Table of Contents

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
Strømme).


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.

About the Author

EVGENIJ BARSOUKOV, PhD, is a Senior Application Engineer at
Texas Instruments, Inc. His current research focuses on the
application of impedance spectroscopy?based modeling to
improve battery monitoring technology.
J. ROSS MACDONALD, DSc, is the William Rand Kenan, Jr.,
Professor Emeritus of Physics at The University of North Carolina.
He has published more than 200 papers in the fields of physics,
chemistry, applied mathematics, and electrical engineering, and he
was the editor of the First Edition of Impedance Spectroscopy
(Wiley). His current research uses impedance spectroscopy to help
analyze the electrical response of high-resistivity ionically
conducting solid materials.

Reviews

"...the only text currently available...that extensively
treats...both the theoretical considerations and the practical
applications...an essential addition to the personal library of any
scientist wishing an in-depth understanding?"
(CORROSION, June 2006)
"This book would serve researchers and engineers working in this
field. It could also be used effectively as a graduate text."
(Materials and Manufacturing Processes, May 2006)


".. an excellent introduction to the theory of impedance
spectroscopy, followed by detailed applications of the technique as
well as experimental methods." (CHOICE, September 2005)


"This book should be consulted, if not owned, by any present and
future practitioners in the field." (Journal of the American
Chemical Society, September 7, 2005)