TiO2/SnO2复合空心球在染料敏化太阳能电池中的应用

采用模板辅助法制备了SnO2/TiO2复合空心球,样品直径为1.5~4.0μm,比表面积达到了92.9 m^2·g^-1,复合空心球表现出优越的光散射性能.以这种复合空心球作为染料敏化太阳能电池的光阳极,电池的光电转换效率可达到7.72%,高于SnO2微米球(2.70%)和TiO2微米球(6.26%).此外,以锐钛矿型TiO2纳米晶作为底层,SnO2/TiO2复合空心球作为光散射层制备的双层结构光阳极,电池光电转换效率进一步提升至8.43%.     

分级微纳结构TiO2空心球的制备及其在DSSC中的应用

以钛酸四丁酯为钛源,无水乙醇为溶剂,通过碳球模板法制备出直径为200nm、壳厚20～25nm的TiO2空心球（HS）.通过X射线衍射（XRD）、透射电子显微镜（TEM）、扫描电子显微镜（SEM）和N2吸附脱附等对产物的形貌、晶相组成、孔结构和紫外-可见光谱性质进行了表征,结果显示所制备的锐钛矿相TiO2空心微球是由初级结构纳米级TiO2晶粒构成的.将这种TiO2空心球应用于染料敏化太阳电池（DSSC）领域可以提高光阳极对光的散射.通过制备P25/HS-TiO2双层膜电极,相比单纯的P25纳米晶电极（Jsc=13.5mAcm？2,Voc=0.653V,FF=0.53,η=4.95%）可以得到更高的光电转化效率（Jsc=15.79mAcm？2,Voc=0.653V,FF=0.55,η=6.66%）.     

Easily manufactured TiO2 hollow fibers for quantum dot sensitized solar cells

TiO(2) hollow fibers with high surface area were manufactured by a simple synthesis method, using natural cellulose fibers as template. The effective light scattering properties of the hollow fibers, originating from their micron size, were observed by diffuse reflectance spectroscopy. In spite of the micrometric length of the TiO(2) hollow fibers, the walls were highly porous and high surface area (78.2 m(2) g(-1)) was obtained by the BET method. TiO(2) hollow fibers alone and mixed with other TiO(2) pastes were sensitized with CdSe quantum dots (QDs) by Successive Ionic Layer Adsorption and Reaction (SILAR) and integrated as a photoanode in quantum dot sensitized solar cells (QDSCs). High power conversion efficiency was obtained, 3.24% (V(oc) = 503 mV, J(sc) = 11.92 mA cm(-2), FF = 0.54), and a clear correspondence of the cell performance with the photoanode structure was observed. The unique properties of these fibers: high surface area, effective light scattering, hollow structure to facile electrolyte diffusion and the rather high efficiencies obtained here suggest that hollow fibers can be introduced as promising nanostructures to make highly efficient quantum dot sensitized solar cells.     

Improved performance of dye sensitized ZnO nanorod solar cells prepared using TiO2 seed layer

Zinc oxide (ZnO) nanorods of different structures have been grown on indium-doped tin oxide substrates by using TiO₂ as seed layer. The ZnO nanorods have been prepared using TiO₂ seed layers annealed at different temperatures via a simple sol–gel method. The X-ray diffraction result indicates that the prepared samples are of wurtzite structure. Dye sensitized solar cells have been fabricated using the prepared ZnO nanorods. The open circuit voltage, short circuit current density, fill factor, and power conversion efficiency of the ZnO nanorod based dye sensitized solar cells prepared using TiO₂ seed layers annealed at different temperatures have been determined. The improvement in power conversion efficiency may be due to the flower like structured ZnO nanorods with smaller diameter and large specific surface area which paves way for the efficient electron transfer in hybrid solar cells.     

Metal-free indoline dye sensitized solar cells based on nanocrystalline Zn2SnO4

Zn₂SnO₄ nanocrystals were synthesized and first used as the electrode materials for the metal-free indoline dyes sensitized solar cells (DSSCs). The highest efficiency of 3.08% was achieved for a D131 DSSC. This might be attributed to the fact that the D131 dye has a greater positive oxidation potential, which can lead to rapid dye regeneration, avoiding the geminate charge recombination between oxidized dye molecules and injected electrons in the Zn₂SnO₄ film. The efficiency can be improved significantly using a mixture solution of D131 and N719 dyes for which an efficiency of 3.6% was obtained.     

