一种新型的染料敏化紫外光电池

利用浸渍提拉法制备了纳米TiO₂多孔膜.采用紫外光源,以[Fe(CN)₆]^3-/[Fe(CN)₆]^4-溶液为电解质,分别以两种染料敏化纳米TiO₂膜为光阳极制成了一种新型的紫外光电池,探讨了该电池的伏安特性曲线.电池最大电压为0.36 mV,最大电流密度为0.02 μA/cm²,同时对染料敏化电极的光电转换机理进行了初步讨论.     

金属氧化物修饰对介孔纳米TiO2电极的染料敏化太阳能电池电化学性能的影响

将介孔TiO₂纳米粒子(m-TiO₂)多孔膜电极浸入相应的金属硝酸盐的500 oC热处理修饰金属氧化物(如Mg、ZnO、Al₂O₃或NiO).结果表明,金属氧化物修饰均可形成能垒对m-TiO₂膜电极的界面电荷传输过程产生影响,但外加偏压下其膜内电子传输和界面电荷复合均明显依赖于修饰氧化物的种类及其存在形态. 金属氧化物修饰的膜电极在电子传输和界面复合方面的变化与DSSCs的电流-电压特性曲线的变化规律具有明显的相关性,可不同程度地提高电池的光电压,而MgO、ZnO和NiO修饰的电池效率分别提高了23%、13%和6%. 上述结果表明调控电池的本征参数可以改善TiO₂-基DSSCs的性能.     

5(6)羧基荧光素敏化TiO2纳米粒子的光致电子转移的荧光特性研究

通过水解TiCl₄制备了锐钛矿结构TiO₂纳米粒子, 并用时间分辨荧光光谱研究了5(6)CFL(5(6)-Carboxyfluorescein, 简称5(6)CFL)染料敏化TiO₂纳米粒子体系的光致电子转移动力学. 5(6)CFL染料敏化TiO₂纳米粒子能形成电荷转移复合物, 这归因于染料分子的激发电子态波函数Ψ(D^*)与电荷分离态波函数Ψ(D⁺ +e^-)之间的耦合作用. 当激发5(6)CFL染料敏化TiO₂纳米粒子体系时, 电子以两种不同方式注入TiO₂纳米粒子导带: 第一, 通过5(6)CFL染料分子的激发态注入; 第二, 从电荷转移复合物(5(6)CFL/TiO₂)直接注入. 时间分辨荧光光谱表明, 在水溶液中纯5(6)CFL染料的荧光以寿命为τ₁=41 ps (74.4%) 和τ₂=3.22 ns (25.6%) 的双e指数衰减, 而5(6)CFL染料敏化TiO₂纳米粒子体系的荧光分别以时间常数为τ₁=44 ps (90.4%), τ₂=478 ps (8.6%) 和τ₃=2.41 ns (1.0%) 的三e指数衰减. 本文的研究工作能够为染料敏化太阳能电池的光致电子转移机理提供有价值的参考.     

TiO2 Nanoparticles Produced by Electric-Discharge-Nanofluid-Process as Photoelectrode of DSSC

利用自制TiO₂纳米粒子研究敏化染敏太阳能电池. 使用自制的旋转涂布加热平台装置将产出的TiO₂粒子均匀的涂布在ITO导电玻璃上形成薄膜,浸泡于N-719 染料中12小时以上作为DSSCs的光电极 元件,最后完成染料敏化太阳能电池的系统组装并进行光电转换效率测量. 实验结果表明,放电过程产出的TiO₂纳米粒子具有锐钛矿晶相,粒径尺寸可控制在20～70 nm,粒子表面电位约为-30 mV,是稳定的纳米悬浮夜. 添加0.5 mL 的Triton X-100在导电玻璃表面上,利用的旋转涂布加热到22 oC可以制得厚度均匀缜密的薄膜结构,不但粒子不受到热处理效应与介面活性剂的影响而发生晶相改变,并且薄膜也有良好的染料吸附效果. 较厚二氧化钛薄膜的光电极会提升敏化染敏太阳能电池的效率. 实验结果得知,以15 μm的二氧化钛薄膜组装DSSCs测得最高效率2.15%,但是当薄膜厚度超过15 μm 则会导致开路电压与充填因子逐渐下降,光电转换效率变差.     

