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1.
A major loss mechanism in dye-sensitized solar cells (DSCs) is recombination at the TiO(2)/electrolyte interface. Here we report a method to reduce greatly this loss mechanism. We deposit insulating and transparent silica (SiO(2)) onto the open areas of a nanoparticulate TiO(2) surface while avoiding any deposition of SiO(2) over or under the organic dye molecules. The SiO(2) coating covers the highly convoluted surface of the TiO(2) conformally and with a uniform thickness throughout the thousands of layers of nanoparticles. DSCs incorporating these selective and self-aligned SiO(2) layers achieved a 36% increase in relative efficiency versus control uncoated cells.  相似文献   

2.
Dye-sensitized solar cells (DSSCs) were fabricated using multiwalled carbon nanotube (MWCNT)-TiO(2) nanocomposite as a light scattering layer. Morphology of the MWCNT-TiO(2) film was investigated by field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM). FESEM and TEM images demonstrate that MWCNTs and TiO(2) nanoparticles can be dispersed with chitosan. Internal resistance in the DSSC was characterized by electrochemical impedance spectroscopy (EIS). EIS results reveal a decrease in the charge resistance of electrolyte/dye/MWCNT-TiO(2)/TiO(2) interface with increasing MWCNT content up to 3 wt% which leads to an improvement in the photovoltaic performance. Compare with a nanocrystalline TiO(2) single-layer cell, the DSSC based on the MWCNT (3 wt%)-TiO(2)/TiO(2) bilayer structure photoelectrode shows ~100% increase in solar-to-electric energy conversion efficiency, which is attributed to the inclusion of MWCNTs in TiO(2) matrix.  相似文献   

3.
Sol-gel-derived Mg(OH)(2) gel was coated onto TiO(2) nanoparticles, and the subsequent thermal topotactic decomposition of the gel formed a highly nanoporous MgO crystalline coating. The specific surface area of the electrode that was prepared from the core-shell-structured TiO(2) nanoparticles significantly increased compared with that of the uncoated TiO(2) electrode. The increase in the specific surface area of the MgO-coated TiO(2) electrode was attributed to the highly nanoporous MgO coating layer that resulted from the topotactic reaction. Dye adsorption behavior and solar cell performance were significantly enhanced by employing the MgO-coated TiO(2) electrode. Optimized coating of a MgO layer on TiO(2) nanoparticles enhanced the energy conversion efficiency as much as 45% compared to that of the uncoated TiO(2) electrode. This indicates that controlling the extrinsic parameters such as the specific surface area is very important to improve the energy conversion efficiency of TiO(2)-based solar cells.  相似文献   

4.
The effect of chenodeoxycholic acid as a coadsorbent on TiO 2 nanocrystalline solar cells incorporating phthalocyanine sensitizers was studied under various conditions. Adding chenodeoxycholic acid onto TiO 2 nanoparticles not only reduces the adsorption of phthalocyanine sensitizers but also prevents sensitizer aggregation, leading to different photovoltaic performance. The inspection of IPCE and absorption spectra showed that the load of phthalocyanine sensitizers is strongly dependent on the molar concentration of chenodeoxycholic acid coadsorbent. The open circuit voltage of the solar cells with chenodeoxycholic acid coadsorbent increases due to the enhanced electron lifetime in TiO 2 nanoparticles coupled with the band edge shift of TiO 2 to negative potentials.  相似文献   

