Photocurrent-voltage of a dye-sensitized nanocrystalline TiO2 solar cells influenced by N719 dye adsorption properties

Titanium particles of single-phase anatase nanocrystallites were prepared by the hydrolysis of titanium tetraisopropoxide. A dye-sensitized solar cell (DSSC) was fabricated by adsorbing cis-bis(isothiocyanato)bis(2,2'-bipyridyl-4,4'-dicarboxylato)-ruthenium(II)bis-tetrabutylammonium dye (N719) onto TiO2 film. The samples were characterized by XRD, TEM, FE-SEM, AFM, and Brunauer-Emmett-Teller (BET) analysis. The influence of the acetic acid treatment of TiO2 electrode with different concentrations on the photovoltaic performance of DSSC was investigated. It was found that DSSC had better photoelectric performance when the TiO2 electrode was treated by acetic acid of 0.5 M. An equivalent circuit analysis using the one-diode model was used to evaluate the influences of adsorption quantity and acetic acid treatment on the energy conversion efficiency of DSSC. A nonlinear least-square optimization method was used to determine five model parameters.     

锂掺杂二氧化钛致密层对染料敏化太阳电池性能的影响

利用脉冲激光沉积(PLD), 在纳米多孔二氧化钛层(np-TiO₂)与透明导电玻璃之间分别沉积了二氧化钛致密层(d-TiO₂)和掺锂二氧化钛致密层(d-Li-TiO₂), XRD衍射结果显示该致密层具有锐钛矿结构. 电池开路电压随时间的衰减实验结果表明, 该结构可以有效减慢开路电压的衰减, 抑制透明导电玻璃上的电子向电解质逆向传输并进行电子复合的几率; 同时, 掺入锂后, 致密TiO₂层(d-TiO₂)能带宽度变窄, 降低了np-TiO₂层与透明导电玻璃之间的界面电阻, 使得np-TiO₂层导带上的光生电子更容易地向透明导电玻璃传输, 进而使得具有d-Li-TiO₂层的染料敏化太阳电池比无致密层的染料敏化太阳电池光电转换效率提高了42%.     

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%.     

Enhanced electron lifetime on nitrogen-doped TiO2 films for dye-sensitized solar cells

Nitrogen-doped TiO2 crystallites were prepared via the hydrolysis of TiCl4 using an ammonia medium in an aqueous solution for DSSC photoelectrodes. The optimized photoelectrode for the DSSC was prepared with 9.4 nm sized N-doped TiO2 crystal (BET; 200 m2/g), which provides a relatively high short circuit current and energy conversion efficiency in the DSSC. The photovoltaic performance of the N-doped TiO2 electrode was confirmed using incident photon-to-current efficient spectra, impedance analyses, and Bode-phase plots which proved that the N-doped TiO2 electrode has a significantly enhanced electron lifetime compared with that of the P25 electrode.     

Mesocrystalline TiO<Subscript>2</Subscript> nanosheet arrays with exposed {001} facets: Synthesis via topotactic transformation and applications in dye-sensitized solar cells

A facile,fluorine-free approach for synthesizing vertically aligned arrays of mesocrystalline anatase TiO2 nanosheets with highly exposed {001} facets was developed through topotactic transformation.Unique mesocrystalline {001}-faceted TiO2 nanosheet arrays vertically aligned on conductive fluorine-doped tin oxide glass were realized through topotactic conversion from single-crystalline precursor nanosheet arrays based on lattice matching between the precursor and the anatase crystals.The morphology and microstructure of the {001}-faceted TiO2 nanosheets could be readily modulated by changing the reactant concentration and annealing temperature.Owing to enhanced dye adsorption,reduced charge recombination,and enhanced light scattering arising from the exposed {001} facets,in addition to the advantageous features of low-dimensional structure arrays (e.g.,fast electron transport and efficient charge collection),the obtained TiO2 nanosheet arrays exhibited superior performance when they were used as anodes for dye-sensitized solar cells (DSSCs).Particularly,{001}-faceted TiO2 nanosheet arrays ～15 μm long annealed at 500 ℃ showed a power conversion efficiency of 7.51％.Furthermore,a remarkable efficiency of 8.85％ was achieved for a DSSC based on double-layered TiO2 nanosheet arrays ～35 μm long,which were prepared by conversion from the precursor nanoarrays produced via secondary hydrothermal growth.     

