Hong Meng, PhD, works in the School of Advanced Materials in the Shenzhen Graduate School at Peking University in Shenzhen, China. He obtained his doctorate from the University of California, Los Angeles in 2002.

• Preface xiiiAbout the Author xiv1 Introduction 11.1 General Introduction 11.2 The History of Electrochromic Materials 31.3 The Key Parameters of Electrochromism 51.3.1 Electrochromic Contrast 51.3.2 Switching Time 81.3.3 Coloration Efficiency 91.3.4 Optical Memory 111.3.5 Stability 121.4 Conclusion 14References 142 Advances in Polymer Electrolytes for Electrochromic Applications 172.1 Introduction 172.2 Requirements of Polymer Electrolytes in Electrochromic Applications 182.3 Types of Polymer Electrolytes 202.3.1 Gel Polymer Electrolytes (GPEs) 202.3.1.1 PEO-/PEG-Based Electrolytes 212.3.1.2 PMMA-Based Polymer Electrolytes 212.3.1.3 PVDF-Based Polymer Electrolytes 222.3.2 Self-Healing Polymer Electrolytes 242.3.3 Cross-Linking Polymer Electrolytes (CPEs) 262.3.4 Ceramic Polymer Electrolytes 272.3.5 Ionic Liquid Polymer Electrolytes 302.3.6 Gelatin-Based Polymer Electrolytes 322.4 Conclusion and Future Outlook 33References 403 Electrochromic Small Molecules 493.1 Background of Small Molecule Electrochromic 493.2 Technology Development of Small Molecule Electrochromic Materials 503.3 Violene–Cyanine Hybrids (AIE PL OEC) 503.4 Terephthalate Derivatives (Multicolor OEC) 563.4.1 Conclusion 633.5 Isophthalate Derivatives 643.5.1 Conclusion 793.6 Methyl Ketone Derivatives 793.6.1 Conclusion 843.7 Diphenylacetylenes 843.8 Fluoran Dye Derivatives 853.9 PH-Responsive Molecule Derivatives 923.10 TPA Dye Derivatives 953.11 Hydrocarbon Derivatives-NIR-OEC 993.12 Conclusions and Perspective 101References 1014 Viologen OEC 1054.1 The Introduction of OEC and Viologen 1054.1.1 General Introduction 1054.1.2 Research History of Viologen 1054.1.2.1 First Stage (1930s–1970s) 1074.1.2.2 Second Stage (1970s–2000s) 1074.1.2.3 Third Stage (2000s–2010s) 1074.1.2.4 Fourth Stage (2010s–Present) 1084.1.3 Electrochromism and Electrochemistry of Viologens and Their Device 1094.2 Different Structures of Viologen-Based Electrochromic Materials 1104.2.1 Synthesis of Viologens 1104.2.1.1 Direct Substitution Reaction 1104.2.1.2 Zincke Reaction 1104.2.1.3 Methods for Synthesizing Bipyridine 1104.2.2 The 1,1 Substituted Viologen 1114.2.2.1 Simple Alkyl 1114.2.2.2 Acid Group 1114.2.2.3 Ester and Nitrogen Heterocycle 1124.2.2.4 Asymmetric Substitution 1134.2.3 Conjugate Ring System Expansion 1134.2.3.1 Thiazolothiazole (TTz) Unit 1134.2.3.2 Perylenediimide (PDI) Unit 1154.2.3.3 PBEDOTPh 1154.2.3.4 Heteroatoms Bridged 1154.2.3.5 Bithiophene Bridged 1184.2.4 Viologen-Based Polymer 1194.2.4.1 Viologen in the Side Chain 1204.2.4.2 Viologen in the Main Chain 1224.3 Viologen Electrochromic Device 1244.3.1 Device Structure 1244.3.1.1 Five-Layer Classic Structure 1244.3.1.2 Simple Sandwich Structure 1254.3.1.3 Cathodic Anode Separation Structure 1254.3.1.4 Reflective Device Structure 1264.3.2 Electrolyte 1264.3.3 Redox Mediator 1264.3.4 Conductive Medium 1284.3.5 Problems with Viologen Compound 1284.3.5.1 Dimerization 1284.3.5.2 Aggregation and Solubility 1314.3.5.3 Response Time 1314.3.5.4 Driving Voltage 1314.3.5.5 Conclusion 1314.3.6 Examples of Viologen-Based ECD 1324.4 Companies Operating in the Field of Viologen Electrochromism 1324.4.1 Gentex 1324.4.2 Essilor 1344.4.3 Haoruo 1344.5 Conclusion 134References 