Dye-sensitized solar cells based on hollow anatase TiO2 spheres prepared by self-transformation method

Dye-sensitized solar cells (DSSCs) are fabricated based on hollow anatase TiO₂ (HA-TiO₂) spheres synthesized by a chemically induced self-transformation (CIST) strategy using urea as a base catalyst, whose walls are composed of anatase nanocrystals and exhibit hierarchical porosity. TiO₂ hollow structured materials not only have low density, high specific surface areas, and hierarchically porous structures, but also exhibit high light-collection efficiency and fast motion of charge carriers. Effects of calcination temperatures on the performance of HA-TiO₂ solar cells are investigated and discussed. With increasing calcination temperatures, the light-electricity conversion efficiencies (η) increase. At 600 °C, HA-TiO₂ cells reach the highest efficiency. The performances of HA-TiO₂ cells are also compared with Degussa P-25 (P25) TiO₂ nanoparticle cells at the same film thickness, and their optimal efficiencies at 600 °C are 4.82 and 4.35%, respectively. The enhanced performance of HA-TiO₂ cells is due to their high surface area and hierarchically nanoporous structures when compared with the nonporous TiO₂ nanoparticles (P25).     

A series of LiI/acetamide phase transition electrolytes and their applications in dye-sensitized solar cells

A new series of electrolytes composed of LiI and acetamide have been investigated in dye-sensitized solar cells (DSSCs). These electrolytes melt at about 50 °C and their ionic conductivities vary drastically below and above the melting points (T_m). They tend to form large crystals at low temperature, leading to poor penetration and contact within porous TiO₂ anode film. This shortage is improved by introducing nano-SiO₂ particles into the electrolyte. A total conversion efficiencies (η) of 0.3% at 35 °C and 4.2% at 75 °C are achieved respectively under AM 1.5 simulated solar light illumination when a LiI/acetamide (1:16) electrolyte with 8 wt% nano-SiO₂ is used. It is expected that the DSSC using phase transition electrolyte could show high efficiency for operation at high temperature and high stability for storage at low temperature.     

Fabrication of hole-patterned TiO2 photoelectrodes for solid-state dye-sensitized solar cells

We suggest a simple process to fabricate a hole-patterned TiO₂ electrode for a solid-state dye-sensitized solar cell (DSSC) to enhance cell performance through interfacial properties of the electrode with the electrolyte with minimum dye loading. The method involves prepatterning of SU-8 photoresist on a conducting glass, followed by the deposition of a nanocrystalline TiO₂ layer, calcination at 450 °C and characterization using scanning electron microscopy (SEM). Hole-patterned TiO₂ photoelectrodes yielded better solar energy conversion efficiency per dye loading compared to a conventional non-patterned photoelectrode. For example, a 50 μm hole-patterned DSSC exhibited 4.50% conversion efficiency in the solid state, which is comparable to an unpatterned flat TiO₂ photoelectrode (4.57%) however the efficiency per dye loading of the former (0.986%/g) was much greater than that of the latter (0.898%/g). The improvement was attributed to improved transmittance through the electrode as well as better interfacial properties between the electrolyte and electrode, as confirmed by UV-visible spectroscopy and electrochemical impedance (EIS) analysis.     

Electrophoretic deposition of nanocrystalline TiO2 films on Ti substrates for use in flexible dye-sensitized solar cells

Nanocrystalline TiO₂ films were prepared on flexible Ti-metal sheets by electrophoretic deposition followed by chemical treatment with tetra-n-butyl titanate (TBT) and sintering at 450 °C. X-ray diffraction (XRD) analysis indicates that TBT treatment led to the formation of additional anatase TiO₂, which plays an important role in improving the interconnection between TiO₂ particles, as well as the adherence of the film to the substrate, and in modifying the surface properties of the nanocrystalline particles. The effect of TBT treatment on the electron transport in the nanocrystalline films was studied by intensity-modulated photocurrent spectroscopy (IMPS). An increase in the conversion efficiency was obtained for the dye-sensitized solar cells with TBT-treated nanocrystalline TiO₂ films. The cell performance was further optimized by designing nanocrystalline TiO₂ films with a double-layer structure composed of a light-scattering layer and a transparent layer. The light-scattering effect of the double-layer nanocrystalline films was evaluated by diffuse reflectance spectra. Employing the double-layer nanocrystalline films as the photoelectrodes resulted in a significant improvement in the incident photo-to-current conversion efficiency of the corresponding cells due to enhanced solar absorption by light scattering. A high conversion efficiency of 6.33% was measured under illumination with 100 mW cm⁻² (AM 1.5) simulated sunlight.     

