三维多孔复合碳层对电极的制备及其光伏性能研究

基于TiO_2光阳极、Pt对电极的染料敏化太阳能电池(DSSC)因其优异的光电转换特性受到了广泛的关注,然而Pt昂贵的价格制约了其发展与应用.针对这一问题,本文设计、制备了一种由相对致密且高导电的石墨膜(PC层,底层)及多孔碳纳米颗粒膜(CC层,顶层)构成的低成本、高性能三维多孔复合碳层对电极.基于该CC/PC对电极的DSSC具有优异的光伏性能:在1.5标准太阳光照射下,其填充因子高达65.28%(较Pt对电极高4.1%)、光电转换效率高达5.9%(为Pt对电极的94.2%). CC/PC对电极的优异光伏性能主要归因于其独特的三维多孔导电结构,该结构有极高的比表面积和丰富的催化反应活性位,有利于电子的快速传输及离子的快速转移,在这些因素的协同作用下,其光电转换性能大大改善.     

Modification and photovoltaic properties of reduced graphene oxide/acetylene black composite electrode

A simple and high efficient reduced graphene oxide/acetylene black (rGO/ACET) nano-composite electrode was prepared as the substitute of high-cost Pt counter electrode in dye-sensitized solar cells (DSSCs). Surface-modified method called solvent-substituting (SS) was firstly used to avoid agglomeration of rGO sheets. The Brunner-Emmet-Teller (BET)-specific surface area of rGO was increased from 195.823 to 355.210 m²/g after modifying with ethanol. Then ACET particles were introduced between rGO layers to improve the electronic transportation properties. The chemical compositions, microstructures, and pore size distributions of rGO/ACET composites were investigated. Electrochemical impedance spectroscopy (EIS) indicated that rGO/ACET counter electrode had a lower charge transfer resistance (R_ct) and its S-shaped current–voltage curves disappeared obviously. The highest power conversion efficiency up to 6.62% was achieved for the DSSCs with rGO/ACET nano-composite counter electrode.     

Low platinum loading PtNPs/graphene composite catalyst with high electrocatalytic activity for dye-sensitized solar cells

Platinum nanoparticles(PtNPs)/graphene composite materials are synthesized by a controlled chemical reduction of H2PtCl6 on graphene sheets.The electrocatalytic activity of a PtNPs/graphene composite counter electrode for a dye-sensitized solar cell(DSSC) is investigated.The results demonstrate that the PtNPs/graphene composite has high electrocatalytic activity for the dye-sensitized solar cell.The cell employing PtNPs(1.6 wt%)/graphene counter electrode reaches an conversion efficiency(η)of 3.89% upon the excitation of 100 mW/cm2 AM 1.5 white light,which is comparable to that of the cell with a Pt-film counter electrode(η=3.76%).It suggests that one can use only 14% Pt content of the conventional Pt-film counter electrode to obtain a comparable conversion efficiency.It may be possible to obtain a high performance DSSC using the PtNPs/graphene composite with a very low Pt content as a counter electrode due to its simplicity,low cost,and large scalability.     

Interface modification of MoS2 counter electrode/electrolyte in dye-sensitized solar cells by incorporating TiO2 nanoparticles

To achieve the high efficiency in dye-sensitized solar cells (DSSCs), the interface modification of MoS₂ counter electrode (CE)/electrolyte should be carried out. Making the modified MoS₂ CE by incorporating TiO₂ nanoparticles provides possibilities to enhance electrocatalytic activity. The DSSCs with the MoS₂/TiO₂ CE show enhanced performance compared with DSSCs with the MoS₂ CE. The experimental results revealed that the MoS₂/TiO₂ nanocomposite influences on the power conversion efficiency by enhancing electrocatalytic activity and increasing the active surface area that serve to increase the short circuit current. This understanding can provide guidance for the development of highly efficient DSSCs with platinum-free CEs.     

