Enhancement of the efficiency of dye-sensitized solar cell with multi-wall carbon nanotubes/polythiophene composite counter electrodes prepared by electrodeposition

For the purpose of increasing the energy conversion efficiency of dye-sensitized solar cells (DSSCs), multi-wall carbon nanotube (MWCNT)/polythiophene (PTh) composite film counter electrode has been fabricated by electrophoresis and cyclic voltammetry (CV) in sequence. The morphology and chemical structure have been characterized by transmission electron microscopy (TEM), scanning electron microscope (SEM), and Raman spectroscopy respectively. The overall energy conversion efficiency of the DSSC employing the MWCNT/PTh composite film has reached 4.72%, which is close to that of the DSSC with a platinum (Pt) counter electrode (5.68%). Compared with a standard DSSC with MWCNT counter electrode whose efficiency is 2.68%, the energy conversion efficiency has been increased by 76.12% for the DSSC with MWCNT/PTh counter electrode. These results indicate that the composite film with high conductivity, high active surface area, and good catalytic properties for I₃⁻ reduction can potentially be used as the counter electrode in a high-performance DSSC.     

Enhanced Performance of Organic/Inorganic Hybrid Nanomaterials bearing Impregnated [PdL2] Complexes as Counter‐Electrode Catalyst for Dye‐Sensitized Solar Cells

N‐coordinate Pd²⁺ complexes [PdL₂] (L: N‐N‐quinoline‐8‐yl‐R‐benzenesulfonamides) ( 6–10 ) and [PdL₂] complexes assembled on multi‐wall carbon nanotubes (MWCNTs) hybrid nanomaterials were fabricated and characterized by various techniques. The [PdL₂] impregnated MWCNTs materials ( 11–15 ) were applied as a counter electrode (CE) catalyst for triiodide to iodide reduction reaction in the dye‐sensitized solar cells (DSSC) and investigated electro‐catalytic activities. The MWCNTs‐supported [PdL₂] CEs ( 11–15 ) are exhibits as Pt‐free CE with good power conversion efficiencies (PCEs), and compared to platinum and bare MWCNTs CEs and the PCE of bare MWCNTs was clearly improved by means of [PdL₂] complexes ( 6–10 ). The DSSCs based on the hybrid counter electrodes (CEs) ( 11–15 ) and bare MWCNTs are indicated a relative efficiency ( ? _rel ) of 64.27%, 54.07%, 53.75%, 51.52% 44.82% and 27.27% concerning a Pt CE control device set at 100%. The report emphasizes that [PdL₂] impregnated MWCNTs type counter electrodes (CEs) ( 11–15 ) are promising as effectively catalyst in working device design, particularly taking into account the eco‐friendly approach of the hybrids.     

Self-Assembled Graphene/MWCNT Bilayers as Platinum-Free Counter Electrode in Dye-Sensitized Solar Cells

We describe the preparation and properties of bilayers of graphene- and multi-walled carbon nanotubes (MWCNTs) as an alternative to conventionally used platinum-based counter electrode for dye-sensitized solar cells (DSSC). The counter electrodes were prepared by a simple and easy-to-implement double self-assembly process. The preparation allows for controlling the surface roughness of electrode in a layer-by-layer deposition. Annealing under N₂ atmosphere improves the electrode's conductivity and the catalytic activity of graphene and MWCNTs to reduce the I₃⁻ species within the electrolyte of the DSSC. The performance of different counter-electrodes is compared for ZnO photoanode-based DSSCs. Bilayer electrodes show higher power conversion efficiencies than monolayer graphene electrodes or monolayer MWCNTs electrodes. The bilayer graphene (bottom)/MWCNTs (top) counter electrode-based DSSC exhibits a maximum power conversion efficiency of 4.1 % exceeding the efficiency of a reference DSSC with a thin film platinum counter electrode (efficiency of 3.4 %). In addition, the double self-assembled counter electrodes are mechanically stable, which enables their recycling for DSSCs fabrication without significant loss of the solar cell performance.     

