In Situ Examination of Nanoscale Reaction Pathways in Battery Materials
Boebinger, Matthew G.
MetadataShow full item record
In order to engineer less expensive and more energy-dense batteries, new materials that can reliably store and transport active ions must be first developed. However, these materials are known for their poor reversibility due to large morphological changes during cycling. To maximize reversibility during charge and discharge, we must be able to understand and control the electrochemical reaction mechanisms of these new electrode materials. This dissertation uses in situ experiments, primarily in situ transmission electron microscopy (TEM), to understand the nanoscale reaction pathways in various high-capacity electrode materials during reactions with Li+, Na+, and K+ ions. Upon reacting with alkali-metal ions, these electrode materials often exhibit much higher specific storage capacities than conventional Li-ion battery electrode materials. In addition, these types of materials can also be used in lower-cost sodium- and potassium-based systems. Hence, they could replace electrode materials in Li-ion batteries, which would make possible engineering batteries with higher specific energy. However, the more substantial volumetric changes that these electrode materials undergo during reaction cause a significant decrease in the capacity retention. This decrease in the capacity retention is caused by the mechanical fracture of the active material and continuous growth of the solid-electrolyte interphase (SEI) on the surface of the anode particles, which both lead to very low cyclability of these systems. If these battery systems are to be improved, it is critical to understand both how the larger Na+ and K+ ions affect the nanoscale phase transformations during these reactions and how to engineer high capacity battery materials with high coulombic efficiency and longer cycle life. As part of the research described in this dissertation, studies on the Cu2S and FeS2 active materials were conducted to examine the effect that larger alkali metal ions have on the reaction mechanisms of large-volume-change materials. Evidence obtained from extensive in situ and ex situ experiments suggests that the larger volume changes associated with the sodium/potassium reactions indicate that the different reaction pathways affect the materials behavior. This altered reaction behavior results in a more stable morphology for the overall cycling of the electrode material. In an effort to aid the engineering of a high capacity battery material with longer cycle life, a study was conducted on Sb nanocrystal electrode materials that exhibited stable electrochemical behavior. This study demonstrated that small spherical particles naturally formed uniform internal voids that were easily filled and vacated during cycling. This was found to be due to the resilient lithiated oxide layer that formed after the first lithiation and subsequently prevented shrinkage during delithiation. A chemomechanical model describing the void formation was developed; this model can serve as a tool to guide the creation of oxide or other shells that enable alloying materials to undergo voiding transformations in situ. When reacting with alkali ions of different sizes, all of these materials (Cu2S, FeS2, and Sb) exhibited counter-intuitive phase evolution and mechanical degradation behavior. The findings indicate that, thanks to their high energy density, large-volume-change materials could make possible the development of next-generation batteries, whether they be Li-ion batteries or batteries with other chemistries that undergo complex morphological changes.