Improved efficiency of TiO2 nanotubes in dye sensitized solar cells by decoration with TiO2 nanoparticles

In the present work we investigate the effect of TiCl₄ treatments on the photoconversion efficiency of TiO₂ arrays used in dye sensitized solar cell. The results clearly show that by an appropriate treatment the decoration of the TiO₂ nanotube arrays with TiO₂ nanocrystallites of a typical size of 3 nm can be achieved. These particles can be converted to mixture of anatase and rutile phase by annealing in air. This decoration of the TiO₂ nanotubes leads to a significantly higher specific dye loading and, for certain annealing treatments, to a doubling of the solar cell efficiency (in our case from 1.9% to 3.8% of AM 1.5 conditions) can be achieved.     

卟啉衍生物敏化纳米TiO2多孔膜电极的光电性质研究

采用中位-四[邻-(3-磺酸基丙氨基)苯基]卟啉(TArP1)和中位-四[对-(3-磺酸基丙氨基)苯基]卟啉(TArP2)分别对纳米TiO2多孔膜电极进行敏化。对两种敏化电极进行了UV-V is光谱测试,结果表明,TiO2与TArP2的作用比与TArP1的作用强。在相同浸泡条件下,TiO2电极吸附TArP2的量大于吸附TArP1的量。将两种敏化电极分别组装成光电化学电池,从光电化学电池的I-V曲线计算TArP2敏化的光电化学电池的总光电转换效率(η)为0.15%,而TArP1敏化的光电化学电池的η为0.09%。     

Barrier effect of dendrons on TiO2 particles in dye sensitized solar cells

The short circuit current of dye sensitised solar cells increased significantly by the simple addition of polyester hydroxyl acetylene bis(hydroxymethyl)propanoic acid dendrons on TiO(2) nanoparticles, resulting in a very high overall energy conversion efficiency.     

A novel ruthenium sensitizer with a hydrophobic 2-thiophen-2-yl-vinyl-conjugated bipyridyl ligand for effective dye sensitized TiO2 solar cells

A hydrophobic and 2-thiophen-2-yl-vinyl-conjugated ruthenium complex, cis-Ru(dhtbpy)(dcbpy)(NCS)2 [dhtbpy = 4,4'-di(hexylthienylvinyl)-2,2'-bipyridyl; dcbpy = 4,4'-dicarboxy-2,2'-bipyridyl], was newly designed, synthesized and applied successfully to sensitization of nanocrystalline TiO2-based solar cells, giving a conversion efficiency of 9.5% under irradiation with AM 1.5 solar light.     

水热法可控合成二氧化钛纳米晶及其在染料敏化太阳能电池中的应用

本文报道了水热法可控合成二氧化钛纳米晶及其在染料敏化太阳能电池中的应用.选择合适的有机碱胶化剂,能很好地控制二氧化钛纳米晶的生长,形成不同形貌和粒径的锐钛矿型二氧化钛纳米晶颗粒.染料敏化太阳能电池光电性能测试结果表明,以四乙基氢氧化铵为胶化剂合成的边长为8～13nm的正方形二氧化钛纳米晶构成的光阳极光电性能优于以四丁基氢氧化铵为胶化剂合成的边长为7～10nm的正方形二氧化钛纳米晶以及长18～35nm,宽10～18nm的长方形二氧化钛纳米晶构成的光阳极.用较高浓度的四甲基氢氧化铵胶化剂能合成球形或椭球形亚微米级二氧化钛颗粒,以其为散射中心在光阳极中构建散射层,染料敏化太阳能电池的光电转换效率能由6.77%提高到8.18%.     

