An inexpensive and efficient pyridine-based additive for the electrolyte of dye-sensitized solar cells

We report on the synthesis and application of an inexpensive pyridine-based additive allyl isonicotinate (AIN) for the efficient dye-sensitized solar cells (DSCs). AIN can be quickly synthesized at room temperature without any solvent. The presence of AIN in the electrolyte enhances the open-circuit voltage (V_oc), fill factor (FF) and short-circuit photocurrent (J_sc), consequently improving the energy conversion efficiency (η) from 6.5% to 8.2%. The impedance experiments show that the adsorption of AIN leads to the negative shift of the conduction band edge of the dye-sensitized TiO₂ around 55 mV. The presence of AIN in the electrolyte can obviously suppress the recombination of the injected electrons, increasing the lifetime of electrons in the TiO₂. The negative shift of the conduction band edge and the suppression of the recombination of the injected electrons contribute to the higher power conversion efficiency.     

A study of stainless steel-based dye-sensitized solar cells and modules

Stainless steel (StSt) has been applied as substrate material for efficient, flexible, nanoporous TiO₂ dye-sensitized solar cells (DSSCs) with the aim of improving the photochemical properties of current plastic-based flexible DSSCs. DSSCs with a StSt substrate show almost equivalent properties in efficiency and convenience to cells with a F-doped tin oxide (FTO) glass substrate. Specifically, the metal substrate allows application of high-temperature sintering processes and shows high conductance even after sintering. Cells fabricated with the StSt substrates have been investigated as individual cells and as modules. A comparison between conventional DSSCs with a FTO glass substrate and flexible DSSCs with a StSt substrate is presented. In addition, Pt-coated electrodes, which can serve as window electrodes for StSt-based DSSCs, are fabricated via two different methods, i.e., chemical reduction and annealing, and compared.     

Optical properties of nano-structured dye-sensitized solar cells

Radiative transfer computations are carried out to describe the intrinsic and effective optical properties of light diffusing and absorbing materials consisting of anatase titania pigments hosted in an electrolyte medium. The intrinsic visible absorption of some of the pigments has been increased by coating them with an absorbing dye monolayer. A multiple scattering approach is applied to compute average path-length parameters and forward-scattering ratios used in four-flux radiative transfer calculations. It is shown that the effective absorption coefficient of the inhomogeneous medium is maximized when the size of the pigments is around 12 nm in diameter, and the effective scattering coefficient is optimized for diameters of the pigments around 250 nm. The intrinsic solar absorptance of the medium is optimized when the diameter of the pigments is around 60 nm.     

A study on the electron transport properties of TiO2 electrodes in dye-sensitized solar cells

The influences of annealing temperature and different poly (ethylene glycol) (PEG) contents in nano-crystalline TiO₂ electrodes with and without N3 dye on the electron transfer in a dye-sensitized solar cell (DSSC) were investigated. It is found that the power conversion efficiency increases with the increase in annealing temperature and becomes saturated at 400–500 °C, and further increase lowers the performance which is consistent with the enhancement of the crystalline TiO₂ particles observed in X-ray diffraction (XRD) patterns and scanning electron microscopy (SEM) images. Electrochemical impedance spectroscopy (EIS) also confirms this behavior. These results have been further verified by studying the electron lifetimes (τ_e) and electron diffusion coefficients (D_e) of a bare TiO₂ and a dye-sensitized TiO₂ film using a pulsed laser spectrometer. It is noted that both the electron lifetime and the electron diffusion coefficient increase with the increase in annealing temperature. However, the evolution of rutile TiO₂ begins beyond 600 °C and this lowers the dye absorbance and the electron diffusion coefficients of TiO₂ electrodes. A similar study was made by varying the content of the PEG in the TiO₂ films. It is found that with the increase in the PEG content, a decrease in the electron lifetimes and a little hike in the electron diffusion coefficients are noted, where the cell performance remains almost the same. In addition, the dye adsorption decreases the electron lifetime and increases the electron diffusion coefficient of the TiO₂ films regardless of the PEG content and the annealing temperature.     

