基于二氧化钛纳米管的染料敏化电池光阳极研究

本文报道了一种基于二氧化钛(TiO₂)纳米管的染料敏化太阳能电池。用二次阳极氧化法在钛箔上生长出高度有序的TiO₂纳米管薄膜, 然后将完整剥落的纳米管薄膜结合TiO₂纳米颗粒的浆料转移到掺杂氟的SnO₂透明导电玻璃(FTO)基底上, 从而获得一种特殊的染料敏化光阳极。对比了不同长度的TiO₂纳米管的电池性能, 发现经TiCl₄处理长度为32.8 μm的TiO₂纳米管对应的电池表现较好的光电转换效率, 达到4.15%。通过X射线衍射分析了高温退火对纳米管晶化结构的影响。电化学阻抗谱分析表明: 光电子传输对光阳极纳米管层厚依赖性强, 随着纳米管长度的增长, 界面电阻呈明显的减小, 这一结果对于理解和进一步改善染料敏化电池光阳极内部电子输运过程具有重要意义。     

Ag2Se量子点共敏化固态染料敏化太阳能电池光电性能研究

采用水相共沉积法制备Ag₂Se量子点(QDs), 并与染料共敏化制备固态染料敏化太阳能电池(DSSCs)。考察了Ag₂Se量子点不同敏化方式(TiO₂/N719/QDs, TiO₂/QDs/N719)及敏化时间(0~5 h)对DSSCs性能的影响。通过透射电子显微镜(TEM)和紫外-可见光谱图(UV-Vis)对Ag₂Se量子点结构及光学性质进行了表征; 采用光调制光电流/电压谱(IMPS/VS)以及交流阻抗谱(EIS)对器件中载流子传输过程进行了研究。TiO₂/QDs/N719的电池器件比TiO₂/ N719/QDs具有更高的单色光量子转化效率(IPCE)及光电转化效率, 这是由于TiO₂/QDs/N719可以吸附更多的量子点和染料。随着Ag₂Se量子点敏化时间的延长, 光电转化效率先提高后降低, 最高达到3.97%。Ag₂Se量子点在器件中起到了阻挡层作用, 可以促进电子传输, 抑制电子-空穴复合。而随着量子点敏化时间超过2 h, 电子陷入陷阱的几率增加, 导致器件的光伏性能下降。     

基于介孔TiO2/石墨烯修饰的TiO2纳米线光阳极的染料敏化太阳能电池

本工作制作了基于介孔TiO₂/石墨烯修饰的TiO₂纳米线光阳极的染料敏化太阳能电池,并进行表征。光阳极结合了介孔TiO₂的高染料吸附率,TiO₂纳米线的高载流子传导率和石墨烯的高电子收获能力等优点,使器件光电转换效率有了很大的提高。制作出的染料敏化太阳能电池光电转换效率高达7.58%,比纯纳米线制作的电池约提高了1.5倍,在拥有相似一维结构的染料敏化太阳能电池中具有较大优势。     

碳掺杂TiO2纳米管电极的简易制备及其光电化学性能

通过阳极氧化方法制备了TiO₂纳米管薄膜, 在NaHCO₃存在下对该薄膜进行热处理得到碳掺杂TiO₂(C-TiO₂)纳米管薄膜, 通过X射线衍射仪(XRD)、扫描电子显微镜(SEM)、X射线光电子能谱(XPS)、紫外-可见漫反射光谱、电化学阻抗谱(EIS)和Mott-Schottky等方法对得到的薄膜进行表征。XRD结果表明C-TiO₂纳米管薄膜中的TiO₂主要为锐钛矿晶型; SEM结果显示薄膜存在纳米管结构; XPS分析表明C-TiO₂纳米管薄膜中的C以替代型掺杂形式进入到TiO₂晶格中; 光电化学性能测试显示, 相对于TiO₂纳米薄膜, C-TiO₂阻抗减小, 平带电位由-0.28 V负移至-0.38 V, 具有更好的紫外-可见光和可见光响应, 紫外-可见光下的光电流是未掺杂的1.7倍。利用阳极氧化的Ti丝作为光阳极和Pt丝作为对电极组装了染料敏化太阳能电池并进行了性能测试, 结果表明, 经过碳掺杂的Ti /TiO₂丝为光阳极电池的短路电流密度和电池效率分别达到0.17 mA/cm²和3.8%, 较未掺杂的Ti/TiO₂丝为光阳极的电池的短路电流密度和电池效率均增大, 表明适量的碳掺杂有利于提高电池效率。     

