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While the process of electrifying transportation is already underway, competing with fossil fuels in applications such as long-range vehicles and aircrafts will require energy densities that are beyond what is achievable using conventional Li-ion battery chemistries. Li metal batteries are promising candidates for such applications, yet meeting cycle life, power density, and safety demands while utilizing the unmatched specific capacity of Li metal anodes is a formidable challenge. It is well known that the interfacial layer of electrolyte decomposition products which forms on the Li surface during electrochemical cycling (i.e. the solid electrolyte interphase (SEI)) is critical in dictating Li deposit morphology and subsequent performance. However, both the composition and arrangement of the SEI are difficult to study because the SEI is just nanometers-thin, air-sensitive, and evolves as a function of electrochemical cycling protocol. Thus, it is important to develop in situ and operando techniques which are capable of characterizing the SEI in its native environment. Here, we study interphase formation in carbonate, ether, solid ceramic, and highly concentrated electrolytes to develop a framework for the general design of electrolytes and SEIs for Li metal batteries. In the first chapter, we broadly motivate electrochemical energy storage devices and define the metrics which make them attractive compared to alternative forms of energy storage. We then describe Li-based batteries, outline the differences between Li-ion and Li metal batteries, and present some of the key advantages and challenges that Li metal chemistries face. After, we provide a classical description of electrodeposition frameworks, focusing on the effects of charge-transfer kinetics and ion transport on deposition morphology. Then, we present the SEI as a factor which convolutes this process in Li metal anodes and describe how the SEI is formed and arranged on the electrode surface. Finally, we describe common tools used to characterize the SEI and how these may be used to design future electrolytes. The second chapter focuses on the effect of potassium additives on conventional carbonate electrolytes. Recent work has shown that alkali metal additives can lead to smooth Li deposits, yet the underlying mechanisms are not well understood. In this work, we demonstrate that alkali metal additives (here, K+) alter SEI composition, thickness, and solubility. Through post-mortem elemental analyses, we find that K+ ions do not deposit, but instead modify the reactivity of the electrode-electrolyte interface. Using quantitative nuclear magnetic resonance (NMR) and density functional theory (DFT), we show that K+ mitigates solvent decomposition at the Li metal surface. These findings suggest that alkali metal additives can be leveraged to suppress the formation of undesired SEI components (e.g., Li2CO3, soluble organic species), serving as an alternative approach for SEI modification compared to sacrificial additives. We believe that our work will spur further interest in the underexplored area of cation engineering. In the third chapter, we examine both chemical structure and ion dynamics in the SEI, correlating these properties to electrochemical performance to guide the design of new electrolytes. We use a combination of NMR spectroscopy and X-ray photoelectron spectroscopy (XPS) to show that fast Li transport, well-ordered SEI architectures, and low solubility at the electrode/SEI interface in 0.5 M LiNO3 + 0.5 M LiTFSI electrolyte bi-salt in 1,3-dioxolane:dimethoxyethane (DOL:DME, 1:1, v/v) are responsible for the formation of low-surface-area Li deposits and high Coulombic efficiency (CE). This improved performance in the presence of LiNO3 is observed despite the fact that there are higher quantities and more types of compounds in the SEI than in LiTFSI alone, suggesting that the identity of the electrolyte decomposition products, rather than the amount, alters plating. SEI design strategies that increase SEI stability and Li interfacial exchange rate are thus expected to lead to more even current distribution, ultimately providing a new framework to generate smooth Li morphologies during plating/stripping. The fourth chapter describes the dynamic behavior of the interface between a lithium metal electrode and a solid-state electrolyte, lithium lanthanum zirconium oxide (Li7La3Zr2O12 or LLZO). The evolution of this interface throughout cycling involves multiscale mechanical and chemical heterogeneity at the micro- and nano-scale and plays a critical role in all-solid-state battery performance. These features are dependent on operating conditions such as current density and stack pressure. Here we report the coupling of operando acoustic transmission measurements with NMR and magnetic resonance imaging (MRI) to correlate changes in interfacial mechanics (such as contact loss and crack formation) with the growth of lithium microstructures during cell cycling. Together, the techniques reveal the chemo-mechanical behavior that governs lithium metal and LLZO interfacial dynamics at various stack pressure regimes and with voltage polarization. In the fifth chapter, we redefine the premise of a class of Li metal battery electrolytes known as localized high concentration electrolytes (LHCE). LHCEs operate on the assumption that high concentration electrolytes (HCEs) may be augmented using a “diluent,” which interacts scarcely with both the ionic species and the Li metal surface, forming pockets of localized high concentration Li+ which have advantageous bulk and interfacial properties. We report on the use of operando NMR spectroscopy to observe electrolyte decomposition during Li stripping/plating and identify the influence of individual components in LHCEs on Li metal battery performance. Data from operando 19F solution NMR indicates that both bis(fluorosulfonyl)imide (FSI–) salt and bis(2,2,2-trifluoroethyl)ether (BTFE) diluent molecules play a key role in SEI formation, in contrast to prior reports that suggest diluents are inert. Using solution 17O NMR, we assess differences in solvation between LHCEs and low concentration electrolytes (LCEs). We find that BTFE diluents are reduced during Li metal battery operation, which can be detected with operando NMR, but not conventional electrochemical methods. Solid-state NMR (SSNMR) and XPS measurements confirm that LHCEs decompose to form an SEI on Li metal that contains organic BTFE reduction products (CF2, CF3), trapped BTFE, and high quantities of lithium fluoride, likely due to both BTFE and FSI– reduction. These chemical characterizations are correlated with changes in interfacial impedance measured separately at the anode and cathode using three-electrode electrochemical impedance spectroscopy (EIS). Insight into the mechanisms of SEI and CEI formation in LHCEs suggests that fluorinated ethers exhibit tunable reactivity that can be leveraged to control Li deposition behavior. To conclude, we reflect on some of the broad guidelines for electrolyte and SEI engineering that we gleaned from the previous chapters. Finally, we highlight recent notable works which we think will enable major advances in interfacial characterization of Li metal batteries (focusing on in situ and operando techniques which can be applied to study both structure and dynamics in commercial setups).

