Skip to main content

Electrochromic Materials and Devices

Electrochromic Materials and Devices

Roger J. Mortimer (Editor), David R. Rosseinsky (Editor), Paul M. S. Monk (Editor)

ISBN: 978-3-527-33610-4

Oct 2015

672 pages

In Stock

$270.00

Description

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.

Preface XIX

Acknowledgements XXI

List of Contributors XXIII

Part I ElectrochromicMaterials and Processing 1

1 ElectrochromicMetal 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

1.3.1 RecentWork on Electrochromic Oxide Thin Films 7

1.3.2 Optical and Electronic Effects 9

1.3.3 Charge Transfer Absorption in Tungsten Oxide 11

1.3.4 Ionic Effects 14

1.3.5 On the Importance of Thin-Film Deposition Parameters 18

1.3.6 Electrochromism in Films of Mixed Oxide: TheW–Ni-Oxide System 21

1.4 Transparent Electrical Conductors and Electrolytes 23

1.4.1 Transparent Electrical Conductors: Oxide Films 25

1.4.2 Transparent Electrical Conductors: Metal-Based Films 26

1.4.3 Transparent Electrical Conductors: Nanowire-Based Coatings and Other Alternatives 27

1.4.4 Electrolytes: Some Examples 29

1.5 Towards Devices 30

1.5.1 Six Hurdles for Device Manufacturing 31

1.5.2 Practical Constructions of Electrochromic Devices 32

1.6 Conclusions 33

2 ElectrochromicMaterials Based on Prussian Blue and Other Metal Metallohexacyanates 41
David R. Rosseinsky and Roger J. Mortimer

2.1 The Electrochromism of Prussian Blue 41

2.1.1 Introduction 41

2.1.2 Electrodeposited PB Film and Comparisons with Bulk PB 42

2.1.3 PB Prepared from Direct Cell Reaction, with No Applied Potential 45

2.1.4 Layer-by-Layer Deposition of PB 46

2.1.5 PB on Graphene 46

2.1.6 Alternative Preparations of PB: PB from Colloid and Similar Origins 46

2.1.7 Alternative Electrolytes Including Polymeric for PB Electrochromism 47

2.2 Metal Metallohexacyanates akin to Prussian Blue 48

2.2.1 Ruthenium Purple RP 48

2.2.2 Vanadium Hexacyanoferrate 48

2.2.3 Nickel Hexacyanoferrate 48

2.3 Copper Hexacyanoferrate 49

2.3.1 Palladium Hexacyanoferrate 49

2.3.2 Indium Hexacyanoferrate and Gallium Hexacyanoferrate 49

2.3.3 Miscellaneous PB Analogues as Hexacyanoferrates 49

2.3.4 Mixed-Metal and Mixed-Ligand PB Analogues Listed 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

3.3.1 Type-1 Viologen Electrochromes 61

3.3.2 Type-2 Viologen Electrochromes 61

3.3.3 Type-3 Viologen Electrochromes 68

3.4 Exemplar Bipyridilium ECDs 72

3.4.1 The Philips Device 72

3.4.2 The ICI Device 72

3.4.3 The IBM Device 74

3.4.4 The Gentex Device 74

3.4.5 The NTERA Device 76

3.4.6 The NanoChromics Cell 76

3.4.7 The Grätzel Device 78

3.5 Elaborations 78

3.5.1 The Use of Pulsed Potentials 79

3.5.2 Electropolychromism 79

3.5.3 Viologen Electrochemiluminescence 79

3.5.4 Viologens Incorporated within Paper 80

4 Electrochromic Devices Based on Metal Hexacyanometallate/Viologen Pairings 91
Kuo-Chuan Ho, Chih-Wei Hu, and Thomas S. Varley

