Review on transition metal compounds based counter electrode for dye-sensitized solar cells

Commercial application of the dye-sensitized solar cells（DSCs） depends on great improvement of the power conversion efficiency and reduction of the fabrication cost. Generally, developing low cost counter electrode catalysts to replace the expensive Pt counter electrode is a feasible path to reduce the production cost of DSCs. In this review article, we summarize the recent progress on the transition metal compound based counter electrode catalysts containing carbides, nitrides, oxides, sulfides, phosphide, selenides, borides, silicide, and telluride toward the regeneration of the traditional iodide redox couple.Moreover, the benefits and drawbacks of each kind of CE catalyst are discussed and the research directions to design new counter electrode catalysts in future research are also proposed.

The effect of transition metal ions (M^(2+)=Mn^(2+),Ni^(2+),Co^(2+),Cu^(2+)) on the chemical synthesis polyaniline as counter electrodes in dye-sensitized solar cells

The effect of transition metal ions(M^(2+)=Mn^(2+),Ni^(2+),Co^(2+),Cu^(2+)) on the chemical synthesis of polyaniline(PANI) used as a platinum-free counter electrode(CE) in dye-sensitized solar cells(DSSCs) was investigated.PANI was synthesized by co-polymerization of aniline in the presence of different transition metal ions by using potassium dichromate in acidic medium. It was found that the ion doping of PANI showed a certain catalytic activity for the regeneration of traditional iodide/triiodide(I^-/I_3^-) redox couples. The power conversion efficiency(η) of PANI CEs doped with Mn^(2+),Ni^(2+),Co^(2+) (4.41%, 2.36% and 2.10%, respectively) were higher than 1.94%, the value measured for PANI CE without doping. Doping with Cu^(2+)decreased the power conversion efficiency of PANI CE(PANI-Cu^(2+) η = 1.41%). The electrical properties of the PANI, PANI-Ni^(2+), PANI-Co^(2+),PANI-Mn^(2+) and PANI-Cu^(2+) were studied by cyclic voltammetry(CV), impedance(EIS), and Tafel polarization curve. The experimental results confirmed that PANI was affected by the doping of different transition metal ions(M^(2+)=Mn^(2+),Ni^(2+),Co^(2+),Cu^(2+)). These results indicate a potential application of ion doped PANI as counter electrode in cost-effective DSSCs.

High-Performance Cobalt Selenide and Nickel Selenide Nanocomposite Counter Electrode for Both Iodide/Triiodide and Cobalt(II/III)Redox Couples in Dye-Sensitized Solar Cells

The nanocomposites of cobalt selenide and nickel selenide(Co_(0.85)Se/Ni_(0.85)Se)were successfully fabricated on FTO glass by a facile co-electrodeposition method at ambient temperature.Nanocomposite films were used as elec-trocatalysts in dye-sensitized solar cell counter electrodes for regeneration of both iodide/triiodide and cobalt(II/III)redox couples.Co_(0.85)Se/Ni_(0.85)Se were mainly composed of nanoflakes and nanoparticles.It is noted that such nanostructure generated by nanoparticles embedded with 2D nanoflakes led to high active sites and was accessible to cobalt(II/III)electrolyte,delivering better catalytic activity for the reduction of larger volume cobalt(II/III).As a result,for cobalt(II/III)electrolyte,the Co_(0.85)Se/Ni_(0.85)Se based dye-sensitized solar cell performed significantly im-proved efficiency than that of Pt and Co_(0.85)Se.Meanwhile,the Co_(0.85)Se/Ni_(0.85)Se based dye-sensitized solar cell held comparable energy conversion efficiency to that of Pt and Co_(0.85)Se for iodide/triiodide electrolyte.

