二次掺杂聚吡咯/聚噻吩膜的制备及其光电性能

为了研究磷酸锌二次掺杂聚吡咯/聚噻吩膜的光电及防腐蚀性能,采用直接接触氧化技术在磷酸锌溶液中制备出掺杂聚吡咯/聚噻吩,再用磷酸锌在脱掺杂聚吡咯的基础上制备出性能优良的二次掺杂聚吡咯/聚噻吩膜。采用循环伏安曲线、扫描电镜和动电位极化曲线测试了二次掺杂聚吡咯/聚噻吩/磷酸锌复合材料的微观形貌及光电性能,并与一次掺杂及未掺杂的聚吡咯/聚噻吩进行了对比。测试结果表明:不锈钢表面覆盖掺杂的聚吡咯/聚噻吩膜都有较好的光电性能,以二次掺杂聚吡咯/聚噻吩膜性能为最好。与未掺杂的聚吡咯/聚噻吩高分子膜相比,二次掺杂聚吡咯膜的腐蚀电位比纯聚苯胺膜提高了约0.989 V,自腐蚀电流降低了约2个数量级。     

用于染料敏化太阳能电池的聚醚型聚氨酯凝胶电解质的研究

以聚乙二醇(PEG)和异氰酸酯为单体,添加由1,4-丁内酯溶解(C4H9)4NI/I2配制的液态电解质,形成一系列的聚醚型聚氨酯凝胶电解质。通过动态机械热分析(DMTA)、傅里叶红外光谱仪(FTIR)、差示扫描量热仪(DSC)、X射线衍射(XRD)等方法对聚氨酯凝胶电解质结构进行表征,测试结果表明此类电解质具有良好的热稳定性和非晶相结构。同时,研究了PEG分子量、异氰酸酯单体的改变对聚氨酯凝胶电解质电导率的影响,发现PEG分子量的增大使聚氨酯凝胶电解质的电导率先增加后降低,当PEG分子量为10000时,所合成凝胶电解质的电导率达到最大,为6.13mS/cm,而异氰酸酯单体的改变对电解质的电导率影响不大。扫描电子显微镜(SEM)测试结果表明这可能与聚氨酯中形成的不同网状结构有关。在100mW/cm2的入射光强下,不同分子量PEG制备的聚氨酯凝胶电解质组装的染料敏化太阳能电池(DSSCs)的光电性能不同,其中PEG分子量为10000合成的聚氨酯凝胶电解质组装的电池的光电转化效率最高,为4.29%。     

电子辐照改性PAN/PEO基体凝胶电解质对染料敏化太阳电池性能的提高

采用电子束（EB）对聚丙烯腈/聚氧化乙烯（PAN/PEO）凝胶电解质进行了剂量为13～260 kGy的辐照, 并对辐照改性的电解质组装的染料敏化太阳电池(DSSC)进行了性能测量。 结果表明, 改性后的DSSC的光电转化效率比改性前的高; 并且随EB辐照剂量的增加, DSSC效率先迅速增加(0～65 kGy), 然后缓慢减小(65～130 kGy)直至趋于一个平衡值(130～260 kGy)。 提升DSSC效率的最佳辐照剂量为65 kGy, 此时效率提高了约36%。 对比DSSC短路电流、 开路电压和填充因子随辐照剂量的变化, 发现DSSC效率的提高主要是由短路电流的提高引起的。 测量表明, 辐照改性后的DSSC时间稳定性得到了改善, 并且辐照剂量越高, 稳定性的改善越明显。 In this work, PAN/PEO (polyacrylonitrile/polyethylene oxide) based gel electrolyte was irradiated by electron beam (EB) with dose from 13 to 260 kGy. Then, DSSC (dye sensitized solar cell) was fabricated by the irradiated electrolyte and characterized. The results show that the efficiency of the DSSC fabricated by irradiated electrolyte is promoted comparing with DSSC fabricated by un irradiated electrolyte. And with irradiation dose increasing, the DSSC efficiency increases rapidly at first (0～65 kGy), then, drops down slowly (65～130 kGy), finally trends to a stable value (130～260 kGy). It indicates that there is an optimal irradiation dose, at which the promotion of DSSC efficiency is the highest, approximate 36%. Observed from the change of short circuit current, open circuit voltage and fill factor, short circuit current promotion by EB irradiation is found to be the main reason of DSSC performance promotion. The time stability measurement of the DSSC indicates that EB irradiation on PAN/PEO electrolyte reduces the loss of efficiency and the limiting effects become more apparent as the irradiation dose increases.     

