Prussian Blue-Derived Synthesis of Hollow Porous Iron Pyrite Nanoparticles as Platinum-Free Counter Electrodes for Highly Efficient Dye-Sensitized Solar Cells.

Iron pyrite has long been an attractive material for environmental and energy applications, but is hampered by a lack of control over morphology and purity. Hollow porous iron pyrite nanoparticles were synthesized by a direct sulfurization of iron oxide derived from Prussian blue. The high efficiencies of these hollow porous iron pyrite nanoparticles as effective dye-sensitized solar cell counter electrodes were demonstrated, with an efficiency of 7.31 %.

Benzimidazole-Branched Isomeric Dyes: Effect of Molecular Constitution on Photophysical, Electrochemical, and Photovoltaic Properties.

Three benzimidazole-based isomeric organic dyes possessing two triphenylamine donors and a cyanoacrylic acid acceptor are prepared by stoichiometrically controlled Stille or Suzuki-Miyaura coupling reaction which predominantly occurs on the N-butyl side of benzimidazole due to electronic preferences. Combined with the steric effect of the N-butyl substituent, placement of the acceptor segment at various nuclear positions of benzimidazole such as C2, C4, and C7 led to remarkable variations in intramolecular charge transfer absorption, electron injection efficiency, and charge recombination kinetics. The substitution of acceptor on the C4 led to red-shifted absorption, while that on C7 retarded the charge transfer due to twisting in the structure caused by the butyl group. Because of the cross-conjugation nature and poor electronic interaction between the donor and acceptor, the dye containing triphenylamine units on C4 and C7 and the acceptor unit on C2 showed the low oxidation potential. Thus, this dye possesses favorable HOMO and LUMO energy levels to render efficient sensitizing action in solar cells. Consequently, it results in high power conversion efficiency (5.01%) in the series with high photocurrent density and open circuit voltage. The high photocurrent generation by this dye is reasoned to it exceptional charge collection efficiency as determined from the electron impedance spectroscopy.

Nanoflower-like P-doped Nickel Oxide as a Catalytic Counter Electrode for Dye-Sensitized Solar Cells.

Flower-like phosphorus-doped nickel oxide (P-NiO) is proposed as a counter electrode (CE) for dye-sensitized solar cells (DSSCs). The flower-like nickel oxide essentially serves as the matrix for the CE, which is expected to promote a two-dimensional electron transport pathway. The phosphorus is intended to improve the catalytic ability by creating more active sites in the NiO for the catalysis of triiodide ions (I3-) to iodide ions (I-) on the surface of the CE. The P-NiO is controlled by a sequencing of precursor concentration, which allows the P-NiO to possess different features. The debris aggregation occurs in the P-NiO-1, while the P-NiO-0.75 leads to the incomplete flower-like nanosheets. The complete flower-like morphology can be observed in the P-NiO-0.5, P-NiO-0.25 and P-NiO-0.1 catalytic electrodes. The DSSC with the P-NiO-0.5 CE achieves a power conversion efficiency (η) of 9.05%, which is better than that of the DSSC using a Pt CE (η = 8.51%); it also performs better than that with the Pt CE, even under rear illumination and dim light conditions. The results indicate the promising potential of the P-NiO CE to replace the expensive Pt CE.

Thioalkyl-Functionalized Bithiophene (SBT)-Based Organic Sensitizers for High-Performance Dye-Sensitized Solar Cells.

A series of 3,3'-dithioalkyl-2,2'-bithiophene (SBT)-based organic chromophores were designed and developed for the use in dye-sensitized solar cells (DSSCs). By appropriate structural modification of the SBT π-linkers with different alkyl chains and conjugated thiophene units, chromophore aggregation and interfacial charge recombination could be suppressed to a remarkable degree. Single-crystal and optical/electrochemical data clearly show that the SBT core is nearly planar with the torsional angle <1°, likely via S(alkyl)···S(thiophene) intramolecular locks. Therefore, this highly π-conjugated unit should enhance panchromatic light-harvesting and prove to be an excellent core for organic dye. For comparison, the 3,3'-dialkyl-2,2'-bithiophene (BT)-based dye was also prepared. Under 1 sun (100 mW cm-2) illumination, an optimized SBT-6 dye-sensitized cell indicates a short-circuit current density (JSC) of 17.21 mA cm-2, an open-circuit voltage (VOC) of 0.78 V, and a fill factor (FF) of 0.71, corresponding to a power conversion efficiency (η) of 9.47%, which is nearly two times higher than that of alkylated bithiophene (BT)-based chromophores. Finally, the proposed sensitizer SBT-6 exhibited an excellent η of 23.57% under the T5 fluorescent illumination of 6000 lux. To the best of our knowledge, this is the highest power conversion efficiencies (PCE) value reported to date among the studied thiophene or bithiophene-based chromophores.