TiO2纳米晶空洞光阳极在染料敏化太阳能电池中的光电增效性能研究

以含炭微球作为模板,制备了TiO₂纳米晶空洞光阳极用于染料敏化太阳能电池(DSSC),通过调整模板的添加量,实现了空洞数目在光阳极中的调控。利用扫描电子显微镜(SEM)、透射电子显微镜(TEM)和X射线衍射(XRD)分析了样品的形貌和结构。结果表明：基于TiO₂纳米晶空洞的DSSC,在标准太阳光强度(100mW/cm²)辐照下,最佳的短路电流密度(J_sc)可以达到18.31mA/cm²,开路电压(V_oc)为0.701V,填充因子(FF)为0.578,电池效率(PCE)达到7.4%,相比基于TiO₂纳米晶的DSSC 4.4%的电池效率,提高了68.18%,其中J_sc的显著提高是电池效率提升的主要因素。光散射、电子寿命的分析表明,适当的空洞结构可以增加光阳极对可见光的散射作用,通过可见光在空洞结构中的多次反射使染料能被多次激发产生光生电子,从而提升了光捕获效率和电子寿命,最终实现了DSSC性能的提高。     

上转换发光材料La(OH)3∶Er3+/Yb3+的制备及在染料敏化太阳能电池中的应用

针对N719染料仅可吸收可见光这一局限,本研究旨在通过引入上转换发光材料并将其应用于染料敏化太阳能电池的光阳极来拓宽光谱吸收范围,提高光的捕获率,进而达到提高电池光电转换效率的目的。首先,采用水热合成法以不同pH值的先驱体溶液,成功制备了Yb~(3+)/Er~(3+)双掺杂La(OH)_3粉末,然后将适量合成的稀土发光粉掺入TiO_2纳米浆料中,采用刮涂法成膜制备光阳极,并将其组装成染料敏化太阳能电池。研究结果表明,稀土发光粉的加入拓宽了光谱吸收范围,在其掺杂量达到3%时,电池的短路电流密度Jsc提高到17.72mA·cm-2,最终获得了8.3%的光电转换效率。     

TiO2空心微球在NaYF4∶Yb3+,Er3+/商业TiO2染料敏化太阳能电池中的应用

以TiCl₃为钛源,水热法制备高散射性能的锐钛矿TiO₂空心微球。以商业TiO₂(P25)/NaYF₄∶Yb~(³⁺),Er³⁺混合材料为底层薄膜,TiO₂空心微球为反射层组成双层结构光阳极薄膜,优化了太阳能电池性能。结果表明:新型结构的太阳能电池短路光电流(J_sc=16.81mA/cm²)、开路光电压(V_oc=0.78V)、填充因子(FF=0.66)和光电转化效率(η=8.65%),其光电转化效率与纯P25(6.70%)光阳极和P25/NaYF₄∶Yb³⁺,Er³⁺(7.35%)光阳极相比较分别提升了29%和18%。     