基于离子特异性效应调控聚电解质络合物水凝胶自修复性能

通过两步聚合法制备了甲基丙烯酰胺丙基三甲基氯化铵（MPTC）和苯乙烯磺酸钠（NaSS）聚电解质络合物（PMPTC/PNaSS）水凝胶,研究了基于离子特异性效应调控聚电解质络合物水凝胶的自修复性能.通过不同种类离子对PMPTC/PNaSS水凝胶的特异性掺杂,可影响水凝胶中聚电解质链间静电相互作用以及链的运动能力,从而控制水凝胶的力学性能以及自修复性能.结果表明,当掺杂阴离子从结构构造型的强水化离子变为结构破坏型的弱水化离子,聚电解质络合物水凝胶的自修复效率会逐渐增加.主要是由于结构破坏型阴离子可以更加有效地打开水凝胶中的离子键,提高聚电解质链的运动能力和自修复效率.     

基于中性水凝胶/取向碳纳米管阵列高电压柔性固态超级电容器

随着科技发展和时代进步,发展质轻便携、安全环保的高性能储能器件变得日趋重要,对柔性固态超级电容器的研究也应运而生.柔性电极材料及电解质的选用是设计柔性固态超级电容器的关键因素,近年来一直是研究的热点.考虑到环境污染及实际需求问题,本文采用中性凝胶电解质对具有高比表面积、良好导电性及取向性的碳纳米管阵列进行包埋处理,所形成的柔性复合薄膜作为电极材料,设计制备三明治结构的柔性超级电容器件.通过改变凝胶电解质中所加入的无机盐电解质种类,调控器件的电化学储能性质.最终在聚乙烯醇PVA-NaCl作为凝胶电解质时,整个器件比容量最高达104.5 mF·cm~(–3),远高于有机离子凝胶与碳管阵列形成的复合器件以及无规分布的碳纳米管与水凝胶形成的复合器件,同时获得了0.034 mW·h·cm~(–3)的最大能量密度,并且具有良好的倍率性能、循环稳定性及抑制自放电的效果,并在高电压1.6 V下依然保持良好的化学稳定性.这种中性凝胶/碳管阵列复合超级电容器件不仅满足了绿色安全、柔性便携的要求,未来在医学可植入器件等领域也具有很好的应用前景.     

TiO_2/Eu~(3+)下转换薄膜的制备及其在染料敏化太阳能电池中的应用

采用溶胶-凝胶法制备了TiO2/Eu3+下转换薄膜,并对其光学特性和光电性能进行了分析。将其应用到染料敏化太阳能电池(DSSC)中,利用其下转换特性将部分紫外光转换为能被染料吸收利用的可见光,提高了DSSC的光照强度,促进了短路电流的增大。荧光光谱显示,下转换薄膜在受到394 nm紫外光照射时可发射出550~640 nm的可见光,具有下转换功能特性。下转换薄膜可以增加电池对太阳光的吸收范围,当涂有二层下转换薄膜时,短路电流密度从8.05 mA·cm-2提高到9.62 mA·cm-2,光电转换效率从3.67%提高到4.32%,转换效率相对提高了17.7%。     

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.     

