Lithium-ion batteries with higher capacity and longer cycle life than that available today are required as secondary energy sources for a wide range of emerging applications. In particular, the cycling performance of several candidate materials for lithium-ion battery electrodes is insufficient because of the fast capacity fading and short cycle life, which is mainly a result of mechanical degradation. This dissertation mainly focuses on the issue of mechanical degradation in advanced lithium-ion battery electrodes. Thin films of tin electrodes were studied where we observed whisker growth as a result of electrochemical cycling. These whiskers bring safety concerns because they may penetrate through the separator, and cause short-circuit of the electrochemical cells. Cracking patterns generated in amorphous silicon thin film electrodes because of electrochemical cycling were observed and analyzed. A two-dimensional spring-block model was proposed to successfully simulate the observed cracking patterns. With semi-quantitative study of the cracking pattern features, two strategies to void cracking in thin-film electrodes were proposed, namely reducing the film thickness and patterning the thin-film electrodes. We also investigated electrodes consisting of low melting point elements and showed that cracks can be self-healed by the solid-to-liquid phase transformation upon cycling. Using gallium as an example, mechanical degradation as a failure mechanism for lithium-ion battery electrodes can be eliminated. In order to quantitatively understand the effect of surface modification on electrodes, we analyzed diffusion equations with boundary conditions of finite interfacial reactions, and proposed a modified potentialstatic intermittent titration technique (PITT) as an electro-analytical technique to study diffusion and interfacial kinetics. The modified PITT has been extended to thin-film geometry and spherical geometry, and thus can be used to study thin-film and composite electrodes consisting of particles as active materials.

<p dir="ltr">The thesis goal was to design a quasi-solid-state battery electrolyte, which was optimized to function at ambient as well as low temperatures. In the first project, an array of quasi-solid-state electrolytes were developed and compared. A series of electrochemical, spectroscopic, and thermal experiments in addition to imaging techniques determined a top performer as well as elucidated possible mechanistic explanations. This systematic study attempted to validate literature conclusions about the failure mechanisms governing batteries (solid-state batteries) at ultralow temperatures, while also offering hypothesis driven additional insight. The optimized electrolyte, which will be deemed as CSPE@2MMeTHF, performed well for several key reasons, traced to the co-solvent used (Me-THF), the salt concentration, and its formation of a stable and suitable cathode-electrolyte interphase. It was able to perform well at 25 °C, and down to -25 °C. The second part of the work, focused on further optimizing the electrolyte by removing a ‘polymer wetting/soaking’ step, removing a ceramic component, and pairing it with a recently discovered anodic electrode material. Given that narrowing the research gap for low temperatures requires both electrolyte and electrode design, it was important to consider this aspect of the problem as well. The cathodic electrode used for the first project, traditionally performs poorly at low temperatures, allowing for a suitable experimental control for the electrolyte. However, the new anodic electrode had two ways of storing lithium ions, as opposed to just one in the former, making it an attractive option for the stated goal of a low-temperature solid-state battery. This second project is akin to a ‘proof-of-concept’ work and there is much more room for further study, especially in preparing a full cell with the aforementioned electrodes cathode (LFP) and anode (NbWO) with the second SPE@51DMMeT electrolyte. In summary, this thesis shows method design to prepare solid-state electrolytes with portion of liquid, two successfully developed electrolyte systems for low temperatures, and a rigorous discussion of factors that affect electrochemical performance. Demonstrated research activities are of great value to defense as the current lithium-ion batteries does not perform well at subzero temperatures.</p>

<p>In this dissertation, the Phase Field Crystal (PFC) Method is used to study a number of problems in which interfaces and elastic effects play important roles in alloys. In particular, the three topics covered in this work are grain boundary thermodynamics in alloys, dislocation-mediated formation of clusters in binary and ternary alloys, and solutal effects in explosive crystallization. Physical phenomena associated with grain boundaries, such as Read-Shockley-like behaviour and Gibbs adsorp- tion theorem, were shown to be accurately captured in both PFC- and XPFC-type models. In fact, a connection between the solute segregation behaviour and physical properties of the system—such as energy of mixing, mismatch, and undercooling—were shown. Also, grain boundary premelting was investigated. It was shown how solute can change the disjoining potential of a grain boundary and a mechanism for hysteresis in grain boundary premelting was discussed. Regarding the phenomenon of cluster formation, a general coexistence approach and a nucleation-like approach were used to describe the mechanism consistently with observations; the process is facilitated by lowering the energy increase associated with it. The final phenomenon studied was explosive crystallization. It was shown that the temperature oscillations due to unsteady motion of an interface could be captured with PFC-type models and that this behaviour leaves patterns, such as solute traces, in the material. The versatility of this PFC formalism was demonstrated by capturing the underlying physics and elucidating the role of misfit strain in altering interface oscillations during explosive crystallization. Finally, it was demonstrated in all projects how PFC model parameters relate to coarse-grained material properties, thereby connecting these phenomena on larger scales to atomistic-scale properties.</p> / Doctor of Philosophy (PhD)

This thesis presents a mathematical model of the nanoporous anode within a dyesensitised solar cell (DSC). The main purpose of this work is to investigate interfacial charge transfer and charge transport within the porous anode of the DSC under both illuminated and non-illuminated conditions. Within the porous anode we consider many of the charge transfer reactions associated with the electrolyte species, adsorbed dye molecules and semiconductor electrons at the semiconductor-dye- electrolyte interface. Each reaction at this interface is modelled explicitly via an electrochemical equation, resulting in an interfacial model that consists of a coupled system of non-linear algebraic equations. We develop a general model framework for charge transfer at the semiconductor-dye-electrolyte interface and simplify this framework to produce a model based on the available interfacial kinetic data. We account for the charge transport mechanisms within the porous semiconductor and the electrolyte filled pores that constitute the anode of the DSC, through a one- dimensional model developed under steady-state conditions. The governing transport equations account for the diffusion and migration of charge species within the porous anode. The transport model consists of a coupled system of non-linear differential equations, and is coupled to the interfacial model via reaction terms within the mass-flux balance equations. An equivalent circuit model is developed to account for those components of the DSC not explicitly included in the mathematical model of the anode. To obtain solutions for our DSC mathematical model we develop code in FORTRAN for the numerical simulation of the governing equations. We additionally employ regular perturbation analysis to obtain analytic approximations to the solutions of the interfacial charge transfer model. These approximations facilitate a reduction in computation time for the coupled mathematical model with no significant loss of accuracy. To obtain predictions of the current generated by the cell we source kinetic and transport parameter values from the literature and from experimental measurements associated with the DSC commissioned for this study. The model solutions we obtain with these values correspond very favourably with experimental data measured from standard DSC configurations consisting of titanium dioxide porous films with iodide/triiodide redox couples within the electrolyte. The mathematical model within this thesis enables thorough investigation of the interfacial reactions and charge transport within the DSC.We investigate the effects of modified cell configurations on the efficiency of the cell by varying associated parameter values in our model. We find, given our model and the DSC configuration investigated, that the efficiency of the DSC is improved with increasing electron diffusion, decreasing internal resistances and with decreasing dark current. We conclude that transport within the electrolyte, as described by the model, appears to have no limiting effect on the current predicted by the model until large positive voltages. Additionally, we observe that the ultrafast injection from the excited dye molecules limits the interfacial reactions that affect the DSC current.