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.     

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.     

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.     

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 %).     

Growth of aligned polypyrrole acicular nanorods and their application as Pt‐free semitransparent counter electrode in dye‐sensitized solar cell

Polypyrrole films on fluorine doped tin oxide (FTO)‐coated glass substrate were prepared in situ by placing FTO/glass substrates where pyrrole was polymerized by methyl orange‐ferric chloride complex. The atomic force microscopy image indicated growth of acicular nanorods of polypyrrole. These films exhibited catalytic activity towards I₃⁻/I⁻ redox couple and have been investigated for counter electrode application in dye‐sensitized solar cell (DSSC). The fabricated DSSC with N719 dye/TiO₂ as photoanode, and PPy/FTO as counter electrode shows ~1.7% efficiency.     

Effect of organic dye on the performance of dye-sensitized solar cell utilizing TiO2 nanostructure films synthesized via CTAB-assisted liquid phase deposition technique

This work is concerned with the growth of TiO₂ nanostructures as photovoltaic materials of dyesensitized solar cell (DSSC) via phase liquid deposition technique treated with CTAB surfactant. This work investigates the influence of organic dyes, N719, N3 and Z907 as photosensitizer on the photovoltaic parameters of TiO₂ nanostructures dye-sensitized solar cells (DSSCs). It also highlights the effect of the concentration of the best dye, N719 on the performance of the cell. The platinum films as counter electrode of the DSSC were prepared by sputtering platinum pellet on ITO substrate. The redox couple of the electrolyte utilized in the DSSC was iodide/triiodide. The cell sensitized with N719 dye demonstrated the best performance compared with the cell sensitized with another two dyes, N3 and Z907. This is due to N719 dye possess the highest optical absorption in visible region. The cell sensitized with 0.8 mM N719 dye performs the highest short-circuit current density, J _sc and power conversion efficiency, η since it posses the highest absorption in visible region. The DSSC utilizing 0.8 mM N719 dye demonstrated the highest J _sc and η of 6.48 mA cm^?2 and 1.69%, respectively.     

A high performance solid-state asymmetric supercapacitor based on Anderson-type polyoxometalate-doped graphene aerogel

The manufacture of single-atom transition metal-doping carbon nanocomposites as electrode materials is crucial for electrochemical energy storage with high energy and power density. However, the simple strategy for preparation of such active materials with controlled structure remains a great challenge. Here, cobalt-doped carbon nanocomposites (Co-POM/rGO) were synthesized successfully by deposition of Anderson-type polyoxometalate (POM) on the surface of reduced graphene oxide (rGO) aerogel via one-pot hydrothermal treatment. The resulting Co-POM/rGO possesses three-dimensional graphene-based frameworks with hierarchical porous structure, high surface area and uniform single-atom metal doping. These intriguing features render Co-POM/rGO to be a promising electrode for applications in electrochemical energy storage. As an electrode material of a supercapacitor, Co-POM/rGO shows high-performance electrochemical energy storage (211.3 F g^?1 at 0.5 A g^?1). Furthermore, the solid-state asymmetric supercapacitor (ASC) device, using Co-POM/rGO as a positive electrode, exhibits the outstanding energy density of 37.6 Wh kg^?1 at a power density of 500 W kg^?1, and high capacitance retention of 95.2% after 5000 charge–discharge cycles. These results indicate that the proposed strategy for rational design of single-atom-metal doped carbon nanocomposites for flexible ASC devices with excellent capacitive properties.

     

Ferrocene-functionalized graphene electrode for biosensing applications

A novel ferrocene-functionalized reduced graphene oxide (rGO)-based electrode is proposed. It was fabricated by the drop casting of ferrocene-functionalized graphene onto polyester substrate as the working electrode integrated within screen-printed reference and counter electrodes. The ferrocene-functionalized rGO has been fully characterized using FTIR, XPS, contact angle measurements, SEM and TEM microscopy, and cyclic voltammetry. The XPS and EDX analysis showed the presence of Fe element related to the introduced ferrocene groups, which is confirmed by a clear CV signal at ca. 0.25 V vs. Ag/AgCl (0.1 KCl). Mediated redox catalysis of H₂O₂ and bio-functionalization with glucose oxidase for glucose detection were achieved by the bioelectrode providing a proof for potential biosensing applications.     

Quasi-solid-state dye-sensitized solar cells assembled with polymeric ionic liquid and poly(3,4-ethylenedioxythiophene) counter electrode

Poly(3,4-ethylenedioxythiophene) nanofibers (PEDOT-NF) with high catalytic activity were synthesized and employed as a counter electrode in dye-sensitized solar cells (DSSCs). A polymeric ionic liquid (PIL) was used as a gelling agent and an iodide source for making a highly conductive gel polymer electrolyte. A quasi-solid-state DSSC assembled with this PIL-based gel polymer electrolyte and PEDOT-NF counter electrode exhibited high conversion efficiency of 8.12% at 100 mW cm^− 2.     

