Solid-State Electrochemistry: Essential Course Notes and Solved Exercises

✍ Scribed by Hammou A., Georges S.

• Publisher: Springer
• Year: 2020
• Tongue: English
• Leaves: 341
• Series: Grenoble Sciences
• Category: Library

✦ Synopsis

This book features the essential material for any graduate or advanced undergraduate course covering solid-state electrochemistry. It provides the reader with fundamental course notes and numerous solved exercises, making it an invaluable guide and compendium for students of the subject. The book places particular emphasis on enhancing the reader's expertise and comprehension of thermodynamics, the Kröger-Vink notation, the variation in stoichiometry in ionic compounds, and of the different types of electrochemical measurements together with their technological applications.
Containing almost 100 illustrations, a glossary and a bibliography, the book is particularly useful for Master and PhD students, industry engineers, university instructors, and researchers working with inorganic solids in general.

✦ Table of Contents

Cover
Half Title
Solid-State Electrochemistry: Essential Course Notes and Solved Exercises
Copyright
Grenoble Sciences Series
Preface
Table of contents
Base quantities, units, and symbols from the international system (IS)
Physical-chemistry: Symbols and units
Acronyms and abbreviations used in this book
1. Description of ionic crystals
Course notes
1.1 – Definitions
1.1.1 – The perfect crystal
1.1.2 – The real crystal
1.1.3 – Structure elements and effective charge
1.2 – Reactions and equilibria
1.2.1 – Atomic disorder and electronic disorder
1.2.2 – Writing the reactions
1.2.3 – Presence of foreign atoms
1.2.4 – Equilibrium with the environment
1.3 – Brouwer diagram
1.3.1 – Equilibria
1.3.2 – Electroneutrality relation and the Brouwer approximation
1.3.3 – Diagram for MX2 crystal
1.3.4 – Case of solid solution (MX2)1−x(DX)x
1.4 – Stoichiometry and departure from stoichiometry
Exercises
Exercise 1.1 – Notation for structure elements and structure defects
Exercise 1.2 – Notation for doping reactions
Exercise 1.3 – Sitoneutrality and expression of chemical formulas
Exercise 1.4 – Calculation of defect concentrations
Exercise 1.5 – Doping strontium fluoride
Exercise 1.6 – Variation of the concentration of structure defects in pure zirconium dioxide ZrO2 as a function of oxygen partial pressure
Exercise 1.7 – The non-stoichiometry of iron monoxide
Exercise 1.8 – Departure from stoichiometry of barium fluoride BaF2
Exercise 1.9 – Crystallographic and thermodynamic study
of thorium dioxide ThO2
Solutions to exercises
Solution 1.1 – Notation for structure elements and structure defects
Solution 1.2 – Notation for doping reactions
Solution 1.3 – Sitoneutrality and notation for chemical formulas
Solution 1.4 – Calculation of defect concentrations
Solution 1.5 – Doping strontium fluoride
Solution 1.6 – Variation of the concentration of structure defects in pure zirconium dioxide ZrO2 as a function of oxygen partial pressure
Solution 1.7 – The non-stoichiometry of iron monoxide
Solution 1.8 – Departure from stoichiometry of barium fluoride BaF2
Solution 1.9 – Crystallographic and thermodynamic study
of thorium dioxide ThO2
2. Methods and techniques
Course notes
2.1 – Complex impedance spectroscopy
2.1.1 – Time domain: principal passive linear dipole devices in sinusoidal regime
2.1.2 – Complex notation
2.1.3 – Graphical representation of complex impedance
2.1.4 – Other dipole devices
2.1.5 – Physical meaning of complex impedance spectra
2.2 – Methods to measure transport number
2.2.1 – Electromotive force method
2.2.2 – Using the results of total conductivity
2.2.3 – Tubandt method
2.2.4 – Dilatocoulometric method to measure cationic transport number
2.2.5 – Electrochemical semipermeability
2.2.6 – Blocking electrode method
Exercises
Exercise 2.1 – Determination of conductivity by four-electrode method
