Modern Aspects Of Electrochemistry

318 Pages·2007·8.76 MB·English

by  Joachim Maier (auth.), Constantinos Vayenas, Ralph E. White, Maria E. Gamboa-Aldeco (eds.)

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Edited by C.G. VAYENAS
MODERN ASPECTS OF
ELECTROCHEMISTRY
No. 41
Modern Aspects of
Electrochemistry
Topics in Number 40 include:
• Polymer Electrolyte Membrane (PEM) fuel cell bipolar
plates, discussion of the difficulties associated with
confronting bipolar plate development
• The use of graphs in electrochemical reaction networks with
focus on analysis of variance (ANOVA) observation methods
• Nano-materials in lithium ion battery electrode design,
presentation of a plasma-assisted method to create a carbon
replica of an alumina template membrane
• Direct methanol fuel cells, extensive discussion and review of
various types of fuel cells and advances made in the
performance of DMFC’s since their inception
• Direct simulation of polymer electrolyte fuel cell catalyst
layers, presentation of a systematic development of the direct
numerical simulation
Topics in Number 39 include:
• Approaches to Solute-Solvent Interactions including two
approaches to computational determination of solution
properties, and several other procedures that establish
correlations between properties of interest and certain features
of the solute and/or solvent molecules
• Porous Silicon, including its morphology and formation
mechanisms, as well as anodic reaction kinetics
• Modeling Electrochemical Phenomena via Markov Chains
and Processes gives an introduction to Markov Theory, then
discusses applications to electrochemistry, including
modeling electrode surface processes, electrolyzers, the repair
of failed cells, analysis of switching-circuit operations, and
other electrochemical systems
• Fractal Approach to Rough Surfaces and Interfaces in
Electrochemistry, from a review of Fractal Geometry to the
application of Fractal Geometry to the classification of
surfaces and Electrochemistry
• Phenomenology and Mechanisms of Electrochemical
Treatment (ECT) of Tumors, starting from fundamentals and
proceeding to electrochemical treatment of tumors in animals
and then in humans
MODERN ASPECTS OF
ELECTROCHEMISTRY
No. 41
Edited by
CONSTANTINOS VAYENAS
University of Patras
Patras, Greece
and
MARIA E. GAMBOA-ALDECO

Managin g Editor
Superior, Colorado, USA
Constantinos Vayenas Maria E. Gamboa-Aldeco
Department of Chemical Engineering 1107 Raymer Lane
University of Patras Superior, CO 80027
Patras 265 00 USA
Greece [email protected]
[email protected]
Department of Chemical Engineering
University of South Carolina
Columbia, SC 29208
USA
[email protected]
L ibrary of Congress Control Number: 2006938037

IS BN-10: 0-387-46107-8 e-ISBN-10: 0-387-46108-6
ISBN-13: 978-0-387-46107-6 e-ISBN-13: 978-0-387-46108-3

Printed on acid-free paper.

© 2007 Springer Science+Business Media, LLC
All rights reserved. This work may not be translated or copied in whole or in part
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Contents
Chapter 1

