Direct assembly of preformed nanoparticles and graft copolymer for the fabrication of micrometer-thick, organized TiO2 films: high efficiency solid-state dye-sensitized solar cells

Solid-state dye-sensitized solar cell with 7.1% efficiency at 100 mW/cm(2) is reported, one of the highest observed for N719 dye. Excellent performance was achieved via a graft copolymer-templated, organized mesoporous TiO(2) film with a large surface area using spindle-shaped, preformed TiO(2) nanoparticles and solid polymer electrolyte.     

Organized mesoporous TiO2 films exhibiting greatly enhanced performance in dye-sensitized solar cells

The Pluronic P123 templated mesoporous TiO2 film was grown via layer-by-layer deposition and characterized by a novel methodology based on the adsorption of n-pentane. Multiple-layer depositions did not perturb the mesoporous structure significantly. Our TiO2 film was sensitized by a newly developed Ru-bipyridine dye (N945) and was applied as a photoanode in dye-sensitized solar cell. The 1-microm-thick mesoporous film, made by the superposition of three layers, showed enhanced solar conversion efficiency by about 50% compared to that of traditional films of the same thickness made from randomly oriented anatase nanocrystals.     

Ag2Se量子点共敏化固态染料敏化太阳能电池光电性能研究

采用水相共沉积法制备Ag₂Se量子点(QDs), 并与染料共敏化制备固态染料敏化太阳能电池(DSSCs)。考察了Ag₂Se量子点不同敏化方式(TiO₂/N719/QDs, TiO₂/QDs/N719)及敏化时间(0~5 h)对DSSCs性能的影响。通过透射电子显微镜(TEM)和紫外-可见光谱图(UV-Vis)对Ag₂Se量子点结构及光学性质进行了表征; 采用光调制光电流/电压谱(IMPS/VS)以及交流阻抗谱(EIS)对器件中载流子传输过程进行了研究。TiO₂/QDs/N719的电池器件比TiO₂/ N719/QDs具有更高的单色光量子转化效率(IPCE)及光电转化效率, 这是由于TiO₂/QDs/N719可以吸附更多的量子点和染料。随着Ag₂Se量子点敏化时间的延长, 光电转化效率先提高后降低, 最高达到3.97%。Ag₂Se量子点在器件中起到了阻挡层作用, 可以促进电子传输, 抑制电子-空穴复合。而随着量子点敏化时间超过2 h, 电子陷入陷阱的几率增加, 导致器件的光伏性能下降。     

The effects of co-sensitization in dye-sensitized solar cells

Triazoloisoquinoline-based organic dyestuff was synthesized and used in the fabrication of dye-sensitized solar cells (DSSCs). After co-sensitization with ruthenium complex, triazoloisoquinoline-based organic dyestuff overcomes the deficiency of ruthenium dyestuff absorption in the blue part of the visible spectrum. The incident photon-to-electron conversion efficiency (IPCE) of cis-dithiocyanate-N,N′-bis-(4-carboxylate-4-tetrabutyl ammoniumcarboxylate-2,2′-bipyridine)ruthenium(II) (N719) at shorter wavelength regions (~350–500 nm) is 35 %. After addition of triazoloisoquinoline-based dyestuff for co-sensitization, the IPCE at 350–500 nm increased significantly. This can be attributed to the increased photocurrent of the cells, which improves the dye-sensitized photoelectric conversion efficiency. After optimization of the cells, an energy conversion efficiency of 8.83 % was achieved using an 12 + 4 μm TiO₂ electrode, under simulated solar illumination (AM 1.5G). As a consequence, this low molecular weight organic dyestuff is a promising candidate as a co-adsorbent and co-sensitizer for highly efficient DSSCs.     

