双电层电容器电化学阻抗谱的实验研究

电化学阻抗谱(EIS)是一种很有用的研究电化学性能的技术. 理想的双电层电容器(EDLC)阻抗谱的尼奎斯特图由中高频的45°线和低频的与实轴垂直的直线组成, 可以用孔径分布-传输线模型来解释. 然而, 在研究工作中还发现, 在阻抗谱的高频区出现了半圆弧区域, 为此, 提出的等效模型认为半圆弧可以归因于活性材料之间的接触电阻和接触电容, 以及电极与集流体之间的接触电阻与接触电容. 还研究了充电过程、活性炭和电解液的电导率、导电添加剂和粘结剂的含量、隔膜、活性物质附载量和极片加压等因素对阻抗谱的影响. 其中, 充电截止电压、活性炭的电导率、导电添加剂的含量和极片加压对半圆弧部分影响较为显著.     

双电层电容器电化学阻抗谱的实验研究(英文)

电化学阻抗谱(EIS)是一种很有用的研究电化学性能的技术.理想的双电层电容器(EDLC)阻抗谱的尼奎斯特图由中高频的45°线和低频的与实轴垂直的直线组成,可以用孔径分布-传输线模型来解释.然而,在研究工作中还发现,在阻抗谱的高频区出现了半圆弧区域,为此,提出的等效模型认为半圆弧可以归因于活性材料之间的接触电阻和接触电容,以及电极与集流体之间的接触电阻与接触电容.还研究了充电过程、活性炭和电解液的电导率、导电添加剂和粘结剂的含量、隔膜、活性物质附载量和极片加压等因素对阻抗谱的影响.其中,充电截止电压、活性炭的电导率、导电添加剂的含量和极片加压对半圆弧部分影响较为显著.     

1-乙基-3-甲基咪唑三氟乙酸盐作为电化学双电层电容器电解液的电化学性能

应用循环伏安法和直流恒流充放电研究了以离子液体1-乙基-3-甲基咪唑三氟乙酸盐([EMIm]CF3COO)和高比表面活性炭电极构成的电化学双电层电容器的电化学性能.实验表明,[EMIm]CF3COO具有高的比电容、良好的循环特性以及高的充放电效率.在离子液体稳定的电化学窗口内,比电容随电化学窗口的增加而增大.能量密度随电流和电化学窗口的增加逐渐提高,功率密度随电流的增加而减小、随电化学窗口的增加而增加,是一种优良的电化学双电层电解液.     

固体氧化物燃料电池LSCM-CeO2/Ni-ScSZ复合阳极制备及性能表征

采用双层流延法制备Ni-ScSZ阳极支撑层-ScSZ电解质复合膜.在烧结的Ni-ScSZ阳极支撑层表面丝网印刷一层LSCM-CeO2阳极催化层,得到LSCM-CeO2/Ni-ScSZ功能梯度层阳极.研究表明,LSCM/CeO2比为1:3(bymass)的功能梯度层阳极Ni-ScSZ13具有较佳的性能.单电池在850℃以H2和乙醇蒸气作燃料的最大功率密度分别为710和669mW/cm2,而LSCM/CeO2为1:0(bymass)的功能梯度层Ni-ScSZ10作阳极的单电池,最大功率密度分别为521和486m W/cm2.两种阳极单电池,分别在700℃于乙醇蒸气中作长时间运行实验,X-射线能量散射分析表明Ni-ScSZ13阳极比Ni-ScSZ10阳极具有较好的抗碳沉积性能.     

Kinetics of Adsorption of Neutral Molecules from a Thin Layer on a Rough Electrode

A theoretical model for the generalized finite adsorption impedance of a rough electrode is offered. A complex function of the roughness of the electrode surface is introduced and its frequency dependence is studied. The frequency characteristics of constituents of the adsorption impedance are shown to depend on the electrode roughness and the diffusion layer thickness. The frequency dependences of the phase angle and impedance components are found to considerably differ from the Frumkin–Melik-Gaikazyan result for an ideal smooth electrode.     