Thermal treatment effect on nanostructured TiO2 films deposited using diethanolamine stabilized precursor sol

A clear ethanol based precursor sol obtained using diethanolamine has been utilized for the deposition of TiO₂ films annealed at different temperatures. The influence of annealing temperature on the structural, optical and electrochemical properties of TiO₂ thin films has been examined. Diethanolamine stabilizes the precursor sol due to its chelate forming ability with the alkoxides. It reacts as a tridentate ligand with the titanium isopropoxide. The threshold for the onset of crystallization in the films is identified at a temperature of 300 °C. The SEM study on the films elucidates segregation of irregularly shaped features into finer round clusters as a function of annealing temperature. As determined from the AFM study, the roughness parameter in the films has shown an increase with the annealing temperature. Photoluminescence measurements have given an indirect evidence for the presence of stoichiometric titanium oxide in the films. An optimum crystallite size and high ion storage capacity in the 300 °C annealed film has led to its superior electrochromic activity with the transmission modulation and coloration efficiency of the same film being 42% and 8.1 cm² C⁻¹, respectively at 550 nm. The highest degree of porosity in the 300 °C annealed film as established from the SEM study is also the reason behind its best electrochromic performance. In addition, the 300 °C annealed film also exhibits the fastest coloration switching kinetics.     

Preparation and photoelectrocatalytic properties of titania/carbon nanotube composite films

Composite films of TiO₂ and carbon nanotubes (CNTs) were prepared on titanium sheets by liquid phase deposition and the photoelectrocatalytic (PEC) properties of the films were investigated through the degradation of methyl orange (MO) in 0.1 M solutions. It was demonstrated that CNTs in the TiO₂ film significantly decreased the charge transfer resistance and increased the anodic photocurrent response of the film under UV light irradiation when the bias was above −0.1 V. The PEC performance of the CNT-based composite film could be tuned by controlling the preparation parameters including the deposition time and calcination temperature. The deposition time and calcination temperature were optimized at 1 h and 450 °C, respectively. On the TiO₂/CNT film prepared under the optimized conditions, 95% of the added MO (10 mg L⁻¹) was degraded within 90 min, which was much higher than the 60% removal seen on the pure TiO₂ films.     

Synthesis of a TiO2 ceramic membrane containing SrCo0.8Fe0.2O3 by the sol-gel method with a wet impregnation process for O2 and N2 permeation

A SrCo_0.8Fe_0.2O₃ impregnated TiO₂ membrane (TiO₂-SrCo_0.8Fe_0.2O₃ membrane) was successfully prepared using a sol-gel method in combination with a wet impregnation process. The membrane was subjected to a single gas permeance test using oxygen (O₂) and nitrogen (N₂). The TiO₂ membrane was immersed in the SrCo_0.8Fe_0.2O₃ solution, dried and then calcined to affix SrCo_0.8Fe_0.2O₃ into the membrane. The effect of the acid/alkoxide (H⁺/Ti⁴⁺) molar ratio of the TiO₂ sol on the TiO₂ phase transformation was investigated. The optimal molar ratio was found to be 0.5, which resulted in nanoparticles with a mean size of 5.30 nm after calcination at 400 °C. The effect of calcination temperature on the phase transformation of TiO₂ and SrCo_0.8Fe_0.2O₃ was investigated by varying the calcination temperature from 300 to 500 °C. X-ray diffraction spectroscopy (XRD) and Fourier transform infrared (FTIR) analysis confirmed that a calcination temperature of 400 °C was preferable for preparing a TiO₂-SrCo_0.8Fe_0.2O₃ membrane with fully crystallized anatase and SrCo_0.8Fe_0.2O₃ phases. The results also showed that polyvinyl alcohol (PVA) and hydroxypropyl cellulose (HPC) were completely removed. Field emission scanning electron microscopy (FESEM) analysis results showed that a crack-free and relatively dense TiO₂ membrane (∼0.75 μm thickness) was created with a multiple dip-coating process and calcination at 400 °C. The gas permeation results show that the TiO₂ and TiO₂-SrCo_0.8Fe_0.2O₃ membranes exhibited high permeances. The TiO₂-SrCo_0.8Fe_0.2O₃ membrane developed provided greater O₂/N₂ selectivity compared to the TiO₂ membrane alone.     