柔性染料敏化太阳电池光阳极的优化及叠层电池的初步研究

在前期对冷等静压制备柔性染料敏化太阳电池(DSC)研究的基础上, 开展了浆料的优化及叠层DSC的研究。首先利用水热法处理由小颗粒P25调配的浆料, 发现处理后浆料的稳定性及DSC的效率得到了大幅提高。在P25浆料中加入不同比例200 nm TiO₂大颗粒提高光散射, 当P25与200 nm TiO₂比例为4:1时, DSC获得最高光电转换效率3.11%。在此基础上, 尝试用N719和N749双层染料敏化, 发现双层染料敏化后电池的效率介于N719和N749单独敏化的电池效率, 这可能是由于光阳极变厚不利于电子传输以及染料相互接触影响染料纯度, 光阳极厚度及电池结构有待于进一步优化。     

Photocurrent-voltage of a dye-sensitized nanocrystalline TiO2 solar cells influenced by N719 dye adsorption properties

Titanium particles of single-phase anatase nanocrystallites were prepared by the hydrolysis of titanium tetraisopropoxide. A dye-sensitized solar cell (DSSC) was fabricated by adsorbing cis-bis(isothiocyanato)bis(2,2'-bipyridyl-4,4'-dicarboxylato)-ruthenium(II)bis-tetrabutylammonium dye (N719) onto TiO2 film. The samples were characterized by XRD, TEM, FE-SEM, AFM, and Brunauer-Emmett-Teller (BET) analysis. The influence of the acetic acid treatment of TiO2 electrode with different concentrations on the photovoltaic performance of DSSC was investigated. It was found that DSSC had better photoelectric performance when the TiO2 electrode was treated by acetic acid of 0.5 M. An equivalent circuit analysis using the one-diode model was used to evaluate the influences of adsorption quantity and acetic acid treatment on the energy conversion efficiency of DSSC. A nonlinear least-square optimization method was used to determine five model parameters.     

Evaluation of microwave plasma sintering for the fabrication of dye sensitized solar cell (DSSC) electrodes

Dye-sensitized solar cells (DSSCs) have demonstrated considerable potential due to their solar energy conversion efficiency and their fabrication from relatively low cost materials. Titanium dioxide (TiO2) nanoparticles are widely used in the fabrication of the DSSC electrodes. There is a considerable energy requirement however required for the sintering of the TiO2 particles during the fabrication of the mesoporous electrodes. This study investigates the use of microwave (MW) plasma treatments as a rapid, energy efficient processing technique for the sintering of the metal oxide particles. A comparison is made with conventional furnace treatments for the sintering of TiO2 nanoparticles (Degussa P25), deposited onto fluorine doped tin oxide (FTO) coated glass substrates. Subsequent to the TiO2 sintering, ruthenium based dye (N719) adsorption studies were carried out for coatings heated using both sintering techniques. Based on UV/Vis absorption spectra measurements of 5 mins plasma and 30 mins furnace sintering, it was observed that both sintering techniques exhibited similar levels of dye adsorption. A decrease in the level of dye adsorption was observed for the TiO2 coatings sintered for longer periods (up to 10 mins in this study). This change with longer plasma treatment times was associated with rutile grain growth and a decrease in surface roughness, possibly due to a densification of the mesoporous structure. The effect of TiO2 coating plasma treatment times on the conversion efficiency of the dye sensitised electrodes was also evaluated. Plasma treatments of 5 mins were found to yield the highest conversion efficiency of 6.4%.     

Surface destruction and performance reduction of the ZnO nanowire arrays electrode in dye sensitization process

ZnO based dye-sensitized solar cells have been widely investigated. The limitation of the conversion efficiency is studied in this work. Obvious morphology changes of the ZnO nanowire electrode occur after a period of time sensitized in the ruthenium N719 dye ethanol solution. The surface dissolution of the ZnO nanowires and the formation of Zn²⁺/dye aggregates have been discovered and characterized. The influence of the sensitization duration on the cell performance is investigated and discussed. The short circuit current density and overall conversion efficiencies of the cells decrease extremely when the sensitization time is prolonged. The results exhibit that ruthenium N719 dye is not suitable enough to the ZnO nanowire arrays electrode.     

Influence of $$\hbox {TiO}_{2}$$ particle size and conductivity of the CuCrO$$_{2}$$2 nanoparticles on the performance of solid-state dye-sensitized solar cells