Photochemical performance of ZnO nanostructures in dye sensitized solar cells

In this work, the photoconversion efficiencies of ZnO having diverse microstructures and structural defects have been investigated. A conversion efficiency of 1.38% was achieved for the DSSCs fabricated with as prepared ZnO nanorods having minimum vacancy defects and a favourable one dimensional directional pathway for electron conduction. The DSSCs fabricated with ZnO nanoparticles exhibited relatively low conversion efficiency of 1.004% probably due to multiple trapping/detrapping phenomena within the grain boundaries and ZnO flowers though exhibited a high dye adsorption capability exhibited the lowest conversion efficiency of 0.59% due to a high concentration of structural defects. Based on the experimental evidences, we believe that the type of defects and their concentrations are more important than shape in controlling the overall performance of ZnO based DSSCs.     

Raman spectroscopic study of dye adsorption on TiO2 electrodes of dye-sensitized solar cells

The state of dye adsorption on TiO₂ electrodes in dye-sensitized solar-cell (DSSC) systems is important for its power-conversion efficiency (PCE). We propose a non-destructive and quantitative method to evaluate the amount of adsorbed dye on TiO₂ electrodes by using micro-Raman spectroscopy. The Raman peak intensity ratio of adsorbed dye to TiO₂, I_d/I_t, is defined as a dye adsorption parameter. Based on a comparison between I_d/I_t and the amount of dye evaluated from UV–vis absorption, the quantitativity and reproducibility of our method are verified.We investigated the change of I_d/I_t spatial distribution of TiO₂ electrodes immersed in a dye solution for different time scales. The statistical analysis of I_d/I_t distribution suggests that dyes adsorbed on TiO₂ electrodes with chemical coordination increase at first, and after their saturation, dye aggregations are formed over the chemisorption layer. We also describe the effect of the I_d/I_t distribution on PCE. From a comparison of PCE and I_d/I_t distribution obtained from various immersion processes, it was considered that the PCE of DSSCs can be optimized by minimizing the I_d/I_t dispersion.     

Double-layer coating of SrCO3/TiO2 on nanoporous TiO2 for efficient dye-sensitized solar cells

Surface modification plays a crucial role in improving the efficiency of dye-sensitized solar cells (DSSCs), but the reported surface treatments are in general superior to the untreated TiO(2) but inferior to the typical TiCl(4)-treated TiO(2) in terms of solar cell performance. This work demonstrates a two-step treatment of the nanoporous titania surface with strontium acetate [Sr(OAc)(2)] and TiCl(4) in order, each step followed by sintering. An electronically insulating layer of SrCO(3) is formed on the TiO(2) surface via the Sr(OAc)(2) treatment and then a fresh TiO(2) layer is deposited on top of the SrCO(3) layer via the TiCl(4) treatment, corresponding to a double layer of Sr(OAc)(2)/TiO(2) coated on the TiO(2) surface. As compared to the typical TiCl(4)-treated DSSC, the Sr(OAc)(2)-TiCl(4) treated DSSC improves short-circuit photocurrent (J(sc)) by 17%, open-circuit photovoltage (V(oc)) by 2%, and power conversion efficiency by 20%. These results indicate that the Sr(OAc)(2)-TiCl(4) treatment is better than the often used TiCl(4) treatment for fabrication of efficient DSSCs. Charge density at open circuit and controlled intensity modulated photocurrent/photovoltage spectroscopy reveal that the two electrodes show almost same conduction band level but different electron diffusion coefficient and charge recombination rate constant. Owing to the blocking effect of the SrCO(3) layer on electron recombination with I(3)(-) ions, the charge recombination rate constant of the Sr(OAc)(2)-TiCl(4) treated DSSC is half that of the TiCl(4)-treated DSSC, accounting well for the difference of their V(oc). The improved J(sc) is also attributed to the middle SrCO(3) layer, which increases dye adsorption and may improve charge separation efficiency due to the blocking effect of SrCO(3) on charge recombination.     