Influence of alkylpyridine additives in electrolyte solution on the performance of dye-sensitized solar cell

The influence of alkylpyridines additive to an I⁻/I₃⁻ redox electrolyte in acetonitrile on the performance of a bis(tetrabutylammonium)cis-bis(thiocyanato)bis(2,2′-bipyridine-4-carboxylic acid, 4′-carboxylate)ruthenium(II) dye-sensitized TiO₂ solar cell was studied. I–V measurements were performed using more than 30 different alkylpyridines. The alkylpyridine additives showed a significant influence on the performance of the cell. All the additives decreased the short-circuit photocurrent (J_sc), but most of the alkylpyridines increased the open-circuit photovoltage (V_oc) and fill factor (ff) of the solar cell. The results of the molecular orbital calculations suggest that the dipole moment of the alkylpyridine molecules correlate with the J_sc of the cell. These results also suggest that both the size and ionization energy of pyridines correlate with the V_oc of the cell. Under AM 1.5 (100 mW/cm²), the highest solar energy conversion efficiency (η) of 7.6% was achieved by using 2-propylpyridine as an additive, which was more effective than the previously reported additive, 4-t-butylpyridine.     

Influence of alkylaminopyridine additives in electrolytes on dye-sensitized solar cell performance

The influence of alkylaminopyridine additives on the performance of a bis(tetrabutylammonium)cis-bis(thiocyanato)bis(2,2′-bipyridine-4-carboxylic acid, 4′-carboxylate)ruthenium(II) dye-sensitized TiO₂ solar cell with an I⁻/I₃⁻ redox electrolyte in acetonitrile was studied. The current–voltage characteristics were measured for more than 20 different alkylaminopyridines under AM 1.5 (100 mW/cm²). The alkylaminopyridine additives tested had varying effects on the performance of the cell. All the additives decreased the short circuit photocurrent density (J_sc), but increased the open-circuit photovoltage (V_oc) of the solar cell. Molecular orbital calculations imply that the dipole moment of the alkylaminopyridine molecules influences the J_sc of the cell and that the size, solvent accessible surface area, and ionization energy all affect the V_oc of the cell. The highest V_oc of 0.88 V was observed in an electrolyte containing 4-pyrrolidinopyridine, which is comparable to the maximum V_oc of 0.9 V for a cell consisting of TiO₂ electrode and I⁻/I₃⁻ redox system.     

Triphenylamine-based organic dye containing the diphenylvinyl and rhodanine-3-acetic acid moieties for efficient dye-sensitized solar cells

In this paper, we report on the synthesis, characterization of a new triphenylamine (TPA) derivative (TPAR14) with a “secondary electron transferring” structure as well as its application to dye-sensitized solar cells (DSCs). The introduction of diphenylvinyl to the adjacent phenyl ring of the TPA core could not only increase the extinction coefficient and λ_max by the extension of π-conjugation, but also form three-dimensional obstacle for dye aggregation and triiodide that is in favor of higher open-circuit photovoltage (V_oc). An overall light-to-electricity conversion efficiency of 6.27% is obtained for the DSC with the as-synthesized dye under AM 1.5 irradiation (100 mW cm⁻²), which is the highest value among the TPA-rhodanine-3-acetic acid-based DSCs. The long-term stability test of TPAR14 under heat shows its character of high stability. The present work indicates that the as-synthesized TPAR14 is promising in the application of DSCs.     