Synthesis and characterization of mesoporous TiO2 nanostructured films prepared by a modified sol-gel method for application in dye solar cells

Anatase TiO₂ colloidal dispersions were obtained by hydrothermal synthesis at 200 °C from titanium isopropoxide gels modified with acetic acid in the presence of a non-ionic surfactant. Absolute ethanol, anhydrous terpineol and ethyl cellulose were added to this anatase dispersion resulting in a 23 wt% TiO₂ paste. Mesoporous films for application as working electrodes in dye-sensitized solar cells were prepared by the screen-printing method, yielding reproducible films with thicknesses about 10 μm and desired porosity levels in a single printing operation. An average energy conversion efficiency of 5.2%, and a fill factor of 0.66 were achieved with anatase particle sizes ranging between 15 and 20 nm. The reproducibility of the results was confirmed by electrochemical impedance spectroscopy analysis.     

Effect of calcination temperature on the structural properties and photocatalytic activities of solvothermal synthesized TiO2 hollow nanoparticles

TiO₂ hollow nanoparticles were prepared by the solvothermal method, calcined at different temperatures and characterized by XRD, BET, SEM, PL and FT-IR. The effects of morphology, size and calcination temperature on the photocatalytic activity of the prepared materials were discussed in detail. It was found that the calcination temperature altered the crystallinity, morphology, surface area, and the porous structure. The photocatalytic activity of the TiO₂ powders evaluated through photocatalytic degradation of gaseous acetone under UV-light irradiation, showed TiO₂ calcined at 250 °C to exhibit a higher photocatalytic activity than commercial powders (Degussa P25).     

Porous titania microspheres with uniform wall thickness and high photoactivity

Highly porous titania particles were prepared by depositing thin films of titania, using alternating reactions of TiCl₄ and hydrogen peroxide, on poly(styrene-divinylbenzene) (PS-DVB) template particles via atomic layer deposition (ALD) at 77 °C. The composition of the titania films was verified by XPS analysis and the titania films were directly observed by TEM. TGA/DSC was used to study the thermal decomposition of the polymer template. Porous titania particles with uniform wall thicknesses were successfully obtained after the template PS-DVB was removed by oxidation in air at 400 °C for 24 h. Verification of the resulting porous structure of the titania particles was done by cross-sectional SEM and nitrogen adsorption–desorption analysis. Porous titania particles were treated at different temperatures. XRD analysis was used to determine the microstructure and phase transformation of titania at elevated temperatures. The photocatalytic activity of these porous titania particles was studied by methylene blue decomposition under UV light at room temperature and was found to be comparable to that of commercial anatase titania nanoparticles (~20 nm). Depositing Na₂SO₄ on TiO₂ retarded the TiO₂ phase transformation from anatase to rutile during calcination and, thus, greatly increased the photoactivity of the porous titania particles.     

Improved performance of dense TiO2/CdSe coupled thin films by low temperature process

Dense TiO₂ and TiO₂/CdSe coupled nanocrystalline thin films were synthesized onto ITO coated glass substrate by chemical route at relatively low temperature (≤100 °C). TiO₂ films were nanocrystalline and crystallinity disappears after CdSe deposition as evidenced by X-ray powder diffraction. Surface morphology and physical appearance of films were studied from SEM and actual photo-images, reveals dense nature of TiO₂ (10-12 nm spherical grains, faint violet) and CdSe (80-90 nm spherical grains, deep brown), respectively. Presence of two absorption edges in UV spectra implies existence of separate phases rather than composite formation. TiO₂ film was found to have higher water contact angle (71°) than TiO₂/CdSe (61°) and CdSe (56°). I-V and stability tests of photo-electrochemical cells were performed with TiO₂ and TiO₂/CdSe film electrodes (under light of illumination intensity 80 mW/cm²) in lithium iodide as an electrolyte using two-electrode system.     

Properties of sol-gel SnO2/TiO2 electrodes and their photoelectrocatalytic activities under UV and visible light illumination

A visible light active binary SnO₂-TiO₂ composite was successfully prepared by a sol-gel method and deposited on Ti sheet as a photoanode to degrade orange II dye. Titanium and SnO₂ can promote the development of rutile phase of TiO₂ and inhibit the formation of anatase phase of TiO₂. Formation of SnO₂ crystalline is insignificant even when the calcination temperature increases to 700 °C. Heterogenized interface between SnO₂ and TiO₂ inhibits growth of TiO₂ linkage and leads to the particle-filled surface morphology of SnO₂-containing films. The carbonaceous, Ti-O-C bonds and Ti³⁺ species are likely to account for the photoabsorption and photoelectrocatalytic (PEC) activity under visible light illumination. The electrode with 30% SnO₂ exhibits higher photocurrent when compared with those in the region of 0-50%. The 600 °C-calcined SnO₂-TiO₂ electrode indicates higher activity when compared with those at 400, 500, 700 and 800 °C. PEC degradation of orange II follows the Langmuir-Hinshelwood model and takes place much effectively in a solution of pH 3.0 than those in pH 7.0 and pH 11.0.     