Performance and electron transport properties of TiO(2) nanocomposite dye-sensitized solar cells

TiO(2) nanowire (NW)/nanoparticle (NP) composite films have been fabricated by hybridizing various ratios of hydrothermal anatase NWs and TiO(2) NPs for use in dye-sensitized solar cells (DSSCs). Scanning electron microscopy (SEM) images reveal that uniform NW/NP composite films were formed on fluorine-doped tin oxide?(FTO) substrates by the dip-coating method. The NWs are randomly but neither vertically nor horizontally oriented within the composite film. The TiO(2) NP DSSC possesses superior performance to those of the NW/NP composite and the pure NW cells, and the efficiency of the NW/NP composite DSSC increases on increasing the NP/NW ratio in the composite anode. All types of DSSC possess the same dependence of performance on the anode thickness that the efficiency increases with the anode thickness to a maximum value, then it decreases when the anode is thickened further. Electrochemical impedance spectroscopy analyses reveal that the NP DSSCs possess larger effective electron diffusion coefficients (D(eff)) in the photoanodes and smaller diffusion resistances of I(3)(-) in electrolytes compared to those in the NW/NP and the NW DSSCs. D(eff) decreases when NWs are added into the photoanode. These results suggest that the vertical feature of the NWs within the anodes is crucial for achieving a high electron transport rate in the anode.     

Enhancement of photovoltaic performance in dye-sensitized solar cells with the spin-coated TiO2 blocking layer

The TiO2 thin film layers were introduced with the spin-coating method between FTO electrode and TiO2 photoanode in dye sensitized solar cell (DSSC) to prevent electron back migration from the FTO electrode to electrolyte. The DSSC containg different thickness of TiO2 thin film (10-30, 40-60 and 120-150 nm) were prepared and photovoltaic performances were analysed with /-Vcurves and electrochemical impedance spectroscopy. The maximum cell performance was observed in DSSC with 10-30 nm of TiO2 thin film thickness (11.92 mA/cm2, 0.74 V, 64%, and 5.62%) to compare with that of pristine DSSC (11.09 mA/cm2, 0.65 V, 62%, and 4.43%). The variation of photoelectric conversion efficiency of the DSSCs with different TiO2 thin film thickness was discussed with the analysis of crystallographic and microstructural properties of TiO2 thin films.     

Sputtered highly ordered TiO2 nanorod arrays and their applications as the electrode in dye-sensitized solar cells

For the first time, the TiO2 nanorod arrays have been prepared on ITO substrates at room temperature by dc reactive magnetron sputtering technique. These TiO2 nanorods have a preferred orientation along the (220) direction and are perpendicular to the ITO substrate. Both the X-ray diffraction and Raman scattering measurements show that the highly ordered TiO2 nanorod arrays have an anatase crystal structure. The diameter of the nanorod varies from 30 nm to 100 nm and the nanorod length can be varied from several hundred nanometers to several micrometers depending on the deposition time. The TiO2 nanorod arrays with about 3 micrometers length have been used as an electrode for dye-sensitized solar cell (DSSC). Short-circuit photocurrent density, open-circuit voltage, fill factor and light-to-electricity conversion efficiency at 100 mW/cm2 light intensity are estimated to be 12.76 mA/cm2, 0.65 V, 0.63 and 5.25%, respectively, for the DSSC made of the TiO2 nanorods.     

Surface modified TiO2 nanostructure with 3D urchin-like morphology for dye-sensitized solar cell application

Three-dimensional (3D) urchin-like rutile TiO2 powders were synthesized by a mild hydrothermal method without any templates. An individual urchin-like TiO2 powder consists of self-assembled nanorods with a length of about 150 nm and width of about 10 nm. Additionally, the urchin-like TiO2 nanopowders were coated with an ultra-thin ZnO layer in order to modify the surface properties of the nanopowders, and the ZnO layer was confirmed by high-resolution transmission electron microscopy (HRTEM) and X-ray photoelectron spectroscopy (XPS) analysis. The ZnO-modified TiO2 was used as a photoelectrode of a dye-sensitized solar cell (DSSC) and the solar cell performances were investigated. In comparison with bare TiO2, ZnO-modified TiO2 improved the photovoltaic performances, i.e., energy conversion efficiency, open circuit voltage, and short circuit current were increased. The higher DSSC performance of ZnO-modified TiO2 was attributed to its higher dye loading and lower charge recombination rate.     

