Zirconium oxide (ZrO2) is acquiring considerable attention of most of the research groups and leading to a large number of publications due to its unique properties, especially in the context of emerging trends in the third generation of solar cell research. ZrO2 films offer magnificent aspects related to physicochemical properties, and the properties are found to be dependent on synthesis methods. In the present review, various deposition techniques used to grow zirconium oxide thin films and their application to enhance the quantum efficiency of titanium oxide (TiO2) based dye-sensitized solar cells (DSSCs) are discussed. Also, the modulated performances of DSSCs fabricated by growing the conformal ZrO2 insulating films to retard interfacial recombination dynamics on preformed TiO2 films are discussed.
The electron transport layer (ETL) plays a crucial role in the rapidly developed perovskite solar cells (PSCs). SnO2 has become one of the most promising alternatives to the TiO2 ETL due to its superior characteristics, such as the wider bandgap and hysteresis-free. However, at this stage, a lot of preparation methods of SnO2 ETL exist in high temperature and long time, those undoubtedly increase the cost and time of preparation. Herein, we report a low-temperature solution-processed SnO2 ETL without high annealing temperature, and a special bromine salt is used to modify SnO2, which leads to a higher transmittance and improved carrier transport ability. Due to the excellent optical and electrical properties, the photoelectric conversion efficiency of the prepared PSC reaches up to 18.8%. Moreover, it can be fabricated using facile solution processing at low temperature, making it particularly attractive for flexible development and low-cost commercialization.
Cadmium selenide (CdSe) thin films were grown by electrochemical technique on fluorine-doped tin oxide (FTO)-coated conducting glass substrates in the presence of organic surfactants. The influence of organic surfactants like polyethylene glycol (PEG) and polyvinylpyrrolidone (PVP) on different physico-chemical properties and its subsequent impact on photoelectrochemical (PEC) performance of CdSe thin films have been investigated. It has observed that the organic surfactants play an important role in modifying the surface morphology of CdSe thin films. The compact grain like morphology of pure CdSe is tuned to interconnected nanofibrous network on addition of PEG and to sprouting nanorods like morphology on addition of PVP. Among these nanostructures, CdSe sprouting nanorods exhibits improved power conversion efficiency of 0.55% as compared to nanofibrous (0.24%) and granular CdSe (0.16%) nanostructures. It reveals the fourfold enhancement in the PEC performance on PVP-mediated growth which can be attributed to conversion of compact dense nanostructure to porous and relatively high surface area nanostructure. This work exemplifies the ability of organic surfactant to modulate the surface morphology of the electrodeposits and pinpoints the organic surfactant that gives rise to the suitable morphology for PEC solar cell application.
Graphical abstract TOC: The morphology of CdSe nanostructure has successfully tuned with use of surfactants to enhance the photoelectrochemical solar cell performance.
A single-step electrochemical deposition of NiS thin films incorporating various carbon nanomaterials as support is described. Advantages of this method are as follows: It is simpler and can be easily scaled up, the precursors employed are cheaper, and the deposition method is energy effective requiring no further heat treatments. Benefits of carbon nanomaterials as catalyst support are manifold including high conductivity and stability. The carbon-supported thin films exhibit high hydrogen evolution activity, low Tafel slopes, and improved double layer capacitance. A remarkable enhancement in the stability of the thin films in the acid medium has been observed. Specifically, NiS/carbon nanofibers have shown the highest activity, lowest Tafel slope, and retained more than 90% of its initial activity after the stability tests.
Graphical abstract NiS/carbon thin films were fabricated through a highly energy-efficient method as active and highly stable electrocatalysts in acid medium for hydrogen evolution reaction.
MoS2 thin films with marigold flower-like nanostructures were grown on conductive fluorine-doped tin oxide (FTO) substrates through a one-step hydrothermal synthesis for their application as counter electrodes (CEs) in dye-sensitized solar cells (DSSCs). Different MoS2 thin film samples (A–D) were grown on FTO slides using different concentrations of precursors (sodium molybdate and thioacetamide), while keeping the Mo/S molar ratio constant (1:4.6), in all samples. The effect of varying precursor concentrations (3.2–12.6 mM on MoS2 basis) on the structure of the nanostructured thin films and their performance as DSSC-CEs was investigated. Scanning electron microscopy revealed a material with an infolded petal-like morphology. With increasing precursor concentration, the petal-like structures tended to form bunched nanostructures (100–300 nm) resembling marigold flowers. X-ray diffraction analysis, X-ray photoelectron, and Raman spectroscopy studies showed that the thin films were composed of hexagonal MoS2 with good crystallinity. Hall effect measurements revealed MoS2 to be a p-type semiconductor with a carrier mobility of 219.80 cm2 V?1 s?1 at room temperature. The electrochemical properties of the thin films were examined using cyclic voltammetry and electrochemical impedance spectroscopy. The marigold flower-like MoS2 thin films showed excellent electrocatalytic activity towards the I¯/I3¯ reaction and low charge transfer resistance (Rct) values of 14.77 Ω cm?1, which was close to that of Pt electrode (12.30 Ω cm?1). The maximum power conversion efficiency obtained with MoS2 CE-based DSSCs was 6.32%, which was comparable to a Pt CE-based DSSC (6.38%) under one sun illumination. Similarly, the maximum incident photon-to-charge carrier efficiency exhibited by MoS2 CE-based DSSCs was 65.84%, which was also comparable to a Pt CE-based DSSC (68.38%). The study demonstrated that the marigold flower-like nanostructured MoS2 films are a promising alternative to the conventional Pt-based CEs in DSSCs.
