The electrochemical double layer (EDL) at the solid–liquid interface is the near surface region where important electrochemical processes (e.g., electrodeposition, corrosion, and heterogeneous catalysis) take place. Subtle changes in the electrode surface material/topography and the nature of the fluid medium can drastically alter interactions between liquid molecules and the solid surface. A better understanding of this interfacial region can help advance numerous applied fields, such as battery technologies, solar cells, double layer capacitors, and carbon dioxide capture/conversion. Ionic liquids (IL) are an emerging class of solvents that could replace traditional aqueous/non-aqueous solvents due to their advantageous physiochemical properties (e.g., wide solvent window, high thermal stability, and excellent solvating power). However, our understanding of the near-surface structure of ILs in the EDL is still being developed. This thesis focuses on the fundamental electrochemical behavior of ILs to help understand its interfacial behavior in three main areas: 1) the nature of capacitance-potential relationships in neat ILs, 2) the role of ‘user-defined’ experimental variables on capacitive electrochemical measurements, and 3) the impact of IL + water mixtures on experimental data. The general shape of capacitance-potential curves can suggest at the broad architecture of the EDL region. Fundamental capacitive studies of the IL EDL show a wide range of results, even for similar electrochemical systems. Theoretical predictions suggest the capacitance-potential curve should exhibit bell- or camel-shaped curvature depending on the nature of the IL. Experimental observations have demonstrated several functional shapes such as U-shaped, bell-shaped, camel-shaped, and relatively featureless responses. Much of the work in this thesis starkly contrasts theoretical expectations by demonstrating capacitive behavior that is analogous to high temperature molten salts and dilute aqueous electrolytes with metallic and non-metallic electrode materials. However, our systematic studies of a model IL electrochemical system reveal that there are several ‘user-defined’ experimental variables (i.e. potential scan direction, data acquisition protocol, experimental technique, and potential range probed) which in some instances can significantly impact the resulting capacitance curvature. Some of these variables are often overlooked in the literature and our efforts are aimed at uniting the scientific community in this area to help better compare and understand results. An additional experimental variable of importance is the sorption of water into ILs, which is nearly impossible to prevent due to their hygroscopic nature. The presence of water is known to have a significant effect on the resulting mixtures’ bulk and interfacial properties. While the interaction between ILs and water can significantly vary depending on the nature of the IL, this thesis demonstrates that within small quantities (e.g., < 5000 ppm) of sorbed water there are only minor changes in spectroscopic and electrochemical responses. Collectively, the work outlined in this thesis helps the scientific community better understand electrochemical measurements in IL solvents by examining key analytical variables associated with capacitive measurements. The fundamental electrochemical studies described in this thesis demonstrate that the solid-liquid interface for IL solvents is response to even subtle changes in surface chemistries. These governing interfacial properties have ramifications in myriad applications from energy storage to lubrication.

The present study presents the current status of research into the production of active carbons from environmental applications using waste newspaper. A number of studies have been performed to investigate the pyrolysis of waste paper ash to carbon gel.Although several studies report the production of carbon from waste tyre, bamboo, coconut shell, this study is first of its kind that for the first time, the waste newspapers have been used as a raw material for supercapacitor electrodes. A cheap raw material, and a simple method of preparation make this carbon gel more economically attractive. By carbonizing a waste paper a new carbon-carbon composite as electrode material was prepared through RF gel. The surface morphology and electrochemical characteristics of the carbon composite were investigated by Scanning Electron Microscopy, Cyclic Voltammetry, Electrochemical impedance spectroscopy and galvanostatic charge-discharge cycle tests with various current densities. The SEM study reveals that the connectivity between the grains increases during cycling thus enhances the cyclic stasitity. The CV’s suggests that there is simultaneous redox and capacitive behavior and these behaviors are highly reversible even after 8 lakh cycles. The reversibility was still maintained even in the range – 3 V to + 3 V. The charge/discharge cycle tests reveal the cycle stasitity and delivered more then 8 lakh cycles at 100 mA/cm2. The maximum specific capacitance of 300 F/g was obtained at 150 mA/cm2 current density. These results imply that this newspaper based carbon gel be used as potential candidate for supercapacitors.

