Electrodeposition from Ionic Liquids

Edited by distinguished experts in this expanding field and with specialist contributions, this overview is the first of its kind to focus on electrodeposition from ionic liquids. This second edition has been completely revised and updated with approximately 20% new content and has been expanded by five chapters to cover the following topics: -Bulk and Interface Theory -Nanoscale Imaging including AFM, In situ STM and UHV-STM -Impedance Spectroscopy -Process Scale-up including Brighteners -Speciation and Redox Properties. The result is essential reading for electrochemists, materials scientists, chemists in industry, physical chemists, chemical engineers, inorganic and organic chemists.

Table of Contents:
List of Contributors xvii Abbreviations xxi 1 Why Use Ionic Liquids for Electrodeposition? 1 Andrew P. Abbott, Frank Endres, and Douglas R. Macfarlane 1.1 Nonaqueous Solutions 2 1.2 Ionic Fluids 3 1.3 What Is an Ionic Liquid? 4 1.4 Technological Potential of Ionic Liquids 6 1.5 Conclusions 11 References 12 2 Synthesis of Ionic Liquids 17 Tom Beyersdorff, Thomas J. S. Schubert, UrsWelz-Biermann,Will Pitner, Andrew P. Abbott, Katy J. McKenzie, and Karl S. Ryder 2.1 Nanostructured Metals and Alloys Deposited from Ionic Liquids 17 Thomas J. S. Schubert References 24 2.2 Air- andWater-Stable Ionic Liquids 26 Thomas J. S. Schubert References 35 2.3 Eutectic-Based Ionic Liquids 38 Andrew P. Abbott References 50 3 Physical Properties of Ionic Liquids for Electrochemical Applications 55 Hiroyuki Ohno 3.1 Introduction 55 3.2 Thermal Properties 55 3.3 Viscosity 62 3.4 Density 64 3.5 Refractive Index 65 3.6 Polarity 67 3.7 Solubility of Metal Salts 73 3.8 Electrochemical Properties 76 3.9 Conclusion and Future Prospects 86 Acknowledgments 86 References 86 4 Electrodeposition of Metals 95 4.1 Electrodeposition in AlCl3-Based Ionic Liquids 95 Thomas Schubert References 103 4.2 Electrodeposition of Refractory Metals from Ionic Liquids 104 Giridhar Pulletikurthi, Natalia Borisenko, and Frank Endres References 115 4.3 Deposition of Metals from Nonchloroaluminate Eutectic Mixtures 119 Andrew P. Abbott and Karl S. Ryder References 131 4.4 Troublesome Aspects 132 Andrew P. Abbott and Frank Endres References 137 4.5 Complexation and Redox Behavior ofMetal Ions in Ionic Liquids 137 References 151 5 Electrodeposition of Alloys 157 I-Wen Sun and Po-Yu Chen 5.1 Introduction 157 5.2 Electrodeposition of Al-Containing Alloys from Chloroaluminate Ionic Liquids 160 5.3 Electrodeposition of Zn-Containing Alloys from Chlorozincate Ionic Liquids 167 5.4 Fabrication of a Porous Metal Surface by Electrochemical Alloying and Dealloying 170 5.5 Nb–Sn 171 5.6 Air- andWater-Stable Ionic Liquids 171 5.7 Deep Eutectic Solvents 178 5.8 Summary 182 References 183 6 Electrodeposition of Semiconductors from Ionic Liquids 187 Natalia Borisenko, Abhishek Lahiri, and Frank Endres 6.1 Introduction 187 6.2 Group IV Semiconductors 188 6.3 II–VI Compound Semiconductors 196 6.4 III–V Compound Semiconductors 198 6.5 Other Compound Semiconductors 201 6.6 Conclusions 202 References 204 7 Conducting Polymers 211 JenniferM. Pringle 7.1 Introduction 211 7.2 Electropolymerization – General Experimental Procedures 214 7.3 Synthesis of Conducting Polymers in Chloroaluminate ILs 219 7.4 Synthesis of Conducting Polymers in Air- andWater-Stable ILs 221 7.5 Characterization 235 7.6 Conclusions and Outlook 244 References 245 8 Nanostructured Materials 253 8.1 Nanostructured Metals and Alloys Deposited from Ionic Liquids 253 Rolf Hempelmann and Harald Natter Acknowledgments 273 References 274 8.2 Electrodeposition of Ordered Macroporous Materials from Ionic Liquids 278 Yao Li and Jiupeng Zhao References 288 8.3 Electrodeposition of Nanowires from Ionic Liquids 289 I-Wen Sun and Po-Yu Chen Acknowledgment 302 References 303 8.4 Electrochemical Synthesis of Nanowire Electrodes for Lithium Batteries 304 Sherif Zein El Abedin Acknowledgments 317 References 317 9 Ionic Liquid–Solid Interfaces 321 Hua Li, Timo Carstens, Aaron Elbourne, Natalia Borisenko, René Gustus, Frank Endres, and Rob Atkin 9.1 Introduction 321 9.2 IL–Au(111) Interface 322 9.3 IL–HOPG Interface 327 