Mechanistic studies on lanthanum fluoride crystal electrodes

A mechanistic study of the fluoride electrode involving the impedance measurement technique was performed. The influence of the reference electrode, the fluoride ion concentration and the convection on the indicatrix were examined. From the results it followed that the linear equivalent model of the fluoride electrode may be represented by three components namely, a parallel R-C network representing the bulk of the membrane, two double layer capacities one on each side of the sensor, each shunted by a charge transfer resistor and finally, a diffusion impedance.     

电化学双石英晶体阻抗分析新方法

电化学石英晶体微天平已被广泛应用于电分析化学与电化学领域[1] .电化学现场的石英晶体阻抗分析法能动态实时地提供电化学扰动下石英晶体谐振的多维信息 ,已用于研究电沉积与溶出[2 ,3] 、高聚物性质[4～ 6 ] 、耗尽层内溶液粘密度效应与金电极腐蚀[7,8] 等 .然而 ,以往的石英晶体阻抗分析均只涉及到一个石英晶体 ,同时对两个晶体 (分别作为工作电极和对电极 )谐振的阻抗分析未见报道 .本文以蔗糖溶液粘密度效应和氨性介质中铜沉积 /溶出过程为例 ,研究电化学双石英晶体阻抗分析新方法 .1　实验部分电化学双石英晶体阻抗分析系统由 HP43 9…     

New method for a graphical portrayal of the electrochemical impedance

A new method of a graphical representation of the electrode impedance is proposed. The method allows one to construct the impedance of a complicated circuit by summing up impedance plots for series and parallel branches. Rules for constructing complex representations are presented. New shapes of impedance plots for some of the most typical circuits are analyzed. The method opens additional possibilities for analyzing how the experiment accuracy impacts the limits of discovery of individual elements of complicated circuits. The method gives grounds to introduce the notion of the information potential of an experimental setup. Conditions for a complete decidability of equivalent circuits are shown by the example of a system that comprises several parallel branches consisting of the Frumkin-Melik-Gaikazyan impedances.     

A new floating electrode structure for generating homogeneous electrical fields in microfluidic channels

In this article a new parallel electrode structure in a microfluidic channel is described that makes use of a floating electrode to get a homogeneous electrical field. Compared to existing parallel electrode structures, the new structure has an easier production process and there is no need for an electrical connection to both sides of the microfluidic chip. With the new chip design, polystyrene beads suspended in background electrolyte have been detected using electrical impedance measurements. The results of electrical impedance changes caused by beads passing the electrodes are compared with results in a similar planar electrode configuration. It is shown that in the new configuration the coefficient of variation of the impedance changes is lower compared to the planar configuration (0.39 versus 0.56) and less dependent on the position of the beads passage in the channel as a result of the homogeneous electrical field. To our knowledge this is the first time that a floating electrode is used for the realization of a parallel electrode structure. The proposed production method for parallel electrodes in microfluidic channels can easily be applied to other applications.     

Electrochemical impedance spectroscopic studies of copper dissolution in glycine–hydrogen peroxide solutions

Anodic dissolution of copper in glycine solution at various hydrogen peroxide concentrations was investigated. The dissolution rate increases, reaches a maximum, and then decreases with hydrogen peroxide concentration. Anodic polarization studies and electrochemical impedance spectroscopy (EIS) studies were carried out to determine the mechanistic pathway of anodic dissolution of copper in glycine system at three different hydrogen peroxide concentrations: one at low hydrogen peroxide concentration in the active dissolution region, another in the maximum dissolution region, and the third at the high hydrogen peroxide concentration in the post-peak-dissolution region. The EIS data in complex plane plots show presence of two capacitance loops and one negative capacitance loop. The impedance plot patterns strongly depend on the hydrogen peroxide concentration in solution. Reaction mechanism analysis technique was employed to model the EIS data. A three-step mechanism with two intermediate adsorbates and a parallel dissolution by catalytic mechanism simulates EIS patterns which match the experimental trends. The intermediates are likely to be cupric and cuprous oxides. The essential features of impedance spectra at various overpotentials at three different hydrogen peroxide concentrations are captured by the proposed mechanism. The results also show that the film present on the copper surface in glycine and hydrogen peroxide solutions does not passivate the surface.     

