Roles of electrolytes on charge recombination in dye-sensitized TiO(2) solar cells (2): the case of solar cells using cobalt complex redox couples

Dye-sensitized solar cells (DSC) were prepared from nanoporous TiO(2) electrodes with two different cobalt complex redox couples, propylene-1,2-bis(o-iminobenzylideneaminato)cobalt(II) {Co(II)(abpn)} and tris(4,4'-di-tert-buthyl-2,2'-bipyridine)cobalt(II) diperchlorate {Co(II)(dtb-bpy)(3)(ClO(4))(2)}. The performances of the DSCs were examined with varying the concentrations of the redox couples and Li cations in methoxyacetonitrile. Under 1 sun conditions, short-circuit currents (J(sc)) increased with the increase of the redox couple concentration, and the maximum J(sc) was found at the Li(+) concentration of 100 mM. To rationalize the observed trends of J(sc), electron diffusion coefficients and lifetimes in the DSCs were measured. Electron diffusion coefficients in the DSCs using cobalt complexes were comparable to the previously reported values of nanoporous TiO(2). Electron lifetime was independent of the concentration of the redox couples when the concentration ratio of Co(II)(L) and Co(III)(L) was fixed. With the increase of Li(+) concentration, the electron lifetime increased. These results were interpreted as due to their slow charge-transfer kinetics and the cationic nature of Co complex redox couples, in contrast to the anionic redox couple of I(-)/I(3)(-). The increase of the lifetimes with Li(+) was interpreted with the decrease of the local concentration of Co(III) near the surface of TiO(2). The addition of 4-tert-butylpyridine (tBP) with the presence of Li(+) increased J(sc) significantly. The observed increase of the electron lifetime by tBP could not explain the large increase of J(sc), implying that tBP facilitates the charge transfer from Co(II)(L) to dye cation, with the association of the change of the reorganization energy between Co(II) and Co(III).     

Organic redox couples and organic counter electrode for efficient organic dye-sensitized solar cells

A series of organic thiolate/disulfide redox couples have been synthesized and have been studied systematically in dye-sensitized solar cells (DSCs) on the basis of an organic dye (TH305). Photophysical, photoelectrochemical, and photovoltaic measurements were performed in order to get insights into the effects of different redox couples on the performance of DSCs. The polymeric, organic poly(3,4-ethylenedioxythiophene) (PEDOT) material has also been introduced as counter electrode in this kind of noniodine-containing DSCs showing a promising conversion efficiency of 6.0% under AM 1.5G, 100 mW·cm(-2) light illumination. Detailed studies using electrochemical impedance spectroscopy and linear-sweep voltammetry reveal that the reduction of disulfide species is more efficient on the PEDOT counter electrode surface than on the commonly used platinized conducting glass electrode. Both pure and solvated ionic-liquid electrolytes based on a thiolate anion have been studied in the DSCs. The pure and solvated ionic-liquid-based electrolytes containing an organic redox couple render efficiencies of 3.4% and 1.2% under 10 mW·cm(-2) light illumination, respectively.     

Sponge-like TiO2 layers for dye-sensitized solar cells

A titanium oxide layer used in a dye-sensitized solar cell (DSSC) has to meet two opponent properties to enable high conversion efficiency: a large surface area (for high dye loading) and good connection between TiO₂ grains (for efficient extraction of electrons toward the front contact). In order to meet a trade-off between these criteria a preparation method for TiO₂ paste formulation based on Pechini sol–gel method and commercial nanocrystalline TiO₂ powder has been developed. A series of TiO₂ pastes with different molar ratios between titanium isopropoxide, citric acid and ethylene glycol (1:X:4X) in the paste have been examined. The structure and morphology as well as cross-cut tests of deposited and sintered TiO₂ layers have been analyzed. Results reveal that the paste with X = 8 exhibits the best properties, resulting in an overall conversion efficiency of DSSC under standard test conditions (100 mW/cm², 25 °C, AM 1.5G) up to 6.6% for ionic liquid based electrolyte.     