ZnO/TiO2纳米管晶膜电极的制备及光电性能

采用水热法制备了ZnO纳米棒,以ZnO纳米棒为原料制备出ZnO/TiO2纳米管晶膜电极并应用于染料敏化太阳能电池.用扫描电镜(SEM)、X射线衍射仪(XRD)、X射线能谱仪(EDX)和N2吸脱附分析等研究了样品的结构、表面形貌和化学组成,并通过紫外可见光度计和电化学工作站探讨了煅烧温度在80~600℃范围内ZnO/TiO2纳米管电极的光电化学性能.此外,研究经TiCl4化学处理的ZnO/TiO2纳米管电极光电性能的改善情况.结果表明,600℃煅烧的ZnO/TiO2纳米管电极制备的染料敏化太阳能电池表现出较优的光电性能,其短路电流密度(Jsc)为2.28 mA/cm2,开路电压(Voc)为0.631 V,光电转换效率η为0.66%.600℃煅烧的ZnO/TiO2纳米管经TiCl4处理后的染料敏化太阳能电池的光电性能得到显著改善,其光电转换效率η提高到1.06%.     

染料敏化太阳电池CuAl2O4/TiO2光阳极制备及性能

采用柠檬酸法制备了尖晶石型纳米晶CuAl2O4,将其添加到P25(degussa,TiO2)中,制备成CuAl2O4/TiO2薄膜光阳极,并组装成染料敏化太阳电池(DSSC),对其光电性能进行表征。结果表明:CuAl2O4的加入,电池性能得到提高;当CuAl2O4含量为2%(质量分数)时,与纯TiO2薄膜光阳极相比,光电转化效率提高了39.1%。     

Dry-spray deposition of TiO2 for a flexible dye-sensitized solar cell (DSSC) using a nanoparticle deposition system (NPDS)

TiO2 powders were deposited on indium tin oxide (ITO) coated polyethylene terephthalate (PET) substrates for application to the photoelectrode of a dye-sensitized solar cell (DSSC). In the conventional DSSC manufacturing process, a semiconductor oxide such as TiO2 powder requires a sintering process at higher temperature than the glass transition temperature (T(g)) of polymers, and thus utilization of flexible polymer substrates in DSSC research has been constrained. To overcome this restriction related to sintering, we used a nanoparticle deposition system (NPDS) that could produce a thin coating layer through a dry-spray method under atmospheric pressure at room temperature. The powder was sprayed through a slit-type nozzle having a 0.4 x 10 mm2 rectangular outlet. In order to determine the deposited TiO2 thickness, five kinds of TiO2 layered specimens were prepared, where the specimens have single and double layer structures. Deposited powders on the ITO coated PET substrates were observed using FE-SEM and a scan profiler The thicker TiO2 photoelectrode with a DSSC having a double layer structure showed higher energy efficiency than the single layer case. The highest fabricated flexible DSSC displayed a short circuit current density J(sc) = 1.99 mA cm(-2), open circuit voltage V(oc) = 0.71 V, and energy efficiency eta = 0.94%. These results demonstrate the possibility of utilizing the dry-spray method to fabricate a TiO2 layer on flexible polymer substrates at room temperature under atmospheric pressure.     

Nanostructured TiO2 films for dye-sensitized solar cells prepared by the sol-gel method

TiO2 films were prepared on glass substrates using the sol-gel process for a dye-sensitized solar cell application. The TiO2 sol was prepared using hydrolysis/polycondensation. Titanium (IV) Tetra Isopropoxide (TTIP) was used as precursor and Nitric acid (HNO3) was used as a catalyst for the peptization. The crystal structure and morphology of the prepared materials were characterized by XRD, and an SEM. The observations confirmed the nanocrystalline nature of the TiO2. The reaction parameters, such as the catalyst concentrations, the calcination time, and the calcination temperature were varied during the synthesis in order to achieve nanosize TiO2 particles. The prepared TiO2 particles were coated onto FTO glass using a screen printing technique. The prepared TiO2 films were characterized by UV-vis. The TiO2 particles calcinated at low temperatures showed an anatase phase they grew into a rutile phase when the calcination temperature increased. The size and structure of the TiO2 particles were adjusted to specific surface areas. It was found that the conversion efficiency of the DSSC was highly affected by the properties of the TiO2 particles.     