4.1 Introduction 91

4.1.1 Overview of Prussian Blue and Viologen Electrochromic Devices 92

4.2 Hybrid (Solid-with-Solution) Electrochromic Devices 93

4.2.1 Prussian Blue and Heptyl Viologen Solid-with-Solution-Type ECD 93

4.2.1.1 Preparation and Characterisation of PBThin Film and HV(BF4)2 94

4.2.1.2 Redox Behaviours and Visible Spectra of the PB Film and HV(BF4)2 Solution 94

4.2.1.3 Operating Parameters and Properties of PHECD 95

4.2.1.4 Analogous Devices 96

4.2.2 PBThin Film and Viologen in Ionic Liquid–Based ECD 97

4.3 All-Solid Electrochromic Devices 97

4.3.1 Prussian Blue and Poly(butyl viologen) Thin-Film ECD 97

4.3.1.1 Preparation of Poly(butyl viologen)Thin Film 97

4.3.1.2 Electrochemical and Optical Properties of Poly(butyl viologen) Thin Films 98

4.3.1.3 Electrochromic Performance of PBV-PB ECD 99

4.3.2 Prussian Blue and Viologen Anchored TiO2-Based ECD 99

4.3.3 Polypyrrole-Prussian Blue Composite Film and Benzylviologen Polymer–Based Thin-Film-Type ECD 100

4.3.3.1 Preparation of PP-PBThin-Film 101

4.3.3.2 Performance of the PP-PB Thin-Film and pBPQ-Based Electrochromic Device 101

4.3.4 PBThin-Film and Viologen-Doped Poly(3,4-ethylenedioxythiopene) Polymer–Based ECD 102

4.3.5 Other Solid-State Viologens 103

4.4 Other Metal Hexacyanometallate-Viologen-Based ECDs 104

4.5 Prospects for Metal Hexacyanometallate-Viologen-Based ECDs 105

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

5.1.1 Source of Electrochromism in Conjugated Polymers 113

5.1.1.3 Steric Interactions 120

5.1.1.4 Fused Aromatics 122

5.2 Representative Systems 123

5.2.1 Coloured-to-Transmissive Polymers 123

5.2.2 Anodically Colouring 139

5.2.3 Inducing Multicoloured States in ECPs 143

5.3 Processability of Electrochromic Polymers 152

5.3.1 Electrochemical Polymerisation 152

5.3.2 Functionalisation of ECPs for Achieving Organic Solubility 156

5.3.3 Aqueous Processability and Compatibility 158

5.3.4 Methods for Patterning 165

5.4 Summary and Perspective 168

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-CastThin Films of Transition-Metal Complexes 200

6.6 Conclusion and Outlook 204

7 Organic Near-Infrared Electrochromic Materials 211
Bin Yao, Jie Zhang, and XinhuaWan

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

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

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

9.1.1 Why Nanostructures? 251

9.1.2 Classification of Nanostructural Electrochromic Materials 252

9.1.3 Preparation Method 253

9.2 Nanostructures of Transition Metal Oxides (TMOs) 253

9.2.1 Introduction 253

9.2.2 Single TMO Systems 257

9.2.3 Binary TMO Systems 261

9.3 Nanostructures of Conjugated Polymers 262

9.3.1 Introduction 262

9.3.2 Polythiophene and Its Derivatives 263

9.3.3 Polyaniline 264

9.3.4 Polypyrrole 266

9.4 Nanostructures of Organic-Metal Complexes and Viologen 267

9.4.1 Introduction 267

9.4.2 Organic-Metal Complexes 267

9.4.3 Viologens 268

9.5 Electrochromic Nanocomposites and Nanohybrids 268

9.5.1 Introduction 268

9.5.2 Nanocomposites of Electrochromic Materials 269

9.5.3 Nanocomposites of Electrochromic/Non-Electrochromic Active Materials 274

9.6 Conclusions and Perspective 281

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

10.3.1 Solid Polymer Electrolytes (SPEs) 292

10.3.2 Gel Polymer Electrolytes (GPEs) 292

10.3.3 Polyelectrolytes 293

10.3.4 Composite Polymer Electrolytes (CPEs) 294

10.4 Polymer Hosts of Interest in Electrochromic Devices 294

10.4.1 PEO/PEG-Based Polymer Electrolytes 295

10.4.2 PMMA-Based Polymer Electrolytes 296

10.4.3 PVDF-Based Polymer Electrolytes 297

10.4.4 Ionic Liquid–Based Polymer Electrolytes 300

10.4.5 Poly(propylene carbonate) (PPC)-Based Polymer Electrolytes 302

10.5 Recent Trends in Polymer Electrolytes 303

10.5.1 Flexible, Imprintable, Bendable and Shape-Conformable Polymer Electrolytes 303

10.5.2 Potentially 'Green' Biodegradable Polymer Electrolytes Using Naturally Available Polymer Host 303

10.6 Future Outlook 305

10.6.1 Recent Trends in Electrochromic Devices 305

10.6.2 Challenges in Creating Versatile Polymer Electrolytes for EC Devices 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

