染料敏化太阳能电池的研究进展

染料敏化太阳能电池由于具有特殊的结构,低廉的制作成本,较高的光电转换效率,成为新型廉价高效太阳能电池的研究热点。近年来,染料敏化太阳能电池的光电转换效率已经突破12%,为其产业化打下良好的基础。本文主要介绍了其关键组成部分如光阳极、对电极和电解质等的组成、结构与性能关系,对国内外该领域的研究进展进行了评述,并介绍本课题组在该领域的研究进展。     

染料敏化太阳能电池的电子传输和复合特性研究

采用丝网印刷方法在透明导电玻璃上制备了不同厚度的TiO2纳米颗粒多孔薄膜光阳极,并与Pt对电极和I-/I3-电解液组装成染料敏化太阳能电池.通过电池的I-V特性、强度调制光电流谱、强度调制光电压谱和电化学阻抗谱分析,获得了电池的光伏性能和反映电子传输、复合和收集的动力学参数.结果表明:随着TiO2光阳极厚度从5μm逐渐增加到14 μm,电池的光电转换效率从4.67;逐渐增加到8.21;,光生电子在光阳极中的传输时间从2.74 ms逐渐增加到7.84 ms,电子扩散系数从3.88×10-5 cm2·s-1增加到1.10×10-4cm2 ·s-1,电荷收集效率逐渐减小,结合这些参数,分析了染料敏化电池中电子传输、复合和收集的动力学过程.     

多壁碳纳米管对电极染料敏化太阳能电池的性能研究

以SnO2/TiO2薄膜为光阳极,与以经酸化处理和与石墨复合的沉积在FTO导电基底的多壁碳纳米管(MWCNTs)薄膜为对电极,I-/I3-为电解液,组装成染料敏化太阳能电池.对电极通过循环伏安法(CV曲线)、电化学阻抗谱(EIS)及极化曲线法(Tafel曲线)进行电化学催化性能的表征,组装后的电池通过伏安特性曲线(J～V)进行光电性能分析,结果表明:酸化处理及与石墨复合有利于提高对电极的催化性能及电池光电性能.开路电压及短路电流密度分别可达0.53 V、4.67 mA/cm2,其中短路电流较未经过处理的MWCNTs对电极提高27.4;,同时讨论了对电极电化学性及电池光电性能增强的机制.     

染料敏化太阳能电池中花青素与β-胡萝卜素天然染料共敏化的研究

从高原格桑花和胡萝卜中提取天然染料花青素和β-胡萝卜素作为敏化剂,并组装染料敏化太阳能电池(DSC).研究了提取的天然染料的光吸收性能、主要成分和共敏化方式,讨论了花青素和β-胡萝卜素的共敏化形式、比例、浓度和时间对DSC光电性能的影响.研究发现,花青素和β-胡萝卜素混合敏化时表现出明显的共敏化作用,而分层敏化时则共敏效果不明显.当花青素含量逐渐降低时,共敏化电池的短路电流和光电转换效率表现出先增大后减小的趋势,且共敏化的最佳体积比为1∶1,同时发现共敏化时间比通常少很多,最佳敏化时间为15min.最佳共敏化条件下组装的DSC的短路电流密度为0.725 mA/cm2,光电转换效率为0.267;,相比于花青素和β-胡萝卜素单独敏化时组装的DSC,短路电流分别提高了60;和505;,光电转换效率分别提高了51;和480;,这主要得益于共敏化后拓宽的光谱吸收范围.     

染料敏化太阳能电池载流子传输的数值模拟

由于在染料敏化太阳能电池(dye-sensitized solar cell, DSSC)中存在染料弛豫、半导体薄膜中电子与氧化态染料分子发生反应和电子在电解质中与氧化态离子复合等不利反应,利用一个更完善的DSSC载流子传输模型对电池的光电性能进行模拟就显得非常重要。为此,本文基于由多重俘获理论建立的DSSC中的包括电子、染料阳离子、碘化物和三碘化物在内的载流子传输模型,数值模拟得到了不同TiO₂薄膜厚度、不同入射光强度与不同染料分子吸收系数下DSSC的J-V曲线。结果表明,随着TiO₂薄膜厚度的增加,太阳能电池的短路电流密度增大,开路电压减小,光电转换效率先增大后减小。当DSSC的TiO₂薄膜厚度为20 μm时,光电转换效率达到最大值7.41%,同时光电转换效率随入射光强度与染料分子吸收系数的增大均有一定程度提高,其中在吸收系数为4 500 cm^-1时,光电转换效率为6.73%。以上结果可以为改进DSSC的光电性能提供理论指导。     