Enhanced dielectric properties of poly(dimethyl siloxane) bimodal network percolative composite with chemically modified graphene

Bimodal network composite was prepared using a two-step method containing graphene modified by γ-(2, 3-epoxypropoxy) propyl trimethoxysilane (KH560), short chain poly(dimethyl siloxane) (C_S-PDMS) and long chain poly(dimethyl siloxane) filled with treated fumed silica (C_L-h-PDMS). A series of composites with different filler contents (including reduced graphene oxide and reduced graphene oxide grafted with KH560, referred to rGO and KrGO, respectively) were prepared to explore their percolation thresholds (fc). We discover that the dielectric constant and loss of 1.32 vol% KrGO/h-PDMS composite were 18.8 and 0.13 at 10² Hz before fc, respectively, which was 2.1 and 0.12 times that of rGO/h-PDMS, and 6.6 and 2.1 times that of pure h-PDMS. The origin is that KH560 insulting layer increases the interlayer distance of graphene sheets to cut down the leakage current. In addition, the modulus of 1.32 vol% KrGO/h-PDMS is less than 3 MPa.     

Tetrazole thiolate/disulfide organic redox couples carrying long alkyl groups in dye-sensitized solar cells with Pt-free electrodes

Colorless tetrazole thiolate/sulfide redox couples carrying long alkyl groups, such as n-butyl, n-hexyl, and n-octyl groups, were synthesized as electrolytes in iodine/iodide-free dye-sensitized solar cells (DSSCs). Among N719/TiO₂-based DSSCs employing these highly soluble redox couples for 3-methoxypropionitrile (3-MPN) and ionic liquid with PEDOT counter electrode, the DSSC with n-hexyl redox analogue gave an optimized η value of 4.32%. An observed respectable quantum efficiency for 400–500 nm light is in sharp contrast to the decreased performance for iodine/iodide systems that originates from the substantial light absorption of iodine. On the other hand, the redox possessing n-octyl group significantly lowered the cell performance, which could be a result of the much increased resistance of electrolyte diffusion in the DSSC.     

Comparative study of dye-sensitized solar cell utilizing selenium and palladium cathode

This work is concerned with the comparative study of dye-sensitized solar cell (DSSC) utilizing selenium (Se) and palladium (Pd) cathode. The influence of concentration of selenium dioxide (SeO₂) and palladium chloride (PdCl₂) on the performance of the device has been investigated. The Se and Pd cathode have been prepared via dip coating-based multilayer deposition technique. The device using Se cathode with seven layers possesses the highest performance in term of short-circuit current density (J_sc). The photovoltaic measurement results show that the device utilizing Pd cathode demonstrates higher power conversion efficiency (η) compared with that of the device using Se cathode. The highest η of the device with Se and Pd cathode are 0.071 and 0.169%, obtained at the 0.5 ?M SeO₂ and 0.60 ?M PdCl₂, respectively. The Pd cathode-based device prepared with 0.60 ?M PdCl₂ owns the highest η due to the lowest sheet resistance (R_s). These photovoltaic results imply single material has potential to be modified into binary or ternary cathode material in order to improve the performance of DSSC.     

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^?.     

Novel technique to form electrode–electrolyte nanointerface in all-solid-state rechargeable lithium batteries

The electrode–electrolyte nanocomposites, where the nano-sized NiS electrode with large capacity was embedded in the 80Li₂S · 20P₂S₅ electrolyte with high Li⁺ conductivity, were successfully prepared by the mechanochemical method. Contact area of solid–solid interface between the electrode and the electrolyte was remarkably increased in the nanocomposites. All-solid-state cell using the nanocomposites as a working electrode exhibited larger capacity and better cycling performance than the cell using the electrode obtained by conventional hand-mixing of powders. The mechanochemical technique sheds light on a new formation process of electrode–electrolyte interfaces endowing solid-state batteries with high power density and high energy density.     