Dye‐Sensitized Solar Cell Counter Electrodes Based on Carbon Nanotubes

Dye‐sensitized solar cells (DSSCs) have received significant attention from the scientific community since their discovery in 1991. However, the high cost and scarcity of platinum has motivated researchers to seek other suitable materials for the counter electrode of DSSCs. Owing to their exceptional properties such as high conductivity, good electrochemical activity, and low cost, carbon nanotubes (CNTs) have been considered as promising alternatives to expensive platinum (Pt) in the counter electrode of DSSCs. Herein, we provide a Minireview of the CNTs use in the counter electrode of DSSCs. A brief overview of Pt‐based counter electrodes is also discussed. Particular attention is given to the recent advances of counter electrodes with CNT‐based composite structures.     

Well‐Dispersed CoS Nanoparticles on a Functionalized Graphene Nanosheet Surface: A Counter Electrode of Dye‐Sensitized Solar Cells

With a facile electrophoretic deposition and chemical bath process, CoS nanoparticles have been uniformly dispersed on the surface of the functionalized graphene nanosheets (FGNS). The composite was employed as a counter electrode of dye‐sensitized solar cells (DSSCs), which yielded a power conversion efficiency of 5.54 %. It is found that this efficiency is higher than those of DSSCs based on the non‐uniform CoS nanoparticles on FGNS (4.45 %) and built on the naked CoS nanoparticles (4.79 %). The achieved efficiency of our cost‐effective DSSC is also comparable to that of noble metal Pt‐based DSSC (5.90 %). Our studies have revealed that both the exceptional electrical conductivity of the FGNS and the excellent catalytic activity of the CoS nanoparticles improve the conversion efficiency of the uniformly FGNS‐CoS composite counter electrode. The electrochemical impedance spectra, cyclic voltammetry, and Tafel polarization have evidenced the best catalytic activity and the fastest electron transport. Additionally, the dispersion condition of CoS nanoparticles on FGNS plays an important role for catalytic reduction of I₃^?.     

Podlike N‐Doped Carbon Nanotubes Encapsulating FeNi Alloy Nanoparticles: High‐Performance Counter Electrode Materials for Dye‐Sensitized Solar Cells

Podlike nitrogen‐doped carbon nanotubes encapsulating FeNi alloy nanoparticles (Pod(N)‐FeNi) were prepared by the direct pyrolysis of organometallic precursors. Cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and Tafel polarization measurements revealed their excellent electrocatalytic activities in the I^?/I₃^? redox reaction of dye‐sensitized solar cells (DSSCs). This is suggested to arise from the modification of the surface electronic properties of the carbon by the encapsulated metal alloy nanoparticles (NPs). Sequential scanning with EIS and CV further showed the high electrochemical stability of the Pod(N)‐FeNi composite. DSSCs with Pod(N)‐FeNi as the counter electrode (CE) presented a power conversion efficiency of 8.82 %, which is superior to that of the control device with sputtered Pt as the CE. The Pod(N)‐FeNi composite thus shows promise as an environmentally friendly, low‐cost, and highly efficient CE material for DSSCs.     

Sol-gel spin coated well adhered MoO3 thin films as an alternative counter electrode for dye sensitized solar cells

In this work, we aim to develop a viable, inexpensive and non-toxic material for counter electrodes in dye sensitized solar cells (DSSCs). We employed an ultra-simple synthesis process to deposit MoO₃ thin films at low temperature by sol-gel spin coating technique. These MoO₃ films showed good transparency. It is predicted that there will be 150 times reduction of precursors cost by realizing MoO₃ thin films as a counter electrode in DSSCs compared to commercial Pt. We achieved a device efficiency of about 20 times higher than that of the previous reported values. In summary we develop a simple low cost preparation of MoO₃ films with an easily scaled up process along with good device efficiency. This work encourages the development of novel and relatively new materials and paves the way for massive reduction of industrial costs which is a prime step for commercialization of DSSCs.     

