Non‐Corrosive,Non‐Absorbing Organic Redox Couple for Dye‐Sensitized Solar Cells

A new colorless electrolyte containing an organic redox couple, tetramethylthiourea (TMTU) and its oxidized dimer tetramethylformaminium disulfide dication ([TMFDS]²⁺), is applied to dye‐sensitized solar cells (DSCs). Advantages of this redox couple include its non‐corrosive nature, low cost, and easy handling. More impressively, it operates well with carbon electrodes. The DSCs fabricated with a lab‐made HCS‐CB carbon counter‐electrode can present up to 3.1% power conversion efficiency under AM 1.5 illumination of 100 mW·cm^?2 and 4.5% under weaker light intensities. This result distinctly outperforms the identical DSCs with a Pt electrode. Corrosive experiments reveal that Al and stainless steel (SS) sheets are stable in the [TMFDS]²⁺/TMTU‐based electrolyte. Its electrochemical impedance spectrum (EIS) is used to evaluate the influence of different counter‐electrodes on the cell performance, and preliminary investigations reveal that carbon electrodes with large surface areas and ideal corrosion‐inertness toward the sulfur‐containing [TMFDS]²⁺/TMTU redox couple exhibit promise for application in iodine‐free DSCs.     

29种天然染料敏化的太阳电池的性能研究

采用超声波萃取法从29种天然植物中提取染料, 测试天然染料的紫外-可见光(UV-vis)吸收光谱,探讨天然染料所 含的色素种类。采用水热法制备了TiO₂薄膜电极,用所提取的29种天然染料敏化TiO₂光 电极并将其组装成染料敏化太阳电池(DSSCs)。测试天然染料敏化的DSSCs 的光电性能结果显示,天然染料敏化的DSSCs的开路 电压Voc为0.46~0.64 V,短路电流I_sc为0.07~3.61mA· cm－2,其中山竹皮敏 化的DSSCs光电性能最佳,对应的I_sc和光电转换 效率η分 别为3.61mA·cm－2和2.13%。从天然 染料中挑选出7种不同吸收波段色素的染料进行协同敏化,UV-vis吸收光谱测试结 果显示混合染料的吸收峰一般有微小偏移。光电性能测试结果表明,协同敏化后的DSSCs的 性能一般都介于天然染料单独敏 化的两个DSSCs的性能之间,其中山竹皮和芥蓝协同敏化的DSSCs的η最高,为1.70%。对实验结果进行深入分析,探讨提高天然染料 敏化的DSSCs光电性能的途径。     

Enhancement of dye sensitized solar cell efficiency via incorporation of upconverting phosphor nanoparticles as spectral converters

Upconverting NaYF₄:Yb³⁺,Er³⁺/NaYF₄ core‐shell (CS) nanoparticles (NPs) were synthesized by thermal decomposition of lanthanide trifluoroacetate precursors and mixed with TiO₂ NPs to fabricate dye‐sensitized solar cells (DSSCs). The CS geometry effectively prevents the capture of electrons because of the surface states and improves photo‐emission. The as‐synthesized CS NPs show upconversion (UC) luminescence, converting near infrared (NIR) light into visible light (450–700 nm), making the photon absorption by the ruthenium‐based dyes (which have little or no absorption in the NIR region) possible. The champion DSSCs fabricated using CS UC NPs (average size = 25 nm) show enhancements of ~12.5% (sensitized with black/N749 dye) and of ~5.5% (sensitized with N719 dye) in overall power conversion efficiency under AM 1.5G illumination. This variation in the enhancement of the DSSC efficiencies for black and N719 dyes is attributed to the difference in the extinction coefficient and the absorption wavelength range of dyes. Incident photon‐to‐current conversion efficiency measurements also evidently showed the photocurrent enhancement in the NIR region of the spectrum because of the UC effect. The results prove that the augmentation in efficiency is primarily due to NIR to visible spectrum modification by the fluorescent UC NPs. Copyright © 2015 John Wiley & Sons, Ltd.     

