Performance of a new polymer electrolyte incorporated with diphenylamine in nanocrystalline dye-sensitized solar cell

A new solvent-free composite polymer electrolyte consisting of poly(ethylene oxide) (PEO) incorporated into diphenyl amine (DPA) along with KI and I₂ has been developed. The current-voltage characteristics of this nanocrystalline dye-sensitized solar cell measured under simulated sunlight with 1.5 AM at 60 mW/cm² have indicated that this cell generates a photocurrent of 10.2 mA/cm², together with a photovoltage of 810 mV and fill factor of 0.47 yielding an overall energy conversion efficiency of 6.5%. This result suggests that the electron donicity of DPA influences the interaction of nanocrystalline TiO₂ electrode and I⁻/I₃⁻ electrolyte, leading to a high performance of the fabricated solar cell.     

Influence of alkyl dihalide gelators on solidification of dye-sensitized solar cells

Quasi-dye-sensitized solar cells were prepared by using ionic liquid-type electrolytes and gelators consisting of polyvinylpyridine and alkyl dihalides. Gelation occurred by the reaction of polyvinylpyridine and alkyl dihalides. When the chain length of the dihalides was varied, the short-circuit current (J_sc) increased with an increase in the chain length. However, the open-circuit voltage (V_oc) and fill factor (ff) slightly decreased. The increase in J_sc was brought about by the decrease in the interfacial resistances between the gel electrolyte and the counter electrode. In addition, the increase in the J_sc was explained by increases in the apparent diffusion coefficient of I⁻/I₃⁻ when the chain length increased. Decreases in V_oc and ff were explained by back-electron transfers from TiO₂ to iodine in the electrolytes. V_oc of the cells solidified by alkyldiiodide was lower than that solidified by alkyldichloride or alkyldibromide. It was explained by negatively shifted redox potential of I⁻/I₃⁻, compared with those for Cl⁻/Cl₂ or Br⁻/Br₂.     

Novel thixotropic gel electrolytes based on dicationic bis-imidazolium salts for quasi-solid-state dye-sensitized solar cells

Novel thixotropic gel electrolytes have been successfully prepared by utilizing oligomeric poly(ethylene oxide) (PEO)-based bis-imidazolium diiodide salts and hydrophilic silica nanoparticles for application in quasi-solid-state dye-sensitized solar cells (DSSCs). The thixotropic gel-state of the ionic liquid-based composite electrolytes is confirmed by observing the typical hysteresis loop and temporary hydrogen bonding. On using the PEO-based composite electrolyte, a quasi-solid-state DSSC exhibited highly improved properties such as easy penetration of the electrolyte into the cell without leakage, long-term stability, high open-circuit voltage without the use of 4-tert-butylpyridine, and a high energy-conversion efficiency of 5.25% under AM 1.5 illumination (100 mW cm⁻²).     

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.     

On the modeling of the dye-sensitized solar cell

A simplified electric model of the dye-sensitized electrochemical solar cell (DSC) is presented. It permits the calculation of internal steady-state cell characteristics like particle density distributions or the electric field as a function of the (measured) external current I_ext. The cell is modeled as an one-dimensional pseudo-homogeneous medium of thickness L, where all the electroactive particles involved in the current supporting process move according to different effective transport coefficients (i.e. effective diffusivities D and effective mobilities μ). The electroactive particles are the electrons e⁻ injected into the nanoporous TiO₂ layer after light absorption by the dye, the reduced and the oxidized counterpart of the redox electrolyte El_Red and El_Ox, and the positively charged cation Kat⁺ being brought into the cell together with the electrolyte. By applying the continuity equation, the transport-equation and Poisson's equation to all the electroactive species involved (e⁻, El_Red, El_Ox and Kat⁺) and by assuming a linear Boltzmann relaxation approximation for the back reaction, a system of differential equations is derived, describing particle densities, particle currents and the electric field within the cell. The underlying simplifying assumptions as well as the resulting limits of the model are stated, and some possible extensions are given. This paper aims to outline the general ideas and limitations of the proposed electric modeling, numerical calculations have been successfully implemented, but will be presented in a future paper.     

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.     

