Preface. Preface to the First Edition. Contributors. Contributors to the First Edition. Chapter 1. Fundamentals of Impedance Spectroscopy (J.Ross Macdonald and William B. Johnson). 1.1. Background, Basic Definitions, and History. 1.1.1 The Importance of Interfaces. 1.1.2 The Basic Impedance Spectroscopy Experiment. 1.1.3 Response to a Small-Signal Stimulus in the Frequency Domain. 1.1.4 Impedance-Related Functions. 1.1.5 Early History. 1.2. Advantages and Limitations. 1.2.1 Differences Between Solid State and Aqueous Electrochemistry. 1.3. Elementary Analysis of Impedance Spectra. 1.3.1 Physical Models for Equivalent Circuit Elements. 1.3.2 Simple RC Circuits. 1.3.3 Analysis of Single Impedance Arcs. 1.4. Selected Applications of IS. Chapter 2. Theory (Ian D. Raistrick, Donald R. Franceschetti, and J. Ross Macdonald). 2.1. The Electrical Analogs of Physical and Chemical Processes. 2.1.1 Introduction. 2.1.2 The Electrical Properties of Bulk Homogeneous Phases. 2.1.2.1 Introduction. 2.1.2.2 Dielectric Relaxation in Materials with a Single Time Constant. 2.1.2.3 Distributions of Relaxation Times. 2.1.2.4 Conductivity and Diffusion in Electrolytes. 2.1.2.5 Conductivity and Diffusion-a Statistical Description. 2.1.2.6 Migration in the Absence of Concentration Gradients. 2.1.2.7 Transport in Disordered Media. 2.1.3 Mass and Charge Transport in the Presence of Concentration Gradients. 2.1.3.1 Diffusion. 2.1.3.2 Mixed Electronic-Ionic Conductors. 2.1.3.3 Concentration Polarization. 2.1.4 Interfaces and Boundary Conditions. 2.1.4.1 Reversible and Irreversible Interfaces. 2.1.4.2 Polarizable Electrodes. 2.1.4.3 Adsorption at the Electrode-Electrolyte Interface. 2.1.4.4 Charge Transfer at the Electrode-Electrolyte Interface. 2.1.5 Grain Boundary Effects. 2.1.6 Current Distribution, Porous and Rough Electrodes- the Effect of Geometry. 2.1.6.1 Current Distribution Problems. 2.1.6.2 Rough and Porous Electrodes. 2.2. Physical and Electrochemical Models. 2.2.1 The Modeling of Electrochemical Systems. 2.2.2 Equivalent Circuits. 2.2.2.1 Unification of Immitance Responses. 2.2.2.2 Distributed Circuit Elements. 2.2.2.3 Ambiguous Circuits. 2.2.3 Modeling Results. 2.2.3.1 Introduction. 2.2.3.2 Supported Situations. 2.2.3.3 Unsupported Situations: Theoretical Models. 2.2.3.4 Unsupported Situations: Equivalent Network Models. 2.2.3.5 Unsupported Situations: Empirical and Semiempirical Models. Chapter 3. Measuring Techniques and Data Analysis. 3.1. Impedance Measurement Techniques (Michael C. H. McKubre and Digby D. Macdonald). 3.1.1 Introduction. 3.1.2 Frequency Domain Methods. 3.1.2.1 Audio Frequency Bridges. 3.1.2.2 Transformer Ratio Arm Bridges. 3.1.2.3 Berberian-Cole Bridge. 3.1.2.4 Considerations of Potentiostatic Control. 3.1.2.5 Oscilloscopic Methods for Direct Measurement. 3.1.2.6 Phase-Sensitive Detection for Direct Measurement. 3.1.2.7 Automated Frequency Response Analysis. 3.1.2.8 Automated Impedance Analyzers. 3.1.2.9 The Use of Kramers-Kronig Transforms. 3.1.2.10 Spectrum Analyzers. 3.1.3 Time Domain Methods. 3.1.3.1 Introduction. 3.1.3.2 Analog-to-Digital (A/D) Conversion. 3.1.3.3 Computer Interfacing. 3.1.3.4 Digital Signal Processing. 3.1.4 Conclusions. 3.2. Commercially Available Impedance Measurement Systems (Brian Sayers). 3.2.1 Electrochemical Impedance Measurement Systems. 3.2.1.1 System Configuration. 3.2.1.2 Why Use a Potentiostat? 3.2.1.3 Measurements Using 2, 3 or 4-Terminal Techniques. 3.2.1.4 Measurement Resolution and Accuracy. 3.2.1.5 Single Sine and FFT Measurement Techniques. 3.2.1.6 Multielectrode Techniques. 3.2.1.7 Effects of Connections and Input Impedance. 3.2.1.8 Verification of Measurement Performance. 3.2.1.9 Floating Measurement Techniques. 3.2.1.10 Multichannel Techniques. 3.2.2 Materials Impedance Measurement Systems. 3.2.2.1 System Configuration. 3.2.2.2 Measurement of Low Impedance Materials. 3.2.2.3 Measurement of High Impedance Materials. 3.2.2.4 Reference Techniques. 3.2.2.5 Normalization Techniques. 3.2.2.6 High Voltage Measurement Techniques. 3.2.2.7 Temperature Control. 3.2.2.8 Sample Holder Considerations. 3.3. Data Analysis (J. Ross Macdonald). 3.3.1 Data Presentation and Adjustment. 3.3.1.1 Previous Approaches. 3.3.1.2 Three-Dimensional Perspective Plotting. 3.3.1.3 Treatment of Anomalies. 3.3.2 Data Analysis Methods. 3.3.2.1 Simple Methods. 3.3.2.2 Complex Nonlinear Least Squares. 3.3.2.3 Weighting. 3.3.2.4 Which Impedance-Related Function to Fit? 3.3.2.5 The Question of "What to Fit" Revisited. 3.3.2.6 Deconvolution Approaches. 3.3.2.7 Examples of CNLS Fitting. 3.3.2.8 Summary and Simple Characterization Example. Chapter 4. Applications of Impedance Spectroscopy. 