Effects of using multi‐component electrolytes on the stability and properties of solar cells sensitized with simple organic dyes

In this paper we present experimental results for electrochemical (dye‐sensitized) solar cells that were prepared in our laboratory in order to examine some of the major factors affecting the efficiency and the stability of such cells. Nanostructured TiO₂ thin films were prepared and sensitized using an organic dye. For the purpose of this study three different types of electrolytes were developed: a standard‐type electrolyte containing potassium iodide and iodine in propylene carbonate (PC) and two novel, multi‐component electrolytes containing potassium iodide and iodine dissolved in varying mixtures of PC and EG (ethylene glycol). It was demonstrated that the combined properties of the two solvents in the multi‐component electrolytes enhance the efficiency and improve considerably the stability of the cells. Copyright © 2010 John Wiley & Sons, Ltd.     

The monolithic multicell: a tool for testing material components in dye‐sensitized solar cells

A multicell is presented as a tool for testing material components in encapsulated dye‐sensitized solar cells. The multicell is based on a four‐layer monolithic cell structure and an industrial process technology. Each multicell plate includes 24 individual well‐encapsulated cells. A sulfur lamp corrected to the solar spectrum has been used to characterize the cells. Efficiencies up to 6·8% at a light‐intensity of 1000 W/m^su2 (up to 7·5% at 250 W/m²) have been obtained with an electrolyte solution based on γ‐butyrolactone. Additionally, a promising long‐term stability at cell efficiencies close to 5% at 1000 W/m² has been obtained with an electrolyte based on glutaronitrile. The reproducibility of the cell performance before and after exposure to accelerated testing has been high. This means that the multicell can be used as an efficient tool for comparative performance and stability tests. Copyright © 2006 John Wiley & Sons, Ltd.     

Efficient Dye‐Sensitized Solar Cells with Potential‐Tunable Organic Sulfide Mediators and Graphene‐Modified Carbon Counter Electrodes

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.     

Nanocrystalline dye‐sensitized solar cells having maximum performance

This paper presents an overview of the research carried out by a European consortium with the aim to develop and test new and improved ways to realise dye‐sensitized solar cells (DSC) with enhanced efficiencies and stabilities. Several new areas have been explored in the field of new concepts and materials, fabrication protocols for TiO₂ and scatterlayers, metal oxide blocking layers, strategies for co‐sensitization and low temperature processes of platinum deposition. Fundamental understanding of the working principles has been gained by means of electrical and optical modelling and advanced characterization techniques. Cost analyses have been made to demonstrate the potential of DSC as a low cost thin film PV technology. The combined efforts have led to maximum non‐certified power conversion efficiencies under full sunlight of 11% for areas <0ċ2 cm² and 10ċ1% for a cell with an active area of 1ċ3 cm². Lifetime studies revealed negligible device degradation after 1000 hrs of accelerated tests under thermal stress at 80°C in the dark and visible light soaking at 60°C. An outlook summarizing future directions in the research and large‐scale production of DSC is presented. Copyright © 2006 John Wiley & Sons, Ltd.     

New interdigital design for large area dye solar modules using a lead‐free glass frit sealing

A new interdigital design for large area dye solar modules is developed for an area of 30×30 cm². This design requires fewer holes in the glass substrate for electrolyte filling, than the conventional strip design. A complete manufacturing process of this module—ranging from screen printed layers to semi‐automated colouring and electrolyte filling—in a laboratory‐scale baseline is illustrated. As primary sealing method, a durable glass frit sealing is used. It is shown, that the lead (Pb) content present in many glass frit powders contaminates the catalytic platinum electrode during the sintering process, resulting in a lowering of the fill factor. A screen printable lead‐free glass frit paste is developed, which solves this problem. Long term stability tests are presented on 2·5 cm² dye solar cells, which have been completely sealed with glass frit. In consecutively performed accelerated ageing tests under 85°C in the dark (about 1400 h) and continuous illumination with visible light (1 sun, about 1700 h), a 2·5 cm² dye solar cell with an electrolyte based on propylmethylimidazolium iodide showed an overall degradation of less than 5% in conversion efficiency. In a subsequently performed thermal cycling test (−40°C to +85°C, 50 cycles) a 2·5 cm² dye solar cell with the same electrolyte composition also showed only a slight degradation of less than 5% in conversion efficiency. Copyright © 2006 John Wiley & Sons, Ltd.     