JONES型电导池测量的LCR电桥等效电路选择

JONES电导池系统的交流阻抗由电极过程的相关阻抗和电极间溶液的电阻两部分组成,可用适当的等效电路模拟。采用LCR电桥测量JONES电导池中溶液的电阻时需要选择合适的等效电路为模型解析测量的交流阻抗。通过等效电路的分析发现,选择串联电路作为LCR电桥的解析等效电路测量JONES型电导池中溶液的电阻时引入的误差比并联电路小。     

Crystallization impedance in the case of D.C. superposition

An expression for the impedance frequency dependence in the case of d.c. superposition has been derived and analyzed for the crystallization process of metals taking into account the two-dimensional diffusion of ions in solution and the surface diffusion of adatoms and using the simplest surface model with parallel step lines. It is shown that in the general case it is impossible to present the crystallization impedance as the sum of the surface diffusion impedance and the Warburg impedance. It has been found that in the case of anode polarization an unusual effect of the impedance increasing with agitation intensity takes place which is typical of this mechanism. Possible methods for determination of the model parameters from impedance measurements are discussed. The authors suggest an iteration procedure which permits to determine all the parameters of the model under consideration including the surface diffusion coefficient of adatoms and the spacing between the growth step lines.     

Complex rate constant for an electrochemical system involving an adsorbed intermediate

Two different methods of obtaining the impedance of a system involving an electrochemical reaction with an adsorbed intermediate are compared. The earlier method combines in parallel an impedance derived separately for the overall reaction with that for the rest of the system. It is appropriate for a fully supported electrolyte system but seems much less applicable to the unsupported situation. In contrast, the method derived and discussed herein involves complex reaction rate constants which may be directly incorporated in expressions for the total system impedance. This method may, therefore, be applied to either supported or unsupported situations. Several specific cases of the general complex rate constant results are discussed, particularly, various frequency dependencies possible. The overall small-signal impedance may be inductive in some parts of the frequency range and the low frequency limiting differential resistance negative, zero, or positive under various conditions.     

Impedance studies of porous lanthanum-phosphate-bonded nickel electrodes in concentrated sodium hydroxide solution

The hydrogen evolution reaction (HER) was investigated on a lanthanum-phosphate-bonded nickel (LPBN) powder electrode in 30 wt.% NaOH at 70°C using ac impedance and steady-state polarization techniques. Circuits containing one or two constant-phase elements (CPEs) in parallel with a resistance and corresponding to fractal and porous electrode models were tested in order to interpret the ac impedance data. The experimental impedance spectra were well described by the porous electrode model and the circuit containing two CPEs. The results obtained from the ac impedance and steady-state measurements allowed the mechanism and kinetics of the HER to be evaluated. Comparison of these parameters with those obtained on the polycrystalline nickel electrode in 1 M alkaline solution at 25°C indicates that an increase in activity is principally due to an increase in the real surface area.     

Characterization of Electrode/Electrolyte Interface of ECIS Devices

Electric cell‐substrate impedance sensing requires low electrode/electrolyte interface impedance for effective biomedical and biophysical applications. Thus a complete understanding of physical processes involved in the formation of an electric double layer is required to design a low interface impedance device. This paper presents the numerical simulation of the impedance for the electrode/electrolyte interface of three‐electrode devices along with the practical realization for the effective workout of impedance sensing devices. The three‐electrode based impedance sensing devices along with phosphate buffered saline as electrolyte is simulated using COMSOL Multiphysics to evaluate the impedance of the electrode/electrolyte interface. Microfabrication technology is used to realize three‐electrode impedance sensing devices with diverse configuration which are used to measure the electrode/electrolyte interface impedance. The measured impedance data were then compared with the COMSOL simulated results and it is found that both the data sets fitted well with less than 5 % RSE. The results obtained from simulation and experiments indicate that the impedance due to double layer diffusion dominates in the low frequency region up to few kHz whereas electrolytic bulk resistance plays a major role in the higher frequency range. The experimental impedance data were further interpreted by electrochemical impedance spectroscopy analysis software to model the equivalent circuit of the electrochemical system.     

Binary electrolyte small-signal frequency response

The frequency response is considered of a two-electrode linearized system containing a single positively charged species and a single negatively charged species. These species may have arbitrary valences and mobilities and may individually react at the electrodes. The results follow from a detailed solution of the equations of charge motion given earlier. Normalized response is exhibited for this unsupported, intrinsic-conduction situation for a wide range of mobility ratios, valence number ratios, and reaction rate ratios. Results are given in the form of specific formulas, impedance-plane plots, and the dependences on normalized frequency of series and parallel resistive and capacitative components of the normalized total impedance of the system.Impedance-plane plots exhibit from one to three connected arcs, depending on the specific situation. Approximate Warburg frequency response appears for the “interface” impedance over a certain frequency region when normalized reaction rate parameters differ, but it only shows up strongly in the total impedance when the mobility ratio departs appreciably from unity as well. Under such conditions, a plateau region, where the total parallel capacitance remains essentially independent of frequency over a wide frequency range, may appear at frequencies just above the Warburg region. The plateau capacitance is close to but not identical to the conventional double-layer capacitance present when both species of charge are completely blocked. In incomplete blocking cases, however, this double-layer capacitance only makes a significant appearance in the approximate equivalent circuit under slow reaction conditions; it is thus not present when one of the reaction rate constants is infinite.In general, the system can show ω^?m frequency response for the parallel capacitance over a wide frequency range with 0?m?2, and with the experimentally common regions where m≌0, 0.5, 1.5, and 2 especially likely. Particular attention is given to deviations from ideal Warburg behavior which led to a combined charge-transfer and heterogeneous chemical reaction resistance. Results are compared to those from conventional supported treatments and show both important similarities and differences. Finally, several new equivalent circuits are presented which are pertinent in various frequency ranges for the unsupported situation.     