ZnO/TiO2复合光阳极染料敏化太阳能电池的研究

采用醇热法制备ZnO纳米粉体,采用水热法制备TiO2纳米粉体,将不同质量分数的ZnO与TiO2混合制备浆料,采用刮涂法在掺氟的SnO2透明导电玻璃(FTO)上制备ZnO/TiO2纳米复合薄膜光阳极,与Pt对电极和电解质组装成染料敏化太阳能电池.采用X射线衍射仪(XRD)、X射线光电子能谱仪(XPS)和扫描电镜(SEM)对所制备的样品进行表征,通过光电性能测试和电化学阻抗谱测试,研究了添加不同质量分数的ZnO对电池性能的影响.结果表明:不添加ZnO纳米粉时,纯TiO2光阳极的电池光电转换效率为7.95;,而添加了2wt; ZnO的ZnO/TiO2复合光阳极电池的效率达到9.54;,比纯TiO2电池的效率提高了20;.     

TiO2包覆SnO2光阳极的制备及其对DSSC性能的影响

以TiCl4溶液浸泡处理的花状SnO2晶体薄膜为光阳极,经N3染料浸渍,与Pt对电极,I-/lf电解质组装成染料敏化太阳能电池(DSSC).通过XRD对花状SnO2粉体物相进行分析;利用SEM对花状SnO2粉体及SnO2-TiO2薄膜表面形貌进行分析;电池的光电性能通过伏安特性曲线(J-V)进行分析.结果表明:花状SnO2-DSSC有利于提高电池的光电性能,光电转换效率较球状SnO2-DSSC提高近38;.经TiCl4处理的SnO2-TiO2-DSSC的短路电流(Jse)和开路电压(Voc)分别达到7.20 mA·cm-2和0.63V,电池的光电转换效率达到3.24;,与纯花状SnO2-DSSC相比提高了近4倍.     

电沉积制备的ZnO薄膜在染料敏化太阳能电池中光电性能的研究

采用阴极电沉积法在导电玻璃基体上制备了ZnO薄膜,研究了工艺条件对ZnO薄膜在染料敏化太阳能电池(DSSC)中的光电性能的影响.通过热分析(TG-DTA),X射线衍射(XRD)和电子扫描电镜(SEM)对ZnO薄膜的结构和形貌进行了表征.实验结果表明,电沉积制备的ZnO薄膜为纤锌矿结构,薄膜颗粒均匀,在DSSC中表现出较好的光伏性能.     

Sr掺杂镧锰氧化物/石墨烯对电极的催化性能研究

以商用TiO2薄膜为光阳极,以溶胶-凝胶法合成的Sr掺杂镧锰氧化物La0.67Sr0.33MnO3 (LSMO)纳米颗粒为对电极,为电解液,组装染料敏化太阳能电池(DSSC).通过电化学阻抗谱(EIS)、塔菲尔极化曲线(Tafel曲线)、循环伏安曲线(CV曲线)、伏安特性曲线(J-V曲线)对制备的对电极进行光电性能分析.为了进一步提高LSMO纳米颗粒对电极的能量转化效率,在LSMO纳米颗粒中加入还原氧化石墨烯(RGO),通过简单的物理混合法制备了LSMO/RGO纳米复合材料.这种复合材料在还原I3-方面表现出更优异的电催化性能.与Pt对电极(6.942;)相比,其能量转化效率(PCE)达到了6.567;.     

三维有序大孔碳的合成及其在染料敏化太阳能电池中的应用

以葡萄糖为碳源、硫酸为脱水剂、聚苯乙烯胶体晶体为模板,采用简单的浸渍-煅烧工艺制备了高度三维有序大孔碳(3DOM-C)材料.利用SEM、FESEM、TEM、紫外-可见光光度计和氮气吸附-脱附分析仪对样品进行了表征,考察了3DOM-C、贵金属Pt和活性碳作为对对电极材料在染料敏化太阳能电池(DSSCs)中的光电转化性能,并进一步对电极进行了电化学阻抗分析.结果表明,3DOM-C材料的孔径约为280 nm,具有三维有序网络空间结构.J-V测试结果显示,3DOM-C/DSSC的光电转化效率为4.61;,达到了Pt/DSSC的90;.阻抗测试结果显示,3DOM-C电极表现出良好的电催化活性及导电性,与Pt电极相近且远高于活性碳.     

Relationship of Morphological Types of Dynamic Forms of Crystals

Crystallography Reports - The relationship of morphological spectra (sets of data on the morphological types of real polyhedral crystals and their probabilities under current physicochemical...     

Development of Pauling's concepts of geometric characteristics of atoms

The evolution of the geometric characteristics introduced by Pauling and their dependence on the specific features of the structure and chemical bonds have been considered. The values of the covalent and van der Waals radii are given as well as their relationships and mutual transitions.     

