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.
220.127.116.11 Dielectric Relaxation in Materials with a Single Time Constant.
18.104.22.168 Distributions of Relaxation Times.
22.214.171.124 Conductivity and Diffusion in Electrolytes.
126.96.36.199 Conductivity and Diffusion—a Statistical Description.
188.8.131.52 Migration in the Absence of Concentration Gradients.
184.108.40.206 Transport in Disordered Media.
2.1.3 Mass and Charge Transport in the Presence of Concentration Gradients.
220.127.116.11 Mixed Electronic–Ionic Conductors.
18.104.22.168 Concentration Polarization.
2.1.4 Interfaces and Boundary Conditions.
22.214.171.124 Reversible and Irreversible Interfaces.
126.96.36.199 Polarizable Electrodes.
188.8.131.52 Adsorption at the Electrode–Electrolyte Interface.
184.108.40.206 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.
220.127.116.11 Current Distribution Problems.
18.104.22.168 Rough and Porous Electrodes.
2.2. Physical and Electrochemical Models.
2.2.1 The Modeling of Electrochemical Systems.
2.2.2 Equivalent Circuits.
22.214.171.124 Unification of Immitance Responses.
126.96.36.199 Distributed Circuit Elements.
188.8.131.52 Ambiguous Circuits.
2.2.3 Modeling Results.
184.108.40.206 Supported Situations.
220.127.116.11 Unsupported Situations: Theoretical Models.
18.104.22.168 Unsupported Situations: Equivalent Network Models.
22.214.171.124 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.
126.96.36.199 Audio Frequency Bridges.
188.8.131.52 Transformer Ratio Arm Bridges.
184.108.40.206 Berberian–Cole Bridge.
220.127.116.11 Considerations of Potentiostatic Control.
18.104.22.168 Oscilloscopic Methods for Direct Measurement.
22.214.171.124 Phase-Sensitive Detection for Direct Measurement.
126.96.36.199 Automated Frequency Response Analysis.
188.8.131.52 Automated Impedance Analyzers.
184.108.40.206 The Use of Kramers–Kronig Transforms.
220.127.116.11 Spectrum Analyzers.
3.1.3 Time Domain Methods.
18.104.22.168 Analog-to-Digital (A/D) Conversion.
22.214.171.124 Computer Interfacing.
126.96.36.199 Digital Signal Processing.
3.2. Commercially Available Impedance Measurement Systems (Brian Sayers).
3.2.1 Electrochemical Impedance Measurement Systems.
188.8.131.52 System Configuration.
184.108.40.206 Why Use a Potentiostat?
220.127.116.11 Measurements Using 2, 3 or 4-Terminal Techniques.
18.104.22.168 Measurement Resolution and Accuracy.
22.214.171.124 Single Sine and FFT Measurement Techniques.
126.96.36.199 Multielectrode Techniques.
188.8.131.52 Effects of Connections and Input Impedance.
184.108.40.206 Verification of Measurement Performance.
220.127.116.11 Floating Measurement Techniques.
18.104.22.168 Multichannel Techniques.
3.2.2 Materials Impedance Measurement Systems.
22.214.171.124 System Configuration.
126.96.36.199 Measurement of Low Impedance Materials.
188.8.131.52 Measurement of High Impedance Materials.
184.108.40.206 Reference Techniques.
220.127.116.11 Normalization Techniques.
18.104.22.168 High Voltage Measurement Techniques.
22.214.171.124 Temperature Control.
126.96.36.199 Sample Holder Considerations.
3.3. Data Analysis (J. Ross Macdonald).
3.3.1 Data Presentation and Adjustment.
188.8.131.52 Previous Approaches.
184.108.40.206 Three-Dimensional Perspective Plotting.
220.127.116.11 Treatment of Anomalies.
3.3.2 Data Analysis Methods.
18.104.22.168 Simple Methods.
22.214.171.124 Complex Nonlinear Least Squares.
126.96.36.199 Which Impedance-Related Function to Fit?
188.8.131.52 The Question of “What to Fit” Revisited.
184.108.40.206 Deconvolution Approaches.
220.127.116.11 Examples of CNLS Fitting.
18.104.22.168 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.
