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.     

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).     

Optimization of the dye-sensitized solar cell performance by mechanical compression

In this study, the P25 titanium dioxide (TiO₂) nanoparticle (NP) thin film was coated on the fluorine-doped tin oxide (FTO) glass substrate by a doctor blade method. The film then compressed mechanically to be the photoanode of dye-sensitized solar cells (DSSCs). Various compression pressures on TiO₂ NP film were tested to optimize the performance of DSSCs. The mechanical compression reduces TiO₂ inter-particle distance improving the electron transport efficiency. The UV–vis spectrophotometer and electrochemical impedance spectroscopy (EIS) were employed to quantify the light-harvesting efficiency and the charge transport impedance at various interfaces in DSSC, respectively. The incident photon-to-current conversion efficiency was also monitored. The results show that when the DSSC fabricated by the TiO₂ NP thin film compressed at pressure of 279 kg/cm², the minimum resistance of 9.38 Ω at dye/TiO₂ NP/electrolyte interfaces, the maximum short-circuit photocurrent density of 15.11 mA/cm², and the photoelectric conversion efficiency of 5.94% were observed. Compared to the DSSC fabricated by the non-compression of TiO₂ NP thin film, the overall conversion efficiency is improved over 19.5%. The study proves that under suitable compression pressure the performance of DSSC can be optimized.     

EIS analysis on low temperature fabrication of TiO2 porous films for dye-sensitized solar cells

A low temperature (<150 °C) fabrication method for preparation of TiO₂ porous films with high efficiency in dye-sensitized solar cells (DSSCs) has been developed. The Ti(IV) tetraisopropoxide (TTIP) was added to the paste of TiO₂ nanoparticles to interconnect the TiO₂ particles. The electrochemical impedance spectroscopy (EIS) technique was employed to quantify the charge transport resistance at the TiO₂/dye/electrolyte interface (R_ct2) and electron lifetime in the TiO₂ film (τ_e) under different molar ratios of TTIP/TiO₂ and also at various TiO₂ thicknesses. It was found that the R_ct2 decreased as the molar ratio increased from 0.02 to 0.08, however, it increased at a molar ratio of 0.2 due to the reduction in surface area for dye adsorption. In addition, the characteristic frequency peak shifted to lower frequency at a molar ratio of 0.08, indicating the longer electron lifetime. As for the thickness effect, TiO₂ film with a thickness around 17 μm achieved the best cell efficiency. EIS study also confirmed that, under illumination, the smallest R_ct2 was associated with a TiO₂ thickness of 17 μm, with the R_ct2 increased as the thickness of TiO₂ film increased. In the Bode plots, the characteristic frequency peaks shifted to higher frequency when the thickness of TiO₂ increased from 17.2 to 48.2 μm, indicating the electron recombination increases as the thickness of the TiO₂ electrode increases.Finally, to make better use of longer wavelength light, 30 wt% of larger TiO₂ particle (300 nm) was mixed with P25 TiO₂ as light scattering particles. It effectively increased the short-circuit current density and cell conversion efficiency from 7.44 to 8.80 mA cm⁻² and 3.75 to 4.20%, respectively.     

Preparation and characterization of core-shell electrodes for application in gel electrolyte-based dye-sensitized solar cells

Core-shell electrodes based on TiO₂ covered with different oxides were prepared and characterized. These electrodes were applied in gel electrolyte-based dye-sensitized solar cells (DSSC). The TiO₂ electrodes were prepared from TiO₂ powder (P25 Degussa) and coated with thin layers of Al₂O₃, MgO, Nb₂O₅, and SrTiO₃ prepared by the sol-gel method. The core-shell electrodes were characterized by X-ray diffraction, scanning electron microscopy and atomic force microscopy measurements. J-V curves in the dark and under standard AM 1.5 conditions and photovoltage decay measurements under open-circuit conditions were carried out in order to evaluate the influence of the oxide layer on the charge recombination dynamics and on the device's performance. The results indicated an improvement in the conversion efficiency as a result of an increase in the open circuit voltage. The photovoltage decay curves under open-circuit conditions showed that the core-shell electrodes provide longer electron lifetime values compared to uncoated TiO₂ electrodes, corroborating with a minimization in the recombination losses at the nanoparticle surface/electrolyte interface. This is the first time that a study has been applied to DSSC based on gel polymer electrolyte. The optimum performance was achieved by solar cells based on TiO₂/MgO core-shell electrodes: fill factor of ∼0.60, short-circuit current density J_sc of 12 mA cm⁻², open-circuit voltage V_oc of 0.78 V and overall energy conversion efficiency of ∼5% (under illumination of 100 mW cm⁻²).     

