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1	Fyzikální analýza hlavních procesů v palivových článcích s pevnými oxidy a jejich matematická formulace / Physical analysis of the main processes in the solid oxide fuel cells and their mathematical description Vágner, Petr January 2014 (has links) Solid oxide fuel cells (SOFC) are mainly used as large stationary elec- tricity sources, therefore an every little improvement in their performance leads to considerable savings. In order to understand the fundamentals of the SOFC operation, we have developed a new model describing the main physical processes. The thermodynamical model of SOFC, developed in this thesis, concerns the gas transport, the transport of the charged particles in- cluding the thermoelectric effect and the electrochemical reactions. Linear irreversible thermodynamics is the key modelling framework, in which the dusty gas model and the Butler-Volmer equations are used. A new relation between the electrochemical affinity and the overpotential is introduced into the Butler-Volmer equation. A weakly formulated statinonary system en- dowed with boundary conditions is solved with the finite element method in one dimensional approximation. 1
2	Hydrogen electrochemistry in room temperature ionic liquids Meng, Yao January 2012 (has links) This thesis primarily focuses on the electrochemical properties of the H<sub>2</sub>/H<sup>+</sup> redox couple, at various metallic electrodes in room temperature ionic liquids. Initially, a comprehensive overview of room temperature ionic liquids, RTILs, compared to conventional organic solvents is presented which identifies their favourable properties and applications, followed by a second chapter describing the basic theory of electrochemistry. A third chapter presents the general experimental reagents, instruments and measurements used in this thesis. The results presented in this thesis are summarized in six further chapters and shown as follows. (1) Hydrogenolysis, hydrogen loaded palladium electrodes by electrolysis of H[NTf<sub>2</sub>] in a RTIL [C<sub>2</sub>mim][NTf<sub>2</sub>]. (2) Palladium nanoparticle-modified carbon nanotubes for electrochemical hydrogenolysis in RTILs. (3) Electrochemistry of hydrogen in the RTIL [C<sub>2</sub>mim][NTf<sub>2</sub>]: dissolved hydrogen lubricates diffusional transport. (4) The hydrogen evolution reaction in a room temperature ionic liquid: mechanism and electrocatalyst trends. (5) The formal potentials and electrode kinetics of the proton_hydrogen couple in various room temperature ionic liquids. (6) The electroreduction of benzoic acid: voltammetric observation of adsorbed hydrogen at a Platinum microelectrode in room temperature ionic liquids. The first two studies show electrochemically formed adsorbed H atoms at a metallic Pt or Pd surface can be used for clean, efficient, safe electrochemical hydrogenolysis of organic compounds in RTIL media. The next study shows the physicochemical changes of RTIL properties, arising from dissolved hydrogen gas. The last three studies looked at the electrochemical properties of H<sub>2</sub>/H<sup>+</sup> redox couple at various metallic electrodes over a range of RTILs vs a stable Ag/Ag<sup>+</sup> reference couple, using H[NTf<sub>2</sub>] and benzoic acid as proton sources. The kinetic and thermodynamic mechanisms of some reactions or processes are the same in RTILs as in conventional organic or aqueous solvents, but other remarkably different behaviours are presented. Most importantly significant constants are seen for platinum, gold and molybdenum electrodes in term of the mechanism of proton reduction to form hydrogen. 541
3	Mathematical modelling of primary alkaline batteries Johansen, Jonathan Frederick January 2007 (has links) Three mathematical models, two of primary alkaline battery cathode discharge, and one of primary alkaline battery discharge, are developed, presented, solved and investigated in this thesis. The primary aim of this work is to improve our understanding of the complex, interrelated and nonlinear processes that occur within primary alkaline batteries during discharge. We use perturbation techniques and Laplace transforms to analyse and simplify an existing model of primary alkaline battery cathode under galvanostatic discharge. The process highlights key phenomena, and removes those phenomena that have very little effect on discharge from the model. We find that electrolyte variation within Electrolytic Manganese Dioxide (EMD) particles is negligible, but proton diffusion within EMD crystals is important. The simplification process results in a significant reduction in the number of model equations, and greatly decreases the computational overhead of the numerical simulation software. In addition, the model results based on this simplified framework compare well with available experimental data. The second model of the primary alkaline battery cathode discharge simulates step potential electrochemical spectroscopy discharges, and is used to improve our understanding of the multi-reaction nature of the reduction of EMD. We find that a single-reaction framework is able to simulate multi-reaction behaviour through the use of a nonlinear ion-ion interaction term. The third model simulates the full primary alkaline battery system, and accounts for the precipitation of zinc oxide within the separator (and other regions), and subsequent internal short circuit through this phase. It was found that an internal short circuit is created at the beginning of discharge, and this self-discharge may be exacerbated by discharging the cell intermittently. We find that using a thicker separator paper is a very effective way of minimising self-discharge behaviour. The equations describing the three models are solved numerically in MATLABR, using three pieces of numerical simulation software. They provide a flexible and powerful set of primary alkaline battery discharge prediction tools, that leverage the simplified model framework, allowing them to be easily run on a desktop PC. advection anode asymptotic analysis BET surface area binary electrolyte boundary condition Butler-Volmer equation cathode closed circuit voltage concentration polarisation control volume current path discretisation diffusion electrochemical reaction electrode electrolytic manganese dioxide EMD crystals EMD particles exchange current density geometric surface area initial condition linearisation macrohomogeneous porous electrode theory mathematical model Nernst equation ohmic losses open circuit voltage ordinary differential equation overpotential partial differential equation perturbation techniques potassium hydroxide potassium zincate precipitation reaction primary battery separator paper simulation ternary electrolyte theoretical capacity utilisation zinc zinc oxide

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