Preparation and characterization of thin films of LaNiO3 for anode application in alkaline water electrolysis

LaNiO₃ electrodes were prepared, in the form of thin films on platinum by the methods of spray pyrolysis and sequential coating of mixed metal nitrate solutions followed by thermal decomposition. The films were adherent and of p-type semiconducting. Cyclic voltammetric studies indicated the formation of a quasireversible surface redox couple, Ni(iii)/Ni(ii), on these films before the onset of oxygen evolution in 1 m KOH. The anodic Tafel slopes were 40 and 65 mV decade^–1, on the sprayed LaNiO₃ film and on the film obtained by a layer method, respectively. The reaction order with respect to OH^– was found to be 2.2 on the sprayed oxide film and 1.2 on the layer film. The sprayed oxide film was found to be electrocatalytically more active. It is suggested that the oxygen evolution reaction proceeds on both the film electrodes via the formation of the physisorbed H₂O₂ as an intermediate in the rate determining step.     

Effect of temperature on the formation and dissolution of anodic oxide films on titanium in acid solutions

The effect of electrolyte and current density on the growth rate of the oxide film on titanium were studied by following the voltage-time characteristics. The barrier oxide grows to greater thickness at lower pH and higher current density. The growth of the oxide in acid medium is lowered by an increase in temperature. In 0.5n H₂SO₄ the oxide grows to greater thicknesses than that grown in 0.5n HCLO₄. This is due to a relatively higher rate of dissolution in HClO₄ during the oxide-growth/oxide-dissolution process during the anodization. The effect of temperature on the dissolution of the oxide previously grown to 12.5 V is followed in 0.5n H₂SO₄ by impedance and potential measurements. The oxide, which is of duplex nature, dissolves with a rate that increases with increasing temperature. The results indicate that the rate of dissolution of the outer layer is affected by temperature more than that of the inner layer, probably owing to higher porosity of the former. The heat of activation, -H, was estimated to be 110.5 kJ mol^–1.     

Analysis of the inductance influence on the measured electrochemical impedance

The high-frequency region of the impedance diagram of an electrochemical cell can be deformed by the inductance of the wiring and/or by the intrinsic inductance of the measuring cell. This effect can be noticeable even in the middle frequency range in the case of low impedance systems such as electrochemical power sources. A theoretical analysis of the errors due to inductance effects is presented here, on the basis of which the admissible limiting measuring frequency can be evaluated. Topology deformations due to the effect of inductance in the case of a single-step electrochemical reaction are studied by the simulation approach. It is shown that an inductance can not only change the actual values of the parameters (electrolytic resistance, double layer capacitance, reaction resistance), but can also substantially alter the shape of the impedance diagram, this leading to erroneous structure interpretations. The effect of the size and surface area of the electrode on its intrinsic inductance is also evaluated.Nomenclature A linear dimension of the surface area confined by the circuit (cm) - C _D double layer capacitance (F) - C _M measured capacitance - d diameter of the mean effective current line (mm) - f _max limiting (maximum) frequency of measurement (Hz) - K ₁,K ₂ shape coefficients with values of 2×10^–9 and 0.7 for a circle, and 8×10^–9 and 2 for a square (dimensionless) - L intrinsic inductance of the electrochemical cell assumed as an additive element (H) - R _E electrolyte resistance () - R _M measured resistance () - R _P reaction resistance () - r ₀ specific resistance ( cm) - S electrode surface area (cm²) - T _c time constant (s) - Z impedance () - Z _lm imaginary component of the impedance without accounting for the influence of inductance () - Z _lm imaginary component of the impedance accounting for the influence of the additive inductance () - shape coefficient; =1 for a square and =^1/2/2 for circle (dimensionless) - _L relative complex error due to the influence of inductance (dimensionless) - _L ^A relative amplitude error due to inductance (%) - ^L relative phase error due to inductance (%) - ratio between the effective inductance time constant and the capacitive time constant (dimensionless) - angular frequency (s^–1) - _R characteristic frequency at which the inductive and capactive parts of the imaginary component of impedance are equal (s^–1)     

