基于石墨烯基电极染料敏化太阳能电池的研究进展

对近几年石墨烯基电极染料敏化太阳能电池的研究成果进行了追踪,分析了多种改性石墨烯电极应用于染料敏化太阳能电池后能量转换效率变化的原因,深入研究了改善石墨烯对电解质的还原电催化反应活性物理机理,为解决该电池存在的问题理清了思路,对该方向未来的研究工作给出了建议,探索和制备新材料以进一步打破石墨烯的层间堆叠是提高该电池性能的关键。     

二硒化铁/还原氧化石墨烯的制备及其在染料敏化太阳能电池中的应用

通过水热反应合成出二硒化铁/还原氧化石墨烯(FeSe₂/rGO)复合材料, 并将其作为对电极材料应用于染料敏化太阳能电池(DSSC). 利用X射线衍射、拉曼光谱、场发射扫描电子显微镜和高分辨透射电子显微镜对FeSe₂/rGO的结构和形貌进行了表征. 利用循环伏安法、电化学阻抗谱和Tafel曲线测试分析了FeSe₂/rGO对电极的电催化活性. 结果表明: FeSe₂呈纳米棒结构, 长度在100-200 nm之间, 且紧密地附着在rGO 的表面, FeSe₂/rGO对电极对I₃^-的还原具有很好的催化活性. 电池的J-V曲线测试显示: 基于FeSe₂/rGO对电极的DSSC的转换效率达到了8.90%, 相比基于单纯的FeSe₂对电极的DSSC(7.91%)和rGO对电极的DSSC(5.24%)都有了显著提高, 甚至优于铂对电极的DSSC(8.52%).     

Light scattering of nanocrystalline TiO2 film used in dye-sensitized solar cells

This paper studies the light scattering and adsorption of nanocrystalline TiO2 porous films used in dye-sensitized solar cells composed of anatase and/or rutile particles by using an optical four-flux radiative transfer model. These light properties are difficult to measure directly on the functioning solar cells and they can not be calculated easily from the first-principle computational or quantitative theoretical evaluations. These simulation results indicate that the light scattering of 1 25 nm TiO2 particles is negligible, but it is effective in the range of 80 and 180 nm. A suitable mixture of small particles （10 nm radius）, which are resulted in a large effective surface, and of larger particles （150 nm radius）, which are effective light scatterers, have the potential to enhance solar absorption significantly. The futile crystals have a larger refractive index and thus the light harvest of the mixtures of such larger rutile and relatively small anatase particles is improved in comparison with that of pure anatase films. The light absorption of the 10μm double-layered films is also examined. A maximal light absorption of double-layered film is gotten when the thickness of the first layer of 10 urn-sized anatase particles is comparable to that of the second larger rutile layer.     

纳米TiO2叶片状阵列电极的制备及其在染料敏化太阳电池中电子的输运性能

在低温条件下采用定向刻蚀技术, 对金属Ti片表面用H₂O₂溶液进行刻蚀氧化, 制备了垂直生长的纳米TiO₂叶片状阵列薄膜电极. 通过X射线衍射分析表明, 纳米TiO₂叶片状阵列薄膜经500 ℃下烧结1 h后, 从无定型转变为锐钛矿相. 场发射扫描电子显微镜观察表明: 在80 ℃下的H₂O₂溶液刻蚀氧化, 经1 d制备得到的是Ti片表面垂直生长的叶片状阵列, 其形貌均匀且完整地 关键词： 2')" href="#">纳米TiO₂ 叶片状阵列电极 染料敏化太阳电池 电子传输     

三维多孔复合碳层对电极的制备及其光伏性能研究

基于TiO_2光阳极、Pt对电极的染料敏化太阳能电池(DSSC)因其优异的光电转换特性受到了广泛的关注,然而Pt昂贵的价格制约了其发展与应用.针对这一问题,本文设计、制备了一种由相对致密且高导电的石墨膜(PC层,底层)及多孔碳纳米颗粒膜(CC层,顶层)构成的低成本、高性能三维多孔复合碳层对电极.基于该CC/PC对电极的DSSC具有优异的光伏性能:在1.5标准太阳光照射下,其填充因子高达65.28%(较Pt对电极高4.1%)、光电转换效率高达5.9%(为Pt对电极的94.2%). CC/PC对电极的优异光伏性能主要归因于其独特的三维多孔导电结构,该结构有极高的比表面积和丰富的催化反应活性位,有利于电子的快速传输及离子的快速转移,在这些因素的协同作用下,其光电转换性能大大改善.     