PAMS基凝胶型聚合物锂电池的制备及电化学性能表征

将丙烯腈、甲基丙烯酸甲酯和苯乙烯按一定的摩尔比同电解液LB-302(1mol/LLiPF6的1∶1EC∶DEC溶液)进行混合制成凝胶型聚合物电解质前驱体,将此凝胶型聚合物电解质前驱体同电极材料和隔膜一起组装成扣式CR2032锂电池,再将此电池经γ射线原位辐照聚合制得三元共聚物(PAMS)为基体的凝胶型聚合物电解质可充电锂电池.用傅里叶红外和差示扫描量热对原位辐照聚合所制得的PAMS的结构和热稳定性进行了表征.并用交流复阻抗谱、循环伏安法和恒流充放电等技术对PAMS基凝胶型聚合物电解质锂电池进行了电化学性能表征.结果表明采用原位聚合法制备凝胶型聚合物锂电池不仅工艺简便,而且所制得的电池的充放电性能较好.     

聚吡咯-钛酸钡复合材料的制备和吸波性能

通过化学氧化法在乳液聚合体系中合成了聚吡咯. 然后以脱脂棉作为模板使用溶胶-凝胶法合成了钛酸钡微带. 以合成的两种材料作为基体相按不同的比例制备了聚吡咯-钛酸钡复合材料. 复合材料的结构形貌和性能通过红外、X射线衍射、扫描电镜以及网络分析仪检测. 使用PNA3629D网络分析仪测定复合材料在S和C波段的复数介电常数和微波损耗. 研究了钛酸钡和聚吡咯的质量比对复合材料吸波性能的影响. 提出了聚吡咯-钛酸钡复合材料的吸波机理.     

离子液体凝胶聚合物电解质PP13TFSI-LiTFSI-P(VdF-HFP)的电化学性能 (cited: 1)

采用溶液浇铸法将N-甲基-N-丙基哌啶二(三氟甲基磺)亚胺(PP13TFSI)、二(三氟甲基磺)亚胺锂与偏氟乙烯-六氟丙烯共聚物(P(VdF-HFP))混合制备离子液体凝胶聚合物电解质(ILGPEs). 通过扫描电子显微镜观察发现,这种离子液体凝胶聚合物电解质由于液体相的均匀分布而具有疏松的结构. 采用电化学阻抗、计时电流法、线性扫描伏安法测试了电解质的离子电导率、锂离子迁移数和电化学窗口. 室温下离子液体凝胶聚合物电解质的离子电导率和锂离子迁移数分别是0.79 mS/cm和0.71,电化学窗口为0～5.1 Vvs. Li⁺/Li. 电池性能测试表明,这种离子液体凝胶聚合物电解质在Li/LiFePO₄电池中是稳定的,放电容量在30、75和150mA/g倍率下分别为135、117和100 mAh/g,电池经100个循环后容量保持在100%而几乎没有衰减.     

Polymer electrolyte for photoelectrochemical cell and dye-sensitized solar cell: a brief review

This paper reviews the use of solid polymeric electrolyte (SPE) and gel polymeric electrolyte (GPE) in photoelectrochemical cell (PEC) and dye-sensitized solar cell (DSSC). The structure of PEC and its working principle are presented. The various types of polymer electrolytes utilized in PEC and DSSC have been highlighted in this review. It also highlights the comparison of performance of PEC and DSSC utilizing those polymer electrolytes. This review is completed with the list of other SPEs that potentially be tested in DSSC.     

Self degradation of polymer electrolyte based dye-sensitized solar cells and their remedy

Self degradation of dye-sensitized solar cells (DSSC) has been observed due to shrinkage of the polymer electrolytes at room temperature with a relatively high humidity atmosphere. The cell efficiency has also shown to depend on the shrinkage of the polymer. The actual interface area between the polymer electrolyte and the dye soaked nanoporous TiO₂ electrode has been observed to become reduced for alkali salt complexed poly(ethylene oxide) (PEO) polymer electrolyte. This problem can relatively easily be reduced by two step casting and by incorporating ionic liquids in the polymer electrolyte. A possible reason has been sought as the reduced crystallinity and growth of spherulites in the polymer matrix.     

