Electrochemical behavior of activated-carbon capacitor material loaded with nickel oxide

In order to enhance specific capacitance and energy density of carbon-based supercapacitor, some nanometer-scale amorphous particles of nickel oxide were loaded into activated-carbon by suspending the activated-carbon in a Ni(NO₃)₂ solution followed by neutralization. A hybrid type electrochemical capacitor was made and tested, in which the activated-carbon loaded with nickel oxide was used as cathode material and activated-carbon was used as anode material. Although the BET surface area of the activated-carbon decreased upon nickel oxide loading compared to that of the starting material, its specific capacitance increased 10.84%, from 175.40 to 194.01 F g⁻¹ and the potential of oxygen evolution on the composite material electrode was 0.076 V higher than that of the pure activated-carbon electrode, in the electrolyte of 6 mol/L KOH solution, so the hybrid capacitor had larger energy density. Similar to the pure activated-carbon electrode, no obvious change appears on the specific capacitances of the composite material electrode at various discharge currents and the composite material electrode exhibiting good power characteristics.     

Anodic, cathodic and cyclic voltammetric deposition of ruthenium oxides from aqueous RuCl3 solutions

Anodic, cathodic and cyclic voltammetric (CV) deposition of ruthenium oxides from aqueous RuCl₃ solutions have been investigated using stationary and rotating disk electrodes (RDE) in this work. The CV deposition behavior was examined using a RDE to differentiate the contribution of current from the reactions of ruthenium ions in the electrolyte and ruthenium oxides already adsorbed on the electrode. The results indicate that the CV growth of ruthenium oxides within the potential range of aqueous electrolyte decomposition is attributed to the anodic oxidation of ruthenium ions in the electrolyte. Cathodic deposition occurs only at potential negative than −0.30 V versus saturated calomel electrode (SCE) when H₂ evolves on the electrodes. Anodic deposition of ruthenium oxides can be obtained effectively in the potential range of ca. 0.9-1.1 V versus SCE, depending on the pH value of the electrolyte. The optimum anodic and cathodic deposition potential for maximum deposition efficiency is 1.0 and −0.9 V versus SCE, respectively, in the electrolyte solution of pH 2.     

Electrochemical reduction of thick oxide film on platinum electrode in alkaline solutions

The electrochemical reduction of the thick oxide film formed on Pt electrode by severe preanodization has been studied in LiOH, NaOH and KOH solutions of different concentrations (0.001 ～ 1.0 M) using a galvanostatic technique.An outermost monolayer oxide and an inner multilayer oxide of the thick oxide film exhibit different potential behaviors in the cathodic reduction. In dilute solution, both the oxides are completely reduced in a potential range of 0.6-0.4 V (vs rhe in the test solution) in a single step. As the concentration is increased, however, the reduction potential of the inner oxide only shifts rapidly into a H-electrosorption potential region and the amount of the oxide reduced at this potential decreases. The remaining oxide is slowly reduced at H₂-evolution potential. The retardation of the reduction of the inner oxide is related to cations adsorbed on Pt electrode. This retardation effect increases in the order, K⁺ < Na⁺ < Li⁺.     

Photoelectrochemical study of nickel base alloys oxide films formed at high temperature and high pressure water

The oxide film formed on nickel base alloys at high temperature and high pressure water exhibits semi-conducting properties evidenced by photocurrent generation when exposed to monochromatic light. The use of macro- and micro-photoelectrochemical techniques (PEC and MPEC) aims to identify the different semiconductor phases and their distribution in the oxide film.Three different nickel base alloys were corroded in recirculation loop at 325 °C in pressurised water reactor primary coolant conditions for different exposition durations.PEC experiments on these materials enable to obtain macroscopic energy spectra showing three contributions. The first one, with a band gap around 2.2 eV, was attributed to the presence of nickel hydroxide and/or nickel ferrite. The second one, with a band gap around 3.5 eV, was attributed to Cr₂O₃. The last contribution, with a band gap in the range of 4.1-4.5 eV, was attributed to the spinel phase Ni_1−xFe_xCr₂O₄. In addition, macroscopic potential spectra recorded at different energies highlight n-type semi-conduction behaviours for both oxides, Cr₂O₃ and Ni_1−xFe_xCr₂O₄.Moreover, MPEC images recorded at different energies exhibit contrasted regions in photocurrent, describing the distribution of nickel hydroxide and/or nickel ferrite and Cr₂O₃ in the oxide film at a micron scale.It is concluded that PEC techniques represent a sensitive and powerful way to locally analyse the various semiconductor phases in the oxide scale.     