5.
In order to investigate the electron dynamics at the alizarin/I2-/TiO2 interface this study uses a novel state-of-the-art quantum-classical approach that combines time-dependent density functional theory with surface hopping in the Kohn-Sham basis. Representing the dye-sensitized semiconductor Gr?tzel cell with the I-/I3- mediator, the system addresses the problems of an organic/inorganic, molecule/bulk interface that are commonly encountered in molecular electronics, photovoltaics, and photoelectrochemistry. The processes studied include the relaxation of the injected electron inside the TiO2 conduction band (CB), the back electron transfer (ET) from TiO2 to alizarin, the ET from the surface to the electrolyte, and the regeneration of the neutral chromophore by ET from the electrolyte to alizarin. Developing a theoretical understanding of these processes is crucial for improving solar cell design and optimizing photovoltaic current and voltage. The simulations carried out for the entire system that contains many electronic states reproduce the experimental time scales and provide detailed insights into the ET dynamics. In particular, they demonstrate the differences between the optimized geometric and electronic structure of the system at 0 K and the experimentally relevant structure at ambient temperature. The relaxation of the injected electron inside the TiO2 CB, which affects the solar cell voltage, is shown to occur on a 100 fs time scale and occurs simultaneously with the electron delocalization into the semiconductor bulk. The transfer of the electron trapped at the surface to the ground state of alizarin proceeds on a 1 ps time scale and is facilitated by vibrational modes localized on alizarin. If the electrolyte mediator is capable of approaching the semiconductor surface, it can form a stable complex and short-circuit the cell by accepting the photoexcited electron on a subpicosecond time scale. The ET from TiO2 to both alizarin and the electrolyte diminishes the solar cell current. Finally, the simulations show that the electrolyte can efficiently regenerate the neutral chromophore. This is true even though the two species do not form a chemical bond and, therefore, the electronic coupling between them is weaker than in the TiO2-chromophore and TiO2-electrolyte donor-acceptor pairs. The chromophore-electrolyte coupling can occur both directly through space and indirectly through bonding to the semiconductor surface. The ET events involving the electrolyte are promoted primarily by the electrolyte vibrational modes.  相似文献   

6.
We demonstrate a facile localized reduction approach to synthesizing a Au nanoparticle-decorated Keggin ion/TiO(2) photococatalyst for improved solar light photocatalysis application. This has been achieved by exploiting the ability of TiO(2)-bound Keggin ions to act as a UV-switchable, highly localized reducing agent. Notably, the approach proposed here does not lead to contamination of the resultant cocatalyst with free metal nanoparticles during aqueous solution-based synthesis. The study shows that for Keggin ions (phosphotungstic acid, PTA), being photoactive molecules, the presence of both Au nanoparticles and PTA on the TiO(2) surface in a cocatalytic system can have a dramatic effect on increasing the photocatalytic performance of the composite system, as opposed to a TiO(2) surface directly decorated with metal nanoparticles without a sandwiched PTA layer. The remarkable increase in the photocatalytic performance of these materials toward the degradation of a model organic Congo red dye correlates to an increase of 2.7-fold over that of anatase TiO(2) after adding Au to it and 4.3-fold after introducing PTA along with Au to it. The generalized localized reduction approach to preparing TiO(2)-PTA-Au cocatalysts reported here can be further extended to other similar systems, wherein a range of metal nanoparticles in the presence of different Keggin ions can be utilized. The composites reported here may have wide potential implications toward the degradation of organic species and solar cell applications.  相似文献   

7.
Different-sized CdSe quantum dots have been assembled on TiO2 films composed of particle and nanotube morphologies using a bifunctional linker molecule. Upon band-gap excitation, CdSe quantum dots inject electrons into TiO2 nanoparticles and nanotubes, thus enabling the generation of photocurrent in a photoelectrochemical solar cell. The results presented in this study highlight two major findings: (i) ability to tune the photoelectrochemical response and photoconversion efficiency via size control of CdSe quantum dots and (ii) improvement in the photoconversion efficiency by facilitating the charge transport through TiO2 nanotube architecture. The maximum IPCE (photon-to-charge carrier generation efficiency) obtained with 3 nm diameter CdSe nanoparticles was 35% for particulate TiO2 and 45% for tubular TiO2 morphology. The maximum IPCE observed at the excitonic band increases with decreasing particle size, whereas the shift in the conduction band to more negative potentials increases the driving force and favors fast electron injection. The maximum power-conversion efficiency 相似文献   