Photovoltaic characterization of dye‐sensitized solar cells: effect of device masking on conversion efficiency

We analyze the effect of masking on the conversion efficiency of dye sensitized solar cells (DSC) by comparing the photovoltaic performance of the device subjected to light from a solar simulator for a variety of mask sizes. The aperture size of the mask had a significant effect on the energy conversion efficiency, which varied by as much as 36%. We identify factors that contribute to measurement errors and propose optimal conditions for the characterization of DSC's of small size. Copyright © 2006 John Wiley & Sons, Ltd.     

Enhanced photovoltaic performance of cross‐linked ruthenium dye with functional cross‐linkers for dye‐sensitized solar cell

Photovoltaic performance of cross‐linkable Ru(2,2′‐bipyridine‐4,4′‐bicarboxylic acid)(4,4′‐bis((4‐vinyl benzyloxy)methyl)‐2,2′‐bipyridine)(NCS)₂ (denoted as RuS dye) adsorbing on TiO₂ mesoporous film was enhanced by polymerizing with either ionic liquid monomer, 1‐(2‐acryloyloxy‐ethyl)‐3‐methyl‐imidazol‐1‐ium iodide (AMImI), to form RuS‐cross‐AMImI or di‐functional acrylic monomer with ether linkage, triethyleneglycodimethacrylate (TGDMA), to form RuS‐cross‐TGDMA. Their cross‐linking properties were investigated by UV–vis spectroscopy by rinsing with 0.1 N NaOH aqueous solution. The power conversion efficiencies (PCEs) of dye‐sensitized solar cells (DSSCs) with RuS‐cross‐AMImI and RuS‐cross‐TGDMA both reached over 8% under standard global air mass 1.5 full sunlight. The increased PCE for DSSCs with RuS‐cross‐AMImI comparing with cross‐linked RuS was attributed to the I⁻ counterion of AMImI increasing the charge regeneration rate of RuS dye, whereas that with RuS‐cross‐TGDMA was attributed to the Li⁺ coordination property of TGDMA. The photovoltaic performance of RuS‐cross‐TGDMA was also slightly better than that of RuS‐cross‐AMImI because of higher open‐circuit photovoltage (V_oc) and short‐circuit photocurrent (J_sc). Its higher V_oc was supported by the Bode plot of impedance under illumination and Nyquist plots at dark, whereas higher J_sc was supported by the incident monochromatic photon‐to‐current conversion efficiency spectra and charge extraction experiments. Copyright © 2013 John Wiley & Sons, Ltd.     

SHORT COMMUNICATION: ACCELERATED PUBLICATION: Dye solar cells without electrolyte or hole‐transport layers: a feasibility study of a concept based on direct regeneration of the dye by metallic conductors

Flat structures consisting of dense dye‐sensitized TiO₂ films with various materials for dye regeneration (TiO₂/dye/regeneration material) are compared. Au and PEDOT:PSS were tested as metal or metal‐like regeneration materials and compared with reference compounds, such as the redox couple I⁻/I in solution and p‐type CuSCN. Under the exclusion of TiO₂ bandgap excitation, the short‐circuit photocurrent densities for the various structures differ by less than ∼30%, suggesting comparable charge separation efficiencies. The good performance of a metallic regeneration material implies, that the frequently assumed requirement of p‐type or ‘hole conducting’ properties for the regeneration material in solid state dye solar cells is questionable. Copyright © 2005 John Wiley & Sons, Ltd.     

Design of conduction band structure of TiO2 electrode using Nb doping for highly efficient dye‐sensitized solar cells

A barrier layer of undoped TiO₂ was deposited on the Nb‐doped TiO₂ electrode to suppress the recombination at the Nb‐doped TiO₂/dye–electrolyte interface for highly efficient dye‐sensitized solar cells (DSCs). The Nb content in TiO₂ was varied in a range of 0.7–3.5 mol% to modify the TiO₂ energy‐band structure. Nb‐doped TiO₂/dye interfaces were characterized by a combination of ultraviolet photoemission spectroscopy and optical absorption spectroscopy measurements, allowing the determination of the conduction band minimum (CBM) of the TiO₂ electrode and the lowest unoccupied molecular orbital of the N719 dye. The lowering of TiO₂ CBM by Nb doping induced the increase in short‐circuit current of DSCs. However, open‐circuit voltage and fill factor are decreased, and this result was ascribed to the enhanced recombination at the Nb‐doped TiO₂/dye–electrolyte interface. The effect of doping on charge transport in DSCs was analyzed using electrochemical impedance spectroscopy. We have shown that by introducing of TiO₂ barrier layer, the Nb doping content, which results in DSC highest efficiency, can be increased because of the suppression of the dopant‐induced recombination. The energy conversion efficiency of the solar cells increased from 7.8% to 9.0% when undoped TiO₂ electrode is replaced with electrode doped with 2.7 mol% of Nb because of the improvement of the electron injection and collection efficiencies. The correlation between the electronic structure of the TiO₂ electrode, charge transfer characteristics, and photovoltaic parameters of DSCs is discussed. Copyright © 2012 John Wiley & Sons, Ltd.     

