The wide applications of energy storage systems in consumer electronics, electric vehicles, and grid storage in the recent decade has created an enormous market globally. The electrochemical flow system has many applications in Li-ion battery recycling and energy storage system design. First, research work on a scalable electrochemical flow system is presented to effectively restore the lithium concentration in end-of-life Li-ion cathode materials. An effective recycling process for end-of-life lithium-ion batteries could relieve the environmental burden and retrieve valuable cathode battery materials. The design is validated in a static configuration with both cathode loose powder and cathode electrode sheet. Materials with comparable electrochemical performance to virgin cathode materials are produced after post heat treatment. Second, research contributions in sulfur-based flow battery systems for long-duration energy storage are presented. Sulfur-based redox flow batteries are promising due to their high theoretical capacity, low cost, and high abundance. The speciation of aqueous sulfur solutions with different nominal concentrations, sulfur concentrations, and pH are studied by Raman spectroscopy. Next, a promising aqueous manganese catholyte to couple with the sulfur anolyte for a full flow battery is investigated. Test protocols and quantification metrics for the catholyte are developed. The stability of the catholyte, including self-discharge rate and precipitation rate, is measured via ex-situ characterizations. The electrochemical performance of the catholyte is investigated and optimized via in-situ experiments. The reaction pathway for the precipitation of catholyte is discussed and several mitigation strategies are proposed. Finally, a semi-solid sodium-sulfur flow battery is developed. The electrochemical performance of the sodium-sulfur battery is studied first in a static configuration at an intermediate temperature (150°C). Then a Na-S semi-solid flow cell is assembled and cycled under the two-aliquots and three-aliquots intermittent flow. / Doctor of Philosophy / The market of energy storage systems has been expanding dramatically in recent years due to their wide applications in portable electronics, electric vehicles, and large-scale grid storage. First, the research on the development of an electrochemical flow system in the Li-ion batteries (LIB) recycling process is presented. The improper disposal of end-of-life LIBs will generate flammable hazardous waste. Recycling spent LIBs could ease the environmental burden and replenish valuable resources such as lithium, cobalt, and nickel, and reduce the cost of battery manufacturing. In this study, an electrochemical flow system is designed to restore the end-of-life cathode materials in LIBs. The design has the potential to scale up and is validated with a static configuration. The recycled materials show comparable electrochemical performance to virgin battery cathode materials. Life cycle analysis shows that the recycling process consumes less energy and is more environmentally friendly. Second, the research contribution in sulfur-based flow battery systems for long-duration energy storage is presented. The aqueous sulfur solutions with different nominal concentrations, sulfur concentrations, and pH are studied by Raman spectroscopy. Next, a promising aqueous manganese catholyte to couple with the sulfur anolyte for a full redox flow battery is investigated. The chemical stability of the catholyte, including self-discharge rate and precipitation rate, is measured via ex-situ characterizations. The electrochemical performance of the catholyte is studied and optimized via in-situ experiments. The reaction mechanisms for the precipitation of aqueous manganese solutions are discussed. Finally, a semi-solid sodium-sulfur (Na-S) flow battery is developed. The electrochemical performance of the sodium-sulfur battery is studied first in a static cell at intermediate temperature. Then a Na-S semi-solid flow cell is demonstrated and cycled under the two-aliquots and three-aliquots intermittent flow.

Low-cost, high-performance energy storage solutions are in great demand for applications such as vehicle electrification and electricity generation from renewable sources. Lithium-based batteries have emerged as strong contenders due to their high energy density and stability. However, their reliance on scarce lithium reserves and high production costs makes them impractical for many applications. Sodium-based batteries (SBBs) are gaining traction as a more affordable option, with costs of $50 to $100 per kWh and an abundant resource base. Despite these advantages, SBBs still face many obstacles, primarily due to limited research on sodium-based chemistries. Additionally, sodium-based batteries have inherent limitations, including lower energy capacity and reduced cycle life, which restrict their viability for long-term use. This thesis addresses several critical challenges faced by SBBs and explores new strategies for enhancing their performance and viability for large-scale applications. First, a low-concentration, non-flammable electrolyte consisting of 0.3 M NaPF6 in a mixed solvent was formulated and tested in SBBs. This electrolyte significantly improves the cyclability and performance of SBBs across a wide temperature range, with high-capacity retention at both elevated and sub-zero temperatures. Molecular simulations reveal that the improved ion-pairing underpins the exceptional performance. This development addresses major challenges in SBBs by offering a safer, more cost-effective solution for large-scale applications. Second, sodium-sulfur (Na-S) batteries were explored to achieve high energy densities. An external acoustic field was implemented to enhance Na-S battery performance by inhibiting the shuttle effect and reducing