The primary objectives of this research are: (1) use a hierarchical structure to study electrode materials for next-generation lithium-ion batteries (LIBs) and (2) understand the fundamentals and utility of solid polymer electrolytes (SPEs) with the addition of halloysite nanotubes (HNTs) for battery applications. Understanding the fundamental principles of electrode and electrolyte materials allows for the development of high-performance LIBs. The contributions of this dissertation are described below. Encapsulated Si-VACNT Electrodes. Two hurdles prevent Si-based electrodes from mass production. First, bulk Si undergoes volume expansion up to 300%. Second, a solid-electrolyte interphase (SEI) forms between the interface of the electrolyte and electrode, which consumes battery capacity and creates more resistance at the interface. Si volume changes were overcome by depositing silicon on vertically-aligned carbon nanotubes (VACNTs). Encapsulating the entire Si-VACNT electrode surface with carbon was used to mitigate SEI formation. Although SEI formation was reduced by the encapsulation layer, capacity fade was still observed for encapsulated electrodes, indicating that SEI formation was not the primary factor affecting capacity fade. Additionally, the impact of the encapsulation layer on Li transport was examined. Two different transport directions and length scales were relevant””(1) radial transport of Li in/out of each Si-coated nanotube (~40 nm diameter) and (2) Li transport along the length of the nanotubes (~10 µm height). Experimental results indicated that the height of the Si-VACNT electrodes did not limit Li transport, even though that height was orders of magnitude greater than the diameter of the tubes. Simulation and experimental data indicated that time constant for Li diffusion into silicon was slow, even though the diffusion distance was short relative to the tube height. Other factors such as diffusion-induced stress likely had a significant impact on diffusion through the thin silicon layer. Solid Polymer Electrolytes. A thorough understanding of the relationships between physical, transport, and electrochemical properties was studied. HNT addition to polyethylene oxide (PEO) electrolytes not only improved the physical properties, such as reduction of the crystallinity of PEO, but also enhanced transport properties like the salt diffusivity. The processing steps were important for achieving enhanced properties. Moreover, HNTs were found to stabilize the interfacial properties of the SPE films during cycling. Specifically, HNT-containing SPE films were successfully cycled at room temperature, which may have important implications for SPE-based batteries.

[Truncated abstract] As mineral deposits continue to be mined, the non economic gangue materials such as sulphides (e.g. pyrite) that are extracted as part of the ore body or overburden are deposited within the waste rock and/or milled tailings. As a result of natural weathering processes, these reactive materials represent a potential hazard to surrounding environments. A major consequence, resulting from mine-waste impoundments containing sulphidic materials, relates to the offsite movement of low pH leachates containing elevated concentrations of metal ions posing a contamination threat. The processes and mechanisms acting in the formation of acid mine drainage (AMD) are highly variable and, to a high extent, controlled by climatic conditions as the main driver of water flow and wetness of the system which in turn determines the availability of oxygen as well as water for pyrite weathering. In particular, this thesis is based on the hypothesis that in semiarid and arid climates the acid production may be water … The experiments were repeated at different water contents ranging from 0.24 to 0.33 cm3 cm-3. Breakthrough curves (BTC) of Li+, K+, Ca2+, Mg2+, Na+ and pH were measured and described with models of different complexities. This included the use of a simple linear and non-linear isotherms for Li+ alone, a binary Li+ - K+ ion exchange, and a complete multicomponent chemical equilibrium description of ion transport. The latter, by including dissolution of primary minerals which released base cations such as Mg2+, Ca2+ and K+ explained some of the elution patterns of base cations for which the Li+ - K+ exchange was the dominant process. Furthermore, under unsaturated water flow conditions, retardation of Li+ increased with decreasing water content. Thus solute mobility in mafic rock tailings appears to decrease under strongly unsaturated water flow conditions.