8.
Effects of incorporation of acid-treated single-wall carbon nanotubes (a-SWCNs) in TiO(2) film and of anchorage of dye-linked, a-SWCNs (hereafter dye-SWCNs) to the TiO(2)/electrolyte interface on photocurrent-voltage characteristics of dye-sensitized solar cells were studied. Compared with an unmodified cell, the modified cell with the a-SWCNs in TiO(2) film showed a 25% increase in short-circuit photocurrent (J(sc)). The J(sc) increase is correlated with improved connectivity between the a-SWCNs and the TiO(2) particles and with enhanced light scattering by TiO(2) clusters formed in the presence of the a-SWCNs. In the case of anchoring dye-SWCNs to the TiO(2)/electrolyte interface, the open-circuit voltage (V(oc)) increased by as much as 0.1 V, possibly due to the basicity of the TiO(2) surface from NH groups of ethylenediamine moieties of the anchored dye-SWCNs.  相似文献   

9.
The interface modification effect within quasi-solid dye-sensitized solar cells and the photovoltaic performance were investigated after the introduction of Mg(OOCCH(3))(2) as an additive into a polymer gel electrolyte. Electrochemical impedance spectroscopy showed that the addition of Mg(OOCCH(3))(2) into the polymer gel electrolyte can efficiently retard charge recombination at the TiO(2)/electrolyte interface. Mg(OOCCH(3))(2) in the electrolyte can also contribute to the enhancement of the incident photon-to-electron conversion efficiency by modifying the dye molecules. This results in an improvement in the photovoltage and photocurrent due to a barrier layer at the TiO(2)/electrolyte interface and the promotion of charge injection at the dye/TiO(2) interface, respectively. Photovoltaic measurements reveal that a conversion efficiency enhancement from 4.05% to 4.96% under 100 mW cm(-2) is obtained after the amount of Mg(OOCCH(3))(2) added was optimized.  相似文献   

10.
Nanocrystalline TiO2 films, surface modified with Al3+, were manufactured by depositing a TiO2 suspension containing small amounts of aluminum nitrate or aluminum chloride onto conducting glass substrates, followed by drying, compression, and finally heating to 530 degrees C. Electrodes prepared with TiO2 nanoparticles coated with less than 0.3 wt % aluminum oxide with respect to TiO2 improved the efficiency of the dye sensitized solar cell. This amount corresponds to less than a monolayer of aluminum oxide. Thus, the Al ions terminate the TiO2 surface rather than form a distinct aluminum oxide layer. The aluminum ion surface treatment affects the solar cell in different ways: the potential of the conduction band is shifted, the electron lifetime is increased, and the electron transport is slower when aluminum ions are present between interconnected TiO2 particles.  相似文献   

11.
Addition of 4-tert-butylpyridine (4TBP) to redox electrolytes used in dye-sensitized TiO2 solar cells has a large effect on their performance. In an electrolyte containing 0.7 M LiI and 0.05 M I2 in 3-methoxypropionitrile, addition of 0.5 M 4TBP gave an increase of the open-circuit potential of 260 mV. Using charge extraction and electron lifetime measurements, this increases could be attributed to a shift of the TiO2 band edge toward negative potentials (responsible for 60% of the voltage increase) and to an increase of the electron lifetime (40%). At a lower 4TBP concentration the shift of the band edge was similar, but the effect on the electron lifetime was less pronounced. The working mechanism of 4TBP can be summarized as follows: (1) 4TBP affects the surface charge of TiO2 by decreasing the amount of adsorbed protons and/or Li+ ions. (2) It decreases the recombination of electrons in TiO2 with triiodide in the electrolyte by preventing triiodide access to the TiO2 surface and/or by complexation with iodine in the electrolyte.  相似文献   