Monitoring the real time growth of a self-assembled monolayer on a polymer electrolyte surface

The growth of a self-assembled monolayer (SAM) at the surface of a polymer electrolyte has been shown to inhibit the formation of the passivating layer that forms when the polymer is in contact with lithium metal. In this work, ac impedance spectroscopy was used to monitor the formation of SAM layers on polyethylene oxide (PEO) polymer electrolyte thin films as a function of time. To monitor SAM growth, thin PEO films were cast onto interdigitated electrodes. The electrodes were subsequently immersed in a saturated SAM solution and the film impedance was measured. SAM molecules with the general formula: H(CH₂)₃₂(CH₂CH₂O)_yH (y = 2, 10, 40) were used. Growth occurred due to interactions with the ethylene oxide portion of the SAM molecules with the PEO surface. To visualize SAM growth impedance data at a single frequency sensitive to changes at the solution interface was plotted verses time. At the point of immersion, a sharp increase in impedance was observed. With time, the rate at which the impedance increased slowed and ultimately leveled off presumably indicating the point at which a nearly complete monolayer had formed. SAM growth was verified using attenuated total reflectance infrared spectroscopy (ATR-IR).     

Electrical properties of polyaniline films formed in acid with and without Cs+ ions in the electrolyte

The effect of Cs⁺ ions added to the electrolyte for polyaniline films electrosynthesized in 0.1 m aniline/0.5m H₂SO₄ was investigated. Some properties of PANI films, such as the capacitance, the ohmic resistance and the charge-transfer resistance were obtained using electrochemical impedance spectroscopy. It was found that Cs⁺ ions used during PANI synthesis change its morphology, with a consequent increase in capacitance and conductivity, and a decrease in charge-transfer resistance.     

Cathodic electrosynthesis of iron oxide films for electrochemical supercapacitors

Cathodic electrosynthesis has been utilized for the fabrication of γ-Fe₂O₃ films, containing chitosan additive as a binder. The films were studied by X-ray diffraction analysis, X-ray photoelectron spectroscopy, scanning electron microscopy, differential thermal analysis, and thermogravimetric analysis. Cyclic voltammetry and chronopotentiometry data showed that the iron oxide films exhibit electrochemical capacitance in the voltage window of −0.9 to −0.1 V vs SCE in 0.25 m Na₂SO₄ and 0.25 m Na₂S₂O₃ aqueous solutions. The highest specific capacitance (SC) of 210 F g⁻¹ was achieved using 0.25 m Na₂S₂O₃ as electrolyte, at a scan rate of 2 mV s⁻¹. The SC decreased with increasing film thickness, scan rate and cycle number. Heat treatment of the films at 140 °C resulted in increasing SC.     

Impedance spectroscopy study of anodic growth of thick zirconium oxide films in H2SO4, Na2SO4 and NaOH solutions

Anodic zirconium oxide films were grown potentiodynamically at a constant sweep rate up to the breakdown potential on rod electrodes made of 99.8% metallic zirconium. Different media of different pH were tested, namely 0.5 M H₂SO₄ (pH 0.3), 0.1 M Na₂SO₄ (pH 9) and 0.1 M NaOH (pH 13). By electrochemical impedance spectroscopy and scanning electron microscopy the oxide film thickness was monitored during the voltage scan. The behaviour was found to be different in the presence and absence of sulphate anions. In the presence of SO₄²⁻, the films were dense but breakdown occurred at 300–340 nm. In NaOH, two relaxations appeared above 50 V and were ascribed to a bi-layered coating structure and the maximum layer thickness was 720 nm before breakdown.     

