染料敏化太阳电池TiO2光阳极研究进展

纳米TiO2是目前性能最为优良的染料敏化太阳电池(DSSC)光阳极材料。文章系统综述了优化纳米TiO2光阳极的染料吸附、电子传输、再生染料等性能的技术和方法,主要包括纳米TiO2光阳极薄膜微结构的调控、TiO2光阳极的离子/元素掺杂、TiO2光阳极的表面包覆、TiO2光阳极的表面处理等方面的国内外研究进展,并分析了目前TiO2光阳极存在的主要问题及未来的发展方向。     

导电聚邻苯二胺的合成及在染料敏化太阳能电池中的应用

制备了聚邻苯二胺,并将其作固体传输材料应用在染料敏化太阳能电池中。用光电化学方法研究了染料酸性湖蓝、聚邻苯二胺(PoPD)、二氧化钛(TiO2)纳米晶电极以及用酸性湖蓝和PoPD复合敏化TiO2纳米晶膜电极的光电化学行为。用聚邻苯二胺作为固体电解质,染料酸性湖蓝,组装了电池,初步测定了TiO2/酸性湖蓝/PoPD电极作为光阳极的光电化学电池的工作特性曲线,测得Voc=0.43V,Isc=0.378mA。     

ZnO的水热合成及其在TiO2/ZnO染料敏化太阳能电池中的应用

通过在不同矿化剂粉末[六亚甲基四胺(hexamethylenetetramine,HMT)、尿素和氢氧化锂]存在下的水热反应制备得到具有不同形貌尺寸的ZnO粉体,通过X射线衍射、扫描电子显微镜、紫外可见漫反射光谱和表面光电压谱研究了不同矿化剂存在下所制备ZnO的尺寸、形貌和光电性能.结果表明:以HMT和LiOH作矿化剂可得到六方纤锌矿结构的ZnO粉体,且尺寸均一;尿素作矿化剂得到产物的结晶性较差;在LiOH存在下制备的ZnO具有明显的光电响应性能,这与带带跃迁及激子跃迁相关的.将所制备的ZnO用于染料敏化太阳能电池中,作为TiO2基染料敏化太阳能电池(dye-sensitized solar cells,DSSCs)光阳极的上层膜,起光散射作用,下层是纳米TiO2晶膜.作为对比,制备了单一ZnO基DSSCs.通过光电流-电压(I-V)曲线研究了2种DSSCs的光电转换效率,结果表明:TiO2/ZnO双层膜光阳极组装的DSSCs的光电性能优于ZnO基DSSCs,说明具有光散射层的DSSCs的光吸收增强归因于下层TiO2纳米晶膜的高比表面积和上层大尺寸ZnO光散射膜的组合效应.     

染料敏化太阳能电池中TiO2光阳极形貌研究进展

纳米TiO2具有合适的禁带宽度(3.2 eV)、良好的光电化学稳定性、价格低廉、易牢固吸附染料等优点,目前仍是应用于染料敏化太阳能电池(DSSC)主要的半导体材料。TiO2光阳极是DSSC的重要组成部分之一,其晶体的形貌与DSSC的光电性能密切相关。本文综述了应用于DSSC中不同形貌TiO2光阳极,重点探讨了常规TiO2光阳极形貌,如纳米粒子、纳米棒、纳米线、纳米管;对新型TiO2光阳极及复合光阳极的形貌也作了介绍。讨论了不同形貌TiO2光阳极的制备方法及其结构对DSSC光电性能的影响,提出TiO2光阳极今后的研究方向是将不同形貌光阳极进行复合或混合掺杂来提高电子传输速率、优化TiO2薄膜厚度、控制TiO2薄膜中晶体结构抑制电荷再结合、提高电荷传输效率。     

TiO_2形状对染料敏化太阳能电池性能的影响

第三代太阳能电池,即染料敏化太阳能电池(DSSCs)是由纳米多孔半导体薄膜(如TiO2)、有机染料敏化剂、氧化还原电解质(如I3-/I-)、对电极和导电基底等几部分构成。不同的TiO2的形状及构造对电池性能有着很大的影响。     