Temperature Effects on the Capacitance of an Imidazolium‐based Ionic Liquid on a Graphite Electrode: A Molecular Dynamics Simulation

Temperature‐dependent electric double layer (EDL) and differential capacitance–potential (C_d–U) curves of the ionic liquid 1‐butyl‐3‐methylimidazolium hexafluorophosphate (BMIM⁺/PF₆^?) were studied on a graphite electrode by molecular dynamics simulations. It was found that all C_d–U curves were asymmetric camel‐shaped with higher C_d at negative polarization, attributed to the specific adsorption of BMIM⁺. In addition, the maxima of C_d at the negative polarization decrease monotonically with temperature due to the thicker EDL, whereas at the positive polarization they gradually increase from 450 to 550 K and decrease at 600 K. Such temperature effects at positive polarization may be understood in terms of the competition between two aspects: the weakening specific adsorption of BMIM⁺ allows more effective screening to the positive charge and overall increasing EDL thickness. Although the former dominates from 450 to 550 K, the latter becomes dominant at 600 K.     

Double Layer Impedance in Mixtures of Acetonitrile and Water

Double layer (DL) impedances were evaluated in mixed solutions of water and acetonitrile at various ratios in the polarized potential domain in order to find competitive orientation of the two solvent molecules on the platinum electrode. The DL capacitance at any ratio of the mixture shows the common power law of the ac‐frequency. The capacitance at molar fractions of water less than 0.2 increases linearly with the fraction, and reaches the value for aqueous solution. This variation indicates accumulation of water molecules on the electrode excluding acetonitrile molecules. It is modelled on the concept of the Langmuir‐type isotherm in which water and acetonitrile molecules have competitive interaction with the electrode. The experimental variations by the use of the isotherm yield the difference in the interaction energy, 6 kJ mol⁻¹. The accumulation of water in the DL is supported by the formation of the adsorbed layer by insoluble ferrocene.     

Electrochemical Impedance Spectroscopy in the Characterisation and Application of Modified Electrodes for Electrochemical Sensors and Biosensors

Electrochemical impedance spectroscopy is finding increasing use in electrochemical sensors and biosensors, both in their characterisation, including during successive phases of sensor construction, and in application as a quantitative determination technique. Much of the published work continues to make little use of all the information that can be furnished by full physical modelling and analysis of the impedance spectra, and thus does not throw more than a superficial light on the processes occurring. Analysis is often restricted to estimating values of charge transfer resistances without interpretation and ignoring other electrical equivalent circuit components. In this article, the important basics of electrochemical impedance for electrochemical sensors and biosensors are presented, focussing on the necessary electrical circuit elements. This is followed by examples of its use in characterisation and in electroanalytical applications, at the same time demonstrating how fuller use can be made of the information obtained from complete modelling and analysis of the data in the spectra, the values of the circuit components and their physical meaning. The future outlook for electrochemical impedance in the sensing field is discussed.     

固体氧化物燃料电池Cu-LSCM-CeO2/LSCM-YSZ/Ni-ScSZ复合阳极制备及性能

采用流延法制得LSCM-YSZ阳极支撑层/Ni-ScSZ阳极活性层/ScSZ电解质层复合膜,在LSCM-YSZ支撑层上印刷一层Cu-LSCM-CeO₂阳极催化层,即Cu-LSCM-CeO₂/LSCM-YSZ/Ni-ScSZ功能梯度层阳极. 研究表明,Cu/LSCM/CeO₂质量配比为2:7:1功能梯度阳极（LSCM-YSZ2010）有较好的性能,单电池以氢气和乙醇为燃料（750 ^oC）最大功率密度分别为511和390 mW?cm^-2,单电池稳定性实验表明,LSCM-YSZ2010阳极单电池以乙醇为燃料750 ^oC长时间运行218 h,性能稳定. X-射线能量散射分析表明该阳极具有较好的抗碳沉积性能.     