Magnesium doped ZnO nanoparticles embedded ZnO nanorod hybrid electrodes for dye sensitized solar cells

We report a novel type of Mg doped ZnO nanoparticles (ZMP) embedded on hydrothermally grown ZnO nanorod (ZR) based photoanode dye sensitized solar cells. The crystallinity, composition and morphology of the photoanodes were characterized by using X-ray diffraction analysis, X-ray photoelectron spectroscopy and scanning electron microscopy. The amount of dye absorbed in the photoanode was observed using UV visible spectral analysis. The improved internal resistance and charge-transfer kinetics of the fabricated cells were analyzed using electrochemical impedance spectroscopy. The ZMP embedded electrode of low thickness (~2.5 μm) gained an enhanced short-circuit current density of 8.56 mA/cm², open-circuit photo voltage of 0.71 V, fill factor of 0.51, and overall conversion efficiency of 2.91 % under 1 sun illumination. This shows high conversion efficiency and performance than that of ZnO nanorod (η ~ 0.22 %) and bare ZnO nanoparticles (ZP) embedded ZnO nanorod (η ~ 1.04 %) based cells. The presence of Mg ions in the ZnO nanoparticle hinders the interfacial recombination of the photo-excited electrons with the electrolyte and also shows better dye absorption than that of ZR. These factors can significantly enhance solar-cell performance and increase the efficiency of the ZMP based dye sensitized solar cells.     

Metal/metal sulfide functionalized single-walled carbon nanotubes: FTO-free counter electrodes for dye sensitized solar cells

The use of single-walled carbon nanotubes (CNT) thin films to replace conventional fluorine-doped tin oxide (FTO) and both FTO and platinum (Pt) as the counter electrode in dye sensitized solar cells (DSSC) requires surface modification due to high sheet resistance and charge transfer resistance. In this paper, we report a simple, solution-based method of preparing FTO-free counter electrodes based on metal (Pt) or metal sulfide (Co(8.4)S(8), Ni(3)S(2)) nanoparticles/CNT composite films to improve device performance. Based on electrochemical studies, the relative catalytic activity of the composite films was Pt > Co(8.4)S(8) > Ni(3)S(2). We achieved a maximum efficiency of 3.76% for the device with an FTO-free counter electrode (Pt/CNT). The device with an FTO- and Pt-free (CoS/CNT) counter electrode gives 3.13% efficiency.     

Nanocrystalline TiO2 solar cells sensitized with InAs quantum dots

We report nanocrystalline TiO2 solar cells sensitized with InAs quantum dots. InAs quantum dots of different sizes were synthesized and incorporated in solar cell devices. Efficient charge transfer from InAs quantum dots to TiO2 particles was achieved without deliberate modification of the quantum dot capping layer. A power conversion efficiency of about 1.7% under 5 mW/cm2 was achieved; this is relatively high for a nanocrystalline metal oxide solar cell sensitized with presynthesized quantum dots, but this efficiency could only be achieved at low light intensity. At one sun, the efficiency decreased to 0.3%. The devices are stable for at least weeks under room light in air.     

A novel photoanode architecture of dye-sensitized solar cells based on TiO2 hollow sphere/nanorod array double-layer film

A novel TiO(2) double-layer (DL) film consisting of TiO(2) hollow spheres (HSs) as overlayer and single-crystalline TiO(2) nanorod arrays (RAs) as underlayer was designed as the photoanode of dye-sensitized solar cells (DSSCs). This new-typed TiO(2) HS/RA DL film could significantly improve the efficiency of DSSCs owing to its synergic effects, i.e. the relatively large specific surface area of TiO(2) HSs for effective dye adsorption, enhanced light harvesting capability originated from TiO(2) RA film, and rapid interfacial electron transport in one-dimensional TiO(2) nanorod arrays. The overall energy-conversion efficiency of 4.57% was achieved by the formation of TiO(2) DL film, which is 16% higher than that formed by TiO(2) HS film and far larger than that formed by TiO(2) RA film (η=0.99%). The light absorption and interfacial electron transport, which play important roles in the efficiency of DSSCs, were investigated by UV-vis absorption spectra and electrochemical impedance spectra.     

