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E-raamat: Electrochemical Engineering Across Scales: From Molecules to Processes

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In Volume XV in the series "Advances in Electrochemical Science and Engineering" various leading experts from the field of electrochemical engineering share their insights into how different experimental and computational methods are used in transferring molecular-scale discoveries into processes and products. Throughout, the focus is on the engineering problem and method of solution, rather than on the specific application, such that scientists from different backgrounds will benefit from the flow of ideas between the various subdisciplines.

A must-read for anyone developing engineering tools for the next-generation design and control of electrochemical process technologies, including chemical, mechanical and electrical engineers, as well as chemists, physicists, biochemists and materials scientists.
Series Preface XI
Preface XIII
List of Contributors XVII
1 The Role of Electrochemical Engineering in Our Energy Future 1(6)
L. Louis Hegedus
References
5(2)
2 The Path from Invention to Product for the Magnetic Thin Film Head 7(52)
Lubomyr T. Romankiw
Sol Krongelb
2.1 Introduction
7(1)
2.2 The State of the Art in the 1960's
8(6)
2.2.1 The Processor
10(1)
2.2.2 Memory
10(1)
2.2.3 Data Storage
11(3)
2.2.4 Electroplating Technology
14(1)
2.3 Finding the Right Path to Production
14(8)
2.3.1 First Demonstrations of a Thin Film Head
14(2)
2.3.2 Interdisciplinary Design of a Functional Head
16(2)
2.3.3 Early Tie-in to Manufacturing
18(3)
2.3.4 The Integration of Many Inventions
21(1)
2.4 Key Inventions for Thin Film Head Production
22(28)
2.4.1 Device Structures
24(1)
2.4.2 The Plating Process
24(9)
2.4.2.1 The Paddle Cell
25(4)
2.4.2.2 The Electroplating Bath, Deposition Parameters, and Controls
29(4)
2.4.3 Patterning
33(11)
2.4.3.1 Through-mask Plating
33(4)
2.4.3.2 Frame Plating
37(4)
2.4.3.3 Ancillary Issues in Pattern Plating
41(3)
2.4.4 Materials
44(6)
2.4.4.1 Magnetic Materials Studies
44(1)
2.4.4.2 Hard-Baked Resist as Insulation
45(5)
2.5 Concluding Thoughts
50(5)
2.5.1 Fabrication Technology — the Key to a Manufactured Product
50(1)
2.5.2 Matching Product and Process
51(1)
2.5.3 An Interdisciplinary Combination of Science, Engineering, and Intuition
52(3)
Acknowledgments
55(1)
References
55(4)
3 Electrochemical Surface Processes and Opportunities for Material Synthesis 59(48)
Stanko R. Brankovic
Giovanni Zangari
3.1 Introduction
59(1)
3.2 Underpotential Deposition (UPD)
60(3)
3.3 Metal Deposition via Surface-Limited Redox Replacement of Underpotentially Deposited Metal Layer
63(13)
3.3.1 General Description
63(1)
3.3.2 Stoichiometry of SLRR Reactions and Deposition Process
64(2)
3.3.3 Driving Force for SLRR Reaction and Nucleation Rate of Depositing Metal
66(3)
3.3.4 Reaction Kinetics of Surface-Limited Redox Replacement
69(5)
3.3.5 Future Directions
74(2)
3.4 Underpotential Codeposition (UPCD)
76(25)
3.4.1 Energetics: Beyond the Thermodynamic Approximation
78(2)
3.4.1.1 Ion Adsorption at the Electrode/Electrolyte Interface
78(1)
3.4.1.2 Potential of Zero Charge (PZC)
79(1)
3.4.1.3 Surface Defects, Reconstruction, and Segregation
79(1)
3.4.1.4 Atomistic Description of the Growth Process
80(1)
3.4.2 Kinetics
80(5)
3.4.3 Equilibrium Alloy Structure and Phase Formation
85(7)
3.4.3.1 Binary Alloys Forming Solid Solutions and Ordered Compounds
86(1)
3.4.3.2 Intermetallic Compounds
