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.     

手性离子对色谱法

阐述了手性离子对色谱分离药物对映体的基本原理。在ＨＰＬＣ流动相中加入光学纯反离子可与流动相中的对映体生成非对映体复合物（离子对）,离子对复合物之间具有不同的稳定性和分配性质,并可与固定相发生不同的静电、疏水和氢键作用,进而差速迁移得以分离。影响方法立体选择性的主要因素有：反离子的性质（酸碱性、亲脂性、光学纯度）、反离子的浓度、流动相的组分、流动相的流速、固定相的性质和色谱柱的温度等。     

Solid-phase microextraction based on polypyrrole films with different counter ions

Solid-phase microextraction (SPME) fiber coatings based on polypyrrole (PPY) films were prepared by electrochemical deposition of PPY films on platinum wires. To evaluate the effects of counter ions in PPY films on their performance in SPME, PPY films with different counter ions were prepared using different electrolytes during the polymerization processes. The results showed that these PPY films had different extraction properties to the compounds studied due to the different functional groups introduced into the films by the counter ions. Unlike the PPY films formed with small counter ions (such as perchlorate ion) that had anion exchange property, the PPY films having large counter ions such as poly(styrenesulfonate) (PSS) ion showed cation exchange property. Compared with the PPY films having small inorganic counter ions, the PPY films having large organic counter ions, such as dodecylsulphate (DS) ion, showed better extraction efficiency towards nonpolar compounds due to the increased hydrophobic interactions between the compounds and the films. In addition, PPY films formed with large aromatic counter ions had better mechanical stability compared with PPY films with small inorganic counter ions. These films could be applied for SPME of a range of analytes.     

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.     

Self-assembled monolayer of graphene/Pt as counter electrode for efficient dye-sensitized solar cell

Monolayer of PDDA/graphene/PDDA/H(2)PtCl(6) is fabricated on conductive glass using electrostatic layer-by-layer self-assembly technique, which is then converted to graphene/Pt monolayer for use as counter electrode in dye-sensitized solar cell (DSSC). As compared to the sputtered Pt counter electrode, the self-assembled monolayer reduces the Pt amount by about 1000-fold but exhibits comparable photovoltaic performance. This finding provides a new route to fabrication of cheap and efficient counter electrodes for flow-line production of DSSCs.     

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.     

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.     

Template‐free synthesis of polyaniline nanobelts as a catalytic counter electrode in dye‐sensitized solar cells

Polyaniline (PAn) nanobelts were synthesized by simply mixing aniline and hydrochloric acid aqueous solution with ammonium peroxydisulfate and hydrochloric acid aqueous solution at room temperature without any templates. The PAn nanobelt paste with polytetrafluoroethylene as binder is proper for low‐cost and efficient casting processes such as doctor blade method, screen printing, spin‐casting, and even roll‐to‐roll painting. The porous network structure of the PAn nanobelt counter electrode was obtained after drying the paste on the conductive glass. The as‐prepared PAn nanobelt counter electrode showed nearly equivalent electrochemical catalytic activity as that of thermal decomposed Pt counter electrode, owing to the well‐connected conductive network and high active surface area. The power conversion efficiency of dye‐sensitized solar cell with PAn nanobelt counter electrode attained 90% of the value of the cell with Pt counter electrode. Copyright © 2014 John Wiley & Sons, Ltd.     

High-performance Pt-NiO nanosheet-based counter electrodes for dye-sensitized solar cells

High-performance counter electrodes for dye-sensitized solar cells (DSSCs) are fabricated with platinum-nickel oxide (Pt-NiO) nanosheets as catalytic materials. Firstly, the Pt-Ni nanosheets are synthesized via galvanic replacement reaction between pre-synthesized Ni nanosheets and an aqueous H₂PtCl₆ solution. Secondly, after thermal treatment in air, the Pt-Ni alloys are turned to Pt-NiO nanosheets. The related data of cyclic voltammetry, electrochemical impedance spectroscopy, and Tafel polarization reveal that Pt-NiO counter electrodes show highly catalytic activity and low charge transfer resistance. The DSSC with Pt-NiO counter electrode exhibits power conversion efficiency (PCE) of 8.40 %, which is lower than that of the DSSC containing commercial available Pt counter electrode (9.15 %) under full sunlight illumination (100 mW cm^?2, AM1.5G). However, owing to the extremely high transparency of Pt-NiO counter electrode, when putting an Ag mirror behind the back side of the DSSC, the reflected light can bring great enhanced PCE (11.27 %).     

