Electrochromic Materials and Devices
By: Roger J. Mortimer (Editor), David R. Rosseinsky (Editor), Paul M. S. Monk (Editor)
eBook | 23 July 2015 | Edition Number 1
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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.
on
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-Goran 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 Gratzel 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. Cordoba 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
Bjorn 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-Goran 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 ? 624
A.3 Write-Erase Efficiency 624
A.4 Cycle Life 624
A.5 Coloration Efficiency ? 625
Index 627
ISBN: 9783527679874
ISBN-10: 3527679871
Published: 23rd July 2015
Format: ePUB
Language: English
Number of Pages: 672
Audience: General Adult
Publisher: Wiley
Country of Publication: DE
Edition Number: 1
