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