Electrochemical impedance spectroscopy /

Provides fundamentals needed to apply impedance spectroscopy to a broad range of applications with emphasis on obtaining physically meaningful insights from measurements. * Emphasizes fundamentals applicable to a broad range of applications including corrosion, biomedical devices, semiconductors, ba...

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Bibliographic Details
Main Author:	Orazem, Mark E.
Other Authors:	Tribollet, Bernard
Format:	eBook
Language:	English
Published:	Hoboken, New Jersey : John Wiley & Sons, Inc., [2017]
Edition:	2nd edition.
Series:	Electrochemical Society series.
Subjects:	Impedance spectroscopy.
Online Access:	Connect to the full text of this electronic book

Table of Contents:

Intro
Electrochemical Impedance Spectroscopy
Contents
Preface to the Second Edition
Preface to the First Edition
Acknowledgments
The Blind Men and the Elephant
A Brief Introduction to Impedance Spectroscopy
History of Impedance Spectroscopy
I Background
1 Complex Variables
1.1 Why Imaginary Numbers?
1.2 Terminology
1.2.1 The Imaginary Number
1.2.2 Complex Variables
1.2.3 Conventions for Notation in Impedance Spectroscopy
1.3 Operations Involving Complex Variables
1.3.1 Multiplication and Division of Complex Numbers
1.3.2 Complex Variables in Polar Coordinates
1.3.3 Properties of Complex Variables
1.4 Elementary Functions of Complex Variables
1.4.1 Exponential
1.4.2 Logarithmic
1.4.3 Polynomial
Problems
2 Differential Equations
2.1 Linear First-Order Differential Equations
2.2 Homogeneous Linear Second-Order Differential Equations
2.3 Nonhomogeneous Linear Second-Order Differential Equations
2.4 Chain Rule for Coordinate Transformations
2.5 Partial Differential Equations by Similarity Transformations
2.6 Differential Equations with Complex Variables
Problems
3 Statistics
3.1 Definitions
3.1.1 Expectation and Mean
3.1.2 Variance, Standard Deviation, and Covariance
3.1.3 Normal Distribution
3.1.4 Probability
3.1.5 Central Limit Theorem
3.2 Error Propagation
3.2.1 Linear Systems
3.2.2 Nonlinear Systems
3.3 Hypothesis Tests
3.3.1 Terminology
3.3.2 Student's t-Test for Equality of Mean
3.3.3 F-Test for Equality of Variance
3.3.4 Chi-Squared Test for Goodness of Fit
Problems
4 Electrical Circuits
4.1 Passive Electrical Circuits
4.1.1 Circuit Elements
Response to a Sinusoidal Signal
Impedance Response of Passive Circuit Elements
4.1.2 Parallel and Series Combinations.
4.2 Fundamental Relationships
4.3 Nested Circuits
4.4 Mathematical Equivalence of Circuits
4.5 Graphical Representation of Circuit Response
Problems
5 Electrochemistry
5.1 Resistors and Electrochemical Cells
5.2 Polarization Behavior for Electrochemical Systems
5.2.1 Zero Current
Equilibrium
Nonequilibrium
5.2.2 Kinetic Control
5.2.3 Mixed-Potential Theory
5.2.4 Mass-Transfer Control
5.3 Definitions of Potential
5.4 Rate Expressions
5.5 Transport Processes
5.5.1 Primary Current and Potential Distributions
5.5.2 Secondary Current and Potential Distributions
5.5.3 Tertiary Current and Potential Distributions
5.5.4 Mass-Transfer-Controlled Current Distributions
5.6 Potential Contributions
5.6.1 Ohmic Potential Drop
5.6.2 Surface Overpotential
5.6.3 Concentration Overpotential
5.7 Capacitance Contributions
5.7.1 Double-Layer Capacitance
5.7.2 Dielectric Capacitance
5.8 Further Reading
Problems
6 Electrochemical Instrumentation
6.1 The Ideal Operational Amplifier
6.2 Elements of Electrochemical Instrumentation
6.3 Electrochemical Interface
6.3.1 Potentiostat
6.3.2 Galvanostat
6.3.3 Potentiostat for EIS Measurement
Problems
II Experimental Considerations
7 Experimental Methods
7.1 Steady-State Polarization Curves
7.2 Transient Response to a Potential Step
7.3 Analysis in Frequency Domain
7.3.1 Lissajous Analysis
7.3.2 Phase-Sensitive Detection (Lock-in Amplifier)
7.3.3 Single-Frequency Fourier Analysis
7.3.4 Multiple-Frequency Fourier Analysis
7.4 Comparison of Measurement Techniques
7.4.1 Lissajous Analysis
7.4.2 Phase-Sensitive Detection (Lock-in Amplifier)
7.4.3 Single-Frequency Fourier Analysis
7.4.4 Multiple-Frequency Fourier Analysis
7.5 Specialized Techniques
7.5.1 Transfer-Function Analysis.
7.5.2 Local Electrochemical Impedance Spectroscopy
Global Impedance
Local Impedance
Local Interfacial Impedance
Local Ohmic Impedance
Global Interfacial Impedance
Global Ohmic Impedance
Problems
8 Experimental Design
8.1 Cell Design
8.1.1 Reference Electrodes
8.1.2 Flow Configurations
Rotating Disk
Disk under Submerged Impinging Jet
Rotating Cylinders
Rotating Hemispherical Electrode
8.1.3 Current Distribution
8.2 Experimental Considerations
8.2.1 Frequency Range