二氧化钛催化剂晶型调控技术的研究进展

综述二氧化钛由锐钛矿向金红石晶型转变调控技术的最新成果,分析温度、氧化物和以及离子掺杂对实现晶型转变的影响规律,重点研究氧化物和离子掺杂对晶型转变的影响。结果显示:复合金属氧化物熔点低于TiO2熔点时,可促进锐钛矿型TiO2向金红石型转变;而金属氧化物熔点高于TiO2熔点时,可阻碍晶型转变;掺杂离子的离子半径、化合价、离子大小对二氧化钛晶型转变及催化性能有明显的影响,当掺杂金属离子半径大于或小于Ti4+半径,使得锐钛矿型TiO2更稳定;当掺杂离子的半径与Ti4+半径相近时,有利于锐钛矿型向金红石型转变,而体积较小的低价阴离子有利于金红石型二氧化钛的的生成,体积较大的高价阴离子则有利于锐钛矿型二氧化钛的的生成;阴阳离子共掺杂可以有效地调控二氧化钛晶型转变,并且能够提高TiO2的光催化活性。探讨二氧化钛多晶之间的协同作用,并基于二氧化钛掺杂改性的计算模拟,指出今后的发展方向。     

FeS2/TiO2复合薄膜光电性能

采用溶液浸渍法在ITO导电玻璃表面的多孔TiO2薄膜上沉积了FeS2薄膜.使用Fe2O3粉末保护裸露在外的ITO导电膜在硫气氛中热处理后,制得了FeS2/TiO2复合薄膜.应用B531/H数显测厚指示表、数字式四探针测试仪、XJCM-8太阳电池测试仪等研究了FeS2/TiO2复合薄膜的厚度、ITO导电玻璃的电阻率以及FeS2/TiO2复合薄膜的光电性能.结果表明：此方法制得的FeS2/TiO2复合薄膜具有良好的光电性能;且ITO导电膜的电阻率变化较小.因而适宜制备色素增感太阳能电池（DSSC）.     

Solution Combustion Synthesis of TiO2 and Its Use for Fabrication of Photoelectrode for Dye-sensitized Solar Cell

Three different types of TiO2 nano powders were synthesized by a solution combustion synthesis (SCS) method using three different fuels and for comparison, another type of TiO2 nano powder was synthesized by calcination of titanyl hydroxide. These TiO2 nano powders were used to fabricate photoelectrodes for the dye-sensitized solar cell (DSSC) and their performance was compared to that of the DSSC fabricated with Degussa P25 TiO2. The results showed that the SCS TiO2 could work well as photoelectrode for DSSC. The SCS TiO2 contained impurities of C and/or S, thus exhibiting visible light absorption and reduced band gap. The open circuit voltage and the fill factor both varied little among the various TiO2 and thus both had little effect on the photoelectrical conversion efficiency (η). However, the variation of η was seen to be in quite a good agreement with that of the short circuit current (Isc), suggesting that η was dominated by Isc. Isc was found to be enhanced by light scattering effect due to the presence of large particles but reduced by high impurity content due to an increase in electron transfer resistance. In addition, the specific surface area of the powders was found to be an important factor affecting the Isc and thus the η.     

金红石型TiO2纳米棒的制备及其在染料敏化太阳电池中的应用

采用十二烷基苯磺酸钠表面活性剂(DBS)辅助水热法合成TiO2纳米材料,XRD和TEM测试表明,不含DBS的TiO2溶胶水热处理后得到10~20nm锐钛矿型TiO2纳米颗粒;添加DBS后,生成了金红石型TiO2纳米棒.虽然金红石型TiO2纳米棒光电极的染料吸附性能和光电性能均不如锐钛矿型TiO2纳米颗粒光电极,但金红石型TiO2纳米棒漫反射性能较高.可用其制备具有光电转换性能的反射层,这种新型反射层使染料敏化太阳能电池光电转换效率提高了26.14%,而含Ti-nanoxide 300大颗粒TiO2构成的反射层仅能使电池光电转换效率提高11.04%.这种差异的根源在于金红石型TiO2纳米棒不仅具有散射光能力,其本身还可吸附染料进行光电转换.随着反射层厚度的增加,电池短路电流逐步提高.而不吸附染料且无光电转换能力的Ti-nanoxide 300传统反射层则没有这种功能.     