基于网状铂电极的新型柔性染料敏化太阳能电池

柔性染料敏化太阳能电池（DSSCs）作为一种新型的化学太阳能电池,因其精简的封装工艺、较低廉的价格、高的化学稳定性以及可弯折等优点而备受关注. 本文介绍了一种新型的柔性DSSC的制备,其光阳极为高度有序的氧化锌（ZnO）纳米线阵列,对电极为柔性、导电、透明的网状铂(Pt networks)电极. 相对于传统的铂对电极而言,这种Pt networks对电极不仅具有优异的导电能力,还展现了极好的透光性（方阻~ 100 Ω•sq^-1,~80%透光率）和催化性能,此外,Pt networks电极可构筑于任意弯曲的衬底,具有优异的机械耐弯折性能. 在ZnO纳米线阵列的DSSCs的应用中,基于Pt networks膜的柔性DSSC的转化效率比铂纳米丝阵列 (Pt nanofiber arrays, Pt NFs）膜高出了32%.     

Pyrolytic carbon from an aromatic precursor and its application as a counter electrode in dye-sensitized solar cells

Pyrolytic carbon thin films were deposited on quartz plates through a chemical vapor deposition process, by using a biphenyl precursor, 4,4'-bis(chloromethyl-1,1'-biphenyl). The pyrolytic carbons were microporous and catalytic toward reduction of tri-iodide, and the films thus obtained possessed a metallic appearance with good mirror reflections, hydrophilic surfaces, and low sheet resistances. The pyrolytic carbon-coated quartz plates were used, in place of the commonly used Pt-coated fluorine-doped tin oxide glass, as the counter electrode for dye-sensitized solar cells (DSSCs). The light to electricity conversion efficiency of the cell thus obtained was reasonably high, achieving 78% of that obtained by using the conventional but much more expensive Pt counter electrode. From the electrochemical impedance spectroscopic analysis, one found that the minor reduction in the conversion efficiency came from the relatively higher resistance and lower catalytic activity of the pyrolytic carbon. This work demonstrates that the newly developed pyrolytic carbon films may be a promising alternative to Pt as the counter electrode material for DSSCs.     

Copper doped manganese dioxide as counter electrode for dye-sensitized solar cells

Many materials have been tried as the counter electrode (CE) material as a substitute to the noble metal Pt in dye-sensitized solar cells (DSSCs). The CE property is critical to the operation of a DSSC as it catalyzes the reduction of I₃^- ions and retrieves the electrons from the photoanode. Here we have explored the application of manganese dioxide (MnO₂) and copper-doped manganese dioxide (Cu-MnO₂) nanoparticles as CE candidates for DSSCs mainly as low-cost alternatives to Pt. A simple hydrothermal method was followed to synthesize α-MnO2 and Cu-MnO2 nanoparticles at a temperature of 140 °C for 14 h. The nanoparticles were characterized to prove its electrocatalytic abilities for DSSCs. DSSC devices fabricated with 10 wt% Cu-MnO₂ as CE showed the best V_OC of 781 mV, I_SC of 3.69 mA/cm², FF of 0.50, and %PCE of 1.7 whereas Pt as CE showed V_OC of 780 mV, I_SC of 14.8 mA/cm², FF of 0.43, and %PCE of 5.83 under 0.85 Sun. The low-cost feature of using Cu-MnO₂ is encouraging to further study the factors that can improve the efficiency of DSSCs with alternative CEs to conventional Pt electrodes.     