Utilization of saffron (<Emphasis Type="Italic">Crocus sativus L.</Emphasis>) as sensitizer in dye-sensitized solar cells (DSSCs)

Photoelectrodes of dye-sensitized solar cells (DSSCs) have been prepared using nanosized titanium dioxide that have soaked in a solution of different saffron (Crocus sativus L.) spice content in ethanol. The optimized polyacrylonitrile (PAN)-based gel polymer electrolyte with 40.93 wt.% ethylene carbonate, 37.97 wt.% propylene carbonate, 4.37 wt.% tetrapropylammonium iodide, 9.86 wt.% PAN, 1.24 wt.% 1-butyl-3-methylimidazolium iodide, 4.35 wt.% lithium iodide and 1.28 wt.% iodine has been used as the electrolyte for DSSC. The electrolyte has conductivity of 2.91 mS cm^?1 at room temperature (298 K). DSSCs were also sensitized with saffron solution that has been added with 30 wt.% chenodeoxycholic acid (CDCA) co-adsorbent and designated as DSSC P4. The solar cell converts light-to-electricity at an efficiency of 0.31%. This is 29% enhancement in efficiency for the DSSC without addition of CDCA in the saffron-ethanol solution. The DSSC exhibits current density at short-circuit (J _sc ) of 1.26 mA cm^?2, voltage at open circuit (V _oc ) of 0.48 V and 51% fill factor. DSSC P4 also exhibits the highest incident photon-to-current density of more than 40% at 340 nm wavelength.     

Dye-sensitized solar cells with polymer bindings based on titanium dioxide

An urgent task in the field of sensitized solar cells (DSSC) is to decrease the temperature of thermal annealing of titanium dioxide photoanode. In this work, we use a titania based polymer as organic “polylinker,” which allows low temperature annealing. This polylinker, which is obtained by means of partial hydrolysis of titanium polybutyltitanate or tianium 2-methoxyethoxide allowed us to decrease the annealing temperature of titanium dioxide down to 150–180°C. This permits the manufacture of DSSC on flexible polymer substrates. DSSC samples with efficiency of energy conversion up to 1% are obtained.     

Organic dopant added polyvinylidene fluoride based solid polymer electrolytes for dye-sensitized solar cells

The effect of phenothiazine (PTZ) as dopant on PVDF/KI/I₂ electrolyte was studied for the fabrication of efficient dye-sensitized solar cell (DSSC). The different weight percentage (wt%) ratios (0, 20, 30, 40 and 50%) of PTZ doped PVDF/KI/I₂ electrolyte films were prepared by solution casting method using DMF as a solvent. The following techniques such as Fourier transform infrared (FT-IR), differential scanning calorimetry (DSC), X-ray diffractometer (XRD) and AC-impedance analysis have been employed to characterize the prepared polymer electrolyte films. The FT-IR studies revealed the complex formation between PVDF/KI/I₂ and PTZ. The crystalline and amorphous nature of polymer electrolytes were confirmed by DSC and XRD analysis respectively. The ionic conductivities of polymer electrolyte films were calculated from the AC-impedance analysis. The undoped PVDF/KI/I₂ electrolyte exhibited the ionic conductivity of 4.68×10⁻⁶ S cm⁻¹ and this value was increased to 7.43×10⁻⁵ S cm⁻¹ when PTZ was added to PVDF/KI/I₂ electrolyte. On comparison with different wt% ratios, the maximum ionic conductivity was observed for 20% PTZ-PVDF/KI/I₂ electrolyte. A DSSC assembled with the optimized wt % of PTZ doped PVDF/KI/I₂ electrolyte exhibited a power conversion efficiency of 2.92%, than the undoped PVDF/KI/I₂ electrolyte (1.41%) at similar conditions. Hence, the 20% PTZ-PVDF/KI/I₂ electrolyte was found to be optimal for DSSC applications.     