Electrochemical formation and characterization of porous titania (TiO2) films on Ti

Galvanostatically and potentiostatically formed surface oxide films on titanium in H₂O₂ free and H₂O₂ containing H₂SO₄ solutions were investigated. Conventional electrochemical techniques, electrochemical impedance spectroscopy (EIS) and scanning electron microscopy, were used. In the absence of H₂O₂, the impedance response indicated a stable thin oxide film which depends on the mode of anodization of the metal. However, in the presence of H₂O₂ the film characteristics were changed. A significant decrease in the corrosion resistance of the surface film was recorded. The film characteristics were also found to be affected by the mode of oxide film growth and polarization time. The EIS results and the impedance data fitting to equivalent circuit models have shown that the oxide film consists of two layers. The electrochemical characteristics of the anodic films formed under different conditions have been discussed.     

The effect of additives on the electrodeposition of copper studied by the impedance technique

The impedance technique has been used to study the effects of NaCl, glue, thiourea and Avitone on the elctrodeposition of copper in a 0.71M CuSO₄-1.80M H₂SO₄ solution. NaCl affects the rate of the two-step reaction and glue is a polarizer due to adsorption on the surface. The degradation of glue by hydrolysis can be followed using impedance measurements. No significant effects of thiourea and Avitone could be detected in the concentration and potential range used in electrorefining.     

A novel EDOT–nonylbithiazole–EDOT based comonomer as an active electrode material for supercapacitor applications

A novel EDOT–nonylbithiazole–EDOT based bis(3,4-ethylene-dioxythiophene)-(4,4′-dinonyl-2,2′-bithiazole) comonomer was synthesized and was electrochemically deposited onto carbon fiber electrode as an active electrode material. An electrochemical impedance study on the prepared electrodes is reported in this paper. Capacitive behavior of the carbon fiber microelectrode/poly(3,4-ethylene-dioxythiophene)-(4,4′-dinonyl-2,2′-bithiazole) system was investigated with cyclic voltammetry (CV) experiments and electrochemical impedance spectroscopy. Variation of capacitance values by scan rate and specific capacitance values at different potentials are presented. Specific capacitance value for a galvanostatically prepared polymer film with a charge of 5 C cm⁻² was obtained about 340 mF cm⁻². Effect of the solvent and the deposition charge on the capacitive behavior of the film was investigated using electrochemical impedance spectroscopy. An equivalent circuit model was proposed and the electrochemical impedance data were fitted to find out numerical values of the proposed components. The galvanostatic charge/discharge characteristic of a film was investigated by chronopotentiometry and the morphology of the films electrodeposited at different deposition charges were monitored using FE-SEM.     

Fundamentals of lead-acid cells. XVII. The a.c. impedance of lead dioxide formed in sulphuric acid on some lead alloys

The impedances of PbO₂ formed on lead and some lead alloys have been measured over a wide range of potential. Conditions were chosen so that well-defined electrode states were obtained. Considerable differences were observed in the behaviour of alloys containing antimony and bismuth. The latter alloying ingredient appears to contribute some semiconducting properties to lead sulphate films formed on PbO₂ by polarizing them at potentials negative to the reversible potential in sulphuric acid.Nomenclature C _L double-layer capacitance - C _X series capacitance - D diffusion coefficient - E potential - R _CT charge-transfer resistance - R electrolyte resistance - Z _D impedance as defined by Equation 1 - Z _F impedance as defined by Equation 2 - Z impedance as defined by Equation 3 - Warburg coefficient - angular frequency     

Preparation and characterization of the electrodeposited Ni-Co oxide thin films for electrochemical capacitors

Nickel-cobalt (Ni-Co) oxide thin films were electrodeposited onto copper substrates in an electrolyte containing cobalt chloride and nickel chloride, and the electrochemical capacitor behaviors of these films were investigated. The XRD pattern revealed that the electrodeposited Ni-Co oxide thin film was comprised of NiCo₂O₄. In the SEM image, the electrodeposited Ni-Co oxide film was covered with hexagonal and cubical shaped particles. The electrodeposited Ni-Co oxide electrode exhibited a specific capacitance of 148 F/g at a scan rate of 20 mV, and the current density was fairly stable over 200 cycles. The charge-discharge test confirmed that capacitance of the electrodeposited Ni-Co oxide electrode resulted from the electric double layer capacitance and pseudocapacitance.     