The performance of proton exchange membrane fuel cell (PEMFC) is highly influenced by its operating conditions. One of the vital parameter is the purity of feed gases. The cathode of PEMFC is normally fed with air from the atmosphere containing certain impurities like CO2, NO2, and SO2, which are the major contaminants for the electrocatalysts used in the fuel cell, causing both reversible and irreversible damages. The irreversible effect is caused due to adsorption of impurities like SO2 on the conventionally used platinum catalyst supported on carbon (Pt/C). It has been observed that carbon facilitates the absorption of SO2 on platinum. Hence, the present objective is to identify the catalysts containing no carbon and study their impurity tolerance in the fuel cell environment. In the present paper, we have attempted to synthesize unsupported mesoporous platinum by hard template method and studied its SO2 impurity tolerance at the cathode side for oxygen reduction reaction (ORR) for PEMFC application. The mesoporous platinum showed for a higher tolerance towards SO2 compared to its counterpart, viz., platinum black. Sulfur tolerance was evaluated by the sulfur coverage on the catalyst and its rate of recovery through electrochemical experiments. Mesoporous platinum has also exhibited a faster removal of adsorbed sulfur compared to the commercial microporous platinum black, revealing that the recovery is also fast comparatively for meso-structured platinum.
Thin films of iron-filled carbon nanotubes prepared through the liquid/liquid interfacial method were modified with a mixture of hexacyanometallates (HCMs) Prussian blue and ruthenium purple. Two different approaches were used in order to obtain both materials in the composites, based on a direct reaction starting from a mixture of both precursors or a step-by-step deposition of each compound. The modified films were characterized by cyclic voltammetry, Raman spectroscopy, X-ray diffraction, scanning electron microscopy, and UV-Vis spectroscopy, confirming the formation of a mixture of HCMs in both methods of synthesis. Stability studies were evaluated in different supporting electrolytes, and composites presented good performances due to carbon nanotube stabilization. Electrochromic properties were also evaluated for selected composites, showing high electrochromic efficiency and stability.
Aluminum-doped ZnO thin films with pebble-like structures have been successfully deposited on glass substrates by successive ionic layer adsorption reaction method. The effect of percentage composition of the aluminum dopant on the flower-like clusters of the ZnO nanostructures on the structure, morphology, and optical properties was investigated. The ZnO thin films which were crystallized in hexagonal wurtzite structures with crystallite sizes of 44, 51, 56, and 43 nm for the intrinsic and 1, 3, and 5% Al-doped ZnO thin films, respectively. Preferred orientation of crystallites is in all cases in [001] direction perpendicular to the sample surface The Raman spectroscopy revealed decrease in the intensity of the ZnO characteristic peak due to the substitution of the Zn2+ atoms by the Al3+ and attributed to potential fluctuations of the alloy disorder. The introduction of the Al3+ dopant significantly increased the optical band gap.
We obtained Tannin-4-azobenzoic acid (azo dye) by the conventional method of diazotization and coupling of aromatic amines. The properties of the azo dye were characterized via ultraviolet-visible (UV–vis), infrared (IR), and nuclear magnetic resonance (NMR) spectroscopy. Nanocrystalline titanium dioxide (TiO2) thin films were deposited by hydrothermal method onto fluorine-doped tin (IV) oxide (FTO)-coated glass substrate at 353 K for 4 h. The as-deposited and annealed films were characterized for structural, morphological, optical, thickness, and wettability properties. The synthesized metal free azo dye was used to sensitize the prepared TiO2 thin film with thickness of 26 μm. The photoelectrochemical (PEC) performance of TiO2 sensitized with the azo dye was evaluated in polyiodide (0.1 M KI + 0.01 M I2 + 0.1 M KCl) electrolyte at 40 mW cm?2 illumination intensity. The cell yielded a short circuit current of 2.82 mA, open circuit voltage of 314.3 mV, a fill factor of 0.30, and a photovoltaic conversion efficiency value of 0.64%.
