Facile synthesis of TiO2 inverse opal electrodes for dye-sensitized solar cells

Engineering of TiO(2) electrode layers is critical to guaranteeing the photoconversion efficiency of dye-sensitized solar cells (DSSCs). Recently, a novel approach has been introduced for producing TiO(2) electrodes using the inverted structures of colloidal crystals. This paper describes a facile route to producing ordered macroporous electrodes from colloidal crystal templates for DSSCs. Using concentrated colloids dispersed in a volatile medium, the colloidal crystal templates were obtained within a few minutes, and the thickness of the template was easily controlled by changing the quantity of colloidal solution deposited. Here, the effects of the structural properties of the inverse opal TiO(2) electrodes on the photovoltaic parameters of DSSCs were investigated. The photovoltaic parameters were measured as a function of pore ordering and electrode film thickness. Moreover, DSSC applications that used either liquid or viscous polymer electrolyte solutions were investigated to reveal the effects of pore size on performance of an inverse opal TiO(2) electrode.     

Ni3S4@C/CNFs对电极膜厚对染料敏化太阳能电池光伏性能的影响

采用静电纺丝技术和水热法合成了负载于碳纳米纤维表面的碳包覆Ni3S4纳米颗粒(Ni3S4@C/CNFs),利用喷涂法制备膜厚分别为2、4、6、7、8、9、10μm的Ni3S4@C/CNFs对电极。应用到染料敏化太阳能电池(DSSCs)中,探究Ni3S4@C/CNFs对电极的膜厚对于DSSCs光伏性能的影响。最终得出当Ni3S4@C/CNFs对电极膜厚为9μm时,DSSCs可以获得最高的光电转换效率(PCE)8.45%,也证明了对电极存在一个最佳膜厚,使DSSCs获得最优的光伏性能。     

Enhancement of the efficiency of dye-sensitized solar cell with multi-wall carbon nanotubes/polythiophene composite counter electrodes prepared by electrodeposition

For the purpose of increasing the energy conversion efficiency of dye-sensitized solar cells (DSSCs), multi-wall carbon nanotube (MWCNT)/polythiophene (PTh) composite film counter electrode has been fabricated by electrophoresis and cyclic voltammetry (CV) in sequence. The morphology and chemical structure have been characterized by transmission electron microscopy (TEM), scanning electron microscope (SEM), and Raman spectroscopy respectively. The overall energy conversion efficiency of the DSSC employing the MWCNT/PTh composite film has reached 4.72%, which is close to that of the DSSC with a platinum (Pt) counter electrode (5.68%). Compared with a standard DSSC with MWCNT counter electrode whose efficiency is 2.68%, the energy conversion efficiency has been increased by 76.12% for the DSSC with MWCNT/PTh counter electrode. These results indicate that the composite film with high conductivity, high active surface area, and good catalytic properties for I₃⁻ reduction can potentially be used as the counter electrode in a high-performance DSSC.     

碳纳米管负载Ni2P作为染料敏化太阳能电池对电极的性能研究

本文以碳纳米管(CNTs)与Ni2P纳米晶制备CNTs-Ni2P复合材料,首次研究其染料敏化太阳能电池(DSSCs)的光阴极材料性能.使用X射线衍射(XRD)和透射电子显微镜(TEM)测定材料结构,观察材料形貌.结果表明,复合材料由碳纳米管和六方结构的磷化镍构成,无其它磷化物杂相,磷化镍纳米晶(约10 nm)分散于CNTs表面.交流阻抗(EIS)测试显示,与CNTs和Ni2P对电极相比,CNTs-Ni2P对电极的电荷转移电阻和扩散阻抗较低,接近Pt-FTO对电极水平.CNTs-Ni2P对电极的DSSCs光电流达12.9 mA·cm-2,能量转化效率达5.6%,接近Pt-FTO对电极的DSSCs能量转化效率(5.9%).这归因于高电催化活性的磷化镍纳米晶与高电导CNTs的协同效应.     

