Local electrochemical impedance spectroscopy: Considerations about the cell geometry

Local electrochemical impedance spectroscopy provides a powerful tool for the investigation of surface heterogeneities on electrode surfaces. However, measurements are greatly influenced by geometry-induced frequency dispersion. In order to account for this frequency dispersion, both simulations and experiments were performed to explore the influence of a recessed electrode on the local and global impedance response. The calculations presented here demonstrated that the depth of the recessed electrode required to achieve a uniform primary current distribution was twice the electrode radius. The calculations provide guidelines for design of LEIS measurements, and were in good agreement with results obtained for a stainless steel disk electrode in a Na₂SO₄ electrolyte.     

Corrosion of steel under the defected coating studied by localized electrochemical impedance spectroscopy

Corrosion of steel under the defected coating in near-neutral pH solution was investigated by localized electrochemical impedance spectroscopy (LEIS) measurements. The LEIS response is dependent on the size of the defect. For small defects, e.g., less than 200 μm in diameter, localized corrosion process and mechanism of steel, as indicated by the measured LEIS plots, change with time. The diffusion process dominates the interfacial corrosion reaction, which is due to the block effect of the deposited corrosion product combined with the geometrical factor of a large coating thickness/defect width ratio. In the presence of a big defect, e.g., up to 1000 μm, the LEIS responses measured at the defect are always featured by a coating impedance in the high-frequency range and an interfacial corrosion reaction in the low-frequency range. The block effect of corrosion product does not apply due to the relatively open geometry. Conventional EIS measurements on a macroscopic-coated electrode reflect the “averaged” impedance results from both coating and defect. The information of the localized electrochemical corrosion processes and mechanisms at the small defect is lost, and the coating impedance information is “averaged” out when a big defect is contained. LEIS measurement provides an essential technique to characterize microscopically the local electrochemical corrosion reaction of steel under the defected coating.     

The origin of the complex character of the Ohmic impedance

The local and global Ohmic response for an electrode exhibiting geometry-induced potential and/or current distributions has recently been shown to be represented by a frequency-dependent complex impedance. A physical explanation for this result is provided in terms of the radial contribution to local current density and the decrease in current density along the current lines. Experiments performed with Cu/Al and Mg/Al galvanic couples show that, in regions where a radial current density does not exist, the local Ohmic impedance is independent of position; whereas, in regions where the radial current density cannot be neglected, the local Ohmic impedance is a function of position. Simulations performed on recessed electrodes show that, even in the absence of a radial current, an axial variation of current density gives rise to a complex Ohmic impedance. The complex character of the Ohmic impedance shows that an equivalent circuit, using the usual two-terminal resistor to represent the Ohmic contribution of the electrolyte, provides an inadequate representation of an electrode with geometry-induced current and potential distributions.     

Localized EIS characterization of corrosion of steel at coating defect under cathodic protection

Localized electrochemical impedance spectroscopy (LEIS) technique was used to investigate localized corrosion of steel at defect of coating and, furthermore, to determine the effects of cathodic protection (CP) on local electrochemical environment and the resultant corrosion reaction at the base of coating defect. The results demonstrated that corrosion of steel is dependent on CP potential and the defect geometry. For coated steel containing defect under appropriate CP potentials, cathodic reaction is dominated by reduction of oxygen. Mass-transfer of oxygen through solution layer and the defect with a narrow, deep geometry (the depth/width ratio is about 5.5) is the rate-limiting step for the corrosion process of steel. Even at a very negative potential, e.g., −1200 mV (SCE), the measured impedance spectroscopy is still associated with the diffusion-controlled charge-transfer reaction of steel at the base of defect. It is attributed to the fact that the applied CP is partially shielded by the defect with a narrow, deep geometry. With the negative increase of cathodic potential, charge-transfer resistance and the local impedance of electrode increase. It is attributed to the elevation of local alkalinity at the base of defect when the coated steel is under CP. This conclusion is subject to the condition that a significant cathodic disbonding of coating has not occurred. Furthermore, with the increase of test time, the charge-transfer resistance increases, which is attributed to the enhancement of the alkaline environment at the base of defect under CP with time.     

Simulative Approach for Linking Electrode and Electrolyte Properties to Supercapacitor Performance

Supercapacitors as energy storage devices show distinct advantages like high power density and high cycle stability. While in current applications, mainly the high power density is leveraged, future non‐mobile storage devices could also benefit from the robustness and materials employed, while lower charging/discharging time constants are acceptable. In this study, a simulative approach is employed to investigate the complex interplay of mass transfer, electric losses, double layer capacitance for different electrode thicknesses, electrode and electrolyte conductivities as well as charging/discharging time constants. Within the simulation cyclic voltammetry, galvanostatic cycling as also electrochemical impedance spectroscopy experiment could be realized, showing the dependency of achievable maximum capacitance and voltage efficiency on various properties.     