NiO-based composite electrode with RuO2 for electrochemical capacitors

NiO/RuO₂ composite materials were prepared for use in electrochemical capacitors (ECs) by co-precipitation method followed by heat treatment. X-ray diffraction (XRD) spectra indicated that no new structural materials were formed and ruthenium oxide particles were coated by NiO particles. RuO₂ partly introduced into NiO-based electrode had improved its electrochemical performance and capacitive properties by using electrochemical measurements. A maximum specific capacitance of 210 F/g was obtained for NiO-based composite electrode with 10 wt.% RuO₂ in the voltage range from −0.4 to 0.5 V in 1 mol/l KOH solution. By comparison of effect of modified modes on the specific capacitance, chemically modified composite electrodes had more stable cycling properties than those of physically modified electrodes. After 200 cycles, specific capacitance of NiO-based chemical composite electrode with 5 wt.% RuO₂ kept 95% above, while that of physical electrode was only 79% of initial specific capacitance.     

Development of three-electrode type micro-electrochemical reactor on anodized aluminum with photon rupture and electrochemistry

Photon rupture with a focused single pulse of pulsed YAG-laser irradiation was used to fabricate an aluminum electrochemical micro-reactor. Porous type anodic oxide film formed on aluminum specimens was irradiated in solutions with a pulsed Nd-YAG laser beam through a convex lens to fabricate micro-channels, micro-electrode, and through holes (for reference electrode, solution inlet, and outlet). During irradiation, specimens were moved by a computer controlled XYZ stage. After irradiation, the surface of the micro-channel and through hole were again treated to form anodic oxide film and the surface of the micro-electrode was treated electrochemically to provide an Au layer. The calculated volume of the micro-reactor including micro-channel and through holes is about 1.5 μl. The cyclic voltammogram of the micro-electrochemical cell was measured in K₃Fe(CN)₆/K₄Fe(CN)₆ with both static and flowing solution at different scanning rates. The anodic and cathodic peak currents were measured and the values depended on scanning rate and ion concentration when the solution was static. With the flowing solution, limiting currents were observed and the anodic limiting current was increased with the cubic root of the solution flow rate.     

Amorphous-to-crystalline transition of silicon-incorporated anodic ZrO2 and improved dielectric properties

Sputter-deposited zirconium and Zr-16 at.% Si alloy have been anodized to various voltages at several formation voltages in 0.1 mol dm⁻³ ammonium pentaborate electrolyte at 298 K for 900 s. The resultant anodic films have been characterized using X-ray diffraction, transmission electron microscopy, Rutherford backscattering spectroscopy, glow discharge optical emission spectroscopy, and electrochemical impedance spectroscopy. The anodic oxide films formed on Zr-16 at.% Si are amorphous up to 30 V, but the outer part of the anodic oxide films crystallizes at higher formation voltages. This is in contrast to the case of sputter-deposited zirconium, on which the crystalline anodic oxide films, composed mainly of monoclinic ZrO₂, are developed even at low formation voltages. The outer crystalline layer on the Zr-16 at.% Si consists of a high-temperature stable tetragonal phase of ZrO₂. Due to immobile nature of silicon species, silicon-free outermost layer is formed by simultaneous migrations of Zr⁴⁺ ions outwards and O²⁻ ions inwards. An intermediate crystalline oxide layer, in which silicon content is lower in comparison with that in the innermost layer, is developed at the boundary of the crystalline layer and amorphous layer. Capacitances of the anodic zirconium oxide are highly enhanced by incorporation of silicon due to reduced film thickness, even though the permittivity of anodic oxide decreases with silicon incorporation.     