基于纳米多孔钛酸锂结构的染料敏化太阳电池复合光阳极研究

本研究探索了具有良好导电性能的多孔钛酸锂结构对传统氧化钛纳米晶光阳极的增强效果。以钛酸四丁酯、氢氧化锂为源, 采用溶胶-凝胶结合溶剂热反应和高温烧结方法, 制备了具有多孔结构的尖晶石型Li₄Ti₅O₁₂纳米粉体; 在表征其结晶性、微观形貌及孔结构的基础上, 将其与TiO₂纳米晶浆料复合, 制备复合光阳极, 并详细考察了钛酸锂掺量、结晶性和孔结构等对电池光电转换性能的影响规律。结果表明: 随热处理温度升高, Li₄Ti₅O₁₂结晶性增强, 晶粒尺寸明显增大, 比表面积下降。掺入Li₄Ti₅O₁₂粉体可以有效提高光阳极膜的染料负载量, 降低TiO₂/染料分子/电解液界面的电子传输阻抗, 从而明显提高复合光阳极的光电流密度(J_sc=13.91 mA/cm²)和开路电压(V_oc =0.8 V)。Li₄Ti₅O₁₂含量为1wt%的复合光阳极电池光电转化效率最好, 达到7.011%, 比纯TiO₂电池(效率: 5.384%)提高30%。     

基于金属网的叠层染料敏化太阳能电池

本文提出了一种新型染料敏化太阳能电池的叠层结构设计, 其中光阳极由导电玻璃上的第一层TiO₂纳米薄膜和不锈钢网上的第二层TiO₂纳米薄膜组成, 不同染料间的负反应相比混染共敏方式少. 此结构中引入的金属网, 减少了导电玻璃的使用片数, 从而减少入射光的损失; 同时也解决了两层不同TiO₂薄膜间的电连接性问题, 并提高电子传输和收集效率. 此叠层电池的光电转换效率达1.96%, 短路电流为8.4mA/cm², 相比相同电池厚度的单层电池, 效率提高约62%. 通过阻抗谱分析了叠层电池内部的电子传输, 给出叠层电池的等效电路图. 此外, 还发现电池厚度的增加及电子在不锈钢网表面的复合对光电性能有显著影响.     

低温制备介孔碳对电极构建的染料敏化太阳电池优化研究

以高比表面积的介孔碳为催化层材料通过低温烧结构建出对电极, 着重优化了其组装的染料敏化太阳电池(DSC)的整体结构和性能. 结果表明: 在碳浆料中添加Triton X100能改善碳颗粒之间以及碳催化层与衬底之间的接触界面, 促使DSC的转换效率从4.50%提升到4.82%, 增幅为7.1%. 随TiO₂薄膜厚度增加, DSC的转换效率先急剧增加, 随后趋于缓和, 其变化趋势是染料吸附量与电子传输路径相互竞争的结果. 在电解质中添加磷酸三丁酯能减小电解质电阻, 促使DSC的转换效率从3.59%提升到4.42%, 增幅为23.1%. 优化后, 介孔碳对电极DSC的转换效率达到4.82%.     

Double-layered TiO2 cavity/nanoparticle photoelectrodes for efficient dye-sensitized solar cells

TiO₂ nanoparticles (NPs) in the size of ~25 nm, namely P25, are very common material as the electron collecting layer in dye-sensitized solar cells (DSSCs). However, the light-scattering improvement of TiO₂ NP photoelectrodes is still a challenge. Here, we built TiO₂ cavities on the top of the TiO₂ NP layer by using carbonaceous microspheres as the template, forming the TiO₂ cavity/nanoparticle (C/NP) photoelectrode for the application in DSSCs. The cavity amount in the TiO₂ C/NP photoelectrode was controlled by adjusting the weight ratio of carbonaceous microspheres. SEM results confirm the successful formation of the double-layered TiO₂ C/NP electrode. J‒V tests show that the optimized TiO₂ C/NP electrode prepared with 25 wt.% carbonaceous microspheres contributes to remarkable improvement of the short-circuit current density (J_sc) and the power conversion efficiency (PCE). The best photovoltaic performance solar cell with the PCE of 9.08% is achieved with the optimized TiO₂ C/NP photoelectrode, which is over 98% higher than that of the TiO₂ NP photoelectrode. Further investigations of UV-vis DRS, IPCE, OCVD, and EIS demonstrate that the competition between light scattering effect and charges recombination in this TiO₂ C/NP photoelectrode is responsible for the PCE enhancement.     