Flexible TiO<Subscript>2</Subscript> nanotube-based dye-sensitized solar cells using laser-drilled microhole array electrodes

Here we report on the growth of TiO₂ nanotube arrays (TNAs) on Ti foil with laser-drilled microhole arrays (MHAs). The MHAs promoted the adhesion of the TNA film to Ti substrate, which is well suited for flexible dye-sensitized solar cells (DSSCs). The MHA photoanode and TNAs were characterized by SEM, 3D optical profiling, XRD and TEM. For such a flexible MHA photoanode, the TNA-based DSSC was assembled using a platinized conductive glass counter electrode, and a conversion efficiency of 3.45% was achieved under AM 1.5 condition. A flexible TNA-based DSSC was also fabricated using a flexible MHA photoanode combined with a platinized indium tin oxide-polyethylene naphthalate counter electrode, which achieved 2.67% photovoltaic conversion efficiency under simulated AM 1.5 sunlight.     

Facile synthesis of nitrogen-doped reduced graphene oxide as an efficient counter electrode for dye-sensitized solar cells

A nitrogen-doped reduced graphene oxide (N-RGO) nanosheet was synthesized by a simple hydrothermal method and characterized by X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy, and scanning electrode microscopy. After being deposited as counter electrode film for dye-sensitized solar cells (DSSCs), it is found that the synthesized N-RGO nanosheet has smaller charge-transfer resistance and better electrocatalytic activity towards reduction of triiodide than the reduced graphene oxide (RGO) nanosheet. Consequently, the DSSCs based on the N-RGO counter electrode achieve an energy conversion efficiency of 4.26%, which is higher than that of the RGO counter electrode (2.85%) prepared under the same conditions, and comparable to the value (5.21%) obtained with the Pt counter electrode as a reference. This N-RGO counter electrode offers the advantages of not only saving the cost of Pt itself but also simplifying the process of counter electrode preparation. Therefore, an inexpensive N-RGO nanosheet is a promising counter electrode material to replace noble metal Pt.

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Graphical abstract A nitrogen-doped reduced graphene oxide nanosheet was synthesized by a simple hydrothermal method, which is a promising counter electrode material to replace noble metal Pt.

     

新型碳材料在钙钛矿太阳电池中的应用研究进展

新型碳材料如石墨烯及其氧化物、碳纳米管、富勒烯及石墨炔等因其优异的热学、力学、电学、光学性能成为了钙钛矿太阳电池研究的又一亮点. 本文总结了新型碳材料在钙钛矿太阳电池对电极、电子传输材料及空穴传输材料中的研究进展, 新型碳材料的引入有效地提高了钙钛矿电池的性能, 为下一步新型碳材料的应用开发以及钙钛矿电池器件的研究提供了新的思路.     

Sputter-deposited ZnO thin films consisting of nano-networks for binder-free dye-sensitized solar cells

ZnO nano-network structures with high porosity were prepared for use in the photoelectrodes of binder-free dye-sensitized solar cells (DSSCs) by DC sputtering and subsequent thermal oxidation. Zn thin films prepared at 100 °C showed nano-network structures with high porosity, while those prepared at 25 °C did not. This was partially attributed to the high mobility of sputter-deposited particles that arrived at the surface of the substrate and partially to a supersaturation mechanism. The prepared nano-network Zn was successfully transformed to ZnO without a morphological change via subsequent annealing in air. The power conversion efficiency of DSSCs based on the ZnO nano-network structures exhibited 10 times higher efficiency than those based on ZnO film prepared at 25 °C because of its large surface area for adsorption of dye molecules. The thickness of the ZnO nano-network structures increased linearly at 10 μm h^?1 as a function of sputter time. As the film thickness increased, the power conversion efficiency of DSSCs increased from 1.09% to 1.82%.     

Functional multi-walled carbon nanotube/polyaniline composite films as supports of platinum for formic acid electrooxidation

Embedding of carbon nanotubes in conducting polymeric matrices for various nanocomposites material is now a popular area. In this article, a concise chemical method has been described for the preparation of homogeneous nanocomposite of multi-walled carbon nanotube (MWNT)/polyaniline (PANI) by electrochemical codeposition. For this we functionalized the MWNTs via the diazotization reaction. This helped to disperse the nanotubes in aniline. The composite films were dispersed Pt by electrodeposition technique. The presence of MWNTs and platinum in the composite films was confirmed by XRD analysis and transmission electron microscopy (TEM). Four-point probe investigations revealed that the MWNT/PANI composite films exhibited a good conductivity. Cyclic voltammograms (CV) showed that Pt-modified MWNT/PANI composite films perform higher electrocatalytic activity and better long-term stability than Pt-modified pure PANI film toward formic acid oxidation. The results imply that the MWNT/PANI composite films as a promising support material improves the electrocatalytic activity for formic acid oxidation greatly.     