Self-Assembled Graphene/MWCNT Bilayers as Platinum-Free Counter Electrode in Dye-Sensitized Solar Cells

We describe the preparation and properties of bilayers of graphene- and multi-walled carbon nanotubes (MWCNTs) as an alternative to conventionally used platinum-based counter electrode for dye-sensitized solar cells (DSSC). The counter electrodes were prepared by a simple and easy-to-implement double self-assembly process. The preparation allows for controlling the surface roughness of electrode in a layer-by-layer deposition. Annealing under N₂ atmosphere improves the electrode's conductivity and the catalytic activity of graphene and MWCNTs to reduce the I₃⁻ species within the electrolyte of the DSSC. The performance of different counter-electrodes is compared for ZnO photoanode-based DSSCs. Bilayer electrodes show higher power conversion efficiencies than monolayer graphene electrodes or monolayer MWCNTs electrodes. The bilayer graphene (bottom)/MWCNTs (top) counter electrode-based DSSC exhibits a maximum power conversion efficiency of 4.1 % exceeding the efficiency of a reference DSSC with a thin film platinum counter electrode (efficiency of 3.4 %). In addition, the double self-assembled counter electrodes are mechanically stable, which enables their recycling for DSSCs fabrication without significant loss of the solar cell performance.     

Hierarchical twin-scale inverse opal TiO2 electrodes for dye-sensitized solar cells

We describe the preparation of three-dimensional hierarchical twin-scale inverse opal (ts-IO) electrodes for dye-sensitized solar cells (DSSCs). The ts-IO TiO(2) structure was obtained from a template fabricated via the assembly of mesoscale colloidal particles (40-80 nm in diameter) in the confined geometry of a macroporous IO structure. The photovoltaic properties of ts-IO electrodes were optimized by varying the layer thickness or the size of mesopores in the mesoscale colloidal assembly. Electron transport was investigated using impedance spectroscopy. The result showed that due to the competing effects of recombination and dye adsorption, the maximum efficiency was observed at an electrode thickness of 12 μm. The electrodes of smaller mesopores diameters yielded the higher photocurrent density due to the decrease in the electron transport resistance at the TiO(2)/dye interface. A maximum efficiency of 6.90% was obtained using an electrode 12 μm thick and a mesopore diameter of 35 nm.     

附着性能优异的碳对电极的制备及其在染料敏化太阳能电池中的应用

通过引入一种低成本商业导电碳浆(CC)作为粘结剂, 以色素碳黑(Cb)作为催化材料, 成功制备了Cb-CC对电极. 着重解决传统碳对电极的主要问题, 即碳与导电基底的附着力问题. 附着力测试结果表明: CC的引入改善了Cb与导电基板之间的附着力, 同时增强了碳对电极的导电性和稳定性. 扫描电镜(SEM)结果显示, CC与Cb混合后, 碳膜的多孔结构依然存在, 即这种对电极能同时增加导电性和催化活性. 采用循环伏安(CV)和电化学阻抗谱(EIS)对Cb-CC对电极的催化活性进行了研究. 光电性能测试结果表明, 基于Cb-CC染料敏化太阳能电池(DSSC)的能量转换效率达到了6.54%, 进一步优化后, 当Cb和CC的质量比为23:77 时效果最佳, 达到最高效率6.81%. 此外, 基于Cb-CC的DSSC长期稳定性测试结果表明, 700 h后各项光电参数无明显下降. 该实验成果为增强整体电池的稳定性和促进低成本DSSC产业化奠定了基础.     

Dye‐Sensitized Solar Cell Counter Electrodes Based on Carbon Nanotubes

Dye‐sensitized solar cells (DSSCs) have received significant attention from the scientific community since their discovery in 1991. However, the high cost and scarcity of platinum has motivated researchers to seek other suitable materials for the counter electrode of DSSCs. Owing to their exceptional properties such as high conductivity, good electrochemical activity, and low cost, carbon nanotubes (CNTs) have been considered as promising alternatives to expensive platinum (Pt) in the counter electrode of DSSCs. Herein, we provide a Minireview of the CNTs use in the counter electrode of DSSCs. A brief overview of Pt‐based counter electrodes is also discussed. Particular attention is given to the recent advances of counter electrodes with CNT‐based composite structures.     

