Surface and Interface Engineering of Conjugated Polymers and Nanomaterials in Applications of Supercapacitors and Surface-functionalization
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AbstractIn this dissertation, three aspects about surface and interface engineering of conjugated polymers and nanomaterials will be discussed. (i) There is a significant promise for electroactive conjugated polymers (ECPs) in applications of electrochemical devices including energy harvesting, electrochromic displays, etc. Among these, ECPs has also been developed as electroactive materials in electrochemical supercapacitors (ESCs). Compared with metal oxides, ECPs are attractive because they have good intrinsic conductivity, low band-gaps, relatively fast doping-and-undoping process, the ease of synthesis, and tunable electronic and structural properties through structural modifications. Here, Multiple-branch-chain 3,4-ethylenedioxythiophene (EDOT) derivatives was designed as crosslinkers in the co-electropolymerization of EDOT to optimize its morphology and improve the cycling stability of PEDOT in the supercapacitor applications. High-surface-area π-conjugated polymeric networks can be synthesized via the electrochemical copolymerization of the 2D (trivalent) motifs benzo[1,2-b:3,4-b’:5,6-b’’]trithiophene (BTT) and tris-EDOT-benzo[1,2-b:3,4-b’:5,6-b’’]trithiophene (TEBTT) with EDOT. Of all the material systems studied, P(TEBTT/EDOT)-based frameworks achieved the highest areal capacitance with values as high as 443.8 mF cm-2 (at 1 mA cm-2), higher than those achieved by the respective homopolymers (PTEBTT and PEDOT) in the same experimental conditions of electrodeposition (PTEBTT: 271.1 mF cm-2 (at 1 mA cm-2); PEDOT: 12.1 mF cm-2 (at 1 mA cm-2). (ii) In electrochemical process, the suitable choice of appropriate electrolytes to enlarge the safe working potential window with electrolyte stability is well known to improve ECPs’ performance in ESCs applications. Ionic liquids (ILs) are ion-composed salts and usually fluid within a wide temperature range with low melting points. There are many unique characteristics for these intrinsic ion conductors, including high ionic conductivity, wide electrochemical voltage windows in neutral conditions, fast ion mobility in redox reaction process (>10-14 m2 V-1 s-1), low vapor pressure, and environmental stability. These properties qualified ambient-temperature ILs to be applied as supporting medium for various devices and materials processing applications in both industry and academia, overcoming the limitation of volatile organic compounds (VOCs). Especially, ILs have been utilized as superior medium to electrodeposit metals, alloys, semiconductors and ECPs in the application of supercapacitors. Electropolymerization of EDOT and its derivative 4,4'-dimethoxy-3,3'-bithiophene (BEDOT) have been studied in three kinds of imidazolium-based ionic liquids and conducting salt in VOCs with different anions both as the growth medium and the supporting electrolyte, to assess the influence of these anions on their morphology and electrochemical activity. It is found these thiophene polymers grown in ILs with higher viscosity and lower diffusion shows much slower growth rate and orderly morphologies than in Tetrabutylammonium hexafluorophosphate (TBAPF6) dissolved in acetonitrile (ACN), and gives better electrochemical performance via cyclic voltammetry (CV) and galvanostatic charge-and-discharge (CD) studies. Polymers displayed multiple redox peaks in several cases, the possible reasons and origins are discussed. The synthesized polymer can be affected greatly by both the ILs with different anion/cation, and its mutal interation with targeted monomer.. As far as known, there is no systematic study on how the anions of ILs and common organic solution could play a role as a medium both for polymerization and post-polymerization electrolyte for PEDOT and its derivatives. This study can be used as an easy reference and provide experimental diagnositc data when selecting ionic liquids to investigate and optimize thiophene-based electrochemical systems, such as batteries and supercapactiors. (iii) Another aspect about interface chemistry of direct functionalization of nanodiamond with maleimide has also been addressed. Functional nanodiamonds are promising candidates for extensive practical applications in surface science, photonics and nanomedicine. Here, a protocol of direct functionalization is described by which maleimide-derivatized substituents can be appended to the outer shell of thermally annealed nanodiamonds through Diels-Alder reaction. This protocol can be carried out in room temperature, ambient atmosphere, without catalyst, and provide functionalized nanodiamonds with good solubility in organic solution. Also, this method can be applied for other maleimide derivatives,e.g.m aleimide-fluorescene, which can be applied in fluorescence labeling, sensing, and drug delivery. A series of techniques, especially Fourier transform infrared spectroscopy (FTIR), and Solid State Nuclear Magnetic Resonance (SS-NMR) was conducted for the analysis of surface chemistry and the investigation of the two-point binding strategy in details.