Metal/metal sulfide functionalized single-walled carbon nanotubes: FTO-free counter electrodes for dye sensitized solar cells

The use of single-walled carbon nanotubes (CNT) thin films to replace conventional fluorine-doped tin oxide (FTO) and both FTO and platinum (Pt) as the counter electrode in dye sensitized solar cells (DSSC) requires surface modification due to high sheet resistance and charge transfer resistance. In this paper, we report a simple, solution-based method of preparing FTO-free counter electrodes based on metal (Pt) or metal sulfide (Co(8.4)S(8), Ni(3)S(2)) nanoparticles/CNT composite films to improve device performance. Based on electrochemical studies, the relative catalytic activity of the composite films was Pt > Co(8.4)S(8) > Ni(3)S(2). We achieved a maximum efficiency of 3.76% for the device with an FTO-free counter electrode (Pt/CNT). The device with an FTO- and Pt-free (CoS/CNT) counter electrode gives 3.13% efficiency.     

Self-assembled monolayer of graphene/Pt as counter electrode for efficient dye-sensitized solar cell

Monolayer of PDDA/graphene/PDDA/H(2)PtCl(6) is fabricated on conductive glass using electrostatic layer-by-layer self-assembly technique, which is then converted to graphene/Pt monolayer for use as counter electrode in dye-sensitized solar cell (DSSC). As compared to the sputtered Pt counter electrode, the self-assembled monolayer reduces the Pt amount by about 1000-fold but exhibits comparable photovoltaic performance. This finding provides a new route to fabrication of cheap and efficient counter electrodes for flow-line production of DSSCs.     

简易合成Cu2SnSe3作染料敏化太阳能电池对电极

采用简易溶剂热法合成直径为150-250 nm的Cu2SnSe3纳米颗粒.以Cu2SnSe3"墨水"为前驱体采用滴落涂布法在掺氟二氧化锡基板上沉积Cu2SnSe3薄膜作为染料敏化太阳能电池(DSSC)对电极.利用场发射扫描电镜(FESEM)、透射电镜(TEM)、X射线衍射(XRD)、拉曼光谱(Raman)、能谱仪(EDS)等对Cu2SnSe3纳米颗粒的形貌、结构和组成进行表征.结果表明:产物纯净无杂项且符合化学计量比.以Cu2SnSe3为对电极的DSSC转化效率为7.75%,与铂对电极DSSC效率相当(7.21%).研究表明,DSSC的光电流密度和影响因子与Cu2SnSe3薄膜厚度密切相关,这是由于不同厚度的Cu2SnSe3薄膜作对电极所对应的催化位置数目和电阻值不同.电化学阻抗谱研究说明,Cu2SnSe3因具有类似铂良好的电催化性能而适合用作染料敏化太阳能电池对电极材料.本文以Cu2SnSe3代替贵金属铂,提供了一种廉价制备高效染料敏化太阳能电池对电极的新方法.     

Ultrathin FeSe2 Nanosheets: Controlled Synthesis and Application as a Heterogeneous Catalyst in Dye‐Sensitized Solar Cells

Two‐dimensional (2D) semiconducting nanosheets have emerged as an important field of materials, owing to their unique properties and potential applications in areas ranging from electronics to catalysis. However, the controlled synthesis of ultrathin 2D nanosheets remains a great challenge, due to the lack of an intrinsic driving force for anisotropic growth. High‐quality ultrathin 2D FeSe₂ nanosheets with average thickness below 7 nm have been synthesized on large scale by a facile solution method, and a formation mechanism has been proposed. Due to their favorable structural features, the as‐synthesized ultrathin FeSe₂ nanosheets exhibit excellent electrocatalytic activity for the reduction of triiodide to iodide and low charge‐transfer resistance at the electrolyte–electrode interface in dye‐sensitized solar cells (DSSCs). The DSSCs with FeSe₂ nanosheets as counter electrode material achieve a high power conversion efficiency of 7.53 % under a simulated solar illumination of 100 mW cm^?2 (AM 1.5), which is comparable with that of Pt‐based devices (7.47 %).     