碳-锌共掺杂锐钛矿相TiO2 电子结构与光学性质的第一性原理研究

近年来的理论和实验研究表明,通过不同离子共掺杂TiO₂是减小其禁带宽度的一种有效方法.本文采用基于第一性原理的平面波超软赝势方法研究了C和Zn共掺杂TiO₂的能带结构、态密度和光学性质.计算结果表明C-Zn共掺杂导致导带相对Fermi能级发生了明显的下降,同时在TiO₂的导带下方与价带上方形成了新的杂质能级,使TiO₂的禁带宽度变小, TiO₂的光学吸收带边产生红移. 杂质能级可以降低光激发产生的电子-空穴对的复合概率, 提高TiO₂的光催化效率. 此外, 掺杂后TiO₂在可见光区的吸收系数有明显增加, 能量损失也明显减小.     

基于薄膜电极溶胶修饰的染料敏化太阳电池光电特性研究

染料敏化太阳电池(DSC)中的纳米薄膜电极 是决定太阳电池光电转换性能的重要组成部分. 为改善薄膜电极特性, 采用了不同浓度的TiO₂溶胶对DSC光阳极导电玻 璃和纳米TiO₂多孔薄膜进行不同方式的界面处理. 利用X射线衍射方法对制备得到的多孔薄膜以及溶胶经高温处理 后致密层中纳米TiO₂颗粒的尺寸及晶型进行了测试. 采用高分辨透射电子显微镜和场发射扫描电子 显微镜观察了纳米颗粒及薄膜微结构形貌. 采用强度调制光电流谱/光电压谱分析了TiO₂溶 胶的不同处理方式对电子传输和复合的影响. 在100 mW· cm^-2光强以及暗环境下分别测试了DSC的伏安输出性能以及暗电流. 结果表明, 不同浓度和处理方式均能较好地抑制暗电流. 溶胶处理后光生电子寿命τ_n延长, 电子传输平均时间τ_d相应缩短. 采用浓度为0.10 mol·L^-1的 溶胶对导电玻璃和多孔膜同时处理, DSC的宏观输出特性最佳, 短路电流密度J_sc提高了10.9%, 光电转换效率η提高了11.9%.     

TiO2表面氧空位对NO分子吸附的作用

采用程序升温热脱附(TPD)实验方法测定了NO在TiO₂表面吸附后的脱附谱，利用 分子轨道 理论研究了TiO₂吸附NO的原子簇模型及吸附前后的原子簇能级变化.结果表明， NO在TiO₂表面吸附后可在两个峰值温度450 和980 K脱附出N₂.TiO ₂表面经预覆氧处理后，N₂ 的脱附量降低.吸附时NO中的O能够占据TiO₂表面氧空位并与N脱离，而N原子则 相互结合成 为N₂脱附.分子轨道理论计算证明在TiO₂(110)表面能够存在氧空位 并具备吸附NO的结构条件.     

飞秒瞬态吸收技术研究有机/无机异质结的超快电荷转移过程

本文检测SQ02在氯苯溶液、Al₂O₃薄膜和TiO₂薄膜中的弛豫过程,从而探究SQ02在单分散态和聚集态下的光物理性质以及相应过程中界面电荷转移过程.实验数据表明,单分散态下SQ02 的寿命约为2 ns,但是,在Al₂O₃薄膜中显著减小到21 ps.电子从激发态SQ02转移到TiO₂薄膜的时间约为2.6 ps,摄入电子量约为89.1%,与基于SQ02的染料敏化太阳能电池光电效应的效率相匹配.此外,一些染料和其他染料一起嵌入纳米晶薄膜中的弛豫时间可达到60 ps.由于其远离TiO₂界面,因此不参与界面电荷转移.     