An electrochemical double-layer capacitor (EDLC) is a potential buffer for current power and energy supply. In this work, activated carbon derived from fluid coke as a brand new electrode material was studied due to its high specific surface area (SSA) and large portion of mesopores. A suitable electrode material formula, current collector, and cell configuration were investigated to fabricate a testable system and ensure the reproducibility of measurements. Cyclic voltammetry (CV) and constant current charge/discharge (CD) techniques were used to characterize the performance of the electrode material, as well as to study its fundamental behaviour. A new procedure was established for quantifying the capacitance (Cc) of EDLC from CV which isolates the effect of internal resistance on the measured capacitance (CM). The specific capacitance of single electrode made of activated carbon (~1900 m2/g) with approximately 80% mesopores and macropores was able to reach 180 F/g at scan rate of 0.5mV/s.

An electrochemical double-layer capacitor (EDLC) is a potential buffer for current power and energy supply. In this work, activated carbon derived from fluid coke as a brand new electrode material was studied due to its high specific surface area (SSA) and large portion of mesopores. A suitable electrode material formula, current collector, and cell configuration were investigated to fabricate a testable system and ensure the reproducibility of measurements. Cyclic voltammetry (CV) and constant current charge/discharge (CD) techniques were used to characterize the performance of the electrode material, as well as to study its fundamental behaviour. A new procedure was established for quantifying the capacitance (Cc) of EDLC from CV which isolates the effect of internal resistance on the measured capacitance (CM). The specific capacitance of single electrode made of activated carbon (~1900 m2/g) with approximately 80% mesopores and macropores was able to reach 180 F/g at scan rate of 0.5mV/s.

Hydrogen is considered one of the best alternatives to fossil-fuels for the transportation sector because hydrogen can be burnt cleanly and efficiently in a fuel cell to drive an electric motor. However, due to the low density of H2 at ambient conditions the conventional H2 storage technologies (cryogenic liquid and compressed gas) cannot achieve energy densities comparable to to gasoline and diesel. A second energy storage challenge onboard electric fuel cell vehicles is fuel cell power management at peak current loads, which requires an auxiliary power source like a battery or supercapacitor. The development of efficient onboard energy storage systems for H2 and auxiliary power is critical to realisation of a hydrogen economy. Mesoporous carbons were investigated as H2 storage materials in composites with magnesium hydride (MgH2),and as electrode materials for electrochemical double-later capacitors. The mesoporous carbons were prepared by two methods: (1) from porous silica and alumina templates, and (2) by chemical activation of a waste carbon source (waste coffee grounds). The experimental approach targeted reducing the cost of mesoporous carbon preparation by using a cheaper template, where the cost of alumina template was one-fifth the cost of the silica template (at the laboratory scale), or by using a waste material as a carbon source. The alumina template was found to be suitable to produce a mesoporous carbon with an average pore size of 4.8 nm. Chemical activation of coffee grounds with ZnCl2 produced activated carbons with BET surface areas up to 1280 m2/g. Mesopore volume increased with ZnCl2 impregnation ratio, with mesopore size distributions in the range 2 - 20 nm. The theoretical H2 capacity of MgH2 is 7.6 % but MgH2 application in fuel cell vehicles is limited by slow hydrogenation kinetics and high temperatures (> 573 K) for H2 release. Magnesium was impregnated on activated carbon fibres (ACF) and mesoporous carbon (prepared from silica and alumina templates) to improve H2 storage kinetics and thermodynamics by reducing the magnesium hydride particle size. Thermal gravimetric analysis (TGA) and temperature programmed desorption (TPD) studies showed that thermal decomposition of MgCl2 supported on ACF at 1173 K in N2 and H2 can produce a Mg-ACF composite. At 573 K and 2 MPa H2 pressure a Mg-ACF composite, containing 11.2 %wt Mg, showed improved H2 adsorption kinetics compared to bulk Mg powder, but the total capacity of the Mg-ACF composite was only 0.4 % wt H2. To achieve a target of 6 %wt for onboard H2 storage higher Mg loadings are required. Attempts to impregnate Mg in mesoporous carbon via the MgCl2 thermal decomposition process highlighted the difficulties of avoiding MgO formation, and show that MgH2 loaded carbon is unlikely to be a practical high density onboard H2 storage technology. Activated carbons from waste coffee grounds (CGCs) were used as electrode materials in electrochemical double-layer capacitors. The specific capacitance of CGCs was as high as 368 F/g in 1 mol/L H2SO4, with good capacitance retention at fast charge rates and stable cycling performance. The good electrochemical performance of CGCs is attributed to a porous structure featuring both micropores 0.5 - 1.0 nm wide, which are effective for double-layer formation, and small mesopores, which facilitate electrolyte transport at fast charge rates. The capacitance of CGCs is enhanced by pseudo-Faradaic reactions involving nitrogen and oxygen functional groups. At fast charge-discharge rates the CGCs had higher energy density and better stability than a commercial benchmark activated carbon (Maxsorb). The ZnCl2 activation process can be optimised to develop mesopores for improved capacitance at fast charge rates and capacitance in organic electrolytes. In 1 mol/L tetra ethyl ammonium tetrafluoroborate (TEABF4) / acetonitrile the CGC with the most mesopores, which was prepared with a ZnCl2 to coffee ratio of 5:1, has the highest capacitance at high power density. CGCs with greater mesopore content retained higher specific capacitance at fast charge-discharge rates as the mesopores acts as channels or reservoirs for electrolyte transport. An improved model for evaluation of contributions to capacitance from micropore surfaces and mesopore surfaces is proposed. From this model the double-layer capacitance of mesopores surface area was found to be about 14 μF/cm2 and did not change considerably with increasing current load. The contribution of micropores to capacitance is dependent on the accessibility of ions to the micropores, and this accessibility is proportional to the mesopore surface area. An exponential function was found to describe the contribution of mesopores and micropore surfaces to capacitance. The effective double-layer capacitance of the micropore surface area drops at fast charge-discharge rates as a result of restricted ion transport, and this result highlights the importance of mesopores to retain energy density for high power supercapacitor applications.

