染料敏化太阳能电池中准固态聚合物电解质的研究进展

染料敏化太阳能电池（DSSC）制备工艺简单、制造成本低廉且转换效率高,是太阳能电池的重要发展方向,具有广泛的应用前景。目前,基于液态电解质的DSSC的光电转换效率最高已达到13%,但液态电解质封装困难、长期稳定性差等问题阻碍了其实际应用。近些年来,固态和准固态电解质引起了研究学者们的广泛关注。其中准固态聚合物电解质因具有较高的离子电导率、良好的电池界面接触和可加工性能,成为制备高性能DSSC的重要研究方向之一。根据特征、形成机制和电解质的物理状态,可将准固态聚合物电解质分为四大类：准固态热塑性聚合物电解质,准固态热固性聚合物电解质,准固态复合型聚合物电解质和准固态离子型聚合物电解质。本文分析了基于这几类准固态聚合物电解质的DSSC的性能参数,并对其存在的问题和未来的研究方向进行了探讨。     

固态锂硫电池电解质及其界面问题研究进展

固态锂硫(Li-S)电池通过固态电解质代替传统液态电解液体系,有望同时解决液态Li-S电池多硫化物的穿梭效应、锂金属与液态电解液的副反应、安全性能差等关键科学问题,发挥其高稳定性、高能量密度的优势.然而,固态Li-S电池在固态电解质和电极/电解质界面问题上面临着巨大挑战,本文详细介绍了硫化物固态电解质和聚合物基体电解质...     

准固态染料敏化太阳电池的制备与性能研究

以AS树脂作为聚合物凝胶电解质基体,乙腈和四氢呋喃作为混合有机溶剂制备准固态染料敏化太阳电池.经过各个组成的优化,聚合物凝胶电解质电导率(30℃)达到5.11mS·cm-1,准固态染料敏化太阳电池的光电转换效率在100mW·cm-2光强下达2.56%.通过在聚合物凝胶电解质中加入氮杂环类添加剂吡啶和1-甲基咪唑,准固态染料敏化太阳电池的光电转换效率在100mW·cm-2光强下分别提高到3.09%和3.00%.     

有机物辅助的硫化物电解质基固态电池

固态电池利用固态电解质替换电解液,为电池的发展提供了高能量密度和高安全性的保障,其中硫化物固态电解质因其高离子电导率等优势受到了广泛关注。然而使用硫化物固态电解质还会面临电极/电解质接触较差、与电极发生界面副反应、空气稳定性差的问题,往往需要与一些有机物配合以改善电池性能,例如有机溶剂、有机电解液或聚合物。本文综述了不同种类有机物对硫化物固态电解质的辅助作用,首先回顾了基于硫化物固态电解质的准固态电池发展现状,分别从正极、电解质、负极及相互界面处添加电解液或溶液的角度,阐述了液体添加对准固态电池产生的界面浸润、构筑保护层等增益作用;其次介绍了聚合物/硫化物复合固态电解质的湿法和干法制备,对比了极性和非极性聚合物黏结剂在制备工艺上的差异,着重分析了有机组分的添加对复合电解质离子电导率等性能的影响;阐述了通过溶液法对复合正极内部界面的改善方法,并补充介绍了薄片状(Sheet-type)电极的制备工艺与发展前景;最后总结了目前有机组分在与硫化物固态电解质配合时面临的难点,展望了未来研究工作的发展方向,为组装高性能硫化物基固态电池提供思路。     

PVDF-HFP基凝胶固态聚合物电解质的合成与锂离子电池性能

聚偏氟乙烯-六氟丙烯(PVDF-HFP)基凝胶聚合物电解质被认为是解决锂电安全性问题的一种有前途的固态电解质.然而,目前报道的是凝胶固态聚合物电解质由于含有大量易燃物质,安全性仍然无法保证.因此,本文合成制备基于PVDF-HFP的新型凝胶聚合物电解质,使用丁二腈(SN)作为塑化剂,双三氟甲基磺酰胺亚锂(LiTFSI)作为锂盐,利用热交联法原位制备了高热稳定性的新型凝胶固态聚合物电解质(GSPE).优化后的凝胶聚合物电解质离子电导率在25℃时可高达3.7×10?3 S/cm,电化学窗口室温下可达4.5 V.此外,凝胶聚合物电解质与电极具有良好的界面相容性;组装的磷酸铁锂电池在1 C下循环80次,容量保持率为89％.本项研究工作展示了高性能凝胶聚合物电解质对提升锂离子电池的循环稳定性与安全性具有较大潜在的应用价值.     