Kinetics of the dissolution behaviour of anodic oxide films on niobium in NaOH solutions

The dissolution behaviour of the anodized niobium electrode in NaOH solutions was investigated as a function of alkali concentration, formation voltage, formation current density and temperature using potential and impedance measurements. The rate of dissolution is dependent on the alkali concentration. In dilute NaOH solutions (1 N) the anodic oxide film formed in 0.5 M H₂SO₄ is reasonably stable. On the other hand, at higher concentrations of NaOH (2 M), the anodized electrode is subject to continuous dissolution depending on the alkali concentration. Also, the dissolution process is considerably affected by temperature; at temperatures greater than 320 K the oxide film is destroyed in less than 30 min. The results show that the current density used during the formation of the oxide film has no effect on its dissolution rate.     

Alternating current impedance studies on oxide films in metal/oxide/electrolyte systems: a modified approach

The accurate determination of the impedance of oxide films in metal/oxide/electrolyte systems is shown to be possible through a modified procedure. The film impedance thus determined is found to be quite different from the measured cell impedance for anodic aluminium oxide formed on pure aluminium. The computed values of tan and conductivity are found to be in agreement with the values reported earlier for anodic and thermal oxides.     

EIS study of potentiostatically formed passive film on 304 stainless steel

Passive film was potentiostatically grown on Type 304 stainless steel at potentials between −0.4 and 0.3 V vs. Hg/HgSO₄ in 50 mV intervals. Electrochemical impedance spectroscopy was used to study properties of the grown passive films. Relevant circuit analogs were selected to fit the electrochemical impedance data obtained at each potential. The resultant parameters were used to calculate film thickness through both film capacitance and resistance. The calculated thicknesses were compared with ellipsometry thickness measurement results. An overestimation occurred when the film resistance was used to calculate the film thickness. On the other hand, when the CPE parameter Q was used, the film thickness was underestimated. Available approaches were employed to calculate the effective capacitance of the film. A comparison between the film thickness calculated from the effective capacitance and ellipsometry measurements suggested a surface distribution of time constants on the surface.     

Electrochemical impedance spectroscopy of electrodes modified with thin films of MgMnCO3 layered double hydroxides

The electrochemical impedance spectra of MgMnCO₃ LDH films oxidized at different dc potentials were recorded. The results were fitted to a Randles type cell by replacing the Warburg impedance with a mass transfer resistance in parallel with a constant phase element. The films charge transfer resistances decreased dramatically at the onset of manganese oxidation. In thin films, R_ct decreased from 10⁴ Ω for an un-oxidized film to a minimum of 40 Ω in a film oxidized at 0.32 V, before increasing back to 10⁴ Ω in a film oxidized at 0.5 V. Iodometry measurements show these changes correspond to increases in the manganese average valence in the films from 3.09+ prior to oxidation, to 3.80+ at 0.32 V and 3.95+ at 0.5 V. In thicker films, however, a much higher dc potential, 1.0 V, was required to return R_ct to 10⁴ Ω. There was also less change in the manganese average valence in the thicker films. Oxidation at 1.0 V only increased the manganese valence to 3.33+. For the partially oxidized films, the Nyquist plots consisted of depressed semicircles at high frequency, followed by linear regions at lower frequency where the impedance was controlled by mass transport. The effective diffusion coefficient estimated from the low frequency impedance was 1 × 10⁻⁹ cm² s⁻¹, consistent with proton diffusion in solid electrodes. The impedance spectrum of a partially oxidized film reduced at −0.2 V was similar to that of the un-oxidized film.     

