Carbon materials are commonly studied as the electrode material for electrochemical double layer capacitance (EDLC) due to their high surface area. The present work aimed to leverage both EDLC and pseudocapacitance through chemical modification of multi-wall carbon nanotubes (MWCNTs) and onion-like carbon (OLC) with polyoxometalates (POMs) to further enhance the performance of these electrodes. Layer-by-layer (LbL) deposition of two commercially available POMs (PMo12O403- and SiMo12O404-) and three synthesized POMs (PMo11VO404-, PMo10V2O405- and PMo9V3O406-) has been investigated. A single-layer of POMs increased the area specific capacitance by approximately three-times, while superimposing of these POMs into two-layer coatings increased the capacitance by approximately five-times. The morphology and composition of these composite materials were investigated using Scanning Electron Microscopy (SEM) and X-ray Photoelectron Spectroscopy (XPS).

Carbon materials are commonly studied as the electrode material for electrochemical double layer capacitance (EDLC) due to their high surface area. The present work aimed to leverage both EDLC and pseudocapacitance through chemical modification of multi-wall carbon nanotubes (MWCNTs) and onion-like carbon (OLC) with polyoxometalates (POMs) to further enhance the performance of these electrodes. Layer-by-layer (LbL) deposition of two commercially available POMs (PMo12O403- and SiMo12O404-) and three synthesized POMs (PMo11VO404-, PMo10V2O405- and PMo9V3O406-) has been investigated. A single-layer of POMs increased the area specific capacitance by approximately three-times, while superimposing of these POMs into two-layer coatings increased the capacitance by approximately five-times. The morphology and composition of these composite materials were investigated using Scanning Electron Microscopy (SEM) and X-ray Photoelectron Spectroscopy (XPS).

Electrochemical capacitors (ECs) have drawn much attention owing to their fast charging/discharging rate, and long lifetime up to millions of cycles. Applications of EC range from large scale transportation to miniaturized electronics. The research reported herein explores the development of an economical process for the synthesis of high performance electrode material for high power ECs. A two stage synthesis process which consists of electroplating of molybdenum oxide followed by thermal nitridation was developed. X-ray diffraction and X-ray photoelectron spectroscopy revealed the material to be Mo oxide with nitrogen substitution, Moz(O,N). In a three electrode system, the Moz(O,N) electrodes showed capacitance as high as 16 mF/cm2. Symmetric EC cells achieved state of the art time constant of 100 ms. Ultrahigh power ECs were demonstrated for the first time using Moδ(O,N) electrodes and SiWA-H3PO4-PVA electrolyte, achieving with 10 ms time constant one of the lowest time constants reported for EC.

Electrochemical capacitors (ECs) have drawn much attention owing to their fast charging/discharging rate, and long lifetime up to millions of cycles. Applications of EC range from large scale transportation to miniaturized electronics. The research reported herein explores the development of an economical process for the synthesis of high performance electrode material for high power ECs. A two stage synthesis process which consists of electroplating of molybdenum oxide followed by thermal nitridation was developed. X-ray diffraction and X-ray photoelectron spectroscopy revealed the material to be Mo oxide with nitrogen substitution, Moz(O,N). In a three electrode system, the Moz(O,N) electrodes showed capacitance as high as 16 mF/cm2. Symmetric EC cells achieved state of the art time constant of 100 ms. Ultrahigh power ECs were demonstrated for the first time using Moδ(O,N) electrodes and SiWA-H3PO4-PVA electrolyte, achieving with 10 ms time constant one of the lowest time constants reported for EC.

This thesis explores a rigorous approach to model the behaviour of an electrochemical cell. A simple planar electrochemical cell consisting of stainless steel electrodes separated by a sulfuric acid electrolyte layer is modeled from first principles. The model is a dynamic model and is valid under constant temperature conditions. The dynamic model is based on the Poisson-Nernst-Planck electrodiffusion theory and physical attributes such as the impact of nonlinear polarization, the stoichiometric reactions of the electrolyte and changes to the transport coefficients are investigated in stages. The system of partial differential equations has been solved using a finite element software package. The simulation results are compared with experimental results and discrepancies are discussed. The results suggest that the existing theory is not adequate in explaining the physics in the immediate vicinity of the electrode/electrolyte interface even though the general experimental and simulation results are in qualitative agreement with each other.

This work examines the role of charge redistribution in the self-discharge of electrochemical capacitor electrodes. Electrochemical capacitors are charge storage devices which have high power capability and a long cycle life, but have a low energy density compared to other devices, coupled with a high rate of self-discharge which further diminishes the available energy. The mechanisms of self-discharge in electrochemical capacitors are poorly understood, and it is important to gain a better understanding of the electrode processes which lead to self-discharge, in order to minimize self-discharge and enhance electrochemical capacitor performance. To learn more about charge redistribution and its role in the self-discharge of electrochemical capacitors, multiple self-discharge experiments were performed on carbons with various surface areas/pore structures and in various electrolytes. Charge redistribution was also examined in a model pore (a transmission line circuit based on de Levie?s model of a porous electrode) and results from this model were compared to the self-discharge of a high surface-area carbon. Results demonstrate that charge redistribution is a major component of the self-discharge in high surface-area carbons. Results also indicate that charge redistribution requires a much longer time than previously thought (tens of hours rather than minutes) which further highlights the importance of charge redistribution during self-discharge. Therefore when performing mechanistic studies of self-discharge in electrochemical capacitors, it is important that effects of charge redistribution are not neglected. The self-discharge profiles of various pore shapes were also examined using the model pore, and results emphasize the superiority of cone and cylindrically shaped pores, and the disadvantages of restrictive pore mouths and bottlenecks for high power applications.

