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1.
A highly efficient ZnO photoanode for dye‐sensitized solar cells was successfully grown by a simple, low cost, and scalable method. A nanostructured coral‐shaped Zn layer was deposited by sputtering onto fluorine‐doped tin oxide/glass slices at room temperature and then thermally oxidized in ambient atmosphere. Stoichiometry, crystalline phase, quality, and morphology of the film were investigated, evidencing the formation of a highly porous branched nanostructure, with a pure wurtzite crystalline structure. ZnO‐based dye‐sensitized solar cells were fabricated with customized microfluidic architecture. Dye loading on the oxide surface was analyzed with ultraviolet‐visible spectroscopy, and the dependence of the cell efficiency on sensitizer incubation time and film thickness was studied by current‐voltage electrical characterization, incident photon‐to‐electron conversion efficiency, and impedance spectroscopy measurements, showing the promising properties of this material for the fabrication of dye‐sensitized solar cell photoanodes with a solar conversion efficiency up to 4.58%. Copyright © 2012 John Wiley & Sons, Ltd.  相似文献   

2.
Edge‐selectively fluorinated graphene nanoplatelets (FGnPs) are prepared by mechanochemically driven reaction between fluorine gas (20 vol% in argon) and activated carbon species from graphitic C–C bonds unzipped by high‐speed stainless steel balls with a high kinetic energy. The fluorination at edges of the unzipped graphene nanoplatelets (GnPs) is confirmed by various analytical techniques while the content of fluorine in FGnPs is determined to be 3.0 and 3.4 at% by X‐ray photoelectron spectroscopy and energy‐dispersive X‐ray spectroscopy, respectively. Because of the large difference in electronegativity between carbon (χ = 2.55) and fluorine (χ = 3.98) and the strong C–F bond, the edge‐fluorination of GnPs can provide the maximized charge polarization with an enhanced chemical stability. Thus, electrodes based on the resultant FGnPs demonstrate superb electrochemical performance with excellent stability/cycle life in dye‐sensitized solar cells (FF: 71.5%; Jsc: 14.44 mA cm?2; Voc: 970 mV; PCE: 10.01%) and lithium ion batteries (650.3 mA h g?1 at 0.5 C, charge retention of 76.6% after 500 cycles).  相似文献   

3.
A new class of organic sulfide mediators with programmable redox properties is designed via density functional theory calculations and synthesized for efficient dye‐sensitized solar cells (DSCs). Photophysical and electrochemical properties of these mediators derived from systematical functionalization of the framework with electron donating and withdrawing groups (MeO, Me, H, Cl, CF3, and NO2) are investigated. With this new class of organic mediators, the redox potential can be fine‐tuned over a 170 mV range, overlapping the conventional I?/I3?couple. Due to the suitable interplay of physical properties and electrochemical characteristics of the mediator involving electron‐donating MeO group, the DSCs based on this mediator behave excellently in various kinetic processes such as dye regeneration, electron recombination, and mass transport. Thus, the MeO derivative of the mediator is identified as having the best performance of this series of redox shuttles. As inferred from electrochemical impedance spectroscopy and cyclic voltammetry measurements, the addition of graphene into the normal carbon counter electrode material dramatically improves the apparent catalytic activity of the counter electrode towards the MeO derivative of mediator, resulting in N719 based DSCs showing a promising conversion efficiency of 6.53% under 100 mW·cm?2 simulated sunlight illumination.  相似文献   