Synthesis of anatase TiO2 microspheres and their efficient performance in dye-sensitized solar cell

Nanomaterials play important role in performance of dye-sensitized solar cells. In this paper, highly phase pure anatase TiO₂ microspheres were synthesized using a low-cost hydrothermal route. Initially, X-ray diffraction studies and Raman spectroscopic analysis were carried out, and the formation of tetragonal structure of TiO₂ with the anatase phase was confirmed. The UV–Vis DRS studies showed the excellent reflectance and optical band-gap energy of 3.29 eV. The well-interconnected spherical nanoparticles with different sizes were examined by Field Emission Scanning Electron Microscopic analysis. The fabricated dye-sensitized solar cell (DSSC) composed of prepared TiO₂ microspheres as photoanode exhibited a higher power conversion efficiency (PCE) (η) of 5.4% as compared to commercial P25 with PCE of 3.6%. The higher J_sc (12.03 mA/cm²) in the fabricated DSSC due to efficient dye loading capacity and high light-scattering property was also observed.

     

TiO2-B/anatase core-shell heterojunction nanowires for photocatalysis

Fast separation and spatial control of electrons and holes after photogeneration is important in photocatalysis. Ideally, after photogeneration, electrons and holes must be segregated to different parts of the photocatalyst to take part in separate oxidation and reduction reactions. One way to achieve this is by building junctions into the catalyst with built-in chemical potential differences that tend to separate the electron and the hole into two different regions of the catalyst. In this work, we sought to accomplish this by controllably forming junctions between different phases of TiO(2). A synthesis method has been developed to prepare TiO(2)-B core and anatase shell core-shell nanowires. We control the anatase phase surface coverage on the TiO(2)-B core and show that the maximum photocatalytic activity is obtained when the solution containing the reactants can contact both the anatase and TiO(2)-B phases. The photocatalytic activity drops both with bare TiO(2)-B nanowires and with completely anatase covered TiO(2)-B nanowires. In contrast, nanowires partially covered with anatase phase gives the highest photocatalytic activity. The improved photocatalytic activity is attributed to the effective electron-hole separation at the junction between the anatase and TiO(2)-B phases.     

Optimized method for preparation of TiO2 nanoparticles dispersion for biological study

The objective of the present study was to develop a practical method to prepare a stable dispersion of TiO2 nanoparticles for biological studies. To address this matter a variety of different approaches for suspension of nanoparticles were conducted. TiO2 (rutile/anatase) dispersions were prepared in distilled water following by treated with different ultrasound energies and various dispersion stabilizers (1.0% carboxymethyl cellulose, 0.5% hydroxypropyl methyl cellulose K4M, 100% fetal bovine serum, and 2.5% bovine serum albumin). The average size of dispersed TiO2 (rutile/anatase) nanoparticles was measured by dynamic light scattering device. Agglomerate sizes of TiO2 in distilled water and 100% FBS were estimated using TEM analysis. Sedimentation rate of TiO2 (rutile/anatase) nanoparticles in dispersion was monitored by optical absorbance detection. In vitro cytotoxicity of various stabilizers in 16-HBE cells was measured using MTT assay. The optimized process for preparation of TiO2 (rutile/anatase) nanoparticles dispersion was first to vibrate the nanoparticles by vortex and disperse particles by ultrasonic vibration in distilled water, then to add dispersion stabilizers to the dispersion, and finally to sonicate the nanoparticles in dispersion. TiO2 (rutile/anatase) nanoparticles were disaggregated sufficiently with an ultrasound energy of 33 W for 10 min. The formation of TiO2 (rutile/anatase) agglomerates in distilled water was decreased obviously by addition of 1.0% CMC, 0.5% HPMC K4M, 100% FBS and 2.5% BSA. For the benefit of cell growth, FBS is the most suitable stabilizer for preparation of TiO2 (rutile/anatase) particle dispersions and subsequent investigation of the in vivo and in vitro behavior of TiO2 (rutile/anatase) nanoparticles. This method is practicable to prepare a stable dispersion of TiO2 (rutile/anatase) nanoparticles for at least 120 h.