Influence of iodine concentration on the photoelectrochemical performance of dye-sensitized solar cells containing non-volatile electrolyte

The effect of iodine concentration in the electrolyte with non-volatile solvent of dye-sensitized solar cells (DSCs) on photovoltaic performance was studied. The electron transport and interfacial recombination kinetics were also systematically investigated by electron impedance spectroscopy (EIS). With the iodine concentration increased from 0.025 to 0.1 M, open-circuit voltage (V_oc) and photocurrent density (J_sc) decreased while fill factor (ff) increased significantly. The decline of the V_oc and J_sc was mainly ascribed to increased electron recombination with tri-iodide ions (I₃⁻). The increased fill factor was primarily brought by a decrease in the total resistance. From impedance spectra of the solar cells, it can be concluded that increasing the iodine concentration in electrolytes could decrease charge transfer resistance (R_ct) and the chemical capacitance (C_μ), increase the electron transport resistance (R_t), and hence decrease the electron lifetime (τ) and the effective diffusion coefficient (D_n) of electrons in the TiO₂ semiconductor. With optimum iodine concentration, device showed a photocurrent density of 16.19 mA cm⁻², an open-circuit voltage of 0.765 V, a fill factor of 0.66, and an overall photo-energy conversion efficiency of 8.15% at standard AM 1.5 simulated sunlight (100 mW cm⁻²).     

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.     

Lithium-ion battery anode properties of TiO2 nanotubes prepared by the hydrothermal synthesis of mixed (anatase and rutile) particles

From mixed (anatase and rutile) bulk particles, anatase TiO₂ nanotubes are synthesized in this study by an alkaline hydrothermal reaction and a consequent annealing at 300-400 °C. The physical and electrochemical properties of the TiO₂ nanotube are investigated for use as an anode active material for lithium-ion batteries. Upon the first discharge-charge sweep and simultaneous impedance measurements at local potentials, this study shows that interfacial resistance decreases significantly when passing lithium ions through a solid electrolyte interface layer at the lithium insertion/deinsertion plateaus of 1.75/2.0 V, corresponding to the redox potentials of anatase TiO₂ nanotubes. For an anatase TiO₂ nanotube containing minor TiO₂(B) phase obtained after annealing at 300 °C, the high-rate capability can be strongly enhanced by an isotropic dispersion of TiO₂ nanotubes to yield a discharge capacity higher than 150 mAh g⁻¹, even upon 100 cycles of 10 C-rate discharge-charge operations. This is suitable for use as a high-power anode material for lithium-ion batteries.     

Improved photovoltage and performance by aminosilane-modified PEO/P(VDF-HFP) composite polymer electrolyte dye-sensitized solar cells

A PEO/P(VDF-HFP) composite polymer electrolyte was modified by different amounts of NH₂-end functional silane (3-amonopropyltriethoxysilane, APTS). Fourier transform infrared (FT-IR), X-ray diffraction (XRD) and differential scanning calorimetry (DSC) were carried out to examine the configuration changes of the polymer electrolyte. The newly formed Si-O-Si network and interactions influenced the ionic conductivity of the APTS-modified polymer electrolyte and also enhanced the connection of the polymer electrolyte with the electrodes of the dye sensitized solar cells (DSSCs). The cyclic voltammograms and electrochemical impedance measurements indicated that the APTS deprotonated the TiO₂ photoanode surface and negatively changed the Fermi energy level and the conduction band edge to the vacuum level. This effectively reduced the interface recombination in the DSSC and improved the open circuit voltage. With moderate APTS content (0.1 M) modification, the DSSC exhibited a 58 mV improvement of photovoltage and an improved performance of 5.08% compared with 3.74% of the original DSSC.     