dendrite growth, two key challenges in Na-S systems. This method offers a scalable, non-chemical solution to improve cycle life and efficiency, making Na-S batteries a more viable candidate for large-scale energy storage. This progress, along with the high theoretical capacity of Na-S batteries, helps address the limitations not resolved by the electrolyte engineering work of SBBs. Third, the mechanisms of Na2Sx (x≤2) precipitation in sodium-sulfur (Na-S) and sodium-oxygen-sulfur (Na/O2-S) systems were investigated. The results reveal that higher-order sodium polysulfides display the lowest current density, indicating a stronger driving force is needed to initiate their reaction. In Na/(O2)-S systems, the transition from high-order to low-order oxy-sulfur intermediates demands less energy compared to Na-S systems. The insights gained here help further optimize Na-S/Na/(O2)-S batteries to enhance their performance and cycle life. Together, the work in this dissertation addressed several critical needs in the development of SBBs and helped advance their commercialization. / Doctor of Philosophy / As the demand for affordable and efficient energy storage grows, especially to support electric vehicles and electricity generation from renewable sources, new types of batteries are needed. While lithium-based batteries are commonly used due to their high energy capacity, they rely on scarce and expensive lithium resources, making them impractical for large-scale applications like storing energy for electrical grids. This has led researchers to explore sodium-based batteries, which use sodium, a much more abundant and cost-effective element. However, sodium-based batteries still face challenges, such as lower energy capacity and shorter lifespan compared to their lithium counterparts. This thesis focuses on improving sodium-based battery performance to make them a more viable option for large-scale energy storage. The first project introduces a new, safer, low-cost electrolyte that significantly enhances the performance of sodium-based batteries, even in extreme temperatures. This solution improves the battery's ability to retain its energy over multiple charging cycles, addressing some of the key issues in current sodium-based battery technology. In the second project, the focus shifts to sodium-sulfur (Na-S) batteries, which offer the potential for higher energy storage due to sulfur's high capacity. To address common issues in Na-S batteries, such as the polysulfide shuttle effect and dendrite formation, a novel acoustic approach is explored. This method reduces the migration of polysulfides between the electrodes, which preserves capacity, and also suppresses the growth of dendrites on the sodium metal anode, improving both safety and battery lifespan. As a result, the efficiency and durability of Na-S batteries are significantly enhanced, bringing them closer to practical, large-scale applications. Despite these advancements, some fundamental questions remain about how sodium polysulfides form and behave inside Na-S batteries. The third project focuses on understanding the precipitation and interaction of these compounds under different conditions. Gaining insight into these processes is essential for further enhancing battery performance and ensuring long-term reliability. In conclusion, this thesis explores several innovative strategies to improve the design and performance of sodium-based batteries, which help make them more practical for large-scale energy storage applications and ultimately contribute to a more sustainable future.

<p>  </p> <p>Room-temperature sodium-sulfur (RT Na-S) batteries are an emergent new technology that are highly attractive due to their low raw materials cost and large theoretical specific energy. However, many fundamental problems still plague RT Na-S batteries that prevent their progression from the research and development phase to the commercial phase. Sulfur and its final discharge product are insulators, and intermediate polysulfide discharge products are soluble in commonly used liquid electrolytes. As a result, RT Na-S cells exhibit large capacity defects, low coulombic efficiencies, and rapid capacity fading. Additionally, the reactive sodium metal anode can form dendrites during cycling, which reduces capacity and shortens cell life. One way to combat these issues is the judicious selection of electrolyte components. In this study, the effects of monoglyme (G1), diglyme (G2), and tetraglyme (G4) glyme ether electrolyte solvents on RT Na-S cell performance are investigated. Galvanostatic cycling of Na/Na symmetric coin cells reveals that the G2 solvent enable stable cycling at low overpotentials over a wide range of current densities. In contrast, the G1-based cells show evidence of dendritic plating, and G4-based cells are not suitable for use at high current densities. Electrochemical impedance spectroscopy during cycling confirms that the G2 solvent facilitates the formation of a strong, stable SEI on the Na electrode surface. Results from galvanostatic cycling of RT Na-S full coin cells demonstrates that G1-based cells deliver the highest initial specific discharge capacities among the three cell types, but G4-based cells are the most reversible. Infinite charging, the indefinite accrual of charge capacity at the high charge voltage plateau, affects all cell types at different cycle numbers and to different extents. This behavior is linked to the strength of the polysulfide shuttle during charge. Optical microscopy experiments show that G2 and G4 facilitate the formation of the S3•- sulfur radical, which reduces capacity. G1 minimizes the radical formation and thus delivers higher initial specific discharge capacity. In order to fully optimize the electrolyte for RT Na-S cells, future work should study glyme solvent blends, additives, and concentrated salts.</p>