Synthesis and Characterisation of Cobalt Ferrite Coatings for Oxygen Evolution Reaction

In this paper, two novel procedures based on powder sedimentation, thermal treatment, and galvanostatic deposition were proposed for the preparation of porous cobalt ferrite (CoFe2O4) coatings with a metallic and organic binder for use as catalysts in the oxygen evolution reaction (OER). The electrochemical properties of the obtained electrode materials were determined as well, using both dc and ac methods. It was found that cobalt ferrite coatings show excellent electrocatalytic properties towards the oxygen evolution reaction (OER) with overpotential measured at a current density of 10 mAcm−2 from 287 to 295 mV and a Tafel slope of 35–45 mVdec−1. It was shown that the increase in the apparent activity of the CoFe2O4 coatings with an organic binder results mainly from a large electrochemically active area. Incorporation of the nickel binder between the CoFe2O4 particles causes an increase in both the conductivity and the electrochemically active area. The Tafel slopes indicate that the same rate-determining step controls the OER for all obtained coatings. Furthermore, it was shown that the CoFe2O4 electrodes exhibit no significant activity decrease after 28 h of oxygen evolution. The proposed coating preparation procedures open a new path to develop high-performance OER electrocatalysts.

Electrodeposition of Cu-Mn Films as Precursor Alloys for the Synthesis of Nanoporous Cu

Cu-Mn alloy films are electrodeposited on Au substrates as precursor alloys for the synthesis of fine-structured nanoporous Cu structures. The alloys are deposited galvanostatically in a solution containing ammonium sulfate, (NH4)2SO4, which serves as a source of the ammine ligand that complexes with Cu, thereby decreasing the inherent standard reduction potential difference between Cu and Mn. The formation of the [Cu(NH3)n]2+ complex was confirmed by UV-Vis spectroscopic and voltammetric studies. Galvanostatic deposition at current densities ranging from 100 to 200 mA⋅cm−2 generally resulted in the formation of type I, crystalline coatings as revealed by scanning electron microscopy. Although the deposition current efficiency is (<30%) generally low, the atomic composition (determined by energy dispersive X-ray spectroscopy) of the deposited alloys range from 70–85 at% Mn, which is controlled by simply adjusting the ratio of the metal ion concentrations in the deposition bath. Anodic stripping characterization revealed a three-stage dissolution of the deposited alloys, which suggests control over the selective removal of Mn. The composition of the alloys obtained in the studies are ideal for electrochemical dealloying to form nanoporous Cu.

Ultrasound Supported Galvanostatic Deposition of Zn Coatings Reinforced with Nano-, Submicro-, and Micro-SiC Particles—Weak Acidic Chloride Baths

In this paper, we present results concerning the electrochemical deposition of Zn-SiC composite coatings reinforced with nano-, submicro-, and microparticles. The influence of current density, particle size, and ultrasound on functional parameters which are especially important from a practical point of view (i.e., concentration of particles in coatings, current efficiency, morphology, reflectivity, roughness, hardness, and corrosion resistance) are investigated and discussed. Coatings were deposited from commercial, chloride-based electrolytes dedicated for the deposition of Zn coatings in a weakly acidic environment. Electrodeposited composites contained up to 1.58, 4.08, and 1.15 wt. % of SiC for coatings reinforced with nano, submicro, and micrometric particles, respectively. The process proceeded with relatively high efficiency, exceeding 80% in almost all cases. The results indicate that ultrasounds strongly increase Faradaic efficiency and affect the kinetics of electrode processes and the properties of synthesized coatings. Moreover, the obtained results show that it is possible to synthesize composite coatings with slightly higher mechanical properties while retaining corrosion resistance compared to metallic Zn coatings.