固体氧化物燃料电池电化学阻抗谱差异化研究方法和分解

电化学阻抗谱技术(EIS)在固体氧化物燃料电池(SOFC)中已获得广泛应用。在EIS分析过程中,研究者能够清楚地获得燃料电池内部因纯离子(电子)导电引起的欧姆电阻和因电化学过程、扩散作用引起的极化阻抗的大小,但是对于极化阻抗的构成缺乏进一步解析。本文选用传统的Ni-YSZ阳极支撑电池,通过改变测试温度、阳极运行气氛和阴极运行气氛,设计了一套完整的阻抗差异分析(ADIS)实验。并基于弛豫时间分布法(DRT)和阻抗差异分析法,系统地分析并解释了阻抗谱中各频率段对应阻抗的物理或(电)化学含义,将该类型电池阻抗谱以6个RQ并联电路予以拟合,为之后燃料电池性能稳定性的研究奠定基础。     

Combination of in situ UV–Vis-NIR spectro-electrochemical and a.c. impedance measurements: A new, effective technique for studying the redox transformation of conducting electroactive materials

Simultaneous in situ UV–Vis-NIR spectro-electrochemical and a.c. impedance techniques have been realized for the first time. Combination of the data obtained by these parallel, independent methods can be exploited in the future in the elucidation of the redox mechanism of various transparent electroactive layers.     

Structure and electrical properties of undoped oriented poly(phenylene vinylene) films

The influence of anisotropic structure on the electrical properties of undoped oriented poly(phenylene vinylene) (PPV) films was investigated with impedance spectroscopy and structural characterization. The oriented structure of the stretched PPV films was studied with wave-guide coupling and infrared dichroism. It was found that the unstretched PPV film had a highly planar structure, and one-way stretching converted the planar structure into a uniaxial structure. The impedance of undoped PPV thin films was measured along three different directions: through the film thickness direction, parallel to the stretch direction in the film plane, and perpendicular to the stretch direction in the film plane. Two relaxations were observed, one corresponding to the bulk behavior in the high-frequency range and the other to an interfacial contact polarization in the low-frequency range. From equivalent circuit modeling, it was found that the bulk conductivity through the film thickness direction decreased with increasing orientation, whereas the high-frequency dielectric constant through the film direction remained constant. In addition, the conductivities measured in the film plane were at least two orders of magnitude higher than the conductivity in the direction normal to the film surface. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 98–116, 2004     

Linking optical and electrical small amplitude perturbation techniques for dynamic performance characterization of dye solar cells

This paper unifies the analytical models used widely but thus far mostly separately for electrical and optical small amplitude perturbation measurements of nanostructured electrochemical dye solar cells (DSC): electrochemical impedance spectroscopy (EIS), intensity-modulated photocurrent spectroscopy (IMPS) and intensity-modulated photovoltage spectroscopy (IMVS). The models are linked by expressing the kinetic boundary condition used for solving the time-dependent continuity equation of electrons in IMPS and IMVS analysis in terms of the series and parallel impedance components found in the complete equivalent circuit impedance model of DSC. As a result, analytical expressions are derived for potentiostatic IMPS and galvanostatic IMVS transfer functions of complete DSCs that are applicable at any operating point along the solar cell current-voltage (IV) curve. In agreement with the theory, impedance spectrum calculated as a ratio of IMVS and IMPS transfer functions measured near the maximum power point matches exactly with the impedance spectrum measured directly with EIS. Consequently, both IMPS-IMVS and EIS yield equal estimates for the electron diffusion length. The role of the chemical capacitance of the nanostructured semiconductor photoelectrode in the interpretation of the so-called RC attenuation of the IMPS response is clarified, as well as the capacitive frequency dispersion in IMPS and IMVS.     