Hydrothermal growth of MoS_2/Co_3S_4 composites as efficient Pt-free counter electrodes for dye-sensitized solar cells

MOS2/Co3S4 composite films were prepared via a facile one-step hydrothermal method, and used as efficient and low-cost Pt-free counter electrodes （CEs） for dye-sen- sitized solar cells （DSSCs）. Characterizations revealed that Co3S4 and MoS2 were obtained simultaneously during the facile hydrothermal process. The composites afforded a promising synergistic effect on the catalyzing of triiodide reduction. Enhanced electrocatalytic performance of the resultant composite films was confirmed through cyclic voltammetry （CV） and electrochemical impedance spec- troscopy （EIS） analyses. DSSCs using MoS2/Co3S4 composite CEs outperform the devices with pristine MoS2 or Co3S4 CEs in power conversion efficiency （PCE）. Furthermore, a PCE of 6.77% is obtained for the optimized devices using MoS2/Co3S4 composite CEs measured under standard 1 sun illumination （100 mW cm-2, AM 1.5G）, which is comparable to that of the devices fabricated under the same conditions with conventional thermally deposited Pt CEs （7.14%）. The results demonstrate that MoS2/Co3S4 composites are promis- ing alternatives to Pt to be applied as CEs for DSSCs,

Synthesis of La_2MoO_6@MWCNTs composite catalysts as Pt-free counter electrodes for dye-sensitized solar cell

Pt-free counter electrode(CE) composed of La2 MoO(LaO-MoO) was successfully synthesized by simple pyrolysis of lanthanum acetate(CHOLa·xHO) and hexaammonium heptamolybdate tetrahydrate((NH4)6 MoO·4 HO). Furthermore,three proportions composites catalysts of La2 MoO@MWCNTs based on La2 MoOand multiwall carbon nanotubes(MWCNTs) were prepared and characterized as Ptfree catalyst for CE in dye-sensitized solar cells(DSSCs). The morphology and structure of La2 MoO@MWCNTs composites were determined by scanning electron microscopy, transmission electron microscope and X-ray diffraction. The electrochemical performance of La2 MoO@MWCNTs composite catalysts for CEs was determined by photocurrent-voltage measurements, cyclic voltammetry,electrochemical impedance spectroscopy, and Tafel polarization. The power conversion efficiencies of4.68%, 4.87% and 5.06% are obtained for La2 MoO:MWCNTs with the mass ratios of 5:1, 3:1 and 1:1 towards the reduction of I~-to I~-under the same conditions,respectively,which are superior to those of MWCNTs(3,94%) and La2 MoO(1.71%) electrodes. The experimental results reveal that the presence of MWCNTs results in an augmented active catalytic surface area and enhanced charge transfer from CE to the electrolyte.

染料敏化太阳能电池用过渡金属化合物对电极的研究进展

由于成本低、制作工艺简单、光电转换效率高,染料敏化太阳能电池被认为是传统太阳能电池最有力的竞争者之一。染料敏化太阳能电池常用的对电极是Pt电极,Pt价格高,储量少,因此寻找一种价格便宜且催化性能较好的材料代替Pt制备对电极是目前的研究热点。过渡金属化合物品种多、制备过程简单、价格低且催化性能好,近年来受到人们的广泛关注,是代替Pt制备染料敏化太阳能电池对电极最好的材料之一。本文综述了染料敏化太阳能电池过渡金属化合物对电极的研究现状,对过渡金属化合物对电极的性能特点及今后研究的重点进行了分析。

染料敏化纳米薄膜太阳电池的新型对电极研究

研究了用金属基板和塑料薄膜制作的4种新型对电极和由这些对电极构成的染料敏化纳米薄膜太阳电池的性能。由不锈钢、镍片和导电聚合物膜为基材的对电极构成的太阳电池的光电转换效率近5％；不锈钢对电极可以通过降低内阻来改善大面积染料敏化纳米薄膜太阳电池的光电转换效率。此外,测试了这些金属基板和塑料薄膜在电解质溶液中的耐腐蚀性和稳定性；考察了由不锈钢和导电聚合物膜对电极构成的染料敏化纳米薄膜太阳电池的长期性能稳定性,并提出了改善这些新型对电极的长期性能稳定性的途径。

MoS2/CNFs对电极膜厚对染料敏化太阳能电池性能影响

通过静电纺丝技术和水热法成功获得了碳纳米纤维负载二维层状硫化钼(MoS_2/CNFs),将其作为对电极组装的染料敏化太阳能电池(DSSCs)表现出优异的电化学特性。在DSSCs制备过程中,对电极膜厚对电池性能有很大影响,所以本文重点探究了喷涂法制备的对电极膜厚对其组装的染料敏化电池光电性能影响,获得最佳对电极膜厚。实验结果表明当MoS_2/CNFs复合对电极材料膜厚为8μm时,电池光电转换效率达到最大值7.78%。