Computational design of cyclic nitroxides as efficient redox mediators for dye-sensitized solar cells

Cyclic nitroxide radicals represent promising alternatives to the iodine-based redox mediator commonly used in dye-sensitized solar cells (DSSCs). To date DSSCs with nitroxide-based redox mediators have achieved energy conversion efficiencies of just over 5?% but efficiencies of over 15?% might be achievable, given an appropriate mediator. The efficacy of the mediator depends upon two main factors: it must reversibly undergo one-electron oxidation and it must possess an oxidation potential in a range of 0.600-0.850?V (vs. a standard hydrogen electrode (SHE) in acetonitrile at 25?°C). Herein, we have examined the effect that structural modifications have on the value of the oxidation potential of cyclic nitroxides as well as the reversibility of the oxidation process. These included alterations to the N-containing skeleton (pyrrolidine, piperidine, isoindoline, azaphenalene, etc.), as well as the introduction of different substituents (alkyl-, methoxy-, amino-, carboxy-, etc.) to the ring. Standard oxidation potentials were calculated using high-level ab initio methodology that was demonstrated to be very accurate (with a mean absolute deviation from experimental values of only 16?mV). An optimal value of 1.45 for the electrostatic scaling factor for UAKS radii in acetonitrile solution was obtained. Established trends in the values of oxidation potentials were used to guide molecular design of stable nitroxides with desired E(ox)°, and a number of compounds were suggested for potential use as enhanced redox mediators in DSSCs.     

Partially nanowire-structured TiO2 electrode for dye-sensitized solar cells

Partially nanowire-structured TiO₂ was prepared by a hydrothermal processing followed by calcination in air. The hydrogen titanate powder as-synthesized was calcined at 300 °C for 4 h to obtain the partially nanowire-structured TiO₂. A dye-sensitized solar cell (DSC) with a film thickness of 5.6 μm, fabricated using the partially nanowire-structured TiO₂ showed better performance than using a fully nanowire-structured TiO₂ or a conventional equi-axed TiO₂ nanopowder. The short-circuit current density (J_SC), the open-circuit voltage (V_OC), the fill factor (FF) and the overall efficiency (η) are 11.9 mA/cm², 0.754 V, 0.673 and 6.01 %, respectively. The effects of one-dimensional nanostructure and electron expressway concept are discussed.     

Rutile TiO2 nano-branched arrays on FTO for dye-sensitized solar cells

Hierarchical TiO(2) nanostructures would be desirable for preparing dye-sensitized solar cells because of their large amount of dye adsorption and superior light harvesting efficiency, as well as efficient charge separation and transport properties. In this study, rutile TiO(2) nano-branched arrays grown directly on transparent conductive glass (FTO) were prepared by a facile two-step wet chemical synthesis process, using a simple aqueous chemical growth method involving immersing the TiO(2) nanorod arrays in an aqueous TiCl(4) solution as seeds, which were prepared by a hydrothermal method. The dye-sensitized solar cells based on the TiO(2) nano-branched arrays which were only about 3 μm in length show a short-circuit current intensity of 10.05 mA cm(-2) and a light-to-electricity conversion efficiency of 3.75%, which is nearly three times as high as that of bare nanorod arrays, due to the preferable nanostructure, which not only retains the efficient charge separation and transport properties of the nanorod arrays, but also can improve the amount of dye adsorption due to the increased specific surface area from the nanobranches.     

Anisotropic TiO2 nanomaterials in dye-sensitized solar cells

The review presented below summarizes the up-to-date research efforts in using one-dimensional TiO(2) nanomaterials in dye-sensitized solar cells. A brief account of the methods of synthesis of the anisotropic nanomaterials as well as their photovoltaic performance in DSCs was summarily presented. The usefulness of the materials as scattering layer in DSCs was also surveyed.     

Highly efficient catalysts for Co(II/III) redox couples in dye-sensitized solar cells

We developed several low-cost catalysts with high catalytic activity, which were used as counter electrodes in dye-sensitized solar cells (DSCs). They showed higher efficiencies than that of Pt. The efficiencies were improved by 18-42% for the DSCs composed of active carbon, niobium dioxide, ordered mesoporous carbon and commercial titanium carbide.     

