Preface. Preface to the First Edition. Contributors. 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. 2.1.1 Introduction. 2.1.2 The Electrical Properties of Bulk Homogeneous Phases. 2.1.2.1 Introduction. 2.1.2.2 Dielectric Relaxation in Materials with a Single Time Constant. 2.1.2.3 Distributions of Relaxation Times. 2.1.2.4 Conductivity and Diffusion in Electrolytes. 2.1.2.5 Conductivity and Diffusion-a Statistical Description. 2.1.2.6 Migration in the Absence of Concentration Gradients. 2.1.2.7 Transport in Disordered Media. 2.1.3 Mass and Charge Transport in the Presence of Concentration Gradients. 2.1.3.1 Diffusion. 2.1.3.2 Mixed Electronic-Ionic Conductors. 2.1.3.3 Concentration Polarization. 2.1.4 Interfaces and Boundary Conditions. 2.1.4.1 Reversible and Irreversible Interfaces. 2.1.4.2 Polarizable Electrodes. 2.1.4.3 Adsorption at the Electrode-Electrolyte Interface. 2.1.4.4 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. 2.1.6.1 Current Distribution Problems. 2.1.6.2 Rough and Porous Electrodes. 2.2. Physical and Electrochemical Models. 2.2.1 The Modeling of Electrochemical Systems. 2.2.2 Equivalent Circuits. 2.2.2.1 Unification of Immitance Responses. 2.2.2.2 Distributed Circuit Elements. 2.2.2.3 Ambiguous Circuits. 2.2.3 Modeling Results. 2.2.3.1 Introduction. 2.2.3.2 Supported Situations. 2.2.3.3 Unsupported Situations: Theoretical Models. 2.2.3.4 Unsupported Situations: Equivalent Network Models. 2.2.3.5 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). 3.1.1 Introduction. 3.1.2 Frequency Domain Methods. 3.1.2.1 Audio Frequency Bridges. 3.1.2.2 Transformer Ratio Arm Bridges. 3.1.2.3 Berberian-Cole Bridge. 3.1.2.4 Considerations of Potentiostatic Control. 3.1.2.5 Oscilloscopic Methods for Direct Measurement. 3.1.2.6 Phase-Sensitive Detection for Direct Measurement. 3.1.2.7 Automated Frequency Response Analysis. 3.1.2.8 Automated Impedance Analyzers. 3.1.2.9 The Use of Kramers-Kronig Transforms. 3.1.2.10 Spectrum Analyzers. 3.1.3 Time Domain Methods. 3.1.3.1 Introduction. 3.1.3.2 Analog-to-Digital (A/D) Conversion. 3.1.3.3 Computer Interfacing. 3.1.3.4 Digital Signal Processing. 3.1.4 Conclusions. 3.2. Commercially Available Impedance Measurement Systems (Brian Sayers). 3.2.1 Electrochemical Impedance Measurement Systems. 3.2.1.1 System Configuration. 3.2.1.2 Why Use a Potentiostat? 3.2.1.3 Measurements Using 2, 3 or 4-Terminal Techniques. 3.2.1.4 Measurement Resolution and Accuracy. 3.2.1.5 Single Sine and FFT Measurement Techniques. 3.2.1.6 Multielectrode Techniques. 3.2.1.7 Effects of Connections and Input Impedance. 3.2.1.8 Verification of Measurement Performance. 3.2.1.9 Floating Measurement Techniques. 3.2.1.10 Multichannel Techniques. 3.2.2 Materials Impedance Measurement Systems. 3.2.2.1 System Configuration. 3.2.2.2 Measurement of Low Impedance Materials. 3.2.2.3 Measurement of High Impedance Materials. 3.2.2.4 Reference Techniques. 3.2.2.5 Normalization Techniques. 3.2.2.6 High Voltage Measurement Techniques. 3.2.2.7 Temperature Control. 3.2.2.8 Sample Holder Considerations. 3.3. Data Analysis (J. Ross Macdonald). 3.3.1 Data Presentation and Adjustment. 3.3.1.1 Previous Approaches. 3.3.1.2 Three-Dimensional Perspective Plotting. 3.3.1.3 Treatment of Anomalies. 3.3.2 Data Analysis Methods. 3.3.2.1 Simple Methods. 3.3.2.2 Complex Nonlinear Least Squares. 3.3.2.3 Weighting. 3.3.2.4 Which Impedance-Related Function to Fit? 3.3.2.5 The Question of "What to Fit" Revisited. 3.3.2.6 Deconvolution Approaches. 3.3.2.7 Examples of CNLS Fitting. 3.3.2.8 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. 4.1.1.1 Introduction. 4.1.1.2 Layer Models. 4.1.1.3 Effective Medium Models. 4.1.1.4 Modeling of Composite Electrodes. 4.1.2 Experimental Techniques. 4.1.2.1 Introduction. 4.1.2.2 Measurement Systems. 4.1.2.3 Sample Preparation-Electrodes. 