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.



College and Department

Ira A. Fulton College of Engineering and Technology; Chemical Engineering



Date Submitted


Document Type





silicon anode, Li transport, encapsulation, polymer electrolyte, halloysite nanotubes, Juichin Fan



Included in

Engineering Commons