Uniform and aligned nanofibers have been obtained by eletrospinning. Activated carbon nanofibers (ACNFs) have been used as electrode materials for battery and electric double layer due to its porous properties. A high value of surface area can be attained (1000 - 3000 nm) by activation, due to the presence of micropores on the surface of nanofibers. A series of nanofibers have been prepared using different polymer precursors and concentrations by electrospinning in this study. Morphological study by SEM reveals a uniform and aligned fibrous structure for the PAN-based CNF (11 wt%) and a curved and twisted fibrous structure for the PAN-based CNF (8 wt%) and the acrylic-based CNF (9 wt%). Thus, the microstructure of CNF can be greatly influenced by the concentration of polymer precursor; high quality of nanofibers can be produced with higher polymer concentration and higher viscosity. The diameter of PAN-based nanofibers is gradually decreased from 400 to 200 nm during stabilization, carbonization, and activation, due mainly to the degradation and condensation. Surface of CNF becomes rough after activation due to the etching by potassium ions at high temperatures. Microstructural study by X-ray diffraction and Raman spectroscopy indicates a discernible diffraction peak at d002 = 0.356 nm and the ratio ID/IG = 1.83 of ACNFs, showing an amorphous and disordered structure, and leading to a low conductivity. Adsorption/desorption isotherms obtained from BET measurements under nitrogen atmosphere suggests a relatively small surface area of 8-10 m2/g, indicating that there might be no adsorption on the porous ACNF or the porous structure has been destroyed after carbonization. This leads to a relatively low conductance of 17 Faraday/g measured from the cyclic voltammetry.

M. Tech. Department of Chemical, Metallurgical and Materials Engineering. / Discusses how to synthesize a titanium-manganese oxide composite electrode with improved supercapacitive properties. The research aim was achieved through the following objectives: 1. the mechanisms of the synergistic incorporation of manganese oxide for improving the supercapacitive properties of titanium oxide electrodes. 2. Investigate possible metallurgical interactions and phenomenon during the sintering of the composite. 3. Investigate the electrochemical characteristics of titanium-manganese composite electrodes.

The objective of this work is to improve the energy density of carbon/carbon supercapacitors. For achieving this objective, two different strategies were followed depending on the electrolyte used: i) in aqueous electrolytes, our efforts were focused on extending the operating cell voltage by using neutral alkali sulfate solutions; ii) in organic electrolyte, the target was to improve the volumetric capacitance by setting a mild activation method able to produce a porous carbon with average pore size matching the ion size, while not enlarging the pores upon porosity development. A practical cell voltage of 1.8 V has been demonstrated by implementing aqueous alkali sulfates in symmetric carbon/carbon capacitors. It has been shown that the voltage is limited by a partial destructive electro-oxidation of the positive electrode. Such irreversible electro-oxidation could be mitigated by mild chemical oxidation of the active carbon material with hydrogen peroxide; consequently, the voltage could be further expanded up to 1.9 V. Even 2.0 V could be attained after mass balancing the electrodes in order to allow them to operate in their stability window. Finally, pouch-cells with carbon coating on stainless steel current collector were realized by using 2 mol L-1 Li2SO4 as electrolyte. An exceptional cycling stability at cell voltages up to 2.1 V was obtained during 10,000 cycles. Hence, the use of alkali sulfate electrolytes is a cost-effective alternative to organic electrolytes for producing environment friendly and safe carbon/carbon supercapacitors. Dense nanoporous carbons with pores fitting the dimension of ions of the Et4NBF4/acetonitrile organic electrolyte were obtained by high pressure oxidation of non-porous carbon at low temperature, followed by a thermal desorption to remove the surface groups and unblock pore entrances. The activation mechanism consisted in drilling the narrow pores existing initially in the char. Due to the low burn-off, the density of the electrodes was remarkably high allowing high volumetric capacitance values to be reached. This novel production method associates the advantages of environment friendly, cost-effective, high yield and low energy consumption characteristics.