染敏太阳能电池中过渡金属硫化物对电极研究进展

近年来,第三代太阳能电池——染料敏化太阳能电池(dye-sensitized solar cells,DSSC)因制造成本低、环境污染少、生产工序简单等优点而备受关注。对电极作为DSSC的重要组成部分是影响其光电转换性能及稳定性的重要因素。综述了对电极材料在DSSC中的作用以及研究现状,重点介绍了过渡金属硫化物(transition-metal sulfides,TMSs)在DSSC中的研究进展,阐述了TMSs与其他对电极材料相比具有的优异性能及其制备方法和性能参数,最后提出了今后DSSC研究的主要方向是继续开发各种原料易得、成本低廉和稳定高效的新型对电极材料。TMSs染料敏化太阳能电池作为化合物薄膜太阳能电池中非常重要的组成部分,具有很大的应用前景。

染料敏化太阳能电池过渡金属氮化物对电极研究进展

对电极作为染料敏化太阳能电池(dye-sensitized solar cells,DSSCs)的核心部分之一,其材料的价格、性能和制备方法直接影响DSSCs的发展和应用.DSSCs常用Pt对电极价格昂贵,因此寻找低成本高性能的催化材料代替Pt对电极是降低DSSCs成本的有效途径之一.过渡金属氮化物的电子结构与Pt相似,具有高的催化活性和耐腐蚀性,价格低廉,使其具有广阔的应用前景.文章综述了利用载体与过渡金属氮化物的协同作用或将过渡金属氮化物制备成独特的纳米结构(纳米管和高度有序的阵列等)来解决过渡金属氮化物易团聚和大规模的物质运输受限制等问题.最后提出,开发双组元或多组元过渡金属氮化物和柔性过渡金属氮化物对电极可以作为未来发展方向.

过渡金属硒化物作为染料敏化太阳能电池对电极催化性能的影响

探索和开发廉价替代铂对电极催化材料已经成为染料敏化太阳能电池(DSCs)研究的热点。人们已经证明过渡金属硒化物(TMSes)是一种很有发展潜力的非铂对电极催化材料而在DSCs体系中得以应用。然而目前对过渡金属硒化物作为对电极催化材料在DSCs中的研究尚不够深入,同时对硒化物材料还缺乏系统的研究。利用热溶剂法合成了两种过渡金属硒化物Cr_(5.6)Se_8和Hf Se_3并用作高效DSCs对电极催化材料。电化学测试结果表明这两种硒化物对I_3^-/I^-电对的还原反应具有良好的催化活性,组装的器件能量转换效率分别为7.27%和7.52%,与Pt相应器件的性能相当。这一结果进一步证实了硒化物作为对电极材料的可行性,为新型硒化物对电极的研究提供基础。

染料敏化太阳电池的新型对电极材料

详细评述了碳材料、导电聚合物、过渡金属化合物以及它们的复合材料等几类新型对电极催化材料,分析了它们各自的优缺点。与单一组分材料相比,复合材料能将两种组分的优点集于一身,是有发展潜力的新型对电极材料。最后,指出了开发高性能低成本对电极材料中存在的问题及今后的发展方向。

染料敏化太阳能电池过渡金属化合物对电极制备方法研究进展

染料敏化太阳能电池(dye-sensitized solar cells,DSSCs)作为制作工艺简易,成本低廉,环境友好的新型太阳能电池,其发展一直备受关注。对电极作为DSSC的核心部件之一,其制备工艺会直接影响到DSSC的发展和应用。以低成本高性能的催化材料代替传统的贵金属Pt对电极是降低DSSC生产成本的有效途径之一。具有类Pt催化性能的过渡金属化合物(TMCs)由于种类繁多,制备方式简单多样,近年来成为DSSC对电极研究中的热点。本文综述了DSSC过渡金属化合物对电极的最新研究进展,总结概括了过渡金属化合物对电极的制备方法以及性能特点,并对其发展方向和应用前景进行了分析。