PVDF基准固态染料敏化太阳电池的研究

以聚偏氟乙烯(PVDF)为凝胶剂,分别将有机溶剂、离子液体电解质固化,并采用这两种体系的电解质分别封装成染料敏化太阳电池,测试了凝胶剂的加入量对太阳电池光电特性的影响,同时利用交流阻抗谱分析了聚合物的加入对抑制暗电流的作用。其中,有机溶剂电解质中PVDF的质量分数分别为5%、20%、25%;离子液体(甲基-丙基咪唑,MPII)电解质中PVDF的质量分数分别为0%、1%、10%。实验中制备的准固态小面积(0.25cm~2)封装电池光电转换效率均高于5.3%,PVDF含量为25%的有机溶剂型准固态电池的效率达到5.92%。此外,实验中还制备了密封的1cm~2的准固态电解质电池,并获得了6.26%的效率,此时对应的J_(SC)=15.4mA/cm~2,V_(OC)=0.672V,FF=60.5%。     

固态锂电池研究及产业化进展

相比于传统液态锂离子电池,固态锂电池(SSLB)用固态电解质代替有机电解液,安全性和能量密度均大大提升,可以有效降低电动汽车安全隐患和缓解用户续航里程焦虑.固态电解质作为电子绝缘体和离子导体是SSLB核心要素之一,同时其存在离子电导率低、界面阻抗大和界面稳定性差等问题.通过研究近期相关文献,对硫化物固态电解质、氧化物固态电解质、聚合物固态电解质以及复合固态电解质锂电池的离子导电机理、研究进展、存在的主要问题及解决方案进行了综述和讨论.对于提高离子电导率,重点介绍了调整固态电解质组分的方法.对于改善界面问题,主要介绍了界面设计和制成工艺方法改善思路.综合分析表明,通过掺杂和包覆改性固态电解质、探索先进界面研究和诊断技术并指导设计具有优良锂离子传输能力的界面、创新和优化工艺能有效地提升固态电解质综合性能.最后列举了国内外重点企业的固态锂电池产业化进程,对固态锂电池未来应用前景进行了分析和展望.     

高分子电解质在染料敏化太阳电池中的应用

用高分子电解质代替液态电解质是解决电解质密封问题的有效途径。本文就高分子电解质,包括可用作空穴传导材料的导电高分子、高分子凝胶电解质及高分子固态电解质的研究进展及存在的问题进行了综述,并就今后的发展进行了分析。     

固态电池复合电解质研究综述

目前单一的无机固态电解质、聚合物固态电解质分别存在着离子电导率低、产生枝晶、界面不稳定等各种问题,无法满足全固态锂金属电池的性能要求.有机聚合物电解质和无机电解质复合形成的复合固态电解质能够不同程度地增强电导率、抑制枝晶产生、提高机械强度、提高界面稳定性以及兼容性等,得到了广泛关注与研究.本文综述了复合固态电解质在提高锂离子电导率、抑制锂枝晶、提高电化学稳定性三个重要方面的改进方向、措施,并展望复合固态电池的发展方向,为复合固态电池的发展和应用提供借鉴.     

固态硫化物电解质与锂金属负极的界面稳定性研究进展

采用固态电解质和金属锂的全固态锂电池被认为是解决传统使用液态电解质的锂离子电池安全性差和能量密度低的终极方案。近年来,固态硫化物电解质在离子电导率和空气稳定性研究等方面取得了较大进展,但固态硫化物电池体系还有一些问题亟需解决,最为重要的就是固态硫化物电解质与锂金属负极的界面稳定性问题。因此,构建稳定的固态电解质/锂金属负极界面是实现高性能全固态锂电池的关键。该文针对目前基于硫化物电解质的全固态锂电池所面临的机遇和挑战,总结了固态硫化物电解质/锂金属负极界面所面临的问题和设计策略。     