Enhancing the performance of dye-sensitized solar cells based on an organic dye by incorporating TiO2 nanotube in a TiO2 nanoparticle film

The photoelectrochemical properties of a high molar extinction coefficient charge transfer organic dye containing thienylfluorene segment called FL, and the effect of incorporating TiO₂ nanotube (TiNT) in TiO₂ nanoparticle film along with the above dye on the photovoltaic performance of dye-sensitized solar cells (DSSCs) were investigated. The influence of soaking time of the TiO₂ electrode in dye solution and the effect of varying its concentration, on the solar cell efficiency was also studied. Cyclic voltammetric (CV) analysis revealed the linear relationship between the anodic peak current and the scan rate, indicating a surface-confined diffusion process.The surface morphology of TiNT was characterized using SEM, TEM and XRD. The open-circuit voltage (V_OC) of the DSSC increased with the increase in the wt% of TiNT and shows optimal value at about 5 wt%, which is correlated with the suppression of the electron recombination as found out from the electron lifetime studies.The electrochemical impedance spectroscopy (EIS) technique was employed to quantify the charge transport resistance (R_ct) and electron lifetime under different ratios of the TiNT/nanoparticle. The electron lifetimes of the DSSCs based on FL and N3 dye were very close to one another and the DSSC based on the FL showed respectable photovoltaic performance of ca. 7.8% under the light intensity of 100 mW cm⁻² (AM 1.5G).     

Microstructure and ionic conductivity properties of gadolinia doped ceria (GdxCe1−xO2−x/2) electrolytes for intermediate temperature SOFCs prepared by the polyol method

Gd_0.1Ce_0.9O_1.95 and Gd_0.2Ce_0.8O_1.9 powders were prepared through the polyol process without using any protective agent. Microstructural and physical properties of the samples were characterized with X-ray diffraction (XRD), scanning electron microscopy (SEM), thermogravimetry (TG) and impedance analysis methods. The results of the thermogravimetry/differential thermal analysis (TG/DTA) and XRD indicated that a single-phase fluorite structure formed at the relatively low calcination temperature of 500 °C. The XRD patterns of the samples revealed that the crystallite size of the samples increased as calcination temperatures increased. The sintering behavior and ionic conductivity of pellets prepared from gadolinia doped ceria (GDC) powders, which were calcined at 500 °C, were also investigated. The relative densities of the pellets, which were sintered at temperatures above 1300 °C, were higher than 95%. The results of the impedance spectroscopy revealed that the GDC-20 sample that was sintered at 1400 °C exhibited an ionic conductivity of 3.25×10⁻² S cm⁻¹ at 800 °C in air. This result clearly indicates that GDC powder with adequate ionic conductivity can be prepared through the polyol process at low temperatures.     

Photocatalytic degradation of methylene blue with TiO2 nanoparticles prepared by a thermal decomposition process

The generation of TiO₂ nanoparticles by the thermal decomposition of titanium tetraisopropoxide (TTIP) was carried out experimentally using a tubular electric furnace at various synthesis temperatures (700-1300 °C) and TTIP heating temperatures (80-110 °C). The photocatalytic activity of the resulting TiO₂ nanoparticles was examined by measuring the rate of methylene blue decomposition. The TiO₂ nanoparticles were characterized by X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) measurements and transmission electron microscopy (TEM). The crystallite size and crystallinity increased with increasing synthesis temperature and TTIP heating temperature. A TTIP heating temperature and synthesis temperature of 95 °C and 900 °C, respectively, were found to be the optimal synthesis conditions. The primary particle diameter obtained under optimum synthesis conditions was considerably smaller than the commercial photocatalyst (Degussa, P25). The specific surface areas were more than 134.4 m² g^− 1. Under the optimal conditions, the photocatalytic activity for methylene blue was higher than that of the commercial photocatalyst.     