Low molecular mass organogelator based gel electrolyte gelated by a quaternary ammonium halide salt for quasi-solid-state dye-sensitized solar cells

Quasi-solid-state dye-sensitized solar cells (DSC) are fabricated using tetradodecylammonium bromide as a low molecular mass organogelator (LMOG) to form gel electrolyte with a high solution-to-gel transition temperature (T_SG) of 75 °C to hinder flow and volatilization of the liquid. The steady-state voltammograms reveal that the diffusion of the I₃⁻ and I⁻ in the gel electrolyte is hindered by the self-assembled network of the gel. An increased interfacial exchange current density (j₀) of 4.95 × 10⁻⁸ A cm⁻² and a decreased electron recombination lifetime (τ) of 117 ms reveal an increased electron recombination at the dyed TiO₂ photoelectrode/electrolyte interface in the DSC after gelation. The results of the accelerated aging tests show that the gel electrolyte based dye-sensitized solar cell can retain over 93% of its initial photoelectric conversion efficiency value after successive heating at 60 °C for 1000 h, and device degradation is negligible after one sun light soaking with UV cutoff filter for 1000 h.     

Stable dye-sensitized solar cells based on organic chromophores and ionic liquid electrolyte

A series of polyene-diphenylaniline based organic dyes (coded as D5, D7, D9 and D11) have been reported for the application in ionic liquid electrolyte based dye-sensitized solar cells. The effects of substitution of organic dyes on the photovoltaic performance have been investigated, which show addition of methoxy groups on the triphenylamine donor group increases short-circuit current, open-circuit voltage and photovoltaic performance. A power conversion efficiency of 6.5% under AM 1.5 sunlight at 100 mW/cm² has been obtained with D11 dye in combination with a binary ionic liquid electrolyte, which when subjected to accelerated testing under one sun light soaking at 60 °C, the efficiency remained 90% of initial efficiency.     

High-performance polypyrrole nanoparticles counter electrode for dye-sensitized solar cells

Polypyrrole (PPy) nanoparticle was synthesized and coated on a conducting FTO glass to construct PPy counter electrode used in dye-sensitized solar cell (DSSC). Scanning electron microscope images show that PPy with porous and particle diameter in 40–60 nm is covered on the FTO glass uniformly and tightly. Cyclic voltammograms of I₂/I⁻ system measurement reveals that the PPy electrode has smaller charge-transfer resistance and higher electrocatalytic activity for the I₂/I⁻ redox reaction than that Pt electrode does. Overall energy conversion efficiency of the DSSC with the PPy counter electrode reaches 7.66%, which is higher (11%) than that of the DSSC with Pt counter electrode. The excellent photoelectric properties, simple preparation procedure and inexpensive cost allow the PPy electrode to be a credible alternative used in DSSCs.     

Quasi-solid-state dye-sensitized solar cells with cyanoacrylate as electrolyte matrix

A quasi-solid-state dye-sensitized solar cells (DSSCs) employing a commercial glue (“SuperGlue^®”) as electrolyte matrix was fabricated. The cyano groups of the cyanoacrylate can form a supramolecular complex with tetrapropylammonium cations. This immobilizes the cations and therefore might lead to a favored anionic charge transport necessary for a good performance of the iodide/triiodide electrolytic conductor. Obtaining energy conversion efficiencies of more than 4% under 100 mW/cm² of simulated A.M. 1.5 illumination, the cyanoacrylate quasi-solid-state electrolyte is an ordinary and low-cost compound which has fast drying property and offers significant advantages in the fabrication of solar cells and modules as it is in itself is a very good laminating agent. The influences of different porous layer thicknesses of titanium oxide and various kinds of cations on DSSC performance and long-term stability are presented.     

Heteropolyacid-impregnated PVDF as a solid polymer electrolyte for dye-sensitized solar cells

Heteropolyacid (HPA)-impregnated polyvinylidene fluoride (PVDF) with iodine/iodide was prepared as a new polymer electrolyte for bio-mimicking natural photosynthesis. With this new polymer electrolyte, dye-sensitized solar cell was fabricated using N3 dye-adsorbed over TiO₂ nanoparticles (photoanode) and conducting carbon cement coated on conducting glass (photocathode). The fabricated cell generates high open circuit voltage (V_OC 426 mV) and short circuit current (I_SC 3.90 mA) upon illumination with visible light. It is also demonstrated that the polymer electrolytes prevent the back-electron transfer reactions taking place in dye-sensitized hetero-junctions and are highly promising for solar energy conversion to electricity.     

Solar module using dye-sensitized solar cells with a polymer electrolyte

Dye-sensitized TiO₂ solar cells assembled with a polymer electrolyte were investigated, aiming at the construction of an 8 V solar module. The individual solar cells were assembled with 4.5 cm² active area and were characterized under outdoor conditions, exhibiting an average efficiency of 0.9% per cell (at 12:00 noon). The solar module was built by connecting 13 cells in series. The integrated average daily power was estimated to be 183 mW. The present paper discusses the performance of the individual cells and the module.     

