Electrochemical Impedance Spectroscopy

by Orazem, Mark E.; Tribollet, Bernard

• ISBN13: 9780470041406
• ISBN10: 0470041404
• Format: Hardcover
• Copyright: 2008-09-09
• Publisher: Wiley-Interscience

Summary

Using electrochemical impedance spectroscopy in a broad range of applicationsThis book provides the background and training suitable for application of impedance spectroscopy to varied applications, such as corrosion, biomedical devices, semiconductors and solid-state devices, sensors, batteries, fuel cells, electrochemical capacitors, dielectric measurements, coatings, electrochromic materials, analytical chemistry, and imaging. The emphasis is on generally applicable fundamentals rather than on detailed treatment of applications. With numerous illustrative examples showing how these principles are applied to common impedance problems, Electrochemical Impedance Spectroscopy is ideal either for course study or for independent self-study, covering: Essential background, including complex variables, differential equations, statistics, electrical circuits, electrochemistry, and instrumentation Experimental techniques, including methods used to measure impedance and other transfer functions Process models, demonstrating how deterministic models of impedance response can be developed from physical and kinetic descriptions Interpretation strategies, describing methods of interpretating of impedance data, ranging from graphical methods to complex nonlinear regression Error structure, providing a conceptual understanding of stochastic, bias, and fitting errors in frequency-domain measurements An overview that provides a philosophy for electrochemical impedance spectroscopy that integrates experimental observation, model development, and error analysisThis is an excellent textbook for graduate students in electrochemistry, materials science, and chemical engineering. It's also a great self-study guide and reference for scientists and engineers who work with electrochemistry, corrosion, and electrochemical technology, including those in the biomedical field, and for users and vendors of impedance-measuring instrumentation.

Author Biography

MARK E. ORAZEM is a Professor in the Department of Chemical Engineering at the University of Florida. He organized the 6th International Symposium on Electrochemical Impedance Spectroscopy and teaches a short course on impedance spectroscopy for The Electrochemical Society. Dr. Orazem is a Fellow of The Electrochemical Society (ECS) and a member of the International Society of Electrochemistry (ISE). BERNARD TRIBOLLET is a Director of Research at the Centre National de la Recherche Scientifique (CNRS) and Associate Director of the Laboratoire Interfaces et Systémes Electrochimique, at Pierre and Marie Curie University. He instructs an annual short course on impedance spectroscopy. Dr. Tribollet is a member of The Electrochemical Society (ECS) and the International Society of Electrochemistry (ISE).

Table of Contents

Preface

Acknowledgments

The Blind Men and the Elephant

History of Impedance Spectroscopy

Background

Complex Variables

Why Imaginary Numbers?

Terminology

Operations Involving Complex variables

Elementary Functions of Complex Variables

Problems

Differential Equations

Linear First-Order Differential Equations

Homogeneous Linear Second-Order Differential Equations

Nonhomogeneous Linear Second-Order Differential Equations

Partial Differential Equations by Similarity Transformations

Differential Equations with Complex Variables

Problems

Statistics

Definitions

Error Propagation

Hypothesis Tests

Problems

Electrical Circuits

Passive Electrical Circuits

Fundamental Relationships

Nested Circuits

Mathematical Equivalence of Circuits

Graphical Representation of Circuit Response

Problems

Electrochemistry

Resistors and Electrochemical Cells

Equilibrium in Electrochemical Systems

Polarization Behavior for Electrochemical Systems

Definitions of Potential

Rate Expressions

Transport Processes

Potential Contributions

Capacitance Contributions

Problems

Electrochemical Instrumentation

The Ideal Operational Amplifier

Elements of Electrochemical Instrumentation

Electrochemical Interface

Problems

Experimental Considerations

Experimental Methods

Steady-State Polarization Curves

Transient Response to a Potential Step

Analysis in Frequency Domain

Comparison of Measurement Techniques

Specialized Techniques

Problems

Experimental Design

Cell Design

Experimental Considerations

Instrumentation Parameters

Problems

Process Models

Equivalent Circuit Analogs

General Approach

Current Addition

Potential Addition

Problems

Kinetic Models

Electrochemical Reactions

Reaction Dependent on Potential Only

Reaction Dependent on Potential and Mass Transfer

Coupled Reactions Dependent on Potential and Surface Coverage

Reactions Dependent on Potential, Surface Coverage, and Transport

Problems

Diffusion Impedance

Uniformly Accessible Electrode

General mathematical Framework

Stagnant Diffusion Layer

Diffusion through a Solid Film

Coupled Diffusion Impendence

Rotating Disk

Submerged Impinging Jet

Rotating Cylinders

Problems

Semiconducting Systems

Semiconductor Physics

Steady-State Models

Impedance Models

Problems

Time-Constant Dispersion

Constant-Phase Elements

Convective Diffusion Impedance at Small Electrodes

Geometry-Induced Current and Potential Distributions

Porous Electrodes

Oxide Layers

Problems

Generalized Transfer Functions

Multi-Input/Multi-Output Systems

Transfer Functions Involving Exclusively Electrical Quantities

Transfer Functions Involving Nonelectrical Quantities

Problems

Electrohydrodynamic Impedance

Hydrodynamic Transfer Function

Mass-Transport Transfer Function

Kinetic Transfer Function for Simple Electrochemical Reactions

Interface with a 2-D or 3-D Insulating Phase

Problems

Interpretation Strategies

Methods for Representing Impedance

Impedance Format

Admittance Format

Complex-Capacitance Format

Effective Capacitance

Problems

Preliminary Graphical Methods

Application to a Randles Circuit

Application to Blocking Electrodes

Overview

Problems

Model-Based Graphical Methods

Mass Transfer

Reaction Kinetics: Arrhenius Relations

Mott-Schottky Plots

Problems

Complex Nonlinear Regression

Concept

Objective Functions

Formalism of Regression Strategies

Regression Strategies for Nonlinear Problems

Influence of Data Quality on Regression

Initial Estimates for regression

Regression Statistics

Problems

Assessing regression Quality

Methods to Assess Regression Quality

Application of Regression Concepts

Statistical Analysis

Error Structure of Impedance Measurements

Error Contributions

Stochastic Errors in Impedance measurements

Bias Errors

Incorporation of Error Structure

Measurement Models for Error Identification

The Kramers-Kronig Relations

mathematical Origin

The Kramers-Kronig in an Expectation Sense

Methods for Application

Problems

Overview

An Integrated Approach to Impedance Spectroscopy

Flowcharts for Regression Analysis

Integration of Measurements, Error Analysis, and Model

Application

Problems

Reference Material

Complex Integrals

Tables of Reference Material

List of Examples

List of Symbols

References

Index

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