Electro-catalytic role of insulator/conductor interface in Mg O/PEDOT composite electrodes for dye-sensitized solar cells

Mg O has not been explored as a counter electrode materials for dye-sensitized solar cells(DSSCs)due to its lack of electrical conductivity.However,herein,it is reported that Mg O insulator with conductive poly(3,4-ethylenedioxythiophene):polysty-renesulfonate(PEDOT:PSS)exhibited excellent performance as a counter electrode for DSSCs,leading to a high power conversion efficiency of 7.45%.Furthermore,it was revealed that the interface between Mg O and PEDOT:PSS plays an important electro-catalytic role in the Mg O/PEDOT composite counter electrodes.     

Bilayer inverse opal TiO2 electrodes for dye-sensitized solar cells via post-treatment

We investigated the formation of bilayer inverse opal TiO(2) (io-TiO(2)) structures via post-treatment with a TiO(2) precursor solution and characterized the photovoltaic performances of the resulting electrodes for use in dye-sensitized solar cells. The post-treatment of TiO(2) inverse opals in a precursor solution grew rutile TiO(2) nanoparticles on anatase crystalline phase io-TiO(2) surfaces, resulting in anatase/rutile bilayer structures. We achieved a maximum photovoltaic conversion efficiency of 4.6% using a 25 μm thick electrode formed with the post-treated io-TiO(2) under simulated AM 1.5 light. This efficiency represents a 183% improvement over the non-post-treated io-TiO(2) electrodes. The shell thickness was controlled by the post-treatment time. The effects of shell thickness on photovoltaic performance were investigated by measuring the morphologies and electrochemical impedance of the post-treated io-TiO(2). We found that post-treatment up to a certain period of time increased the surface area and electron lifetime, but further treatment resulted in decreased area and saturated lifetimes. The optimal post-treatment time was identified, and the optimal io-TiO(2) electrodes were characterized.     

Pyrolytic carbon from an aromatic precursor and its application as a counter electrode in dye-sensitized solar cells

Pyrolytic carbon thin films were deposited on quartz plates through a chemical vapor deposition process, by using a biphenyl precursor, 4,4'-bis(chloromethyl-1,1'-biphenyl). The pyrolytic carbons were microporous and catalytic toward reduction of tri-iodide, and the films thus obtained possessed a metallic appearance with good mirror reflections, hydrophilic surfaces, and low sheet resistances. The pyrolytic carbon-coated quartz plates were used, in place of the commonly used Pt-coated fluorine-doped tin oxide glass, as the counter electrode for dye-sensitized solar cells (DSSCs). The light to electricity conversion efficiency of the cell thus obtained was reasonably high, achieving 78% of that obtained by using the conventional but much more expensive Pt counter electrode. From the electrochemical impedance spectroscopic analysis, one found that the minor reduction in the conversion efficiency came from the relatively higher resistance and lower catalytic activity of the pyrolytic carbon. This work demonstrates that the newly developed pyrolytic carbon films may be a promising alternative to Pt as the counter electrode material for DSSCs.     

Well‐Dispersed CoS Nanoparticles on a Functionalized Graphene Nanosheet Surface: A Counter Electrode of Dye‐Sensitized Solar Cells

With a facile electrophoretic deposition and chemical bath process, CoS nanoparticles have been uniformly dispersed on the surface of the functionalized graphene nanosheets (FGNS). The composite was employed as a counter electrode of dye‐sensitized solar cells (DSSCs), which yielded a power conversion efficiency of 5.54 %. It is found that this efficiency is higher than those of DSSCs based on the non‐uniform CoS nanoparticles on FGNS (4.45 %) and built on the naked CoS nanoparticles (4.79 %). The achieved efficiency of our cost‐effective DSSC is also comparable to that of noble metal Pt‐based DSSC (5.90 %). Our studies have revealed that both the exceptional electrical conductivity of the FGNS and the excellent catalytic activity of the CoS nanoparticles improve the conversion efficiency of the uniformly FGNS‐CoS composite counter electrode. The electrochemical impedance spectra, cyclic voltammetry, and Tafel polarization have evidenced the best catalytic activity and the fastest electron transport. Additionally, the dispersion condition of CoS nanoparticles on FGNS plays an important role for catalytic reduction of I₃^?.     