4.
A high‐energy conversion efficiency of 8.2% at 100 mW cm?2 is reported, one of the highest values for N719‐based, solid‐state, dye‐sensitized solar cells (ssDSSCs). The solar cells are based on hierarchical double‐shell nanostructures consisting of inner SnO2 hollow spheres (SHS) surrounded by outer TiO2 nanosheets (TNSs). Deposition of the TNS on the SHS outer surface is performed via solvothermal reactions in order to generate a double‐shell SHS@TNS nanostructure that provides a large surface area and suppresses recombination of photogenerated electrons. An organized mesoporous (OM)‐TiO2 film with high porosity, large pores, and good interconnectivity is also prepared via a sol‐gel process using a poly(vinyl chloride)‐g‐poly(oxyethylene methacrylate) (PVC‐g‐POEM) graft copolymer template. This film is utilized as a matrix to disperse the double‐shell nanostructures. Such nanostructures provide good pore‐filling for solid polymer electrolytes, faster electron transfer, and enhanced light scattering, as confirmed by reflectance spectroscopy, incident photon‐to‐electron conversion efficiency (IPCE), and intensity‐modulated photocurrent spectroscopy (IMPS)/intensity‐modulated photovoltage spectroscopy (IMVS).  相似文献   

5.
A novel hybrid electrocatalyst consisting of nitrogen‐doped graphene/cobalt‐embedded porous carbon polyhedron (N/Co‐doped PCP//NRGO) is prepared through simple pyrolysis of graphene oxide‐supported cobalt‐based zeolitic imidazolate‐frameworks. Remarkable features of the porous carbon structure, N/Co‐doping effect, introduction of NRGO, and good contact between N/Co‐doped PCP and NRGO result in a high catalytic efficiency. The hybrid shows excellent electrocatalytic activities and kinetics for oxygen reduction reaction in basic media, which compares favorably with those of the Pt/C catalyst, together with superior durability, a four‐electron pathway, and excellent methanol tolerance. The hybrid also exhibits superior performance for hydrogen evolution reaction, offering a low onset overpotential of 58 mV and a stable current density of 10 mA cm?2 at 229 mV in acid media, as well as good catalytic performance for oxygen evolution reaction (a small overpotential of 1.66 V for 10 mA cm?2 current density). The dual‐active‐site mechanism originating from synergic effects between N/Co‐doped PCP and NRGO is responsible for the excellent performance of the hybrid. This development offers an attractive catalyst material for large‐scale fuel cells and water splitting technologies.  相似文献   

6.
Spray coating, a simple and low‐cost technique for large‐scale film deposition, is employed to fabricate mesoporous titania films, which are electron‐transporting layers in all‐solid‐state dye‐sensitized solar cells (DSSCs). To optimize solar cell performance, presynthesized crystalline titania nanoparticles are introduced into the mesoporous titania films. The composite film morphology is examined with scanning electron microscopy, grazing incidence small‐angle X‐ray scattering, and nitrogen adsorption–desorption isotherms. The crystal phase and crystallite sizes are verified by X‐ray diffraction measurements. The photovoltaic performance of all‐solid‐state DSSCs is investigated. The findings reveal that an optimal active layer of the all‐solid‐state DSSC is obtained by including 50 wt% titania nanoparticles, showing a foam‐like morphology with an average pore size of 20 nm, featuring an anatase phase, and presenting a surface area of 225.2 m2 g?1. The optimized morphology obtained by adding 50 wt% presynthesized crystalline titania nanoparticles yields, correspondingly, the best solar cell efficiency of 2.7 ± 0.1%.  相似文献   