Dye-sensitized solar cells based on ZnO nanowire array/TiO2 nanoparticle composite photoelectrodes with controllable nanowire aspect ratio

The ZnO nanowire (NW) array/TiO₂ nanoparticle (NP) composite photoelectrode with controllable NW aspect ratio has been grown from aqueous solutions for the fabrication of dye-sensitized solar cells (DSSCs), which combines the advantages of the rapid electron transport in ZnO NW array and the high surface area of TiO₂ NPs. The results indicate that the composite photoelectrode achieves higher overall photoelectrical conversion efficiency (η) than the ZnO NW alone. As a result, DSSCs based on the ZnO NW array/TiO₂ NP composite photoelectrodes get the enhanced photoelectrical conversion efficiency, and the highest η is also achieved by rational tuning the aspect ratio of ZnO NWs. With the proper aspect ratio (ca. 6) of ZnO NW, the ZnO NW array/TiO₂ NP composite DSSC exhibits the highest conversion efficiency (5.5 %). It is elucidated by the dye adsorption amount and interfacial electron transport of DSSCs with the ZnO NW array/TiO₂ NP composite photoelectrode, which is quantitatively characterized using the UV-Vis absorption spectra and electrochemical impedance spectra. It is evident that the DSSC with the proper aspect ratio of ZnO NW displays the high dye adsorption amount and fastest interfacial electron transfer.     

Low resistance dye-sensitized solar cells based on all-titanium substrates using wires and sheets

Low resistance dye-sensitized solar cells (DSSCs) based on all-titanium substrates were proposed in this paper. To minimize the internal resistance of DSSCs, the titanium wires and titanium sheets were used as the substrates of the photoanode and the counter electrode, respectively. Compared with the FTO substrate, titanium wires could absorb much diffused light by back reflection since the reflectivity in the titanium sheet was highly increased up to 53.12%. Furthermore, the transmittance of the front cover was increased by 13.2% using the super white glass instead of FTO substrate. The thickness of TiO₂ thin film coated on titanium wire was optimized to achieve a high cell performance. The efficiency of 5.6% for the cell was obtained with a J_sc of 15.41 mA cm⁻², V_oc of 0.59 V, and FF of 0.62. The results showed that the titanium-based DSSCs had superiority for producing the large-scale DSSCs without metal grid line.     

Zinc oxide nanostructures for applications as ethanol sensors and dye-sensitized solar cells

ZnO nanostructures were prepared by thermal oxidation technique for applying as ethanol sensors and dye-sensitized solar cells. To improve sensitivity of the sensor based on ZnO nanostructures, gold doping was performed in ZnO nanostructures. Gold-doped with 0%, 5%, and 10% by weight were investigated. The improvement of sensor sensitivity toward ethanol due to gold doping was observed at entire operating temperature and ethanol concentration. The sensitivity up to 145 was obtained for 10% Au-doped ZnO sensor. This can be explained by an increase of the quantity of oxygen ion due to catalytic effect of gold. Also, it was found that oxygen ion species at the surface of the Au-doped ZnO sensor remained O²⁻ as pure ZnO sensor. For dye-sensitized solar cell application, the dye-sensitized solar cell structure based on ZnO as a photoelectrode was FTO/ZnO/Eosin-Y/electrolyte/Pt counter electrode. ZnO with different morphologies of nanobelt, nano-tetrapod, and powder were investigated. It was found that DSSCs with ZnO powder showed higher photocurrent, photovoltage and overall energy conversion efficiencies than that of ZnO nanobelt and ZnO nano-tetrapod. The best results of DSSCs were the short circuit current (J_sc) of 1.25 mA/cm², the open circuit voltage (V_oc) of 0.45 V, the fill factor (FF) of 0.65 and the overall energy conversion efficiency (η) of 0.68%.     