Solid-state dye-sensitized solar cells have been fabricated with mesoporous \(\hbox {TiO}_{2 }\) photoanode and N719 dye as photosensitizer. First, \(\hbox {TiO}_{2}\) and non-doped, Zn- and Mg-doped CuCrO\(_{2}\) nanoparticles have been synthesized by sol–gel method. In addition, the \(\hbox {TiO}_{2}\) pastes have been prepared through Pechini-type sol–gel method. The effect of \(\hbox {TiO}_{2}\) particle size, mesoporous \(\hbox {TiO}_{2}\) photoanode thickness and solid-state electrolyte thickness on the efficiency of the fabricated devices has been investigated. Our results show that in spite of the low amount of dye loading for photoanode with large \(\hbox {TiO}_{2}\) nanoparticles (80–180 nm), the dye-sensitized solar cell made from it has higher efficiency than that constructed from the photoanode comprising of small particles about 10–15 nm in size. The higher efficiency is attributed to the longer diffusion length of electrons because of a better electron transport and penetration of a large amount of \(\hbox {CuCrO}_{2 }\) nanoparticles in the porous structure of \(\hbox {TiO}_{2}\) photoanode. By using the doped \(\hbox {CuCrO}_{2}\) nanoparticles, the efficiency has been increased from 0.027% for \(\hbox {TiO}_{2}\)/N719 dye/CuCrO\(_{2}\) to 0.033% for \(\hbox {TiO}_{2}\)/N719 dye/CuCrO\(_{2}\):Zn and further increased to 0.042% for \(\hbox {TiO}_{2}\)/N719 dye/CuCrO\(_{2}\):Mg. The efficiency enhancement by doping is ascribed to the conductivity improvement due to the presence of impurity atoms.     

介孔TiO2微球水热法合成及在染料敏化太阳能电池中的应用

以Ti(SO4)2为钛源,采用尿素辅助水热法合成了介孔TiO2微球,利用XRD、FESEM和比表面积分析仪对样品的晶型、形貌和比表面积进行分析,探讨了尿素加入量对TiO2微球的颗粒尺寸、比表面积、孔径和孔容的影响。采用刮涂法,用所合成的介孔TiO2微球制备了染料敏化太阳能电池(DSSC)的光阳极,结果表明,尿素用量为1.2g合成的介孔TiO2微球所组装的电池在模拟太阳光的照射下(100mW/cm2,AM1.5),光电转换效率为6.2%,明显高于商用P25纳晶所组装的电池光电转换效率(4.24%)。     

Nanoforest Nb2O5 photoanodes for dye-sensitized solar cells by pulsed laser deposition

Vertically aligned bundles of Nb(2)O(5) nanocrystals were fabricated by pulsed laser deposition (PLD) and tested as a photoanode material in dye-sensitized solar cells (DSSC). They were characterized using scanning and transmission electron microscopies, optical absorption spectroscopy (UV-vis), and incident-photon-to-current efficiency (IPCE) experiments. The background gas composition and the thickness of the films were varied to determine the influence of those parameters in the photoanode behavior. An optimal background pressure of oxygen during deposition was found to produce a photoanode structure that both achieves high dye loading and enhanced photoelectrochemical performance. For optimal structures, IPCE values up to 40% and APCE values around 90% were obtained with the N(3) dye and I(3)(-)/I(-) couple in acetonitrile with open circuit voltage of 0.71 V and 2.41% power conversion efficiency.     

Simple metal-free organic D-pi-A dyes with alkoxy- or fluorine substitutions: application in dye sensitized solar cells

Two new metal-free organic sensitizers with simplest structural variations have been synthesized for application in nanocrystalline TiO2 sensitized solar cells. The donor-pi-bridge-acceptor (D-pi-A) structure dyes, Y2 and Y3 each designed with three parts, an electron donor unit (substituted phenyl), a linker unit (thiophene), and an anchor unit (cyanoacrylic acid) showed maximal monochromatic incident photon to current conversion efficiencies (IPCE) in a device reaching upto 67% and 82% respectively. The organic sensitizers with 3,4,5-trimethoxy phenyl (Y3) as donor moieties obtained better solar light to electrical energy conversion efficiencies of 3.30% where as the organic sensitizer with 2,4-difluoro phenyl as donor (Y2) showed comparatively lower efficiency of 1.02%. The efficiency obtained with the reference sensitizer N719 under similar fabrication and evaluation conditions was 5.84%.     