Novel agarose polymer electrolyte for quasi-solid state dye-sensitized solar cell

Quasi-solid state dye-sensitized solar cells (DSSCs) are fabricated with a novel polysaccharide gel electrolyte composed of agarose in 1-methyl-2-pyrrolidinone (NMP) as polymer matrix, lithium iodide (LiI)/iodine (I₂) as redox couple and titania nanoparticles as fillers. The polysaccharide electrolyte with different agarose concentrations (1-5 wt%) and various inorganic filler TiO₂ concentrations (0-10 wt%) are studied systematically by differential scanning calorimetry (DSC) and the AC impedance spectra. The electrochemical and photoelectric performances of DSSCs with these electrolytes are also investigated. It is found that increasing agarose and inorganic filler concentration leads to a decrease in T_g in the range of 1-2 wt% for agarose and 0-2.5 wt% for TiO₂ changed electrolytes, which results in high conductivity in these electrolytes. From the electrochemical analysis, it is observed that the electron lifetime in TiO₂ of DSSCs increases with agarose, while decreases with inorganic filler contents. The prolonged electron lifetime in DSSCs is advantageous to improve open-circuit voltage (V_oc). Based on these results, the cell with the electrolyte of 2 wt% agarose shows the optimized energy conversion efficiency of 4.14%. The optimized efficiency of the DSSC with added titania is 4.74% at 2.5 wt% titania concentration.     

Novel hydrophobic ionic liquids electrolyte based on cyclic sulfonium used in dye-sensitized solar cells

A novel series of hydrophobic room temperature ionic liquids based on six cyclic sulfonium cations were first time synthesized and applied in dye-sensitized solar cells as pure solvents for electrolyte system. The chronoamperograms result showed that the length of substituent on sulfonium cations could inhibit the diffusion and the five-ring structure of sulfonium was benefit for fast triiodide ion diffusion. The electrochemical impendence spectra measurement of dye-sensitized solar cells with these ionic liquid electrolytes was carried out and the result indicated that the cations’ structure had indeed influence on the cells’ performance especially for the fill factor, which was further proved by the measurement result of I-V curves of these dye-sensitized solar cells. The conclusion was obtained that the electron exchange reaction on Pt counter electrode/electrolyte interface dominated the cells’ performance for these ionic liquid electrolyte-based DSCs.     

An investigation on the performance of a silver ionic solid electrolyte system for a new detergent-based nanocrystalline dye-sensitized solar cell

A new dye-sensitized solar cell containing a detergent-based solid-state composite electrolyte has been investigated. The electrolyte is composed of Triton-X (C₁₆H₂₆O₂)n, with a powder mixture of surface-treated carbon powder, a fast ion-conducting material (FCM) 40(Cu_1−xAg_xI)−30(Ag₂O)−30(WO₃), (x=0.2), I⁻/I₃⁻ redox couple and an iodine complexing agent. The introduction of this detergent-based solid-state composite electrolyte forms a mosaic-like surface for the smooth transfer of photo-ejected electrons between electrodes. The current-voltage characteristics of TiO₂ nanocrystalline dye-sensitized solar cells based on the above solid-state composite electrolyte measured under simulated sunlight with AM 1.5 at 40 mW/cm² have revealed a short circuit current of 0.7 mA, open circuit voltage of 588 mV and fill-factor of 0.4, thus yielding an over-all conversion efficiency of 0.4%. These results have suggested the origin of appreciably, high charge transfer and the suppressed reverse reaction of electrons as due to the presence of the detergent dispersed with suspensions of electron- and ion-conducting phases.     

Improvement of the performance of dye-sensitized solar cells using Sn-doped ZnO nanoparticles

Sn-doped and undoped ZnO nanoparticles were synthesized by hydrothermal method and their performance as the photoanode of dye-sensitized solar cells (DSSCs) was investigated. Energy dispersive X-ray spectroscopy and X-ray diffraction showed that the Sn had been doped into the ZnO lattice. A red shift of photoluminescence spectra which was induced by Sn doping was observed. The photocurrent density-voltage curves of DSSCs indicated that the efficiency was increased by as high as 140% on bare-FTO substrate and 105% on ZnO compact layer/FTO substrate via Sn doping. Also the effect of the ZnO compact layer was discussed by both of Sn-doped or undoped DSSCs.     