Recent Advances on Pt-Free Electro-Catalysts for Dye-Sensitized Solar Cells

Since Prof. Grätzel and co-workers achieved breakthrough progress on dye-sensitized solar cells (DSSCs) in 1991, DSSCs have been extensively investigated and wildly developed as a potential renewable power source in the last two decades due to their low cost, low energy-intensive processing, and high roll-to-roll compatibility. During this period, the highest efficiency recorded for DSSC under ideal solar light (AM 1.5G, 100 mW cm⁻²) has increased from ~7% to ~14.3%. For the practical use of solar cells, the performance of photovoltaic devices in several conditions with weak light irradiation (e.g., indoor) or various light incident angles are also an important item. Accordingly, DSSCs exhibit high competitiveness in solar cell markets because their performances are less affected by the light intensity and are less sensitive to the light incident angle. However, the most used catalyst in the counter electrode (CE) of a typical DSSC is platinum (Pt), which is an expensive noble metal and is rare on earth. To further reduce the cost of the fabrication of DSSCs on the industrial scale, it is better to develop Pt-free electro-catalysts for the CEs of DSSCs, such as transition metallic compounds, conducting polymers, carbonaceous materials, and their composites. In this article, we will provide a short review on the Pt-free electro-catalyst CEs of DSSCs with superior cell compared to Pt CEs; additionally, those selected reports were published within the past 5 years.     

Platinum‐Free Binary Co‐Ni Alloy Counter Electrodes for Efficient Dye‐Sensitized Solar Cells

Dye‐sensitized solar cells (DSSCs) have attracted growing interest because of their application in renewable energy technologies in developing modern low‐carbon economies. However, the commercial application of DSSCs has been hindered by the high expenses of platinum (Pt) counter electrodes (CEs). Here we use Pt‐free binary Co‐Ni alloys synthesized by a mild hydrothermal strategy as CE materials in efficient DSSCs. As a result of the rapid charge transfer, good electrical conduction, and reasonable electrocatalysis, the power conversion efficiencies of Co‐Ni‐based DSSCs are higher than those of Pt‐only CEs, and the fabrication expense is markedly reduced. The DSSCs based on a CoNi_0.25 alloy CE displays an impressive power conversion efficiency of 8.39 %, fast start‐up, multiple start/stop cycling, and good stability under extended irradiation.     

A long-term stable Pt counter electrode modified by POM-based multilayer film for high conversion efficiency dye-sensitized solar cells

A long-term stable Pt counter electrode modified by POM-based multilayer film has been fabricated by the electrochemical deposition method, which can markedly increase short-circuit photocurrent, open-circuit voltage and the conversion efficiency when used in dye-sensitized solar cells (DSSCs).     

Synthesis of Ternary Ni/Mo2C/Carbon Nanofibers as Low-cost Counter Electrode for Efficient Dye-sensitized Solar Cells

To reduce the cost of manufacture, it is urgent to develop efficient and stable platinum(Pt)-free counter electrode(CEs) electrocatalysts for dye-sensitized solar cells(DSSCs). In this study, a simple electrospinning and carbonization strategy has been developed to synthesize carbon nanofibers(CNFs) loaded with Ni and Mo₂C nanoparticles(Ni/Mo₂C/CNFs) as CE. Owing to the high electrical conductivity of CNFs and the large catalytic activity of Ni and Mo₂C, an excellent electrochemical performance of Ni/Mo₂C/CNFs as CE is achieved. The optimized DSSC assembled with Ni/Mo₂C(2:1)/CNFs-based CE exhibits a power conversion efficiency(PCE) of 8.90%, which exceeds the corresponding values of the device using the Pt(8.07%), Ni/Mo₂C(1:1)/CNFs(8.68%), Ni/Mo₂C(1:2)/CNFs(8.20%), Ni/CNFs(7.50%) and Mo₂C/CNFs(6.10%). This work provides a new strategy for developing effective and low-cost CE materials in DSSCs.     