4.1.2.4 Problems Associated With the Measurement of Electrode Properties. 4.1.3 Interpretation of the Impedance Spectra of Ionic Conductors and Interfaces. 4.1.3.1 Introduction. 4.1.3.2 Characterization of Grain Boundaries by IS. 4.1.3.3 Characterization of Two-Phase Dispersions by IS. 4.1.3.4 Impedance Spectra of Unusual Two-phase Systems. 4.1.3.5 Impedance Spectra of Composite Electrodes. 4.1.3.6 Closing Remarks. 4.2. Characterization of the Electrical Response of High Resistivity Ionic and Dielectric Solid Materials by Immittance Spectroscopy (J. Ross Macdonald). 4.2.1 Introduction. 4.2.2 Types of Dispersive Response Models: Strengths and Weaknesses. 4.2.2.1 Overview. 4.2.2.2 Variable-slope Models. 4.2.2.3 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 Stromme). 4.3.4.1 Introduction. 4.3.4.2 Materials. 4.3.4.3 Experimental Techniques. 4.3.4.4 Experimental Results on Single Materials. 4.3.4.5 Experimental Results on Electrochromic Devices. 4.3.4.6 Conclusions and Outlook. 4.3.5 Time-Resolved Photocurrent Generation (Albert Goossens). 4.3.5.1 Introduction-Semiconductors. 4.3.5.2 Steady-State Photocurrents. 4.3.5.3 Time-of-Flight. 4.3.5.4 Intensity-Modulated Photocurrent Spectroscopy. 4.3.5.5 Final Remarks. 4.4. Corrosion of Materials (Digby D. Macdonald and Michael C. H. McKubre). 4.4.1 Introduction. 4.4.2 Fundamentals. 4.4.3 Measurement of Corrosion Rate. 4.4.4 Harmonic Analysis. 4.4.5 Kramer-Kronig Transforms. 4.4.6 Corrosion Mechanisms. 4.4.6.1 Active Dissolution. 4.4.6.2 Active-Passive Transition. 4.4.6.3 The Passive State. 4.4.7 Point Defect Model of the Passive State (Digby D. Macdonald). 4.4.7.1 Introduction. 4.4.7.2 Point Defect Model. 4.4.7.3 Electrochemical Impedance Spectroscopy. 4.4.7.4 Bilayer Passive Films. 4.4.8 Equivalent Circuit Analysis (Digby D. Macdonald and Michael C. H. McKubre). 4.4.8.1 Coatings. 4.4.9 Other Impedance Techniques. 4.4.9.1 Electrochemical Hydrodynamic Impedance (EHI). 4.4.9.2 Fracture Transfer Function (FTF). 4.4.9.3 Electrochemical Mechanical Impedance. 4.5. Electrochemical Power Sources. 4.5.1 Special Aspects of Impedance Modeling of Power Sources (Evgenij Barsoukov). 4.5.1.1 Intrinsic Relation Between Impedance Properties and Power Sources Performance. 4.5.1.2 Linear Time-Domain Modeling Based on Impedance Models, Laplace Transform. 4.5.1.3 Expressing Model Parameters in Electrical Terms, Limiting Resistances and Capacitances of Distributed Elements. 4.5.1.4 Discretization of Distributed Elements, Augmenting Equivalent Circuits. 4.5.1.5 Nonlinear Time-Domain Modeling of Power Sources Based on Impedance Models. 4.5.1.6 Special Kinds of Impedance Measurement Possible with Power Sources-Passive Load Excitation and Load Interrupt. 4.5.2 Batteries (Evgenij Barsoukov). 4.5.2.1 Generic Approach to Battery Impedance Modeling. 4.5.2.2 Lead Acid Batteries. 4.5.2.3 Nickel Cadmium Batteries. 4.5.2.4 Nickel Metal-hydride Batteries. 4.5.2.5 Li-ion Batteries. 4.5.3 Impedance Behavior of Electrochemical Supercapacitors and Porous Electrodes (Brian E. Conway). 4.5.3.1 Introduction. 4.5.3.2 The Time Factor in Capacitance Charge or Discharge. 4.5.3.3 Nyquist (or Argand) Complex-Plane Plots for Representation of Impedance Behavior. 4.5.3.4 Bode Plots of Impedance Parameters for Capacitors. 4.5.3.5 Hierarchy of Equivalent Circuits and Representation of Electrochemical Capacitor Behavior. 4.5.3.6 Impedance and Voltammetry Behavior of Brush Electrode Models of Porous Electrodes. 4.5.3.7 Impedance Behavior of Supercapacitors Based on Pseudocapacitance. 4.5.3.8 Deviations of Double-layer Capacitance from Ideal Behavior: Representation by a Constant-phase Element (CPE). 4.5.4 Fuel Cells (Norbert Wagner). 4.5.4.1 Introduction. 4.5.4.2 Alkaline Fuel Cells (AFC). 4.5.4.3 Polymer Electrolyte Fuel Cells (PEFC). 4.5.4.4 Solid Oxide Fuel Cells (SOFC). Appendix. Abbreviations and Definitions of Models. References. Index.