7.
An investigation of the function of an indolene‐based organic dye, termed D149, incorporated in to solid‐state dye‐sensitized solar cells using 2,2′,7,7′‐tetrakis(N,N‐di‐p‐methoxypheny‐amine)‐9,9′‐spirobifluorene (spiro‐OMeTAD) as the hole transport material is reported. Solar cell performance characteristics are unprecedented under low light levels, with the solar cells delivering up to 70% incident photon‐to‐current efficiency (IPCE) and over 6% power conversion efficiency, as measured under simulated air mass (AM) 1.5 sun light at 1 and 10 mW cm?2. However, a considerable nonlinearity in the photocurrent as intensities approach “full sun” conditions is observed and the devices deliver up to 4.2% power conversion efficiency under simulated sun light of 100 mW cm?2. The influence of dye‐loading upon solar cell operation is investigated and the thin films are probed via photoinduced absorption (PIA) spectroscopy, time‐correlated single‐photon counting (TCSPC), and photoluminescence quantum efficiency (PLQE) measurements in order to deduce the cause for the non ideal solar cell performance. The data suggest that electron transfer from the photoexcited sensitizer into the TiO2 is only between 10 to 50% efficient and that ionization of the photo excited dye via hole transfer directly to spiro‐OMeTAD dominates the charge generation process. A persistent dye bleaching signal is also observed, and assigned to a remarkably high density of electrons “trapped” within the dye phase, equivalent to 1.8 × 1017 cm?3 under full sun illumination. it is believed that this localized space charge build‐up upon the sensitizer is responsible for the non‐linearity of photocurrent with intensity and nonoptimum solar cell performance under full sun conditions.  相似文献   

8.
An organic fluorophore is doped into a mesoporous TiO2 photoelectrode to absorb ultraviolet light and convert it to green light for more efficient light harvesting of N719 dye. This fluorescence conversion enables the absorption of additional green light by dye molecules by means of Förster resonance energy transfer between fluorescent compound donor and N719 dye acceptor. Owing to close fit between the emission peak of fluorophore and the absorption peak of N719 dye, the Förster resonance energy transfer effect enhances the incident photon to current conversion efficiency of the dye‐sensitized solar cells based on fluorophore‐doped TiO2 photoelectrodes. Improved power conversion efficiency (8.03–8.13%) is also achieved for the fluorophore‐doped (10−4 M) dye‐sensitized solar cells compared with a cell without the doping of fluorophore (7.63%). Copyright © 2013 John Wiley & Sons, Ltd.  相似文献   

9.
A double‐layer film, consisting of an upper layer of ZnO nanosheets and a lower layer of ZnO nanoparticles (designated as ZnONS/NP), was synthesized for the photoanode of a dye‐sensitized solar cell (DSSC) by a one‐step potentiostatic electrodeposition on a conducting fluorine‐doped tin oxide substrate at 70 °C in a solution containing zinc nitrate and sodium acetate, followed by the pyrolysis of the film at 300 °C. The growth mechanism of the double‐layer nanostructure was studied by monitoring the morphological changes at various periods of electrodeposition. The effects of the concentration of acetate anion on the morphology of the double‐layer structure were also studied. The double‐layer film of ZnONS/NP showed a better self‐established light scattering property, compared with that of a thin film of ZnO nanoparticles, prepared without acetate anion. The concentration of an acetate anion in the electrolyte for the electrodeposition of the double‐layer film, the electrodeposition period, and the period for dye adsorption were optimized for obtaining the best performance for a DSSC with a photoanode consisting of the double layer. A metal‐free dye, coded as D149, was used in this research. A conversion efficiency of 4.65% was achieved for a DSSC (0.2376 cm2) with the photoanode, consisting of the double‐layer film, under 100 mW/cm2 illumination in the wavelength range of 400–800 nm. X‐ray diffraction patterns, thermo gravimetric curves, elemental analysis, scanning electron microscopic images, transmission electron microscopic image, transmission spectra, and electrochemical impedance spectra were used to explain observations. Copyright © 2012 John Wiley & Sons, Ltd.  相似文献   

10.
Well‐crystallized Nb‐doped anatase TiO2 nanoparticles are prepared by a novel synthetic route and successfully used as the photoanode of dye‐sensitized solar cells (DSSCs). The homogenous distribution of Nb in the TiO2 lattice is confirmed by scanning transmission electron microscopy (STEM) elemental mapping and line‐scanning analyses. After Nb doping, the conductivity of the TiO2 powder increases, and its flat‐band potential (Vfb) has a positive shift. The energy‐conversion efficiency of a cell based on 5.0 mol% Nb‐doped TiO2 is significantly better, by about 18.2%, compared to that of a cell based on undoped TiO2. The as‐prepared Nb‐doped TiO2 material is proven in detail to be a better photoanode material than pure TiO2, and this new synthetic approach using a water‐soluble precursor provides a simple and versatile way to prepare excellent photoanode materials.  相似文献   

