Heteroatom‐doped graphene and its application as a counter electrode in dye‐sensitized solar cells

The most frequently used counter electrode (CE) in dye‐sensitized solar cells (DSSCs) is platinum on fluorine‐doped tin oxide glass. This electrode has excellent electrical conductivity, chemical stability, and high electrocatalytic affinity for the reduction of triiodide. However, the high cost of metallic platinum and the poor electrochemical stability pose a major drawback in the commercial production. This has necessitated a search for a non‐precious metal and metal‐free electrocatalyst that demonstrates better catalytic activity and longer electrochemical stability for practical use in DSSCs. Graphene has been at the centre of attention due to its excellent optoelectronic properties. However, a defect‐free graphene sheet is not suitable as a CE in DSSCs, because of its neutral polarity which often restricts efficient charge transfer at the graphene/liquid interface, irrespective of the high in‐plane charge mobility. Hence, heteroatom‐doped graphene‐based CEs are being developed with the aim to balance electrical conductivity for efficient charge transfer and charge polarization for enhanced reduction activity of redox couples simultaneously. The elements commonly used in chemical doping of graphene are nitrogen, oxygen, boron, sulfur, and phosphorus. Halogens have also recently shown great promise. It has been demonstrated that edge‐selective heteroatom‐doping of graphene imparts both efficient in‐plane charge transfers and polarity, thereby enhancing electrocatalytic activity. Thus, heteroatom‐doped graphene serves as a good material to replace conventional electrodes and enhance power conversion efficiency in DSSCs. The focus is to reduce the cost of DSSCs. This review explores the performance of DSSCs, factors that influence the power conversion efficiency, and various physicochemical properties of graphene. It further outlines current progress on the synthetic approaches for chemical doping (substitutional and surface transfer doping) of graphene and graphene oxide with different heteroatoms in order to fine‐tune the electronic properties. The use of heteroatom‐doped graphene as a CE in DSSCs and how it improves the photovoltaic performance of cells is discussed.     

Role of graphene and transition metal dichalcogenides as hole transport layer and counter electrode in solar cells

Photovoltaic (PV) technology got much attention in the past few decades in developing advanced and environment friendly solar cells (SCs). However, high cost, unstable nature, and low efficiency are major limitations towards commercialization of SCs. To overcome the issues, two-dimensional materials (2DMs) have been exploited due to low cost, high catalytic activity, fast charge separation, and better electrochemical performance. The review emphasis on (a) the electrochemical performance of graphene and transition metal dichalcogenides (TMDCs) as a hole transport layer (HTL) in SCs and (b) to explore low-cost and effective counter electrode (CE) based on graphene and TMDCs for dye-sensitized solar cell (DSSC). The review presents a comparative analysis of 2DMs as HTL and CE to attain highly efficient and low-cost PV devices. Multiple combinations of the material with graphene, graphene oxide (GO), reduced graphene oxide (rGO), tungsten disulfide (WS₂), molybdenum disulfide (MoS₂) as HTL, and CE material in PV cells are discussed and comparatively analyzed. Numerous strategies are briefly discussed to enhance the efficiency of SCs by utilizing graphene and TMDCs based HTL and CEs. The review focuses on the recent progress in developing low-cost and highly efficient PV devices by using 2DMs. Our study reveals that GO/PEDOT:PSS demonstrate a maximum power conversion efficiency (PCE) of 13.1% when fabricated at different revolutions. Moreover, our statistical analysis unveils that efficiency of the cell can be enhanced by optimizing the layer thickness, which provide a route to develop highly efficient and better performance SCs that can be exploited for future commercial applications.     

Photocatalytic properties of two-dimensional graphene and layered transition-metal dichalcogenides based photocatalyst for photoelectrochemical hydrogen generation: An overview

Hydrogen production through photoelectrochemical (PEC) water-splitting process has drawn significant research attention because it is a promising clean source of energy for improving earth climate in the future. Two-dimensional (2D) graphene and transition metal dichalcogenides (TMDCs), as the core of the system, have become versatile materials for the development of photocatalyst due to their distinct optical, electrical, thermal and mechanical properties. TMDCs have received significant consideration because of low-cost and earth-abundant catalysts that can replace noble metals, such as Pt. Therefore, comprehensive discussions on the structure and properties of 2D graphene and layered TMDCs materials are presented. We also gather and review various fabrication methods for TMDCs-based and graphene-TMDCs-based photocatalysts that can affect the PEC performance and hydrogen evolution. The inherent limitations and several future trends on 2D graphene and layered TMDCs-based photocatalyst for PEC water-splitting application are also discussed.     

