Impedance Spectroscopy: Theory, Experiment, and Applications, 2nd Edition
Backed by a team of expert contributors, the Second Edition of this highly acclaimed publication brings a solid understanding of impedance spectroscopy to students, researchers, and engineers in physical chemistry, electrochemistry, and physics. Starting with general principles, the book moves on to explain in detail practical applications for the characterization of materials in electrochemistry, semiconductors, solid electrolytes, corrosion, solid-state devices, and electrochemical power sources. The book covers all of the topics needed to help readers identify whether impedance spectroscopy may be an appropriate method for their particular research problem.
The book helps readers quickly grasp how to apply their new knowledge of impedance spectroscopy methods to their own research problems through the use of unique features such as:
* Step-by-step instructions for setting up experiments and then analyzing the results
* Theoretical considerations for dealing with modeling, equivalent circuits, and equations in the complex domain
* Best measurement methods for particular systems and alerts to potential sources of errors
* Equations for the most widely used impedance models
* Figures depicting impedance spectra of typical materials and devices
* Extensive references to the scientific literature for more information on particular topics and current research
This Second Edition incorporates the results of the last two decades of research on the theories and applications of impedance spectroscopy. Most notably, it includes new chapters on batteries, supercapacitors, fuel cells, and photochromic materials. A new chapter on commercially available measurement systems reflects the emergence of impedance spectroscopy as a mainstream research tool.
With its balanced focus on both theory and practical problem solving, Impedance Spectroscopy: Theory, Experiment, and Applications, Second Edition serves as an excellent graduate-level textbook as well as a hands-on guide and reference for researchers and engineers.
Preface to the First Edition.
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.
2.1.2 The Electrical Properties of Bulk Homogeneous Phases.
188.8.131.52 Dielectric Relaxation in Materials with a Single Time Constant.
184.108.40.206 Distributions of Relaxation Times.
220.127.116.11 Conductivity and Diffusion in Electrolytes.
18.104.22.168 Conductivity and Diffusion—a Statistical Description.
22.214.171.124 Migration in the Absence of Concentration Gradients.
126.96.36.199 Transport in Disordered Media.
2.1.3 Mass and Charge Transport in the Presence of Concentration Gradients.
188.8.131.52 Mixed Electronic–Ionic Conductors.
184.108.40.206 Concentration Polarization.
2.1.4 Interfaces and Boundary Conditions.
220.127.116.11 Reversible and Irreversible Interfaces.
18.104.22.168 Polarizable Electrodes.
22.214.171.124 Adsorption at the Electrode–Electrolyte Interface.
126.96.36.199 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.
188.8.131.52 Current Distribution Problems.
184.108.40.206 Rough and Porous Electrodes.
2.2. Physical and Electrochemical Models.
2.2.1 The Modeling of Electrochemical Systems.
2.2.2 Equivalent Circuits.
220.127.116.11 Unification of Immitance Responses.
18.104.22.168 Distributed Circuit Elements.
22.214.171.124 Ambiguous Circuits.
2.2.3 Modeling Results.
126.96.36.199 Supported Situations.
188.8.131.52 Unsupported Situations: Theoretical Models.
184.108.40.206 Unsupported Situations: Equivalent Network Models.
220.127.116.11 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).
3.1.2 Frequency Domain Methods.
18.104.22.168 Audio Frequency Bridges.
22.214.171.124 Transformer Ratio Arm Bridges.
126.96.36.199 Berberian–Cole Bridge.
188.8.131.52 Considerations of Potentiostatic Control.
184.108.40.206 Oscilloscopic Methods for Direct Measurement.
220.127.116.11 Phase-Sensitive Detection for Direct Measurement.
18.104.22.168 Automated Frequency Response Analysis.
22.214.171.124 Automated Impedance Analyzers.
126.96.36.199 The Use of Kramers–Kronig Transforms.
188.8.131.52 Spectrum Analyzers.
3.1.3 Time Domain Methods.
184.108.40.206 Analog-to-Digital (A/D) Conversion.
220.127.116.11 Computer Interfacing.
18.104.22.168 Digital Signal Processing.
3.2. Commercially Available Impedance Measurement Systems (Brian Sayers).
3.2.1 Electrochemical Impedance Measurement Systems.
22.214.171.124 System Configuration.
126.96.36.199 Why Use a Potentiostat?
188.8.131.52 Measurements Using 2, 3 or 4-Terminal Techniques.
184.108.40.206 Measurement Resolution and Accuracy.
220.127.116.11 Single Sine and FFT Measurement Techniques.
18.104.22.168 Multielectrode Techniques.
22.214.171.124 Effects of Connections and Input Impedance.
126.96.36.199 Verification of Measurement Performance.
188.8.131.52 Floating Measurement Techniques.
184.108.40.206 Multichannel Techniques.
3.2.2 Materials Impedance Measurement Systems.
220.127.116.11 System Configuration.
18.104.22.168 Measurement of Low Impedance Materials.
22.214.171.124 Measurement of High Impedance Materials.
126.96.36.199 Reference Techniques.
188.8.131.52 Normalization Techniques.
184.108.40.206 High Voltage Measurement Techniques.
220.127.116.11 Temperature Control.
18.104.22.168 Sample Holder Considerations.
3.3. Data Analysis (J. Ross Macdonald).
3.3.1 Data Presentation and Adjustment.
22.214.171.124 Previous Approaches.
126.96.36.199 Three-Dimensional Perspective Plotting.
188.8.131.52 Treatment of Anomalies.
3.3.2 Data Analysis Methods.
184.108.40.206 Simple Methods.
220.127.116.11 Complex Nonlinear Least Squares.
18.104.22.168 Which Impedance-Related Function to Fit?
22.214.171.124 The Question of “What to Fit” Revisited.
126.96.36.199 Deconvolution Approaches.
188.8.131.52 Examples of CNLS Fitting.
184.108.40.206 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.