Impedance spectroscopy : theory, experiment, and applications

Objective evaluation of the activity of electrocatalysts for water oxidation is of fundamental importance for the development of promising energy conversion technologies including integrated solar water-splitting devices, water electrolyzers, and Li-air batteries. However, current methods employed to evaluate oxygen-evolving catalysts are not standardized, making it difficult to compare the activity and stability of these materials. We report a protocol for evaluating the activity, stability, and Faradaic efficiency of electrodeposited oxygen-evolving electrocatalysts. In particular, we focus on methods for determining electrochemically active surface area and measuring electrocatalytic activity and stability under conditions relevant to an integrated solar water-splitting device. Our primary figure of merit is the overpotential required to achieve a current density of 10 mA cm–2 per geometric area, approximately the current density expected for a 10% efficient solar-to-fuels conversion device. Utilizing ...

Benchmarking Heterogeneous Electrocatalysts for the Oxygen Evolution Reaction

A fundamental change has been achieved in understanding surface electrochemistry due to the profound knowledge of the nature of electrocatalytic processes accumulated over the past several decades and to the recent technological advances in spectroscopy and high resolution imaging. Nowadays one can preferably design electrocatalysts based on the deep theoretical knowledge of electronic structures, via computer-guided engineering of the surface and (electro)chemical properties of materials, followed by the synthesis of practical materials with high performance for specific reactions. This review provides insights into both theoretical and experimental electrochemistry toward a better understanding of a series of key clean energy conversion reactions including oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER). The emphasis of this review is on the origin of the electrocatalytic activity of nanostructured catalysts toward the aforementioned reactions by correlating the apparent electrode performance with their intrinsic electrochemical properties. Also, a rational design of electrocatalysts is proposed starting from the most fundamental aspects of the electronic structure engineering to a more practical level of nanotechnological fabrication.