12.
近红外光约占入射太阳能的 44% 以上, 为实现太阳能量的最大化利用, 近红外光 (NIR) 驱动的光催化技术成为科学研究的热点. 由于上转换荧光纳米材料 (UCNPs) 是优良的红外能量转换器, 合金半导体 ZnxCd1-xS 具有较好的化学稳定性以及生物相容性, 本文发展了一种简易的水热法, 将 UCNPs 和 ZnxCd1-xS 合金结合, 成功构建了 NIR 与可见光响应的核壳纳米结构. 由于这两种材料的晶格失配度较高, 很难直接外延生长, 我们通过引入非晶 TiO2将形成的催化剂纳米颗粒ZnxCd1-xS 紧紧束缚在 UCNPs 外面形成蛋黄-蛋壳结构, 在 NIR 光照下获得了较高的能量转换效率.首先, 在 UCNPs 外面外延生长一层 AA-Zn[(OH)4]2–复合物, 形成 UCNPs@AA-Zn[(OH)4]2–复合纳米结构, 然后在其核壳结构外面外延生长薄层的非晶 TiO2, 以稳定后续要制备的合金半导体 ZnxCd1-xS; 在水热条件下, UCNPs@AA-Zn[(OH)4]2–/TiO2与醋酸镉和硫脲反应, 形成 UCNPs@ZnxCd1-xS/TiO2复合材料. 在此, 我们选择β-NaYF4:Yb(30%),Tm(0.5%)@NaYF4:Yb(20%),Er(2%) 作为 NIR 的能量转换器. 样品的形貌、物相及化学组成分别采用场发射扫描电子显微镜、透射电子显微镜、X 射线衍射和原子吸收光谱法进行表征.研究表明, 我们成功制备了具有蛋黄-蛋壳结构的 UCNPs@ZnxCd1-xS/TiO2纳米颗粒. 此外, 非晶态 TiO2将 UCNPs 与ZnxCd1-xS 紧密结合, 对最终样品 UCNPs@ZnxCd1-xS 核壳纳米粒子的形成起到重要作用. 而且, 合金 ZnxCd1-xS 的化学组成可通过调整镉源和锌源的用量进行调节. 所制备的 UCNPs@ZnxCd1-xS 核壳纳米粒子在 NIR 光线或模拟太阳光照射下显示出高效的光化学还原 Cr(VI) 性能. 溶液中 70% 以上的 Cr(VI) 在 NIR 光照射 30 min 后被还原为 Cr(III). 本研究将为环境污水处理和太阳能利用提供一种可供选择的策略, 且所制的复合纳米结构在肿瘤治疗、药物释放和能量转换等领域也有着潜在的应用价值.  相似文献   

13.
由于近红外光在太阳光谱中占44%,因此,近红外光驱动的光催化剂的研制具有十分重要的意义.上转换发光材料可将低能量的近红外光子转换为高能光子,这种高能光子可以通过构建荧光共振转移系统将能量转移并活化量子效率较高的半导体材料,对于太阳能的转化利用具有潜在的应用前景.在本文中,通过胶体化学的过程在电纺丝制备的内嵌CdS纳米颗粒以及上转换荧光纳米颗粒(UCNPs)的二氧化硅复合纳米纤维表面外延生长一层二氧化钛层,通过高温煅烧得到二氧化钛复合纳米管.我们通过二氧化硅结构将CdS纳米颗粒与上转换荧光纳米颗粒紧紧束缚在一起,实现较高的荧光共振能量转移.而且,选择β-NaYF4:Yb(30%),Tm(0.5%)@NaYF4:Yb(20%),Er(2%)作为纳米能量转换器,替代以前研究工作中使用的β-NaYF4:Yb(30%),Tm(0.5%)或者β-NaYF4:Yb(30%),Tm(0.5%)@NaYF4纳米颗粒,来进一步提高近红外光的转换效率.通过透射电子显微镜照片很清楚的观察到制备的TiO2复合纳米管内部内嵌有大量的CdS与上转换纳米颗粒.通过X-射线衍射以及X-射线光电子能谱能仪器对产物的物相以及表面的化学组成进行了细致的表征.结果显示,通过本实验方法已经成功获得了TiO2复合纳米管.用稳态与瞬态荧光仪研究了最终样品的荧光性质.研究结果揭示,与上转换纳米颗粒以及二氧化硅复合纳米纤维相比,复合二氧化钛纳米管可以将上转换荧光纳米颗粒的(UV-Vis)部分荧光完全淬灭了.特别是,铒离子的荧光(650 nm)也被有效淬灭转移,说明本研究采用β-NaYF4:Yb(30%),Tm(0.5%)@NaYF4:Yb(20%),Er(2%)纳米能量转换器,可以提高近红外光的转换效率,紫外-可见吸收光谱证实,这种二氧化钛纳米管在紫外-可见光区中的吸收光谱与β-NaYF4:Yb(30%),Tm(0.5%)@NaYF4:Yb(20%),Er(2%)纳米颗粒的荧光光谱具有较大的重叠,使得上转换荧光纳米颗粒与CdS以及二氧化钛组分之间的荧光共振转移的效率大大提高,进而会显著提高光催化的效果.以罗丹明染料作为污染物为模型,我们研究了罗丹明染料在氙灯下或者近红外光光照下的光催化分解实验.研究结果表明,90%的罗丹明染料分子在20 min内就被降解掉,效率高于其它的近红外光催化剂.上转换荧光纳米颗粒的能量转换效率可以得到大幅度提高,本研究工作中制备的光催化剂利用太阳能的效率将会得到极大提高,在未来为能源危机以及环境保护提供一种可供选择的方法与技术.  相似文献   