Voltammetric and galvanostatic studies of hydrous and anhydrous iridium oxide films

Electrolytically grown hydrous oxide films on iridium wire electrodes have been thermally treated from 473 to 773 K. Anhydrous oxide films formed by this treatment have been subjected to cathodic polarization at the potential of the hydrogen evolution reaction, square-wave pulsing of potential from –0.25 to +1.25 V with respoect to SCE and to anodic galvanostatic polarization in 0.5 mol dm^–3 H₂SO₄. Cathodic pretreatment caused an increase of the voltammetric charge in the oxide formation region while the square-wave pulsing formed a hydrous oxide film whose voltammetric charge was superimposed on the charge of the anhydrous oxide film. Both procedures restored the hydrophilic nature of the electrode/solution interface. Potential-time curves during anodic galvanostatic polarization served as a diagnostic criterion for the stability and the state of the oxide film.     

Corrosion resistance of plasma-anodized AZ91D magnesium alloy by electrochemical methods

Anodic coatings formed on magnesium alloys by plasma anodization process are mainly used as protective coatings against corrosion. The effects of KOH concentration, anodization time and current density on properties of anodic layers formed on AZ91D magnesium alloy were investigated to obtain coatings with improved corrosion behaviour. The coatings were characterized by scanning electron microscopy (SEM), electron dispersion X-ray spectroscopy (EDX), X-ray diffraction (XRD) and micro-Raman spectroscopy. The film is porous and cracked, mainly composed of magnesium oxide (MgO), but contains all the elements present in the electrolyte and alloy. The corrosion behaviour of anodized Mg alloy was examined by using stationary and dynamic electrochemical techniques in corrosive water. The best corrosion resistance measured by electrochemical methods is obtained in the more concentrated electrolyte 3 M KOH + 0.5 M KF + 0.25 M Na₃PO₄·12 H₂O, with a long anodization time and a low current density. A double electrochemical effects of the anodized layer on the magnesium corrosion is observed: a large inhibition of the cathodic process and a stabilization of a large passivation plateau.     

Photo-electrochemical investigation of anodic oxide films on cast Ti-Mo alloys. I. Anodic behaviour and effect of alloy composition

The anodic behaviour of cast Ti-Mo alloys, having different Mo contents (6-20 wt.%), was investigated in acidic and neutral aerated aqueous solutions. All sample showed a valve-metal behaviour, owing to formation and thickening of barrier-type anodic oxides displaying interference colours. Growth kinetics of passive films is influenced by both anodizing electrolyte and composition of the starting alloy. This last parameter was found to change also the solid-state properties of the films, explored by photoelectrochemical and impedance spectroscopy experiments. Thicker films (U_f = 8 V/MSE) grown on alloys richer in Mo showed more resistive character and a photocurrent sign inversion under negative bias, that revealed an insulating character, whereas corresponding films grown on alloys with lower Mo content, as well as thinner films, behaved as n-type semiconductors. Results are discussed in terms of formation of a mixed Ti-Mo oxide phase.     

Effect of hydrogen on discharge behaviour of the nickel oxide electrode

The effect of hydrogen on the discharge behaviour of the nickel oxide electrode has been investigated in 30% KOH solution at 25°C. Open-circuit potentials of the nickel oxide electrodes, previously fully charged, decrease more rapidly in a hydrogen atmosphere than in an argon environment. Voltammograms of the nickel oxide electrode show that the amount of cathodic charge decreases considerably when the nickel oxide electrode is exposed to hydrogen rather than to argon. These results, along with X-ray diffraction data, indicate that hydrogen can increase the self-discharge rate of the nickel oxide electrode as a result of reduction of -NiOOH to -Ni(OH)₂ and the simultaneous oxidation of hydrogen. In addition, hydrogen can produce changes in the nickel oxide electrode during charge that persist to modify discharge behaviour and open-circuit potential.     