Design of electrocatalysts for oxygen- and hydrogen-involving energy conversion reactions

1. Setting the Scope of the Challenge 6474 1.1. The Need for Solar Energy Supply and Storage 6474 1.2. An Imperative for Discovery Research 6477 1.3. Scope of Review 6478 2. Large-Scale Centralized Energy Storage 6478 2.1. Pumped Hydroelectric Energy Storage (PHES) 6479 2.2. Compressed Air Energy Storage (CAES) 6480 3. Smaller Scale Grid and Distributed Energy Storage 6481 3.1. Flywheel Energy Storage (FES) 6481 3.2. Superconducting Magnetic Energy Storage 6482 4. Chemical Energy Storage: Electrochemical 6482 4.1. Batteries 6482 4.1.1. Lead-Acid Batteries 6483 4.1.2. Alkaline Batteries 6484 4.1.3. Lithium-Ion Batteries 6484 4.1.4. High-Temperature Sodium Batteries 6484 4.1.5. Liquid Flow Batteries 6485 4.1.6. Metal-Air Batteries 6485 4.2. Capacitors 6485 5. Chemical Energy Storage: Solar Fuels 6486 5.1. Solar Fuels in Nature 6486 5.2. Artificial Photosynthesis and General Considerations of Water Splitting 6486

Solar Energy Supply and Storage for the Legacy and Nonlegacy Worlds

Recent progress in alkaline water electrolysis for hydrogen production and applications

Electrochemical impedance spectroscopy has become a mature and well-understood technique. It is now possible to acquire, validate, and quantitatively interpret the experimental impedances. This chapter has been addressed to understanding the fundamental processes of diffusion and faradaic reaction at electrodes. However, the most difficult problem in EIS is modeling the electrode processes, which is where most of the problems and errors arise. There is an almost infinite variety of different reactions and interfaces that can be studied (corrosion, coatings, conducting polymers, batteries and fuel cells, semiconductors, electrocatalytic reactions, chemical reactions coupled with faradaic processes, etc.) and the main effort is now being applied to understanding and analyzing these processes. These applications will be the subject of a second review in a forthcoming volume in this series.

Electrochemical Impedance Spectroscopy and its Applications

Kinetics of hydrogen evolution on nickel electrodes

Experimental study and modeling of impedance of the her on porous Ni electrodes

The hydrogen evolution reaction was studied in 1 M KOH at 25 °C on two types of electrodes:(i) pressed powders of Ni or NiMo with Al, heated at 700 °C; (ii) Ni—Al—Mo powders deposited by vacuum plasma spraying. These materials were treated with alkaline solution to leach out aluminum. Very active and stable Raney nickel—molybdenum electrodes were obtained from Al rich alloys. Adding molybdenum significantly improved catalytic activity. Electrochemical impedance spectroscopy was used to determine the apparent and intrinsic activities. Different ac models were tested and the appropriate one was selected. Intrinsic activities of these electrodes are smaller or equal to that of polycrystalline Ni and the origin of high apparent activities is related to the increase in real surface area.

Studies of the Hydrogen Evolution Reaction on Raney Nickel—Molybdenum Electrodes

The electrodeposition and surface morphology of aluminium on tungsten (W) and aluminium (Al) electrodes from 2 : 1 molar ratio AlCl 3 –[EMIm]Cl ionic liquids were investigated. Analyses of the chronoamperograms indicate that the deposition process of aluminium on W substrates was controlled by instantaneous nucleation with diffusion-controlled growth, while the deposition processes of aluminium on Al electrodes were found to be associated with kinetic limitations. Constant potential deposition experiments showed that the electrodeposits obtained on both W and Al electrodes between − 0.10 and − 0.40 V (vs. Al(III)/Al) are dense, continuous and well adherent. Dense aluminium deposits were also obtained on Al substrates using constant current deposition between 10 and 70 mA/cm 2 , and the current efficiency was found to be dependent of the current density varying from 85% to 100%.

Electrodeposition of aluminium from ionic liquids: Part I—electrodeposition and surface morphology of aluminium from aluminium chloride (AlCl3)–1-ethyl-3-methylimidazolium chloride ([EMIm]Cl) ionic liquids

Andrzej Lasia

Papers

Electrochemical Impedance Spectroscopy and its Applications

Kinetics of hydrogen evolution on nickel electrodes

Experimental study and modeling of impedance of the her on porous Ni electrodes

Studies of the Hydrogen Evolution Reaction on Raney Nickel—Molybdenum Electrodes

Electrodeposition of aluminium from ionic liquids: Part I—electrodeposition and surface morphology of aluminium from aluminium chloride (AlCl3)–1-ethyl-3-methylimidazolium chloride ([EMIm]Cl) ionic liquids