A novel paper-based device coupled with a silver nanoparticle-modified boron-doped diamond electrode for cholesterol detection

A novel paper-based analytical device (PAD) coupled with a silver nanoparticle-modified boron-doped diamond (AgNP/BDD) electrode was first developed as a cholesterol sensor. The AgNP/BDD electrode was used as working electrode after modification by AgNPs using an electrodeposition method. Wax printing was used to define the hydrophilic and hydrophobic areas on filter paper, and then counter and reference electrodes were fabricated on the hydrophilic area by screen-printing in house. For the amperometric detection, cholesterol and cholesterol oxidase (ChOx) were directly drop-cast onto the hydrophilic area, and H₂O₂ produced from the enzymatic reaction was monitored. The fabricated device demonstrated a good linearity (0.39 mg dL⁻¹ to 270.69 mg dL⁻¹), low detection limit (0.25 mg dL⁻¹), and high sensitivity (49.61 μA mM⁻¹ cm⁻²). The precision value for ten replicates was 3.76% RSD for 1 mM H₂O₂. In addition, this biosensor exhibited very high selectivity for cholesterol detection and excellent recoveries for bovine serum analysis (in the range of 99.6–100.8%). The results showed that this new sensing platform will be an alternative tool for cholesterol detection in routine diagnosis and offers the advantages of low sample/reagent consumption, low cost, portability, and short analysis time.     

Spray coated multi-wall carbon nanotube counter electrode for tri-iodide (I3-) reduction in dye-sensitized solar cells

Spray coated multi-wall carbon nanotube (CNT) film on fluorine-doped tin oxide glass substrate has been investigated as a counter electrode for tri-iodide reduction in dye-sensitized solar cells. The photovoltaic parameters, in particular, the fill factor shows a strong dependency on the spraying time of multi-wall CNTs. Under one sun illumination (100 mW cm⁻², AM 1.5 G), the device shows a maximum energy conversion efficiency of 7.59%. Electrochemical impedance spectroscopy analysis reveals a decrease in the charge transfer resistance of multi-wall CNT counter electrode with increase of spraying time; leads to an improvement in the photovoltaic parameters.     

Facile synthesis of cobalt oxide/reduced graphene oxide composites for electrochemical capacitor and sensor applications

Reduced graphene oxide sheets decorated with cobalt oxide nanoparticles (Co₃O₄/rGO) were produced using a hydrothermal method without surfactants. Both the reduction of GO and the formation of Co₃O₄ nanoparticles occurred simultaneously under this condition. At the same current density of 0.5 A g⁻¹, the Co₃O₄/rGO nanocomposites exhibited much a higher specific capacitance (545 F g⁻¹) than that of bare Co₃O₄ (100 F g⁻¹). On the other hand, for the detection of H₂O₂, the peak current of Co₃O₄/rGO was 4 times higher than that of Co₃O₄. Moreover, the resulting composite displayed a low detection limit of 0.62 μM and a high sensitivity of 28,500 μA mM⁻¹cm⁻² for the H₂O₂ sensor. These results suggest that the Co₃O₄/rGO nanocomposite is a promising material for both supercapacitor and non-enzymatic H₂O₂ sensor applications.     

A microfluidic electrochemical device for high sensitivity biosensing: Detection of nanomolar hydrogen peroxide

We report herein a simple device for rapid biosensing consisting of a single microfluidic channel made from poly(dimethylsiloxane) (PDMS) coupled to an injector, and incorporating a biocatalytic sensing electrode, reference and counter electrodes. The sensing electrode was a gold wire coated with 5 nm glutathione-decorated gold nanoparticles (AuNPs). Sensitive detection of H₂O₂ based on direct bioelectrocatalysis by horseradish peroxidase (HRP) was used for evaluation. HRP was covalently linked the glutathione–AuNPs. This electrode presented quasi-reversible cyclic voltammetry peaks at ?0.01 V vs. Ag/AgCl at pH 6.5 for the HRP heme Fe^III/Fe^II couple. Direct electrochemical activity of HRP was used to detect H₂O₂ at high sensitivity with a detection limit of 5 nM in an unmediated system.     

A new composite electrode of Ni-Ferrite/TiOx/Si(111): Preparations and photoelectrochemical studies

A composite electrode of Ni-ferrite/TiO_x/Si(111) was synthesized by grafting Ni²⁺Fe²⁺Fe³⁺–LDH–TiCl₃ (LDH: Layered Double Hydroxides) on n-Si(111) surface and calcined under 1100 °C. Photoelectric research results indicated that the electrode had good photovoltaic effects in an electrolyte solution containing 7.6 M HI and 0.05 M I₂, while platinum plate was used as counter-electrode. The observed photo-voltages (U_pv) and photocurrent densities (j_pc) of the electrode were at ?0.75 V and 5.35 mA/cm², respectively. Compared with electrodes of oxidized n-Si(111) crystal and n-Si(111) wafer covered by Ni-ferrites, j_pc of the electrode Ni-ferrite/TiO_x/Si(111) was increased greatly.     

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.