Transparent graphene/PEDOT–PSS composite films as counter electrodes of dye-sensitized solar cells

Composite films of graphene and polystyreneslufonate doped poly(3,4-ethylenedioxythiophene) (graphene/PEDOT–PSS) were deposited on indium tin oxide (ITO) substrates by spin coating at room temperature and applied as counter electrodes of dye-sensitized solar cells (DSSCs). A 60 nm thick composite film (contained 1 wt% graphene) coated ITO electrode exhibited high transmittance (>80%) at visible wavelengths and high electrocatalytic activity. The energy conversion efficiency of the cell with this film as counter electrode reached 4.5%, which is comparable to 6.3% of the cell with platinum counter electrode under the same experimental condition.     

New strategy for drastic enhancement of selectivity via chemical modification of counter anions in ionic liquid polymer phase

A new strategy for the design of a new chromatographic stationary phase via simple modifications of the counter anions in poly(ionic liquid)-grafted silica phase based on ionic self-assembly technology is proposed. The phase with methyl orange dye as counter anions exhibits ultra-high selectivity towards shape-constrained isomers.     

Voltammetric study on ion transport across a bilayer lipid membrane in the presence of a hydrophobic ion or an ionophore

This review describes voltammetric studies on ion transport from one aqueous phase (W1) to another (W2) across a bilayer lipid membrane (BLM) containing a hydrophobic ion, valinomycin (Val) or gramicidin A (GA). In particular, the ion transport mechanisms are discussed in terms of the distribution of a pair of ions between aqueous and BLM phases. By addition of a small amount of hydrophobic ion into W1 and/or W2 containing a hydrophilic salt as a supporting electrolyte, the hydrophobic ion was distributed into the BLM with the counter ion to maintain electroneutrality within the BLM phase. It was found that the counter ion was transferred between W1 and W2 across the BLM by applying a membrane potential. Facilitated transport of alkali ions across a BLM containing Val as an ion carrier compound, could be interpreted by considering not only the formation of the alkali metal ion–Val complex but also the distribution of both the objective cation and the counter ion. In the case of addition of GA as a channel-forming compound into the BLM, the facilitated transport of alkali ions across the BLM depended on the ionic species of the counter ions. It was discovered that the influence of the counter ion on the facilitated transport of alkali ions across the BLM could be explained in terms of the hydrophobicity and the ionic radius of the counter ion.     

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.     

CoSe/TiN同轴纳米管阵列在染料敏化太阳能电池对电极中的应用研究

以钛网作为基底,采用阳极氧化、氨气氮化的方法制备了TiN纳米管,随后电沉积CoSe,制备了CoSe/TiN/Ti同轴纳米管阵列电极。循环伏安结果表明,CoSe/TiN/Ti电极对I-3具有高的电催化还原性能,这归因于高催化活性的CoSe和高导电的TiN的协同效应。以CoSe/TiN/Ti电极作为对电极组装染料敏化太阳能电池,电池的能量转换效率高达9.25%,比传统Pt/FTO对电极组装的电池(8.09%)高1%。这一结果为非Pt对电极纳米结构的设计提供了一个很好的思路。     

Effect of the flow profile on separation efficiency in pressure‐assisted reversed‐polarity capillary zone electrophoresis of anions: Simulation and experimental evaluation

Capillary electrophoresis connected to electrospray ionization mass spectrometry is a promising combination to analyze complex biological samples. The use of sheathless electrospray ionization interfaces, such as a porous nanoelectrospray capillary emitter, requires the application of forward flow (either by pressure or electroosmosis) to maintain the electrospray process. The analysis of solute molecules with strong negative charges (e.g., aminopyrenetrisulfonate labeled glycans) necessitates a reversed‐polarity capillary electrophoresis separation mode, in which case the electroosmotic flow is counter current, thus pressure assistance is necessary. In this study, we compared the effect of forced convection with and without counter electroosmotic flow on the resulting separation efficiency in capillary electrophoresis based on flow profile simulations by computational fluid dynamics technique and by actual experiments. The efficiencies of the detected peaks were calculated from the resulting electropherograms and found approximately 950 000 plates/m for electrophoresis with counter electroosmotic flow, 20 000 plates/m with pressure only (such as would be in open tubular liquid chromatography), and 480 000 plates/m for electrophoresis with simultaneous counter electroosmotic flow and forward pressure assistance, which validates the simulation data.     