Synthesis of Surfactant-Free and Morphology-Controllable Vanadium Diselenide for Efficient Counter Electrodes in Dye-Sensitized Solar Cells.

In this study, a transition-metal selenide, vanadium diselenide (VSe2), with various morphologies was synthesized by employing a surfactant-free hydrothermal method under varied temperature conditions (190-220 °C). Although the physical properties of VSe2 have been studied before, only limited morphological change or application were explored. This study, for the first time, applied VSe2 as the electrocatalytic counter electrode (CE) in dye-sensitized solar cells (DSSCs) and showed an attractive cell efficiency. The mechanism of forming the tunable VSe2 morphologies is proposed. The evaluation of solar cell efficiency shows the correlation between morphology and electrocatalytic properties. It was further shown that VSe2-200 with the cauliflower-like morphology shows the highest cell performance of DSSC with an efficiency of 9.23 ± 0.07% under 1 sun irradiance, superior to that of the Pt-based DSSC (8.48 ± 0.08%). An electrochemical technique equipped with a rotating disk electrode system was introduced to confirm the high electrocatalytic performance with this particular morphology. The optimized VSe2 demonstrated good long-term stability with 78% retention after 500 cycles of the consecutive cyclic voltammetry, compared to 60% for the Pt CE. The control in morphology in vanadium diselenide synthesis and its usage in Pt-free CE DSSC have advanced the progress in electrochemistry.

Performance Characterization of Dye-Sensitized Photovoltaics under Indoor Lighting.

Indoor utilization of emerging photovoltaics is promising; however, efficiency characterization under room lighting is challenging. We report the first round-robin interlaboratory study of performance measurement for dye-sensitized photovoltaics (cells and mini-modules) and one silicon solar cell under a fluorescent dim light. Among 15 research groups, the relative deviation in power conversion efficiency (PCE) of the samples reaches an unprecedented 152%. On the basis of the comprehensive results, the gap between photometry and radiometry measurements and the response of devices to the dim illumination are identified as critical obstacles to the correct PCE. Therefore, we use an illuminometer as a prime standard with a spectroradiometer to quantify the intensity of indoor lighting and adopt the reverse-biased current-voltage (I-V) characteristics as an indicator to qualify the I-V sampling time for dye-sensitized photovoltaics. The recommendations can brighten the prospects of emerging photovoltaics for indoor applications.

Bi-anchoring Organic Dyes that Contain Benzimidazole Branches for Dye-Sensitized Solar Cells: Effects of π†Spacer and Peripheral Donor Groups.

Benzimidazole-branched bi-anchoring organic dyes that contained triphenylamine/phenothiazine donors, 2-cyanoacrylic acid acceptors, and various π linkers were synthesized and examined as sensitizers for dye-sensitized solar cells. The structure-activity relationships in these dyes were systematically investigated by using absorption spectroscopy, cyclic voltammetry, and density functional theory calculations. The wavelength of the absorption peak was more-heavily influenced by the nature of the π linker than by the nature of the donor. For a given donor, the absorption maximum (λmax ) was red-shifted on changing the π linker from phenyl to 2,2'-bithiophene, whilst the dyes that contained triphenylamine units displayed higher molar extinction coefficients (ϵ) than their analogous phenothiazine-based triphenylamine dyes, which led to good light-harvesting properties in the triphenylamine-based dyes. Electrochemical data for the dyes indicated that the triphenylamine-based dyes possessed relatively low-lying HOMOs, which could be beneficial for suppressing back electron transfer from the conduction band of TiO2 to the oxidized dyes, owing to facile regeneration of the oxidized dye by the electrolyte. The best performance in the DSSCs was observed for a dye that possessed a triphenylamine donor and 2,2'-bithiophene π linkers. Electron impedance spectroscopy (EIS) studies revealed that the use of triphenylamine as the donor and phenyl or 2,2'-bithiophene as the π linkers was beneficial for disrupting the dark current and charge-recombination kinetics, which led to a long electron lifetime of the injected electrons in the conduction band of TiO2 .

Anthracene/phenothiazine π-conjugated sensitizers for dye-sensitized solar cells using redox mediator in organic and water-based solvents.

Metal-free dyes (MD1 to MD5) containing an anthracene/phenothiazine unit in the spacer have been synthesized. The conversion efficiency (7.13 %) of the dye-sensitized solar cell using MD3 as the sensitizer reached approximately 85 % of the N719-based standard cell (8.47 %). The cell efficiency (8.42 %) of MD3-based dye-sensitized solar cells (DSSCs) with addition of chenodeoxycholic acid is comparable with that of N719-based standard cell. The MD3 water-based DSSCs using a dual-TEMPO (2,2,6,6-tetramethylpiperidine-N-oxyl)/iodide electrolyte exhibited very promising cell performance of 4.96 % with an excellent Voc of 0.77 V.