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, Rene 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
Jurgen Janek, Marcus Rohnke, Manuel Polleth, 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 Thoming
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