A review of measurement of thermophysical properties of silicon melt

Measurements of thermophysical properties of Si melt and supplementary study of X-ray scattering/diffraction by the authors' group were reviewed. The values obtained differed variously from those of literature. Density was 2–3% larger, surface tension 20–30% smaller, viscosity up to 40% larger, electrical conductivity 8% smaller, spectral emissivity more or less in good agreement with literature values, and thermal diffusivity a few percent larger. An anomalous density jump was found near the melting point. Surface tension and viscosity also showed anomaly. A strange time-dependent change of density was observed over 3 h after melting. X-ray analyses suggested a slight change in local atom ordering, but showed no sign of cluster formation. An addition of 0.1 at% gallium caused the density jump to disappear, while that of boron caused no change. An EXAFS study of the former melt indicated a strong interaction between Ga and Si atoms as if molecules of GaSi₃ existed. The implications of the measured properties are a possibility of soft-turbulence in an Si melt in a relatively large crucible, a more complicated manner of intake of oxygen depleted molten Si from the free surface region to underneath the growing crystal, and a relaxation of the melt after melting arising from trapped gas species.     

Generation of crystal structures of heteromolecular compounds by the method of discrete modeling of packings

Within the method of discrete modeling of packings, an algorithm of generation of possible crystal structures of heteromolecular compounds containing two or three molecules in the primitive unit cell, one of which has an arbitrary shape and the other (two others) has a shape close to spherical, is proposed. On the basis of this algorithm, a software package for personal computers is developed. This package has been approved for a number of compounds, investigated previously by X-ray diffraction analysis. The results of generation of structures of five compounds—four organic salts (with one or two spherical anions) and one solvate—are represented.     

Velocities of Disappearance and Lifetime of Faces of Growing Crystals

The formulae for absolute R_disap and relative R velocities of disappearance and lifetime τ of faces of growing crystals have been derived for stationary growth. It was shown that the quantities are determined by the relative growth velocity R_A/R_critA of the vanishing face A with respect to the critical growth velocity R_critA and by the geometry of a crystal expressed by the trigonometric functions of interfacial angles β and γ formed between face A and the adjacent faces. R increases and τ decreases with the increase in R_A/R_critA to certain limiting values. The calculations have been verified and illustrated by the experimental results for triclinic potassium bichromate (KBC) crystals. Results enable ones to predict values of velocities of disappearance and lifetimes of undesirable, supplementary faces of any real crystal.     

Comparative analysis of two methods of calculation of the orientation of domain walls in ferroelastics

Two types of domain-wall equations are analyzed: the equations derived by the Sapriel method and the equations obtained by interface matching of the thermal-expansion tensor. It is shown that, for W-type domain walls, these methods yield the same equations. For W′-type domain walls, the equations obtained by different methods coincide for proper ferroelastics and differ for improper ferroelastics.     

Dependence of the parameters of equations of viscous flow on chemical composition of silicate melts

The temperature dependence of viscosity of silicate melts is discussed in the framework of the Avramov–Milchev (AM) equation. The composition is described by means of two parameters: the molar fraction, x, and the “lubricant fraction”, l. The molar fraction is the sum of the molar parts x_i of all oxides dissolved in SiO₂, the molar fraction of the latter being 1 ? x. It is shown that, with sufficient precision, two of the parameters of the AM equation can be presented as unique functions of the molar fraction. On the other hand, x is not sufficient to determine properly the reference temperature T_r , at which viscosity is η_r = 10¹³ [dPa.s]. Therefore, additional parameter, “lubricant fraction” l, is introduced. For each of the components, l_i is a product of molar part x_i and a specific dimensionless coefficient 0 ≤ k_i ≤ 1 accounting for the specific contribution of this component to the increased mobility of the system. It is demonstrated that, for l > 0, the reference temperature is related to the “lubricant fraction” l through the reference temperature T_r,SiO2 of pure SiO₂.     

Mechanism of thermal expansion of structural modifications of zinc pyrovanadate

Crystal chemical characteristics of the α and β modifications of Zn₂V₂O₇ are calculated based on in situ high-temperature X-ray measurements. The expansion of the structure is found to be strongly anisotropic up to the negative volumetric thermal expansion of the α-Zn₂V₂O₇ unit cell in the temperature range of 300–600°С, α _V =–17.94 × 10^–6 1/K. The transformations of the “hard” and “soft” sublattices with an increase temperature and at the phase transition are considered in detail. It is shown that the negative volumetric thermal expansion of α-Zn₂V₂O₇ is due to the degeneracy of the zigzag-like shape of zinc–oxygen columns at constant distances between their vertices.     

A SAXS study of kinetics of aggregation of silica sols

SAXS in situ experiments on the evolution of TMOS solutions during hydrolysis and polycondensation lead to power laws with scaling exponents ≈ 2. It is suggested that this could be the result of the polydispersity of the samples and that only an apparent fractal dimension can be obtained in this way. Kinetic studies tend to indicate that agglomeration in the sol is the result of a diffusion-controlled process.