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About Supramolecular Assemblies of π-Conjugated Systems

Electrolytes have been identified as some of the most influential components in the performance of electrochemical supercapacitors (ESs), which include: electrical double-layer capacitors, pseudocapacitors and hybrid supercapacitors. This paper reviews recent progress in the research and development of ES electrolytes. The electrolytes are classified into several categories, including: aqueous, organic, ionic liquids, solid-state or quasi-solid-state, as well as redox-active electrolytes. Effects of electrolyte properties on ES performance are discussed in detail. The principles and methods of designing and optimizing electrolytes for ES performance and application are highlighted through a comprehensive analysis of the literature. Interaction among the electrolytes, electro-active materials and inactive components (current collectors, binders, and separators) is discussed. The challenges in producing high-performing electrolytes are analyzed. Several possible research directions to overcome these challenges are proposed for future efforts, with the main aim of improving ESs' energy density without sacrificing existing advantages (e.g., a high power density and a long cycle-life) (507 references).

A review of electrolyte materials and compositions for electrochemical supercapacitors

A review was presented to demonstrate a historical description of the synthesis of light-emitting conjugated polymers for applications in electroluminescent devices. Electroluminescence (EL) was first reported in poly(para-phenylene vinylene) (PPV) in 1990 and researchers continued to make significant efforts to develop conjugated materials as the active units in light-emitting devices (LED) to be used in display applications. Conjugated oligomers were used as luminescent materials and as models for conjugated polymers in the review. Oligomers were used to demonstrate a structure and property relationship to determine a key polymer property or to demonstrate a technique that was to be applied to polymers. The review focused on demonstrating the way polymer structures were made and the way their properties were controlled by intelligent and rational and synthetic design.

Synthesis of Light-Emitting Conjugated Polymers for Applications in Electroluminescent Devices

Recent Advances in Bulk Heterojunction Polymer Solar Cells

The First Truly All‐Polymer Electrochromic Devices

Four new disubstituted propylenedioxythiophene polymers have been synthesized by Grignard metathesis on the 1−5 g scale. All polymers were found to be soluble in chloroform, methylene chloride, toluene, and tetrahydrofuran and were fully structurally characterized having GPC determined number-average molecular weights ranging from 33000 to 47000 g mol-1. Dilute polymer solutions in toluene exhibited strong red fluorescence with moderate quantum efficiencies from 0.38 to 0.50. Homogeneous thin films were formed by electropolymerization and spray casting polymer solutions onto ITO coated glass slides at thicknesses of ca. 150 nm. The films were electroactive, switching from a dark blue-purple to a transmissive sky blue upon p-doping, often with subsecond switching times, and high electrochromic contrast luminance changes (% ΔY) of 40−70%. These studies revealed that the branched derivatives, [poly(3,3-bis(2-ethylhexyl)-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepine)] and [poly(6,8-dibromo-3,3-bis(2-ethylhexylox...

Spray Coatable Electrochromic Dioxythiophene Polymers with High Coloration Efficiencies

Donor−acceptor diblock copolymers, composed of regioregular poly(3-hexylthiophene) (rrP3HT) as the electron donor block and poly(perylene diimide acrylate) (PPDA) as the electron acceptor block, were prepared and used to fabricate a solar cell. Vinyl-terminated rrP3HT was synthesized by Grignard metathesis polymerization and converted to an alkoxyamine macroinitiator. This polythiophene macroinitiator was used in controlled free radical polymerization of a perylene diimide-containing acrylate. The targeted donor−acceptor diblock copolymers were prepared with low-to-moderate polydispersity indices (1.2−1.4) and molecular weights sufficiently high for producing films by spin-coating. These copolymers showed efficient photoluminescence quenching in the solid state, indicative of charge separation, and were used to produce a solar cell with power conversion efficiency of 0.49%.

Donor−Acceptor Poly(thiophene-block-perylene diimide) Copolymers: Synthesis and Solar Cell Fabrication

Reflective and absorptive/transmissive polymer electrochromic devices (ECDs) composed of spray-coated films of poly(3,3-bis(octadecyloxymethyl)-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepine)
(PProDOT(CH2OC18H37)2) and poly(3,3-bis(2-ethylhexyloxymethyl)-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepine)
(PProDOT(CH2OEtHx)2) layers as cathodically coloring polymers and poly(3,6-bis(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)-9-methyl-9H-carbazole)
(PBEDOT-NMeCz) as the anodically coloring polymer have been constructed and evaluated. These devices exhibit low switching voltages (±1.2 V), high visible contrast values, sub-second switching times, and high switching stability in atmospheric conditions. The reflective ECD comprising PProDOT(CH2OEtHx)2 as the active layer demonstrates an unusual electrochromic behavior. By regulating the applied voltage, a high reflectance contrast of greater than 70%
ΔT was achieved in the NIR region (2 µm) without any noticeable color change of the device.

Electrochromic devices based on soluble and processable dioxythiophene polymers

A new, well-defined diblock copolymer (P3HT-b-C60) based on regioregular poly(3-hexylthiophene) (P3HT) and fullerene was synthesized. First, regioregular P3HT was synthesized through Grignard metathesis polymerization, and then methyl methacrylate (MMA) and 2-hydroxyethyl methacrylate (HEMA) were copolymerized by using an end-functionalized P3HT as a macroinitiator for the atom transfer radical polymerization to yield a diblock copolymer (P3HT-b-P(MMA-r-HEMA)). A fullerene derivative functionalized with carboxylic acid, [6,6]-phenyl-C61-butyric acid (PCBA), was then chemically linked to the HEMA unit in the second block (P(MMA-r-HEMA)) to produce a diblock copolymer with the second block containing fullerenes. Annealing thin films of the copolymer revealed nanometer-scale phase separation, a more suitable morphology for enabling excitons generated in the P3HT domain to more efficiently reach the donor–acceptor interface, relative to simple blends of P3HT and C60. As a result, photoluminescence of the P3HT-b-C60diblock copolymer in the films showed a complete quenching of photoluminescence of P3HT, which is indicative of charge transfer between P3HT and fullerene.

Ali Cirpan

Papers

The First Truly All‐Polymer Electrochromic Devices

Spray Coatable Electrochromic Dioxythiophene Polymers with High Coloration Efficiencies

Donor−Acceptor Poly(thiophene-block-perylene diimide) Copolymers: Synthesis and Solar Cell Fabrication

Electrochromic devices based on soluble and processable dioxythiophene polymers

Synthesis and photophysical property of well-defined donor–acceptor diblock copolymer based on regioregular poly(3-hexylthiophene) and fullerene