Crystal formation involving 1-methylbenzimidazole in iodide/triiodide electrolytes for dye-sensitized solar cells

Nitrogen heterocyclic compounds, such as N-methylbenzimidazole (MBI), are commonly used as additives to electrolytes for dye-sensitized solar cells (DSCs), but the chemical transformation of additives in electrolyte solutions remains poorly understood. Solid crystalline compound (MBI)₆(MBI-H⁺)₂(I⁻)(I₃⁻) (1) was isolated from different electrolytes for DSCs containing MBI as additive. The crystal structure of 1 was determined by single-crystal X-ray diffraction. In the crystal structure, 1 contains neutral and protonated MBI fragments; iodide and triiodide anions form infinite chains along the crystallographic a-axis. The role of the solvent and additives in the crystallization process in electrolytes is discussed.     

Novel quasi-solid electrolyte for dye-sensitized solar cells

A novel alkyloxy-imidazole polymer was prepared by in situ co-polymerization of alkyloxy-imidazole and diiodide to develop an ionic polymer gel electrolyte for quasi-solid dye-sensitized solar cells (DSCs). The DSCs with the polymer gel electrolyte of 1-methyl-3-propylimidazolium iodide (MPII) showed good photovoltaic performance including the short-circuit photocurrent density (J_sc) of 3.6 mA cm⁻², the open-circuit voltage (V_oc) of 714.8 mV, the fill factor (FF) of 0.60 and the light-to-electricity conversion efficiency (η) of 1.56% under AM 1.5 (100 mW cm⁻²). As a comparison, the DSCs with the polymer gel electrolyte of 1,2-dimethyl-3-propylimidazolium iodide (DMPII) yielded a light-to-electricity conversion efficiency of 1.33%. The results indicated that the as-prepared polymers were suitable for the solidification of liquid electrolytes in DSCs.     

Production and characterization of ITO-Pt semiconductor powder containing nanoscale noble metal particles catalytically active in dye-sensitized solar cells

Doped indium tin oxide (ITO) samples of a surface area around 60 m²/g have been synthesized. As doping component platinum and gold atoms were utilized, respectively. The powders were produced by pyrolyzing mixed metal oxide precursors in a first zone in a flame consisting of hydrogen and air, metering a noble metal compound and reducing gas into a second zone of the flame and separating off the solid obtained in a third zone. Well-defined solid phases In₂Pt and In₂Au in ITO were obtained, respectively. The production of a mixture with discrete SnO₂ entities could be avoided. The mixed oxide powder doped with platinum can be used as a catalyst. The structure and composition of materials obtained at different levels of platinum dosing into a flame reactor has been determined. The size of the noble metal-containing entities ranged at about 3.5–5.5 nm. The catalytic properties of these oxides containing noble metal have been utilized in the fabrication of dye-sensitized solar cells (DSCs). Long term stability of DSCs containing liquid electrolytes requires a glass sealing of the two electrodes at a temperature of over 600 °C. Such high temperatures are detrimental to the catalytic activity of the conventional platinum layers in the counter electrode. Improved catalytic activity could be achieved by platinum entities bound to indium tin oxide. This catalytic material can effectively be used in the DSCs with glass sealing, the sealing temperature being over 600 °C. Spray pyrolysis in a flame reactor is highly suitable to produce noble metal-containing oxides in one single production step. Platinum-containing ITO particles from flame pyrolysis production exhibit superior catalytic activity in dye-sensitized solar cells compared to material from conventional thermal decomposition.     

Fabrication of dye-sensitized solar cells by transplanting highly ordered TiO2 nanotube arrays

Highly ordered TiO₂ nanotube arrays fabricated by anodization are very attractive to dye-sensitized solar cells (DSCs) due to their superior charge percolation and slower charge recombination. However, the efficiency of TiO₂-nanotube-based DSCs is 6.89%, which is still lower than that of TiO₂-nanoparticle-based DSCs. We have suggested the transplanting the highly ordered TiO₂ nanotube arrays to FTO glass to improve the performance of TiO₂-nanotube-based DSCs. DSCs based on transplanted TiO₂ nanotube arrays and TiO₂ nanoparticles were fabricated by same process and materials to exclude the unexpected factors. In TiO₂ thickness of ca. 15 μm, the efficiency of 2.91% in front-side illuminated DSCs based on TiO₂ nanotube arrays was higher than those in back-side illuminated DSCs based on TiO₂ nanotube arrays and in front-side illuminated DSCs based on TiO₂ nanoparticle. Front-side illuminated DSCs based on TiO₂ nanotube arrays having various thicknesses were successfully fabricated. The efficiency in DSCs having 20.0 μm thick TiO₂ nanotube arrays was improved to 5.36% by TiCl₄ treatment.     

