Electrochromic Materials and Devices

Electrochromic materials can change their properties under the influence of an electrical voltage or current. Different classes of materials show this behavior such as transition metal oxides, conjugated polymers, metal-coordinated complexes and organic molecules. As the color change is persistent, the electric field needs only to be applied to initiate the switching, allowing for applications such as low-energy consumption displays, light-adapting mirrors in the automobile industry and smart windows for which the amount of transmitted light and heat can be controlled. The first part of this book describes the different classes and processing techniques of electrochromic materials. The second part highlights nanostructured electrochromic materials and device fabrication, and the third part focuses on the applications such as smart windows, adaptive camouflage, biomimicry, wearable displays and fashion. The last part rounds off the book by device case studies and environmental impact issues.

Table of Contents:
Preface xix Acknowledgements xxi List of Contributors xxiii Part I Electrochromic Materials and Processing 1 1 Electrochromic Metal Oxides: An Introduction to Materials and Devices 3 Claes-Göran Granqvist 1.1 Introduction 3 1.2 Some Notes on History and Early Applications 5 1.3 Overview of Electrochromic Oxides 6 1.4 Transparent Electrical Conductors and Electrolytes 23 1.5 Towards Devices 30 1.6 Conclusions 33 Acknowledgement 33 References 33 2 Electrochromic Materials Based on Prussian Blue and Other Metal Metallohexacyanates 41 David R. Rosseinsky and Roger J. Mortimer 2.1 The Electrochromism of Prussian Blue 41 2.2 Metal Metallohexacyanates akin to Prussian Blue 48 2.3 Copper Hexacyanoferrate 49 References 50 3 Electrochromic Materials and Devices Based on Viologens 57 Paul M. S. Monk, David R. Rosseinsky, and Roger J. Mortimer 3.1 Introduction, Naming and Previous Studies 57 3.2 Redox Chemistry of Bipyridilium Electrochromes 58 3.3 Physicochemical Considerations for Including Bipyridilium Species in ECDs 61 3.4 Exemplar Bipyridilium ECDs 72 3.5 Elaborations 78 References 81 4 Electrochromic Devices Based on Metal Hexacyanometallate/Viologen Pairings 91 Kuo-Chuan Ho, Chih-Wei Hu, and Thomas S. Varley 4.1 Introduction 91 4.2 Hybrid (Solid-with-Solution) Electrochromic Devices 93 4.3 All-Solid Electrochromic Devices 97 4.4 Other Metal Hexacyanometallate-Viologen-Based ECDs 104 4.5 Prospects for Metal Hexacyanometallate-Viologen-Based ECDs 105 References 106 5 Conjugated Electrochromic Polymers: Structure-Driven Colour and Processing Control 113 Aubrey L. Dyer, Anna M. Österholm, D. Eric Shen, Keith E. Johnson, and John R. Reynolds 5.1 Introduction and Background 113 5.2 Representative Systems 123 5.3 Processability of Electrochromic Polymers 152 5.4 Summary and Perspective 168 Acknowledgements 169 References 169 6 Electrochromism within Transition-Metal Coordination Complexes and Polymers 185 Yu-Wu Zhong 6.1 Electronic Transitions and Redox Properties of Transition-Metal Complexes 185 6.2 Electrochromism in Reductively Electropolymerised Films of Polypyridyl Complexes 187 6.3 Electrochromism in Oxidatively Electropolymerised Films of Transition-Metal Complexes 192 6.4 Electrochromism in Self-Assembled or Self-Adsorbed Multilayer Films of Transition-Metal Complexes 196 6.5 Electrochromism in Spin-Coated or Drop-Cast Thin Films of Transition-Metal Complexes 200 6.6 Conclusion and Outlook 204 Acknowledgements 205 References 205 7 Organic Near-Infrared Electrochromic Materials 211 Bin Yao, Jie Zhang, and Xinhua Wan 7.1 Introduction 211 7.2 Aromatic Quinones 212 7.3 Aromatic Imides 216 7.4 Anthraquinone Imides 218 7.5 Poly(triarylamine)s 221 7.6 Conjugated Polymers 228 7.7 Other