Perchlorate and oxygen reduction during Zn corrosion in a neutral medium

A comparison between the potentiodynamic behaviour of the stationary and the rotating Zn disc electrodes in naturally aerated and de-aerated 0.1 M KClO₄ solution was performed. The voltammograms of the stationary electrode in both solutions exhibited one anodic peak and two cathodic peaks. The anodic peak is replaced by two mass transport controlled O₂ reduction cathodic current plateaus in the forward scan by rotating the electrode in naturally aerated solutions. However, the reverse scan is characterized by only one cathodic peak observed at a potential depends on the experimental conditions. The more cathodic reduction peak was referred to the reduction of the passive layer and split into two peaks at low scan rates. Interpretation of these data was made adopting a multi-path mechanism and a two layer passive film model. A correlation between the ClO₄⁻ and dissolved O₂ reduction and the thickness of the two passive layers was performed. The protective nature of the passive layers formed in different experimental conditions was found to decrease with rotating the electrode and de-aerating the solution. Chrono-potentiometry and electrochemical impedance measurements were also used in this study. Impedance technique showed a change in the ZnO thickness with the experimental conditions as a result of changing the reactions occurring in the electrode vicinity.     

Thermal effects on the measurement of photocurrent at anodic films on nickel electrodes

The influence of heat on the measurement of photocurrents at nickel electrodes in a 1 M NaOH solution was investigated by using photocurrent, photothermal and thermal current methods under the irradiation of laser beams with wavelengths of 488, 532 and 632 nm, respectively. It was found that the photocurrent appeared in the potential (vs. Hg/HgO electrode) region lower than −0.1 V was caused by the p-type semiconductor property of Ni(OH)₂ anodic film. In the Ni(OH)₂/NiOOH redox potential region the appearance of photocurrent was likely caused by the local temperature variation rather than the semiconductor properties of the anodic layer. Similar phenomena was observed for β-Ni(OH)₂ electrode. During the light irradiation an increase of temperature at the surface of the working electrode may disturb the measurement of photocurrent.     

Electrochemical properties of boron-carbon-nitride films formed by magnetron sputtering

The electrochemical behavior of B_1.0C_2.4N_1.0 thin film was investigated in acidic, neutral and alkaline solutions. The anodic polarization curve of the film in 1 M NaOH showed the anodic dissolution of the film. The curve of the film in 1 M HCl showed no anodic dissolution. The cathodic polarization curve in 1 M NaCl showed shift to a negative potential side, but the anodic polarization curve was the same as that of Pt. The anodic dissolution in 1 M NaOH depended on potentials, that is, no anodic dissolution was recognized in a potential range of −0.2 to 0.1 V but the dissolution rate increased with increasing potential in a range of 0.1-0.6 V. The anodic current density of the film is directly proportional to the dissolution rate at potentials higher than 0.1 V. The dissolution rate of the film was increased with increasing solution pH.     

A transmission electron microscopy study of hard anodic oxide layers on AlSi(Cu) alloys

Transmission electron microscopy (TEM) has been employed to examine anodic oxide film formation on 99.8 wt.% aluminium, Al-10 wt.%Si and Al-10 wt.%Si-3 wt.%Cu alloys under conditions relevant to hard anodizing. In particular, anodic oxidation of silicon particles proceeded at a significantly reduced rate compared with that of the adjacent aluminium matrix. This gave rise to alumina film encroachment beneath the particles with development of tortuous porosity and, eventually, occlusion of partially anodized particle in the anodic film. Additional effects included the presence of gas-filled cavities above the silicon particles, associated with oxygen generation above the anodizing particle. The presence of such particles and the corresponding gas-filled voids across the anodic film thickness and at the alloy/film interface is considered responsible for the continuous voltage rise during anodizing of the Al-10 wt.%Si alloy, effectively blocking electrolyte access to the pore base and providing local region of high resistance at the alloy/film interface. A direct consequence of the voltage rise was a thickening of the barrier layer at the base of the porous anodic film. For the ternary alloy, with the additional presence of copper and the CuAl₂ particles, the latter appear to have undergone complete oxidation, with copper detected in local film regions.     

Investigation on characteristics of anodic film formed on PbCaSnCe alloy in sulfuric acid solution