1355 Metallohexacyanates 1435.1 Background 1435.2 Technology Development of PB 1445.3 Crystal Structure 1445.4 Electrochromic Mechanism 1455.5 Synthesis 1475.6 Electrochromic Devices (ECDs) 1505.7 Nanocomposites 1545.8 PB Analogs 1605.9 Multifunctional Applications 170References 1756 Electrochromic Conjugated Polymers (ECPs) 1836.1 Introduction 1836.1.1 Common Categories and Operation Mechanism 1836.1.2 Synthetic Methods 1866.2 Thiophene-Based Conjugated Electrochromic Polymers 1906.2.1 Introduction 1906.2.2 Color-Tuning Strategies for Thiophene-Based Polymers 1916.2.2.1 Steric Effects 1926.2.2.2 Substituent and Electronic Effects 1936.2.3 Typical Colored Polymers 1956.2.3.1 Yellow and Orange 1966.2.3.2 Red 1986.2.3.3 Magenta and Purple 1996.2.3.4 Black 2026.2.3.5 Multicolored 2036.2.3.6 Anodically Coloring Polymers 2056.2.4 Water- or “Green Solvents”-Soluble ECPs 2086.3 Polypyrroles-Based Conjugated Electrochromic Polymers 2166.3.1 Introduction 2166.3.2 Electrochromic Properties of Polypyrroles (PPy) 2186.3.3 Tuning of Electrochromic Properties of Polypyrrole (PPy) 2186.3.3.1 Structural Modification 2186.3.3.2 3- and 3,4-Substituted Polypyrroles 2356.3.3.3 Donor–Acceptor Approach 2366.3.3.4 Terarylene Systems 2376.4 Polycarbazole-Based Conjugated Electrochromic Polymers 2376.4.1 Introduction 2376.4.2 Electrochromic Properties of Polycarbazoles (PCARB) 2386.4.3 Electrochromic Properties of Polycarbazoles Derivatives 2386.4.3.1 Linear Polycarbazole Derivatives 2416.4.3.2 Cross-Linked Polycarbazoles Derivatives 249References 2607 TA-Based Electrochromic Polyimides and Polyamides 2697.1 Introduction 2697.1.1 Aromatic Polyimides and Polyamides 2697.1.2 Triarylamine-Based Aromatic Polymers 2707.1.3 Electrochemical and Electrochromic Behaviors of MV Triarylamine Systems 2727.2 Development of TA-Based Electrochromic Polyimides and Polyamides 2727.2.1 Side Group Engineering 2767.2.1.1 Introduction of Protecting Groups 2767.2.1.2 Introduction of Electroactive Groups to Achieve Color Tuning of EC Material 2777.2.1.3 Introduction of Side Groups to Achieve Electrofluorochromic Materials 2787.2.1.4 Introduction of Other Functional Side Groups to Achieve Multiple Functions EC Material 2817.2.2 Backbone Modulation 2837.2.2.1 Extending the Polymer Backbone by Introducing More Electroactive Groups 2837.2.2.2 Introduction of Amide Linkage into Polyimide Backbone 2857.2.2.3 Introduction of Ether Linkage into PIs/PAs Backbone 2857.2.2.4 Introduction of Alicyclic Structures into PIs/PAs Backbone 2887.3 Conclusions 290References 2908 Metallo-Supermolecular Polymers 2958.1 Introduction 2958.2 Single Metallic System 2968.2.1 Fe(II)- and Ru(II)-Based Metallo-Supramolecular Polymers 2968.2.2 CoII-Based Metallo-Supramolecular Polymers 2998.2.3 ZnII-Based Metallo-Supramolecular Polymers 3018.2.4 Cu-Based Metallo-Supramolecular Polymers 3058.2.5 EuIII-Based Metallo-Supramolecular Polymers 3088.3 Hetero-Metallic System 3118.4 The Fabrication Method of Metallopolymer Film 3148.4.1 Layer-by-Layer Self-Assembly and Dip-Coating Methods 3148.4.2 Electropolymerized Conducting Metallopolymers 3158.5 Conclusion 323References 3239 Metal-Organic Framework (MOF)- and Covalent Organic Framework (COF)-Based Electrochromism (EC) 3279.1 Introduction 3279.2 Current Studies in EC MOFs 3279.2.1 The Organic Linkers in EC MOFs 3289.2.1.1 NDI-Based Organic Linkers 3289.2.1.2 Other Organic Linkers 3329.2.2 The Transport