Hybrid photoanode films based on sparse ZnO rod array-TiO2 nanoparticles in dye-sensitized solar cells

ZnO-TiO2 hybrid photoanodes were fabricated via the doctor-blade method by integrating vertically-grown sparse ZnO arrays with hydrothermal TiO2 nanoparticles. A special surface-coating technique was developed to deposit a thin TiO2 layer on the surface of ZnO rods. Microstructure, optical and photoelectrochemical performance of the hybrid photoanodes were investigated. The denser ZnO array exhibited bad filling behavior of nanoparticles in the interspace of ZnO rods, strong scattering and low conversion efficiency (0.27%). The sparser array showed a much better integrated microstructure, improved transmittance and high conversion efficiency (2.68%). The surface modification of ZnO rods by the TiO2 thin layer was found useful in improving the interfacial microstructure between the ZnO rod and the TiO2 bulk film, and the total conversion efficiency of 3.01% was achieved, higher than that of the pure TiO2 nanoparticle cell (2.93%). The increased scattering effects on the incident light, the enhanced electron transportation at TiO2/dye/electrolyte interface, and the inhabited recombination were responsible for this improvement.     

Electrochemical properties of TiO2 nanoparticle/nanorod composite photoanode for dye-sensitized solar cells

A unique composite of TiO₂ nanoparticles (NPs) and nanorods (NRs) has been used to fabricate a photoelectrode for developing dye-sensitized solar cells (DSSCs) with higher sensitivity. The TiO₂ nanorods were synthesized using a mechanical process, in which electrospun TiO₂ nanofibers was grinded in a controlled way to obtain uniform size distribution. The characteristics of electron transport, recombination lifetime and charge collection were investigated by intensity-modulated photocurrent spectroscopy (IMPS) and intensity-modulated photovoltage spectroscopy (IMVS). Photoelectrodes prepared with the composites of NRs and NPs showed significant improvements in electron transportation compared to only NP photoelectrodes, which would enhance the photovoltaic performance of DSSCs. IMPS and IMVS measurements show that fast electron transport and slightly decreased recombination lifetime resulted in the improvement of efficiency. The highest energy conversion efficiency obtained from the photoelectrodes fabricated with the as-prepared rutile TiO₂ nanofibers at 5 wt% NR content was up to 6.1% under AM1.5G solar illumination. The results demonstrate that the composite nanostructure can take advantage of both the fast electron transport of the nanorods and the high surface area of the nanoparticles.     

Correlation between microstructure and property of electroless deposited Pt counter electrodes on plastic substrate for dye-sensitized solar cells

Flexible Pt counter electrodes (CEs) were prepared on indium-doped tin oxide coated polyethylene naphthalate (ITO-PEN) substrate by electroless deposition. The correlation between the microstructure and the property of the Pt CEs was investigated. Results showed that isolated Pt nanoparticles were uniformly distributed on the ITO surface at a short deposition duration, and then grew with the deposition duration, leading to the interconnection of adjacent Pt nanoparticles. The interconnection of Pt nanoparticles was beneficial to the electrical property of the Pt CEs, while it was unfavorable to the electrocatalytic property of the Pt CEs. A microstructure model was proposed to explain the correlation between the microstructure and the property of the Pt CEs. In addition, the Pt CEs showed low charge transfer resistance (1.66-0.58 Ω cm²), which was comparable to that (1.16 Ω cm²) of the conventional sputtered Pt CE. The high electrocatalytic property of the electroless deposited Pt CEs makes the assembled DSCs present comparable energy conversion efficiency of the DSCs using sputtered Pt CE.     

Electron transport in dye-sensitized solar cells based on TiO2 nanowires

Anatase titanium dioxide nanowire arrays were prepared by hydrothermally oxidizing titanium foils in aqueous alkali and transferred onto fluorinated tin oxide(FTO)glass for use as the photoanodes of front side illuminated dye-sensitized solar cells(DSCs).Electrochemical impedance spectroscopy(EIS)measurement was applied to compare the electron transport and recombination properties of DSCs using TiO2nanowire films and TiO2nanoparticle films as photoanodes.It was found that the nanowire array films possess smaller electron transport resistance(Rt)and larger electron diffusion length(Le)in the photoanodes,suggesting that the nanowire arrays can enhance the electron transport rate and have a potential to improve the charge collection efficiency of DSCs.     

