Electrochemical Engineering

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.Marc Koper studied chemistry at Utrecht University and obtained his PhD (cum laude) with Prof. J.H. Sluyters from Utrecht University. He was a postdoctoral Marie Curie Fellow in the group of Prof. W. Schmickler at the University of Ulm (Germany). He then returned to the Netherlands to join the group of Prof. R.A. van Santen at Eindhoven University of Technology, where he initially was a Fellow of the Royal Netherlands Academy of Arts and Sciences and later associate professor. In 2005 he was appointed full professor in fundamental surface science at Leiden University.

• Series Preface xiPreface xiii1 Introductory Perspectives 1A. Paul Alivisatos andWojciech T. OsowieckiReferences 42 The Joint Center for Energy Storage Research: A New Paradigm of Research, Development, and Demonstration 7Thomas J. Carney, Devin S. Hodge, Lynn Trahey, and Fikile R. Brushett2.1 Background and Motivation 72.2 Lithium-ion Batteries: Current State of the Art 82.3 Beyond Li-Ion Batteries 92.4 JCESR Legacies and a New Paradigm for Research 92.5 The JCESR Team 132.6 JCESR Operational Tools 162.7 Intellectual Property Management 172.8 Communication Tools 172.9 JCESR Change Decision Process 172.10 Safety in JCESR 192.11 Battery Technology Readiness Level 202.12 JCESR Deliverables 212.13 Scientific Tools in JCESR 222.14 Techno-economic Modeling 232.14.1 Techno-economic Modeling of a Metal–Air System for Transportation Applications 232.14.2 Techno-economic Modeling of Flow Batteries for Grid Storage Applications 252.15 The Electrochemical Discovery Laboratory 272.15.1 The Effect of TraceWater on Beyond Li-ion Devices 272.15.2 Stability of Redox Active Molecules 282.16 Electrolyte Genome 282.16.1 Screening of Redox Active Molecules for Redox Flow 292.16.2 Examination of Multivalent Intercalation Materials 302.17 Combining the Electrolyte Genome with Techno-economic Modeling 312.18 Prototype Development 312.19 Legacy of JCESR 332.20 Conclusion 34Acknowledgments 34References 343 Determination of Redox Reaction Mechanisms in Lithium–Sulfur Batteries 41Kevin H.Wujcik, Dunyang R.Wang, Alexander A. Teran, Eduard Nasybulin, Tod A. Pascal, David Prendergast, and Nitash P. Balsara3.1 Basics of Lithium–Sulfur Chemistry 413.2 End Products of Electrochemical Reactions in the Sulfur Cathode 443.3 Intermediate Products of Electrochemical Reactions in the Sulfur Cathode 453.3.1 Reactions of S8 453.3.2 Reactions of Li2S8 463.3.3 Reactions of Li2S4 473.3.4 Reactions of Li2S2 483.3.5 Production of Radical Anions 493.4 Fingerprinting Lithium Polysulfide Intermediates 493.4.1 X-ray Absorption Spectroscopy 503.4.2 Electron Paramagnetic Resonance Spectroscopy 533.4.3 UV–Vis Spectroscopy 543.4.4 Raman Spectroscopy 573.4.5 Nuclear Magnetic Resonance Spectroscopy 573.5 In Situ Spectroscopic Studies of Li–S Batteries 583.5.1 X-ray Absorption Spectroscopy 583.5.2 Electron Paramagnetic Resonance Spectroscopy 593.5.3 UV–Vis Spectroscopy 603.5.4 Raman Spectroscopy 603.5.5 Nuclear Magnetic Resonance Spectroscopy 613.6 Practical Considerations 623.7 Concluding Remarks 64Acknowledgment 68References 684 From the Lab to Scaling-up Thin Film Solar Absorbers 75Hariklia Deligianni, Lubomyr T. Romankiw, Daniel Lincot, and Pierre-Philippe Grand4.1 Introduction 754.2 State-of-the-art