Omnidirectional light‐harvesting enhancement of dye‐sensitized solar cells with ZnO nanorods

In this work, the chemical solution method was used to prepare one‐dimensional (1‐D) ZnO nanorod (NR) photoelectrodes, which were subsequently used in dye‐sensitized solar cells (DSSCs). The effects of ZnO NRs on the omnidirectional light‐harvesting performance of DSSCs were investigated by growing ZnO NRs with varying lengths as photoelectrodes. On the basis of field‐emission scanning electron microscopy and ultraviolet (UV)–vis‐near infrared (NIR) spectroscopy measurements on the ZnO NR photoelectrodes of varying lengths, it was observed that the dye adsorption and light‐scattering properties of NRs are affected by their length. In addition, DSSCs were prepared using ZnO NRs of varying lengths. These DSSCs were examined via electrochemical impedance spectroscopy, monochromatic incident photon‐to‐electron conversion efficiency measurements, and solar simulations to measure their photovoltaic efficiencies, carrier lifetimes, and device characteristics in omnidirectional antireflection measurements. The highest photovoltaic efficiency between these DSSCs was 0.33%. Omnidirectional antireflection measurements were performed on DSSCs with different ZnO NR lengths, and it was observed that the smallest change in efficiency between angles of incidence of 0° and 60° was 23%. Therefore, the light‐scattering properties of ZnO NR photoelectrodes improve the omnidirectional antireflection light capture characteristics of DSSCs.     

Reduced graphene oxide films as transparent counter-electrodes for dye-sensitized solar cells

Stand-alone graphene-based films were prepared from graphene oxide (GO) nanoplatelets and their use as counter-electrodes (CEs) in dye-sensitized solar cells (DSCs) was investigated. The graphene-based CEs were produced by spray deposition of GO and chemically reduced GO, followed by thermal annealing under an inert atmosphere. These GO-based CEs were shown to have similar transparency as a reference CE made of Pt. Consistent with impedance data from symmetrical half-cells, DSCs assembled with such GO-based CEs exhibited relative efficiencies of ca. 75% comparatively to the reference Pt CE. The possibility of obtaining transparent (transmittance higher than 80%) and reasonable catalytic films for DSCs (energy conversion efficiency of 2.64%) from GO nanoplatelets was demonstrated. The need for reduction of the graphene oxide nanoplatelets prior to deposition was not observed, allowing for a simplified CE manufacturing process. However, further work is still needed to equal or surpass the performance of Pt CEs.     

3D graphene from CO2 and K as an excellent counter electrode for dye‐sensitized solar cells

3D graphene, which was synthesized directly from CO₂ via its exothermic reaction with liquid K, exhibited excellent performance as a counter electrode for a dye‐sensitized solar cell (DSSC). The DSSC has achieved a high power conversion efficiency of 8.25%, which is 10 times larger than that (0.74%) of a DSSC with a counter electrode of the regular graphene synthesized via chemical exfoliation of graphite. The efficiency is even higher than that (7.73%) of a dye‐sensitized solar cell with an expensive standard Pt counter electrode. This work provides a novel approach to utilize a greenhouse gas for DSSCs.     