Expanding the spectral response of a dye-sensitized solar cell by applying a selective positioning method

We have developed a facile method to position different dyes (N719 and N749) sequentially in a mesoporous TiO(2) layer through selective desorption and adsorption processes. From the selective removal of the only upper part of the first adsorbed dye, double-layered dye-sensitized solar cells have been successfully achieved without any damage to the dye. From the incident photon-to-current conversion efficiency (IPCE) measurement, the multi-layered dye-sensitized solar cell (MDSSC) was found to exhibit an expanded spectral response for the solar spectrum while maintaining the maximum IPCE value of each single-layered cell. The highest photocurrent density, 19.3 mA cm( - 2), was obtained from the MDSSC utilizing an N719/N749 bi-layered mesoporous TiO(2) film. The power conversion efficiency of 9.8% was achieved from the MDSSC, which is higher than that of single N719-or N749-based cells and cocktail-dyed (a mixture of N719 and N749) cells.     

染料敏化太阳能电池的研究进展

光导电极材料在染料敏化太阳能电池(DSSC)中起到关键作用,直接影响到太阳能电池的总效率,所以一直是DSSC研究的热点.介绍了DSSC的基本工作原理,概述了当前DSSC中最流行的TiO<,2>和ZnO两种薄膜光导电极材料的制备方法,并从结构、工艺和转换效率等方面对染料敏化TiO<,2>薄膜太阳能电池和染料敏化ZnO薄膜太阳能电池进行了介绍和讨论;同时简要介绍了目前研究非常热门的叠层染料敏化太阳电池的研究进程,最后展望了染料敏化太阳能电池的未来发展前景.     

Tuning the dye aerosol impaction and TiO2 nanoparticle stacking structures for High-Efficiency Dye-Sensitized solar cells

The rapid manufacturing of high-efficiency dye-sensitized solar cells (DSSCs) is limited by the slow dye adsorption on TiO₂ nanoparticles (NPs)-accumulated photoelectrode using conventional dip-coating process. Therefore, we aim to accelerate the adsorption of dyes that are attached on TiO₂ NPs by employing an aerosol impactor. Herein the aerosolized dyes are designed to get deposited rapidly on the TiO₂ NPs-accumulated photoelectrode. In addition, to effectively trap the irradiated sunlight in DSSCs, we assemble the photoelectrodes incorporated with bilayered TiO₂ thin films comprising small TiO₂ NPs-based underlayer and large TiO₂ NPs-based overlayer as dye-supporting and light-scattering mediums, respectively. Furthermore, the effects of dye aerosol impaction and TiO₂ stacking structures on the efficiency of DSSCs are examined. The power conversion efficiency (PCE) of DSSCs comprising a N719 dye-supporting layer treated with dip-coating process was determined as ～ 5.67%; however, when the bilayered TiO₂ thin films with an optimized thickness ratio of light-scattering overlayer and dye-supporting underlayer were coated with N719 dyes using dye aerosol impactor, the resulting PCE increased to ～ 7.46%. This suggests that the photovoltaic characteristics of DSSCs can be enhanced considerably using the effective TiO₂ NP stacking structures coated with rapid, uniform, and strong aerosol dye adsorption throughout the TiO₂-based photoelectrodes.     

CdS/TiO2纳米棒阵列复合材料的制备及其光电化学特性

以水热法在氟掺杂的氧化锡透明导电玻璃(FTO)上制备的TiO₂纳米棒阵列为衬底, 通过连续化学水浴沉积(S-CBD)法将CdS量子点 (QDs)沉积在TiO₂纳米棒上, 形成CdS/TiO₂阵列复合材料。分别利用高分辨透射电子显微镜(HRTEM)、 场发射扫描电子显微镜(FESEM)、 X射线衍射(XRD)和紫外可见光谱(UV-vis)等对样品的形貌、 晶型以及光吸收性能进行了表征。结果表明, TiO₂纳米棒阵列长度约为2.9 μm, CdS QDs的尺寸大约在5~9 nm。随着沉积层数的增加, CdS QDs的厚度增加, 同时伴随着光吸收边的红移。通过电流-电压特性曲线对其光电流-电压特性进行了分析, 发现光电流和光电转换效率均呈现出先增大后减小的规律。100 mW/cm²的光照下, 在S-CBD为7层时, 光电流和开路电压最大值分别达到2.49 mA·cm^-2和1.10 V, 而电池的效率达到最大值1.91%。     