14.
We have investigated the electrostatic potential distribution in compact and nanoporous TiO2 films, deposited on conducting F-doped SnO2 substrate (FTO), which are used in dye-sensitized solar cells. The TiO2 films were immersed into aqueous electrolyte and excited from the FTO side by light pulses of a N2 laser while the current response was measured as a function of time. The measurements were carried out as a function of the pH value of the electrolyte and at different electrostatic potentials. For compact TiO2 films, the sign of the transient current at short response times changed when the applied electrostatic potential or the pH value was decreased. This was not observed for mesoporous TiO2 films directly deposited onto the FTO substrate without a compact TiO2 layer. We interpret the results in terms of a macroscopic electric field across the compact layer which is changed by the applied potential or the pH of the electrolyte. In contrast, measurements on mesoporous TiO2 films indicate that the contact region is mainly field-free, and we explain our results by a very sharp electrostatic potential drop within the first layer of particles at the TiO2/FTO interface.  相似文献   

15.
Submicrometer-sized hollow TiO(2) spheres are directly self-assembled from TiO(2) nanoparticles without using any template or surfactant as a scattering layer for dye-sensitized solar cells, showing good visible light scattering match to significantly improve the photoconversion efficiency.  相似文献   

16.
二氧化钛因其在光催化、染料敏化太阳电池、生物医药等应用领域表现出优异性能而成为材料科学领域重点研究的化合物之一。本文介绍了近年来阳极氧化法制备不同形貌的TiO2纳米管(TiO2NTs)阵列,探讨了电解液、阳极氧化时间、电压三个因素对TiO2纳米管形貌的影响,综述了掺杂、复合、表面修饰这三种能对TiO2纳米管进行化学或物理修饰的改性手段以及改性后的TiO2纳米管阵列在光催化、太阳能电池、生物医学、传感等领域的应用研究进展。最后,指出国内外针对二氧化钛纳米管阵列研究现状所存在的问题,并对今后的研究工作提出了展望。  相似文献   

17.
In this study, we investigated the interplay of three-dimensional morphologies and the photocarrier dynamics of polymer/inorganic nanocrystal hybrid photoactive layers consisting of TiO(2) nanoparticles and nanorods. Electron tomography based on scanning transmission electron microscopy using high-angle annular dark-field imaging was performed to analyze the morphological organization of TiO(2) nanocrystals in poly(3-hexylthiophene) (P3HT) in optimal solar cell devices. The Three-dimensional (3D) morphologies of these hybrid films were correlated with the photocarrier dynamics of charge separation, transport, and recombination, which were comprehensively probed by various transient techniques. Visualization of these 3D bulk heterojunction morphologies clearly reveals that elongated and anisotropic TiO(2) nanorods in P3HT not only can significantly reduce the probability of the interparticle hopping transport of electrons by providing better connectivity with respect to the TiO(2) nanoparticles, but also tend to form a large-scale donor-acceptor phase-separated morphology, which was found to enhance hole transport. The results support the establishment of a favorable morphology for polymer/inorganic hybrid solar cells due to the presence of the dimensionality of TiO(2) nanocrystals as a result of more effective mobile carrier generation and more efficient and balanced transport of carriers.  相似文献   