220.127.116.11 Layer Models.
18.104.22.168 Effective Medium Models.
22.214.171.124 Modeling of Composite Electrodes.
4.1.2 Experimental Techniques.
126.96.36.199 Measurement Systems.
188.8.131.52 Sample Preparation—Electrodes.
184.108.40.206 Problems Associated With the Measurement of Electrode Properties.
4.1.3 Interpretation of the Impedance Spectra of Ionic Conductors and Interfaces.
220.127.116.11 Characterization of Grain Boundaries by IS.
18.104.22.168 Characterization of Two-Phase Dispersions by IS.
22.214.171.124 Impedance Spectra of Unusual Two-phase Systems.
126.96.36.199 Impedance Spectra of Composite Electrodes.
188.8.131.52 Closing Remarks.
4.2. Characterization of the Electrical Response of High Resistivity Ionic and Dielectric Solid Materials by Immittance Spectroscopy (J. Ross Macdonald).
4.2.2 Types of Dispersive Response Models: Strengths and Weaknesses.
184.108.40.206 Variable-slope Models.
220.127.116.11 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).
18.104.22.168 Experimental Techniques.
22.214.171.124 Experimental Results on Single Materials.
126.96.36.199 Experimental Results on Electrochromic Devices.
188.8.131.52 Conclusions and Outlook.
4.3.5 Time-Resolved Photocurrent Generation (Albert Goossens).
184.108.40.206 Steady-State Photocurrents.
220.127.116.11 Intensity-Modulated Photocurrent Spectroscopy.
18.104.22.168 Final Remarks.
4.4. Corrosion of Materials (Digby D. Macdonald and Michael C. H. McKubre).
4.4.3 Measurement of Corrosion Rate.
4.4.4 Harmonic Analysis.
4.4.5 Kramer–Kronig Transforms.
4.4.6 Corrosion Mechanisms.
22.214.171.124 Active Dissolution.
126.96.36.199 Active–Passive Transition.
188.8.131.52 The Passive State.
4.4.7 Point Defect Model of the Passive State (Digby D. Macdonald).
184.108.40.206 Point Defect Model.
220.127.116.11 Electrochemical Impedance Spectroscopy.
18.104.22.168 Bilayer Passive Films.
4.4.8 Equivalent Circuit Analysis (Digby D. Macdonald and Michael C. H. McKubre).
4.4.9 Other Impedance Techniques.
22.214.171.124 Electrochemical Hydrodynamic Impedance (EHI).
126.96.36.199 Fracture Transfer Function (FTF).
188.8.131.52 Electrochemical Mechanical Impedance.
4.5. Electrochemical Power Sources.
4.5.1 Special Aspects of Impedance Modeling of Power Sources (Evgenij Barsoukov).
184.108.40.206 Intrinsic Relation Between Impedance Properties and Power Sources Performance.
220.127.116.11 Linear Time-Domain Modeling Based on Impedance Models, Laplace Transform.
18.104.22.168 Expressing Model Parameters in Electrical Terms, Limiting Resistances and Capacitances of Distributed Elements.
22.214.171.124 Discretization of Distributed Elements, Augmenting Equivalent Circuits.
126.96.36.199 Nonlinear Time-Domain Modeling of Power Sources Based on Impedance Models.
188.8.131.52 Special Kinds of Impedance Measurement Possible with Power Sources—Passive Load Excitation and Load Interrupt.
4.5.2 Batteries (Evgenij Barsoukov).
184.108.40.206 Generic Approach to Battery Impedance Modeling.
220.127.116.11 Lead Acid Batteries.
18.104.22.168 Nickel Cadmium Batteries.
22.214.171.124 Nickel Metal-hydride Batteries.
126.96.36.199 Li-ion Batteries.
4.5.3 Impedance Behavior of Electrochemical Supercapacitors and Porous Electrodes (Brian E. Conway).
188.8.131.52 The Time Factor in Capacitance Charge or Discharge.
184.108.40.206 Nyquist (or Argand) Complex-Plane Plots for Representation of Impedance Behavior.
220.127.116.11 Bode Plots of Impedance Parameters for Capacitors.
18.104.22.168 Hierarchy of Equivalent Circuits and Representation of Electrochemical Capacitor Behavior.
22.214.171.124 Impedance and Voltammetry Behavior of Brush Electrode Models of Porous Electrodes.
126.96.36.199 Impedance Behavior of Supercapacitors Based on Pseudocapacitance.
188.8.131.52 Deviations of Double-layer Capacitance from Ideal Behavior: Representation by a Constant-phase Element (CPE).
4.5.4 Fuel Cells (Norbert Wagner).
184.108.40.206 Alkaline Fuel Cells (AFC).
220.127.116.11 Polymer Electrolyte Fuel Cells (PEFC).
18.104.22.168 Solid Oxide Fuel Cells (SOFC).
Appendix. Abbreviations and Definitions of Models.
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.
"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)