Aerosol assisted chemical vapour deposited (AACVD) of TiO2 thin film as compact layer for dye-sensitised solar cell

Compact TiO₂ has been introduced onto the surface of an indium tin oxide glass slide (ITO), using an aerosol-assisted chemical vapour deposition method. This serves as a blocking layer for a dye-sensitised solar cell (DSSC). The thickness of the compact TiO₂ could be controlled by deposition time. X-ray diffraction and Raman spectroscopy analyses reveal that the compact TiO₂ is made up of mixed anatase and rutile phases. The field emission scanning electron microscopy image displays a pyramidal morphology of the compact TiO₂. A layer of P25 paste was then smeared onto the compact TiO₂-modified ITO, using the doctor's blade method. A post-treatment procedure was applied to remove the contaminants from the prepared hybrid film, by immersing in a hydrochloric acid solution. The photoelectrochemical measurements and J–V characterisation of the hybrid film show an approximately fourfold increase in photocurrent density generation (114.22 µA/cm²), and approximately 25% enhancement of DSSC conversion efficiency (4.63%), compared to the acid-treated P25 paste alone (3.68%).     

Performance improvement of dye-sensitizing solar cell by semi-rigid triarylamine-based donors

Novel organic dyes (IDB and ISB dyes), which contain 5-phenyl-iminodibenzyl (IDB) and 5-phenyl-iminostilbene (ISB) as electron donors and a cyanoacrylic acid moiety as an electron acceptor and an anchoring group, connected with a thiophene as a π-conjugated system, have been synthesized and used as the sensitizers for dye-sensitized solar cells (DSSCs). The photophysical and electrochemical properties of the dyes were investigated by absorption spectrometry, cyclic voltammetry and density functional theory calculations. As demonstrated, the IDB and ISB unit exhibited stronger electron-donating ability and broader absorption spectra when coated onto TiO₂. The DSSC based on ISB-2 consisting of ISB unit produced 5.83% of η (J_sc = 13.14 mA cm⁻², V_oc = 0.64 V, and ff = 0.68) under 100 mW cm⁻² simulated AM 1.5 G solar irradiation.     

Photoelectro-Fenton combined with photocatalytic process for degradation of an azo dye using supported TiO2 nanoparticles and carbon nanotube cathode: Neural network modeling

In this work, treatment of an azo dye solution containing C.I. Basic Red 46 (BR46) by photoelectro-Fenton (PEF) combined with photocatalytic process was studied. Carbon nanotube-polytetrafluoroethylene (CNT-PTFE) electrode was used as cathode. The investigated photocatalyst was TiO₂ nanoparticles (Degussa P25) having 80% anatase and 20% rutile, specific surface area (BET) 50 m²/g, and particle size 21 nm immobilized on glass plates. A comparison of electro-Fenton (EF), UV/TiO₂, PEF and PEF/TiO₂ processes for decolorization of BR46 solution was performed. Results showed that color removal follows the decreasing order: PEF/TiO₂ > PEF > EF > UV/TiO₂. The influence of the basic operational parameters such as initial pH of the solution, initial dye concentration, the size of anode, applied current, kind of ultraviolet (UV) light and initial Fe³⁺ concentration on the degradation efficiency of BR46 was studied. The mineralization of the dye was investigated by total organic carbon (TOC) measurements that showed 98.8% mineralization of 20 mg/l dye at 6 h using PEF/TiO₂ process. An artificial neural network (ANN) model was developed to predict the decolorization of BR46 solution. The findings indicated that artificial neural network provided reasonable predictive performance (R² = 0.986).     