The behavior of 2D materials has become of great interest in the wake of development of electrochemical double-layer capacitors (EDLCs) and the discovery of monolayer graphene by Geim and Novoselov. This study aims to analyze the response variance of 2D electrode materials for EDLCs prepared through the liquid-phase exfoliation method when subjected to differing conditions. Once exfoliated, samples are tested with a series of structural characterization methods, including tunneling electron microscopy, atomic force microscopy, Raman spectroscopy, and x-ray photoelectron spectroscopy. A new ionic liquid for EDLC use, 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate is compared in performance to 6M potassium hydroxide aqueous electrolyte. Devices composed of liquid-phase exfoliated graphene / MoS2 composites are analyzed by concentration for ideal performance. Device performance under cold extreme temperatures for the ionic fluid is presented as well. A brief overview of by-layer analysis of graphene electrode materials is presented as-is. All samples were tested with cyclic voltammetry, galvanostatic charge-discharge, and electrochemical impedance spectroscopy, with good capacitive results. The evolution of electrochemical behavior through the altered parameters is tracked as well.

In this research we have investigated electrochemical and impedance characteristics of liquid phase exfoliated graphene electrodes. The exfoliated graphene electrodes were characterized in Electrochemical Double Layer Capacitors (EDLCs) geometry. Liquid phase exfoliation was performed on bulk graphite powder in order to produces few layer graphene flakes in large quantities. The exfoliation processes produced few layer graphene based materials with increased specific surface area and were found to have suitable electrochemical charge storage capacities. Electrochemical evaluation and performance of exfoliated graphene electrodes were tested with Cyclic Voltammetry, constant current charging discharging and Electrochemical Impedance Spectroscopy (EIS) at ambient conditions. We have used several electrolytes in order to evaluate the effect of electrolyte in charge storage capacities. Specific capacitance value of ~ 47F/g and ~ 262F/g was measured for aqueous and ionic electrolytes respectively. These values are at least an order of magnitude higher than those obtained by using EDLC's electrodes fabricated with the bulk graphite powder. In addition these EDLC electrodes give consistently good performance over a wide range of scan rates and voltage windows. These encouraging results illustrate the exciting potential for high performance electrical energy storage devices based on liquid phase exfoliated graphene electrodes.