22.214.171.124 Layer Models.
126.96.36.199 Effective Medium Models.
188.8.131.52 Modeling of Composite Electrodes.
4.1.2 Experimental Techniques.
184.108.40.206 Measurement Systems.
220.127.116.11 Sample Preparation—Electrodes.
18.104.22.168 Problems Associated With the Measurement of Electrode Properties.
4.1.3 Interpretation of the Impedance Spectra of Ionic Conductors and Interfaces.
22.214.171.124 Characterization of Grain Boundaries by IS.
126.96.36.199 Characterization of Two-Phase Dispersions by IS.
188.8.131.52 Impedance Spectra of Unusual Two-phase Systems.
184.108.40.206 Impedance Spectra of Composite Electrodes.
220.127.116.11 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.
18.104.22.168 Variable-slope Models.
22.214.171.124 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).
126.96.36.199 Experimental Techniques.
188.8.131.52 Experimental Results on Single Materials.
184.108.40.206 Experimental Results on Electrochromic Devices.
220.127.116.11 Conclusions and Outlook.
4.3.5 Time-Resolved Photocurrent Generation (Albert Goossens).
18.104.22.168 Steady-State Photocurrents.
22.214.171.124 Intensity-Modulated Photocurrent Spectroscopy.
126.96.36.199 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.
188.8.131.52 Active Dissolution.
184.108.40.206 Active–Passive Transition.
220.127.116.11 The Passive State.
4.4.7 Point Defect Model of the Passive State (Digby D. Macdonald).
18.104.22.168 Point Defect Model.
22.214.171.124 Electrochemical Impedance Spectroscopy.
126.96.36.199 Bilayer Passive Films.
4.4.8 Equivalent Circuit Analysis (Digby D. Macdonald and Michael C. H. McKubre).
4.4.9 Other Impedance Techniques.
188.8.131.52 Electrochemical Hydrodynamic Impedance (EHI).
184.108.40.206 Fracture Transfer Function (FTF).
220.127.116.11 Electrochemical Mechanical Impedance.
4.5. Electrochemical Power Sources.
4.5.1 Special Aspects of Impedance Modeling of Power Sources (Evgenij Barsoukov).
18.104.22.168 Intrinsic Relation Between Impedance Properties and Power Sources Performance.
22.214.171.124 Linear Time-Domain Modeling Based on Impedance Models, Laplace Transform.
126.96.36.199 Expressing Model Parameters in Electrical Terms, Limiting Resistances and Capacitances of Distributed Elements.
188.8.131.52 Discretization of Distributed Elements, Augmenting Equivalent Circuits.
184.108.40.206 Nonlinear Time-Domain Modeling of Power Sources Based on Impedance Models.
220.127.116.11 Special Kinds of Impedance Measurement Possible with Power Sources—Passive Load Excitation and Load Interrupt.
4.5.2 Batteries (Evgenij Barsoukov).
18.104.22.168 Generic Approach to Battery Impedance Modeling.
22.214.171.124 Lead Acid Batteries.
126.96.36.199 Nickel Cadmium Batteries.
188.8.131.52 Nickel Metal-hydride Batteries.
184.108.40.206 Li-ion Batteries.
4.5.3 Impedance Behavior of Electrochemical Supercapacitors and Porous Electrodes (Brian E. Conway).
220.127.116.11 The Time Factor in Capacitance Charge or Discharge.
18.104.22.168 Nyquist (or Argand) Complex-Plane Plots for Representation of Impedance Behavior.
22.214.171.124 Bode Plots of Impedance Parameters for Capacitors.
126.96.36.199 Hierarchy of Equivalent Circuits and Representation of Electrochemical Capacitor Behavior.
188.8.131.52 Impedance and Voltammetry Behavior of Brush Electrode Models of Porous Electrodes.
184.108.40.206 Impedance Behavior of Supercapacitors Based on Pseudocapacitance.
220.127.116.11 Deviations of Double-layer Capacitance from Ideal Behavior: Representation by a Constant-phase Element (CPE).
4.5.4 Fuel Cells (Norbert Wagner).
18.104.22.168 Alkaline Fuel Cells (AFC).
22.214.171.124 Polymer Electrolyte Fuel Cells (PEFC).
126.96.36.199 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)