SOLID STATE ELECTROCHEMISTRY II: DEVICES
AND TECHNIQUES

Joachim Maier

I. Introduction........................................................................... 1
II. Electrochemical Devices and Applications.......................... 6
1. Electrochemical (Composition) Sensors........................ 7
(i) Bulk Conductivity Sensor (Mode 1)....................... 10
(ii) Surface Conductivity Sensors (Mode 2)................. 11
(iii) Galvanic Sensors (Mode 3).................................... 14
(iv) Extension to Acid–Base Active Gases................... 18
2. Electrochemical (Composition) Actors.......................... 23
3. Electrochemical Energy Storage
and Conversion Devices................................................. 29
(i) Fuel Cells................................................................ 30
(ii) Batteries.................................................................. 58
(iii) Other Storage Devices:
Supercapacitors and Photobatteries........................ 68
III. Electrochemical Techniques................................................. 74
1. Determination of Bulk Parameters................................. 76
2. Determination of Boundary Parameters......................... 77
3. Electrochemical Polarization—The Effect
of Selectively Blocking Electrodes................................ 81
(i) Heuristic Considerations......................................... 81
(ii) The Steady-State Response: The Evaluation
of Partial Conductivities......................................... 88
(iii) The Instationary Behavior: The Evaluation
of the Chemical Diffusion Coefficient................... 94
4. Chemically Imposed Gradients...................................... 97
(i) Chemical Polarization and Concentration
Cell Experiment...................................................... 97
(ii) Oxygen Permeation................................................. 100
(iii) Zero-Driving Force Method................................... 100
(iv) Chemical Relaxation............................................... 101
5. Coulometric Titration..................................................... 104
6. Thermodynamic Data from Electrochemical Cells
Involving Solid Electrolytes........................................... 106
vii
viii Contents
7. Modifications in the Evaluation of Electrochemical
Measurements Due to Internal Defect Reactions........... 109
8. Dynamic Interactions...................................................... 112
9. Transport in Inhomogeneous, Heterogeneous,
and Composite Systems................................................. 114
10. Related Techniques......................................................... 120
IV. Conclusions........................................................................... 120
Acknowledgment.................................................................. 121
A Appendix 1—Terminal Potential Difference................. 121
B Appendix 2—Electrochemical Polarization................... 122
C Appendix 3—Chemical Polarization and Relaxation.... 124
D Appendix 4—Electrolytic Domain Boundaries............. 125
E Appendix 5—Coulometric Titration.............................. 126
F Appendix 6—Point Electrode Resistance...................... 127
Symbols................................................................................ 127
References............................................................................ 128
Chapter 2

SYNTHESIS AND CHARACTERIZATION OF NANOPOROUS
CARBON AND ITS ELECTROCHEMICAL APPLICATION TO
ELECTRODE MATERIAL FOR SUPERCAPACITORS

Gyoung-Ja Lee and Su-Il Pyun

I. Introduction........................................................................... 139
II. Preparation of Porous Carbons............................................. 141
1. Activation Method.......................................................... 141
2. Templating Method........................................................ 143
III. Structural Characteristics of Porous Carbons....................... 145
1. Types of Adsorption Isotherms
and Hysteresis Loops...................................................... 145
2. Determinations of Surface Area
and Pore Size Distribution.............................................. 150
IV. Fractal Characteristics of Porous Carbons............................ 154
1. Molecular Probe Method Using Gas Adsorption........... 155
2. Image Analysis Method.................................................. 162
V. Electrochemical Characteristics of Carbon-Based Porous
Electrodes For Supercapacitor: The Uses of AC-Impedance
Spectroscopy, Current Transient and
Cyclic Voltammetry.............................................................. 166
1. General Theory of Electrochemical Behavior
of Porous Electrodes....................................................... 166
Contents ix
2. Effect of Geometric Heterogeneity on Ion
Penetration into the Pores during Double-Layer
Charging/Discharging..................................................... 169
3. Effect of Surface Inhomogeneity on Ion
Penetration into the Pores during Double-Layer
Charging/Discharging..................................................... 175
VI. Concluding Remark.............................................................. 183
Acknowledgements.............................................................. 185
Notation................................................................................ 186
References............................................................................ 190
Chapter 3

THE USE OF GRAPHS IN THE STUDY OF
ELECTROCHEMICAL REACTION NETWORKS

Joseph D. Fehribach

I. Introduction........................................................................... 197
II. Reaction Species Graphs...................................................... 200
1. Kinetic Graphs................................................................ 201
2. Bipartite Graphs.............................................................. 203
III. Reaction Mechanism Graphs................................................ 205
1. MCFC Cathodic Reactions............................................. 206
(i) Peroxide Mechanism.............................................. 206
(ii) Superoxide-Peroxide Mechanism........................... 208
2. HER Reactions............................................................... 209
IV. Reaction Route Graphs......................................................... 211
1. MCFC Cathodic Reactions............................................. 212
2. HER Reactions............................................................... 213
V. Discussion: Other Reaction Graphs...................................... 217
Acknowledgments................................................................ 218
References............................................................................ 218
Chapter 4

APPROXIMATE ANALYTICAL SOLUTIONS FOR MODELS
OF THREE-DIMENSIONAL ELECTRODES BY ADOMIAN’S
DECOMPOSITION METHOD

Keith Scott and Yan-Ping Sun

I. Introduction........................................................................... 222
II. Adomian’s Decomposition Method (ADM)......................... 223