盐酸在柔性染料敏化太阳能电池中的应用

以水热法加入不同浓度的HCl溶液制备二氧化钛胶体。采用刮涂法制备柔性染料敏化太阳能电池(DSSC)光阳极,对其进行各种性能研究,以此来分析不同制备条件对DSSCs的影响。结果表明,盐酸能够促进TiO_2颗粒的分散,TiO_2颗粒与柔性ITO/PEN导电衬底的连接以及TiO_2薄膜的染料吸附量。经优化,测得含有0.05 M(mol/L)HCl的柔性DSSC的光电转换效率为2.84%。     

染料敏化太阳能电池中TiO_2光阳极的包覆效果

采用原位包覆和浸泡包覆在染料敏化太阳能电池的TiO2光阳极表面包覆了一薄层Al2O3,MgO或ZnO,讨论了不同包覆方法和实验条件对染料敏化太阳能电池性能的影响。研究表明,无论是原位包覆还是浸泡包覆,都可以在TiO2光阳极表面均匀的形成一层厚度约为1～2nm的氧化物包覆层,抑制了TiO2光阳极中的光生电子与氧化态染料和氧化态电解质的复合,从而导致光电压都有明显增大。特别是浸泡包覆不仅可以提高光电压,而且在较大的TiO2浆料粒径、合适的前驱体溶液浓度下,还可以增加光电流,导致光电转换效率明显增加。     

TiO_2反蛋白石结构光阳极结构改性及光电性能研究

将TiO_2反蛋白石结构(Inverse Opal)光阳极置于氟钛酸铵、硼酸和水的反应液中,通过液相反应,在光阳极表面沉积TiO_2纳米颗粒。结果表明,该处理使TiO_2反opal光阳极比表面积增大、染料吸附能力增强,组装为染料敏化太阳能电池(DSSCs)后电池交流阻抗降低,进而能显著提高DSSCs光电性能。研究发现,当反应液中硼酸浓度为0.22 mol/L时,DSSCs短路电流密度和光转化效率分别提高了134.0%和105.2%。     

电泳沉积法制备多层膜染料敏化太阳能电池

将纳米TiO2颗粒以电泳沉积法披覆于导电玻璃上,同时整合光电极、反电极、电解质及染料制备出染料敏化太阳能电池.首先将TiO2纳米颗粒与异丙醇所混合的电泳悬浮液通过电泳技术沉积出适当厚度的多层膜结构;精确控制制程中的电流、电压与沉积时间而获得单层厚度为3.3μm的TiO2薄膜.此多层膜通过低温烧结增加其致密性及染料披覆效果.最后将此多层薄膜作为工作电极,封装成染料敏化太阳能电池,经由I-V曲线检测结果显示,所制染料敏化太阳能电池的光电转换效率为5.29%,且这种染料敏化太阳能电池的制造成本十分低廉.     

基于锐钛矿相二氧化钛溶胶的高效染料敏化太阳能电池

用稀硝酸或双氧水对TiO2沉淀进行处理,分别得到锐钛矿相TiO2溶胶及过氧钛酸溶液,两者经水热处理后通过“定向附着”得到比表面积均大于100m2/g的TiO2纳米棒溶胶,制成染料敏化太阳能电池后,电池的开路电压得到提高.溶胶在导电玻璃上形成致密阻挡层,也能渗入到Degussa P25为原料经刮涂法制备的光阳极内,消除其...     

Growth of Comb-like ZnO Nanostructures for Dye-sensitized Solar Cells Applications

Dye-sensitized solar cells (DSSCs) were fabricated by using well-crystallized ZnO nanocombs directly grown onto the fluorine-doped tin oxide (FTO) via noncatalytic thermal evaporation process. The thin films of as-grown ZnO nanocombs were used as photoanode materials to fabricate the DSSCs, which exhibited an overall light to electricity conversion efficiency of 0.68% with a fill factor of 34%, short-circuit current of 3.14 mA/cm², and open-circuit voltage of 0.671 V. To the best of our knowledge, this is first report in which thin film of ZnO nanocombs was used as photoanode materials to fabricate the DSSCs.     

A natural tomato slurry as a photosensitizer for dye-sensitized solar cells with TiO2/CuO composite thin films

We have studied the performance of dye-sensitized solar cells by employing natural dye “anthocyanins” extracted from the tomato slurry as a sensitizer for the TiO₂/CuO photoanode. The extracts were anchored on TiO₂/CuO films deposited on an ITO substrate which was used as a photoanode. The dye adsorbed TiO₂/CuO films electrode, the copper plate as a counter electrode, and iodolyte as an electrolyte were assembled into DSSCs. The conversion efficiency of the DSSCs was found to be 2.96% with a V_OC of 0.615 V, J_SC of 6.6 mA/cm², and an FF of 0.73. This work highlights the use of contribution of the tomato slurry as a natural sensitizer to enhance the efficiency of DSSCs.     