Coumarin derivatives for dye sensitized solar cells: a TD-DFT study

Time dependent density functional theory (TD-DFT) calculations have been carried out to study the electronic structure and the optical properties of five coumarin based dyes: C343, NKX-2311, NKX-2586, NKX-2753 and NKX-2593. We have found out that the position and width of the first band in the electronic absorption spectra, the absorption threshold and the LUMO energy with respect to the conduction band edge are key parameters in order to establish some criteria that allow evaluating the efficiency of coumarin derivatives as sensitizers in Dye Sensitized Solar Cells (DSSC). Those criteria predict the efficiency ordering for the coumarin series in good agreement with the experimental evidence. Presumably, they might be used in the design of new efficient organic based DSSC.     

原位制备氧化钛/氮掺杂石墨烯空心球光催化剂及其光催化CO2还原性能研究

利用光催化技术将二氧化碳转化为化学燃料是缓解温室效应以及能源危机的理想途径之一.因此,开发高效的光催化剂是当务之急.氧化钛由于具有优异的物理化学稳定性、成本低廉、无毒性以及环境友好等优点,近年来被广泛关注.此外,空心球结构光催化剂具有短的载流子扩散距离、良好的光散射性以及较大的比表面积等优点,从而成为光催化二氧化碳还原最有潜力的候选材料.但纯的氧化钛空心球由于较快的光生载流子复合速率从而导致低的光催化效率.因此,为了应对这一挑战,我们尝试在氧化钛空心球表面负载助催化剂用以促进光生载流子的分离,从而提高光催化二氧化碳还原转换效率.在各种助催化剂中,贵金属被证明是有效的.然而,高成本以及稀缺性限制了贵金属的广泛应用.因此,有必要设计成本低廉的助催化剂替代品.石墨烯以其优异的导电性、较大的功函数以及来源丰富而备受关注.当石墨烯与n型半导体光催化剂结合在一起时,能够显著促进光生电子从半导体光催化剂向石墨烯的定向迁移,从而有效地抑制光生电子与空穴的复合.当石墨烯中掺杂氮元素时,石墨烯骨架中的电子密度会进一步提高,同时,氮原子中的孤对电子更加有利于石墨烯骨架中的电子传输.此外,氮掺杂石墨烯中不同的氮位点(吡啶氮、吡咯氮和石墨氮)作为路易斯碱位点,能够用以二氧化碳分子的吸附以及活化.然而,迄今为止,最常用的制备半导体/氮掺杂石墨烯纳米复合光催化剂的方法是在氮掺杂石墨烯表面生长半导体光催化剂.所制备的光催化剂与氮掺杂石墨烯之间界面接触有限,不利于光生载流子的快速传递与分离.此外,助催化剂和光催化剂之间建立高质量的界面接触可以有效地抑制光生电子与空穴的复合.因此,有必要绕开传统制备方法的弊端,从而设计与光催化剂之间具有大的接触面积和紧密的界面接触以及具有丰富活性位点的高质量氮掺杂石墨烯助催化剂.本文提出了一种新的策略,以吡啶为氮掺杂石墨烯的前驱体,通过化学气相沉积方法在氧化钛空心球表面原位生长超薄氮掺杂石墨烯层(1～2层).此外,在高温状态下,吡啶分子脱氢生成具有优异扩散性质的脱氢吡啶自由基气相分子,随着反应的进行,氧化钛表面的每个纳米颗粒基元表面都能够与吡啶分子充分接触,从而保障两者之间大面积以及紧密的界面接触.光催化二氧化碳还原性能测试结果表明,优化后的氧化钛/氮掺杂石墨烯空心球纳米复合材料的二氧化碳光催化总转化率(一氧化碳、甲醇和甲烷的总产率)为18.11 μmol g-1 h-1,是空白氧化钛空心球的4.6倍和商业P25的10.7倍.高分辨透射电子显微镜、X射线光电子能谱以及拉曼光谱结果表明,成功构建了氧化钛与氮掺杂石墨烯之间紧密接触的界面.同时,氮掺杂石墨烯的引入能够显著增强复合光催化剂的表面光热效应以及氧化钛与氮掺杂石墨烯界面肖特基势垒的形成均有助于促进光催化二氧化碳还原反应的进行.因此,本文为石墨烯基光助催化剂的原位构建提供了一种行之有效的策略.