双光窗夹套式红外反射薄层电化学池的制作与表征

现场红外光谱电化学;亚铁氰化钾;对苯二酚;双光窗夹套式红外反射薄层电化学池的制作与表征     

On the Integration of Dielectrometry into Electrochemical Impedance Spectroscopy to Obtain Characteristic Properties of a Dielectric Thin Film

We demonstrate a novel impedimetric approach providing unprecedented insight into characteristic properties of dielectric thin films covering electrode surfaces. The concept is based on the joint interpretation of electrochemical impedance spectroscopy (EIS) together with dielectrometry (DEM) whose informative value is mutually interconnected. The advantage lies in the synergistic compensation of individual shortcomings adversely affecting conventional impedimetric analysis strategies relying exclusively on either DEM or the traditional EIS approach, which in turn allows a reliable determination of thickness and permittivity values. The versatility of the method proposed is showcased by an in-situ growth-monitoring of a nanoporous, crystalline thin film (HKUST-1) on an interdigitated electrode geometry.     

Electrochemical Impedance Spectroscopic Measurements of Sexithiophene—Effect of the Electrode Nature and the Dopant (CuCl2) Content

Electrochemical impedance spectroscopic (EIS) measurements of sexithiophene (6T) were carried out according to the Pt/6T/M sandwich structure configuration, for various electrode materials (M＝GC, ITO, Ag, Cu, Al) and for different doping levels of copper chloride (CuCl2). The results demonstrate that two types of charge transport are involved in the redox process at the electrode/6T interface and inside the bulk oligomer. The complex-plane impedance plots obtained for various doping levels of CuCl2 exhibit arc shapes. The charge-transfer resistance measured from the diagrams decreases systematically with the addition of the salt, leading to an increase of the oligothiophene conductivity.     

New Analysis of Data on the Differential Capacitance of a Mercury Electrode during the Adsorption of tert-Butanol

A regression analysis of data on the differential capacitance of a mercury electrode in aqueous solutions of tert-butanol, which were published previously, is performed. It is shown that, in contradistinction to an analogous analysis of electrocapillary curves (ECC), in order to describe the adsorption of this compound in the framework of a model of two parallel capacitors, it is necessary to take into account the linear dependence of the parameter of an intermolecular interaction on the electrode potential. It is established on the basis of modeling calculations that, in order to obtain the same result in the case of a regression analysis of ECC, the relative accuracy of measurements of the interfacial tension must be two orders of magnitude the relative accuracy of measurements of the differential capacitance.     

A Study on a Partially Immersed Gold Electrode Using an Electrochemical Quartz Crystal Impedance System

Simultaneous and fast measurement of the piezoelectric quartz crystal (PQC) impedanceduring electrochemical pertUrbations, i.e., the electrochemical quartz crystal impedancesystem (EQCIS) called by us, characterizes the PQC resonance better by providingmultidimensional in sl'tu piezoelectric information than the conventional electrochemicalquartz crystal microbalance (EQCM)'-'. The PQC impedance has been analyzed basedon the Butterworth-Van Dyke (BVD) equivalent electrical circuit com…     

Si／C复合材料电极首次嵌锂过程的电化学阻抗谱研究

采用球磨法制备了Si／C复合材料,X射线衍射（XRD）和扫描电子显微镜（SEM）测试结果显示Si／C复合材料中硅保持着良好的晶体结构且均匀的分散于炭黑基体中．充放电测试结果表明Si／C复合材料首次放电容量高达3393mAh／g,4周之后可逆容量均保持在1000mAh／g左右,表现出较好的循环性能．电化学阻抗谱测试结果显...     

A Highly Sensitive Electrochemical Impedance Spectroscopy Immunosensor for Determination of 1‐Pyrenebutyric Acid Based on the Bifunctionality of Nafion/Gold Nanoparticles Composite Electrode

A simple, highly sensitive and label‐free electrochemical impedance spectroscopy (EIS) immunosensor was developed using Nafion and gold nanoparticles (nano‐Au/Nafion) composites for the determination of 1‐pyrenebutyric acid (PBA). Under the optimal conditions, the amount of immobilized antibody was significantly improved on the nano‐Au/Nafion electrode due to the synergistic effect and biocompatibility of Nafion film and gold nanoparticles composites. The results showed that the sensitivity and stability of nano‐Au/Nafion composite electrode for PBA detection were much better than those of nano‐Au modified glassy carbon electrode (nano‐Au/GCE). The plot of increased electron transfer resistances (R_ets) against the logarithm of PBA concentration is linear over the range from 0.1 to 150 ng·mL^?1 with the detection limit of 0.03 ng·mL^?1. The selectivity and accuracy of the proposed EIS immunosensor were evaluated with satisfactory results.     