掺杂质子化石墨相氮化碳增强碳基太阳能电池中钙钛矿的结晶

钙钛矿层的品质极大影响钙钛矿太阳能电池性能. 然而,在溶液法生成多晶钙钛矿膜过程中会不可避免地形成缺陷和陷阱位. 通过在钙钛矿层中嵌入添加物改善钙钛矿晶化,用于减少和钝化缺陷是非常重要的. 本文合成一种环境友好的二维纳米材料质子化石墨相氮化碳(p-g-C₃N₄),并掺杂于碳基钙太阳能电池的钙钛矿层中. 实验证明,在钙钛矿前驱体溶液中添加p-g-C₃N₄不仅能调解碘铅甲胺(MAPbI₃)结晶的成核和生长速率,获得大晶粒尺寸的平滑表面,还能减少钙钛矿层的本征缺陷. 质子化过程在氮化碳表面引入活性基团-NH₂/-NH₃,它们和钙钛矿晶体表面N-H键发生强化学作用,有效地钝化电子陷阱,提高钙钛矿结晶质量. 结果表明,与不掺杂的对照电池(效率为4.48%)和掺杂石墨相氮化碳(g-C₃N₄)电池(效率为5.93%)相比,掺杂质子化石墨相氮化碳(p-g-C₃N₄)的电池获得了6.61%的较高效率. 本工作展示了一种通过掺杂改性添加物改善钙钛矿膜的简单方法,为碳基钙钛矿太阳能电池的低成本制备提供了建议.     

氧化还原可逆Nb2TiO7复合阴极电解池高温水蒸气电解研究

系统地研究Nb₂TiO₇与Nb_1.33Ti_0.67O₄材料相互转变的氧化还原循环可逆性能,同时研究Nb2TiO7和Nb_1.33Ti_0.67O₄样品随温度和氧分压变化的电导率,并与复合电极对称电池和电解池的电化学性能相关联. 在830 oC下,对Nb_1.33Ti_0.67O₄复合电极电解池进行水蒸气的电解研究测试. 电流电压曲线和电解池短期性能测试表明在低电压下主要为电极的还原和活化过程;而在高电压下主要为水蒸气的电解. 当3%H₂O/Ar/4%H_{2气体通入阴极时电解池水蒸气电解的法拉第效率为98.9%;而当通入气体转换为3%H2O/Ar时效率为89%.}     

A novel TiO2 nanoparticles/nanowires composite core with ZrO2 nanoparticles shell coating photoanode for high-performance dye-sensitized solar cell based on different electrolytes

The novel TiO₂ nanopartilces/nanowires (TNPWs) composite with ZrO₂ nanoparticles (ZNPs) shell-coated photoanodes were prepared to fabricate high-performance dye-sensitized solar cell (DSSC) based on different types of electrolytes. Hafnium oxide (HfO₂) is a new and efficient blocking layer material applied over the TNPWs-ZNPs core-shell photoanode film. TiO₂ nanoparticles (TNPs) and TiO₂ nanowires (TNWs) were characterized by X-ray diffractometer (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). DSSCs were fabricated using the novel photoanodes with an organic sensitizer D149 dye and different types of electrolytes namely liquid electrolyte, ionic liquid electrolyte, solid-state electrolyte, and quasi-solid-state electrolyte. The DSSC-4 made through the novel core-shell photoanode using quasi-solid-state electrolyte showed better photocurrent efficiency (PCE) as compared to the other DSSCs. It has such photocurrent-voltage characteristics: short circuit photocurrent (Jsc)?=?19 mA/cm², the open circuit voltage (Voc)?=?650 mV, fill factor (FF)?=?65 %, and PCE (η)?=?8.03 %. The improved performance of DSSC-4 is ascribed to the core-shell with blocking layer photoanode could increased electron transport and suppressed recombination of charge carriers at the TNPWs-ZNPs/dye/electrolyte interface.     