Conductive polymers are promising pseudo capacitive materials as they feature both good conductivity and high capacitance. Formation of composite between conductive polymers and carbon nanotubes is a proven technique in enhancing the material electroactivity. In-situ polymerization of conductive polymers includes polyaniline, polypyrrole and PEDOT: PSS and composite with MWCNT has been successfully achieved. Composites fabricated by using different dopants and their performance were studied. Excellent achieved capacitive performance is due to the combination of pseudo capacitance and double layer capacitance. The MWCNTs content has significant influence on the morphology and structure of the polymerized ECP in the composite. And therefore affects the material conductivity and the charge storage performance. Two electrodes cell performance shows that Ppy/MWCNT composite shows a more promising performance as electrode materials for EC applications in contrast to PANI/MWCNT and PEDOT: PSS/MWCNT composites.

Conductive polymers are promising pseudo capacitive materials as they feature both good conductivity and high capacitance. Formation of composite between conductive polymers and carbon nanotubes is a proven technique in enhancing the material electroactivity. In-situ polymerization of conductive polymers includes polyaniline, polypyrrole and PEDOT: PSS and composite with MWCNT has been successfully achieved. Composites fabricated by using different dopants and their performance were studied. Excellent achieved capacitive performance is due to the combination of pseudo capacitance and double layer capacitance. The MWCNTs content has significant influence on the morphology and structure of the polymerized ECP in the composite. And therefore affects the material conductivity and the charge storage performance. Two electrodes cell performance shows that Ppy/MWCNT composite shows a more promising performance as electrode materials for EC applications in contrast to PANI/MWCNT and PEDOT: PSS/MWCNT composites.

The mounting concern for renewable energies from ecologically conscious alternatives is growing in parallel with the demand for portable energy storage devices, fuelling research in the fields of electrochemical energy storage technologies. The supercapacitor, also known as electrochemical capacitor, is an energy storage device possessing a near infinite life-cycle and high power density recognized to store energy in an electrostatic double-layer, or through a pseudocapacitance mechanism as a result of an applied potential. The power density of supercapacitors far exceeds that of batteries with an ability to charge and discharge stored energy within seconds. Supercapacitors compliment this characteristic very well with a cycle life in excess of 106 cycles of deep discharge within a wide operational temperature range, and generally require no further maintenance upon integration. Conscientious of environmental standards, these devices are also recyclable. Electrochemical capacitors are currently a promising candidate to assist in addressing energy storage concerns, particularly in hybridized energy storage systems where batteries and supercapacitors compliment each other’s strengths; however specific challenges must be addressed to realize their potential. In order to further build upon the range of supercapacitors for future market applications, advancements made in nanomaterial research and design are expected to continue the materials development trend with a goal to improve the energy density through the development of a cost-efficient and correspondingly plentiful material. However, it is important to note that the characteristic power performance and exceptional life-cycle should be preserved alongside these efforts to maintain their niche as a power device, and not simply develop an alternative to the average battery. It is with this clear objective that this thesis presents research on an emerging carbon material derived from an abundant precursor, where the investigations focus on its potential to achieve high energy and power density, stability and integration with other electroactive materials. Activated carbons have been the dominant carbon material used in electric double-layer capacitors since their inception in the early 1970s. Despite a wide range of carbon precursors and activation methods available for the generation of high surface area carbons, difficulties remain in controlling the pore size distribution, pore shape and an interconnected pore structure to achieve a high energy density. These factors have restricted the market growth for supercapacitors in terms of the price per unit of energy storage. Activation procedures and subsequent processes for these materials can also be energy intensive (i.e. high temperatures) or environmentally unfriendly, thus the challenge remains in fabricating an inexpensive high surface-area electroactive material with favourable physical properties from a source available in abundance. Double-layer capacitive materials researched to replace active carbons generally require properties that include: high, accessible surface-area; good electrical conductivity; a pore size distribution that includes mesopore and micropore; structural stability; and possibly functional groups that lend to energy storage through pseudocapacitive mechanisms. Templated, fibrous and aerogel carbons offer an alternative to activated carbons; however the drawbacks to these materials can include difficult preparation procedures or deficient physical properties with respect to those listed above. In recent years nanostructured carbon materials possessing favourable properties have also contributed to the field. Graphene nanoplatelet (GNP) and carbon nanotube (CNT) are nanostructured materials that are being progressively explored for suitable development as supercapacitor electrodes. As carbon lattice structured materials either in the form of a 2-dimensional sheet or rolled into a cylinder both of these materials possess unique properties desirable in for electrode development. In the proceeding report, GNPs are investigated as a primary material for the synthesis of electrodes in both a pure and composite form. Three projects are presented herein that emphasize the suitability of GNP as a singular carbon electrode material as well as a structural substrate for additional electroactive materials. Investigation in these projects focuses on the electrochemical activity of the materials for supercapacitor devices, and elucidation of the physical factors which contribute towards the observed capacitance. An initial study of the GNPs investigates their distinct capacitive ability as an electric double-layer material for thin-film applications. The high electrically conductivity and sheet-like structure of GNPs supported the fabrication of flexible and transparent films with a thickness ranging from 25 to 100 nm. The thinnest film fabricated (25 nm) yielded a high specific capacitance from preliminary evaluation with a notable high energy and power density. Furthermore, fast charging capabilities were observed from the GNP thin film electrodes. The second study examines the use of CNT entanglements dispersed between GNP to increase the active surface area and reduce contact resistances with thin-film electrodes. Through the use MWNT/GNP and SWNT/GNP composites it was determined that tube aspect ratio influences the resulting capacitive performance, with the formation of micropores in SWNT/GNP yielding favourable results as a composite EDLC. The third study utilizes electrically conducting polypyrrole (PPy) deposited onto a GNP film through pulse electrodeposition for use as a supercapacitor electrode. Total pulse deposition times were evaluated in terms of their corresponding improvements to the specific capacitance, where an optimal deposition time was discovered. A significant increase to the total specific capacitance was observed through the integration PPy, with the majority charge storage being developed via psuedocapacitive redox mechanisms. A summary of the studies presented here centers on the development of GNP electrodes for application in high power supercapacitor devices. The potential use for GNP in both pure and composite electrode films is explored for electrochemical activity and capacitive capabilities, with corresponding physical characterization techniques performed to examine influential factors which contribute to the final results. The work emphasizes the suitability of GNP material for future investigations into their application as carbon or carbon composite electrodes in supercapacitor devices.