Long-term stable dye-sensitized solar cells based on UV photo-crosslinkable poly(ethylene glycol) and poly(ethylene glycol) diacrylate based electrolytes

UV photo-crosslinkable polymer electrolytes based on poly(ethylene glycol) (PEG) and poly(ethylene glycol) diacrylate (PEGDA) were used in dye-sensitized solar cells (DSSCs). PEG and bifunctional PEGDA formed a crosslinked structure upon UV light illumination, confirmed by the solubility test and FTIR spectroscopy. The polymeric electrolyte was prepared by photo-polymerization after injecting the monomer electrolyte solution into the porous film in order to make close contact with the TiO₂ porous film. Under AM 1.5 (100 mW/cm²) light irradiation for up to 20 min, a maximum 62% increase in the photo-conversion efficiency (η%) was observed. The DSSCs with the crosslinkable PEG/PEGDA based polymer electrolyte showed improved long-term stability in comparison to those with electrolytes containing only PEG. Also, the effects of solvent on stability of the DSSCs were investigated.     

Enhanced performance of a quasi-solid-state dye-sensitized solar cell with aluminum nitride in its gel polymer electrolyte

The effects of incorporation of aluminum nitride (AlN) in the gel polymer electrolyte (GPE) of a quasi-solid-state dye-sensitized solar cell (DSSC) were studied in terms of performance of the cell. The electrolyte, consisting of lithium iodide (LiI), iodine (I₂), and 4-tert-butylpyridine (TBP) in 3-methoxypropionitrile (MPN), was solidified with poly(vinyidene fluoride-co-hexafluoro propylene) (PVDF-HFP). The 0.05, 0.1, 0.3, and 0.5 wt% of AlN were added to the electrolyte for this study. XRD analysis showed a reduction of crystallinity in the polymer PVDF-HFP for all the additions of AlN. The DSSC fabricated with a GPE containing 0.1 wt% AlN showed a short-circuit current density (J_SC) and power-conversion efficiency (η) of 12.92±0.54 mA/cm² and 5.27±0.23%, respectively, at 100 mW/cm² illumination, in contrast to the corresponding values of 11.52±0.21 mA/cm² and 4.75±0.08% for a cell without AlN. The increases both in J_SC and in η of the promoted DSSC are attributed to the higher apparent diffusion coefficient of I⁻ in its electrolyte (3.52×10⁻⁶ cm²/s), compared to that in the electrolyte without AlN of a DSSC (2.97×10⁻⁶ cm²/s). At-rest stability of the quasi-solid-state DSSC with 0.1 wt% of AlN was found to decrease hardly by 5% and 7% at room temperature and at 40 °C, respectively, after 1000 h duration. The DSSC with a liquid electrolyte showed a decrease of about 40% at room temperature, while it virtually lost its performance in about 150 h at 40 °C. Explanations are further substantiated by means of electrochemical impedance spectroscopy (EIS), scanning electron microscopy (SEM), and by porosity measurements.     

Industrial sheet metals for nanocrystalline dye-sensitized solar cell structures

Direct integration of dye-sensitized solar cells (DSSC) onto industrial sheet metals has been studied. The stability of the metals, including zinc-coated and plain carbon steel, stainless steel and copper in a standard iodine electrolyte was investigated with soaking and encapsulation tests. Stainless and carbon steel showed sufficient stability and were used as the cell counter-electrodes, yielding cells with energy conversion efficiencies of 3.6% and 3.1%, respectively. A DSSC built on flexible steel substrates is a promising approach especially from the viewpoint of large-scale, cost-effective industrial manufacturing of the cells.     

Synthesis of nanocrystalline ZnO powder via sol-gel route for dye-sensitized solar cells

This paper reports the growth mechanism of sol-gel-derived nanocrystalline ZnO powder. The influence of pH value of the sol on the crystallite size, morphology and structure of ZnO powder was investigated by using X-ray diffraction, transmission and scanning electron microscopy. Maximum size nanocrystallite (∼14 nm) of ZnO powder was obtained for pH value of 9. An increase in the band gap (blue shift) was observed with decrease in the size of the ZnO nanocrystallites. The variation in band gap was found to be in agreement with theoretical calculations using effective mass model. The growth mechanism of ZnO particles from zinc acetate dihydrate precursor by the sol-gel process has been discussed in terms of solvation, hydrolysis and polymerization. The synthesized ZnO powders were successfully used as the electrode material for dye-sensitized solar cells.