Efficient dye-sensitized solar cells based on surfactant-mediated TiO2 nanostructures

Journal of Solid State Electrochemistry - Dye-sensitized solar cells (DSSCs) based on TiO2 nanostructures have attracted much attention due to their high photoconversion efficiency. Here, we report...     

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%.     

Microwave processing of TiO2 blocking layers for dye-sensitized solar cells

The microwave heat treatment of blocking layers for dye-sensitized solar cells has been investigated. It has been found that the solar cell efficiencies achieved with microwave heating were considerably higher than those achieved with conventional heating at low temperatures (100°C). This was attributed to microwave heating providing better sintering of the blocking layer and better interfacial contact between the substrate and the TiO₂ layers. These results are promising with regard to the application of microwave heating to the production of dye-sensitized solar cells on flexible polymer substrates.     

Hierarchical twin-scale inverse opal TiO2 electrodes for dye-sensitized solar cells

We describe the preparation of three-dimensional hierarchical twin-scale inverse opal (ts-IO) electrodes for dye-sensitized solar cells (DSSCs). The ts-IO TiO(2) structure was obtained from a template fabricated via the assembly of mesoscale colloidal particles (40-80 nm in diameter) in the confined geometry of a macroporous IO structure. The photovoltaic properties of ts-IO electrodes were optimized by varying the layer thickness or the size of mesopores in the mesoscale colloidal assembly. Electron transport was investigated using impedance spectroscopy. The result showed that due to the competing effects of recombination and dye adsorption, the maximum efficiency was observed at an electrode thickness of 12 μm. The electrodes of smaller mesopores diameters yielded the higher photocurrent density due to the decrease in the electron transport resistance at the TiO(2)/dye interface. A maximum efficiency of 6.90% was obtained using an electrode 12 μm thick and a mesopore diameter of 35 nm.     

Preparation of highly ordered TiO2 nanotubes on Ti-foil for dye-sensitized solar cells

TiO₂ nanotube arrays were grown on Ti foil in mixed electrolyte by the anodizing process. TiO₂ nanotube arrays were immersed in the TiCl₄ solution to improve the photocurrent by enhanced charge transfer between TiO₂ and dye molecules on the activity surface. Internal resistance of dye-sensitized solar cells (DSSC) was measured by impedance spectroscopy measurements. Backside illuminated DSSC with TiCl₄-treated TiO₂ nanotubes exhibited a conversion efficiency of 1.45% and showed improved electron transfer.     

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.     

Surface-treated TiO2 nanoparticles for dye-sensitized solar cells with remarkably enhanced performance

Dye-sensitized solar cells (DSSCs) were prepared by capitalizing on mesoporous P-25 TiO(2) nanoparticle film sensitized with N719 dyes. Subjecting TiO(2) nanoparticle films to TiCl(4) treatment, the device performance was improved. More importantly, O(2) plasma processing of TiO(2) film that was not previously TiCl(4)-treated resulted in a lower efficiency; by contrast, subsequent O(2) plasma exposure after TiCl(4) treatment markedly enhanced the power conversion efficiency, PCE, of DSSCs. Remarkably, with TiCl(4) and O(2) plasma treatments dye-sensitized TiO(2) nanoparticle solar cells produced with 21 μm thick TiO(2) film illuminated under 100 mW/cm(2) exhibited a PCE as high as 8.35%, twice of untreated cells of 3.86%.     