Synthesis of FePO4·xH2O for fabricating submicrometer structured LiFePO4/C by a co-precipitation method

Amorphous hydrated iron (III) phosphate has been synthesized by a coordinate precipitation method from equimolecular Fe(NO₃)₃ and (NH₄)₂HPO₄ solutions at an elevated temperature. Hydrated iron (III) phosphate samples and the corresponding LiFePO₄/C products were characterized by XRD and SEM. The electrochemical behavior was studied by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The LiFePO₄/C fabricated from as-synthesized FePO₄ delivered discharge capacities of 162.5, 147.3, 133.0, 114.7, 97.2, 91.3 and 88.5 mAh g⁻¹ at rates of 0.1C, 0.2C, 0.5C, 1C, 2C, 3C and 4C with satisfactory capacity retention, respectively.     

Investigation of lithium diffusion in nano-sized rutile TiO2 by impedance spectroscopy

The kinetics of the electrochemical lithium insertion reaction in nano-sized rutile TiO₂ has been investigated using ac impedance spectroscopy. The experimental data are obtained for a rutile compound synthesized via a solution technique and characterized by a morphology corresponding to spherical particles made of a large number of very thin nanorods 20 nm thick. The results are discussed as a function of the Li content x for 0 < x ≤ 0.8 in Li_xTiO₂, the temperature over the range 10-50 °C and the number of discharge-charge cycles. The significant linear decrease of the chemical diffusion coefficient D_Livs. the lithium content and the high values of D_Li found in the composition range 0 < x ≤ 0.5 are discussed and related with the electrochemical behaviour of the nano-sized material. From comparison with the bulk material, a promoting effect of the morphology on the kinetic characteristics is evidenced. For the first time an experimental evaluation of the activation energy for Li diffusion in nano-sized rutile TiO₂ is obtained; the value of 0.35 eV being much lower than that reported from computational experiments for the micro-sized oxide. This work also demonstrates a new system takes place from the second cycle, characterized by a significant improvement of Li diffusion by a factor five and allowing high rates to be used.     

An approach to laminated flexible Dye sensitized solar cells

We have built TiO₂ Dye sensitized solar cells (DSSCs) that combined flexible TiO₂ photoanodes coated on ITO/PET substrates with a gel electrolyte based on PVDF-HFP-SiO₂ films. Titanium isopropoxide (TiP₄) was used as additive to TiO₂ nanoparticles for increasing power conversion efficiency in Dye sensitized solar cell electrodes prepared at low-temperature (130 °C). An efficiency η_AM1.5G = 3.55% on ITO/PET substrates is obtained at 48 mW/cm² illumination with a standard liquid electrolyte based on methoxypropionitrile. Among several solvents forming gels with PVDF-HFP-SiO₂, N-methyl (pyrrolidone) (NMP) was found to enable the most stable devices. A power conversion efficiency η_AM1.5G = 2% was obtained under 10 mW/cm² with flexible TiO₂-ITO-PET photoanodes and the PVDF-HFP-SiO₂ + NMP gel electrolyte.     

Electrochemical performances of poly(3,4-ethylenedioxythiophene)-NiFe2O4 nanocomposite as electrode for supercapacitor

Poly 3,4-ethylenedioxythiophene (PEDOT)-based NiFe₂O₄ conducting nanocomposites were synthesized and their electrochemical properties were studied in order to find out their suitability as electrode materials for supercapacitor. Nanocrystalline nickel ferrites (5-20 nm) have been synthesized by sol-gel method. Reverse microemulsion polymerization in n-hexane medium for PEDOT nanotube and aqueous miceller dispersion polymerization for bulk PEDOT formation using different surfactants have been adopted. Structural morphology and characterization were studied using XRD, SEM, TEM and IR spectroscopy. Electrochemical performances of these electrode materials were carried out using cyclic voltammetry at different scan rates (2-20 mV/s) and galvanostatic charge-discharge at different constant current densities (0.5-10 mA/cm²) in acetonitrile solvent containing 1 M LiClO₄ electrolyte. Nanocomposite electrode material shows high specific capacitance (251 F/g) in comparison to its constituents viz NiFe₂O₄ (127 F/g) and PEDOT (156 F/g) where morphology of the pore structure plays a significant role over the total surface area. Contribution of pseudocapacitance (C_FS) arising from the redox reactions over the electrical double layer capacitance (C_DL) in the composite materials have also been investigated through the measurement of AC impedance in the frequency range 10 kHz-10 mHz with a potential amplitude of 5 mV. The small attenuation (∼16%) in capacitance of PEDOT-NiFe₂O₄ composite over 500 continuous charging/discharging cycles suggests its excellent electrochemical stability.     