基于网状铂电极的新型柔性染料敏化太阳能电池

柔性染料敏化太阳能电池（DSSCs）作为一种新型的化学太阳能电池,因其精简的封装工艺、较低廉的价格、高的化学稳定性以及可弯折等优点而备受关注. 本文介绍了一种新型的柔性DSSC的制备,其光阳极为高度有序的氧化锌（ZnO）纳米线阵列,对电极为柔性、导电、透明的网状铂(Pt networks)电极. 相对于传统的铂对电极而言,这种Pt networks对电极不仅具有优异的导电能力,还展现了极好的透光性（方阻~ 100 Ω•sq^-1,~80%透光率）和催化性能,此外,Pt networks电极可构筑于任意弯曲的衬底,具有优异的机械耐弯折性能. 在ZnO纳米线阵列的DSSCs的应用中,基于Pt networks膜的柔性DSSC的转化效率比铂纳米丝阵列 (Pt nanofiber arrays, Pt NFs）膜高出了32%.     

Improved charge transport in dye-sensitized solar cells employing viscous non-volatile electrolytes

Dye-sensitized solar cells (DSSCs) employing a viscous non-volatile electrolyte were prepared by utilizing anatase TiO₂ nanorods (synthesized via oriented attachment) as a photoanode material. One promising way to enhance the photovoltaic performance of DSSCs employing viscous electrolytes is to increase ion conductivity by increasing the salt concentration. This is accompanied by an acceleration of the charge recombination reaction and the limiting of the overall conversion efficiency. The results showed that a TiO₂ nanorod electrode enables more favorable electron transport than a conventional nanoparticle-based electrode due to the improved electron diffusion length and the large intrinsic surface area.     

Balance of catalytic activity and conductivity of Cu2ZnSnS4/graphene counter electrode for dye-sensitized solar cells: using hydrothermal-synthesized kesterite Cu2ZnSnS4 and graphene obtained by product line

Journal of Solid State Electrochemistry - The catalytic activity and conductivity of Cu2ZnSnS4/graphene counter electrode for dye-sensitized solar cells (DSSCs) was balanced using...     

Highly ordered mesoporous carbon arrays from natural wood materials as counter electrode for dye-sensitized solar cells

Highly ordered mesoporous carbon arrays are prepared by a facile carbonization of the natural bamboo and oak wood in argon atmosphere. The as-prepared oak mesoporous carbon arrays have good electrocatalytic activity and high conductivity, based on their well connected framework, highly ordered microtexture, wider mesopores and larger surface area. Consequentially, the photovoltaic performance of the DSSC with the oak mesoporous carbon array film as counter electrode is excellent and comparable to that of the DSSC with FTO/Pt counter electrode. In addition, it is a simple method for a mass production of mesoporous carbon arrays with natural wood materials.     

Low temperature fabrication of flexible carbon counter electrode on ITO-PEN for dye-sensitized solar cells

<正>A novel low temperature method was used to prepare the mesoporous carbon(MC) counter electrode(CE) on indium-doped tin oxide coated polyethylene naphthalate(ITO-PEN) for flexible dye-sensitized solar cells(DSSCs).The obtained flexible MC CEs with carbon loading of 280μg cm~(-2) were characterized by SEM,XRD and electrochemical impedance.The light-to-electricity conversion efficiency of the DSSC fabricated with the prepared flexible MC CE was 86%of that of DSSC based on the decomposited Pt CE.     