11.1.1 Three-Dimensional Nanostructuring Strategies 313

11.2 Polymer Self-Assembly and the Gyroid Nanomorphology 315

11.2.1 Copolymer Microphase Separation 315

11.2.2 Double-Gyroid 316

11.2.3 Synthesis of Mesoporous DG Templates 318

11.3 Gyroid-Structured Vanadium Pentoxide 320

11.3.1 Electrochemical Characterisation of V2O5 Electrodes 322

11.3.2 Electrochromic Displays Based on V2O5 Electrodes 322

11.3.3 Electrochromic V2O5 Supercapacitors 324

11.4 Gyroid-Structured Nickel Oxide 326

11.4.1 Electrochromic Displays Based on NiO Electrodes 328

11.5 Concluding Remarks 329

12 Layer-by-Layer Assembly of ElectrochromicMaterials: 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

12.2.1 Layer-by-Layer Assembly of Conjugated Conducting Polymers 338

12.2.2 Layer-by-Layer Assembly of Intervalence Charge Transfer Coloration Materials 340

12.3 Layer-by-Layer Assembly of Metal Oxides 342

12.3.1 Tungsten Oxide 344

12.3.2 Hexaniobate 346

12.3.3 Vanadium Oxide 346

12.3.4 Titanium Oxide 348

12.3.5 Nickel Hydroxide 349

12.4 Layer-by-Layer and Electrophoretic Deposition for Nanoparticles Immobilisation 351

12.4.1 Comparing Layer-by-Layer and Electrophoretic Deposition 351

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

13.3.1 Colloidal Synthesis of Doped Metal Oxide Nanocrystals 377

13.3.2 Plasmonic Electrochromic Electrodes Based on Colloidal ITO and AZO Nanocrystals 379

13.3.3 Design Principles for Nanocrystal-Based Plasmonic Electrochromics 382

13.4 Advanced Electrochromic Electrodes Constructed from Colloidal Plasmonic NCs 383

13.4.1 NIR-Selective Mesoporous Architectured Electrodes Based on Plasmonic Colloidal Nanocrystals 384

13.4.2 Dual-Band Nanocrystal-in-Glass Composite Electrodes Based on Plasmonic Colloidal Nanocrystals and Conventional Electrochromic Materials 385

13.4.3 Other Advanced Composite Electrochromic Electrodes Obtained from Non-Colloidal Approaches 391

13.5 Conclusions and Outlook 393

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

15 Electrochromic SmartWindows 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 throughWindow Panes and Glass Structures 421

15.4 Solar Radiation Modulation by Electrochromic Windows 425

15.5 Experimental 427

15.5.1 Glass Samples and Window Pane Configurations 427

15.5.2 UV-VIS-NIR Spectrophotometry 428

15.5.3 Emissivity Determination by Specular IR Reflectance 428

15.5.4 Emissivity Determination by Heat Flow Meter 428

15.5.5 Emissivity Determination by Hemispherical Reflectance 429

15.5.6 Actual Emissivity Determinations inThis Study 430

15.6 Measurement and Calculation Method of Solar Radiation Glazing Factors 430

15.6.1 Ultraviolet Solar Transmittance 430

15.6.2 Visible Solar Transmittance 431

15.6.3 Solar Transmittance 431

15.6.4 Solar Material Protection Factor (SMPF) 432

15.6.5 Solar Skin Protection Factor (SSPF) 433

15.6.6 External Visible Solar Reflectance 434

15.6.7 Internal Visible Solar Reflectance 434

15.6.8 Solar Reflectance 435

15.6.9 Solar Absorbance 436

15.6.10 Emissivity 436

15.6.11 Solar Factor (SF) 440

15.6.12 Colour Rendering Factor (CRF) 449

15.6.13 Additional Heat Transfer 451

15.6.14 Number of Glass Layers in a Window Pane 452

15.6.15 General Calculation Procedures 452

15.7 Spectroscopic Measurement and Calculation of Solar Radiation Glazing Factors 452

15.7.1 Spectroscopic Data for Float Glass and Low Emittance Glass 453

15.7.2 Spectroscopic Data for Dark Silver Coated Glass 455

15.7.3 Spectroscopic Data for Electrochromic Windows 456

15.7.4 Solar Radiation Glazing Factors for Float Glass, Low Emittance Glass, Dark Silver Coated Glass and Two-Layer and Three-Layer Window Pane Configurations 461

