Electrodeposition from Ionic Liquids

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.

• List of Contributors xviiAbbreviations xxi1 Why Use Ionic Liquids for Electrodeposition? 1Andrew P. Abbott, Frank Endres, and Douglas R. Macfarlane1.1 Nonaqueous Solutions 21.2 Ionic Fluids 31.3 What Is an Ionic Liquid? 41.4 Technological Potential of Ionic Liquids 61.5 Conclusions 11References 122 Synthesis of Ionic Liquids 17Tom Beyersdorff, Thomas J. S. Schubert, UrsWelz-Biermann,Will Pitner, Andrew P. Abbott, Katy J. McKenzie, and Karl S. Ryder2.1 Nanostructured Metals and Alloys Deposited from Ionic Liquids 17Thomas J. S. SchubertReferences 242.2 Air- andWater-Stable Ionic Liquids 26Thomas J. S. SchubertReferences 352.3 Eutectic-Based Ionic Liquids 38Andrew P. AbbottReferences 503 Physical Properties of Ionic Liquids for Electrochemical Applications 55Hiroyuki Ohno3.1 Introduction 553.2 Thermal Properties 553.3 Viscosity 623.4 Density 643.5 Refractive Index 653.6 Polarity 673.7 Solubility of Metal Salts 733.8 Electrochemical Properties 763.9 Conclusion and Future Prospects 86Acknowledgments 86References 864 Electrodeposition of Metals 954.1 Electrodeposition in AlCl3-Based Ionic Liquids 95Thomas SchubertReferences 1034.2 Electrodeposition of Refractory Metals from Ionic Liquids 104Giridhar Pulletikurthi, Natalia Borisenko, and Frank EndresReferences 1154.3 Deposition of Metals from Nonchloroaluminate Eutectic Mixtures 119Andrew P. Abbott and Karl S. RyderReferences 1314.4 Troublesome Aspects 132Andrew P. Abbott and Frank EndresReferences 1374.5 Complexation and Redox Behavior ofMetal Ions in Ionic Liquids 137References 1515 Electrodeposition of Alloys 157I-Wen Sun and Po-Yu Chen5.1 Introduction 1575.2 Electrodeposition of Al-Containing Alloys from Chloroaluminate Ionic Liquids 1605.3 Electrodeposition of Zn-Containing Alloys from Chlorozincate Ionic Liquids 1675.4 Fabrication of a Porous Metal Surface by Electrochemical Alloying and Dealloying 1705.5 Nb–Sn 1715.6 Air- andWater-Stable Ionic Liquids 1715.7 Deep Eutectic Solvents 1785.8 Summary 182References 1836 Electrodeposition of Semiconductors from Ionic Liquids 187Natalia Borisenko, Abhishek Lahiri, and Frank Endres6.1 Introduction 1876.2 Group IV Semiconductors 1886.3 II–VI Compound Semiconductors 1966.4 III–V Compound Semiconductors 1986.5 Other Compound Semiconductors 2016.6 Conclusions 202References 2047 Conducting Polymers 211JenniferM. Pringle7.1 Introduction 2117.2 Electropolymerization – General Experimental Procedures 2147.3 Synthesis of Conducting Polymers in Chloroaluminate ILs 2197.4 Synthesis of Conducting Polymers in Air- andWater-Stable ILs 2217.5 Characterization 2357.6 Conclusions and Outlook 244References 2458 Nanostructured Materials 2538.1 Nanostructured Metals and Alloys Deposited from Ionic Liquids 253Rolf Hempelmann and Harald NatterAcknowledgments 273References 2748.2 Electrodeposition of Ordered Macroporous Materials from Ionic Liquids 278Yao Li and Jiupeng ZhaoReferences 2888.3 Electrodeposition of Nanowires from Ionic Liquids 289I-Wen Sun and Po-Yu ChenAcknowledgment 