NIR Electrochromic Materials 235 7.8 Conclusion 236 References 237 8 Metal Hydrides for Smart-Window Applications 241 Kazuki Yoshimura 8.1 Switchable-Mirror Thin Films 241 8.2 Optical Switching Property 242 8.3 Switching Durability 243 8.4 Colour in the Transparent State 244 8.5 Electrochromic Switchable Mirror 245 8.6 Smart-Window Application 246 References 247 Part II Nanostructured Electrochromic Materials and Device Fabrication 249 9 Nanostructures in Electrochromic Materials 251 Shanxin Xiong, Pooi See Lee, and Xuehong Lu 9.1 Introduction 251 9.2 Nanostructures of Transition Metal Oxides (TMOs) 253 9.3 Nanostructures of Conjugated Polymers 262 9.4 Nanostructures of Organic-Metal Complexes and Viologen 267 9.5 Electrochromic Nanocomposites and Nanohybrids 268 9.6 Conclusions and Perspective 281 References 282 10 Advances in Polymer Electrolytes for Electrochromic Applications 289 Alice Lee-Sie Eh, Xuehong Lu, and Pooi See Lee 10.1 Introduction 289 10.2 Requirements of Polymer Electrolytes in Electrochromic Applications 290 10.3 Types of Polymer Electrolytes 291 10.4 Polymer Hosts of Interest in Electrochromic Devices 294 10.5 Recent Trends in Polymer Electrolytes 303 10.6 Future Outlook 305 References 307 11 Gyroid-Structured Electrodes for Electrochromic and Supercapacitor Applications 311 Maik R.J. Scherer and Ullrich Steiner 11.1 Introduction to Nanostructured Electrochromic Electrodes 311 11.2 Polymer Self-Assembly and the Gyroid Nanomorphology 315 11.3 Gyroid-Structured Vanadium Pentoxide 320 11.4 Gyroid-Structured Nickel Oxide 326 11.5 Concluding Remarks 329 References 331 12 Layer-by-Layer Assembly of Electrochromic Materials: On the Efficient Method for Immobilisation of Nanomaterials 337 Susana I. Córdoba de Torresi, Jose R. Martins Neto, Marcio Vidotti, and Fritz Huguenin 12.1 Introduction to the Layer-by-Layer Deposition Technique 337 12.2 Layer-by-Layer Assembly in Electrochromic Materials 337 12.3 Layer-by-Layer Assembly of Metal Oxides 342 12.4 Layer-by-Layer and Electrophoretic Deposition for Nanoparticles Immobilisation 351 Acknowledgements 357 References 357 13 Plasmonic Electrochromism of Metal Oxide Nanocrystals 363 Anna Llordes, Evan L. Runnerstrom, Sebastien D. Lounis, and Delia J. Milliron 13.1 Introduction to Plasmonic Electrochromic Nanocrystals 363 13.2 History of Electrochromism in Metal and Semiconductor Nanocrystals 368 13.3 Doped Metal Oxide Colloidal Nanocrystals as Plasmonic Electrochromic Materials 377 13.4 Advanced Electrochromic Electrodes Constructed from Colloidal Plasmonic NCs 383 13.5 Conclusions and Outlook 393 References 394 Part III Applications of Electrochromic Materials 399 14 Solution-Phase Electrochromic Devices and Systems 401 Harlan J. Byker 14.1 Introduction 401 14.2 Early History of Solution-Phase EC 402 14.3 The World’s Most Widely Used Electrochromic Material 405 14.4 Commercialisation of EC Devices 406 14.5 Reversibility and Stability in Solution-Phase EC Systems 409 14.6 Thickened and Gelled Solution-Phase Systems 411 14.7 Nernst Equilibrium, Disproportionation and Stability 413 14.8 Closing Remarks 415 References 416 15 Electrochromic Smart Windows for Dynamic Daylight and Solar Energy Control in Buildings 419 Bjørn Petter Jelle 15.1 Introduction 419 15.2 Solar Radiation 421 15.3 Solar Radiation through Window Panes and Glass Structures 421 15.4 Solar Radiation Modulation by Electrochromic Windows 425 15.5 Experimental 427 15.6 Measurement and Calculation Method of Solar Radiation Glazing Factors 430 15.7 Spectroscopic Measurement and Calculation of Solar Radiation Glazing Factors 452 15.8 Commercial Electrochromic Windows and the Path Ahead 475 15.9 Increased Application of Solar Radiation Glazing Factors 476 15.10 Conclusions 476 Acknowledgements 477 15.A Appendix: Tables for Calculation of Solar Radiation Glazing Factors 477 15.B Appendix: Tables for Calculation of Thermal Conductance 488 References 492 16 Fabric Electrochromic Displays for Adaptive Camouflage, Biomimicry, Wearable Displays and Fashion 503 Michael T. Otley, Michael A. Invernale, and Gregory A. Sotzing 16.1 Introduction 503 16.2 Non-Electrochromic Colour-Changing Fabric 517 16.3 Conclusion 519 References 521 Part IV Device Case Studies, Environmental Impact Issues and Elaborations 525 17 Electrochromic Foil: A Case Study 527 Claes-Göran Granqvist 17.1 Introduction 527 17.2 Device Design and Optical Properties of Electrochromic Foil 528 17.3 Comments on Lifetime and Durability 532 17.4 Electrolyte Functionalisation by Nanoparticles 538 17.5 Comments and Conclusion 541 Acknowledgements 542 References 542 18 Life Cycle Analysis (LCA) of Electrochromic Smart Windows 545 Uwe Posset and Matthias Harsch 18.1 Life Cycle Analysis 545 18.2 Application of LCA to Electrochromic Smart Windows 549 18.3 LCA of Novel Plastic-Film-Based Electrochromic Devices 560 18.4 LCA for EC Target Applications 564 18.5 Conclusion 568 References 568 19 Electrochromic Glazing in Buildings: A Case Study 571 John Mardaljevic, Ruth Kelly Waskett, and Birgit Painter 19.1 Introduction 571 19.2 Variable Transmission Glazing for Use in Buildings 573 19.3 Case Study: The De Montfort EC Office Installation 584 19.4 Summary 591 References 591 20 Photoelectrochromic Materials and Devices 593 Kuo-Chuan Ho, Hsin-Wei Chen, and Chih-Yu Hsu 20.1 Introduction 593 20.2 Structure Design of the PECDs 594 References 620 Appendix Definitions of Electrochromic Materials and Device Performance Parameters 623 Roger J. Mortimer, Paul M. S. Monk, and David R. Rosseinsky A.1 Contrast Ratio CR 623 A.2 Response Time τ 624 A.3 Write–Erase Efficiency 624 A.4 Cycle Life 624 A.5 Coloration Efficiency η 625 References 625 Index 627

About the Author :
Paul M. S. Monk received his PhD in the electrochemistry of novel electrochromic viologen species at Exeter University in 1989. A postdoctoral research fellow position (1989-91) at the University of Aberdeen, in Scotland, was followed by lecturing positions in Physical Chemistry at Manchester Polytechnic (1991-2) then Manchester Metropolitan University (1992-2007). He is currently employed as a Vicar in an inner-city parish in Oldham, Greater Manchester, UK. Roger J. Mortimer was Professor in Physical Chemistry at Loughborough University between 2006 and his untimely death in 2015. He graduated from Imperial College London with a PhD in heterogeneous catalysis at sold-liquid interfaces. After a postdoctoral research fellowship (1980-81) and visiting associate in chemistry (1988) at the California Institute of Technology, he became demonstrator and a Research Assistant at Exeter University. Lecturing positions in Physical Chemistry ensued at Anglia Ruskin University (1984-87) and Analytical Chemistry at Sheffield Hallam University (1987-89), followed by his appointment as a Lecturer in Physical Chemistry at Loughborough University in 1989. David R. Rosseinsky is an Emeritus Professor and Honorary Research Fellow in Physics at Exeter University, having been Reader in Physical Chemistry there from 1979-1998. After Rhodes University he pursued studies leading to PhD then DSc on charge transfer interactions at Manchester University. Following a sojourn at the University of Pennsylvania, from 1959 he became a lecturer at the University of the Witwatersrand in Johannesburg and in 1961, lecturer at Exeter University. With his ex research-student H Kellawi (by then Prof at Damascus University, on sabbatical), they studied Prussian blue and other electrochromic systems, extended in an invited appointment to SIMTech, Singapore, 2000-2002.