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

This article introduces the radical approach of applying alkaline anion-exchange membranes (AAEMs) to meet the current challenges with regards to direct methanol fuel cells (DMFCs). A review of the literature is presented with regards to the testing of fuel cells with alkaline membranes (fuelled with hydrogen or methanol) and also to candidate alkaline anion-exchange membranes for such an application. A brief review of the directly related patent literature is also included. Current and future research challenges are identified along with potential strategies to overcome them. Finally, the advantages and challenges with the direct electrochemical oxidation of alternative fuels are discussed, along with how the application of alkaline membranes in such fuel cells may assist in improving performance and fuel efficiency.

https://epubs.surrey.ac.uk/1696/1/fulltext.pdf

Prospects for Alkaline Anion-Exchange Membranes in Low Temperature Fuel Cells†

Carbon supported platinum is commonly used as anode and cathode electrocatalyst in low-temperature fuel cells fuelled with hydrogen or low molecular weight alcohols. The cost of Pt and the limited world supply are significant barriers to the widespread use of these types of fuel cells. Moreover, platinum used as anode material is readily poisoned by carbon monoxide, present in the reformate gas used as H2 carrier in the case of polymer electrolyte fuel cells, and a byproduct of alcohol oxidation in the case of direct alcohol fuel cells. In addition, Pt alone does not present satisfactory activity for the oxygen reduction reaction when used as cathode material. For all these reasons, binary and ternary platinum-based catalysts and non-platinum-based catalysts have been tested as electrode materials for low temperature fuel cells. Palladium and platinum have very similar properties because they belong to the same group in the periodic table. The activity for the oxygen reduction reaction (ORR) of Pd is only slightly lower than that of Pt, and by addition of a suitable metal, such as Co or Fe, the ORR activity of Pd can overcome that of Pt. Conversely, the activity for the hydrogen oxidation reaction (HOR) of Pd is considerably lower than that of Pt, but by adding of a very small amount (5 at%) of Pt, the HOR activity of Pd attains that of pure Pt. This paper presents an overview of Pd and Pd-containing catalysts, tested both as anode and cathode materials for low-temperature fuel cells.

Palladium in fuel cell catalysis

Influence of the Discretization Methods on the Distribution of Relaxation Times Deconvolution: Implementing Radial Basis Functions with DRTtools

▪ Abstract After a brief survey of fuel cell types, attention is focused on material requirements for SOFC and PEMFC stacks, with an introductory section on materials technology for reformers. Materials cost and processing, together with durability issues, are emphasized as these now dominate materials selection processes for prototype stack units. In addition to optimizing the cell components, increasing attention is being given to the composition and processing of the bipolar plate component as the weight and volume of the relevant material has a major influence on the overall power density and cost of the fuel cell stack. It is concluded that the introduction of alternative materials/processes that would enable PEMFC stacks to operate at 150–200°C, and IT-SOFC stacks to operate at 500–700°C, would have a major impact on the successful commercialization of fuel cell technology.

Recent Advances in Materials for Fuel Cells

Impedance studies on direct methanol fuel cell anodes

The possibility of using dimethyl ether (DME) as a fuel in direct oxidation polymer‐electrolyte‐membrane (PEM) fuel cells is investigated. A mechanism for DME electro‐oxidation is proposed based on the results of half‐cell experiments using cyclic voltammetry combined with gas‐chromatographic (GC) analyses of a single direct DME fuel cell. It is shown that, as a consequence of this mechanism, there is an additional overpotential at the anode of a direct DME fuel cell which is related to the initial adsorption step on the catalyst surface. DME is typically not oxidized at the cathode of a PEM fuel cell. This minimizes unwanted effects of fuel crossover, leading to improved fuel‐cell efficiencies compared to direct methanol fuel cells, especially at low‐to‐medium current densities. © 2000 The Electrochemical Society. All rights reserved.

https://iopscience.iop.org/article/10.1149/1.1394018/pdf

Electro‐oxidation of Dimethyl Ether in a Polymer‐Electrolyte‐Membrane Fuel Cell

Industrial application of fuel cell technology requires suitable electrocatalysts. This is true for all different types of fuel cells. These catalysts are responsible for the oxidation of the fuel (i.e. hydrogen, hydrogen rich gases or methanol) as well as for the oxygen reduction. This paper focuses on solid polymer electrolyte fuel cell systems for mobile applications. Here the demands on the catalyst are most severe due to the low-temperature operating regime. Two system configurations are possible: either the carbon containing fuel is processed by a fuel converter to a hydrogen rich gas mixture and this in turn is fed into the fuel cell. Alternatively fuels such as methanol can be supplied directly into the fuel cell. In the first case, contaminations of CO in the feed gas have to be taken into account. These strongly absorbs on the surface of the catalysts (carbon-supported Pt or Pt-alloys) thereby inhibiting the hydrogen oxidation reaction. Electro-oxidation mechanisms of adsorbed CO as well as methanol—as an example for a direct fuel cell system—is discussed on Pt-Ru and other catalysts. Finally catalysts for methanol and hydrocarbon reforming reactions as well as for the shift reaction are reviewed.

Catalytic processes in solid polymer electrolyte fuel cell systems

A fuel cell includes an electrolyte electrode assembly having a cathode disposed on a first side and an anode disposed on a second side of the electrolyte electrode assembly, a first flow module disposed adjacent the cathode, and a second flow module disposed adjacent the anode. At least one of the first and second flow modules includes a material suitable for exothermal hydride formation. In addition, a method for cold-starting a such fuel cell that includes at least one of the first and second flow modules with a hydrogen-containing gas so as to induce the exothermic hydride formation and release heat; and heating the fuel cell using the heat.

Fuel cell and method for cold-starting such a fuel cell

The invention relates to a pivoting device, by means of which a vehicle door (10), in particular a wing door, is in the normal case mounted on a body (36) of a motor vehicle and can be pivoted between an open position and a closed position, wherein the pivoting device comprises a separating device (18), by means of which the vehicle door (10) can be detached from the body in an emergency, in particular after a rollover. The invention also relates to a method for controlling a separating device (18).

Jens Müller

Papers

Impedance studies on direct methanol fuel cell anodes

Electro‐oxidation of Dimethyl Ether in a Polymer‐Electrolyte‐Membrane Fuel Cell

Catalytic processes in solid polymer electrolyte fuel cell systems

Fuel cell and method for cold-starting such a fuel cell

Pivoting device for a vehicle door