Supercapacitors have attracted great attention because of their high power density, long life cycle and high efficiency. They can be generally classified into two types: electrical double-layer capacitors (EDLCs) and pseudocapacitors. Compared with pseudocapacitors, EDLCs have a very fast charge/discharge rate, higher power density, higher coulombic efficiency and longer cycle life. Recently, in order to meet the requirements of portable and wearable electronics, supercapacitor development is moving towards flexible and stretchable solutions. This thesis presents the design, fabrication, performance testing and optimisation of flexible strip and fibre EDLCs. In this research, a sandwich structured strip EDLC was designed and manufactured. Experimental design was utilised to optimise the operation parameters of the EDLC in order to improve its capacity for energy storage. The flexibility of the strip EDLCs was studied extensively by mechanical tests under static and dynamic loading conditions, and the correlation between the electrochemical performance of the EDLCs and the mechanical testing process was investigated. Novel coaxial fibre EDLCs have also been studied and developed in this study. Fibre supercapacitors showed a good flexibility and weavability. The activated carbon produced by ball-milling method with optimum specific capacitance was mixed with commercial ink to produce active material to optimise the electrochemical performance of fibre EDLCs. The flexible EDLCs were applied into different appliances to demonstrate the stability of performance and the usability of EDLCs developed in this study. The electrical current and potential range can be altered by connecting multiple strip or fibre EDLCs in parallel or in series to meet the power and energy requirements. It has been proved that the flexible EDLCs developed have a great potential to be used as energy storage devices for smart electronics. This thesis makes original contributions to knowledge, including using an advanced test method to study the electrochemical performance of flexible supercapacitors under static and dynamic mechanical testing, investigation of the effect of key parameters in the manufacturing process on the performance of strip supercapacitors using experimental design method to optimise the supercapacitors’ performance, and optimisation of the performance of fibre supercapacitors by improving the structure and using a new active material with higher specific capacitance.