N、Fe共掺杂纳米TiO2的制备和性能

以钛酸丁酯为钛源,用醇热法制备了N、Fe单掺杂及共掺杂纳米TiO₂。对样品的晶型结构、表面形貌、比表面积、紫外可见吸收、光致发光和分解水制氢催化性能分别进行了表征。结果表明,在500℃退火的N、Fe共掺杂TiO₂样品均为锐钛矿相棱形纳米颗粒,分散性较好,平均粒径约20 nm;N、Fe共掺杂的摩尔分数分别为5.0%和2.0%时,样品具有良好的可见光吸收活性,对光的吸收从387 nm（未掺杂锐钛矿相TiO₂）红移至510 nm处。主要原因可能是,N和Fe共掺杂在其禁带中产生杂质能级,导致其禁带宽度减小;N、Fe单掺杂及共掺杂改性,有效抑制了电子-空穴的复合,提高了光生载流子的分离效率;在可见光下（λ>400 nm）N、Fe共掺杂TiO₂具有较高的光催化分解水制氢活性,氢气生成速率为299.2μmol·g^-1·h^-1。     

Chemical bath deposition of ZnO nanorods for dye sensitized solar cell applications

ZnO nanorods using various molar concentrations have been synthesized through the chemical bath deposition method. X-ray diffraction result shows that the ZnO nanorods are of hexagonal structure. The morphology of the ZnO nanorods has been examined by scanning electron microscopy. The ZnO nanorods have diameters ranging from 100 to 200 nm and length of 1–3 μm. Dye-sensitized solar cells have been assembled by using ZnO nanorod film photoelectrode sensitized using natural dye extracted from lantana camara as sensitizer. The ZnO nanorods have been used as electrode material to fabricate dye sensitized solar cells which exhibited an efficiency of 0.71 %, the maximum efficiency was obtained for films deposited for 0.07 M concentration.     

Application of TiO2 nanoparticles coated multi-wall carbon nanotube to dye-sensitized solar cells

This study uses the sol-gel method to prepare TiO2 nanoparticle, and further applies TiO2 nanoparticle coating on the surface of the multi-wall carbon nanotube (MWCNT). As a result, TiO2-CNT composite nanoparticles are prepared to serve as photoelectrode material in dye-sensitized solar cell (DSSC). First, after acid treatment of MWCNT is used to remove impurities. Then, the sol-gel method is employed to prepare TiO2-CNT composite nanopowder. X-ray diffraction (XRD) pattern shows that after the TiO2 in TiO2-CNT composite nanopowder has been thermally treated at 450 degrees C, it can be completely changed to anatase phase. Furthermore, as shown from the SEM image, TiO2 has been successfully coated on CNT. The photoelectrode of DSSC is prepared using the electrophoretic deposition method (EPD) to mix the Degassa P25 TiO2 nanoparticles with TiO2-CNT powder for deposition on the indium tin oxide (ITO) conductive glass. After secondary EPD, a thin film of TiO2/CNTs with thickness 17 microm can be acquired. For the prepared TiO2-CNT composite nanoparticles, since MWCNT can increase the short-circuit current density of DSSC, the light-to-electricity conversion efficiency of DSSC can be effectively increased. Experimental results show that the photoelectric conversion efficiency of DSSC using CNT/TiO2 photoelectrode and N719 dye is increased by 41% from the original 3.45% to 4.87%.