Electrochemical characteristics of LSCF-SDC composite cathode for intermediate temperature SOFC

A kind of composite cathode, La_0.58Sr_0.4Co_0.2Fe_0.8O_3−δ-Ce_0.8Sm_0.2O_2−δ (LSCF-SDC), was presented in this paper. The electrochemical performance of the cathode on the electrolyte of SDC and YSZ coated with a thin SDC (YSZ/SDC) layer was studied by electrochemical impedance spectroscopy (EIS) and cathodic polarization techniques for their potential utilization in the intermediate temperature solid oxide fuel cell (IT-SOFC). Also studied was the relationship between the electro-catalytic characteristics and the electrode microstructure. Results showed that the LSCF-SDC composite electrode performed better on the SDC electrolyte than on the electrolyte of YSZ/SDC. The polarization resistance, R_p, of the cathode on the SDC electrolyte was 0.23 Ω cm² at 700 °C and 0.067 Ω cm² at 750 °C, much lower than the corresponding R_p of the same cathode on the YSZ/SDC electrolyte. At 750 °C, the cathodic overpotential of the composite cathode on the SDC electrolyte was 99.7 mV at the current density of 1.0 A cm⁻².     

Efficiency improvement of dye-sensitized solar cells based on electrodeposited TiO2 films by low temperature post-treatment

Porous crystalline TiO₂ films can be prepared at low temperatures (80 °C) by surfactant-assisted electrodeposition from TiCl₃ solution. Nevertheless, up to now calcination at high temperatures (typically 450 °C) was still necessary to establish a good performance of these films in dye-sensitized solar cells (DSSC). With this study we report that water vapour treatment at much lower temperatures (150 °C) for 1 week improves the performance of the films in DSSC to the same degree as calcination although the overall crystallinity remains lower. Reason for the good efficiency is that the porous structure stays intact and thus the dye molecules can be better adsorbed. Avoiding high temperatures during the preparation process of TiO₂ films for the application in DSSC enables the use of polymer substrates for the fabrication of flexible solar cells.     

Electrochemical tuning of titania nanotube morphology in inhibitor electrolytes

The electrochemical behavior of fluorine containing electrolytes and its influence in controlling the lateral dimensions of TiO₂ nanotubes is thoroughly investigated. Potentiostatic anodization is carried out in three different electrolytes, viz., aqueous hydrofluoric acid (HF), HF containing dimethyl sulphoxide (DMSO) and HF containing ethylene glycol (EG). The experiments were carried out over a broad voltage range from 2 to 200 V in 0.1-48 wt% HF concentrations and different electrolytic compositions for anodization times ranging from 5 s to 70 h. The chemistry that dictates how the nature of electrolytes influences the morphology of nanotubes is discussed. Electrochemical impedance spectra were recorded for varying compositions of all the electrolytes. It was observed that composition of the electrolyte and its fluorine inhibiting nature has significant impact on nanotube formation as well as in controlling the aspect ratio. The inhibiting nature of EG is helpful in holding fluorine at the titanium anode, thereby allowing controlled etching at appropriate voltages. Thus our study demonstrates that HF containing EG is a promising electrolytic system providing wide tunability in lateral dimensions and aspect ratio of TiO₂ nanotubes by systematically varying the anodization voltage and electrolyte composition.     

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.