Fabrication of CZTS Solar Cells Using Electrodeposition Techniques

Copper zinc tin sulphide (CZTS) is a p-type semiconductor that can be used as the light absorbing layer in thin-film heterojunction solar cells, with the specific advantage of being comprised only of non-toxic, earth abundant elements. There are many methods through which CZTS can by synthesised, one of which is electrodeposition, which is an industrially scalable process used extensively in the steel industry. This thesis details a study of the electrodeposition of stacked elemental layers and their subsequent sulphurisation in the manufacture of CZTS. A range of electrodeposition parameters are tested for each elemental layer, each of which is characterised through a range of techniques, including scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS), which enables the development of optimised conditions. It was found that the deposition of copper favoured potentiostatic deposition, with a smooth granular structure being deposited onto molybdenum at -0.98V vs Hg|HgO from a sodium hydroxide based electrolyte, while tin required galvanostatic deposition from a methanesulfonic acid electrolyte in order to return consistent results. This was optimised to an initial high current density period of -20 mA cm-2 for 1.2 s to nucleate grains, falling to -5 mA cm-2 to minimise hydrogen evolution thereafter. Trial of numerous electrolyte formulae found that an acid-sulphate electrolyte gave the most promising results, with galvanostatic deposition at -50 mA cm-2 being found to be suitable. Optimised stacked elemental layer precursors are then progressed to the annealing and sulphurisation stage for conversion into CZTS. One key area of study is the inclusion of a pre-alloying annealing step prior to sulphurisation, and its effect on the morphology of the CZTS films and subsequent solar cell device performance. Pre-alloyed metallic films are extensively characterised by means of X-ray photoelectron spectroscopy (XPS) depth profiling, X-ray diffractometry (XRD) and EDS elemental mapping as part of an optimisation process, and Raman spectroscopy is used in conjunction with XRD and EDS in the analysis of CZTS films sulphurised in a rapid thermal processing (RTP) furnace. A pre-alloying step at 300 °C for 10 minutes was found to be sufficient for the deposited elements to fully intermix. It was discovered that not only does the inclusion of an optimised pre-alloying step improve the morphology of the CZTS films and the subsequent solar cell performance, but the integration of a pre-alloying stage with the sulphurisation in a single furnace operation does not lead to any evidence of disadvantage when compared with pre-alloying and sulphurisation processes conducted separately. In fact, 8 out of 45 cells with an integrated pre-alloying process achieved 0.1% efficiency or greater, compared to 5 out of 45 for those that underwent a separate pre-alloying process, and 0 out of 45 for those that received no pre-alloying process. This positive result for the integration of the pre-alloy offers simplification of the manufacturing process for a potential future scaled-up CZTS solar cell device.

Electrodeposition of aluminum-doped thin silicon films from the KF-KCl-KI-K2SiF6-AlF3 melt

Cyclic voltammetry, chronoamperometry, scanning electron microscopy, atomic force microscopy, and Raman spectroscopy were used to study the regularities of silicon and aluminum co-deposition on glassy carbon from KF-KCl (2:1) - 75 mol% KI - 0.15 mol% K2SiF6 - (up to 0.15 mol%) AlF3 melts at 998 K. Cyclic voltammograms demonstrated the presence of only one cathodic peak (or nucleation loop at a low reverse potential) and the corresponding anodic peak. The cathodic peak shifted in the cathodic direction with a decrease in the concentration of aluminum ions in the melt or an increase in the scan rate. The Scharifker - Hills model was used to analyze potentiostatic current density transients and estimate the values of the apparent diffusion coefficient and the number density of nuclei. The morphology and elemental analysis of the samples obtained during potentiostatic and galvanostatic deposition for 30-60 s were studied. Continuous thin silicon films doped with aluminum were obtained under galvanostatic conditions.

An Electrochemical Sensor Based on Gold Nanodendrite/Surfactant Modified Electrode for Bisphenol A Detection

In the present work, we reported the simple way to fabricate an electrochemical sensing platform to detect Bisphenol A (BPA) using galvanostatic deposition of Au on a glassy carbon electrode covered by cetyltrimethylammonium bromide (CTAB). This material (CTAB) enhances the sensitivity of electrochemical sensors with respect to the detection of BPA. The electrochemical response of the modified GCE to BPA was investigated by cyclic voltammetry and differential pulse voltammetry. The results displayed a low detection limit (22 nm) and a linear range from 0.025 to 10 µm along side with high reproducibility (RSD = 4.9% for seven independent sensors). Importantly, the prepared sensors were selective enough against interferences with other pollutants in the same electrochemical window. Notably, the presented sensors have already proven their ability in detecting BPA in real plastic water drinking bottle samples with high accuracy (recovery range = 96.60%–102.82%) and it is in good agreement with fluorescence measurements.