海水压力对深海用环氧涂层防护性能的影响

采用电化学阻抗谱(EIS)技术与局部交流阻抗技术(LEIS)研究了深海环境用重防腐环氧涂层H44-61在深海模拟环境(青岛海水,常压以及6 MPa交变压力)下的腐蚀电化学行为,探讨了交变压力对深海用涂层防护性能的影响。结果表明,涂层在6 MPa交变压力下的涂层电容较常压下高且涂层电阻较低,涂层的防护性能下降,但低频阻抗膜值均在10⁷ Ω·cm²以上,说明涂层仍有较好的防护性能;LEIS的研究表明交变压力下人造缺陷区域的阻抗值较小,缺陷周围涂层的剥离面积较大,说明压力交变能加快电解质溶液向涂层金属界面扩散,加速涂层下金属的腐蚀过程,降低涂层的防护性能。     

Distortions in Electrochemical Impedance Spectroscopy Measurements Using 3‐Electrode Methods in SOFC. II. Effect of Electrode Activity and Relaxation Times

The 3‐electrode configuration is commonly applied to quantify the overpotential of anodes or cathodes in solid‐oxide fuel cells (SOFC). In this type of set‐up, a reference electrode (RE) is used to isolate the potential loss of one electrode from that of the entire cell; however, erroneous results can be obtained whenever the RE does not precisely separate the potential drop between the two active electrodes. In this study, we present the results of a theoretical and experimental analysis focused on verifying the effectiveness of the 3‐electrode configuration in electrochemical impedance spectroscopy measurements for the kinetic characterisation of SOFC electrode reactions. The focus of this paper is on the distortion of impedance measurements caused by differences in the area‐specific polarisation resistance and impedance time constants of the working and counter electrodes. The results obtained numerically and experimentally, both for planar and tubular SOFC cell geometries, prove the reliability of the theoretical model used. From the systematic simulation presented here and in our previous work, it was possible to formulate general guidelines for the design of 3‐electrode experimental SOFC. The theoretical model used here can also be used to verify the consistency of EIS measurements obtained with thin planar cells.     

Corrosion of the stressed pipe steel in carbonate-bicarbonate solution studied by scanning localized electrochemical impedance spectroscopy

Corrosion of X-70 pipe steel as a function of stress distribution was investigated by scanning localized electrochemical impedance spectroscopy (LEIS) technique. The deformation-induced stress, if not sufficiently high, has an inhibitive effect on corrosion reaction, pitting occurrence and crack initiation in pipe steel under high-pH condition. Such an inhibitive effect is due to the enhanced generation of carbonate product and the resultant surface block effect at the stressed zones. The tensile and compressive stresses have identical effect on inhibition of dissolution and pitting of the steel. However, tensile stress enhances the steel dissolution more significantly than compressive stress, and thus, generates more carbonate product, resulting in higher localized impedance. Pits are easy to occur around the neutral axis of the U-bend specimen, where the steel deformation and the resultant stress are ignorable. For pipelines encountering non-uniform stress distribution, the role of stress in crack initiation is critically different. Scanning LEIS technique provides a promising method to map and characterize corrosion of the steel as a function of the stress distribution.     

Bifunctional electrodes for unitised regenerative fuel cells

The effects of different configurations and compositions of platinum and iridium oxide electrodes for the oxygen reaction of unitised regenerative fuel cells (URFC) are reported. Bifunctional oxygen electrodes are important for URFC development because favourable properties for the fuel cell and the electrolysis modes must be combined into a single electrode. The bifunctional electrodes were studied under different combinations of catalyst mixtures, multilayer arrangements and segmented configurations with single catalyst areas. Distinct electrochemical behaviour was observed for both modes and can be explained on the basis of impedance spectroscopy. The mixture of both catalysts performs best for the present stage of electrode development. Also, the multilayer electrodes yielded good results with the potential for optimisation. The influence of ionic and electronic resistances on the relative performance is demonstrated. However, penalties due to cross currents in the heterogeneous electrodes were identified and explained by comparing the performance curves with electrodes composed of a single catalyst. Potential improvements for the different compositions are discussed.     

An electrochemical and surface analytical study of the formation of nanoporous oxides on niobium

In the present paper, the anodization of Nb in mixed sulphate + fluoride electrolytes resulting in the formation of a nanoporous oxide film has been studied. Chronoamperometry and electrochemical impedance spectroscopy have been employed to characterise in situ the kinetics of the oxidation process. In addition, the evolution of the layer structure and morphology has been followed by ex situ scanning electron microscopy. Particularly, local electrochemical impedance spectroscopy has been used to discern between the mesoscopic 2D and 3D distributions of time constants at the electrode surface. The similarity between local and global impedance spectra during anodic oxidation of Nb demonstrates the presence of an inherent 3D distribution of the high-frequency time constant, which is interpreted as in-depth variation of the steady state conductivity of the passive film. The experimental and calculational results are discussed in relation to the micro- and nanoscopic structure of the formed oxide.