Development of an enrofloxacin immunosensor based on label-free electrochemical impedance spectroscopy

Enrofloxacin is the most widespread antibiotic in the fluoroquinolone family. As such, the development of a rapid and sensitive method for the determination of trace amounts of enrofloxacin is an important issue in the health field. The interaction of the enrofloxacin antigen to a specific antibody (Ab) immobilized on an 11-mercapto-undecanoic acid-coated gold electrode was quantified by electrochemical impedance spectroscopy. Two equivalent circuits were separately used to interpret the obtained impedance spectra. These circuits included one resistor in series with one parallel circuit comprised of a resistor and a capacitor (1R//C), and one resistor in series with two parallel RC circuits (2R//C). The results indicate that the antigen-antibody reaction analyzed using the 1R//C circuit provided a more sensitive resistance increment against the enrofloxacin concentration than that of the 2R//C circuit. However, the 2R//C circuit provided a better fitting for impedance spectra, and therefore supplies more detailed results of the enrofloxacin-antibody interaction, causing the increase of electron transfer resistance selectively to the modified layer, and not the electrical double layer. The antibody-modified electrode allowed for analysis of the dynamic linear range of 1-1000 ng/ml enrofloxacin with a detection limit of 1 ng/ml. The reagentless and label-free impedimetric immunosensors provide a simple and sensitive detection method for the specific determination of enrofloxacin.     

N80油套管钢应力状态下的CO2腐蚀行为研究

利用交流阻抗技术研究了拉伸、压缩和弯曲三种应力状态下N80油套管钢在饱和CO₂地层水中的腐蚀过程. 结果表明, 三种状态下的阳极电化学阻抗谱均出现了高频容抗弧、中低频感抗弧和低频容抗弧三个时间常数, 其中高频容抗弧与双电层电容和传递电阻有关, 感抗弧对应膜的活性溶解, 低频容抗弧与试样表面膜的生成有关. 随着三种状态下应变的增加, 感抗弧逐渐扩大, 而低频容抗弧则逐渐缩小, 表明应力状态下N80钢的CO₂腐蚀会加剧. 三种状态下的阴极阻抗谱高频均由容抗弧组成, 中低频由Warburg阻抗和容抗弧共同组成, 三种状态下随着应变程度的增加, Warburg阻抗增加, 反应电阻减小, 双电层电容减小, 说明应力会加速阴极反应过程的进行, 从而增加N80钢的CO₂腐蚀速率.     

Contact Free Impedance Methodology for Investigating Enzymatic Reactions into Dielectric Polymer Microchip

A methodology for free contact microchannel impedance measurements through a dielectric microchip was developed for monitoring the kinetics of enzymatic reactions. For that purpose, we propose a procedure which consists of subtracting the impedance contribution of the dielectric polymer layer, which separates the two parallel microband electrodes embedded in it, from the global microchip impedance. This operation allows microchannel impedance enhancement for real time monitoring of impedance modulus changes without direct electrical contact. Application for determination of kinetic parameters of enzyme‐substrate reaction independently of optical or electrochemical properties of the substrates is demonstrated. Hydrolysis 4‐nitrophenylphosphate (pNPP) and 4‐aminophenylphosphate (pAPP), which are two substrates for Alkaline Phosphatase (ALP), are taken as examples. Moreover, signal amplification response of the impedance modulus is achieved by the use of superparamagnetic microbeads as enzyme supports. Plotting the maximum rate against the ALP concentration gives rise to straight lines with a slope that is the hydrolysis catalytic pseudo first‐order rate constant, k_cat. Sensitivity, selectivity and reproducibility of these measurements have been demonstrated comparatively with both substrates. k_cat values were 103 s^?1 and 52 s^?1 with pAPP and pNPP, respectively.     

Impedance and Photoadmittance of Passive Iron Electrodes in Different Solutions

Electric characteristics of the oxide film at the surface of an anodized iron electrode in 0.5 M Na₂SO₄, NaNO₃, and Na₂MoO₄ solutions are studied using the impedance and photoadmittance measurements and taking polarization curves. The impedance frequency spectra correspond to an equivalent circuit comprising two parallel (RC) chains connected in a series. The relaxation time of the high-frequency circuit approaches that of the photopotential; hence, it can be related to the impedance of the oxide film. The low-frequency component of the impedance describes the impedance of the film/solution interface. In the Na₂SO₄ solution, the oxide film resistance is significantly higher and the capacitance is lower than in two other solutions, which can be explained by the film thickening. The marked concurrent decrease in the resistance and increase in the capacitance of the film/solution interface at 1.2 V in all solutions is caused by oxygen adsorption, which precedes oxygen evolution.     

A universal equivalent circuit for carbon-based supercapacitors

A universal equivalent circuit is proposed for carbon-based supercapacitors. The circuit, which actually applies to all porous electrodes having non-branching pores, consists of a single vertical ladder network in series with an RC parallel network. This elegant arrangement explains the three most important shortcomings of present-day supercapacitors, namely open circuit voltage decay, capacitance loss at high frequency, and voltammetric distortion at high scan rate. It also explains the shape of the complex plane impedance plots of commercial devices and reveals why the equivalent series capacitance increases with temperature. Finally, the construction of a solid-state supercapacitor simulator is described. This device is based on a truncated version of the universal equivalent circuit, and it allows experimenters to explore the responses of different supercapacitor designs without having to modify real supercapacitors.