302References 3038.4 Electrochemical Synthesis of Nanowire Electrodes for Lithium Batteries 304Sherif Zein El AbedinAcknowledgments 317References 3179 Ionic Liquid–Solid Interfaces 321Hua Li, Timo Carstens, Aaron Elbourne, Natalia Borisenko, René Gustus, Frank Endres, and Rob Atkin9.1 Introduction 3219.2 IL–Au(111) Interface 3229.3 IL–HOPG Interface 3279.4 Influence of Solutes on the IL–Electrode Interfacial Structure 3329.5 Thin Films of Ionic Liquids in Ultrahigh Vacuum (UHV) 3359.6 Outlook 339References 33910 Plasma Electrochemistry with Ionic Liquids 345Jürgen Janek, Marcus Rohnke, Manuel Pölleth, and Sebastian A.Meiss10.1 Introduction 34510.2 Concepts and Principles 34610.3 Early Studies 35110.4 The Stability of Ionic Liquids in Plasma Experiments 35510.5 Plasma Electrochemical Metal Deposition in Ionic Liquids 35910.6 Conclusions and Outlook 367Acknowledgments 368References 36811 Impedance Spectroscopy on Electrode | Ionic Liquid Interfaces 373Jens Wallauer, Marco Balabajew, and Bernhard Roling11.1 Introduction 37311.2 Measurement: Basics and Pitfalls 37811.3 Analysis of Experimental Data 38111.4 Application: IL Interfaces at Metal Electrodes 387References 39512 Technical Aspects 40112.1 Metal Dissolution Processes 401Andrew P. Abbott,Wrya Karim, and Karl S. RyderReferences 40812.2 Reference Electrodes for Use in Room-Temperature Ionic Liquids 408Douglas R. MacFarlaneReferences 42212.3 Process Scale-Up 424Andrew P. AbbottReferences 43612.4 Toward Regeneration and Reuse of Ionic Liquids in Electroplating 438Daniel Watercamp and Jorg ThömingAcknowledgments 453References 45312.5 Impurities 457Andrew P. Abbott, Frank Endres and Douglas MacFarlaneA.1 Protocol for the Deposition of Zinc from a Type III Ionic Liquid 467A.1.1 Preparation of Ionic Liquids 467A.2 Electroplating Experiment 467A.2.1 Method 467A.2.2 Safety Precautions 468References 46813 Plating Protocols 469Frank Endres, Sherif Zein El Abedin, Douglas R.MacFarlane, Karl S. Ryder, and Andrew P. Abbott13.1 Electrodeposition of Al from [C2mim]Cl/AlCl3 46913.2 Electrodeposition of Al from 1-Butyl-3-methylimidazoliumchloride–AlCl3–Toluene 47213.3 Electrodeposition of Al from [C2mim] NTf2/AlCl3 47313.4 Electrodeposition of Al from [C4mpyr]NTf2/AlCl3 47613.5 Electrodeposition of Li from [C4mpyr]NTf2/LiNTf2 47713.6 Electrodeposition of Ta from [C4mpyr]NTf2 47913.7 Electrodeposition of Zinc Coatings from a Choline Chloride: Ethylene-Glycol-Based Deep Eutectic Solvent 48013.8 Electrodeposition of Nickel Coatings from a Choline Chloride: Ethylene-Glycol-Based Deep Eutectic Solvent 481References 48214 Future Directions and Challenges 483Frank Endres, Andrew P. Abbott, and Douglas MacFarlane14.1 Impurities 48314.2 Counter Electrodes/Compartments 48514.3 Ionic Liquids for Reactive (Nano)materials 48614.4 Nanomaterials/Nanoparticles 48614.5 Cation/Anion Effects 48714.6 Polymers for Batteries and Solar Cells 48714.7 Variable-Temperature Studies 48814.8 Intrinsic Process Safety 48814.9 Economics (Price, Recycling) 48914.10 Fundamental Knowledge Gaps 490Index 491

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