Micropatterning and Impedance Characterization of an Electrically Percolating Layer‐by‐Layer Assembly

Micropatterned layer‐by‐layer (LbL) assemblies were studied as a potential platform for sensor applications by performing impedance characterization throughout a range of electrolyte concentrations. Conductive LbL thin films were prepared with carbon black nanoparticles dispersed in the polymer matrix to provide an electrically conductive network. LbL assemblies were micropatterned using a photolithographic lift‐off method, and a test circuit was constructed as multiple interdigitating coplanar electrodes. Impedance spectra were collected between 10⁴ and 10⁶ Hz within a flow cell containing NaCl solutions ranging from 0.001–1.0 M. These preliminary results demonstrate the ability to pattern conductive LbL composites and underscore the potential utility and shortcomings of their use in sensor applications.     

Electrochemical Impedance Spectroscopy of Oxide Layers on the Titanium Surface

The method of electrochemical impedance spectroscopy is used to study oxide layers formed at the titanium surface by a variety of methods. The sample’s polarization permitted the isolation, in an impedance spectrum, of the response caused by the capacitance of the space-charge region, which obeys the Mott-Schottky dependence. It is established that the high-frequency portion of an impedance spectrum is defined by morphological peculiarities of the porous portion of coatings. Assumptions, concerning the nature of a time constant, which reveals itself in the region of low frequencies at polarizing biases, are made. Equivalent circuits, intended for modeling impedance spectra, are proposed. The circuits take into consideration the effect of the space-charge region, as well as the peculiarities of the structure and morphology of the oxide film formed at the titanium surface.__________Translated from Elektrokhimiya, Vol. 41, No. 8, 2005, pp. 963–971.Original Russian Text Copyright © 2005 by Gnedenkov, Sinebryukhov.     

AC Impedance Studies on the Relationship between the Fractal Characteristics and Electrochemical Properties of Poly(Para‐Phenylene) Film

The effects of experimental conditions on the fractal structure of electrosynthetic polyparaphenylene films were studied by electrochemical impedance spectroscopy. The results indicate that, at the potential range (0‐0.6 V), the film surface fractal dimension rises while the corresponding charge transfer resistances R_ct decrease as charge increases. This is consistent with the oxidized behavior of the conducting polymer. As for the degradation of electrolytes, scanning electron microscopy observations of poly(para‐pheneylene) (PPP) film provide evidence of the close relationship between the degradation of electrolytes and the film morphology, also in good agreement with the electrochemical impedance results interpretation. The X‐ray photoelectron spectroscopic analysis results present that the relative oxygen content ratio (O/C) of the films increases with the times the electrolyte is used, which reveals that the degradation of the electrolyte may result in a compact and passivation PPP film.     

Effect of the Structure of Nonuniform Conducting Polymer Films on Their Electrochemical Impedance Response

Electrochemical impedance spectroscopy is used to characterize thin p-doped polypyrrole (PPy) films in propylene carbonate (PC) solutions and poly(trifluorophenyl)thiophene (PTFPT), in solutions based on sulfolane (SF). It appears that the latter film is much less swelled compared to the former one. One consequence of this difference is that the PTFPT film shows a much higher bulk resistance compared to that for the PPy film. Another important consequence is that the swelling of the PTFPT film is essentially physically non-homogeneous. Two parallel, uncoupled paths, with different chemical diffusion coefficients, model the experimental results adequately. In order to quantify the impedance spectra for both polymer films, we use a model proposed by Rubinstein et al. explaining the difference in the diffusion coefficients of Ru(bpy)^3+/2+ ₃ within a thin Nafion film. The model can also predict the impedance spectra for composite powdery electrodes containing different particle sizes, such as composite cathodes and graphite anodes used in lithium batteries.