Transparent conductive oxide‐less back contact dye‐sensitized solar cells using cobalt electrolyte

Transparent conductive oxide‐less (TCO‐less) dye‐sensitized solar cells (DSSCs) have been fabricated and characterized using nanoporous TiO₂‐coated stainless steel metal mesh as flexible photoanode and cobalt bipyridyl complex (Co(bpy))‐based one electron redox shuttle electrolyte. Attempts have been made towards enhancing the efficiency of TCO‐less DSSCs to match with their TCO‐based DSSC counterparts. It has been found that surface protection of metal mesh is highly required for enhancing the efficiency of TCO‐less DSSCs specially using cobalt electrolytes as confirmed by dark current–voltage characteristics. Photocurrent action spectra clearly reveal that TCO‐based DSSCs using (Co(bpy)) electrolyte exhibits photon harvesting (incident photon to current conversion efficiency (IPCE) 52%) in the 370–450 nm wavelength region as compared to photon harvesting at peak absorption of the dye (IPCE 56% at 550 nm), which is almost the same (IPCE 47%) in the 400–610 nm wavelength region for TCO‐less DSSCs. Under similar experimental conditions, replacing indoline dye D‐205 to porphyrin‐based dye YD2‐o‐C8 led to the enhancement in the photoconversion efficiency from 3.33% to 4.84% under simulated solar irradiation. Copyright © 2014 John Wiley & Sons, Ltd.     

Catalytic materials manufactured by the polyol process for monolithic dye‐sensitized solar cells

Three types of screen‐printable catalytic pastes were successfully prepared to be used as counterelectrode for monolithic dye solar cells encapsulated with glass frit. The electroless bottom‐up method or so‐called polyol process has been applied to fabricate thermally stable SnO₂:Sb/Pt and carbon black/Pt nanocomposites. The catalytic and electric properties of these materials were compared with a new platinum‐free type of carbon counterelectrode. The layers containing low platinum amounts (less than 5 µg/cm²) exhibit a very low charge transfer resistance of about 0·4 Ω · cm². Also the conductive carbon layer shows an acceptable charge transfer resistance of 1·6 Ω · cm². Additionally the catalytic layer containing porous carbon black reveals excellent sheet resistance below 5 Ω/□; this feature has enabled to work out a low cost counterelectrode which combined suitable catalytic and conductive properties. The layers have been characterized using following methods: electrochemical impedance spectroscopy (EIS), field emission scanning electron microscopy (FE‐SEM), energy filter transmission electron microscopy (EF‐TEM) and inductively coupled plasma mass spectroscopy (ICP‐MS). Copyright © 2008 John Wiley & Sons, Ltd.     

The use of Ti meshes with self‐organized TiO2 nanotubes as photoanodes of all‐Ti dye‐sensitized solar cells

This paper reports a simple and facile method for directly growing self‐organized TiO₂ nanotubular arrays around the whole Ti mesh by electrochemical anodization in organic electrolytes and their application in all‐Ti dye‐sensitized solar cells (DSSCs). Compared with the traditional fluorine‐doped tin oxide (FTO)‐based DSSC and the backside illuminated DSSC, this type of DSSC showed advantages such as low resistance, cheap fabrication cost and enhanced sunlight utilization. Different thicknesses of nanotubular array layers were investigated to find their influence on the photovoltaic parameters of the cell. We also considered three types of meshes as the substrates of anodes and found that the cell with 6 openings/mm² exhibited the highest conversion efficiency of 5.3%. The area of the cell had only a little impact on the photovoltaic performances. Copyright © 2010 John Wiley & Sons, Ltd.     