Enhanced photovoltaic characterization and charge transport of TIO2 nanoparticles/nanotubes composite photoanode based on indigo carmine dye-sensitized solar cells

Dye-sensitized solar cells (DSSCs) have established themselves as an alternative to conventional solar cells owing to their remarkably high power conversion efficiency, longtime stability and low-cost production. DSSCs composed of a dyed oxide semiconductor photoanode, a redox electrolyte and a counter electrode. In these devices, conversion efficiency is achieved by ultra-fast injection of an electron from a photo excited dye into the conduction band of metal oxide followed by subsequent dye regeneration and holes transportation to the counter electrode. The energy conversion efficiency of DSSC is to be dependent on the morphology and structure of the dye adsorbed metal oxide photoanode. Worldwide considerable efforts of DSSCs have been invested in morphology control of photoanode film, synthesis of stable optical sensitizers and improved ionic conductivity electrolytes. In the present investigation, a new composite nano structured photoanodes were prepared using TiO₂ nano tubes (TNTs) with TiO₂ nano particles (TNPs). TNPs were synthesized by sol–gel method and TNTs were prepared through an alkali hydrothermal transformation. Working photoanodes were prepared using five pastes of TNTs concentrations of 0, 10, 50, 90, and 100 % with TNPs. The DSSCs were fabricated using Indigo carmine dye as photo sensitizer and PMII (1-propyl-3-methylimmidazolium iodide) ionic liquid as electrolyte. The counter electrode was prepared using Copper sulfide. The structure and morphology of TNPs and TNTs were characterized by X-ray diffraction and electron microscopes (TEM and SEM). The photocurrent efficiency is measured using a solar simulator (100 mW/cm²). The prepared composite TNTs/TNPs photoanode could significantly improve the efficiency of dye-sensitized solar cells owing to its synergic effects, i.e. effective dye adsorption mainly originated from TiO₂ nanoparticles and rapid electron transport in one-dimensional TiO₂ nanotubes. The results of the present investigation suggested that the DSSC based on 10 % TNTs/TNPs showed better photovoltaic performance than cell made pure TiO₂ nanoparticles. The highest energy-conversion efficiency of 2.80 % is achieved by composite TNTs (10 %)/TNPs film, which is 68 % higher than that pure TNPs film and far larger than that formed by bare TNTs film (94 %). The charge transport and charge recombination behaviors of DSSCs were investigated by electrochemical impedance spectra and the results showed that composite TNTs/TNPs film-based cell possessed the lowest transfer resistances and the longest electron lifetime. Hence, it could be concluded that the composite TNTs/TNPs photoanodes facilitate the charge transport and enhancing the efficiencies of DSSCs.     

Application of carbon materials as counter electrodes of dye-sensitized solar cells

Hard carbon spherule (HCS) has been investigated as a counter electrode for dye-sensitized solar cells. The overall conversion efficiency of the cell reached 5.7%, which is comparable to 6.5% of the counter electrode of platinum-sputtered fluorine-doped tin oxide used in Grätzel-type solar cells under the same experimental condition. It is found that the photovoltaic performance was strongly affected by the specific surface areas of the carbon materials.     

功能化多壁碳纳米管填充的凝胶电解质在染料敏化太阳能电池的应用

纯聚偏氟乙烯-六氟丙烯共聚物(PVDF-HFP)基凝胶电解质常常受制于低离子电导率,阻碍了其在染料敏化太阳电池(dye-sensitized solar cells,DSSCs)中的应用。 而利用纳米填充可提高凝胶电解质离子电导率及凝胶电解质DSSCs的性能。 本文使用功能化的多壁碳纳米管(f-MWCNT)作为PVDF-HFP凝胶电解质的纳米填充物,通过改变f-MWCNT的质量分数来研究其对电解质的离子电导率和离子扩散的影响,进而研究其对DSSCs的转化效率和长期稳定性的增强作用。 研究发现:质量分数0.5%的f-MWCNT明显提高了PVDF-HFP凝胶电解质的离子电导率和离子扩散系数。 并且,该凝胶电解质基DSSCs的光转换效率可达5.28%,相比于未填充的PVDF-HFP凝胶电解质基DSSCs(4.01%),其效率提高了31.7%。 42 d后,该电池依然可以保持最初转化效率的86.5%。 实验结果证实了f-MWCNT在纳米填充方面的巨大潜能,为采用纳米填充物提高凝胶电解质DSSCs的性能提供参考。