Bilayer inverse opal TiO2 electrodes for dye-sensitized solar cells via post-treatment

We investigated the formation of bilayer inverse opal TiO(2) (io-TiO(2)) structures via post-treatment with a TiO(2) precursor solution and characterized the photovoltaic performances of the resulting electrodes for use in dye-sensitized solar cells. The post-treatment of TiO(2) inverse opals in a precursor solution grew rutile TiO(2) nanoparticles on anatase crystalline phase io-TiO(2) surfaces, resulting in anatase/rutile bilayer structures. We achieved a maximum photovoltaic conversion efficiency of 4.6% using a 25 μm thick electrode formed with the post-treated io-TiO(2) under simulated AM 1.5 light. This efficiency represents a 183% improvement over the non-post-treated io-TiO(2) electrodes. The shell thickness was controlled by the post-treatment time. The effects of shell thickness on photovoltaic performance were investigated by measuring the morphologies and electrochemical impedance of the post-treated io-TiO(2). We found that post-treatment up to a certain period of time increased the surface area and electron lifetime, but further treatment resulted in decreased area and saturated lifetimes. The optimal post-treatment time was identified, and the optimal io-TiO(2) electrodes were characterized.     

Addition of TiO2 nanowires in different polymorphs for dye-sensitized solar cells

TiO₂ (B) and TiO₂ anatase nanowires were prepared at 150 °C for 120 h by a hydrothermal method followed by calcination in air at 400 °C for 2 h and at 700 °C for 2 h for TiO₂ (B) and TiO₂ anatase, respectively. Although dye-sensitized solar cells (DSC) with fully nanowire electrodes showed a rather low light-to-electricity conversion efficiency of 1.33 % for TiO₂ (B) and 2.42% for TiO₂ anatase, 10 wt % nanowire-dispersed electrodes in a P-25 TiO₂-nanoparticle matrix demonstrated improved efficiency of 6.17 % for TiO₂ (B) and 6.53% for TiO₂ anatase, these exceeding that of pure P-25 electrodes in this work (η=5.59%). The dominant mechanisms of the improvement at 10 wt% for the two different polymorphs are thought to be different, i.e., a light-scattering and film-thickness increment for the TiO₂ (B) system, whereas there is an improved conduction path through the matrix for the TiO₂ anatase system.      

Facile synthesis of TiO2 inverse opal electrodes for dye-sensitized solar cells

Engineering of TiO(2) electrode layers is critical to guaranteeing the photoconversion efficiency of dye-sensitized solar cells (DSSCs). Recently, a novel approach has been introduced for producing TiO(2) electrodes using the inverted structures of colloidal crystals. This paper describes a facile route to producing ordered macroporous electrodes from colloidal crystal templates for DSSCs. Using concentrated colloids dispersed in a volatile medium, the colloidal crystal templates were obtained within a few minutes, and the thickness of the template was easily controlled by changing the quantity of colloidal solution deposited. Here, the effects of the structural properties of the inverse opal TiO(2) electrodes on the photovoltaic parameters of DSSCs were investigated. The photovoltaic parameters were measured as a function of pore ordering and electrode film thickness. Moreover, DSSC applications that used either liquid or viscous polymer electrolyte solutions were investigated to reveal the effects of pore size on performance of an inverse opal TiO(2) electrode.     

Activation energy of electron transport in dye-sensitized TiO2 solar cells

Various characteristics of dye-sensitized nanostructured TiO2 solar cells, such as electron transport and electron lifetime, were studied in detail using monochromatic illumination conditions. The electron transport was found to be a thermally activated process with activation energies in the range of 0.10-0.15 eV for light intensities that varied 2 orders of magnitude. Electron lifetimes were determined using a new method and found to be significantly larger (>1 s) than previously determined. An average potential was determined for electrons in the nanostructured TiO2 under illumination in short-circuit conditions. This potential is about 0.2 V lower than the open-circuit potential at the same light intensity. The electron transport time varies exponentially with the internal potential at short-circuit conditions, indicating that the gradient in the electrochemical potential is the driving force for electron transport in the nanostructured TiO2 film. The applicability of the conventionally used trapping/detrapping model is critically analyzed. Although experimental results can be fitted using a trapping/detrapping model with an exponential distribution of traps, the distribution parameters differ significantly between different types of experiment. Furthermore, the experimental activation energies for electron transport are smaller than those expected in a trapping/detrapping model.     

One-pot easily-processed TiO2 macroporous photoanodes (Ti-HIPE) for dye-sensitized solar cells

1. Download : Download full-size image