Rechargeable lithium-sulfur batteries with novel electrodes, cell configurations, and recharge strategies



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Entering a new era of green energy, several criteria such as cost, cycle life, safety, efficiency, energy, and power need to be considered in developing electrical energy storage systems for transportation and grid storage. Lithium-sulfur (Li-S) batteries are one of the prospective candidates in this regard as sulfur offers a high theoretical capacity of 1675 mAh g⁻¹ at a safer operating voltage range of ~ 2.1 V and low-cost benefit. This dissertation explores various original designs of novel electrodes, new cell configurations, and recharge strategies that can boost the cycle performance of Li-S cells. An in situ sulfur deposition route has been developed for synthesizing sulfur-carbon composites as cathode materials. This facile synthesis method involves the precipitation of elemental sulfur at the interspaces between carbon nanoparticles in aqueous solution at room temperature. Thus, a sulfur/multi-wall carbon nanotube (MWCNT) composite cathode with high-rate cyclability has been synthesized by the same process. Due to the self-weaving behavior of MWCNTs, extra cell components such as binders and current collectors are rendered unnecessary, thereby streamlining the electrode manufacturing process and decreasing the cell weight. A novel Li-S cell configuration with a carbon interlayer inserted between the separator and cathode has been designed to enhance the battery cyclability as well. A conductive MWCNT interlayer acting as a pseudo-upper current collector not only reduces the charge transfer resistance of sulfur cathodes significantly, but also localizes and retains the dissolved active material during cycling. Moreover, with a bi-functional microporous carbon paper intrerlayer, we observe a significant improvement not only in the active material utilization but also in capacity retention, without involving complex synthesis or surface modification. The kinetics of the sulfur/long-chain polysulfide redox couple (S₈ [double-sided arrow] Li₂S₄, theoretical capacity = 419 mAh g⁻¹) is experimentally proven to be very fast in the Li-S system. The Li-S cell with a blended carbon interlayer retains excellent cycle stability and possesses a high percentage of active material utilization over 250 cycles at high C rates (up to 15C). The meso-/micro- pores in the interlayer are in charge of accommodating the shuttling polysulfides and offering sufficient electrolyte accessibility. An appropriate and applicable way to recharge Li-S cells within the lower plateau region has been designed to offer tremendous improvement with various Li-S battery systems. Adjusting the charging condition led to long cycle life (over 500 cycles) with excellent capacity retention (> 99%) by inhibiting the electrochemical reactions along with polysulfide dissolution. In addition, the redox products determined by ex situ x-ray photoelectron spectroscopy (XPS) further clarify the mechanism of polysulfide formation upon cycling, which is partially different from the general consensus. These approaches of novel electrode designs, new cell configurations, charging strategy, and understanding of the reactions in different discharge steps could progress the development and advancement of Li-S batteries.