11.
This work describes a new one‐step large‐scale electrochemical synthesis of graphene/polyaniline (PANI) composite films using graphite oxide (GO) and aniline as the starting materials. The size of the film could be controlled by the area of indium tin oxide (ITO). Scanning electron microscopy (SEM), transmission electron microscopy (TEM), X‐ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), and ultraviolet–visible absorption spectrum (UV–vis) results demonstrated that the graphene/PANI composite film was successfully synthesized. The obtained graphene/PANI composite film showed large specific area, high conductivity, good biocompatibility, and fast redox properties and had perfect layered and encapsulated structures. Electrochemical experiments indicated that the composite film had high performances and could be widely used in applied electrochemical fields. As a model, horseradish peroxidase (HRP) was entrapped onto the film‐modi?ed glassy carbon electrode (GCE) and used to construct a biosensor. The immobilized HRP showed a pair of well‐de?ned redox peaks and high catalytic activity for the reduction of H2O2. Furthermore, the graphene/PANI composite film could be directly used as the supercapacitor electrode. The supercapacitor showed a high specific capacitance of 640 F g?1 with a retention life of 90% after 1000 charge/discharge cycles.  相似文献   

12.
The control of interfacial charge transfer is central to the design of photovoltaic devices. This charge transfer is strongly dependent upon the local chemical environment at each interface. In this paper we report a methodology for the fabrication of a novel nanostructured multicomponent film, employing a dual‐function supramolecular organic semiconductor to allow molecular‐level control of the local chemical composition at a nanostructured inorganic/organic semiconductor heterojunction. The multicomponent film comprises a lithium ion doped dual‐functional hole‐transporting material (Li+–DFHTM), sandwiched between a dye‐sensitized nanocrystalline TiO2 film and a mono‐functional organic hole‐transporting material (MFHTM). The DFHTM consists of a conjugated organic semiconductor with ion supporting side chains, designed to allow both electronic and ionic charge transport properties. The Li+–DFHTM layers provide a new and versatile way to control the interface electrostatics, and consequently the charge transfer, at a nanostructured dye‐sensitized inorganic/organic semiconductor heterojunction.  相似文献   

13.
Development of low cost electrocatalysts with outstanding catalytic activity and stability for oxygen evolution reaction (OER) in acid is a major challenge to produce hydrogen energy from water splitting. Herein, a novel metal‐free electrocatalyst consisting of a oxygen‐functionalized electrochemically exfoliated graphene (OEEG) nanosheets array is reported. Benefitting from a vertically aligned arrays structure and introducing oxygen functional groups, the metal‐free OEEG nanosheets array exhibits superior electrocatalytic activity and stability toward OER with a low overpotential of 334 mV at 10 mA cm?2 in acidic electrolyte. Such a high OER performance is thus far the best among all previously reported metal‐free carbon‐based materials, and even superior to commercial Ir/C catalysts (420 mV at 10 mA cm?2) in acid. Characterization results and electrochemical measurements identify the COOH species in the OEEG acting as active sites for acidic OER, which is further supported by atomic‐scale scanning transmission electron microscopy imaging and electron energy‐loss spectroscopy. Density functional theory calculations reveal that the reaction pathway of dual sites that is mixed by zigzag and armchair edges (COOH‐zig‐corner) is better than the pathway of single site.  相似文献   