Enhancing the performance of dye-sensitized solar cells by incorporating nanosilicate platelets in gel electrolyte

Two kinds of gel-type dye-sensitized solar cells (DSSCs), composed of two types of electrolytes, were constructed and the respective cell performance was evaluated in this study. One electrolyte, TEOS-Triton X-100 gel, was based on a hybrid organic/inorganic gel electrolyte made by the sol–gel method and the other was based on poly(vinyidene fluoride-co-hexafluoro propylene) (PVDF-HFP) copolymer. TEOS-Triton X-100 gel was based on the reticulate structure of silica, formed by hydrolysis, and condensation of tetraethoxysilane (TEOS), while its organic subphase was a mixture of surfactant (Triton X-100) and ionic liquid electrolytes. Both DSSC gel-type electrolytes were composed of iodine, 1-propy-3-methyl-imidazolium iodide, and 3-methoxypropionitrile to create the redox couple of I₃⁻/I⁻. Based on the results obtained from the I–V characteristics, it was found that the optimal iodine concentrations for the TEOS-Triton X-100 gel electrolyte and PVDF-HFP gel electrolyte are 0.05 M and 0.1 M, respectively. Although the increase in the iodine concentration could enhance the short-circuit current density (J_SC), a further increase in the iodine concentration would reduce the J_SC due to increased dark current. Therefore, the concentration of I₂ is a significant factor in determining the performance of DSSCs.In order to enhance cell performance, the addition of nanosilicate platelets (NSPs) in the above-mentioned gel electrolytes was investigated. By incorporating NSP-Triton X-100 into the electrolytes, the J_SC of the cells increased due to the decrease of diffusion resistance, while the open circuit voltage (V_OC) remained almost the same. As the loading of the NSP-Triton X-100 in the TEOS-Triton X-100 gel electrolyte increased to 0.5 wt%, the J_SC and the conversion efficiency increased from 8.5 to 12 mA/cm² and from 3.6% to 4.7%, respectively. However, the J_SC decreased as the loading of NSP-Triton X-100 exceeded 0.5 wt%. At higher NSP-Triton X-100 loading, NSPs acted as a barrier interface between the electrolyte and the dye molecules, hindering electron transfer, hence, reducing the cell's photocurrent density. The same behavior was also observed in the PVDF-HFP gel electrolyte DSSC system.     

On the photophysical and electrochemical studies of dye-sensitized solar cells with the new dye CYC-B1

In this study, the photoelectrochemical characteristics of a ruthenium photosensitizer with an alkyl bithiophene group, designated as CYC-B1, are studied. The effect of mesoporous TiO₂ film thickness on the photovoltaic performance of CYC-B1 and N3 dye-sensitized solar cells was investigated. The performance of the dye-sensitized nanocrystalline TiO₂ solar cells (DSSC) fabricated using CYC-B1 dye-anchored TiO₂ photoelectrode showed a convincing enhancement in cell efficiency when the TiO₂ film thickness was increased from 3 μm (eff.=5.41%) to 6 μm (eff.=7.19%). The efficiency of the CYC-B1-sensitized DSSC was maximum at 6 μm of the TiO₂ film thickness, reached its limiting value and remained constant up to 53 μm, although a similar trend was also observed for N3 dye-sensitized DSSC, however, the maximum efficiency achieved was only at 27 μm thickness (eff.=6.75%). As expected, the photocurrent density generated in the DSSC modified by CYC-B1 dye is larger than that from N3 dye. The effect of guanidinium thiocyanate (GuSCN) (additive) addition to the electrolyte on the photovoltaic performance of DSSCs based on CYC-B1 was also investigated. Furthermore, the electrochemical impedance spectroscopy (EIS) technique and photo-transient laser method have been employed to analyze the charge transfer resistances (R_ct) and the lifetime of the injected electrons on the TiO₂ containing different thicknesses.     