Synthesis and Characterization of a NiCo2O4@NiCo2O4 Hierarchical Mesoporous Nanoflake Electrode for Supercapacitor Applications

In this study, we synthesized binder-free NiCo2O4@NiCo2O4 nanostructured materials on nickel foam (NF) by combined hydrothermal and cyclic voltammetry deposition techniques followed by calcination at 350 °C to attain high-performance supercapacitors. The hierarchical porous NiCo2O4@NiCo2O4 structure, facilitating faster mass transport, exhibited good cycling stability of 83.6% after 5000 cycles and outstanding specific capacitance of 1398.73 F g−1 at the current density of 2 A·g−1, signifying its potential for energy storage applications. A solid-state supercapacitor was fabricated with the NiCo2O4@NiCo2O4 on NF as the positive electrode and the active carbon (AC) was deposited on NF as the negative electrode, delivering a high energy density of 46.46 Wh kg−1 at the power density of 269.77 W kg−1. This outstanding performance was attributed to its layered morphological characteristics. This study explored the potential application of cyclic voltammetry depositions in preparing binder-free NiCo2O4@NiCo2O4 materials with more uniform architecture for energy storage, in contrast to the traditional galvanostatic deposition methods.

A Review on Nano-/Microstructured Materials Constructed by Electrochemical Technologies for Supercapacitors

The article reviews the recent progress of electrochemical techniques on synthesizing nano-/microstructures as supercapacitor electrodes. With a history of more than a century, electrochemical techniques have evolved from metal plating since their inception to versatile synthesis tools for electrochemically active materials of diverse morphologies, compositions, and functions. The review begins with tutorials on the operating mechanisms of five commonly used electrochemical techniques, including cyclic voltammetry, potentiostatic deposition, galvanostatic deposition, pulse deposition, and electrophoretic deposition, followed by thorough surveys of the nano-/microstructured materials synthesized electrochemically. Specifically, representative synthesis mechanisms and the state-of-the-art electrochemical performances of exfoliated graphene, conducting polymers, metal oxides, metal sulfides, and their composites are surveyed. The article concludes with summaries of the unique merits, potential challenges, and associated opportunities of electrochemical synthesis techniques for electrode materials in supercapacitors.

Fabrication of Large Area Ag Gas Diffusion Electrode via Electrodeposition for Electrochemical CO2 Reduction

For the improvement for the commercialization of electrochemical carbon dioxide (CO2) conversion technology, it is important to develop a large area Ag gas diffusion electrode (GDE), that exhibits a high electrochemical CO2 conversion efficiency and high cell performance in a membrane electrode assembly (MEA)-type CO2 electrolyzer. In this study, the electrodeposition of Ag on a carbon-paper gas diffusion layer was performed to fabricate a large area (25.5 and 136 cm2) Ag GDE for application to an MEA-type CO2 electrolyzer. To achieve uniformity throughout this large area, an optimization of the electrodeposition variables, such as the electrodes system, electrodes arrangement, deposition current and deposition time was performed with respect to the total electrolysis current, CO production current, Faradaic efficiency (FE), and deposition morphology. The optimal conditions, that is, galvanostatic deposition at 0.83 mA/cm2 for 50 min in a horizontal, two-electrode system with a working-counter electrode distance of 4 cm, did ensure a uniform performance throughout the electrode. The position-averaged CO current densities of 2.72 and 2.76 mA/cm2 and FEs of 83.78% (with a variation of 3.25%) and 82.78% (with a variation of 8.68%) were obtained for 25.5 and 136 cm2 Ag GDEs, respectively. The fabricated 136 cm2 Ag GDE was further used in MEA-type CO2 electrolyzers having an active geometric area of 107.44 cm2, giving potential-dependent CO conversion efficiencies of 41.99%–57.75% at Vcell = 2.2–2.6 V.