Exercise 2.2 – Measurement of electric quantities by complex impedance spectroscopy
Exercise 2.3 – Measurement of electronic conductivity in a mixed conductor
Exercise 2.4 – Measurement of ionic conductivity in a mixed conductor
Exercise 2.5 – Determination of cationic transport numberby dilatocoulometry
Exercise 2.6 – Determination of cationic transport number in CaF2 by dilatocoulometry
Exercise 2.7 – Electrochemical semipermeability
Exercise 2.8 – Determination of transport number by electrochemical semipermeability
Exercise 2.9 – Determination of conduction mode in α-AgI by Tubandt method
Solutions to exercises
Solution 2.1 – Determination of conductivity by four-electrode method
Solution 2.2 – Measurement of electric quantities by complex impedance spectroscopy
Solution 2.3 – Measurement of electronic conductivity in a mixed conductor
Solution 2.4 – Measurement of ionic conductivity in a mixed conductor
Solution 2.5 – Determination of cationic transport number by dilatocoulometry
Solution 2.6 – Determination of cationic transport number in CaF2 by dilatocoulometry
Solution 2.7 – Electrochemical semipermeability
Solution 2.8 – Determination of transport number by electrochemical semipermeability
Solution 2.9 – Determination of conduction mode in α-AgI by Tubandt method
3. Transport in ionic solids
Course notes
3.1 – Phenomenological approach to ionic transport
in ionic crystals
3.1.1 – Electrochemical mobility and flux density
3.1.2 – Electrical conductivity and transport number
3.2 – Microscopic approach to ionic transport in crystals: Activated-hopping model
3.2.1 – Electric mobility
3.2.2 – Ionic conductivity
3.2.3 – Conductivity and temperature
3.2.4 – Conductivity and environment
3.2.5 – Ionic conductivity and composition
3.2.6 – Other parameters
3.3 – Basic description of Wagner theory
Exercises
Exercise 3.1 – Influence of geometric factor
Exercise 3.2 – Study of oxygen mobility in solid solutions (ThO2)1−x(YO1.5)x
Exercise 3.3 – Study of electronic conductivity in solid solutions (CeO2)1−x(CaO)x
Exercise 3.4 – Electronic transport number in a glass
Exercise 3.5 – Electrical properties of potassium chloride KCl
Exercise 3.6 – Application of Nernst-Einstein relation to LiCF3SO3
in poly(ethylene oxide) P(EO)
Exercise 3.7 – Electrical conductivity as a function of composition
in (CeO2)1−x(YO1.5)x
Exercise 3.8 – Conductivity of nickel oxide
Exercise 3.9 – Ionic conductivity-activity relationship of glass modifier in oxide-based glasses
Exercise 3.10 – Electrochemical coloration
Exercise 3.11 – Oxygen diffusion in gadolinia-doped ceria
Exercise 3.12 – Electrical conductivity of solid vitreous solution (SiO2)1−x(Na2O)x
Exercise 3.13 – High-temperature protonic conductor SrZrO3
Exercise 3.14 – Free-volume model
Exercise 3.15 – Study of single-crystal calcium fluoride CaF2
in the presence of oxygen
Exercise 3.16 – emf of a membrane crossed by an electrochemical semipermeability flux
Exercise 3.17 – Determination of electronic conductivityby electrochemical semipermeability
Solutions to exercises
Solution 3.1 – Influence of geometric factor
Solution 3.2 – Study of oxygen mobility in solid solutions (ThO2)1−x(YO1.5)x
Solution 3.3 – Study of electronic conductivity in solid solutions (CeO2)1−x(CaO)x
Solution 3.4 – Electronic transport number in a glass
Solution 3.5 – Electrical properties of potassium chloride KCl
Solution 3.6 – Application of Nernst-Einstein relation to LiCF3SO3
in poly(ethylene oxide) P(EO)
Solution 3.7 – Electrical conductivity as a function of composition in (CeO2)1−x(YO1.5)x
Solution 3.8 – Conductivity of nickel oxide
Solution 3.9 – Ionic conductivity-activity relationship of oxide modifier in oxide-based glasses
Solution 3.10 – Electrochemical coloration
Solution 3.11 – Oxygen diffusion in gadolinia-doped ceria
Solution 3.12 – Electrical conductivity of solid vitreous solution (SiO2)1−x(Na2O)x
Solution 3.13 – High-temperature protonic conductor SrZrO3
Solution 3.14 – Free-volume model