Toward high‐efficiency dye‐sensitized solar cells with a photoanode fabricated via a simple water‐based formulation

An aqueous formulation containing commercially available P25 nanoparticles and a water‐soluble precursor—titanium (IV) bis(ammonium lactato)dihydroxide (TALH) has been developed and optimized for fabricating photoanodes in dye‐sensitized solar cells. An optimal formulation achieved a power conversion efficiency of 9.2%. Solar cell performance is significantly influenced by precursor concentration impacting the porosity and electron transport of the thin film. The use of TALH during processing is shown to enhance the electron transport in the resulting titanium dioxide nanoparticle network using transient decay measurements. Bridging between neighboring nanoparticles is confirmed using transmission electron microscopy explaining the enhanced electron transport. The developed formulation has several advantages, as it is water‐based, composed of inexpensive, non‐hazardous components, is easy to make, and does not require special handling. The formulation has great potential for industrial applications, in particular for DSC manufacturing using roll‐to‐roll technology. Copyright © 2014 John Wiley & Sons, Ltd.     

A polyfluoroalkyl imidazolium ionic liquid as iodide ion source in dye sensitized solar cells

We report on the use of a fluorinated imidazolium ionic liquid as a source of iodide ions in solvent-based electrolytes for DSSCs. Efficient dye regeneration and fast charge transport in the fluorinated electrolyte result in an overall improvement of the device performances compared to conventional hydrogenated ionic liquids.     

Enhanced efficiency of phenothiazine derivative organic dye‐sensitized ionic liquid solar cells on aging

We have used electrochemical impedance to investigate the improvement in photovoltaic performance in aging of ionic liquid dye‐sensitized solar cells using a high‐absorption coefficient organic dye (2E)‐2‐cyano‐3‐(5‐(5‐((E)‐2‐(10‐(2‐ethylhexyl)‐10H‐phenothiazin‐7‐yl)vinyl)thiophen‐2‐yl)thiophen‐2‐yl)acrylic acid, which is in contrast to N719‐based devices. It was found that the enhancement is due to reduced recombination of the photoexcited electrons. The decreased recombination plausibly originates from molecular re‐orientation along with cation adsorption, with Fourier transform infrared spectra lending support to the former mechanism. After aging, the photovoltaic device using the organic dye outperforms the counterpart by the ruthenium complex dye and achieves an impressive efficiency of 5.6% under AM 1.5 100 mW/cm² illumination. Copyright © 2011 John Wiley & Sons, Ltd.     

Coumarin based sensitizers with ortho-halides substituted phenylene spacer for dye sensitized solar cells

The performance of DSSCs (dye sensitized solar cells) with a new series of dyes having different halide groups (i.e. F, Cl and Br) on o-position substituted phenyl spacers with same coumarin donor moieties have been reported. Optical, electrochemical, molecular orbital and photovoltaic properties were studied by varying the halide groups using these dyes. The replacement of halide atoms in same coumarin based dye had a significant effect on the short circuit current density (J_sc), open circuit voltage (V_oc), and photo conversion efficiency (PCE). The J_sc and PCE of dye CD-1 (fluorine substituted) are 10.3 mA/cm² and 5.2% respectively, which is higher than CD-2 (chlorine substituted) and CD-3 (bromine substituted) dyes (having PCE 4.1% and 3.5% respectively) devices. The optimized geometry calculation of o-halide phenyl π-spacer dyes were ascertained by density functional theory (DFT) using the B3LYP/6-31G(d,p) basis set. Moreover, we have checked the effect of various substituents in the same dye structure by DFT analysis.     

Ultrafast near infrared sintering of TiO2 layers on metal substrates for dye‐sensitized solar cells

A limiting step to roll‐to‐roll production of dye‐sensitized solar cells on metals is TiO₂ sintering (10–30 min). Near infrared (NIR) heating is a novel process innovation which directly heats titanium substrates giving rapid binder removal and sintering. NIR heating (for 12.5 s) at varying power gave titanium temperatures of 545, 685 and 817°C yielding cells with efficiencies of 2.9, 2.8 and 2.5%. Identical cells prepared in a conventional oven (1800 s) at 500, 600 and 800°C gave 2.9, 2.6 and 0.2% efficiency. NIR sintering is ultrafast and has a wide process window making it ideal for rapid manufacturing on metals. Copyright © 2010 John Wiley & Sons, Ltd.