In conventional polymer materials, mechanical performance is traditionally engineered via material structure, using motifs such as polymer molecular weight, polymer branching, or copolymer-block design1. Here, by means of a model system of 4-arm poly(ethylene glycol) hydrogels crosslinked with multiple, kinetically distinct dynamic metal-ligand coordinate complexes, we show that polymer materials with decoupled spatial structure and mechanical performance can be designed. By tuning the relative concentration of two types of metal-ligand crosslinks, we demonstrate control over the material’s mechanical hierarchy of energy-dissipating modes under dynamic mechanical loading, and therefore the ability to engineer a priori the viscoelastic properties of these materials by controlling the types of crosslinks rather than by modifying the polymer itself. This strategy to decouple material mechanics from structure may inform the design of soft materials for use in complex mechanical environments.

Control of hierarchical polymer mechanics with bioinspired metal-coordination dynamics

Electrochromic devices (ECDs) have been regarded as promising candidates for energy-saving smart windows, next-generation displays and wearable electronics due to their significant benefits of simple and adjustable structures, low power consumption, flexible and stretchable features, and eye-friendly modes for displays. However, there are many existing issues waiting to be solved such as durability, reversibility and inadequate switching performances. These insurmountable technical bottlenecks significantly slow down the commercialization of next-generation ECDs. Nanomaterials with superior active reaction surface area have played indispensable roles in optimizing heterogeneous electron transfer and homogeneous ion transfer for ECDs and other optoelectronic devices. In recent years, with the joint efforts of various outstanding research teams, new kinds and methods for nanomaterials to fabricate ECDs with excellent performances have been rapidly developing. This review highlights the latest exciting results regarding the design and application of new and unique nanomaterials for each layer of ECDs. Meanwhile, the structures, mechanisms, features and preparation of the reported nanomaterials to improve the electrochromic properties have been discussed in detail. In addition, the remaining challenges and corresponding strategies of this field are also proposed. Hopefully, this review can inspire more and more researchers to enrich the nanomaterials for ECDs and other related fields to overcome faced technical barriers by innovative means and promote industrialization of ECDs and other optoelectronic technologies.

Advances in nanomaterials for electrochromic devices

Dual-band electrochromic smart windows capable of the spectrally selective modulation of visible (VIS) light and near-infrared (NIR) can regulate solar light and solar heat transmittance to reduce the building energy consumption. The development of these windows is however limited by the number of available dual-band electrochromic materials. Here, plasmonic oxygen-deficient TiO2-x nanocrystals (NCs) are discovered to be an effective single-component dual-band electrochromic material, and that oxygen-vacancy creation is more effective than aliovalent substitutional doping to introduce dual-band properties to TiO2 NCs. Oxygen vacancies not only confer good near-infrared (NIR)-selective modulation, but also improve the Li+ diffusion in the TiO2-x host, circumventing the disadvantage of aliovalent substitutional doping with ion diffusion. Consequently optimized TiO2-x NC films are able to modulate the NIR and visible light transmittance independently and effectively in three distinct modes with high optical modulation (95.5% at 633 nm and 90.5% at 1200 nm), fast switching speed, high bistability, and long cycle life. An impressive dual-band electrochromic performance is also demonstrated in prototype devices. The use of TiO2-x NCs enables the assembled windows to recycle a large fraction of energy consumed in the coloration process ("energy recycling") to reduce the energy consumption in a round-trip electrochromic operation.

Plasmonic Oxygen-Deficient TiO2-x Nanocrystals for Dual-Band Electrochromic Smart Windows with Efficient Energy Recycling.

Bistable electrochromic materials have been explored as a viable alternative to reduce energy consumption in display applications. However, the development of ideal bistable electrochromic displays (especially multicolour displays) remains challenging due to the intrinsic limitations associated with existing electrochromic processes. Here, a bistable electrochromic device with good overall performance—including bistability (>52 h), reversibility (>12,000 cycles), colouration efficiency (≥1,240 cm2 C−1) and transmittance change (70%) with fast switching (≤1.5 s)—was designed and developed based on concerted intramolecular proton-coupled electron transfer. This approach was used to develop black, magenta, yellow and blue displays as well as a multicolour bistable electrochromic shelf label. The design principles derived from this unconventional exploration of concerted intramolecular proton-coupled electron transfer may also be useful in different optoelectronic applications. Electrochromic displays that are stable in the coloured state for up to 52 h with no applied voltage are fabricated using molecules hosting concerted intramolecular proton-coupled electron transfer processes.