Enhancing the photovoltaic performances of dye-sensitized solar-cells by modifying the TiO2 electrode-sensitized dye interface

Enhanced photovoltaic performances of N719 dye-sensitized solar-cells were achieved by modifying the titanium oxide (TiO₂) electrode-sensitized dye interface. Surface of TiO₂ thin film electrode was coated with a calcium oxide (CaO) or lithium fluoride (LiF) thin layer, respectively, in a thermal deposition chamber. As compared to a cell using a bare TiO₂ nanoparticle (NTP) electrode, the solar energy conversion efficiency (η)? was enhanced by 15.1% and 12.8% for the surface of a NTP electrode coated with CaO and LiF, respectively. Moreover, for the surface of a TiO₂ nanotube electrode respectively coated with CaO and LiF, the efficiency was enhanced by 4.8% and 11.6%. This increase in efficiency is attributed to an increase in the adsorption of N719 dye on the CaO or LiF coated TiO₂ thin film electrodes, and the formation of a potential barrier by a CaO or LiF interlayer at the TiO₂ electrode-sensitized dye interface.     

染料敏化太阳能电池的研究进展

光导电极材料在染料敏化太阳能电池(DSSC)中起到关键作用,直接影响到太阳能电池的总效率,所以一直是DSSC研究的热点.介绍了DSSC的基本工作原理,概述了当前DSSC中最流行的TiO<,2>和ZnO两种薄膜光导电极材料的制备方法,并从结构、工艺和转换效率等方面对染料敏化TiO<,2>薄膜太阳能电池和染料敏化ZnO薄膜太阳能电池进行了介绍和讨论;同时简要介绍了目前研究非常热门的叠层染料敏化太阳电池的研究进程,最后展望了染料敏化太阳能电池的未来发展前景.     

Application of TiO2 nanoparticles coated multi-wall carbon nanotube to dye-sensitized solar cells

This study uses the sol-gel method to prepare TiO2 nanoparticle, and further applies TiO2 nanoparticle coating on the surface of the multi-wall carbon nanotube (MWCNT). As a result, TiO2-CNT composite nanoparticles are prepared to serve as photoelectrode material in dye-sensitized solar cell (DSSC). First, after acid treatment of MWCNT is used to remove impurities. Then, the sol-gel method is employed to prepare TiO2-CNT composite nanopowder. X-ray diffraction (XRD) pattern shows that after the TiO2 in TiO2-CNT composite nanopowder has been thermally treated at 450 degrees C, it can be completely changed to anatase phase. Furthermore, as shown from the SEM image, TiO2 has been successfully coated on CNT. The photoelectrode of DSSC is prepared using the electrophoretic deposition method (EPD) to mix the Degassa P25 TiO2 nanoparticles with TiO2-CNT powder for deposition on the indium tin oxide (ITO) conductive glass. After secondary EPD, a thin film of TiO2/CNTs with thickness 17 microm can be acquired. For the prepared TiO2-CNT composite nanoparticles, since MWCNT can increase the short-circuit current density of DSSC, the light-to-electricity conversion efficiency of DSSC can be effectively increased. Experimental results show that the photoelectric conversion efficiency of DSSC using CNT/TiO2 photoelectrode and N719 dye is increased by 41% from the original 3.45% to 4.87%.     

上转换发光材料La(OH)3∶Er3+/Yb3+的制备及在染料敏化太阳能电池中的应用

针对N719染料仅可吸收可见光这一局限,本研究旨在通过引入上转换发光材料并将其应用于染料敏化太阳能电池的光阳极来拓宽光谱吸收范围,提高光的捕获率,进而达到提高电池光电转换效率的目的。首先,采用水热合成法以不同pH值的先驱体溶液,成功制备了Yb~(3+)/Er~(3+)双掺杂La(OH)_3粉末,然后将适量合成的稀土发光粉掺入TiO_2纳米浆料中,采用刮涂法成膜制备光阳极,并将其组装成染料敏化太阳能电池。研究结果表明,稀土发光粉的加入拓宽了光谱吸收范围,在其掺杂量达到3%时,电池的短路电流密度Jsc提高到17.72mA·cm-2,最终获得了8.3%的光电转换效率。     

Sodium fluoride-assisted modulation of anodized TiO₂ nanotube for dye-sensitized solar cells application