Dye-sensitized solar cells based on different nano-oxides on plastic PET substrate

Polyethylene-terephthalate (PET) foils and glass slides coated with thin conductive layers were used as substrates for TiO2 or ZnO based photoactive electrodes of dye-sensitized solar cells (DSSC) with organo-metallic Ru-dye, standard iodine electrolyte and Pt coated FTO/glass counterelectrode (CE). Different compositions of nanoparticle oxides in forms of alcohol pastes as well as the CE paste were applied onto the substrates by screen printing or by doctor blade techniques. Photocurrents and I–V loading characteristics were measured depending on the solar cell structure and preparation, including the oxide composition, electrode conductivity and the dye type. The influence of thin TiO2 blocking layer prepared by sol–gel technique is also discussed.     

Application of Pt sputter-deposited counter electrodes based on micro-patterned ITO glass to quasi-solid state dye-sensitized solar cells

The effects of the Pt catalyst sputter deposited on the patterned ITO glass (SD-Pt/pITO) on the photovoltaic properties and charge-transfer characteristics at the Pt/electrolyte interface of dye-sensitized solar cells (DSSCs) are studied and compared with those of a conventional Pt counter electrode deposited by thermal reduction on fluorine-doped tin oxide (FTO) glass (TD-Pt/FTO). The DSSC with the SD-Pt/pITO (sample cell) shows a lower charge-transfer resistance than that of the DSSC with the TD-Pt/FTO (reference cell), which leads to an improvement of its fill factor by about 7.6%. The long-term durability test performed for 1000 h at room temperature reveals that the sample cell retains up to 99% of its energy conversion efficiency, while that of the reference cell is degraded by about 7.2%.     

Layer-by-layer Au nanoparticles as a Schottky barrier in a water-based dye-sensitized solar cell

We fabricated layer-by-layer gold nanoparticles (Au NPs) onto an electrode as a Schottky barrier in a water-based dye-sensitized solar cell. The Maxwell–Garnett equation was used to fit the characteristics of the Au film. The short-circuit current for four layers of Au NPs in a water-based dye-sensitized solar cell (DSSC) ranges from 2.76 mA/cm² to 5.96 mA/cm², which is due to the Schottky barrier reducing the number of electrons going from the semiconductor back to either the dye or the electrolyte. The efficiency of photo-electric conversion for four layers of Au NPs in water-based DSSC can be enhanced from 0.26% up to 0.95%. PACS 85.30.Hi; 82.47.Jk; 73.63.-b; 81.16.-c; 78.67.Bf     

Poly(vinyl chloride)-<Emphasis Type="Italic">graft</Emphasis>-poly(<Emphasis Type="Italic">N</Emphasis>-vinyl caprolactam) graft copolymer: synthesis and use as template for porous TiO<Subscript>2</Subscript> thin films in dye-sensitized solar cells

Poly(N-vinyl caprolactam) (PNVCL) side chains were grafted to a poly(vinyl chloride) (PVC) backbone via atom transfer radical polymerization. The synthesized PVC-g-PNVCL graft copolymer was templated for the preparation of porous TiO₂ thin films, which involved a sol–gel reaction and calcination process. The interaction of the carbonyl groups in the PVC-g-PNVCL with the titania was revealed by FT-IR spectroscopy. X-ray diffraction and transmission electron microscopy analysis showed the formation of porous TiO₂ thin films with the anatase phase. A series of porous TiO₂ thin films with different pore sizes and porosities was prepared by varying the solution compositions and were used as photoelectrodes in dye-sensitized solar cells (DSSC) with a polymer electrolyte. The DSSC performed best when using the TiO₂ film with higher porosity, lower interfacial resistance, and longer electron life time. The highest energy conversion efficiency, photovoltage (V _oc), photocurrent density (J _sc), and fill factor (FF) were 1.2%, 0.68 V, 3.2 mA/cm², and 0.57 at 100 mW/cm², respectively, for the quasi-solid state DSSC with a 730-nm-thick TiO₂ film.