14.
Chemical modification with foreign atoms is a leading strategy to intrinsically modify the properties of host materials. Among them, potassium (K) modification plays a critical role in adjusting the electronic properties of carbon materials. Graphene, a true 2D carbon material, has shown fascinating applications in electrochemical sensing and biosensing. In this work, a facile and mild strategy to K‐modifying in graphene at room‐temperature is reported for the first time. X‐ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), transmission electron microscopy (TEM), Raman spectra, and cyclic voltammetry are used to characterize this K‐modified graphene. The K‐modified graphene is capable of acting as an electron transfer medium and more efficiently promotes charge transfer than unmodified graphene. A highly sensitive and stable amperometric sensor based on its excellent electrocatalytic activity toward the oxidation of NO2? is proposed. The sensor shows a linear range from 0.5 μM to 7.8 mM with a detection limit of 0.2 μM at a signal‐to‐noise ratio of 3. The modified electrode has excellent analytical performance and can be successfully applied in the determination of NO2? released from liver cancer and leukemia cells and shows good application potential in biological systems.  相似文献   

15.
A novel heteroleptic RuII complex (BTC‐2) employing 5,5′‐(2,2′‐bipyridine‐4,4′‐diyl)‐bis(thiophene‐2‐carboxylic acid) (BTC) as the anchoring group and 4,4′‐ dinonyl‐2,2′‐bipiridyl and two thiocyanates as ligands is prepared. The photovoltaic performance and device stability achieved with this sensitizer are compared to those of the Z‐907 dye, which lacks the thiophene moieties. For thin mesoporous TiO2 films, the devices with BTC‐2 achieve higher power conversion efficiencies than those of Z‐907 but with a double‐layer thicker film the device performance is similar. Using a volatile electrolyte and a double layer 7 + 5 μm mesoporous TiO2 film, BTC‐2 achieves a solar‐to‐electricity conversion efficiency of 9.1% under standard global AM 1.5 sunlight. Using this sensitizer in combination with a low volatile electrolyte, a photovoltaic efficiency of 8.3% is obtained under standard global AM 1.5 sunlight. These devices show excellent stability when subjected to light soaking at 60 °C for 1000 h. Electrochemical impedance spectroscopy and transient photovoltage decay measurements are performed to help understand the changes in the photovoltaic parameters during the aging process. In solid state dye‐sensitized solar cells (DSSCs) using an organic hole‐transporting material (spiro‐MeOTAD, 2,2′,7,7′‐tetrakis‐(N,N‐di‐p‐methoxyphenylamine)‐9,9′‐spirobifluorene), the BTC‐2 sensitizer exhibits an overall power conversion efficiency of 3.6% under AM 1.5 solar (100 mW cm?2) irradiation.  相似文献   

16.
Cadmium sulfide (CdS) and cadmium selenide (CdSe) quantum dots (QDs) are sequentially assembled onto a nanocrystalline TiO2 film to prepare a CdS/CdSe co‐sensitized photoelectrode for QD‐sensitized solar cell application. The results show that CdS and CdSe QDs have a complementary effect in the light harvest and the performance of a QDs co‐sensitized solar cell is strongly dependent on the order of CdS and CdSe respected to the TiO2. In the cascade structure of TiO2/CdS/CdSe electrode, the re‐organization of energy levels between CdS and CdSe forms a stepwise structure of band‐edge levels which is advantageous to the electron injection and hole‐recovery of CdS and CdSe QDs. An energy conversion efficiency of 4.22% is achieved using a TiO2/CdS/CdSe/ZnS electrode, under the illumination of one sun (AM1.5,100 mW cm?2). This efficiency is relatively higher than other QD‐sensitized solar cells previously reported in the literature.  相似文献   