The electrochemical properties of the anodic films formed on PbCaSnCe and PbCaSn alloys at 0.9 V (versus Hg/Hg₂SO₄ electrode) in 4.5 mol/L sulfuric acid solution were investigated by linear sweeping voltammetry (LSV), ac voltammetry (ACV), electrochemical spectroscopy impedance (EIS), capacitance measurement and X-ray photoelectron spectroscopy (XPS) technology. Based on Mott-Schottky analysis, the effect of cerium on the semiconductor properties of anodic film is discussed as well in this paper. The experimental data shows that cerium can significantly decrease the impedance of the anodic film on PbCaSn alloy, and can improve the corrosion resistance of the alloy. It can be inferred from the capacitance measurement result that the passive film should be an n-type semiconductor. The addition of cerium can decrease the slope of M-S plot, which indicates the increasing of defect density in the film, and this can contribute to improve the conductivity of the anodic film on PbCaSn alloy. XPS results shows that the anodic film formed on PbCaSnCe alloy is consisted of PbO_1+x (0 < x < 1) and PbSO₄, while for the anodic film formed on PbCaSn alloy, PbO and PbSO₄ are the major component. Considering the better conductivity of PbO_1+x (0 < x < 1) than that of PbO, it is concluded that PbCaSnCe may serve as the candidate of the new grid material for maintenance-free lead acid battery.     

The influence of temperature on the current peak multiplicity related to the nickel hydroxide electrode

The splitting of the anodic and cathodic potentiodynamic E/I display of the nickel hydroxide electrode in 1 N KOH between 0 and 75° C is reported. The formal first order rate constants for the chemical reactions which occur simultaneously with the electrochemical steps, and the corresponding activation energies are evaluated. The results are discussed on the basis of the reaction model recently proposed for the nickel hydroxide electrode.     

Investigation of self-healing mechanism on galvanized steels cut edges by coupling SVET and numerical modeling

Local cathodic inhibition has been observed on the cut-edge of galvanized steel immersed in 0.03 M NaCl solution using the scanning vibrating electrode technique. The current distribution results indicate that cathodic inhibition occurs in a limited spatial zone located between the cathodic sites on the steel and the anodic sites on the exposed zinc surface. The experimental current distributions are compared with the results of numerical simulations that show the specific diagnostic features for the detection of cathodic inhibition from scanning vibrating electrode technique (SVET) data so as to distinguish the zero current regions from experimental artifacts due to the lateral resolution of the technique. The inhibition is attributed to the formation of a zinc-based oxide film at the steel surface controlled by an increase of the interfacial pH.     

Ni-Mo alloying of nickel surface by alternating pulsed electrolysis using molybdenum(VI) baths

Electrochemical Ni-Mo alloying of the surface of a nickel substrate was investigated using alternating pulsed electrolysis in an aqueous solution containing only molybdate ions (MoO₄²⁻) as a metal ion component. In this electrochemical process, the nickel substrate was slightly dissolved during the anodic pulses, providing nickel ions into the solution in the vicinity of the substrate, while Ni and Mo were both electrodeposited on the substrate surface during the subsequent cathodic pulses. Through the optimization of anodic and cathodic conditions independently based on a set of direct-current electrolysis data, amorphous Ni-Mo alloy layers were found to be formed at the surface of the nickel substrate by the alternating pulsed electrolysis using the MoO₄²⁻ solution of pH 3.0-5.0. The conditions for Ni-Mo alloy formation were discussed in terms of the dissolving regime of ionic species in the electrolytes determined by an equilibrium calculation.     

Enhanced hydrogen entry into iron from 0.1 M NaOH at definite potentials

This work aimed at explaining the enhancement of hydrogen entry into iron from alkaline solution occurring at definite potentials. Hydrogen permeation rate (HPR) through a 35-μm thick iron membrane was measured with the electrochemical technique in 0.1 M NaOH at 25 °C during cathodic and anodic polarizations. Enhanced HPR was observed at potentials of oxide reduction or iron oxidation, and potentials more cathodic than about −1.65 V_NHE during prolonged galvanostatic polarization. XPS analysis showed that after the polarization, surface layers contained hydrated iron oxides and that amount of these products increased with the polarization time. It is suggested that the enhanced hydrogen entry can be explained by acidification of the near-metal solution due to iron oxidation and/or oxide reduction, and probably by a promoting effect of some Fe-O species. It is proposed that these effects are associated with surface layers. They can affect hydrogen entry as a source of protons in the oxide reduction, as a diffusion barrier making the near-metal acidification possible, and as a resistance causing an IR drop. Strong enhancement of HPR after prolonged galvanostatic polarizations can be associated with the formation of thick surface layers with IR drop enabling anodic oxidation of iron under these layers.