Use of electrochemical impedance spectroscopy for the study of corrosion protection by polymer coatings

A discussion of the requirements for hardware and software necessary for collection and analysis of electrochemical impedance spectroscopy data for polymer coated metals is presented. Most authors agree that a simple model can describe the frequency dependence of impedance spectra for polymer coated metals exposed to corrosive environments. The water uptake of the coating can be estimated from the time dependence of the coating capacitance C _c, The pore resistance R _po depends both on the resistivity of the coating and the disbonded area A _d. The polarization resistance R _P of the corroding area under the coating and the corresponding capacitance C _dl both depend on A _d. The breakpoint frequency method is discussed in detail and the dependence of the breakpoint frequency f _b on and A _d is derived. In addition to f _b other parameters can be obtained which depend on the ratio A _d/ or only on A _d or . Since these parameters can be obtained at frequencies exceeding 1 Hz without the need for an analysis of the impedance spectra in the entire frequency region, this approach is considered especially useful for corrosion monitoring. The concepts proposed for the analysis and interpretation of EIS data for polymer coated metals are illustrated using data for Al alloys, Mg and steel exposed to NaCl. For an alkyd coating on cold rolled steel the time dependence of A _d and during exposure to 0.5 m NaCl has been determined qualitatively using the modified breakpoint frequency method.     

Nature and corrodability of thin oxide films formed on niobium in NaOH solutions

The corrodability of thin oxide films formed on niobium either naturally or anodically was investigated in NaOH solutions of different concentrations (0.05–3.0 M) using impedance and potential measurements. Naturally formed films were found to thicken in NaOH solutions of concentrations 0.1 M, while they were subjected to dissolution in NaOH solutions of concentrations1.0 M. The dissolution behaviour of anodically formed oxide films on niobium was found to depend on the thickness and alkali concentration. Anodically formed thin films (4 nm resist dissolution in NaOH solutions of concentrations0.1 M, partially dissolve at [NaOH]0.5 and 1.0 M and are subject to aggressive dissolution at higher concentrations. Thick films (50 nm) resist dissolution at [NaOH]1.0 M, while they dissolve at higher alkali concentrations. The corrosion potential was found to depend on the alkali concentration and the oxide film thickness. The impedance of the oxide film was found to be purely capacitive and to increase with increasing film thickness.     

A kinetic study on the corrodability of anodic oxide films formed on molybdenum in NaOH solutions

The corrodability of anodic oxide films formed on molybdenum in NaOH solutions was studied using impedance and potential measurements. The corrosion rate was found to increase with increase of alkali concentration, film thickness and temperature and was nearly independent of the rate of oxide formation. The dissolution process was found to involve a valency change from Mo(IV) to Mo(VI) where it seemed, from cathodic polarization, that no electron transfer through the oxide film to/from the metal surface was involved during the dissolution process. In concentrated NaOH solutions ([OH^–]9 M), the dissolution process appeared to follow zero-order kinetics.     

Physicochemical and electrocatalytic properties of LaNiO3 prepared by a low-temperature route for anode application in alkaline water electrolysis

LaNi_1–x Fe_xO₃ (x = 0, 0.25, 0.5) has been synthesized by the hydroxide solid solution precursor method for electrochemical characterization as oxygen anode in strongly alkaline medium. Studies were made at the oxide film, which was obtained by the oxide-slurry painting technique. The cyclic voltammetric study showed the formation of a diffusion-controlled quasireversible redox couple, Ni(ii)/Ni(iii), (E ⁰ - 430 ± 10 mV) at the oxide surface in 1 m KOH. The reaction was observed to follow approximately first-order kinetics in OH^– concentration. Values of the Tafel slope ranged between 59 and 86 mV decade^–1 with all the oxide film electrodes. The electrocatalytic activity was found to be greatest with the Ni/LaNi_0.75Fe_0.25O₃ electrode. A comparison was made between the electrocatalytic activities of LaNiO₃ prepared by the hydroxide solid solution precursor and by the hydroxide coprecipitation technique.