Tailoring short-chain sulfur molecules to drive redox dynamics for sulfur-based aqueous battery

Solid-solid reactions stand out in rechargeable sulfur-based batteries due to the robust redox couples and high sulfur utilization in theory. However, conventional solid-solid reactions in sulfur cathode always present slow reaction kinetics and huge redox polarization due to the low electronic conductivity of sulfur and the generation of various electrochemical inert intermediates. In view of this, it is crucial to improve the electrochemical activity of sulfur cathode and tailor the redox direction. Guided by thermodynamics analysis, short-chain sulfur molecules (S_2-4) are successfully synthesized by space-limited domain principle. Unlike conventional cyclic S₈ molecules with complex routes in solid-solid reaction, short-chain sulfur molecules not only shorten the length of the redox chain but also inhibit the formation of irreversible intermediates, which brings excellent redox dynamics and reversibility. As a result, the Cu-S battery built by short-chain sulfur molecules can deliver a high reversible capacity of 3,133 mAh g^-1. To put this into practice, quasi-solid-state aqueous flexible battery based on short-chain sulfur molecules is also designed and evaluated, showing superior mechanical flexibility and electrochemical property. It indicates that the introduction of short-chain sulfur molecules in rechargeable battery can promote the development and application of high-performance sulfur-based aqueous energy storage systems.