Incorporation of plasma-functionalized carbon nanocapsules into a nanocrystalline TiO2 photoanode for use in dye-sensitized solar cells

Dye-sensitized solar cells (DSSCs) were fabricated using TiO₂ nanoparticles incorporating different amounts of plasma functionalized carbon nanocapsules (CNCs) as the photoanode. The functionalization was obtained by grafting maleic anhydride (MA) onto the walls of CNCs immediately after the in situ argon plasma treatment. Nanocrystalline semiconductor film electrodes were prepared by sintering TiO₂ with added MA-CNCs on a conducting glass substrate. Capacitance measurements obtained from electrochemical impedance spectroscopy (EIS) analysis in an aqueous electrolyte are fitted using the Mott–Schottky relationship and demonstrate the variation of flatband potential (V_fb) for the composite with MA-CNC content. The potential chronoamperometric and cyclic voltammetric data supports the argument that the increased V_fb minimizes the defect state for trapping/detrapping of electrons within the MA-CNC/TiO₂. As a result of higher film capacitance and electron accumulation, the MA-CNC/TiO₂ shows increased conversion efficiency and photocurrent density when used as the photoanode in DSSCs. EIS measurement further demonstrates that charge recombination at the interface of MA-CNC/TiO₂ and electrolyte is suppressed with increasing electron lifetime and is in good agreement with the photovoltaic performance. The amount of MA-CNCs added, however needs to be optimized due to the unavoidable issue of aggregation.     

纳米颗粒在有序多孔陶瓷中的行为研究

本文详细研究了纳米颗粒在有序多孔陶瓷中形成协同体的过程。实验结果表明:纳米TiO2和炭黑(CB)能比较容易进入到有序多孔陶瓷中形成具有特定功能的协同体。当纳米TiO2的浓度增加到5wt%和炭黑浓度增加到15 wt%时,有序多孔陶瓷的孔壁上粘附纳米TiO2和炭黑颗粒的量最大从而形成大量的活性点;浓度对两种纳米颗粒的渗透力具有很大的影响,炭黑粒子的渗透能力比纳米纳米TiO2颗粒强。     

聚苯胺/乙炔炭黑多孔类棒状复合材料的制备及电化学性质

以纳米乙炔炭黑在盐酸掺杂的反应体系中的聚集体为硬模板,原位吸附化学氧化法制备了聚苯胺/炭黑复合材料。实验结果显示,聚苯胺复合物为表面附着大量纳米颗粒的类棒状结构,且棒与棒间富有孔隙。复合材料分解温度在350℃左右。循环伏安曲线表现出该复合材料法拉第准(赝)电容有良好的电极可逆性,在5,10 mA/cm2电流密度下,单电极比电容高达376 F/g和311 F/g。     

Carbon/polymer composite counter‐electrode application in dye‐sensitized solar cells

Carbon black was embedded in mixtures of poly(ethylene oxide) and poly(vinylidene fluoride–hexafluoropropylene) to make a carbon/polymer composite slurry, which was deposited onto a transparent conducting glass substrate by a doctor‐blade coating for application in dye‐sensitized solar cells (DSSCs) as a counter‐electrode (CE) material. The experiments indicated that the photovoltaic parameters of the DSSCs were strongly dependent on the carbon concentration in the slurry. The device with a carbon CE whose mass ratio was 1 : 1 (mass ratio = carbon black mass to polymer mass) exhibited an overall energy conversion efficiency of 4.62%; this was comparable to that of a device with platinum as a CE (5.32%) under the same test conditions. The better electrocatalytic activity of CE‐1.0 (where 1.0 indicates the mass ratio of carbon black to polymer) for the reduction of triiodide resulted a higher performance of the DSSC with such a CE. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Vertically building Zn2SnO4 nanowire arrays on stainless steel mesh toward fabrication of large-area, flexible dye-sensitized solar cells