Application of Pt sputter-deposited counter electrodes based on micro-patterned ITO glass to quasi-solid state dye-sensitized solar cells

The effects of the Pt catalyst sputter deposited on the patterned ITO glass (SD-Pt/pITO) on the photovoltaic properties and charge-transfer characteristics at the Pt/electrolyte interface of dye-sensitized solar cells (DSSCs) are studied and compared with those of a conventional Pt counter electrode deposited by thermal reduction on fluorine-doped tin oxide (FTO) glass (TD-Pt/FTO). The DSSC with the SD-Pt/pITO (sample cell) shows a lower charge-transfer resistance than that of the DSSC with the TD-Pt/FTO (reference cell), which leads to an improvement of its fill factor by about 7.6%. The long-term durability test performed for 1000 h at room temperature reveals that the sample cell retains up to 99% of its energy conversion efficiency, while that of the reference cell is degraded by about 7.2%.     

二硒化铁/还原氧化石墨烯的制备及其在染料敏化太阳能电池中的应用

通过水热反应合成出二硒化铁/还原氧化石墨烯(FeSe₂/rGO)复合材料, 并将其作为对电极材料应用于染料敏化太阳能电池(DSSC). 利用X射线衍射、拉曼光谱、场发射扫描电子显微镜和高分辨透射电子显微镜对FeSe₂/rGO的结构和形貌进行了表征. 利用循环伏安法、电化学阻抗谱和Tafel曲线测试分析了FeSe₂/rGO对电极的电催化活性. 结果表明: FeSe₂呈纳米棒结构, 长度在100-200 nm之间, 且紧密地附着在rGO 的表面, FeSe₂/rGO对电极对I₃^-的还原具有很好的催化活性. 电池的J-V曲线测试显示: 基于FeSe₂/rGO对电极的DSSC的转换效率达到了8.90%, 相比基于单纯的FeSe₂对电极的DSSC(7.91%)和rGO对电极的DSSC(5.24%)都有了显著提高, 甚至优于铂对电极的DSSC(8.52%).     

Interfacial engineering of CuO nanorod/ZnO nanowire hybrid nanostructure photoanode in dye-sensitized solar cell

Developing efficient and cost-effective photoanode plays a vital role determining the photocurrent and photovoltage in dye-sensitized solar cells (DSSCs). Here, we demonstrate DSSCs that achieve relatively high power conversion efficiencies (PCEs) by using one-dimensional (1D) zinc oxide (ZnO) nanowires and copper (II) oxide (CuO) nanorods hybrid nanostructures. CuO nanorod-based thin films were prepared by hydrothermal method and used as a blocking layer on top of the ZnO nanowires’ layer. The use of 1D ZnO nanowire/CuO nanorod hybrid nanostructures led to an exceptionally high photovoltaic performance of DSSCs with a remarkably high open-circuit voltage (0.764 V), short current density (14.76 mA/cm² under AM1.5G conditions), and relatively high solar to power conversion efficiency (6.18%) . The enhancement of the solar to power conversion efficiency can be explained in terms of the lag effect of the interfacial recombination dynamics of CuO nanorod-blocking layer on ZnO nanowires. This work shows more economically feasible method to bring down the cost of the nano-hybrid cells and promises for the growth of other important materials to further enhance the solar to power conversion efficiency.     

Performance characteristics of dye-sensitized solar cells with counter electrode based on NiP-plated glass and titanium plate

The counter electrodes based on NiP-plated glass and titanium plate were prepared. The performance characteristics of the dye-sensitized solar cells with platinized NiP-plated glass electrode (Pt/NiP electrode) and platinized titanium plate electrode (Pt/TP electrode) were discussed. Pt/NiP electrode and Pt/TP electrode showed the same catalytic activity for triiodide reduction compared with platinized fluorine-doped tin oxide conducting glass electrode (Pt/FTO electrode). However, Pt/NiP electrode and Pt/TP electrode have the advantage over Pt/FTO electrode in reducing the sheet resistance and increasing light reflectivity, which resulted in improving the photovoltaic performance of dye-sensitized solar cells effectively. Compared with the cell using Pt/FTO electrode, the incident photon conversion efficiency of dye-sensitized solar cells with Pt/NiP electrode and Pt/TP electrode was increased by 20% and 5%, respectively, the overall energy efficiency of dye-sensitized solar cells with Pt/NiP electrode and Pt/TP electrode was increased by 32% and 27%, respectively.     