8.2.2 Linearity
8.2.3 Modulation Technique
8.2.4 Oscilloscope
8.3 Instrumentation Parameters
8.3.1 Improve Signal-to-Noise Ratio
8.3.2 Reduce Bias Errors
Nonstationary Effects
Instrument Bias
8.3.3 Improve Information Content
Problems
III Process Models
9 Equivalent Circuit Analogs
9.1 General Approach
9.2 Current Addition
9.2.1 Impedance at the Corrosion Potential
9.2.2 Partially Blocked Electrode
9.3 Potential Addition
9.3.1 Electrode Coated with an Inert Porous Layer
9.3.2 Electrode Coated with Two Inert Porous Layers
Problems
10 Kinetic Models
10.1 General Mathematical Framework
10.2 Electrochemical Reactions
10.2.1 Potential Dependent
10.2.2 Potential and Concentration Dependent
Charge-Transfer Resistance
Diffusion Impedance
Cell Impedance
10.3 Multiple Independent Electrochemical Reactions
10.4 Coupled Electrochemical Reactions
10.4.1 Potential and Surface Coverage Dependent
10.4.2 Potential, Surface Coverage, and Concentration Dependent
10.5 Electrochemical and Heterogeneous Chemical Reactions
Problems
11 Diffusion Impedance
11.1 Uniformly Accessible Electrode
11.2 Porous Film
11.2.1 Diffusion with Exchange of Electroactive Species
11.2.2 Diffusion without Exchange of Electroactive Species
11.3 Rotating Disk.
11.3.1 Fluid Flow
11.3.2 Steady-State Mass Transfer
11.3.3 Convective Diffusion Impedance
11.3.4 Analytic and Numerical Solutions
Nernst Hypothesis
Assumption of an Infinite Schmidt Number
Treatment of a Finite Schmidt Number
11.4 Submerged Impinging Jet
11.4.1 Fluid Flow
11.4.2 Steady-State Mass Transfer
11.4.3 Convective Diffusion Impedance
11.5 Rotating Cylinders
11.6 Electrode Coated by a Porous Film
11.6.1 Steady-State Solutions
11.6.2 Coupled Diffusion Impedance
11.7 Impedance with Homogeneous Chemical Reactions
11.8 Dynamic Surface Films
11.8.1 Mass Transfer in the Salt Layer
11.8.2 Mass Transfer in the Electrolyte
11.8.3 Oscillating Film Thickness
11.8.4 Faradaic Impedance
Problems
12 Impedance of Materials
12.1 Electrical Properties of Materials
12.2 Dielectric Response in Homogeneous Media
12.3 Cole-Cole Relaxation
12.4 Geometric Capacitance
12.5 Dielectric Response of Insulating Nonhomogeneous Media
12.6 Mott-Schottky Analysis
Problems
13 Time-Constant Dispersion
13.1 Transmission Line Models
13.1.1 Telegrapher's Equations
13.1.2 Porous Electrodes
13.1.3 Pore-in-Pore Model
13.1.4 Thin-Layer Cell
13.2 Geometry-Induced Current and Potential Distributions
13.2.1 Mathematical Development
Blocking Electrode
Blocking Electrode with CPE Behavior
Electrode with Faradaic Reactions
Electrode with Faradaic Reactions Coupled by Adsorbed Intermediates
13.2.2 Numerical Method
13.2.3 Complex Ohmic Impedance at High Frequencies
13.2.4 Complex Ohmic Impedance at High and Low Frequencies
13.3 Electrode Surface Property Distributions
13.3.1 Electrode Roughness
Influence of Roughness on a Disk Electrode
Influence of Surface Roughness on a Recessed Electrode
13.3.2 Capacitance.
Capacitance Distribution on Recessed Electrodes
Capacitance Distribution on Disk Electrodes
13.3.3 Reactivity
13.4 Characteristic Dimension for Frequency Dispersion
13.5 Convective Diffusion Impedance at Small Electrodes
13.5.1 Analysis
13.5.2 Local Convective Diffusion Impedance
Low-Frequency Solution
High-Frequency Solution
13.5.3 Global Convective Diffusion Impedance
13.6 Coupled Charging and Faradaic Currents
13.6.1 Theoretical Development
Mass Transport in Dilute Solutions
Coupled Faradaic and Charging Currents
Double-Layer Model
Decoupled Faradaic and Charging Currents
13.6.2 Numerical Method
Steady-State Calculations
Double-Layer Properties
Impedance Calculations
13.6.3 Consequence of Coupled Charging and Faradaic Currents
13.7 Exponential Resistivity Distributions
Problems
14 Constant-Phase Elements
14.1 Mathematical Formulation for a CPE
14.2 When Is a Time-Constant Distribution a CPE?
14.3 Origin of Distributions Resulting in a CPE
14.4 Approaches for Extracting Physical Properties
14.4.1 Simple Substitution
14.4.2 Characteristic Frequency: Normal Distribution
14.4.3 Characteristic Frequency: Surface Distribution
14.4.4 Power-Law Distribution
Bounds for Resistivity
Comparative Analysis
14.5 Limitations to the Use of the CPE
Problems
15 Generalized Transfer Functions
15.1 Multi-input/Multi-output Systems
15.1.1 Current or Potential Are the Output Quantity
15.1.2 Current or Potential Are the Input Quantity
15.1.3 Experimental Quantities
15.2 Transfer Functions Involving Exclusively Electrical Quantities
15.2.1 Ring-Disk Impedance Measurements
15.2.2 Multifrequency Measurements for Double-Layer Studies
15.3 Transfer Functions Involving Nonelectrical Quantities.