The large conductance calcium dependent potassium (BKCa) channels are expressed in a large variety of cell types including neurons where they modulate excitability and action potential shape. Within the enteric nervous system, stretch-sensitive BKCa channels are expressed on intrinsic primary afferent neurons (IPANs) where they decrease the neurons’ excitability during intestinal contractions. A major determinant of peristalsis is slow excitatory neurotransmission (sEPSPs) within the IPAN to IPAN sensory network, and we wondered whether such transmission might also alter BKCa channel opening. All experiments were performed on longitudinal-muscle myenteric preparations prepared from jejunal segment taken from freshly euthanized adult male Swiss Webster mice. With the myenteric plexus exposed by microdissection, BKCa channel activity was recorded in cell-attached mode via the patch clamp technique. BKCa channel activity was recorded before and after presynaptic electrical stimulation, which was designed to evoke postsynaptic sEPSPs. The morphotype was verified by intracellular injection of a marker dye (neurobiotin). In addition, a blocker and opener were used to identify the effects of BKCa currents on IPAN properties. Analysis of unitary channel recordings revealed increased BKCa open probability (NPo) at fixed trans-patch potentials following sEPSPs. All BKCa channels were independently voltage sensitive with increased NPo during patch depolarisation. Analysis of whole-cell experiments also revealed BKCa channels have a significant effect on the undershoot amplitude of action potentials, and the rate at which IPANs repolarise. This study demonstrates that sEPSPs within the enteric nervous system modulate the function of BKCa channels in IPANs adding to the mechanistic understanding of enteric synaptic transmission and providing a potential target for therapeutic modulation of enteric nervous system excitability. / Thesis / Master of Science (MSc)

Abstract Not Provided. / Thesis / Master of Science (MSc)

This thesis addresses two hypotheses: 1) ooplasmic ion activity is regulated during water uptake by locust eggs, and, 2) activities of Ca⁺⁺ and H⁺ are maintained at levels appropriate for their use as signals for developmental processes, including activation, in insect eggs. Hypothesis 1 is based on the perturbing effect of large changes in intracellular Na and/or K activity on enzyme function in eukaryotic cells. Hypothesis 2 is based on the ionic hypothesis of activation developed from studies of eggs of marine invertebrates. Electrical potential difference across egg membranes (PD_egg), and ooplasmic activities of Na⁺, K⁺, Cl⁻, Ca⁺⁺ and H⁺ were measured with double-barrelled ion-selective microelectrodes. Locust eggs maintained a measurable potential difference across egg membranes throughout development. Input resistance (Rᵢₙ) decreased by approximately 5-fold in eggs after fertilization suggesting that the chorion is not the major barrier to ion movements into and out from the egg. Chilling and anoxia decreased the contribution of a metabolic component to PD_egg. The effects of hypercapnia on PD_egg and ooplasmic pH suggest that the metabolic component may be a H⁺-pump. Chloride diffusion contributes to PD_egg in eggs after fertilization; contributions of other ions were relatively small. Potential differences measured in internally perfused locust eggs after osmotic lysis of the serosal epithelium indicated that the chloride-dependent component of PD_egg is developed across the chorion and/or serosal cuticle. In vivo values of PD_egg are probably less negative than values measured in control saline because chloride content of ground water is low. Ooplasmic sodium and potassium activities remained at typically intracellular levels during water uptake, possibly due to release from internal stores. Chloride activities were typical of extracellular fluids and were not regulated during water uptake. Measurements of pH and pea in locust eggs are consistent with the increases in these parameters predicted by the ionic hypothesis of activation. calcium activity in the ooplasm of unfertilized locust eggs (pCa 6.4 -4.9) appeared to be at a level appropriate for the use of calcium as a signal or second messenger. Calcium activity increased 100fold within 1 day of fertilization, and 1000-fold by day 3. Calcium entry from external sources at fertilization and release from internal stores later in development may contribute to the progressive increase in ooplasmic Ca⁺⁺ activity. The ooplasm likely alkalinizes after oviposition as ambient pCo₂ declines. Available data suggest a metabolically-dependent proton pump may control ooplasmic pH in locust eggs, in contrast to the Na⁺/H⁺ exchanger implicated in alkalinization of marine invertebrate eggs. / Thesis / Master of Science (MS)

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