Finite element analysis of electric double layer capacitors using a transient nonlinear Nernst-Planck-Poisson (NPP) model and Nernst-Planck-Poisson-modified Stern layer (NPPMS) model are presented in 1D and 2D. The NPP model provided unrealistic ion concentrations for high electrode surface potential. The NPPMS model uses a modified Stern layer to account for finite ion size, resulting in realistic ion concentrations even at high surface potential. The finite element solution algorithm uses the Newton-Raphson method to solve the nonlinear problem and the alpha family approximation for time integration to solve the NPP and NPPMS models for transient cases. Cubic Hermite elements are used for interfacing the modified Stern and diffuse layers in 1D while serendipity elements are used for the same in 2D. Effects of the surface potential and bulk molarity on the electric potential and ion concentrations are studied. The ability of the models to predict energy storage capacity is investigated and the predicted solutions from the 1D NPP and NPPMS models are compared for various cases. It is observed that NPPMS model provided realistic and correct results for low and high values of surface potential. Furthermore, the 1D NPPMS model is extended into 2D. The pore structure on the electrode surface, the electrode surface area and its geometry are important factors in determining the performance of the electric double layer capacitor. Thus 2D models containing a porous electrode are modeled and analyzed for understanding of the behavior of the electric double layer capacitor. The effect of pore radius and pore depth on the predicted electric potential, ion concentrations, surface charge density, surface energy density, and charging time are discussed using the 2D Nernst-Planck-Poissonmodified Stern layer (NPPMS) model.

The intrusion of chlorides and carbon dioxide into a reinforced concrete (RC) structure can initiate corrosion of the reinforcing steel, which, due to its expansive nature, can damage the structure and adversely affects its serviceability and safety. Corrosion will initiate if at the steel surface the concrete free chloride concentration exceeds a defined limit, or its pH falls below a critical level. Hence, determination of the time to reaching these critical limits is key to the assessment of RC structures durability and service life. Due to the ionic nature of the chlorides and the bicarbonate anion (HCO3-) formed by the CO2 in the multi-ionic pore solution, the transport of both species is driven by Fickian diffusion combined with electromigration and ionic activity, which can be mathematically expressed by the Nernst-Planck-Poisson (NPP) equations. For a complete representation of the phenomenon, however, the NPP equations must be supplemented by the relevant chemical equilibrium equations to ensure chemical balance among the various species within the concrete pore solution. The combination of NPP with the chemical equilibrium equations is often termed the NPP reactive transport model. In this study, such a model is developed, coded into the MATLAB platform, validated by available experimental data, and applied to analyze the time-dependent concrete carbonation and the movement of chlorides in carbonated and non-carbonated concrete. The results of these analyses can be used to predict the time to corrosion initiation. The transient one-dimensional governing equations of NPP are numerically solved using the Galerkin’s finite element formulation in space and the backward (implicit) Euler scheme in the time domain. The associated system of chemical equilibrium equations accounts for the key homogeneous and heterogeneous chemical reactions that take place in the concrete during carbonation and chlorides transport. At each stage of the analysis, the effects of these reactions on the changes in the pore solution chemical composition, pH, cement chloride binding capacity, concrete porosity, and the hydrated cement solids volumetric ratio are determined. The study demonstrates that given accurate input data, the presently developed NPP reactive transport model can accurately simulate the complex transport processes of chlorides and CO2 in concrete as a reactive porous medium, and the ensuing physical and chemical changes that occur due to the reaction of these species with the pore solution and the other cement hydration products. This conclusion is supported by the good agreement between results of the current analyses with the corresponding available experimental data from physical tests involving carbonation, and chloride diffusion in non-carbonated and carbonated concrete. / Thesis / Doctor of Philosophy (PhD)

Electrolytic solutions contain mobile ions that can pass current, and are essential components of any solution-phase electrochemical system. The Nernst–Planck–Poisson equations describe the electrodynamics and transport dynamics of electrolytic solutions. This thesis applies modern numerical and mathematical techniques in order to solve these equations, and hence determine the behaviour of electrochemical systems involving charge transport. The following systems are studied: a liquid junction where a concentration gradient causes charge transport; an ideally polarisable electrode where an applied potential difference causes charge transport; and an electrochemical cell where electrolysis causes charge transport. The nanometre Debye length and nanosecond Debye time scales are shown to control charge separation in electrolytic solutions. At equilibrium, charge separation is confined to within a Debye length scale of a charged electrode surface. Non-equilibrium charge separation is compensated in solution on a Debye time scale following a perturbation, whereafter electroneutrality dictates charge transport. The mechanism for the recovery of electroneutrality involves both migration and diffusion, and is non-linear for larger electrical potentials. Charge separation is an extremely important consideration on length scales comparable to the Debye length. The predicted features of capacitive charging and electrolysis at nanoelectrodes are shown to differ qualitatively from the behaviour of larger electrodes. Nanoscale charge separation can influence the behaviour of a larger system if it limits the overall rate of mass transport or electron transfer. This thesis advocates the use of numerical methods to solve the Nernst–Planck–Poisson equations, in order to avoid the simplifying approximations required by traditional analytical methods. As this thesis demonstrates, this methodology can reveal the behaviour of increasingly elaborate electrochemical systems, while illustrating the self-consistency and generality of fundamental theories concerning charge transport.

Electrochemical systems, which rely on coupled phenomena of the chemical change and electricity, have been utilized for development an interface between biological systems and conventional electronics.  The development and detailed understanding of the operation mechanism of such interfaces have a great importance to many fields within life science and conventional electronics. Conducting polymer materials are extensively used as a building block in various applications due to their ability to transduce chemical signal to electrical one and vice versa. The mechanism of the coupling between the mass and charge transfer in electrochemical systems, and particularly in conductive polymer based system, is highly complex and depends on various physical and chemical properties of the materials composing the system of interest. The aims of this thesis have been to study electrochemical systems including conductive polymer based systems and provide knowledge for future development of the devices, which can operate with both chemical and electrical signals. Within the thesis, we studied the operation mechanism of ion bipolar junction transistor (IBJT), which have been previously utilized to modulate delivery of charged molecules. We analysed the different operation modes of IBJT and transition between them on the basis of detailed concentration and potential profiles provided by the model. We also performed investigation of capacitive charging in conductive PEDOT:PSS polymer electrode. We demonstrated that capacitive charging of PEDOT:PSS electrode at the cyclic voltammetry, can be understood within a modified Nernst-Planck-Poisson formalism for two phase system in terms of the coupled ion-electron diffusion and migration without invoking the assumption of any redox reactions. Further, we studied electronic structure and optical properties of a self-doped p-type conducting polymer, which can polymerize itself along the stem of the plants. We performed ab initio calculations for this system in undoped, polaron and bipolaron electronic states. Comparison with experimental data confirmed the formation of undoped or bipolaron states in polymer film depending on applied biases. Finally, we performed simulation of the reduction-oxidation reaction at microband array electrodes. We showed that faradaic current density at microband array electrodes increases due to non-linear mass transport on the microscale compared to the corresponding macroscale systems.  The studied microband array electrode was used for developing a laccase-based microband biosensor. The biosensor revealed improved analytical performance, and was utilized for in situ phenol detection.