CoxMo(1−x)S2 intermixed reduced graphene oxide as efficient counter electrode materials for high-performance dye-sensitized solar cells

In this study, nanocomposite electrocatalysts composed of cobalt molybdenum sulfide flower-like nanosheets intermixed with reduced graphene oxide (Co_xMo_(1?x)S₂/rGO) were prepared by a facile one-step hydrothermal method and were used to prepare counter electrodes (CE) of high-performance dye-sensitized solar cells (DSSCs). The structural and morphological analysis of the nanocomposites were carried out using field emission scanning electron microscopy, micro-Raman, and X-ray photoelectron spectroscopies, which revealed 2-dimensional petal-like nanosheets of the ternary metal sulfides intermixed with the reduced graphene oxide sheets. The DSSCs fabricated using Co_xMo_(1?x)S₂/rGO (CMS-2/rGO) as the counter electrode material exhibited power conversion efficiency (PCE) of 9.04%, which was found to be superior to the PCEs of DSSCs with CEs made of MoS₂/rGO (7.56%), Co_xMo_(1-x)S₂ (7.04–7.78%), and conventional Pt (8.72%). The electrochemical measurements showed that the excellent electrocatalytic activity of the Co_xMo_(1?x)S₂/rGO on I₃^- can be attributed to the expanded active sites, improved charge transfer across the CE, and reduced electrode/electrolyte interface resistance. The facile preparation approach and outstanding catalytic behavior of Co_xMo_(1?x)S₂/rGO indicate that the nanostructured Co_xMo_(1-x)S₂/rGO intermix would be a cost-effective material over the platinum used in the CE of DSSCs.     

VC@C composites derived from polyoxovanadate assisted by dicyandiamide as low-cost platinum-free counter electrode electrocatalyst for dye-sensitized solar cells

Vanadium-based carbides have been applied as Pt-free counter electrodes (CEs) electro-catalysts for dye-sensitized solar cells (DSSCs) due to the advantages of earth-abundant reserves, diverse composition, ease modification, and low cost. Herein, the polyoxovanadate (NH₄)₂V₆O₁₆ as V source assisted by dicyandiamide (C₂H₄N₄) as C source via simply physical mixing by ball-milling to assemble VC@C precursors. And then, five different VC@C composites derived from precursors with mass ratios of dicyandiamide to polyoxovanadate of 5:1, 10:1, 15:1, 20:1 and 25:1 at 900 °C, and further achieved power conversion efficiencies (PCEs) of 5.4%, 5.6%, 6.6%, 6.2% and 5.1% as CEs for regenerate traditional I₃⁻/I⁻ couple in the encapsulated DSSCs, respectively. The effects of different mass ratio of dicyandiamide on the catalytic performances of VC@C composite CEs were also assessed using cyclic voltammetry, electrochemical impedance spectroscopy and Tafel polarization experiments. The photocurrent-photovoltage (J-V) results indicated that VC@C composites CEs had high conductivity and rich number of active sites, which indicated that VC@C composites could be a cost-effective and high-performance alternative Pt-based CEs catalyst for DSSCs.     

Facile synthesis and promising application of iron-doped nickel selenide nanoparticles as high-efficiency counter electrodes of dye-sensitized solar cells

The coexistence of different metal cations in single crystal structure may improve electron transfer rate and catalytic activity. Hence, a series of iron-doped nickel selenide nanoparticles were engineered by adjusting the iron amount as counter electrodes (CEs) in dye-sensitized solar cells. By contrast, the as-designed iron-doped nickel selenides possess more excellent electrochemical properties than the pure nickel selenides. In particular, 10% Fe-Ni_0.85Se achieves the lowest charge-transfer resistance and highest electrocatalytic performance, outperforming that of Pt. As expected, based on the optimal 10% Fe-Ni_0.85Se CE, the dummy dye-sensitized solar cell yields a higher power conversion efficiency of 8.57% compared with that of 15% Fe-Ni_0.85Se (8.33%), 5% Fe-Ni_0.85Se (8.15%), Ni_0.85Se (7.89%), and even Pt CEs (8.04%).     

Evaluation of decay photocurrent measurements in dye‐sensitized solar cells: Application to laser beam‐induced current technique

The use of the laser beam‐induced current (LBIC) technique in photovoltaic devices is widespread, but its use in photoelectrochemical cells, such as dye‐sensitized solar cells (DSSCs), is limited due to the configuration of these devices. The main reason is the very slow response time of DSSCs in the decay process, and therefore LBIC scans take too long to perform. We have designed a procedure published in the literature to correct the photocurrent values obtained by the LBIC technique, based on an algorithm that uses a decreasing mono‐exponential model. This work presents a study of the decay measurements in DSSCs using several functions, in order to improve the algorithm designed. It concludes that functions such as a decreasing bi‐exponential or Becquerel function generate better fits to experimental data. Copyright © 2010 John Wiley & Sons, Ltd.     

