3redox electrolyte. Under an optimized condition withP3HT/PCBM mass ratio of1:2, the heterojunction hybrid solar cell achieved alight-to-electric energy conversion efficiency of2.97%.In chapter3, the poly （3,4-ethylenedioxythiophene）:polystyrenesulfonate（PEDOT:PSS） with high conductivity served as electron-hole transporting materialto construct a heterojunction solid-state hybrid solar cell with the structure ofFTO/PEDOT:PSS/TiO₂/PCBM:P3HT/Pt. The PEDOT:PSS film and device wereheated at120℃in vacuum environment, and the heterojunction hybrid solar cellobtained the power conversion efficience of1.90%under a simulated solar light illumination of100mW·cm^-2.In chapter4, an ultraviolet responsive hybrid solar cell based on titaniumdioxide/poly （3-octylthiophene-2,5-diyl）（TiO₂/P3OT） or TiO₂/P3HT heterojunctionwas devised. In the solar cell, TiO₂as an ultraviolet light absorber and electronicconductor, P3OT or P3HT as a hole conductor, the light-to-electric conversion wasrealized by the cooperation between these two components. It could be demonstratedby the UV-vis spectra and IPCE curves that the TiO₂film, the P3HT/TiO₂film, andthe P3OT/TiO₂film all showed wide and strong absorption in300-400nm. UnderUV light irradiation with the intensity of100mW·cm^-2, the light-to-electric energyconversion efficiency of the heterojunction hybrid solar cells with P3HT and P3OTwere1.28%and1.16%, respectively. The stabilities of solar cells based on P3HTand P3OT polymer were measured in dark and UV light soaking, and optimized theperformance of the heterojunction hybrid solar cell by doping inorganic salt in theconductive polymer solution.In chapter5, a novel CdTe quantum dots sensitized heterojunction hybrid solarcell was fabricated with Pt/C60counter electrode and TiO₂–polydimethyldiallylammonium （PDDA）-CdTe photoanode. In this solar cell, the microporous Pt/C60counter electrode was prepared by using a facile thermal decomposition method andthe TiO₂–PDDA–CdTe photoanode was prepared by using chemical bath depositionmethod. When comparing the device with different transferring medium of I/I3,S2/Sx and PCBM/P3HT, significant improvement on the power conservsionefficiency was observed in the device based on PCBM/P3HT, and resulted in a highpower conversion efficiency of3.40%under light irradiation with intensity of100mW·cm–2.In chapter6, a novel counter electrode with high conductivity and excellentelectrochemical catalytic activity for dye-sensitized solar cell was prepared bycoating PEDOT:PSS on FTO at low temperature. The experimental results showedthat DSSC obtained the optimal photoelectric performance for PEDOT:PSS/carboncounter electrode annealed at80℃under vacuum condition. The overall energyconversion efficiency of the DSSC with PEDOT:PSS/carbon counter electrode reached7.61%under a simulated solar light illumination of100mW·cm^-2. Thescanning electron microscopy （SEM） indicated that the PEDOT:PSS/carbon counterelectrode prossessed large specific surface area. It was demonstrated by the cyclicvoltammetry, resistivity and conductivity measurements that the PEDOT:PSS/carboncounter electrode illustrated excellent electrocatalytic activity in the I/I3system.In chapter7, a PEDOT:PSS/polypyrrole （PPy） composite film was preparedand employed as counter electrode in dye-sensitized solar cell by cyclicvoltammetry polymerization method. The power conversion efficiency of the DSSCbased on the PEDOT:PSS/PPy counter electrode obtained7.60%under a simulatedsolar light illumination of100mW·cm^-2. It could be inferred from the SEM that thePEDOT:PSS/PPy film was expected to possess a high effective electrochemicalsurface area and large rough surface. The electrochemical measurements showedthat the PEDOT:PSS/PPy film had a low surface resistance, high conductivity, andexcellent catalytic performance for the I/I3electrolyte.In chapter8, multi-wall carbon nanotubes decorated with tungsten sulfide（MWCNT-WS2） were synthesized by using a hydrothermal method and wasincorporated into a Pt-free DSSC system as counter electrode with doctor blademethod for the first time. Cyclic voltammetry and electrochemical impedancespectroscopy characterizations indicated that the counter electrode had a highcatalytic activity for the reduction of triiodide to iodide and a low charge transferresistance at the electrolyte–electrode interface. The influence of MWCNT contentsto the catalytic activity of counter electrode and performance of the dye-sensitizedsolar cell were discussed, and it was found that the device possessed the optimalperformance with MWCNT ratio of5wt.%. A high power conversion efficiency ofDSSC based on the counter electrode achieved6.41%under a simulated solarillumination of100mW·cm–2, and corresponding to the short-circuit current density（Jsc） of13.51mA·cm–2, the open-circuit voltage （Voc） of0.73V and the fill factor（FF） of0.65, respectively.In chapter9, it gave a summation for the major research and innovation of thethesis, and offered prospects on the future progress of the work.更多还原