Effect of the eluent pH and acidic modifiers in high-performance liquid chromatography retention of basic analytes

The retention of ionogenic bases in liquid chromatography is strongly dependent upon the pH of the mobile phase. Chromatographic behavior of a series of substituted aniline and pyridine basic compounds has been studied on C18 bonded silica using acetonitrile-water (10:90) as the eluent with different pHs and at various concentrations of the acidic modifier counter anions. The effect of different acidic modifiers on solute retention over a pH range from 1.3 to 8.6 was studied. Ionized basic compounds showed increased retention with a decrease of the mobile phase pH. This increase in retention was attributed to the interaction with counter anions of the acidic modifiers. The increase in retention is dependent on the nature of the counter anion and its concentration in the mobile phase. It was shown that altering the concentration of counter anion of the acidic modifier allows the optimization of the selectivity between basic compounds as well as for neutral and acidic compounds.     

Metal/metal sulfide functionalized single-walled carbon nanotubes: FTO-free counter electrodes for dye sensitized solar cells

The use of single-walled carbon nanotubes (CNT) thin films to replace conventional fluorine-doped tin oxide (FTO) and both FTO and platinum (Pt) as the counter electrode in dye sensitized solar cells (DSSC) requires surface modification due to high sheet resistance and charge transfer resistance. In this paper, we report a simple, solution-based method of preparing FTO-free counter electrodes based on metal (Pt) or metal sulfide (Co(8.4)S(8), Ni(3)S(2)) nanoparticles/CNT composite films to improve device performance. Based on electrochemical studies, the relative catalytic activity of the composite films was Pt > Co(8.4)S(8) > Ni(3)S(2). We achieved a maximum efficiency of 3.76% for the device with an FTO-free counter electrode (Pt/CNT). The device with an FTO- and Pt-free (CoS/CNT) counter electrode gives 3.13% efficiency.     

Electrophoretic Deposition of a Reduced Graphene–Au Nanoparticle Composite Film as Counter Electrode for CdS Quantum Dot‐Sensitized Solar Cells

A reduced graphene (RG)‐Au nanoparticle composite film is successfully fabricated by electrophoretic deposition and used as counter electrode for quantum dot‐sensitized solar cells. The RG‐Au composite is prepared by one‐step microwave‐assisted reduction of chloroaurate in alkaline solution with graphite oxide dispersion. Under one sun illumination (AM 1.5 G, 100 mW cm^?2), the cell with a RG‐Au counter electrode shows an energy conversion efficiency of 1.36 %, which is higher than those of cells employing conventional Pt or Au counter electrodes, due to the superior combination of highly catalytic Au nanoparticles and the conductive graphene network structure.     

对电极性能对染料敏化太阳电池动力学过程的影响

借助电化学阻抗谱(EIS)和强度调制光电流谱(IMPS)/强度调制光电压谱(IMVS)技术, 采用不同纳米TiO₂多孔薄膜对电极研究了染料敏化太阳电池(DSC)内部2个主要电荷输运过程的内在联系, 并探讨了载Pt材料对DSC界面动力学过程及电池宏观性能的影响机理. 借助等效电路模型分析了基于不同对电极材料电池的填充因子变化原因. 结果表明, 对电极材料的电极电荷交换过程制约光阳极膜内电子传输, 进而影响电池光伏性能; 同时对电极催化反应速率主要与催化剂活性、 载Pt材料电导率和催化反应面积有关.     

Room temperature polymerization of poly(3,4‐ethylenedioxythiophene) as transparent counter electrodes for dye‐sensitized solar cells

Poly(3,4‐ethylenedioxythiophene) (PEDOT) counter electrode is prepared with in situ polymerization of 3,4‐ethylenedioxythiophene on a fluorine‐doped tin oxide over‐layer glass at room temperature. The cyclic voltammetry, electrochemical impedance spectroscopy, and Tafel polarization are measured to evaluate the catalytic activity of PEDOT counter electrode for I₃^?/I^? redox couple. Comparing the data with that of traditional thermal decomposed Pt counter electrode, it is found that PEDOT has higher catalytic activity than that of Pt counterpart. Power conversion efficiency of the dye‐sensitized solar cell (DSC) with PEDOT counter electrode can attain to 7.713%, a little higher than that of the cell with Pt counter electrode (7.300%). Taking the advantage of high transparency of PEDOT counter electrode, an Ag mirror is put on the back side of PEDOT counter electrode of the DSC to reflect light back for power conversion. Power conversion efficiency of the DSC with this special structure can be further enhanced to 8.359%, which mainly stems from the improved short‐circuit current density by the increased irradiated light intensity. Copyright © 2014 John Wiley & Sons, Ltd.