17.
A new ionic liquid, 1‐vinyl‐3‐heptylimidazolium iodide (VHpII), was synthesized and applied as a redox electrolyte for dye‐sensitized solar cells. The chemical structure of the synthesized VHpII was confirmed using 1H NMR. Thermogravimetric analysis showed that the VHpII was stable for thermal stress of up to 250°C. The energy conversion efficiencies of the VHpII‐based dye‐sensitized solar cells were investigated in terms of the effect of a lithium iodide addition. A solar cell containing the redox couple of VHpII and iodine showed a conversion efficiency of 2.63% under 1 sun light intensity at AM 1.5. Adding 0.4 M LiI results in a conversion efficiency of 3.63%, which was an improvement of about 40%. The increased conversion efficiency was ascribed to an increase in external quantum efficiency.  相似文献   

18.
The synthesis of a novel fluorinated n‐type small molecule based on an indacenodithiophene core is reported. Fluorination is found to have a significant impact on the physical properties, including a surprisingly dramatic improvement in solubility, in addition to effectively stabilizing the lowest‐unoccupied molecular orbital energy (?4.24 eV). Single‐crystal analysis and density functional theory calculations indicate the improved solubility can be attributed to backbone torsion resulting from the positioning of the fluorine group in close proximity to the strongly electron‐withdrawing dicyanomethylene group. Organic thin‐film transistors made via blade coating display high electron mobility (up to 0.49 cm2 V?1 s?1) along with good retention of performance in ambient conditions.  相似文献   

19.
Two triphenylamine‐based metal‐free organic sensitizers, D35 with a single anchor group and M14 with two anchor groups, have been applied in dye‐sensitized solar cells (DSCs) with a solid hole transporting material or liquid iodide/triiodide based electrolyte. Using the molecular hole conductor 2,2',7,7'‐tetrakis‐(N,N‐di‐p‐methoxyphenyl‐amine)9,9'‐spirobifluorene (spiro‐OMeTAD), good overall conversion efficiencies of 4.5% for D35 and 4.4% for M14 were obtained under standard AM 1.5G illumination (100 mW cm?2). Although M14 has a higher molar extinction coefficient (by ~ 60%) and a slightly broader absorption spectrum compared to D35 , the latter performs slightly better due to longer lifetime of electrons in the TiO2, which can be attributed to differences in the molecular structure. In iodide/triiodide electrolyte‐based DSCs, D35 outperforms M14 to a much greater extent, due to a very large increase in electron lifetime. This can be explained by both the greater blocking capability of the D35 monolayer and the smaller degree of interaction of triiodide (iodine) with D35 compared to M14 . The present work gives some insight into how the molecular structure of sensitizer affects the performance in solid‐state and iodide/triiodide‐based DSCs.  相似文献   

20.
An iodine‐free solid‐state dye‐sensitized solar cell (ssDSSC) is reported here, with 6.8% energy conversion efficiency—one of the highest yet reported for N719 dye—as a result of enhanced light harvesting from the increased transmittance of an organized mesoporous TiO2 interfacial layer and the good hole conductivity of the solid‐state‐polymerized material. The organized mesoporous TiO2 (OM‐TiO2) interfacial layer is prepared on large‐area substrates by a sol‐gel process, and is confirmed by scanning electron microscopy (SEM) and grazing incidence small‐angle X‐ray scattering (GISAXS). A 550‐nm‐thick OM‐TiO2 film coated on fluorine‐doped tin oxide (FTO) glass is highly transparent, resulting in transmittance increases of 8 and 4% compared to those of the bare FTO and conventional compact TiO2 film on FTO, respectively. The high cell performance is achieved through careful control of the electrode/hole transport material (HTM) and nanocrystalline TiO2/conductive glass interfaces, which affect the interfacial resistance of the cell. Furthermore, the transparent OM‐TiO2 film, with its high porosity and good connectivity, exhibits improved cell performance due to increased transmittance in the visible light region, decreased interfacial resistance ( Ω ), and enhanced electron lifetime ( τ ). The cell performance also depends on the conductivity of HTMs, which indicates that both highly conductive HTM and the transparent OM‐TiO2 film interface are crucial for obtaining high‐energy conversion efficiencies in I2‐free ssDSSCs.  相似文献   

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