15.7.5 Solar Radiation Glazing Factors for Electrochromic Windows 465

15.7.6 Miscellaneous Other Electrochromic Properties 470

15.8 Commercial Electrochromic Windows and the Path Ahead 475

15.9 Increased Application of Solar Radiation Glazing Factors 476

15.10 Conclusions 476

15.A Appendix: Tables for Calculation of Solar Radiation Glazing Factors 477

15.B Appendix: Tables for Calculation ofThermal Conductance 488

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

16.1.1 Colour-Changing Technologies Background 504

16.1.2 Previous Work 505

16.1.3 Conductivity Trends of PEDOT-PSS Impregnated Fabric and the Effect of Conductivity on Electrochromic Textile 510

16.1.4 The Effects of Coloured-Based Fabric on Electrochromic Textile 513

16.1.5 Other Electrochromic Fabric 514

16.2 Non-Electrochromic Colour-Changing Fabric 517

16.2.1 Thermochromic Fabric 517

16.2.2 Photochromic Fabric 517

16.2.3 LED and LCD Technology 518

16.3 Conclusion 519

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

18 Life Cycle Analysis (LCA) of Electrochromic SmartWindows 545
Uwe Posset and Matthias Harsch

18.1 Life Cycle Analysis 545

18.2 Application of LCA to Electrochromic SmartWindows 549

18.3 LCA of Novel Plastic-Film-Based Electrochromic Devices 560

18.4 LCA for EC Target Applications 564

18.4.1 Automotive Sunroof Case 564

18.4.2 Appliance Example:Window Case for a House-Hold Oven 566

18.4.3 Aircraft CabinWindow Case 567

18.5 Conclusion 568

19 Electrochromic Glazing in Buildings: A Case Study 571
John Mardaljevic, Ruth KellyWaskett, and Birgit Painter

19.1 Introduction 571

19.1.1 Daylight in Buildings 572

19.1.2 The Importance of View 572

19.2 Variable Transmission Glazing for Use in Buildings 573

19.2.1 Chromogenic Glass 573

19.2.2 VTG Performance Characteristics 574

19.2.3 EC Product Details and Practicalities 577

19.2.4 Operational Factors 578

19.2.5 Zoning of EC Glazing 580

19.2.6 Performance Prediction Using Building Simulation Tools 582

19.2.7 Occupant-Based Studies 583

19.3 Case Study:The De Montfort EC Office Installation 584

19.3.1 Background 584

19.3.2 Installation of the EC Glazing 585

19.3.3 Subjective Data Collection 587

19.3.4 Measurement of Physical Quantities 587

19.3.5 The Daylight Illumination Spectrum with EC Glazing 588

19.4 Summary 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

20.2.1 Separated-Type PECD (Type I):The Dye-Sensitised TiO2 Layer is Separated from the Electrochromic Layer 594

20.2.1.1 Inorganic Materials as EC Layers 599

20.2.1.2 Conjugated Conducting Polymer Materials as EC Layers 604

20.2.2 Combined-Type PECD (Type II):The Dye-Sensitised TiO2 Layer is Combined with the Electrochromic Layer 610

20.2.3 Non-Symmetric-Type PECDs (Type III): The Active Area of the Dye-Sensitised TiO2 Layer is Non-Symmetric to the Electrochromic Layer 613

20.2.4 Parallel-Type PECDs: Where the Dye-Sensitised TiO2 Layer is Parallel and Separated with the Electrochromic Layer. The Electrolytes for Both Layers are Different forTheir Optimal Performance 616

20.2.5 Prospects 619

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

Index 627