Enabling new electrochemical methods with redox-active ionic liquids

Redox-active ionic liquids are obtained by tethering an electroactive center to either the cation, the anion, or both ions in an ionic liquid. While such phases were studied back in the 1990s for their particular electrochemical behavior, they are currently under increased scrutiny for applications in electrochemical systems. This contribution identifies the redox-active ionic liquids’ most important aspects to promote their development. This article provides a review of their features and offers several design guidelines. In addition, it offers an overview of the key properties which enhance their suitability as electrolytes in electrochemical systems, with particular attention paid to lithium-ion batteries and electrochromic devices.     

GelatinnZn(CF3SO3)2 Polymer Electrolytes for Electrochromic Devices

The present work is focused on gelatin‐based electrolytes doped with a range of concentration of zinc triflate (Zn(CF₃SO₃)₂). The transparent‐thin‐film samples have been represented by the notation Gelatin_nZn(CF₃SO₃)₂, where n represents the zinc triflate salt concentration in the electrolyte membranes from 0.00 wt% to 10.93 wt% . The samples have been characterized by conductivity measurements, thermal analysis, cyclic voltammetry, X‐ray diffraction (XRD), polarized optical microscopy (POM) and scanning electron microscopy (SEM). The gelatin‐based electrolytes were also tested as ionic conductors in electrochromic devices with the glass/ITO/WO₃/gelatin‐based electrolyte/CeO₂‐TiO₂/ITO/glass configuration.     

壳聚糖辅助制备WO_3薄膜材料及其电致变色性能

以壳聚糖(CS)为辅助材料,利用层层自组装方法(LbL)制备了WO3复合薄膜材料(CS/WO3).采用紫外-可见吸收光谱(UV-Vis)、扫描电子显微镜(SEM)和循环伏安扫描(CV)等手段对CS/WO3纳米复合材料的形貌和电化学性能进行了表征.利用电化学和UV-Vis联机技术研究了复合材料的电致变色性能.结果表明,该复合材料呈现出从无色到蓝色的颜色调变,其光反差可达48.0%,着色效率为58.5cm2/C,着色与褪色时间分别为9.5和1.8s.     

Modulating the Properties of Azulene‐containing Polymers Through Functionalization at the 2‐Position of Azulene

Poly(2‐arylazulene‐alt‐fluorene) and poly(2‐arylazulene‐alt‐thiophene) are synthesized via Suzuki and Stille cross‐coupling polymerization, respectively, using 1,3‐dibromo‐2‐arylazulenes as monomers, which are prepared by a novel directed C?H activation method of 2‐carboxylic azulene and subsequent bromination reaction. Our study shows that functionalization at the 2‐position of azulene monomers influences polymer properties. For instance, different from electron‐withdrawing groups that discourage the protonation of azulene, electron‐donating aryl groups, however, enhances the sensitivity of response to acid. Protonation of the polymers leads to significant shifts in absorption spectra accompanying with obvious color changes from green to brown in majority cases because of the formation of poly(azulenium cation). The electrochromic properties of polymers are examined, exhibiting that nature of aryl group at the 2‐position of azulene influences the stability of their electrochromic devices.     

Anomalous lithium ion diffusion into CeO2·TiO2 thin film by film thickness variations

CeO₂·TiO₂ thin film is considered as an excellent candidate for a passive ion storage layer due to its good electrochemical stability and comparatively great charge capacitance. When cerium-titanium oxide thin film is adopted as an ion storage layer against cathodic tungsten oxide layer, the electrochromic device shows long term durability and cyclability. Therefore, many researchers investigated the composition and crystallinity effects to the charge density. In our study, we prepared CeO₂·TiO₂ thin by sol–gel dip-coating method, varying thickness by controlling withdrawal speeds. As investigating results of cyclic voltammetry and chronocoulometry, we found that there are three regions in the film thicknesses: (1) fast lithium ion diffusion region under 100 nm, (2) slow diffusion region in the range of 100 to 150 nm, and (3) fast and great charge capacitance region over 150 nm. In region 1, lithium ions diffuse very fast and reach into indium-tin oxide (ITO) layers, and slow diffusion region follows in region 2, probably due to the remains or impurities within the film, and in region 3, lithium ion diffusion gets fast again, accompanied with charge capacitance increase with thickness.     

The effect of composition variables on precursor degradation and their consequence on Nb2O5 film properties prepared by the Pecchini Method

The calcination of Nb₂O₅ prepared by the Pecchini method was investigated using thermal analysis. The polymer precursor was prepared with different citric acid/ethylene glycol (CA/EG) and citric acid/niobium precursor (CA/Nb) molar ratios. The results suggest a strong influence of the CA/EG molar ratio, mainly on the polymerization degree. The CA/Nb ratio also modifies the degradation process of the precursor solution. The effect of the precursor compositional variation was also observed in the oxide structure, as well as in its electrochemical and electrochromic behavior. Films prepared using high CA/EG and a Nb salt precursor amount have the highest values of charge density and coloration efficiency. Moreover XRD data for this sample show a crystalline structure while the samples prepared with low CA/EG ratio are amorphous.     

Colours from electroactive polymers: Electrochromic, electroluminescent and laser devices based on organic materials

This paper focuses on the most relevant devices currently used in order to achieve electrically stimulated generations of colours from electroactive polymers, either as coloured light emissions from the material or as modifications of its intrinsic colour properties. For this purpose, most relevant materials, fundamental principles of operations, latest developments and current applications of organic-based electrochromic, electroluminescent and lasing devices are reviewed here. The very promising performances resulting from the analysis of state-of-the-art products, and in particular of those which are currently approaching commercial applications, suggest likely roles played by such devices for niche applications in the very near future.     

New β-linked pyrrole monomers: approaches to highly stable and conductive electrochromic polymers

An efficient synthetic route to β-linked dipyrrole monomers has been developed. Electrochemical polymerization of these monomers leads to the incorporation of polycyclic aromatic residues into a polymer backbone. The resulting conjugated polymer films are electroactive, robust electrochromic materials that are highly delocalized in their oxidized forms.     

Electrochromic properties of WO3 thin film onto gold nanoparticles modified indium tin oxide electrodes

Gold nanoparticles (GNPs) thin films, electrochemically deposited from hydrogen tetrachloroaurate onto transparent indium tin oxide (ITO) thin film coated glass, have different color prepared by variation of the deposition condition. The color of GNP film can vary from pale red to blue due to different particle size and their interaction. The characteristic of GNPs modified ITO electrodes was studied by UV-vis spectroscopy, scanning electron microscope (SEM) images and cyclic voltammetry. WO₃ thin films were fabricated by sol-gel method onto the surface of GNPs modified electrode to form the WO₃/GNPs composite films. The electrochromic properties of WO₃/GNPs composite modified ITO electrode were investigated by UV-vis spectroscopy and cyclic voltammetry. It was found that the electrochromic performance of WO₃/GNPs composite films was improved in comparison with a single component system of WO₃.