Dye-sensitized solar cells using graphene-based carbon nano composite as counter electrode

We demonstrated a counter electrode in dye-sensitized solar cells (DSSCs) using the graphene-based multi-walled carbon nanotubes (GMWNTs) structure. Graphene layers were prepared by drop casting on a SiO₂/Si substrate and multi-walled carbon nanotubes (MWNTs) were synthesized on graphene layers using iron catalyst by chemical vapor deposition. The structural properties of GMWNTs were investigated by transmission electron microscope and field-emission scanning electron microscopy. The GMWNTs sheets were lifted off from the Si substrate by buffered oxide etching and were transplanted on fluorine-doped tin oxide glass by Van der Waals force as a counter electrode. From the electrochemical impedance spectroscopy and energy conversion efficiencies, electrochemical properties of GMWNTs were comparable with those of MWNTs counter electrode. The results suggested that GMWNTs were one of the candidates for a counter electrode for dye-sensitized solar cells.     

Graphene‐based ternary composites for supercapacitors

The research on electrode materials for supercapacitor application continues to evolve as the request of high‐energy storage system has increased globally due to the demand for energy consumption. Over the past decades, various types of carbon‐based materials have been employed as electrode materials for high‐performance supercapacitor application. Among them, graphene is 1 of the most widely used carbon‐based materials due to its excellent properties including high surface area and excellent conductivity. To exploit more of its interesting properties, graphene is tailored to produce graphene oxide and reduced graphene oxide to improve the dispersibility in water and easy to be incorporated with other materials to form binary composites or even ternary composites. Nowadays, ternary composites have attracted enormous interest as 2 materials (binary composites) cannot satisfy the requirement of the high‐performance supercapacitor. Thus, many approaches have been employed to fabricate ternary composites by combining 3 different types of electroactive materials for high‐performance supercapacitor application. This review focuses on the supercapacitive performance of graphene‐based ternary composites with different types of active materials, ie, conducting polymers, metal oxide, and other carbon‐based materials.     

Effect of microfluidic electrolyte on the photovoltaic performance of ZnO-nanowire-based dye-sensitised solar cells

ZnO-nanowire-based dye-sensitised solar cells (DSSCs) were prepared to investigate the effect of microfluidic electrolyte on the photovoltaic performance of solar cells. At first, long and well-aligned ZnO nanowires were synthesised on FTO substrate via the improved hydrothermal method. The structure and crystallinity properties of ZnO nanowires were characterised by using SEM, TEM and XRD. The photovoltaic characteristics of the assembled DSSCs were measured under various flowrates of microfluidic electrolyte. The results showed that variations of the microfluidic electrolyte had little effect on the fill factor of the cells. However, the photocurrent and photovoltage of the solar cells exhibited systematic changes with the decrease of microfluidic electrolyte: the short-circuited current of the DSSCs decreased while the open-circuit voltage increased. The phenomenon could remain in some extent after cessation of injecting the electrolyte within a short time. The possible influencing mechanism of the microfluidic electrolyte on the photovoltaic performance was discussed.     

Improvement on the long-term stability of flexible plastic dye-sensitized solar cells

We investigate the long-term stability of performance for plastic dye-sensitized solar cells (DSSCs) based on organic iodides (TBAI or PMII) in methoxypropionitrile-based electrolytes. Plastic DSSCs containing TBAI maintain 96.9% of baseline efficiency under more than 1000 h prolonged one sun light irradiation and thermal stress (60 °C) aging. The factors of device long-term stability, such as the effects of organic iodides, cell-sealing conditions, and the sheet resistance of indium tin oxide coated polyethylene naphthalate substrate (ITO/PEN) are discussed via using electrochemical impedance spectroscopy and electrical resistance measurement.     