This work reports the use of sodium fluoride (in ethylene glycol electrolyte) as the replacement of hydrofluoric acid and ammonium fluoride to fabricate long and perpendicularly well-aligned TiO? nanotube (TNT) (up to 21 μm) using anodization. Anodizing duration, applied voltage and electrolyte composition influenced the geometry and surface morphologies of TNT. The growth mechanism of TNT is interpreted by analyzing the current transient profile and the total charge density generated during anodization. The system with low water content (2 wt %) yielded a membrane-like mesoporous TiO? film, whereas high anodizing voltage (70 V) resulted in the unstable film of TNT arrays. An optimized condition using 5 wt % water content and 60 V of anodizing voltage gave a stable array of nanotube with controllable length and pore diameter. Upon photoexcitation, TNTs synthesized under this condition exhibited a slower charge recombination rate as nanotube length increased. When made into cis-diisothiocyanato-bis(2,2?-bipyridyl-4,4?-dicarboxylato) ruthenium(II) bis (tetrabutyl-ammonium)(N719) dye-sensitized solar cells, good device efficiency at 3.33 % based on the optimized TNT arrays was achieved with longer electron time compared with most mesoporous TiO? films.     

Layer-by-layer formation of block-copolymer-derived TiO(2) for solid-state dye-sensitized solar cells

Morphology control on the 10 nm length scale in mesoporous TiO(2) films is crucial for the manufacture of high-performance dye-sensitized solar cells. While the combination of block-copolymer self-assembly with sol-gel chemistry yields good results for very thin films, the shrinkage during the film manufacture typically prevents the build-up of sufficiently thick layers to enable optimum solar cell operation. Here, a study on the temporal evolution of block-copolymer-directed mesoporous TiO(2) films during annealing and calcination is presented. The in-situ investigation of the shrinkage process enables the establishment of a simple and fast protocol for the fabrication of thicker films. When used as photoanodes in solid-state dye-sensitized solar cells, the mesoporous networks exhibit significantly enhanced transport and collection rates compared to the state-of-the-art nanoparticle-based devices. As a consequence of the increased film thickness, power conversion efficiencies above 4% are reached.     

An unconventional route to high-efficiency dye-sensitized solar cells via embedding graphitic thin films into TiO2 nanoparticle photoanode

Graphitic thin films embedded with highly dispersed titanium dioxide (TiO(2)) nanoparticles were incorporated for the first time into the conventional dye-sensitized solar cells (DSSCs), resulting in a remarkably improved cell efficiency due to its superior electron conductivity. Massively ordered arrays of TiO(2) dots embedded in carbon matrix were fabricated via UV-stabilization of polystyrene-block-poly(4-vinylpyridine) films containing TiO(2) precursors followed by direct carbonization. For dye-sensitized TiO(2) based solar cells containing carbon/TiO(2) thin layers at both sides of pristine TiO(2) layer, an increase of 62.3% [corrected] in overall power conversion efficiency was achieved compared with neat TiO(2)-based DSSCs. Such a remarkably improved cell efficiency was ascribed to the superior electron conductivity and extended electron lifetime elucidated by cyclic voltammetry and impedance spectroscopy.     

Self-assembled TiO₂ with increased photoelectron production, and improved conduction and transfer: enhancing photovoltaic performance of dye-sensitized solar cells

Highly crystalline mesoporous anatase TiO(2) is prepared through supramolecular self-assembly and by utilizing cetyltrimethylammonium bromide (CTAB) as templating material. Photoanodes of dye-sensitized solar cells (DSSCs) made from these TiO(2) nanoparticles are found to have a high specific surface area of 153 m(2)/g and high surface roughness. Optical absorption spectroscopy studies reveal that the photoanode films adsorb four times more dye than films made of commercial P25 TiO(2). Mercury porosimetry and field emission scanning electron microscope (FESEM) studies show hierarchical macro- and meso-porosity of the photoanode films leading to better dye and electrolyte percolation, combined with improved electron conduction pathways compared to P25 films. Electrochemical impedance studies confirm lower impedance and higher electron lifetime in the synthesized mesoporous TiO(2) films compared to P25 films. Higher photovoltaic efficiency was recorded of cells made from the synthesized mesoporous TiO(2) in comparison to the corresponding cells made from P25. Incident-photon-to-current efficiency data provided critical understanding of recombination kinetics, and provided proof of Mie scattering by the self-assembled submicrometer sized TiO(2) aggregates and the macropores in their structure. The scattering phenomenon was further corroborated by diffused reflectance studies. An in-depth analysis of CTAB-templated mesoporous TiO(2) has been conducted to show how it can be a good candidate photoanode material for enhancing the performance of DSSCs.