Solution 3.15 – Study of single-crystal calcium fluoride CaF2
in the presence of oxygen
Solution 3.16 – emf of membrane crossed by an electrochemical semipermeability flux
Solution 3.17 – Determination of electronic conductivity by electrochemical semipermeability
4. Electrode reactions
Course notesThermodynamics and electrochemical kinetics
4.1 – Electrode thermodynamics
4.1.1 – Electrode
4.1.2 – Electrode potential
4.1.3 – Electrode polarization
4.1.4 – Electrode overpotential
4.1.5 – Current density
4.2 – Electrochemical kinetics
4.2.1 – Review
4.2.2 – Pure-charge-transfer regime (extreme case)
4.2.3 – Mixed transfer-diffusion regime
4.2.4 – Regime of pure diffusion kinetics (extreme case)
4.2.5 – Regime of adsorption of gaseous species
Exercises
Exercise 4.1 – Oxygen-diffusion-limited electrode
Exercise 4.2 – Study of oxygen-electrode reaction
Exercise 4.3 – Overpotential in an oxygen electrochemical pump
Exercise 4.4 – Determination of exchange current
Exercise 4.5 – Reduction of water vapor at the M / YSZ interface with M = Pt, Ni
Exercise 4.6 – Hydrogen oxidation at Ni / YSZ interface
Solutions to exercises
Solution 4.1 – Oxygen-diffusion-limited electrode
Solution 4.2 – Study of oxygen-electrode reaction
Solution 4.3 – Overpotential in an oxygen electrochemical pump
Solution 4.4 – Determination of exchange current
Solution 4.5 – Reduction of water vapor at the M / YSZ interface with M = Pt, Ni
Solution 4.6 – Hydrogen oxidation at Ni / YSZ interface
5. Applications
Course notes
5.1 – Electrochemical sensors
5.1.1 – Definition and characteristics
5.1.2 – Potentiometric sensor for gas analysis
5.1.3 – Amperometric sensor
5.1.4 – Coulometric sensor
5.1.5 – Conductometric sensor for gas analysis
5.2 – Electrochemical generators
5.2.1 – Definition and characteristics
5.2.2 – Discharge and (re)charge of electrochemical generators
5.2.3 – Primary batteries, fuel cells, and secondary batteries
Exercises
Exercise 5.1 – Determination of standard free enthalpy of formation for AgCl
Exercise 5.2 – Measurement of thermodynamic quantities of metal fluorides
Exercise 5.3 – Measurement of O2− ion activity in a molten salt
Exercise 5.4 – Calculation of equilibrium constants for defect formation in Cu2O
Exercise 5.5 – TiS2: insertion material
Exercise 5.6 – Chlorine sensor based on doped strontium chloride
Exercise 5.7 – CO2 sensor (a)
Exercise 5.8 – CO2 sensor (b)
Exercise 5.9 – Sulfur oxide sensor
Exercise 5.10 – Oxygen semiconductor sensor
Exercise 5.11 – Amperometric oxygen sensor
Exercise 5.12 – Coulometric oxygen sensor
Exercise 5.13 – Nitrogen oxide sensor
Exercise 5.14 – The sodium-sulfur battery
Exercise 5.15 – General information on fuel cells
Exercise 5.16 – Solid oxide fuel cell (SOFC)
Exercise 5.17 – Use of hydrocarbons in SOFCs
Exercise 5.18 – Thermodynamic study of methane reforming in SOFC
Exercise 5.19 – Electrochemical integrator
Solutions to exercises
Solution 5.1 – Determination of standard free enthalpy of formation for AgCl
Solution 5.2 – Measurement of thermodynamic quantities of metal fluorides
Solution 5.3 – Measurement of O2− ion activity in a molten salt
Solution 5.4 – Calculation of equilibrium constants for defect formation in Cu2O
Solution 5.5 – TiS2: insertion material
Solution 5.6 – Chlorine sensor based on doped strontium chloride
Solution 5.7 – CO2 sensor (a)
Solution 5.8 – CO2 sensor (b)
Solution 5.9 – Sulfur oxide sensor
Solution 5.10 – Oxygen semiconductor sensor
Solution 5.11 – Amperometric oxygen sensor
Solution 5.12 – Coulometric oxygen sensor
Solution 5.13 – Nitrogen oxide sensor
Solution 5.14 – The sodium-sulfur battery
Solution 5.15 – General information on fuel cells
Solution 5.16 – Solid oxide fuel cell (SOFC)
Solution 5.17 – Use of hydrocarbons in SOFCs
Solution 5.18 – Thermodynamic study of methane reforming in SOFC
Solution 5.19 – Electrochemical integrator
Appendix – Fick’s laws of diffusion
Bibliography
Glossary
Index