A multicolour bistable electronic shelf label based on intramolecular proton-coupled electron transfer

Flexible Bicolorimetric Polyacrylamide/Chitosan Hydrogels for Smart Real-Time Monitoring and Promotion of Wound Healing

Bistable display has been a long-awaited goal due to its zero energy cost when maintaining colored or colorless state and electrochromic material has been highly considered as a potential way to achieve bistable display due to its simple structure and possible manipulation. However, it is extremely challenging with insurmountable technical barriers related to traditional electrochromic mechanisms. Herein a prototype for bistable electronic billboard and reader with high energy efficiency is demonstrated with excellent bistability (decay 7% in an hour), reversibility (104 cycles), coloration efficiency (430 cm2 C−1) and very short voltage stimulation time (2 ms) for color switching, which greatly outperforms current products. This is achieved by stabilization of redox molecule via intermolecular ion transfer to the supramolecular bonded colorant and further stabilization of the electrochromic molecules in semi-solid media. This promising approach for ultra-energy-efficient display will promote the development of switching molecules, devices and applications in various fields of driving/navigation/industry as display to save energy. For electrochromic materials to reach their full potential for high efficiency bistable displays, technical challenges related to their underlying mechanism must be addressed. Here, the authors, through intelligent molecular design, report a solid bistable device with state-of-the-art performance.

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Bio-inspired ultra-high energy efficiency bistable electronic billboard and reader

Thermoswitchable fluorescent materials (TFMs) have received special attention due to their unique fluorescent colorimetric responses to temperature. Conventional TFMs generally display unicolor with switching from one color to another, showing unprintable and unsatisfied performances. These limitations greatly hinder their development and expansion toward advanced applications. Herein, the superior integration of full-color, off-on switching mode, printability, and high performance to TFMs is achieved successfully. The success is due to a thermally induced synchronous "dual/multichannel" stimulus-response mode regulated by a self-crystalline phase-change material; that is, synergistic changes of the molecular existence states and subsequent colors/spectra of the fluorescent modifier and fluorophores, accompanied by corresponding high-efficiency on-off switching of Forster resonance energy transfer. These TFMs are simple to prepare and show good performance, such as high fluorescence emission contrast (>100), great reversibility (>200 cycles), and easy-to-adjust response temperature. Particularly, these R/G/B TFMs can be prepared as tricolor fluorescent inks, and thus full-color emissions on flexible substrate can be easily obtained by printing. Finally, their great potential in switchable dynamic interior decoration, programmatic temperature-control information display, and senior information encryption are illustrated. This successful exploration offers a new perspective for designing and optimizing various other switchable materials with higher comprehensive performances.

Printable Off-On Thermoswitchable Fluorescent Materials for Programmable Thermally Controlled Full-Color Displays and Multiple Encryption.

With the rapid development of optoelectronic fields, electrochromic (EC) materials and devices have received remarkable attention and have shown attractive potential for use in emerging wearable and portable electronics, electronic papers/billboards, see-through displays, and other new-generation displays, due to the advantages of low power consumption, easy viewing, flexibility, stretchability, etc. Despite continuous progress in related fields, determining how to make electrochromics truly meet the requirements of mature displays (e.g., ideal overall performance) has been a long-term problem. Therefore, the commercialization of relevant high-quality products is still in its infancy. In this review, we will focus on the progress in emerging EC materials and devices for potential displays, including two mainstream EC display prototypes (segmented displays and pixel displays) and their commercial applications. Among these topics, the related materials/devices, EC performance, construction approaches, and processing techniques are comprehensively disscussed and reviewed. We also outline the current barriers with possible solutions and discuss the future of this field.

Chang Gu

Papers

Advances in nanomaterials for electrochromic devices

Bio-inspired ultra-high energy efficiency bistable electronic billboard and reader

Printable Off-On Thermoswitchable Fluorescent Materials for Programmable Thermally Controlled Full-Color Displays and Multiple Encryption.

Emerging Electrochromic Materials and Devices for Future Displays

An RGB color-tunable turn-on electrofluorochromic device and its potential for information encryption