The effect of temperature on the performance of dye-sensitized solar cells based on a propyl-methyl-imidazolium iodide electrolyte

The performance of dye-sensitized solar cells (DSSC), based on an ionic liquid (propyl-methyl-imidazolium iodide) electrolyte, has been evaluated at varying iodine concentrations and cell temperatures (5–50 °C) for two irradiancies (0.1 and 1 sun). At 1 sun and at lower temperatures, the short-circuit current (J_SC) is limited by the diffusion of tri-iodide, while at higher temperatures, the J_SC decreases due to more pronounced recombinations. Also, the conversion efficiency of a DSSC resembles the J_SC behaviour. At 0.1 sun irradiance, the efficiency monotonically decreases with increasing temperature, while at 1 sun, a five-fold increase in efficiency is observed.     

A novel UV-mediated low-temperature sintering of TiO2 for dye-sensitized solar cells

Titania pastes were fired at 450 °C in oxygen to give white titania that was used to prepare dye-sensitized solar cells (DSSC). Titania fired at lower temperature and/or under inert atmosphere have brown stripes and cells made from these stripes had no measurable efficiency. When the titania paste was screen printed and then heated and simultaneously irradiated with UV light, white stripes were obtained. Improved efficiency was noted for PV cells made from pastes heated at lower temperature under irradiation vs. cells made from low-temperature heated paste but without irradiation. UV irradiation appears to facilitate clean oxidation of residual organic materials in the titania precursor pastes. The best cells in our study made with our titania paste treated at 450 °C in oxygen had the following characteristics: efficiency=3.45%; V_oc=630 mV; J_sc=8.5 mA/cm²; and a fill factor=0.64.     

Anthraquinone dyes as photosensitizers for dye-sensitized solar cells

Three anthraquinone dyes with carboxylic acid as anchoring group are designed and synthesized as sensitizers for dye-sensitized solar cells (DSSCs). Preliminary photophysical and photoelectrochemical measurements show that these anthraquinone dyes have very low performance on DSSC applications, although they have broad and intense absorption spectra in the visible region (up to 800 nm). Transient absorption kinetics, fluorescence lifetime measurements and density functional theory (DFT) calculations are conducted to investigate the cause of such low DSSC performance for these dyes. The results show that the strong electron-withdrawing character of the two carbonyl groups on anthraquinone framework may lie behind the low performance by suppressing the efficient electron injection from the dye to the conduction band of TiO₂.     

Utilization of natural carotenoids as photosensitizers for dye-sensitized solar cells

The dye-sensitized solar cells (DSCs) were assembled by using natural carotenoids, crocetin (8,8′-diapocarotenedioic acid) and crocin (crocetin-di-gentiobioside), as sensitizers and their photoelectrochemical properties were investigated taking a presence or absence of carboxylic group in the dye molecule into consideration. In these carotenoids, crocetin that has carboxylic groups in the molecule can attach effectively to the surface of TiO₂ film so that it performed the best photosensitized effect resulting in the short-circuit photocurrent with 2.84 mA under irradiation of 1.0 cm². On the other hand, crocin that has no carboxylic group in the molecule showed lower photoelectrochemical performance because of its lower affinity to the surface of TiO₂ film. These results indicate that it is possible to apply carotenoid as sensitizers for DSCs at the presence of effective function groups.     

Effect of electrode geometry on the photovoltaic performance of dye-sensitized solar cells

Effect of electrode geometry on the photovoltaic performance of dye-sensitized solar cell (DSSC) has been investigated to optimize the device geometry for reliable energy conversion efficiency assessment. Mesoporous TiO₂ layers with an identical active area (0.40 cm²) and different dimension are prepared on FTO glass substrate by the screen printing method and used as photoanodes for DSSCs. Under 1 sun illumination (AM 1.5G, 100 mW cm⁻²), both the open-circuit voltage and the short-circuit current density are independent of electrode geometry whereas the fill factor and hence energy conversion efficiency show strong dependency. Electrochemical impedance spectroscopy analysis indicates that the distance between active layer and ohmic contact directly contributes to internal series resistance and influence photovoltaic performance.     