of Electrolyte Ions in EC MOFs 3359.2.3 Special EC MOFs 3389.2.3.1 Photochromic and Electrochromic Multi-Responsive MOF 3389.2.3.2 MOF-Based Double-Sided EC Device and Other Color-Switching Mechanisms 3399.2.3.3 EC Base on “Guest@MOF” Composite System 3409.3 Current Studies in EC COFs 3419.4 Conclusion and Prospect 348References 34810 Nanostructure-Based Electrochromism 35310.1 Introduction 35310.2 Current Studies of Nanostructure in Electrochromism 35410.2.1 Non-Electrochromic Active Materials as a Template for ECs 35410.2.1.1 Photonic Crystals as Templates for ECs 35410.2.1.2 Plasmonic Structures as Templates for ECs 35910.2.2 Nanostructured Electrochromic Materials in ECs 36510.3 Conclusion and Prospect 369References 36911 Organic Electroluminochromic Materials 37311.1 Introduction 37311.2 Conventional Mechanisms of Electroluminochromism 37511.2.1 Intrinsic Mechanism 37511.2.2 Electron Transfer (ET) Mechanism 37611.2.3 Energy Transfer (EnT) Mechanism 37611.3 Electroluminochromic Performance Parameters 37611.3.1 Emission Contrast 37611.3.2 Switching Time 37711.3.3 Long-Term Stability/Cycle Life 37711.4 Classical Materials 37811.4.1 Small Molecules 37811.4.1.1 Small Molecular Dyads 37811.4.1.2 Redox-Active Moiety and Luminophores System 38011.4.1.3 Electroactive Luminophores 38211.4.2 Transition Metal Complexes 38611.4.3 Polymers 38711.4.3.1 Non-Conjugated Polymers 38711.4.3.2 Conjugated Polymers 39611.4.4 Nanocomposite Films 40711.5 Future Perspectives and Conclusion 408References 40812 Organic Photoelectrochromic Devices 41512.1 Introduction 41512.2 Structure Design of PECDs 41712.2.1 Power Supply for PECD 41712.2.1.1 DSSC-Based PECD 41812.2.1.2 PSC-Based PECD 42312.2.1.3 OPV-Based PECD 42312.2.2 Electrochromic Materials in PECD 42512.2.2.1 Small Molecule 42512.2.2.2 Conducting Polymers 42712.2.2.3 Near-Infrared (NIR) Electrochromic Materials 43312.2.3 Electrolytes in PECD 43512.2.4 Substrates in PECD 43512.3 Future Perspectives and Conclusion 436References 43613 Application of OEC Devices 44513.1 Smart Window 44513.1.1 The Structure andWorking Mechanism of Smart Windows 44513.1.2 The Materials for Electrochromic Windows 44613.1.3 Prospects 45013.2 Dimmable Rearview Mirror 45013.3 Sensors 45113.3.1 Application of Electrochromic Sensors on Food Preservation 45113.3.2 Application in Bio-Sensing 45413.4 The Application of Electrochromic Device in Display 46013.5 Other Applications of OEC 462References 46914 Commercialized OEC Materials and Related Analysis of Company Patents 47114.1 General Introduction 47114.2 Gentex Corporation 47114.3 Ricoh Company, Ltd. 47514.4 Canon Inc. 47614.5 BOE Technology Group Co., Ltd. and OPPO Guangdong Mobile Communications Co., Ltd. 47714.6 Other Important Enterprises 48114.6.1 Ninbo Ninuo Electronic Technology Co., Ltd. 48114.6.2 Ambilight Inc. 48314.6.3 Furcifer Inc. 48314.6.4 Changzhou Spectrum New Material Co. Ltd. 48414.7 Conclusion 485References 48515 Main Challenges for the Commercialization of OEC 49115.1 Introduction 49115.2 The Long-Term Stability of OEC Materials 49115.3 The Mechanical Stability of OEC Devices (Encapsulation Technology) 49515.4 Large-Area Process Technology: Spray Coating and Roll-to-Roll Processes 49815.4.1 Inkjet Printing 49815.4.2 Spray Coating 50015.4.3 Slot-Die Coating 50015.4.4 Screen Printing 50115.5 Conclusions and Perspective 501References 502Index 505

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