No description available.

The focus of this thesis has been to determine the usable voltage range of carbon-based supercapacitors (SC). Supercapacitors are a relatively new type of capacitors with a vast increase in capacitance compared to capacitors which utilize a dielectric as charge separator. A SC consists of two electrodes and an electrolyte separating the electrodes. The charges are stored by electrostatic forces in the interface between the electrode and the electrolyte, forming the so called electrochemical double-layer (EDL). With porous electrodes the effective surface area of the interfacial zone can be made very large, giving SCs a large storage capacity. The limiting factors of a SC is the decomposition potential of the electrolyte and the decomposition of the electrodes. For commercially manufactured SCs the electrolyte is usually an organic solvent, which has a decomposition potential of up to 2.7-2.8 V. Compared to aqueous electrolytes with a thermodynamic limit of 1.23 V. The drawback of using non-aqueous electrolytes is that they are not environmentally friendly, and they increase the production cost. It is claimed that the voltage range can be up to 1.9 V using aqueous electrolytes. Some researchers have focused on aqueous electrolytes for these reasons. In this thesis two different electrolytes were tested to determine if the voltage range could be extended. The experiments were conducted using a three electrode cell and performing cyclic voltammogram measurements (CV). The carbon electrodes were made of  two different sources of grahite, battery graphite or exfoliated graphite, and nano fibrilated cellulose was added to increase the mechanical stability. The results show that the oxidation potential of the carbon electrode was the positive limit. A usable potential of about 1 V was shown. However, when cycling the electrodes to potentials below the decomposition limit, for hydrogen evolution, interesting effects were seen. A decrease in reaction kinetics, indicating a type of conditioning of the electrode was observed. An increase in charge storage capacitance was also observed when comparing the initial measurements with the final, probably corresponding to an increase in porosity. / KEPS projekt Sundsvall Mitt Universitet

Philosophiae Doctor - PhD / To meet a fast-growing market demand for next generation portable electronic devices with higher performance and increased device functionalities, efficient electrical energy devices with substantially higher energy, power densities and faster recharge times such as supercapacitors are needed. The overall aim of this thesis was to synthesize nanostructured sulphonated polyaniline and transition metal single, binary and ternary mixed oxide doped nanocomposites with electro-conductive properties. These nanocomposites were anchored on activated graphitic carbon and used in design of asymmetric supercapacitors. Tantalum(IV)oxide, tantalum(IV)oxide-nickel(II)oxide, tantalum(II)oxide-manganese(III)oxide, tantalum(II)oxide-nickel(II)oxide-manganese(II,III)oxide nanoparticles were synthesised using modified sol-gel methods. These were then dispersed, individually, in acidic media through sonication and incorporated in-situ into the polymeric matrix during the oxidative chemical polymerization of aniline doped with poly(4-styrene sulphonic acid). These novel polymeric nanocomposites were characterised with FTIR, UV-visible, TEM, SEM, EDS, XRD to ascertain successful polymerization, doping, morphology and entrapment of the metal oxide nanoparticles. SECM approach curves and interrogation of CV revealed that these nanocomposites are conductive and electro-active. The cells showed good supercapacitor characteristics with high specific capacitances of 170.5 Fg⁻¹ in TaO₂- PANi-PSSA, 166.1 Fg⁻¹ in TaO₂-NiO-PANi-PSSA, 248.4 Fg-1 in TaO-Mn₂O₃-PANi- PSSA and 119.6 Fg⁻¹ in TaO-NiO-Mn₃O₄-PANi-PSSA. Their corresponding energy densities were calculated as 245.5 Whg⁻¹, 179.4 Whg⁻¹, 357.7 Whg⁻¹ and 172.3 Whg⁻¹ respectively. They also gave respective power densities of 0.50 Whg⁻¹, 0.61 Whg⁻¹, 0.57 Whg⁻¹ and 0.65 Whg⁻¹ and showed good coulombic efficiencies ranging between 77.97% and 83.19%. These materials are found to have a long cycle life and therefore good electrode materials for constructing supercapacitor cells. / National Research Foundation (NRF)