Electrodeposition for Photovoltaics 794.2.1 Electrodeposited CuInGaSe2 (CIGS) 804.2.1.1 Metal Layers 804.2.1.2 Electrodeposition of Copper 814.2.1.3 Electrodeposition of Indium 824.2.1.4 Electrodeposition of Gallium 854.2.2 Single Cu—In—Ga—Se—O Multicomponent Chemistries 894.2.2.1 Cu—In—Se Co-deposition 894.2.2.2 Cu—In—Ga—Se Co-deposition 914.2.2.3 Cu—In—Ga—O Co-deposition 924.2.2.4 Cu—In—Ga Co-deposition 934.2.3 AnnealingMethods 934.2.4 Fabrication of Solar Cells 954.3 Electrodeposited Cu2ZnSn(Se,S)4 (CZTS) and Emerging Materials 974.3.1 Cu2ZnSn(Se,S)4 (CZTS) 974.4 From the Rotating Disk to the Paddle Cell as a Scale-up Platform 994.4.1 Introduction to Scale-up 994.4.2 Entirely New Solution Agitation Method 1004.4.3 The Paddle Agitation Technique Is More Readily Scalable 1014.4.4 Electrical Contact Between the Thin Seed Layer and the Source of Current 1034.4.5 Previous Scale-up of the Paddle Cell 1034.4.6 Scale-up of the Paddle Cell to 15 cm× 15 cm 1044.4.7 Scale-up of the Paddle Cell to 30 cm× 60 cm 1074.4.8 ImprovingWithin-Wafer Uniformity, Reproducibility, and Demonstration of Scalability 1084.4.8.1 Within-Wafer Uniformity 1084.4.8.2 Wafer-to-Wafer Reproducibility 1094.5 Scaling-up to 60 cm× 120 cm from Tiny Electrodes to Meters 1104.5.1 A 1 m2 min−1 Continuous Industrial Scale 1104.5.2 Bath Control 1164.5.2.1 Insoluble Anode 1184.5.2.2 Soluble Anode 1184.5.2.3 Bath Maintenance and Reproducibility and Steady-State Operation 1194.6 Conclusions 121Acknowledgments 122References 1235 Thin-film Head and the Innovator’s Dilemma 129Keishi Ohashi5.1 Introduction 1295.2 Thin-film Head Technology 1305.2.1 Magnetic Properties for HDD 1305.2.2 Permalloy 1305.2.3 Thin-film Head 1325.2.4 Magnetic Domain Noise 1335.3 Data Storage Business in Japan 1375.3.1 MagneticThin-films for HDD in the 1980s 1375.3.2 Use of Optics 1385.3.3 High-Moment Head Core Material 1385.3.4 High-Ms Write Heads 1415.4 The Innovator’s Dilemma 1425.4.1 Thin-film Head is not Disruptive 1425.4.2 Small HDD 1435.4.3 MR Head 1445.4.4 GMR Head 1455.5 TMR Head 1475.5.1 Infinite MR Ratio 1475.5.2 Suspicions Surrounding the TMR Head 1475.5.3 Low-Resistance TMR Head 1485.5.4 MGO:The Final Push 1505.5.5 Exploring New Markets 1515.6 Discussion 151Acknowledgments 152References 1536 Development of Fully-Continuous Electrokinetic Dewatering of Phosphatic Clay Suspensions 159Rui Kong, Arthur Dizon, Saeed Moghaddam, andMark E. Orazem6.1 Introduction 1596.1.1 Phosphatic Clay Suspensions 1606.1.2 Industrial Scope 1606.1.3 Why is Separation ofWater from Clay Difficult? 1616.2 Current Methods 1626.2.1 Flocculation 1626.2.2 Mechanical Dewatering 1636.2.3 Electrokinetic Separation 1636.3 Development of Dewatering Technologies for Phosphatic Clays 1646.3.1 Lab-scale Batch Dewatering 1656.3.2 Semi-continuous Operation to Recover Clear Supernatant 1686.3.3 Semi-continuous Operation to Recover Solids 1706.3.4 Continuous Operation 1726.3.5 Energy and Power Requirements for All Prototypes Tested 1756.4 Economic Assessment for On-site Implementation 1796.4.1 Hydrogen Emission 1796.4.2 Capital and Operation Costs 1806.4.2.1 Power and Energy consumption for On-site Operations 1816.4.2.2 Operation cost 1816.4.2.3 Capital Cost 1836.4.3 Results 1846.5 Our Next Prototype: Dual-zone Continuous Operation 1856.6 Conclusions 186Acknowledgments 187References 187Contents ix7 