温度对多硫电解质及量子点敏化太阳能电池性能的影响

采用电化学的方法研究了温度对多硫电解质导电性能及量子点敏化太阳能电池光电性能的影响.结果表明:随着温度的升高,电解质的电导率逐步升高,多硫离子在电解质中的扩散阻力变小;另外,随着温度的升高,量子点敏化太阳能电池的光电转化效率逐渐降低,这主要是由于在较高的温度下,电池的暗反应逐渐增大和量子点的脱附引起的.     

Treatment of TiO2 with COOH‐Functionalized Germanium Nanoparticles to Enhance the Photocurrent of Dye‐Sensitized Solar Cells

A dye‐sensitized solar cell (DSSC) containing a TiO₂ film treated with COOH‐functionalized germanium nanoparticles (Ge COOH Nps) exhibited a higher short‐circuit photocurrent density (J_sc; 15.4 mA cm⁻²) compared to the corresponding untreated DSSC (13.4 mA cm⁻²) using N719 and a 12 μm thick TiO₂ film at 100 mW cm⁻². The amount of N719 attached to the treated TiO₂ film was 21 % greater than that attached to the untreated TiO₂ film. Enhancement of the J_sc value by 15 % was attributed mostly to an intramolecular charge transfer from N719 attached to the Ge COOH Nps to the TiO₂ conduction band through the Ge COOH Nps.     

Adsorption of N719 Dye on Anatase TiO2 Nanoparticles and Nanosheets with Exposed (001) Facets: Equilibrium,Kinetic, and Thermodynamic Studies

Anatase TiO₂ nanosheets (TiO₂ NS) with dominant (001) facets and TiO₂ nanoparticles (TiO₂ NP) with dominant (101) facets are fabricated by hydrothermal hydrolysis of Ti(OC₄H₉)₄ in the presence and absence of hydrogen fluoride (HF), respectively. Adsorption of N719 onto the as‐prepared samples from ethanol solutions is investigated and discussed. The adsorption kinetic data are modeled using the pseudo‐first‐order, pseudo‐second‐order, and intraparticle diffusion kinetics equations, and indicate that the pseudo‐second‐order kinetic equation and intraparticle diffusion model can better describe the adsorption kinetics. Furthermore, adsorption equilibrium data of N719 on the as‐prepared samples are analyzed by Langmuir and Freundlich models; this suggests that the Langmuir model provides a better correlation of the experimental data. The adsorption capacities (q_max) of N719 on TiO₂ NS at various temperatures, determined using the Langmuir equation, are 65.2 (30 °C), 68.2 (40 °C), and 76.6 (50 °C) mg g⁻¹, which are smaller than those on TiO₂ NP, 92.4 (30 °C), 100.0 (40 °C), and 108.2 (50 °C) mg g⁻¹, respectively. The larger adsorption capacities of N719 for TiO₂ NP versus NS are attributed to its higher specific surface areas. However, the specific adsorption capacities (q_max/S_BET) at various temperatures are 1.5 (30 °C), 1.6 (40 °C), and 1.7 (50 °C) mg m⁻² for TiO₂ NS, which are otherwise higher than those for NP, 0.9 (30 °C), 1.0 (40 °C), and 1.1 (50 °C) mg m⁻², respectively. The larger specific adsorption capacities of N719 for TiO₂ NS versus NP are because the (001) surface is more reactive for dissociative adsorption of reactant molecules compared with (101) facets. Notably, the q_max and q_max/S_BET for both TiO₂ samples increase with increasing temperature, suggesting that adsorption of N719 on the TiO₂ surface is an endothermic process, which is further confirmed by the calculated thermodynamic parameters including free energy, enthalpy, and entropy of adsorption process. The present work will provide a new understanding on the adsorption process and mechanism of N719 molecules onto TiO₂ NS and NP, and this should be of great importance for enhancing the performance of dye‐sensitized solar cells.     

溴化十六烷基三甲基铵增敏光度法测定定影废液中的银

在pH=6.86时,Ag+与二甲酚橙(XO)、表面活性剂溴化十六烷基三甲基铵(CTMAB)发生显色反应,Ag+-XO-CTMAB三元配合物的最大吸收波长为594nm,表观摩尔吸光系数为2.08×106L/(mol·cm),Ag+含量在0.0～50.0μg/(25mL)内服从比耳定律。将该法用于定影废液中微量Ag+的测定,回收率为96.7%～100.8%。     

Theoretical study of quinolines-I(2) intermolecular interaction and implications on dye-sensitized solar cell performance

The monomer and intermolecular charge-transfer complexes of 13 different quinoline derivatives with diiodine were studied using ab initio molecular orbital (MO) and density functional theory (DFT) methods. Calculations revealed that the sigma* orbital of iodine interacts with the nitrogen lone pair in the quinoline ring. The open-circuit photovoltage (V(oc)) values of an Ru(II) complex dye-sensitized nanocrystalline TiO(2) solar cell with an I(-)/I(3) (-) redox electrolyte in acetonitrile using quinoline additives were compared to the computational calculations on the intermolecular interaction between quinolines and I(2). The optimized geometries, frequency analyses, Mulliken population analyses, natural bond orbital (NBO) analyses, and interaction energies indicate that the V(oc) value of the solar cell is higher when quinoline complexes more favorably interact with I(2). Therefore, the interaction between the quinoline additives and iodine redox electrolyte is an important factor for controlling dye-sensitized solar cell performance.     