电极表面改性对染料敏化太阳电池性能影响的机理研究

采用强度调制光电流谱(IMPS)和强度调制光电压谱(IMVS)技术,从染料敏化太阳电池(DSC)电子传输和复合角度对比了不同光强下导电玻璃表面阻挡层及TiO₂薄膜优化使电池性能改善的内在原因.阻挡层的引入和TiO₂薄膜的优化均通过电沉积法实现.结果表明,对多孔薄膜电极的不同改性均提高了电池的短路电流J_sc和效率η,但对电子传输和复合过程的作用机理有所不同:前者延长了电子寿命τ _n,但电子传输时间τ _d变化不明显;而后者则主要是延长τ _n的同时也缩短了τ _d. 关键词： 染料敏化 太阳电池 调制光电流谱/调制光电压谱 电子输运     

Theoretical study of electronic structure and excited states properties of two dyes for dye-sensitized solar cells

Two conjugated organic dyes comprising the benzo[b]furan moieties as the electron donor and cyanoacetic acid moieties as the electron acceptor/anchoring groups have been investigated using a quantum chemical method. The molecular equilibrium geometries and ground state character were studied using density functional theory. Absorption spectra were obtained using time-dependent density functional theory and semiempirical ZINDO. The nature of absorption spectra was further studied using 2D and 3D real-space analysis; here, 2D real-space analysis showed electron–hole coherence, and 3D real-space analysis showed intramolecular charge transfer during photo-excitation. As important parameters, excited state oxidation potential and driving force energy were obtained to reveal the relationship between molecular structure and performance of two compounds.     

大面积染料敏化太阳电池的串联阻抗特性研究

在电子扩散微分方程的基础上,研究了染料敏化太阳电池光生电流和光生电压随光照强度不同的变化关系.提出敏化太阳电池串联阻抗功率损耗模型,理论模拟了大面积电池（有效面积>1 cm²）光电转换效率随多孔薄膜有效面积宽度变化的曲线、透明导电基底膜与银栅极的比接触电阻以及在不同入射光强下银栅极体电阻对大面积染料敏化太阳电池光伏性能的影响.结果表明透明导电基底膜的方块电阻和银栅极体电阻对大面积染料敏化太阳电池的性能有很大影响,而这种影响随光强的减弱逐渐减小. 关键词： 染料敏化 太阳电池 串联阻抗 光电转换效率     

石墨烯衍生物作为有机太阳能电池界面材料的研究进展

本文综述了石墨烯及其衍生物作为界面材料在有机太阳能电池中的应用, 包括作为阳极界面层、阴极界面层和叠层电池中间层等方面. 氧化石墨烯由于较好的透光性, 易于分散在水溶液中与溶液加工等优点已被应用在有机太阳能电池中. 对氧化石墨烯作为阳极界面层的研究包括通过部分还原或掺杂提高其导电性、通过引入高负电性原子提高其表面功函数, 以及通过与其他材料复合提高性能等. 同时, 本文综述了石墨烯衍生物及复合材料作为有机太阳能电池阴极界面层和叠层电池中间层的研究. 最后本文展望了石墨烯及其衍生物在有机太阳能电池与有机无机复合钙钛矿太阳能电池中的应用前景.     

基于半经验模型对大面积染料敏化太阳电池性能影响因素的研究

以影响大面积染料敏化太阳电池性能的几个物理参量和几何参量为切入点, 分析了内部电阻对电池性能的影响, 针对几种构型不同的大面积电池, 建立了效率的半经验模型. 根据并联、串联、和各单元独立式串并联的大面积电池的相关物理参量和几何参量, 对电池效率进行了计算. 通过比较计算值与测试值的偏差, 分析了半经验模型的适用性. 在半经验模型的基础上, 分析了相关物理参量和几何参量对电池性能的影响. 结果表明, 在实际应用中, 通过半经验模型分析物理参量和几何参量的影响, 可以优化大面积电池的性能.     