Preparation of nanosized anatase TiO2-coated kaolin composites and their pigmentary properties

Nanosized anatase TiO₂-coated kaolin composites were prepared by the chemical deposition method starting from calcined kaolin and TiCl₄. The resultant TiO₂ nanoparticles on the kaolin surfaces existed in anatase phase after calcination at 200, 400, and 900 °C for 1 h, respectively. The surfaces of the kaolin powders were uniformly coated by a monolayer of TiO₂ nanoparticles. The higher calcination temperature was beneficial to formation of well crystallized anatase TiO₂ nanoparticles. The light scattering indexes of the TiO₂-coated calcined kaolin composites were two times higher than that of the kaolin substrate. XPS analysis shows that TiO₂ coating layers anchored at the kaolin surfaces via the Ti-O-Si and Ti-O-Al bonds.     

Formation of LiNi0.5Co0.5VO4 nano-crystals by solvothermal reaction

LiNi_0.5Co_0.5VO₄ nano-crystals were solvothermally prepared using a mixture of LiOH·H₂O, Ni(NO₃)₂·6H₂O, Co(NO₃)₂·6H₂O and NH₄VO₃ in isopropanol at 150–200 °C followed by 300–600 °C calcination to form powders. TGA curves of the solvothermal products show weight losses due to evaporation and decomposition processes. The purified products seem to form at 500 °C and above. The products analyzed by XRD, selected area electron diffraction (SAED), energy dispersive X-ray (EDX) and atomic absorption spectrophotometer (AAS) correspond to LiNi_0.5Co_0.5VO₄. V–O stretching vibrations of VO₄ tetrahedrons analyzed using FTIR and Raman spectrometer are in the range of 620–900 cm⁻¹. A solvothermal reaction at 150 °C for 10 h followed by calcination at 600 °C for 6 h yields crystals with lattice parameter of 0.8252 ± 0.0008 nm. Transmission electron microscope (TEM) images clearly show that the solvothermal temperatures play a more important role in the size formation than the reaction times.     

Titania-silica composites with less aggregated particles

Less aggregated titania-silica composite was developed by a versatile and reproducible method using relatively cheap precursors. The final product has more suitable properties than the conventional materials. The composite was synthesized by using sodium silicate, as a silica precursor, and freshly prepared TiOCl₂ as a titania source. The final product was obtained after subsequent calcination for 5 h at 300 to 1000 °C. The primary particles of the composite, as examined by SEM technique, are generally less aggregated. The XRD patterns for the calcined samples indicate the presence of TiO₂ and there is a significant increase of peak intensity as the calcination temperature increases. EDS and XPS analyses confirmed the formation of pure composite rich in Ti, Si, and O. Nitrogen physisorption studies reveal that the composite is mesoporous and have large BET surface area (~ 375 m²/g). A simple experiment of photoreduction of methyl orange under solar radiation was attempted to demonstrate the reliability and improvement of titania-silica composite in practice. It was found out that its efficiency is high as compared to P-25 TiO₂ under solar light. The results demonstrate that composite with desirable properties for various applications can be obtained via the present route.     

A high temperature stable electrolyte system for dye-sensitized solar cells

The effect of the addition of single and binary additives to a mixed solvent, ethylene carbonate + γ-butyrolactone, on the performance of dye-sensitized TiO₂ solar cells (DSSCs) has been investigated. The addition of a single additive, 2-(dimethylamino)-pyridine, to the electrolyte containing an ionic salt, 1,2-dimethyl-3-propylimidazolium iodide, in the mixed solvent results in an enhancement of the cell performance. The performance of the cell has been further enhanced by the addition of the second additive, 5-chloro-1-ethyl-2-methylimidazole. The resulting DSSC has performed better than the one based on the conventional electrolyte in acetonitrile. The dependence of the stability of the cells on the temperature has been evaluated over the range of 30-120 °C for outdoor applications.     

Experimental determination of the eutectic temperature in air of the CuO-TiO2 pseudobinary system

Eutectic temperature and composition in the CuO-TiO₂ pseudobinary system have been experimentally determined in air by means differential thermal analysis (DTA), thermogravimetry (TG) and hot-stage microscopy (HSM). Samples of the new eutectic composition treated at different temperatures have been characterized by X-ray diffraction (XRD) and X-ray absorption near-edge structural spectroscopy (XANES) to identify phases and to determine the Cu valence state, respectively. The results show that the eutectic temperature in air is higher by 100 °C (∼1000 °C) for a Ti-richer composition (XTiO₂=25 mol%) than the one calculated in the literature. The reduction of Cu²⁺ to Cu⁺ takes places at about 1030 °C. The existence of Cu₂TiO₃ and Cu₃TiO₄ has been confirmed by XRD in the temperature range between 1045 and 1200 °C.