4.1. Characterization of Materials (N. Bonanos, B. C. H. Steele, and E. P. Butler). 4.1.1 Microstructural Models for Impedance Spectra of Materials. 4.1.1.1 Introduction. 4.1.1.2 Layer Models. 4.1.1.3 Effective Medium Models. 4.1.1.4 Modeling of Composite Electrodes. 4.1.2 Experimental Techniques. 4.1.2.1 Introduction. 4.1.2.2 Measurement Systems. 4.1.2.3 Sample Preparation-Electrodes. 4.1.2.4 Problems Associated With the Measurement of Electrode Properties. 4.1.3 Interpretation of the Impedance Spectra of Ionic Conductors and Interfaces. 4.1.3.1 Introduction. 4.1.3.2 Characterization of Grain Boundaries by IS. 4.1.3.3 Characterization of Two-Phase Dispersions by IS. 4.1.3.4 Impedance Spectra of Unusual Two-phase Systems. 4.1.3.5 Impedance Spectra of Composite Electrodes. 4.1.3.6 Closing Remarks. 4.2. Characterization of the Electrical Response of High Resistivity Ionic and Dielectric Solid Materials by Immittance Spectroscopy (J. Ross Macdonald). 4.2.1 Introduction. 4.2.2 Types of Dispersive Response Models: Strengths and Weaknesses. 4.2.2.1 Overview. 4.2.2.2 Variable-slope Models. 4.2.2.3 Composite Models. 4.2.3 Illustration of Typical Data Fitting Results for an Ionic Conductor. 4.3. Solid State Devices (William B. Johnson and Wayne L. Worrell). 4.3.1 Electrolyte-Insulator-Semiconductor (EIS) Sensors. 4.3.2 Solid Electrolyte Chemical Sensors. 4.3.3 Photoelectrochemical Solar Cells. 4.3.4 Impedance Response of Electrochromic Materials and Devices (Gunnar A. Niklasson, Anna Karin Johsson, and Maria Stromme). 4.3.4.1 Introduction. 4.3.4.2 Materials. 4.3.4.3 Experimental Techniques. 4.3.4.4 Experimental Results on Single Materials. 4.3.4.5 Experimental Results on Electrochromic Devices. 4.3.4.6 Conclusions and Outlook. 4.3.5 Time-Resolved Photocurrent Generation (Albert Goossens). 4.3.5.1 Introduction-Semiconductors. 4.3.5.2 Steady-State Photocurrents. 4.3.5.3 Time-of-Flight. 4.3.5.4 Intensity-Modulated Photocurrent Spectroscopy. 4.3.5.5 Final Remarks. 4.4. Corrosion of Materials (Digby D. Macdonald and Michael C. H. McKubre). 4.4.1 Introduction. 4.4.2 Fundamentals. 4.4.3 Measurement of Corrosion Rate. 4.4.4 Harmonic Analysis. 4.4.5 Kramer-Kronig Transforms. 4.4.6 Corrosion Mechanisms. 4.4.6.1 Active Dissolution. 4.4.6.2 Active-Passive Transition. 4.4.6.3 The Passive State. 4.4.7 Point Defect Model of the Passive State (Digby D. Macdonald). 4.4.7.1 Introduction. 4.4.7.2 Point Defect Model. 4.4.7.3 Electrochemical Impedance Spectroscopy. 4.4.7.4 Bilayer Passive Films. 4.4.8 Equivalent Circuit Analysis (Digby D. Macdonald and Michael C. H. McKubre). 4.4.8.1 Coatings. 4.4.9 Other Impedance Techniques. 4.4.9.1 Electrochemical Hydrodynamic Impedance (EHI). 4.4.9.2 Fracture Transfer Function (FTF). 4.4.9.3 Electrochemical Mechanical Impedance. 4.5. Electrochemical Power Sources. 4.5.1 Special Aspects of Impedance Modeling of Power Sources (Evgenij Barsoukov). 4.5.1.1 Intrinsic Relation Between Impedance Properties and Power Sources Performance. 4.5.1.2 Linear Time-Domain Modeling Based on Impedance Models, Laplace Transform. 4.5.1.3 Expressing Model Parameters in Electrical Terms, Limiting Resistances and Capacitances of Distributed Elements. 4.5.1.4 Discretization of Distributed Elements, Augmenting Equivalent Circuits. 4.5.1.5 Nonlinear Time-Domain Modeling of Power Sources Based on Impedance Models. 4.5.1.6 Special Kinds of Impedance Measurement Possible with Power Sources-Passive Load Excitation and Load Interrupt. 4.5.2 Batteries (Evgenij Barsoukov). 4.5.2.1 Generic Approach to Battery Impedance Modeling. 4.5.2.2 Lead Acid Batteries. 4.5.2.3 Nickel Cadmium Batteries. 4.5.2.4 Nickel Metal-hydride Batteries. 4.5.2.5 Li-ion Batteries. 4.5.3 Impedance Behavior of Electrochemical Supercapacitors and Porous Electrodes (Brian E. Conway). 4.5.3.1 Introduction. 4.5.3.2 The Time Factor in Capacitance Charge or Discharge. 4.5.3.3 Nyquist (or Argand) Complex-Plane Plots for Representation of Impedance Behavior. 4.5.3.4 Bode Plots of Impedance Parameters for Capacitors. 4.5.3.5 Hierarchy of Equivalent Circuits and Representation of Electrochemical Capacitor Behavior. 4.5.3.6 Impedance and Voltammetry Behavior of Brush Electrode Models of Porous Electrodes. 4.5.3.7 Impedance Behavior of Supercapacitors Based on Pseudocapacitance. 4.5.3.8 Deviations of Double-layer Capacitance from Ideal Behavior: Representation by a Constant-phase Element (CPE). 4.5.4 Fuel Cells (Norbert Wagner). 4.5.4.1 Introduction. 4.5.4.2 Alkaline Fuel Cells (AFC). 4.5.4.3 Polymer Electrolyte Fuel Cells (PEFC). 4.5.4.4 Solid Oxide Fuel Cells (SOFC). Appendix. Abbreviations and Definitions of Models. References. Index.