Electrodeposition is a common technique for coating metallic or semiconducting substrates. The growth of the layers occurs through faradaic processes in which charges are transferred across the substrate-electrolyte interface. Since more than one reaction can occur simultaneously, it is important to study the faradaic efficiency (ε) associated to the growth of the desired layers and relate it to other parameters in order to optimize the process. In this work, an indirect method to determine the faradaic efficiency of electrodeposits with porosity (p) is proposed. The method was satisfactorily applied to porous β-Ni(OH)2 films obtained by light-assisted anodic electrodeposition. These films were grown using different electrolyte concentrations (C) and temperatures (T). In this case, a direct dependence of p and ε with C and T was found.
LiNi1-x-yCoxMnyO2 (NCM) with excessive lithium is known to exhibit high rate capability and charge–discharge cycling durability. However, the practical usage of NCM is difficult, because the positive electrode slurry is unstable and battery cells swell due to the alkaline residual lithium compound generated on the surface of NCM particles. To reduce the residual lithium compound, ammonium metatungstate (AMT) added to NCM is studied, and the effect is investigated by scanning electron microscopy, aberration-corrected scanning transmission electron microscopy, X-ray diffractometry, synchrotron X-ray diffractometry, and several electrochemical measurements. It is found that the AMT modification reduces the amount of alkaline residual lithium compound and improves the rate capability due to the ~1-nm-thick W-rich layer generated on the NCM surface.
The preparation of molybdenum-modified hematite electrodes by means of chemical bath deposition and their photoelectrochemical behavior toward water oxidation are reported in this work. The addition of a molybdenum precursor to the bath solution for hematite deposition induces a remarkable change of morphology in the resulting film from (110)-oriented nanorods to polyhedral nanoparticles. Despite the resulting loss of order, by controlling the Mo/Fe molar ratio in the bath solution, a significant improvement of the water oxidation photocurrent is achieved compared to nanorod pristine hematite electrodes. Such a (photo)electrochemical enhancement is mainly explained by an effective surface state passivation in Mo-modified hematite films. FE-SEM, TEM, XRD, and XPS were employed for electrode structural and morphological characterization.
A gold bare template modified with self-assembled layers (SAMs) composed of gold nanoparticles and organic S-containing compound: cysteamine and dihydrolipoic acid were prepared. The electrode with SAMs endowed with gold nanoparticles gave a high catalytic effect for dopamine electrooxidation alone and in the presence of biogenic interfering compounds: ascorbic acid and uric acid in solution at pH 7. For this novel sensor, a linear relationship between the current response of dopamine at the potential of peak maximum (jp) and the concentration of this compound in solution (cDA) was found over the range 0.1 μM to 0.85 mM with the detection limit of 0.023 μM.
Nanoporous gold (NPG) prepared via chemical de-alloying has been recently shown to dramatically improve the reversibility and kinetics of Li-O2 batteries, but high cost makes its use as practical electrode material difficult. Recently developed electrochemical routines for synthesis of very thin NPG layers (<100 nm) on various low-cost substrates could potentially provide a feasible economic alternative. In this work, NPG on both gold and glassy carbon (GC) substrates was successfully synthesized via electrochemical de-alloying method and tested as cathode material in Li-O2 batteries. The results show that electrochemically synthesized NPG cathode cycles repeatedly with LiFePO4 anode. The voltage hysteresis is also significantly reduced when NPG is used in comparison with plain GC. Along with these results, challenges that need to be addressed for future implementation of NPG cathode in practical Li-O2 batteries are also discussed.
Sulfonated polyvinylchloride (SPVC) cation-exchange membranes were coated using chitosan solutions comprising different amounts of Fe3O4 nanoparticles. Influence of chitosan immobilization as well as nanofiller concentration on the electrochemical performance of the membranes was investigated. Electrochemical properties of the membranes including permselectivity, ionic permeability, and areal resistance were studied using an equipped electrodialysis setup and NaCl solution as model electrolyte. Scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR) were employed for membrane characterization. Electrochemical performance of the SPVC membranes was improved by coating chitosan polymer. In addition, ionic permeability and permselectivity of the membranes were initially raised by increasing nanoparticles concentration from nil to 2 wt% and then decreased by further insertion of the nanofiller. The areal resistance of the plain SPVC membrane was decreased from 9.4 to 2.9 (ohm) by coating of chitosan solution including optimum value of nano-Fe3O4 due to electrical potential field enhancement across the membrane.
Galvanic exchange involving dissolution of iron and the simultaneous growth of platinum onto 316 L stainless steel was investigated for specimens manufactured by 3D-printing, and the behavior was compared to conventional stainless steel. Novel phenomena associated with the 3D-printed steel, but not conventional steel, reacting in three distinct phases were observed: first, with low platinum loading, a bright etching pattern linked to the laser-manufacturing process is revealed at the steel surface; second, a nanostructured pore pattern with platinum nano-deposits forms; and third, a darker platinum film coating of typically 500-nm thickness forms and then peels off the steel surface with further platinum growth underneath. Unlike the conventional steel (and mainly due to residual porosity), 3D-printed steel supports well-adhered platinum films for potential application in electrocatalysis, as demonstrated for alkaline methanol oxidation.