TiO2 treatment using ultrasonication for bubble cavitation generation and efficiency assessment of a dye-sensitized solar cell

In this study, the impacts of different ultrasonic treatments on TiO₂ particles were determined and they were used to manufacture the photoelectrodes of a dye-sensitized solar cell (DSSC). Two methods were used to prepare TiO₂ particles directly sonicated by an ultrasonic horn, and TiO₂ treated indirectly by an ultrasonic cleaner. TEM, XPS analysis was confirmed that cavitation bubbles generated during ultrasonication resulted in defects on the surface of TiO₂ particles, and the defect induced surface activation. To understand the effect of TiO₂ surface activation on energy conversion efficiency of DSSC, ultrasonic horn DSSC and ultrasonic cleaner DSSC were prepared. The UV–vis analysis exhibited that the ultrasonic horn DSSC possessed higher dye adsorption when compared to the ultrasonic cleaner DSSC, and the EIS analysis confirmed that the electron mobility was greatly increased in the ultrasonic horn DSSC. The energy conversion efficiency of the ultrasonic horn DSSC was measured to be 3.35%, which is about 45% increase in comparison to that of the non-ultrasonic treated DSSC (2.35%). In addition to this regard, recombination resistance of ultrasonic horn DSSC was calculated to be 450 Ω·cm², increasing more than two times compared to the non-ultrasonic treated DSSC (200 Ω·cm²). Taken together, these ultrasonic treatments significantly improved the energy conversion efficiency of DSSC, which was not tried in DSSC-related research, and might lead us to develop more efficient practical route in the manufacturing of DSSC.     

Photovoltaic and impedance properties of dye-sensitized solar cell based on nature dye from beetroot

The present study involves fabrication and photovoltaic characterization including impedance properties of dye-sensitized solar cells based on natural dye from beetroot. The electrode of the cell was prepared with commercial Fluorine-doped Tin Oxide glass with 100 μm layer of nanostructured TiO₂ whereas, the counter electrode consisted of platinum-coated glass. Fresh juice was extracted from beetroot to use as dye. The dye exhibited high absorption in visible range. Photovoltaic measurements of the solar cell gave a short circuit current density (Jsc) of 130 μA/cm² and an open-circuit voltage (VOC) of 0.38 V under AM 1.5 illumination intensity. The VOC and Jsc showed linear behavior at higher values of illumination intensities. The conductance-voltage, the capacitance-voltage and the series resistance voltage characteristics of the dye solar cell was measured at frequency range from 5 kHz to 5 MHz to study performance of the dye-sensitized solar cells with natural dyes.     

Analysis of adsorption properties of N719 dye molecules on nanoporous TiO2 surface for dye-sensitized solar cell

Ordered nanoporous TiO₂ materials (MK-TiO₂, MS-TiO₂, and MU-TiO₂) were synthesized for the dye-sensitized solar cell (DSSC) by using different silica templates such as KIT-6, SBA-15, and MSU-H. To prepare a photoelectrode in DSSC, cis-bis(isothiocyanato)bis(2,2′-bipyridyl-4,4′-dicarboxylato)-ruthenium(II)bis-tetrabutylammonium dye (N719) was adsorbed onto the synthesized nanoporous TiO₂ materials. The samples were characterized by XRD, TEM, FE-SEM, AFM, and N₂ adsorption analyses. The photovoltaic performance of DSSC was evaluated from the overall conversion efficiency, fill factor, open-circuit voltage, and short-circuit current from the I-V curves measured. It was found that the photoelectric performance is highly dependent on the adsorption properties of N719 dye molecules on the nanoporous TiO₂ replicas (MK-TiO₂, MS-TiO₂, and MU-TiO₂) synthesized from different silica templates.     

Effect of surface roughness of TiO2 films on short-circuit current density of photoelectrochemical cell of ITO/TiO2/PVC-LiClO4/graphite

This paper reports the effect of surface topography of titanium dioxide films on short-circuit current density of photoelectrochemical solar cell of ITO/TiO₂/PVC-LiCLO₄/graphite. The films were deposited onto ITO-covered glass substrate by screen-printing technique. The films were tempered at 300 °C, 350 °C, 400 °C, 450 °C and 500 °C for 30 min to burn out the organic parts and to achieve the films with porous structure. The surface roughness of the films were studied using scanning electron microscope (SEM). Current–voltage relationship of the devices were characterized in dark at room temperature and under illumination of 100 mW cm⁻² light from tungsten halogen lamp at 50 °C. The device utilising the TiO₂ film annealed at 400 °C produces the highest short-circuit current density and open-circuit voltage as it posses the smoothest surface topography with the electrolyte. The short-circuit current density and open-circuit voltage of the devices increase with the decreasing grain size of the TiO₂ films. The short-circuit current density and open-circuit voltage are 0.6 μA/cm² and 109 mV respectively.     