18.
二氢吲哚类染料用于染料敏化太阳能电池光敏剂的比较   总被引:1,自引:0,他引:1  
采用密度泛函理论(DFT)和含时密度泛函理论(TD-DFT)对四种二氢吲哚染料进行研究, 从中筛选出相对优秀的染料敏化太阳能电池光敏剂. 对前线分子轨道的计算表明, 二氢吲哚染料的前线分子轨道结构非常有利于染料激发态向TiO2电极的电子注入. 对真空中的紫外和可见光吸收光谱的计算表明, 二氢吲哚染料的吸收光谱与太阳辐射光谱匹配较好. 对染料分子的能级计算表明, 二氢吲哚染料的能级结构比较适合于I-/I-3作电解液的TiO2纳米晶太阳能电池的光敏剂. 二氢吲哚染料最低未占据分子轨道(LUMO) 能级均比TiO2晶体导带边能级高, 能够保证激发态染料分子高效地向TiO2电极转移电子. 二氢吲哚染料最高占据分子轨道(HOMO)的能级比I-/I-3能级低, 保证了失去电子的染料分子能够顺利地从电解液中得到电子. 与实验数据比较, 得出在提高染料敏化太阳能电池转换效率方面, 对染料的关键要求是LUMO能级的位置. 染料分子的稳定性是染料敏化太阳能电池使用寿命的关键因素. 通过对化学键键长的比较表明, 二氢吲哚染料的分子稳定性基本相同. 对计算结果的分析表明, 二氢吲哚染料1(ID1)的LUMO能级最高, 分子稳定性最好, 在酒精溶液中的吸收光谱与太阳辐射光谱匹配很好, 在同类染料中是较好的染料敏化太阳能电池光敏剂.  相似文献   

19.
A nanoporous CaCO3 overlayer-coated TiO2 thick film was prepared by the topotactic thermal decomposition of Ca(OH)2, and its performance as an electrode of a dye-sensitized solar cell was investigated. As compared to bare TiO2, nanoporous CaCO3-coated TiO2 provided higher specific surface area and, subsequently, a larger amount of dye adsorption; this in turn increased short-circuit current (Jsc). Furthermore, the CaCO3 coating demonstrated increased impedance at the TiO2/dye/electrolyte interface and increased the lifetime of the photoelectrons, indicating the improved retardation of the back electron transfer, which increases Jsc, open-circuit voltage (Voc), and fill factor (ff). Thereby, the energy conversion efficiency (eta) of the solar cell improved from 7.8 to 9.7% (an improvement of 24.4%) as the nanoporous CaCO3 layer was coated onto TiO2 thick films.  相似文献   

20.
黄先威  邓继勇  许律  沈平  赵斌  谭松庭 《化学学报》2012,70(15):1604-1610
利用静电纺丝技术,制备了不同的聚合物/TiO2杂化纳米纤维微孔膜,吸附液体电解质后形成聚合物/TiO2杂化纳米纤维微孔膜准固态电解质,应用于制备准固态染料敏化太阳能电池(DSSCs).测试了电纺聚合物纳米纤维微孔膜电解质的吸液率、孔隙率、离子电导率等参数,研究了纳米纤维微孔膜准固态电解质DSSCs的光伏性能.结果显示,TiO2的掺入可提高聚合物/TiO2杂化纳米纤维微孔膜对液态电解质的浸润扩散性能,从而提高纳米纤维微孔膜对液态电解质的吸附能力.组装的DSSCs的光电转换效率可达液态电解质的90%以上,并具有较好的长期工作稳定性.  相似文献   

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