Generally adopted strategies to improve capacitance of the electrode materials are tuning various properties of the electrode material or increasing the cell voltage. While tuning the properties of the electrode material is tedious, increasing the cell voltage is restricted by the stability of the electrolyte. Herein, we report a facile approach to improve the capacitance of MnCO3 by the influence of SiOx nanofluid in the electrolyte. The capacitance properties of MnCO3 are studied in 0.1 M Mg(ClO4)2 electrolyte in the presence and in the absence of SiOx nanofluid. The presence of small amount of SiOx nanofluid in the electrolyte provides higher diffusivity and more conductive percolation paths for ions and thus decreases internal resistance and increases ionic conductivity of the electrolyte. As a result, 60% enhancement in the capacitance is witnessed for MnCO3. Further, nanofluid containing electrolyte is found to be stable over a month.
The present work has studied electrochemical and optical properties of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) film electrodes drop-casted from commercial PEDOT:PSS aqueous dispersion with preliminary addition and without addition of LiClO4 electrolyte (further denoted as PEDOT:PSS/LiClO4 and PEDOT:PSS). Cyclic voltammetry measurements showed the significant increase in capacitance of PEDOT:PSS/LiClO4 film electrodes in comparison to PEDOT:PSS. Furthermore, the improved charge transport in PEDOT:PSS/LiClO4 films was demonstrated by electrochemical impedance spectra. In situ spectroelectrochemical measurements revealed that preliminary addition of LiClO4 into PEDOT:PSS aqueous dispersion allows to increase amount of free charge carriers (polaron and bipolaron states) in the resulting film during electrochemical oxidation in LiClO4 propylene carbonate solution. This increase was attributed to ion-induced charge screening between positively charged PEDOT and negatively charged PSS in polyelectrolyte structure, which was supported by structural investigations of both types of film electrodes by using FTIR, SEM, and XPS measurements. Charge screening results from a more open structure that allows conformational relaxation of PEDOT molecules during charge transport, which leads to partial separation of oppositely charged PSS and PEDOT molecules and facilitating the increase of electrochemical activity.
The doping effects of Cu on structural, morphological and optical properties of ZnO thin films and their PEC properties have been investigated via chemical bath deposition (CBD) technique at 353 K bath temperature and a pH of 11.5 with post-deposition annealing at 673 K. The concentration of Cu in ZnO varied between 1 and 5 at.%. X-ray diffraction analysis revealed that the synthesized Cu-doped ZnO (CZO) thin films were highly crystalline with hexagonal wurtzite structure, showing strong preferential growth along the c-axis for 3 at.% Cu concentration. A shift in angular peak position of 0.545o in 2θ towards higher angle was observed for CZO films which is an indication of effective substitution of Cu atoms on Zn lattice. Crystallite sizes were enhanced from 28 to 32 nm in the (002) crystal plane. Optical analysis indicates a red shift in the absorption band edge up to 450 nm upon Cu doping. Transmittance characteristics increased slightly from 80 to 90% in the visible range at optimum Cu concentration of 3 at.%. Optical energy band gap was found to decrease from 3.03 eV for undoped ZnO to 2.7 eV upon Cu doping. The morphological structures of the CZO thin films were strongly influenced by Cu impurities and its concentration. The water contact angles showed strong dependence on Cu impurities in ZnO and decreased considerably from 71.3 to 15.2°. The synthesized CZO films showed enhanced photoelectrochemical properties, giving a short circuit current (Isc) of 0.098 mAcm?2 and open circuit voltage (Voc) of 796 mV for an optimum Cu concentration of 3 at.% with photoconversion efficiency of 0.062% and fill factor of 63%.
In this paper, a facile immobilization of copper hexacyanoferrate nanoparticles (CuHCFNP) on a paraffin wax-impregnated graphite electrode (PIGE) was carried out using the room-temperature ionic liquid (RTIL) 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIMBF4) as an ionic binder. The characteristics of the CuHCFNP/EMIMBF4 gel-modified electrode were investigated by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) techniques, and the modified electrode morphology was also characterized using field emission scanning electron microscopy (FESEM). The electrocatalytic behavior of butylated hydroxyl anisole (BHA) at the modified electrode has been investigated in 0.1 M KNO3 in static and dynamic conditions. Under the optimum conditions, the oxidation peak current was proportional to the BHA concentration in the range from 1.5 to 1000 μM with a detection limit of 0.5 μM (S/N = 3). The proposed method was applied to determine BHA content in real samples with satisfactory results.
