Lithium-sulfur (Li-S) batteries have garnered immense interest due to their potential to surpass the energy densities of state-of-the-art lithium-ion batteries. However, severe technical problems of polysulfide dissolution and shuttle effect still prohibit the commercialization of Li-S batteries. This review focuses on the recent advances of polysulfide mediation in conventional Li-S batteries with liquid electrolytes. Simple yet effective solutions to control polysulfide dissolution and shuttling via facile modification of the cathode and the electrolyte are highlighted. The rational design of cathode composition, the use of polysulfide barrier layers, and the selection of electrolyte components are discussed. These strategies offer significant promise to address the challenges and increase the viability of the large-scale application of Li-S batteries.

The solid electrolyte interphase (SEI) formed during the cycling of lithium-ion batteries (LIBs) by decomposition of electrolyte molecules has key impact on device performance. However, the detailed decomposition process and distribution of products remain a mystery due to the wide variety of electrochemical pathways and the lack of facile analytical methods for chemical characterization of SEIs. In this report, a gradient polarity solvent wash technique involving the use of solvents with gradually increased polarities is employed to sequentially remove different SEI components from electrode surfaces. Fourier transform infrared (FTIR) spectroscopy is utilized to characterize the SEI composition. The impacts of electrolyte additives and discharge rates over SEI formation are illustrated. This study presents a new concept of rationally controlled solvent wash technique for electrode surface analysis that can selectively remove targeted components. The findings in this study provide experimental support for the slow charge formation processes commonly employed for LIBs in industry.

The Li-S battery is a promising next-generation technology due to its high theoretical energy density (2600 Wh kg^-1) and low active material cost. However, poor cycling stability and coulombic efficiency caused by polysulfide dissolution have proven to be major obstacles for a practical Li-S battery implementation. In this work, we develop a novel strategy to suppress polysulfide dissolution using hydrofluoroethers (HFEs) with bi-functional, amphiphlic surfactant-like design: a polar lithiophilic "head" attached to a fluorinated lithiophobic "tail." A unique solvation mechanism is proposed for these solvents whereby dissociated lithium ions are readily coordinated with lithiophilic "head" to induce self-assembly into micelle-like complex structures. Complex formation is verified experimentally by changing the additive structure and concentration using small angle X-ray scattering (SAXS). These HFE-based electrolytes are found to prevent polysulfide dissolution and to have excellent chemical compatibility with lithium metal: Li||Cu stripping/plating tests reveal high coulombic efficiency (>99.5%), modest polarization, and smooth surface morphology of the uniformly deposited lithium. Li-S cells are demonstrated with 1395 mAh g^-1 initial capacity and 71.9% retention over 100 cycles at >99.5% efficiency-evidence that the micelle structure of the amphiphilic additives in HFEs can prohibit polysulfide dissolution while enabling facile Li⁺ transport and anode passivation.