High-performance Pt-NiO nanosheet-based counter electrodes for dye-sensitized solar cells

High-performance counter electrodes for dye-sensitized solar cells (DSSCs) are fabricated with platinum-nickel oxide (Pt-NiO) nanosheets as catalytic materials. Firstly, the Pt-Ni nanosheets are synthesized via galvanic replacement reaction between pre-synthesized Ni nanosheets and an aqueous H₂PtCl₆ solution. Secondly, after thermal treatment in air, the Pt-Ni alloys are turned to Pt-NiO nanosheets. The related data of cyclic voltammetry, electrochemical impedance spectroscopy, and Tafel polarization reveal that Pt-NiO counter electrodes show highly catalytic activity and low charge transfer resistance. The DSSC with Pt-NiO counter electrode exhibits power conversion efficiency (PCE) of 8.40 %, which is lower than that of the DSSC containing commercial available Pt counter electrode (9.15 %) under full sunlight illumination (100 mW cm^?2, AM1.5G). However, owing to the extremely high transparency of Pt-NiO counter electrode, when putting an Ag mirror behind the back side of the DSSC, the reflected light can bring great enhanced PCE (11.27 %).     

Enhanced photovoltaic characterization and charge transport of TIO2 nanoparticles/nanotubes composite photoanode based on indigo carmine dye-sensitized solar cells

Dye-sensitized solar cells (DSSCs) have established themselves as an alternative to conventional solar cells owing to their remarkably high power conversion efficiency, longtime stability and low-cost production. DSSCs composed of a dyed oxide semiconductor photoanode, a redox electrolyte and a counter electrode. In these devices, conversion efficiency is achieved by ultra-fast injection of an electron from a photo excited dye into the conduction band of metal oxide followed by subsequent dye regeneration and holes transportation to the counter electrode. The energy conversion efficiency of DSSC is to be dependent on the morphology and structure of the dye adsorbed metal oxide photoanode. Worldwide considerable efforts of DSSCs have been invested in morphology control of photoanode film, synthesis of stable optical sensitizers and improved ionic conductivity electrolytes. In the present investigation, a new composite nano structured photoanodes were prepared using TiO₂ nano tubes (TNTs) with TiO₂ nano particles (TNPs). TNPs were synthesized by sol–gel method and TNTs were prepared through an alkali hydrothermal transformation. Working photoanodes were prepared using five pastes of TNTs concentrations of 0, 10, 50, 90, and 100 % with TNPs. The DSSCs were fabricated using Indigo carmine dye as photo sensitizer and PMII (1-propyl-3-methylimmidazolium iodide) ionic liquid as electrolyte. The counter electrode was prepared using Copper sulfide. The structure and morphology of TNPs and TNTs were characterized by X-ray diffraction and electron microscopes (TEM and SEM). The photocurrent efficiency is measured using a solar simulator (100 mW/cm²). The prepared composite TNTs/TNPs photoanode could significantly improve the efficiency of dye-sensitized solar cells owing to its synergic effects, i.e. effective dye adsorption mainly originated from TiO₂ nanoparticles and rapid electron transport in one-dimensional TiO₂ nanotubes. The results of the present investigation suggested that the DSSC based on 10 % TNTs/TNPs showed better photovoltaic performance than cell made pure TiO₂ nanoparticles. The highest energy-conversion efficiency of 2.80 % is achieved by composite TNTs (10 %)/TNPs film, which is 68 % higher than that pure TNPs film and far larger than that formed by bare TNTs film (94 %). The charge transport and charge recombination behaviors of DSSCs were investigated by electrochemical impedance spectra and the results showed that composite TNTs/TNPs film-based cell possessed the lowest transfer resistances and the longest electron lifetime. Hence, it could be concluded that the composite TNTs/TNPs photoanodes facilitate the charge transport and enhancing the efficiencies of DSSCs.