Impedance spectroscopy : theory, experiment, and applications

Electrochemical impedance spectroscopy has become a mature and well-understood technique. It is now possible to acquire, validate, and quantitatively interpret the experimental impedances. This chapter has been addressed to understanding the fundamental processes of diffusion and faradaic reaction at electrodes. However, the most difficult problem in EIS is modeling the electrode processes, which is where most of the problems and errors arise. There is an almost infinite variety of different reactions and interfaces that can be studied (corrosion, coatings, conducting polymers, batteries and fuel cells, semiconductors, electrocatalytic reactions, chemical reactions coupled with faradaic processes, etc.) and the main effort is now being applied to understanding and analyzing these processes. These applications will be the subject of a second review in a forthcoming volume in this series.

Electrochemical Impedance Spectroscopy and its Applications

Impedance biosensors are a class of electrical biosensors that show promise for point-of-care and other applications due to low cost, ease of miniaturization, and label-free operation. Unlabeled DNA and protein targets can be detected by monitoring changes in surface impedance when a target molecule binds to an immobilized probe. The affinity capture step leads to challenges shared by all label-free affinity biosensors; these challenges are discussed along with others unique to impedance readout. Various possible mechanisms for impedance change upon target binding are discussed. We critically summarize accomplishments of past label-free impedance biosensors and identify areas for future research.

/pdf/label-free-impedance-biosensors-opportunities-and-challenges-3b721lxxqy.pdf

Label-Free Impedance Biosensors: Opportunities and Challenges.