Neste estudo foi investigado o processo de redução térmica do óxido de grafeno em médio vácuo como uma rota viável de baixo custo econômico para obtenção do óxido de grafeno reduzido para aplicação em supercapacitores. O objetivo principal foi estudar a influência da temperatura de processamento no grau de redução do óxido de grafeno utilizando um sistema de vácuo com bomba mecânica de duplo estágio. O processamento constituiu na exposição do óxido de grafeno em várias temperaturas (200, 400, 600, 800 e 1000 °C) com pressão reduzida (10-2mbar) condição de médio vácuo. Foram utilizadas técnicas convencionais para caracterização dos materiais precursores e processados, tais como: microscopia eletrônica de varredura (MEV), difração de raios-X (DRX) e espectroscopia no infravermelho com transformada de Fourier (FTIR). Com os resultados deste estudo foi demostrado que é possível obter o óxido de grafeno reduzido utilizando um sistema de vácuo com bomba mecânica de duplo estágio e temperaturas de processamento superiores a 200°C. / In this study the process of medium vacuum thermal reduction of the graphene oxide as a low cost route for obtaining reduced graphene oxide has been investigated. The main objective was to study the influence of the processing temperature on the degree of reduction of the graphene oxide using a vacuum system with two stage backing pump. The processing was carried out by exposing the graphene oxide at various temperatures (200, 400, 600, 800 e 1000 °C) with reduced pressure (10-2 mbar). Conventional techniques have been employed to the characterization of the starting and processed materials, such as: scanning electron microscopy (SEM), X-ray diffraction and Fourier transformed infrared spectroscopy (FTIR). With the results of this study it has been demonstrated that it is possible to obtain the reduced graphene oxide using a vacuum system with a two stage backing pump and processing temperatures superior to 200°C.

Due to the increasing demand for high power and reliable miniaturized energy storage devices, the development of micro-supercapacitors or electrochemical micro-capacitors have attracted much attention in recent years. This dissertation investigates several strategies to develop on-chip micro-supercapacitors with high power and energy density. Micro-supercapacitors based on interdigitated carbon micro-electrode arrays are fabricated through carbon microelectromechanical systems (C-MEMS) technique which is based on carbonization of patterned photoresist. To improve the capacitive behavior, electrochemical activation is performed on carbon micro-electrode arrays. The developed micro-supercapacitors show specific capacitances as high as 75 mFcm-2 at a scan rate of 5 mVs-1 after electrochemical activation for 30 minutes. The capacitance loss is less than 13% after 1000 cyclic voltammetry (CV) cycles. These results indicate that electrochemically activated C-MEMS micro-electrode arrays are promising candidates for on-chip electrochemical micro-capacitor applications. The energy density of micro-supercapacitors was further improved by conformal coating of polypyrrole (PPy) on C-MEMS structures. In these types of micro-devices the three dimensional (3D) carbon microstructures serve as current collectors for high energy density PPy electrodes. The electrochemical characterizations of these micro-supercapacitors show that they can deliver a specific capacitance of about 162.07 mFcm-2 and a specific power of 1.62mWcm-2 at a 20 mVs-1 scan rate. Addressing the need for high power micro-supercapacitors, the application of graphene as electrode materials for micro-supercapacitor was also investigated. The present study suggests a novel method to fabricate graphene-based micro-supercapacitors with thin film or in-plane interdigital electrodes. The fabricated micro-supercapacitors show exceptional frequency response and power handling performance and could effectively charge and discharge at rates as high as 50 Vs-1. CV measurements show that the specific capacitance of the micro-supercapacitor based on reduced graphene oxide and carbon nanotube composites is 6.1 mFcm-2 at scan rate of 0.01Vs-1. At a very high scan rate of 50 Vs-1, a specific capacitance of 2.8 mFcm-2 (stack capacitance of 3.1 Fcm-3) is recorded. This unprecedented performance can potentially broaden the future applications of micro-supercapacitors.

In 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.