Synthesis of supported Pt nanoparticles by sonication for ORR: Effect of the graphene oxide-carbon composite

Pt supported on graphene oxide (GO), reduced graphene oxide (RGO), carbon Vulcan (C) and GO-C composite were prepared by using sonication as a simple synthesis method in the absence of any special capping agent or thermal treatment. X-ray diffraction (XRD), Raman spectroscopy, Transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) techniques were used to characterize the materials synthesized. The electrocatalysts synthesized were evaluated for oxygen reduction reaction (ORR) in acid medium by using cyclic and linear voltammetry tests. The characterization results indicated that the highest dispersion of small Pt particles was observed on the samples supported on GO materials compared to carbon Vulcan due to the oxygen functional surface groups, which promoted a homogeneous distribution of Pt nanoparticles. The electrochemical characterization indicated that Pt/GO-C composite exhibited a 50% more specific and mass activity at 0.85 V for ORR than the conventional Pt/C catalysts, which is associated to Pt-support interaction that modifies the electronic properties of Pt for electrochemical application in fuel cell. GO-C (1:1) can be a promising support for improving the electrochemical activity for ORR.     

Use of single‐wall carbon nanohorns as counter electrodes in dye‐sensitized solar cells

The catalytic activity of single‐wall carbon nanohorns (SWNH) as counter electrodes (CE) of dye‐sensitized solar cells (DSC) was studied for the iodide/triiodide redox reaction. The catalytic activities of SWNH and high surface SWNH (HS‐SWNH) obtained by partial oxidation of SWNH were assessed based on charge‐transfer resistances (R_ct) and current–voltage curves. A half‐cell configuration was used, and CE performances were compared to CEs made of carbon black (CB) and Pt. A CE assembled with HS‐SWNH and mixed with 10 wt.% of hydroxyethyl cellulose (HEC) ‐ HS‐SWNH/HEC was found to have the highest electrocatalytic activity (lowest R_ct) among all the carbon‐based CEs tested when annealed at 180 °C (R_ct = 141 Ω cm²); however, a very thick film (several tens of µm) would be required in order to perform comparably to a Pt CE. The annealing of such CE at higher temperatures (above 400 °C) did not improve its catalytic activity, contrary to the other studied carbonaceous CEs. The redox catalytic activity of SWNH and HS‐SWNH decorated with Pt was also studied on a half‐cell configuration and compared to that of Pt/CB and pristine Pt. The Pt/SWNH/HEC CE showed the highest electrocatalytic activity per mass of Pt, needing just 50% of Pt load to yield the same electrocatalytic activity of a DSC equipped with a Pt CE, but having half of its transparency. Additionally, applications in temperature‐sensitive substrates are envisioned for the Pt/SWNH/HEC CE due to the use of lower annealing temperatures. Copyright © 2012 John Wiley & Sons, Ltd.     

Synthesis of nitrogen‐doped graphene catalyst by high‐energy wet ball milling for electrochemical systems

Platinum group metal‐based (PGM) catalysts are widely applied in many electrochemical systems such as fuel cells or metal–air batteries because of their excellent catalytic performance. But the high raw material cost of PGM catalysts has become a significant issue. In recent years, huge efforts have been made to reduce the material cost of electrochemical systems by developing non‐PGM catalysts, and as one of the promising non‐PGM catalysts, nitrogen‐doped graphene (N‐G) has emerged. In this research, nanoscale high‐energy wet ball milling methodology was investigated as an effective synthesis method for N‐G catalysts by using graphene oxide and melamine as raw materials. The main purpose is to study reaction mechanism of the synthesis process and the physical, chemical, and electrochemical properties of N‐G catalysts generated by this mechanochemical approach. The elemental composition, chemical bonding composition, and electron transfer number of the synthesized products were characterized. The results show that the electron transfer number of the N‐G catalyst with 23.2 at% nitrogen doping content, synthesized by the high‐energy wet ball milling method, has attained a value of 3.87, which is close to the number (3.95) of Pt/C catalysts, and the grinding time was found to be a significant factor in the properties of N‐G catalysts in the experiments. The results also show that the high‐energy wet ball milling developed in this research is a promising method to synthesize high‐performance N‐G catalysts with a simple and easy controllable approach. Copyright © 2016 John Wiley & Sons, Ltd.     