Mixed cation effect and iodide ion conductivity in electrolytes for dye sensitized solar cells

Dye-sensitized solar cells (DSSCs) offer an alternative to conventional silicon solar cell because of low cost and easy fabrication. However, one major drawback in DSSCs is their low efficiency. This paper reports the effect of using a binary iodide salt mixture with different size cations on the efficiency enhancement in dye sensitized solar cells based on polymer gel electrolytes. Several different polymers, such as polyacrylonitrile (PAN), polymethylmethacrylate (PMMA), poly (vinylidenefluoride (PVdF)), and polyethylene oxide (PEO) have been used as host polymers. A binary iodide mixture consisting of an alkaline iodide salt (small cation) and a quaternary ammonium iodide salt such as tetrapropyl ammonium iodide (Pr₄NI) (large cation) has been used as the iodide ion source. In some of these systems, efficiency enhancement of more than 25% has been reached due to the “mixed cation effect”. From these studies, it was established that the variation of the power conversion efficiency with the concentration ratio of the two iodide salts follows the same trend as the short circuit current density (J _sc) and goes through a maximum at a particular salt concentration ratio. The maximum efficiency was found to be higher than the efficiencies of the DSSCs with only a single iodide salt in the electrolyte. The J _sc in these DSSCs appears to be governed by the iodide ion conductivity of the gel electrolyte. The observed efficiency enhancement has been explained on the basis of the electrode effects as well as electrolyte effects where the cations play a dominant role.

     

Ni3S2@MWCNTs films for effective counter electrodes of dye-sensitized solar cells

Composite films nickel sulfide (Ni₃S₂) nanoparticles were grown on multiwall carbon nanotubes (MWCNTs) and in situ coated onto conducting glass substrates by the hydrothermal process at 170 °C. These Ni₃S₂@MWCNTs films were applied for counter electrodes (CEs) of dye-sensitized solar cells (DSSCs). In this work, nanostructure, crystalline structure, electrochemical activities and electron-charge transfer resistance of CEs were studied. In addition, the effective surface areas of CEs were analyzed and discussed as well. The power conversion efficiency (PCE) enhancement of up to 7.48%, compared with that of Ni₃S₂-DSSC, was demonstrated for a Ni₃S₂@MWCNTs DSSC.     

Performance of dye-sensitized solar cells based on natural dyes

The natural dyes were successfully extracted from spinach, pitaya pericarp, orange peel, ginkgo leaf, purple cabbage and carrot, and then fabricated a dye-sensitized solar cells (DSSCs). It suggested that the absorption properties of natural dyes were strongly dependent on the types and concentration of pigments, and the purple cabbage exhibited an obvious absorption at 317 nm. Meanwhile, a higher conversion efficiency of 0.157% was obtained as the DSSCs were prepared by using purple cabbage, but the DSSCs showed a poor performance when the carrot was used as natural dyes, just achieved 0.01%. FTIR spectra revealed that purple cabbage showed a better adsorption properties between TiO₂ films and dyes than carrot. The dipping time was further investigated and proved that an optimal dipping time was 6 min, the DSSCs using purple cabbage could achieve 0.146% in photoelectric conversion efficiency.     

Promise of commercialization: Carbon materials for low-cost perovskite solar cells

Perovskite solar cells(PVSCs) have attracted extensive studies due to their high power conversion efficiency(PCE)with low-cost in both raw material and processes. However, there remain obstacles that hinder the way to their commercialization. Among many drawbacks in PVSCs, we note the problems brought by the use of noble metal counter electrodes(CEs) such as gold and silver. The costly Au and Ag need high energy-consumption thermal evaporation process which can be made only with expensive evaporation equipment under vacuum. All the factors elevate the threshold of PVSCs' commercialization. Carbon material, on the other hand, is a readily available electrode candidate for the application as CE in the PVSCs. In this review, endeavors on PVSCs with low-cost carbon materials will be comprehensively discussed based on different device structures and carbon compositions. We believe that the PVSCs with carbon-based CE hold the promise of commercialization of this new technology.