The nature of fractals and the use of fractals instead of classical scaling concepts to describe the irregular surfaces, structures, and processes exhibited by physiological systems are described. The mathematical development of fractals is reviewed, and examples of natural fractals are cited. Relationships among power laws, noise, and fractal time signals are examined. >

Fractal Physiology

Magnetic flux can penetrate a type-II superconductor in the form of Abrikosov vortices (also called flux lines, flux tubes, or fluxons) each carrying a quantum of magnetic flux phi 0=h/2e. These tiny vortices of supercurrent tend to arrange themselves in a triangular flux-line lattice (FLL), which is more or less perturbed by material inhomogeneities that pin the flux lines, and in high-Tc superconductors (HTSCs) also by thermal fluctuations. Many properties of the FLL are well described by the phenomenological Ginzburg-Landau theory or by the electromagnetic London theory, which treats the vortex core as a singularity. In Nb alloys and HTSCs the FLL is very soft mainly because of the large magnetic penetration depth lambda . The shear modulus of the FLL is c66~1/ lambda 2, and the tilt modulus c44(k)~(1+k2 lambda 2)-1 is dispersive and becomes very small for short distortion wavelengths 2 pi /k<< lambda . This softness is enhanced further by the pronounced anisotropy and layered structure of HTSCs, which strongly increases the penetration depth for currents along the c axis of these (nearly uniaxial) crystals and may even cause a decoupling of two-dimensional vortex lattices in the Cu-O layers. Thermal fluctuations and softening may `melt` the FLL and cause thermally activated depinning of the flux lines or ofthe two-dimensional `pancake vortices` in the layers. Various phase transitions are predicted for the FLL in layered HTSCs. Although large pinning forces and high critical currents have been achieved, the small depinning energy so far prevents the application of HTSCs as conductors at high temperatures except in cases when the applied current and the surrounding magnetic field are small.

https://iopscience.iop.org/article/10.1088/0034-4885/58/11/003/pdf

The flux-line lattice in superconductors

A fractal model is proposed for a rough interface between two materials of very different conductivities, e.g., an electrode and an electrolyte. The equivalent circuit of the model, which takes into consideration the resistance in the two substances and the capacitance of the interface, has the property of the so-called constant-phase-angle element, i.e., a passive circuit element whose complex impedance has a power-law singularity at low frequencies. The exponent of the frequency dependence is related to the fractal dimension. The model also provides insight into the conducting properties of the percolating cluster and the source of the 1/f noise in electronic components.

Fractal model for the ac response of a rough interface

Fractal models of rough interfaces have provided a possible explanation for the observed ac response of an interface between a metal and an electrolyte with blocking contacts which displays the constant-phase-angle (CPA) behavior. For this system, two different relations between the exponent eta of the frequency dependence of the CPA element and the fractal dimension d/sub s/ of the interface have been proposed. By solving for the properties of a self-affine fractal model of an interface and using Mandelbrot's box dimension for the fractal dimension it is demonstrated that there is no universal relation in which eta is simply a function of d/sub s/.

Self-affine fractal model for a metal-electrolyte interface

It is shown that the two-peak structure of the $4f$ electron photoemission spectrum of Ce metal and its compounds may arise from two kinds of final states, those with and those without screening by a Ce $5d$ electron in an impurity state. A comparison between theory and experiment reveals that the $\ensuremath{\gamma}\ensuremath{-}\ensuremath{\alpha}$ phase transition is accompanied by a very slight increase in conduction-electron population.

Theory of photoemission from metallic Ce

We calculate the penetration depth $\ensuremath{\lambda}\left(T\right)$ for a model of the high- ${T}_{c}$ superconductors based upon proximity coupling between one superconducting $\left(S\right)$ and one normal $\left(N\right)$ layer per unit cell. The linear, low- $T$ region of the ${\ensuremath{\lambda}}_{\mathrm{ab}}\left(T\right)$ data of Bonn et al. on ${\mathrm{YBa}}_{2}{\mathrm{Cu}}_{3}{\mathrm{O}}_{7\ensuremath{-}\ensuremath{\delta}}$ is fitted quantitatively for both $s$-wave and ${d}_{{x}^{2}{\ensuremath{-}y}^{2}}$ order parameters. However, these fitted models give very different predictions for ${\ensuremath{\lambda}}_{c}\left(T\right)$, which may serve as a new test for the order parameter, or at least for the role of $N$ layers.

Role of Normal Layers in Penetration Depth Determinations of the Pairing State in High- T c Superconductors

In a recent paper it was suggested that the double-peak $4f$ photoemission spectra of Ce and ${\mathrm{Ce}}_{0.9}$${\mathrm{Th}}_{0.1}$ indicate strong $d\ensuremath{-}f$ correlation. This paper discusses the effects of this correlation on the mixed-valent properties of Ce systems. In the impurity-lattice approximation, which is valid at high temperatures, the $f$-electron spectrum has the well-known x-ray-edge singularity at the Fermi level. The inclusion of $d\ensuremath{-}f$ hybridization adds fine structures to the spectrum near the Fermi level. Furthermore, the singularity can account for the Kondo-type resistivity and specific-heat anomalies without the need to invoke spin-flip scattering.

S. H. Liu

Papers

Fractal model for the ac response of a rough interface

Self-affine fractal model for a metal-electrolyte interface

Theory of photoemission from metallic Ce

Role of Normal Layers in Penetration Depth Determinations of the Pairing State in High- T c Superconductors

Effects of d − f correlation on the mixed-valent properties of Ce systems