This thesis explores a rigorous approach to model the behaviour of an electrochemical cell. A simple planar electrochemical cell consisting of stainless steel electrodes separated by a sulfuric acid electrolyte layer is modeled from first principles. The model is a dynamic model and is valid under constant temperature conditions. The dynamic model is based on the Poisson-Nernst-Planck electrodiffusion theory and physical attributes such as the impact of nonlinear polarization, the stoichiometric reactions of the electrolyte and changes to the transport coefficients are investigated in stages. The system of partial differential equations has been solved using a finite element software package. The simulation results are compared with experimental results and discrepancies are discussed. The results suggest that the existing theory is not adequate in explaining the physics in the immediate vicinity of the electrode/electrolyte interface even though the general experimental and simulation results are in qualitative agreement with each other.

Multi-walled carbon nanotubes (MWCNTs) were successfully coated with two different pseudocapacitive polyoxometalates (POMs) (SiMo12O40-4 (SiMo12) and PMo12O40-3 (PMo12)) via “Layer-by-Layer” deposition. Even with merely a “single-layer” of POM, the modified nanotubes exhibited more than 2X increase in capacitance compared with that of bare nanotubes. To further improve their electrochemical performances, the deposition sequence of the POM layers was adjusted to form “alternate layer” coating to modify MWCNT. A synergistic effect on the capacitance and kinetics was observed with the alternate layer coatings. X-ray Photoelectron Spectroscopy (XPS) and Scanning Electron Microscopy (SEM) also proved the successful coating of POMs on MWCNTs. The potential-pH relationship provided important insights in terms of the deposition mechanism and suggested that the bottom layer close to the electrode substrate was the dominating layer in alternate layer coated MWCNT electrodes.

Multi-walled carbon nanotubes (MWCNTs) were successfully coated with two different pseudocapacitive polyoxometalates (POMs) (SiMo12O40-4 (SiMo12) and PMo12O40-3 (PMo12)) via “Layer-by-Layer” deposition. Even with merely a “single-layer” of POM, the modified nanotubes exhibited more than 2X increase in capacitance compared with that of bare nanotubes. To further improve their electrochemical performances, the deposition sequence of the POM layers was adjusted to form “alternate layer” coating to modify MWCNT. A synergistic effect on the capacitance and kinetics was observed with the alternate layer coatings. X-ray Photoelectron Spectroscopy (XPS) and Scanning Electron Microscopy (SEM) also proved the successful coating of POMs on MWCNTs. The potential-pH relationship provided important insights in terms of the deposition mechanism and suggested that the bottom layer close to the electrode substrate was the dominating layer in alternate layer coated MWCNT electrodes.

The objective of this work is to electrospin poly(acrylonitrile) (PAN) based nanofibers with controlled diameter and to stabilize and carbonize them for developing meso-porous carbon for application as electrochemical capacitor electrodes. A sacrificial polymer, poly(styrene-co-acrylonitrile) (SAN) has been used to control porosity. Carbon nanotubes (CNT) have been used to increase electrode conductivity and hence power density. The study has been divided into two parts. In part I, electrospinning behavior of PAN and PAN/CNT has been studied. The diameter of electrospun PAN fibers was monitored as a function of polymer molecular weight, solution concentration, solution flow rate, distance between the spinneret and the target, and the applied voltage. Bead free PAN fibers of 60 nm diameter have been electrospun. Various electrospun fibers have been characterized by wide angle X-ray diffraction and by Raman spectroscopy. Electrospinning process has been observed by high speed photography. In part II, the electrospun PAN, PAN/SAN, and PAN/SAN/CNT fiber mats were stabilized, carbonized, and processed into electrochemical capacitor electrodes. The performance of the electrochemical capacitors was tested by the constant current charge/discharge and cyclic voltammetry in 6 molar potassium hydroxide aqueous solution. The surface area and pore size distribution of the electrodes were measured using N2 adsorption and desorption. The effect of surface area and pore size distribution on the capacitance performance has been studied. The capacitance performance of various carbonized electrospun fibers mats have been compared to those of the PAN/SAN/CNT film, carbon nanotube bucky paper, and activated carbon pellet. The capacitance of PAN/SAN/CNT fiber mat over 200 F/g (at a current density of 1 A/g) and the power density approaching 1 kW/kg have been observed. Addition of 1 wt% carbon nanotubes in PAN/SAN, improves the power density by a factor of four. For comparison, the capacitance of single wall carbon nanotube bucky paper at a current density of 1 A/g is about 50 F/g.