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