Breaking the Chemical Paradigm in Electrochemical Engineering: Case Studies and Lessons Learned from Plating to Polishing 193E. Jennings Taylor, Maria E. Inman, Holly M. Garich, Heather A. McCrabb, Stephen T. Snyder, and Timothy D. Hall7.1 Introduction 1937.1.1 Perspective 1947.2 A Brief Overview of Pulse Reverse Current Plating 1967.2.1 Mass Transport Effects in Pulse Current Plating 1987.2.2 Current Distribution Effects in Pulse Current Plating 2007.2.3 Grain Size Effects in Pulse Current Plating 2047.2.4 Current Efficiency Effects in Pulse Current Plating 2057.2.5 Concluding Remarks for Pulse Current Plating 2057.3 Early Developments in Pulse Plating 2067.3.1 LevelingWithout Levelers Using Pulse Reverse Current Plating 2077.3.2 DuctilityWithout Brighteners Using Pulse Current Plating 2107.4 Transition of Pulse Current Plating Concepts to Surface Finishing 2117.4.1 Pulse Voltage Deburring of Automotive Planetary Gears 2127.4.2 Transition to Pulse Reverse Voltage Electropolishing of Passive Materials 2147.4.3 Sequenced Pulse Reverse Voltage Electropolishing of Semiconductor Valves 2167.4.4 Pulse Reverse Voltage Electropolishing of Strongly Passive Materials 2207.4.5 Pulse Reverse Voltage Electropolishing of Niobium Superconducting Radio Frequency Cavities 2237.4.6 Transition Pulse Reverse Voltage Electropolishing to Niobium Superconducting Radio Frequency Cavities 2267.5 ConcludingThoughts 232Acknowledgments 233References 2348 The Interaction Between a Proton and the Atomic Network in Amorphous Silica Glass Made a Highly Sensitive Trace Moisture Sensor 241Yusuke Tsukahara, Nobuo Takeda, Kazushi Yamanaka, and Shingo Akao8.1 Unexpected Long Propagation of Surface AcousticWaves Around a Sphere 2418.2 Invention of a Ball SAWDevice and Application to Gas Sensors 2438.3 Unexpected Fluctuations in the Output Signal of the Gas Sensor Leading to the Development of Trace Moisture Sensors 2498.4 Sol–Gel Silica Film for the Trace Moisture Sensors 2538.5 A Thermodynamic Model of Interaction ofWater Vapor with Amorphous Silica Glass 2548.6 Concluding Remarks 257References 2579 From Sensors to Low-cost Instruments to Networks: Semiconducting Oxides as Gas-Sensitive Resistors 261David E.Williams9.1 Overview 2619.2 Basic Science of Semiconducting Oxides as Gas-Sensitive Resistors 2669.2.1 Multiscale Modeling of Gas-Sensitive Resistors 2669.2.1.1 Introduction 2669.2.1.2 Effective Medium Model 1: Rationalization of Composition Effects on Response 2689.2.1.3 Effective Medium Model 2: Diffusion–Reaction Effects on Response; Effects of Electrode Geometry and “Self-Diagnostic” Devices 2709.2.1.4 Microstructure Model: Percolation and Equivalent Circuit Representation 2779.2.2 Surface Segregation and Surface Modification Effects 2849.2.2.1 Surface Modification by “Poisoning” 2849.2.2.2 Surface Modification by Segregation 2869.2.2.3 Surface Grafting as a Means for Altering Response 2889.2.3 Surface Defect and Reaction Models 2889.3 Commercial Development of Sensors and Instruments 2919.3.1 Introduction 2919.3.2 Development of a Low-Cost Instrument for Measurement of Ozone in theAtmosphere 2989.3.3 Signal Drift Detection 3039.3.4 A Low-Cost Instrument for Measurement of Atmospheric Nitrogen Dioxide 3049.3.5 Networks of Instruments in the Atmosphere 3069.4 Conclusion and Prospects 311Acknowledgment 313References 314Index 323