Recent research progress on polymer electrolytes for dye-sensitized solar cells

Dye-sensitized solar cells (DSSCs) have attracted large attention due to their easy fabrication, low cost and high conversion efficiency. Electrolytes play an important role in the photovoltaic performance of the DSSCs and many efforts have been contributed to study different kinds of electrolytes with various characteristics such as liquid electrolytes, polymer electrolytes and so on. Because the leakage and the volatilization of liquid electrolytes hinder their practical applications in the DSSCs, polymer electrolytes with high ionic conductivity, excellent thermal stability and long-term stability of the DSSCs based on them are alternatives to liquid electrolytes especially for the quasi-solid-state DSSCs. In this paper, research on solid polymer electrolytes is summarized and the influence of salt concentration on ionic conductivity of solid polymer electrolytes is described and thoroughly explained. On the other hand, the advantages of gel polymer electrolytes (GPEs) are introduced. The factors affecting the ionic conductivity of GPE and the performance of their DSSCs, consisting of the polymer concentration and type, the iodide salts, the solvents and the temperature are discussed. The tendency and the reasons of their influence are expounded in detail. To enhance the properties of GPE, many strategies are taken such as the fabrication of porous structure in the GPE membrane, the incorporation of proton donors, the introduction of inorganic nanoparticles and the addition of pyridine derivatives. Their improving effect and the causes for the enhancement are set forth.     

Novel improvements in the sensitizers of dye‐sensitized solar cells for enhancement in efficiency—a review

In the present review article, we have focused our study on the novel improvements that have been brought about in the molecular design of various sensitizers for application in dye‐sensitized solar cells (DSSCs). The sensitizers based on noble metals such as ruthenium, osmium, and rhenium showed high efficiency, but their cost and complicated synthesis restrict their wide applications. Further, to reduce the cost of fabrication of DSSCs, researchers are focusing their interest in organic sensitizers. In this context, organic dyes have offered several possibilities, as by improving their molecular structure brings about improvement in the light harvesting ability of dyes, and with the help of such dyes, optimal DSSCs have been fabricated. Further, to reduce the cost of DSSCs, researchers are also focusing on natural sensitizers such as betacyanin and anthocyanin or chlorophyll, as natural sensitizers are easy to prepare, cost effective, and environmentally friendly. With the help of these natural sensitizers, eco‐friendly and more cost‐effective DSSCs can be fabricated. Thus, we found from our study that beside metal‐based sensitizers, organic and natural sensitizers also offer a vast potential for the optimization of efficiency in DSSCs. Copyright © 2015 John Wiley & Sons, Ltd.     

Triphenylamine- and benzothiadiazole-based dyes with multiple acceptors for application in dye-sensitized solar cells

Two novel dyes TPAR3 and BTDR2 based on triphenylamine and benzothiadiazole, respectively, with multiple electron acceptors were synthesized and characterized by FT-IR, ¹H NMR, TGA and thermomechanical analysis (TMA). They carried terminal cyanoacrylic acid electron acceptors/anchoring moieties, which were connected with the central unit through a thiophene ring. The absorption bands of the dyes were extended up to ∼570 nm with long-wave absorption maximum at 425-455 nm and optical band gap of 2.10-2.17 eV. The dyes emitted yellow-orange light with photoluminescence maximum at 547-615 nm. We have investigated the photovoltaic properties of quasi solid state dye sensitized solar cells (DSSCs) based on these metal free organic dyes. It has been found that the power conversion efficiency of the DSSCs based on composite zinc titanium oxide (ZTO) nanocrystalline photoelectrode is higher than that for TiO₂ based DSSCs. This has been attributed to the longer electron lifetime and more negative conduction band edge of ZTO. The overall power conversion efficiency of the DSSCs based on TPAR3 and BTDR2 employing ZTO photoelectrode is 6.3% and 3.6%, respectively. These results indicate that both the acceptor moiety of metal free organic dyes and ZTO photoelectrode have an effect on the photovoltaic performance of DSSCs.