染料敏化太阳电池中TiO2颗粒界面接触对电子输运影响的研究

采用溶胶-凝胶法制备TiO₂浆料,通过丝网印刷技术印刷和不同温度曲线烧结TiO₂薄膜,并应用于染料敏化太阳电池(DSC).高分辨透射电子显微镜发现,低温下多孔薄膜中TiO₂颗粒之间呈现点接触,510 ℃烧结后TiO₂颗粒间由点接触变为面接触,近邻颗粒数增多,接触面积增大.同时采用强度调制光电流谱(IMPS)和强度调制光电压谱(IMVS)技术,研究了不同颗粒接触方式和接触面积对电子传输与复合的影响.结果表明:在420- 510 ℃之间,随着烧结温度提高,颗粒接触面积增大,电子传输时间(τ _d)缩短,电子有效扩散长度(L _n)增大,暗电流减小;当烧结温度达到550 ℃时,薄膜比表面积减小,多孔结构坍塌,表面态密度增大,电子传输时间(τ _d)增大.电池光伏特性研究表明:在480-510 ℃范围内烧结得到的TiO₂薄膜,电池短路电流密度(J_sc)最佳,电池效率(η)最好. 关键词： 界面接触 电子输运 暗电流 染料敏化太阳电池     

Microwave-reduced graphene oxide for efficient and stable hole extraction layers of polymer solar cells

Microwave-assisted reduced graphene oxide (MR-GO) layer was applied to hole extraction layer (HEL) of polymer solar cells (PSCs) and was compared with the widely used poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) (PEDOT:PSS) in bulk hetero-junction (BHJ) solar cells. The power conversion efficiency (PCE) of 3.57% was achieved with the MR-GO layer, which is 21% higher than that of PSCs with the conventional PEDOT:PSS HEL material. This enhancement of PCE is mainly attributed to the increase of short-circuit current density originated from the hydrophobic surface of the MR-GO layer. The hydrophobic graphene oxide surface is believed to improve wetting property and physical contact of active blends. In addition, the MR-GO interfacial layer is found to show the excellent device stability in atmospheric condition. The PCE of conventional PEDOT:PSS based PSCs showed total degradation when the device was exposed to atmospheric condition for 1000 h without any encapsulation, while that of MR-GO based PSC showed over 85% of PCE.     

染料敏化太阳电池中TiO2膜内电子传输和背反应特性研究

采用强度调制光电流谱(IMPS)和强度调制光电压谱(IMVS)研究电池内部电子传输机理和电子背反应动力学特性.利用理论表达式对不同TiO₂多孔膜厚度(d)的电池实验数据进行了拟合,得到了电池的吸收系数(α)、电子扩散系数(D_n)、电子寿命(τ_n)、电子传输时间(τ_d)和入射单色光光电转化效率(IPCE)等微观参数的数值.研究表明：膜薄有利于加快电子传 关键词： 染料敏化 太阳电池 IMPS/IMVS 传输     

Application of polyaniline nanowires electrodeposited on the FTO glass substrate as a counter electrode for low-cost dye-sensitized solar cells

Polyaniline nanowires (PANI NWs) were deposited onto fluorine-doped tin oxide (FTO) glass substrate using the cyclic voltammetric method with aniline monomer precursor in HCl aqueous solution. The secondary oxidation peak plays an important role in polymerization of aniline monomer and the optimization of catalytic activity of PANI-based counter electrodes was achieved by controlling the number of cycles. The photovoltaic performance of the dye-sensitized solar cells (DSSCs) with PANI NWs counter electrodes (CEs) was optimized at 4th cycles, and then following parameters were obtained: J_sc = 17.2 mA cm⁻², V_oc = 0.71 V, FF = 59.3%, and efficiency (η) = 7.24%. While, J_sc = 14.7 mA cm⁻², V_oc = 0.77 V, FF = 70.6%, and efficiency (η) = 7.98% in cells with Pt CEs. The PANI NWs were attractive as an alternative CEs for the low-cost DSSCs instead of Pt.     

TiO2颗粒尺寸对染料敏化太阳电池内电子输运特性影响研究

采用强度调制光电流谱(IMPS)和强度调制光电压谱(IMVS)研究了染料敏化太阳电池(DSC)内部电子传输和背反应动力学特性.在纳米TiO₂薄膜厚度相同的情况下,借助于IMPS/IMVS测量了由3种不同TiO₂颗粒尺寸大小薄膜制备出DSC的电荷传输特征参数值.IMPS/IMVS理论模型拟合实验测量数据的结果表明：在不同入射光强下,随着颗粒尺寸的增大,电子扩散系数(D_n)增大,而电子寿命(τ_n 关键词： 染料敏化 太阳电池 IMPS/IMVS 电子传输