9.4 Influence of Solutes on the IL–Electrode Interfacial Structure 332 9.5 Thin Films of Ionic Liquids in Ultrahigh Vacuum (UHV) 335 9.6 Outlook 339 References 339 10 Plasma Electrochemistry with Ionic Liquids 345 Jürgen Janek, Marcus Rohnke, Manuel Pölleth, and Sebastian A.Meiss 10.1 Introduction 345 10.2 Concepts and Principles 346 10.3 Early Studies 351 10.4 The Stability of Ionic Liquids in Plasma Experiments 355 10.5 Plasma Electrochemical Metal Deposition in Ionic Liquids 359 10.6 Conclusions and Outlook 367 Acknowledgments 368 References 368 11 Impedance Spectroscopy on Electrode | Ionic Liquid Interfaces 373 Jens Wallauer, Marco Balabajew, and Bernhard Roling 11.1 Introduction 373 11.2 Measurement: Basics and Pitfalls 378 11.3 Analysis of Experimental Data 381 11.4 Application: IL Interfaces at Metal Electrodes 387 References 395 12 Technical Aspects 401 12.1 Metal Dissolution Processes 401 Andrew P. Abbott,Wrya Karim, and Karl S. Ryder References 408 12.2 Reference Electrodes for Use in Room-Temperature Ionic Liquids 408 Douglas R. MacFarlane References 422 12.3 Process Scale-Up 424 Andrew P. Abbott References 436 12.4 Toward Regeneration and Reuse of Ionic Liquids in Electroplating 438 Daniel Watercamp and Jorg Thöming Acknowledgments 453 References 453 12.5 Impurities 457 Andrew P. Abbott, Frank Endres and Douglas MacFarlane A.1 Protocol for the Deposition of Zinc from a Type III Ionic Liquid 467 A.1.1 Preparation of Ionic Liquids 467 A.2 Electroplating Experiment 467 A.2.1 Method 467 A.2.2 Safety Precautions 468 References 468 13 Plating Protocols 469 Frank Endres, Sherif Zein El Abedin, Douglas R.MacFarlane, Karl S. Ryder, and Andrew P. Abbott 13.1 Electrodeposition of Al from [C2mim]Cl/AlCl3 469 13.2 Electrodeposition of Al from 1-Butyl-3-methylimidazoliumchloride–AlCl3–Toluene 472 13.3 Electrodeposition of Al from [C2mim] NTf2/AlCl3 473 13.4 Electrodeposition of Al from [C4mpyr]NTf2/AlCl3 476 13.5 Electrodeposition of Li from [C4mpyr]NTf2/LiNTf2 477 13.6 Electrodeposition of Ta from [C4mpyr]NTf2 479 13.7 Electrodeposition of Zinc Coatings from a Choline Chloride: Ethylene-Glycol-Based Deep Eutectic Solvent 480 13.8 Electrodeposition of Nickel Coatings from a Choline Chloride: Ethylene-Glycol-Based Deep Eutectic Solvent 481 References 482 14 Future Directions and Challenges 483 Frank Endres, Andrew P. Abbott, and Douglas MacFarlane 14.1 Impurities 483 14.2 Counter Electrodes/Compartments 485 14.3 Ionic Liquids for Reactive (Nano)materials 486 14.4 Nanomaterials/Nanoparticles 486 14.5 Cation/Anion Effects 487 14.6 Polymers for Batteries and Solar Cells 487 14.7 Variable-Temperature Studies 488 14.8 Intrinsic Process Safety 488 14.9 Economics (Price, Recycling) 489 14.10 Fundamental Knowledge Gaps 490 Index 491

About the Author :
Frank Endres studied chemistry and physics at Saarland University, Germany, gaining his doctorate in 1996. He obtained his lecturing qualification at Karlsruhe University in 2002, since when he has been a full professor at Clausthal University of Technology. Andrew Abbott gained his PhD in electrochemistry from Southampton University in 1989. Following post-doctoral studies at the universities of Connecticut and Liverpool, he became a lecturer at the University of Leicester in 1993, and Professor of Physical Chemistry there in 2005. Since 1999, Professor Abbott has been Research Director of Scionix Ltd. Professor Doug MacFarlane leads the Monash Ionic Liquids Group at Monash University. He is currently the holder of an Australian Research Council Laureate Fellowship. He is also the Program Leader of the Energy Program in the Australian Centre of Excellence for Electromaterials Science. His group focuses on a range of aspects of ionic liquids and their application in the energy sciences and sustainable chemistry. Professor MacFarlane was a BSc(Hons) graduate of Victoria University of Wellington, New Zealand and then undertook his graduate work in the Angell group at Purdue University, Indiana, graduating in 1983. After postdoctoral fellowships in France and New Zealand he took up an academic position at Monash. He has been a Professor of Chemistry at Monash since 1995 and was Head of School 2003-2006.