Zn(2)SnO(4) nanowire arrays were for the first time grown onto a stainless steel mesh (SSM) in a binary ethylenediamine (En)/water solvent system using a solvothermal route. The morphology evolution following this reaction was carefully followed to understand the formation mechanism. The SSM-supported Zn(2)SnO(4) nanowire was utilized as a photoanode for fabrication of large-area (10 cm × 5 cm size as a typical sample), flexible dye-sensitized solar cells (DSSCs). The synthesized Zn(2)SnO(4) nanowires exhibit great bendability and flexibility, proving potential advantage over other metal oxide nanowires such as TiO(2), ZnO, and SnO(2) for application in flexible solar cells. Relative to the analogous Zn(2)SnO(4) nanoparticle-based flexible DSSCs, the nanowire geometry proves to enhance solar energy conversion efficiency through enhancement of electron transport. The bendable nature of the DSSCs without obvious degradation of efficiency and facile scale up gives the as-made flexible solar cell device potential for practical application.     

Optimization of the dye-sensitized solar cell performance by mechanical compression

In this study, the P25 titanium dioxide (TiO₂) nanoparticle (NP) thin film was coated on the fluorine-doped tin oxide (FTO) glass substrate by a doctor blade method. The film then compressed mechanically to be the photoanode of dye-sensitized solar cells (DSSCs). Various compression pressures on TiO₂ NP film were tested to optimize the performance of DSSCs. The mechanical compression reduces TiO₂ inter-particle distance improving the electron transport efficiency. The UV–vis spectrophotometer and electrochemical impedance spectroscopy (EIS) were employed to quantify the light-harvesting efficiency and the charge transport impedance at various interfaces in DSSC, respectively. The incident photon-to-current conversion efficiency was also monitored. The results show that when the DSSC fabricated by the TiO₂ NP thin film compressed at pressure of 279 kg/cm², the minimum resistance of 9.38 Ω at dye/TiO₂ NP/electrolyte interfaces, the maximum short-circuit photocurrent density of 15.11 mA/cm², and the photoelectric conversion efficiency of 5.94% were observed. Compared to the DSSC fabricated by the non-compression of TiO₂ NP thin film, the overall conversion efficiency is improved over 19.5%. The study proves that under suitable compression pressure the performance of DSSC can be optimized.     

ZnO-ZnGa2O4 core-shell nanowire array for stable photoelectrochemical water splitting

A dense array of vertically aligned ZnO-ZnGa(2)O(4) core-shell nanowires was synthesized on a large scale on an a-plane sapphire substrate by a simple two-step chemical vapor deposition method. The ZnO cores and ZnGa(2)O(4) shells of the nanowires are of single crystal quality and have aligned crystallographic orientations as evidenced from XRD and TEM analyses. Mott-Schottky analysis and voltage onset from the photocurrent-voltage curve confirm an n-type semiconductor property, a flat-band potential of -0.4 V (versus NHE) and a carrier density of 7 × 10(18) cm(-3) for the ZnO-ZnGa(2)O(4) core-shell nanowires. A stable and large photocurrent of 1.2 mA cm(-2) was obtained with the ZnO-ZnGa(2)O(4) core-shell nanowire array when used as a photoanode at an applied bias of +0.7 V (versus Ag/AgCl) under a 300 W xenon lamp illumination. Moreover, a low dark current of <10(-4) mA cm(-2) was obtained at an applied bias of +0.7 V (versus Ag/AgCl) without light illumination for the ZnO-ZnGa(2)O(4) nanowire array. These results suggest that the dense array of ZnO-ZnGa(2)O(4) core-shell nanowires provides enhanced electronic properties and stable anti-photocorrosion ability and, therefore, is promising as a photoanode in photoelectrochemical water splitting.     

Double‐Layer Structure Photoanode with TiO2 Nanotubes and Nanoparticles for Dye‐Sensitized Solar Cells

Here, we report a novel double‐layer structure photoanode with TiO₂ nanotube (TNT) layer and TiO₂ nanoparticle (TP) layer via a two‐step method of electrochemical anodization and screen printing for dye‐sensitized solar cells (DSSCs). The results indicate that DSSCs with this double‐layer structure have significant advantages of large surface area, long electron lifetime, superior electron recombination restraint characteristics, and high light scattering. The layer thickness of nanotubes and nanoparticles is also investigated and finally an optimized double‐layer structure with excellent performance is prepared. With such a double‐layer structure photoanode, DSSC with a relative high conversion efficiency of 6.43% and a short‐circuit photocurrent density of 16.40 mA·cm^?2 is obtained.