金属有机框架制备染料敏化太阳能电池对电极

为了降低染料敏化太阳能电池对电极的成本,通过碳化旋涂在导电玻璃基底上的金属有机框架薄膜制备纳米多孔碳对电极,采用SEM和EIS分别对多孔碳电极的形貌、结构和电极性能进行表征,并将金属有机框架配合物在不同碳化条件下所得多孔碳电极作为对电极,以方酸敏化Ti O2纳晶薄膜作为工作电极,组装成染料敏化太阳能电池,通过测定电池的J-U数据分析不同多孔碳材料的催化性能.结果表明:控制碳化金属有机框架薄膜条件可以制备结构和形貌可调的多孔碳电极,碳化温度和时间是影响多孔碳电极微结构和光电性能的主要因素,400℃下碳化4 h所得多孔碳对电极组装的方酸敏化太阳能电池的光电转换效率最高,达到1.01%,高于常用的铂电极.

由电泳沉积ZIF-67薄膜制备高效染料敏化太阳能电池对电极

为了提高碳化ZIF-67薄膜制备的染料敏化太阳能对电极的光电性能,本研究通过碳化电泳沉积ZIF-67薄膜得到多孔碳电极,并进一步在多孔碳电极热分解氯铂酸得到负载铂的多孔碳复合电极。通过光电流-电压曲线、电化学阻抗谱和强度调制光电流谱等的测试,对比单独在FTO导电玻璃基底热分解氯铂酸得到的铂电极和单独碳化电泳沉积ZIF-67薄膜得到的多孔碳电极,研究了负载铂的多孔碳复合电极作为染料敏化太阳能电池对电极的光电性能。与其它两种对电极相比,以负载铂的多孔碳复合电极为对电极的染料敏化太阳能电池光电转换效率最高,因碳化ZIF-67薄膜的多孔电极具有较大的比表面积,能负载足够量的铂,从而提供更多的催化位点,具有更好的催化性能,从而使染料敏化太阳能电池的光电转换效率得到显著提升。

金属-有机框架薄膜衍生的CoSe2/N共掺杂碳膜作DSSC对电极

针对粉体MOF衍生材料存在制备工艺复杂、薄膜厚度难以控制等问题,我们通过液相外延分步生长法制备了一种金属有机框架薄膜(PIZA-1),然后以其作牺牲模板,在惰性氛围中制备了一种CoSe2和N共掺杂的碳膜(CoSe2/N-CF),并用作DSSC对电极,其具有制备简单、粘结力强、厚度可调等优势。系统表征了CoSe2/N-CF形貌特点、结构性质及电化学性能,并深入研究了不同厚度薄膜、CoSe2颗粒大小对DSSC的光伏性能的影响。结果表明,CoSe2/N-CF-15电极具有优异的催化活性,所组装的DSSC获得了8.68%的光电转化效率(PCE),高于相同条件下Pt电极组装电池的PCE(7.97%)。

Fe/Cu修饰氮掺杂碳纳米管的构筑及催化性能

通过简单的原位化学合成法结合离子交换法制备了Cu修饰氮掺杂碳(Cu-N-C)和Fe/Cu修饰氮掺杂碳纳米管(Fe/Cu-N-C/CNT),并系统评估了2种催化剂作为染料敏化太阳能电池(dye-sensitized solar cells,DSSCs)对电极在I_(3)^(-)/I^(-)体系中的电化学特性和光伏性能。采用X射线衍射(XRD)、拉曼(Raman)、X射线光电子能谱(XPS)和场发射扫描电镜(FESEM)对合成的催化剂进行组分和形貌表征。结果表明:纳米管状的Fe/Cu-N-C/CNT的石墨化程度比纳米颗粒状的Cu-N-C更高,更有利于I_(3)^(-)还原反应中电荷的传输。光伏性能测试结果表明:基于Fe/Cu-N-C/CNT对电极的DSSCs的光电能量转换效率(power conversion efficiency,PCE)达到7.55%,高于相同测试条件下Cu-N-C(6.99%)和Pt(6.76%)对电极的PCE。50圈连续循环伏安测试结果表明:Fe/Cu-N-C/CNT催化剂具有比Cu-N-C更好的电化学稳定性。