87(3)
3.4.3.3 Alloys Immiscible in the Bulk
90(2)
3.4.4 Structure and Morphology of UPCD Alloy Films
92(3)
3.4.4.1 Crystallographic Structure and Microstructure
92(2)
3.4.4.2 Film Morphology
94(1)
3.4.5 Applications of UPCD Growth Methods
95(25)
3.4.5.1 Catalysis and Electrocatalysis
96(1)
3.4.5.2 Photovoltaics
97(2)
3.4.5.3 Magnetic Recording and Microsystems
99(2)
Acknowledgments
101(1)
References
101(6)
4 Mathematical Modeling of Self-Organized Porous Anodic Oxide Films 107(38)
Kurt R. Hebert
4.1 Introduction
107(1)
4.2 Phenomenology of Porous Anodic Oxide Formation
108(10)
4.3 Mechanisms for Porous Anodic Oxide Formation
118(2)
4.4 Elements of Porous Anodic Oxide Models
120(8)
4.4.1 Ionic Migration Fluxes and Field Equations
120(2)
4.4.2 Bulk Motion of Oxide
122(1)
4.4.3 Interfacial Reactions
123(2)
4.4.4 Boundary Conditions
125(1)
4.4.5 Interface Motion
126(2)
4.5 Modeling Results
128(13)
4.5.1 Steady-State Porous Layer Growth
128(2)
4.5.2 Linear Stability Analysis
130(3)
4.5.3 Morphology Evolution
133(8)
4.6 Summary and Outlook
141(1)
References
141(4)
5 Engineering of Self-Organizing Electrochemistry: Porous Alumina and Titania Nanotubes 145(48)
Chong-Yong Lee
Patrik Schmuki
5.1 Introduction
145(2)
5.2 Formation and Growth of TiO2 and Al2O3 Nanotubes/Pores
147(14)
5.2.1 General Aspects of Electrochemical Anodization and Self-Organization
147(2)
5.2.2 Some Critical Factors/Aspects in the Self-Organization Phenomenology
149(12)
5.2.2.1 Duplex or Double Wall Structure of Al2O3 and TiO2
152(1)
5.2.2.2 Tubes versus Pores
153(1)
5.2.2.3 Geometry Control
154(7)
5.3 Improved Ordering via Nanopatterning
161(3)
5.3.1 Al2O3
162(1)
5.3.2 TiO2
163(1)
5.4 Crystallinity and Composition
164(1)
5.5 Applications
165(16)
5.5.1 Anodic Al2O3 as Template Materials
166(2)
5.5.2 Anodic TiO2 for Dye-Sensitized Solar Cells
168(9)
5.5.2.1 Tube Geometry
170(3)
5.5.2.2 Crystallinity
173(1)
5.5.2.3 Approaches to Enhance the Surface Area
174(1)
5.5.2.4 Doping
175(2)
5.5.2.5 Single Wall Morphology
177(1)
5.5.3 Prospect for Commercialization
177(21)
5.5.3.1 Processing Speed
177(1)
5.5.3.2 Design: Backside versus Front-Side Illumination
178(2)
5.5.3.3 Flexible Substrate
180(1)
5.5.3.4 Scale-Up
180(1)
5.5.3.5 Long-Term Stability
181(1)
5.6 Conclusions
181(1)
References
182(11)
6 Diffusion-Induced Stress within Core-Shell Structures and Implications for Robust Electrode Design and Materials Selection 193(34)
Mark W. Verbrugge
Yue Qi
Daniel R. Baker
Yang-Tse Cheng
6.1 Introduction
193(2)
6.2 Ab initio Simulations: Informing Continuum Models
195(3)
6.3 Governing Equations for the Continuum Model
198(10)
6.3.1 Thermodynamics
198(1)
6.3.2 Solute Diffusion
199(1)
6.3.3 Solid Mechanics
200(5)
6.3.4 Analytic Solution for Initial Stress Distribution
205(3)
6.4 Results and Discussion
208(13)
6.4.1 Initial Condition
209(3)
6.4.2 Transient Behavior
212(3)
6.4.3 Application to a Host-SEI Core-Shell System
215(6)
6.5 Summary and Conclusions
221(1)
References
221(6)
7 Cost-Based Discovery for Engineering Solutions 227(36)
Brian L. Spatocco
Donald R. Sadoway
7.1 Introduction
227(3)
7.1.1 The Winds of Change: Integrating Intermittent Renewables
227(2)
7.1.2 Cost is the Determining Factor
229(1)
7.1.3 The Path Forward
230(1)
7.2 The Liquid Metal Battery as a Grid Storage Solution
230(11)
7.2.1 Principles of Operation
230(1)
7.2.2 Strengths and Weaknesses
231(3)
7.2.2.1 Scientific Advantages
231(1)
7.2.2.2 Technology Scale-Up
232(1)
7.2.2.3 Market Flexibility
233(1)
7.2.3 Review of Competitive Technologies