High performance quasi-solid-state dye-sensitized solar cells based on poly(lactic acid-co-glycolic acid)

A stable quasi-solid-state dye-sensitized solar cell (DSC) with a novel amphiphilic polymer gel electrolyte (APGE) based on poly(lactic acid-co-glycolic acid) (PLGA) is fabricated. The APGE could be readily prepared by a simple method at low temperature of 50 °C and exhibits a quasi-solid property, high conductivity, and long-term stability. The 20 and 40 wt% APGE-based DSCs show high photovoltaic conversion efficiency of 7.5 and 7.4%, respectively, under AM 1.5 simulated sunlight, which is comparable to the liquid electrolyte-based DSC with the efficiency of 7.6%. The 40 wt% APGE-based DSC maintains 95% of the initial performance after 60 days in practical conditions. It is also noteworthy that the APGE endows with higher short-circuit current density than the liquid electrolyte. Different natures of the APGE from the typical polymer gel electrolytes have been elucidated by the I-V measurements, electrochemical impedance spectroscopy, electrophoretic measurements, and transmission electron microscopy.     

小面积染料敏化纳米薄膜太阳电池的优化研究

论述了对小面积染料敏化纳米薄膜太阳电池各个组成部分优化实验的研究,主要包括纳米TiO2多孔薄膜、染料光敏化剂、电解质、反电极及其它工艺的优化选择。通过对电池各种参数的优化和实验,获得了8.73%的光电转换效率。实验结果表明,小面积电池的实验是研究染料敏化纳米薄膜太阳电池光伏性能的一种极好的途经,将为保证大面积DSCs的光伏性能和将来的产业化打下良好的基础。     

氧化钛纳米管对DSCs电池性能的影响

主要从DSCs的工作原理出发,比较了TiO2纳米管(特别是规则和单晶纳米管)相比于传统的TiO2纳米颗粒作为DSCs的半导体氧化物的优点;介绍了TiO2纳米管的不同制备工艺过程;比较了不同制备工艺的优缺点;并指出了目前TiO2纳米管DSCs的研究和应用中的问题.     

Influence of acceptor moiety in triphenylamine-based dyes on the properties of dye-sensitized solar cells

Triphenylamine-based organic dyes with different acceptor parts have been synthesized in an attempt to investigate the effect of the acceptor moiety on the properties of dye-sensitized solar cells. The light-to-electricity conversion efficiencies of 4.67% and 5.05% were obtained for the DSCs based on 2-(4-oxo-5-(4-(phenyl(4-styrylphenyl)amino)benzylidene)-2-thioxothiazolidin-3-yl)acetic acid (TPAR11) and 2-cyano-3-(4-(phenyl(4-styrylphenyl)amino)phenyl)acrylic acid (TC12), respectively. A molecular-orbital calculation shows that the delocalization of the excited state for TPAR11 is broken between the 4-oxo-2-thioxothiazolidine ring and the acetic acid, which affects the electron movement from dye molecule to the semiconductor film. The effects of chenodeoxycholic acid (CDCA) as the coadsorbent on the photovoltaic performance of the DSCs based on TPAR11 and TC12 have been also studied. It has been found that the addition of 1 mM CDCA coadsorbent improves the photocurrent for TPAR11 and the photovoltage for TC12, owing to the suppression of the quenching processes of the excited electrons between dye molecules or/and a more negative conductive band edge of TiO₂ film. With the addition of 1 mM CDCA, the light-to-electricity conversion efficiencies of the DSCs based on TPAR11 and TC12 were 5.46% and 5.96%, respectively. This result indicates that both the acceptor moiety of metal-free organic dyes and the coadsorbent added in the electrode preparation have the effect on the photovoltaic performance of DSCs.