Low band gap dyes based on 2-styryl-5-phenylazo-pyrrole: Synthesis and application for efficient dye-sensitized solar cells

A new series of low band gap dyes, C1, C2 and S, based on 2-styryl-5-phenylazo-pyrrole was synthesized. These dyes contain one carboxy, two carboxy and one sulfonic acid anchoring groups, respectively. They were soluble in common organic solvents, showed long-wavelength absorption maximum at ∼620 nm and optical band gap of 1.66-1.68 eV. The photophysical and electrochemical properties of these dyes were investigated and found to be suitable as photosensitizers for dye sensitized solar cells (DSSCs). The quasi solid state DSSCs with dye S showed a maximum monochromatic incident photon to current efficiency (IPCE) of 78% and an overall power conversion efficiency (PCE) of 4.17% under illumination intensity of 100 mW cm⁻² (1.5 AM), which is higher than the other dyes (3.26% for C2 and 2.59% for C1). Even though dye S contains one sulfonic acid anchoring group, the higher PCE for the DSSCs based on this dye has been attributed to the higher dye loading at the TiO₂ surface and enhanced electron lifetime in the device, as indicated by absorption spectra and electrochemical impedance spectra measurements. Finally, by increasing the molecular weight of poly(ethylene oxide) (PEO) in electrolyte, the PCE also increases up to 4.8% for the electrolyte with PEO molecular weight of 2.0 × 10⁶. This improvement has been attributed to the enhancement in iodide ions diffusion due to the increase in free volume of polymer gel electrolyte.     

Influences of water in bis-benzimidazole-derivative electrolyte additives to the degradation of the dye-sensitized solar cells

The chemical stability of dye-sensitized solar cells (DSSC) determines both the cell performance and the cell life-time. The presence of water in the solar cell from surrounding leakage through the imperfection packaging sealants causes the decrease in life-time of photogenerated electrons on the working electrodes, which induces the occurrence of the dark current to the electrolytes and thus leakage current significantly deteriorated the life-time of the DSSC. Reliable electrolyte additives diminishing the influences of water to the DSSCs degradation process becomes a critical issue in maintaining an acceptable cell life-time.In this work, the effects of four benzimidazole derivatives a-d as the electrolyte additives in the presence of water were comprehensively examined by time-dependent photovoltaic performance of the cells. As a result, open-circuit voltage (V_oc), short-circuit current (J_sc), efficiency (η), and fill factor (FF) collected from I-V curves were studied. In addition, electrochemical impedance spectroscopy (EIS) technique was implemented to evaluate the effects of the charge-transfer resistance (R_ct) at the interfaces between TiO₂/dye/electrolyte. Results showed that the bis-benzimidazole derivative c gives significant improvement in the long-term stability due to the effective protection of the ligands between dye and working electrodes from the attack by environmental water molecules.     

Low-Pt-loading acetylene-black cathode for high-efficient dye-sensitized solar cells

We reported on the synthesis, characterization, and photovoltaic/electrochemical properties of Pt/acetylene-black (AB) cathode as well as their application in dye-sensitized solar cells (DSCs). The Pt/AB electrode was prepared through a thermal decomposition of H₂PtCl₆ on the AB substrate. SEM and TEM observations showed that the Pt nanoparticles were homogeneously dispersed on the AB surface. The Pt-loading content in the Pt/AB electrode was only about 2.0 μg cm⁻², which was much lower than 5–10 μg cm⁻² generally used for the Pt electrode in DSCs. Electrochemical measurements displayed a low charge-transfer resistance of 1.48 Ω cm² for the Pt/AB electrode. Furthermore, when this low-Pt-loading electrode was used as the cathode of DSCs, an overall light-to-electricity energy conversion efficiency of 8.6% was achieved, showing commercially realistic energy conversion efficiency in the application of DSCs.     