234(1)
7.2.4 Down-Selection
235(6)
7.2.4.1 Cost
235(2)
7.2.4.2 Temperature
237(2)
7.2.4.3 Scalability
239(2)
7.3 Historical Odyssey
241(15)
7.3.1 Molten Salts in Sodium Electrodeposition
241(4)
7.3.2 Molten Salts in Nuclear Reactor Development
245(7)
7.3.2.1 Aggregated Properties
245(1)
7.3.2.2 Corrosion Mechanisms
246(6)
7.3.3 Molten Salts in Energy Storage Devices
252(3)
7.3.4 The Window of Opportunity
255(1)
7.4 Project Description
256(1)
7.5 Conclusion
257(1)
References
257(6)
8 Multiscale Study of Electrochemical Energy Systems 263(60)
Hany El-Sayed
Alois Knoll
Ulrich Stimming
8.1 Introduction
263(2)
8.2 Architectures of Energy Systems
265(16)
8.2.1 The System and Its Boundary Conditions
266(2)
8.2.2 Architectures of Multiscale Energy Systems
268(7)
8.2.3 Agent-Based Approaches for Run-Time Simulation and Optimization
275(6)
8.3 The Big Picture
281(4)
8.3.1 Centralized versus Decentralized Systems
281(1)
8.3.2 Decentralized Energy Systems: a Closer Look
282(3)
8.4 Storage Components
285(7)
8.4.1 How to Store Energy
285(1)
8.4.2 Selected Energy Storage Devices
286(5)
8.4.2.1 Li-Ion Batteries
286(2)
8.4.2.2 Post Li-Ion Batteries
288(2)
8.4.2.3 Redox Flow Batteries
290(1)
8.4.3 Application to a City Block
291(1)
8.5 Conversion Components, DEFC
292(7)
8.5.1 Introduction to DEFC
292(3)
8.5.2 Ethanol versus Other Fuels
295(1)
8.5.3 Indirect versus Direct Ethanol Fuel Cell
295(4)
8.5.3.1 Effect of Temperature on DEFC Performance
297(1)
8.5.3.2 Stack Hardware and Design
297(2)
8.6 Materials and Molecular Processes
299(16)
8.6.1 DEFC Components
299(1)
8.6.2 MEA and Electrodes
300(1)
8.6.3 DEFC Processes
301(2)
8.6.3.1 Ethanol Oxidation Reaction in Acidic Media
301(2)
8.6.4 Anode Catalysts
303(5)
8.6.4.1 Pt—Sn as DEFC Anode Catalyst
304(1)
8.6.4.2 Ethanol Oxidation Reaction in Alkaline Media
305(1)
8.6.4.3 Elevated Temperature Direct Ethanol Fuel Cell Membranes — Pros and Cons
305(3)
8.6.5 Model Catalysts
308(7)
8.6.5.1 Creating Nanostructured Model Surfaces
309(1)
8.6.5.2 Acidic Media
310(3)
8.6.5.3 Alkaline Media
313(1)
8.6.5.4 A Few Words about Cathode Catalysts (Conventional and MeOH Tolerant Catalysts)
314(1)
8.7 Conclusions — Folding It Back
315(1)
Acknowledgments
316(1)
References
316(7)
Index 323
Richard C. Alkire is Professor Emeritus of Chemical & Biomolecular Engineering Charles and Dorothy Prizer Chair at the University of Illinois, Urbana, USA. He obtained his degrees at Lafayette College and University of California at Berkeley. He has received numerous prizes, including Vittorio de Nora Award and Lifetime National Associate award from National Academy.

Philip N. Bartlett is Head of the Electrochemistry Section, Deputy Head of Chemistry for Strategy, and Associate Dean for Enterprise in the Faculty of Natural and Environmental Sciences at the University of Southampton. He received his PhD from Imperial College London and was a Lecturer at the University of Warwick and a Professor for Physical Chemistry at the University of Bath, before moving to his current position. His research interests include bioelectrochemistry, nanostructured materials, and chemical sensors.

Jacek Lipkowski is Professor at the Department of Chemistry and Biochemistry at the University of Guelph, Canada. His research interests focus on surface analysis and interfacial electrochemistry. He has authored over 120 publications and is a member of several societies, including a Fellow of the International Society of Electrochemistry.
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