Explanation of Effect of Added Water on Dye-Sensitized Nanocrystalline TiO2 Solar Cell： Correlation between Performance and Carrier Relaxation Kinetics

Time-resolved mid-IR transient absorption spectroscopy is employed to explore the mechanism of improving the performance of dye-sensitized TiO2 solar cell （DSSC） when a certain amount of H2 0 is added into the electrolyte. The relaxation kinetics of dye-sensitized TiO2 nanocrystalline film and the corresponding DSSC performance are investigated under different conditions. It is found that the interracial charge recombination is retarded and electron injection efficiency is increased in the water vapour and in the electrolyte when D20 is added. The values of open-circuit photovoltage Voc and the short-circuit photocarrent Jsc of the cells are linearly correlated to the product of the two decay time constants. We also observed that Voc well correlates with electron injection efficiency. It provides a preliminary microscopic account for the function of the added water in improving the performance of DSSCs.     

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.     

负偏压作用下染料敏化太阳电池界面及光电性能研究

太阳电池组件由于局部电压不匹配,其中部分电池可能较长时间工作在负偏压状态下,从而影响电池光电性能.借助拉曼光谱、电化学阻抗谱和入射单色光量子效率(IPCE)等测试手段,研究长期负偏压作用下染料敏化太阳电池光电性能的变化及其影响机理.拉曼光谱研究结果表明:电池在1000 h负偏压作用下,电解质中阳离子(Li⁺)会向光阳极(TiO₂电极)移动并嵌入TiO₂薄膜中;长期负偏压作用还会致使TiO₂/电解质界面阻抗增大和IPCE下降,导致电池开路电压升高和短路电流减小.通过加入苯并咪唑(BI)添加剂,经1000 h负偏压后电池的拉曼光谱实验表明,BI能在一定程度阻碍Li⁺的嵌入,电池具有较好的长期稳定性.不同负偏压下的老化实验进一步表明,通过加入添加剂能够使电池在长期负偏压下保持较好的稳定性. 关键词： 染料敏化 太阳电池 组件 负偏压     

Cocktail effect of Fe2O3 and TiO2 semiconductors for a high performance dye-sensitized solar cell

The bi-semiconductors of TiO₂ and Fe₂O₃ were used as a photoelectrode material in a high performance dye-sensitized solar cell due to cocktail effects from the two conduction bands. The size of the semiconductors was reduced by using a paint shaker to enlarge the contact area of the semiconductor with the dye or electrolyte. The fill factor and the efficiency of the prepared dye-sensitized solar cell were improved by over 16% and 300%, respectively; these parameters were measured from a current-voltage curve that was based on the effects of the Fe₂O₃ co-semiconductor and the size reduction. A mechanism is suggested wherein the conduction band of Fe₂O₃ works to prohibit the trapping effects of electrons in the conduction band of TiO₂. This result is attributed to the prevention of electron recombination between electrons in the TiO₂ conduction band with dye or electrolytes. The mechanism is suggested based on impedance results, which indicate improved electron transport at the interface of the TiO₂/dye/electrolyte.     

Titania surface modification and photovoltaic characteristics with tungsten oxide

WO₃-coated TiO₂ film was prepared by depositing TiO₂ suspension containing small amounts of ammonium tungstate solution. The morphology and structure of the samples were characterized with high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and photoluminescence (PL) emission spectrum. The results showed that WO₃ formed a coating layer on surface of TiO₂ and significantly reduced the surface traps of TiO₂ nanoparticles. Transient photovoltage and electrochemical impedance measurements (EIS) were employed to study the charge separation/recombination process. The results revealed that the charge recombination was greatly retarded and the electron lifetime was increased due to the coating layer of WO₃. These observations showed good correlation with current-voltage analyses of dye-sensitized solar cell fabricated from these films, with WO₃ overlayer resulting in an increase in open-circuit voltage of up to 37 mV and 11% improvement in overall device efficiency.