Hydrogen treated TiO2 nanoparticles onto FTO glass as photoanode for dye-sensitized solar cells with remarkably enhanced performance

Hydrogen treatment is a facile and efficient approach for the enhancement in the functioning of TiO₂ nanoparticles for dye-sensitized solar cells (DSSC). In this work, TiO₂ nanoparticles have been synthesized in the hydrogen environment followed by the deposition onto FTO glass substrates with various film thickness as photoanodes for DSSC. The synthesized hydrogen treated TiO₂ nanoparticles based photoanodes have showed significantly improved photocurrent in the resulting fabricated devices. SEM and TEM analyses have confirmed the particle size and morphology of TiO₂ nanoparticles at various magnifications. The crystalline structure and phase identification were studied by XRD analysis and Raman spectroscopic measurements. The UV–Vis spectroscopy analysis was carried out to find the response of samples for ultraviolet and visible light. The current-voltage measurements have confirmed the improvement of photocurrent that is principally due to improved photo-activity of hydrogen treated TiO₂ nanoparticles. Moreover, hydrogen treated TiO₂ nanoparticles-based photoanode with the film thickness of 11.65 μm has remarkably enhanced power conversion efficiency of 6.05% in DSSCs. The ability of highly photoactive hydrogen treated TiO₂ nanoparticles will provide the new openings in different fields that include photo-electrochemical water splitting and in many other applications.     

Carbon-nanofiber counter electrodes for quasi-solid state dye-sensitized solar cells

Carbon-nanofibers (CNFs) with antler and herringbone structures are studied as a tri-iodide (I₃⁻) reduction electrocatalyst in combination with the liquid electrolyte or an alternative stable quasi-solid state electrolyte. The catalytic properties of the counter electrode (CE) are characterized by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The doctor bladed low temperature CNFs-CE has faster I₃⁻ reduction rate and low charge transfer resistance (R_CT) of ∼0.5 Ω cm² than platinum (Pt) (∼2.3 Ω cm²) due to the nanofiber stacking morphology. Its herringbone and antler structures with graphitic layers lead to defect rich edge planes and larger diameter of CNFs facilitate the electron transfer kinetics. The cells with CNF counter electrodes are showing promising energy conversion efficiency greater than 7.0% for the glass based devices and 5.0% for the flexible cells filled with the quasi-solid state electrolyte, which is similar to Pt performance. Application of CNFs-CE in flexible and quasi-solid state electrolyte increases the possibility of roll to roll process, low cost and stable dye-sensitized solar cells (DSCs).     

Influences of different TiO2 morphologies and solvents on the photovoltaic performance of dye-sensitized solar cells

The effects of TiO₂ photoelectrode's surface morphology and different solvents on the photovoltaic performance of dye-sensitized solar cells (DSSCs) were studied. By successive coating of TiO₂ suspension, composed of low and high molecular weight poly(ethylene)glycol (PEG) as a binder, double layered TiO₂ photoelectrodes with four different structures were obtained. Among the DSSCs with different TiO₂ electrodes, DSSC with P2P1 electrode (P2 and P1 correspond to PEG molecular weights of 20,000 and 200,000, respectively) showed higher performance under identical film thickness at a constant irradiation of 100 mW cm⁻², which may be correlated with large pore size and high surface area of the corresponding TiO₂ electrode. This was confirmed by electrochemical impedance spectroscopy (EIS) analysis of the DSSC and the transient photovoltage measurement of electrons in the TiO₂ electrode. Among the different solvents investigated here, the DSSC containing acetonitrile showed high conversion efficiency and the order of performance of the DSSCs with different solvents were AN > MPN > PC > GBL > DMA > DMF > DMSO. Better correlation was observed between the donor number of solvents and photoelectrochemical parameters of the DSSCs containing different solvents rather than the measured viscosity and dielectric constant of solvents. The reasons for the low performance of the DSSCs containing DMA, DMSO and DMF, respectively, were due to the negative shift of TiO₂ conduction band and the desorption of dye molecules from the TiO₂ photoelectrode by those solvents.