锐钛矿相TiO2纳米管的制备及其染料敏化太阳电池

以商用金红石相TiO₂粉末为原料,通过在碱性溶液中150℃水热48h的方法合成TiO₂纳米管.采用SEM,TEM,XRD分析手段对TiO₂纳米管的形貌和结构演变进行了表征.制成的TiO₂纳米管与TritonX-100,乙酰丙酮混合后,通过丝网印刷的方法涂敷到ITO导电玻璃衬底上,并且在450℃下烧结30min后得到可应用于染料敏化太阳电池的多孔光阳极.将此光阳极浸泡于N719染料敏化后,与镀铂对电极组装电池,两者之间灌 关键词： 2纳米管')" href="#">TiO₂纳米管 染料敏化太阳电池 水热法     

Exploring the relevance of thiophene rings as bridge unit in acceptor‐bridge‐donor dyes on self‐aggregation and performance in DSSCs

The possibility of dye charge recombination in DSSCs remains a challenge for the field. This consists of: (a) back‐transfer from the TiO₂ to the oxidized dye and (b) intermolecular electron transfer between dyes. The latter is attributed to dye aggregation due to dimeric conformations. This leads to poor electron injection which decreases the photocurrent conversion efficiency. Most organic sensitizers are characterized by an Acceptor‐Bridge‐Donor ( A ‐Bridge‐ D ) arrangement that is commonly employed to provide charge separation and, therefore, lowering the unwanted back‐transfer. Here, we address the intermolecular electron transfer by studying the dimerization and photovoltaic performance of a group of A ‐Bridge‐ D structured dyes. Specifically, eight famous sulfur containing π‐bridges were analyzed ( A and D remained fixed). Through quantum mechanical and molecular dynamics approaches, it was found that the formation of weakly stabilized dimers is allowed. The dyes with covalently bonded and fused thiophene rings as Bridges, 6d and 7d as well as 8d with a fluorene, would present high aggregation and, therefore, high probability of recombination processes. Conversely, using TiO₂ cluster and surface models, delineated the shortest bridges to improve the adsorption energy and the stability of the system. Finally, the elongation of the bridge up to 2 and 3 units and their photovoltaic parameters were studied. These results showed that all the sensitizers are able to provide similar photocurrent outcomes, regardless of whether the bridge is elongated. © 2017 Wiley Periodicals, Inc.     

Synthesis and Characterization of Heteroleptic Ru(II) Complexes Based on 4,4′‐Bis((E)‐styryl)‐2,2′‐bipyridine as Ancillary Ligand and Application for Dye‐Sensitized Solar Cells

Heteroleptic Ru(II) complexes were designed based on 4,4′‐bis((E)‐styryl)‐2,2′‐bipyridine (bsbpy) as an ancillary ligand for dye‐sensitized solar cells (DSSCs), and those Ru(II) sensitizers, [Ru(L)(bsbpy)(NCS)₂][TBA] (TBA; tetrabutylammonium), were synthesized according to a typical one‐pot reaction of [RuCl₂(p‐cymene)]₂ with the corresponding anchoring ligands (where L = 4,4′‐dicarboxy‐2,2′‐bipyridine (dcbpy), 4,4′‐bis((E)‐carboxyvinyl)‐2,2′‐bipyridine (dcvbpy), 4,7‐dicarboxy‐1,10‐phenanthroline (dcphen), or 4,7‐bis((E)‐carboxyvinyl)‐1,10‐phenanthroline (dcvphen)). The new Ru(II) dyes, [Ru(L)(bsbpy)(NCS)₂][TBA] that incorporated vinyl spacer(s) into ancillary and/or anchoring ligand displayed red‐shifted bands over the overall UV/VIS region relative to the absorption spectra of N719 . A combination of bsbpy ancillary and dcphen anchoring ligand showed the best result for the overall power conversion efficiency (η); i.e., a DSSC fabricated with [Ru(dcphen)(bsbpy)(NCS)₂][TBA] exhibited a power conversion efficiency (η) of 2.98% (compare to N719 , 4.82%).     

Terpyridine Based Heteroleptic Ruthenium Complexes: Influence of Donor and Acceptor Ligands in Photosensitization

We report heteroleptic ruthenium complexes of terpyridine (tpy) ligands with directly linked carboxylic acid anchors. These complexes feature methyl or methoxy-substituted ^4′−Phtpy as donor ligands. We prepared these heteroleptic complexes from the ruthenium (II) precursor via a milder route to preclude the homoleptic complex formation. The donor−acceptor arrangement of tpy ligands in these ruthenium complexes renders visible light absorption giving metal and ligand-to-ligand charge transfer excitations at c.a. 490 nm. We evaluate the effect of the tpy donor substituents on the light-harvesting ability in Dye-Sensitized Solar Cells (DSSCs) and compare their photosensitizing ability with heteroleptic complexes bearing phenyl spacer at the acceptor end. Further, scrutinizing their photovoltaic performance, we studied their electron transfer kinetics in DSSCs using electrochemical impedance spectroscopy. This paper presents the structure-photosensitization relationship of these heteroleptic ruthenium complexes through a combined experimental and computational approach.