RESUMO
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 (S2-4) 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.
RESUMO
Dissolution of intermediate sodium polysulfides (Na2Sx; 4≤x≤8) is a crucial obstacle for the development of room-temperature sodium-sulfur (Na-S) batteries. One promising strategy to avoid this issue is to load short-chain sulfur (S2-4), which could prohibit the generation of soluble polysulfides during the sodiation process. Herein, unlike in the previous reported cases where short-chain sulfur was stored by confinement within a small-pore-size (≤0.5 nm) carbon host, we report a new strategy to generate short-chain sulfur in larger pores (>0.5 nm) by the synergistic catalytic effect of CoS2 and appropriate pore size. Based on density functional theory calculations, we predict that CoS2 can serve as a catalyst to weaken the S-S bond in the S8 ring structure, facilitating the formation of short-chain sulfur molecules. By experimentally tuning the pore size of the CoS2-based hosts and comparing their performances as cathodes in Na-S and Li-S batteries, we conclude that such a catalytic effect depends on the proximity of sulfur to CoS2. This avoids the generation of soluble polysulfides and results in superior electrochemical properties of the composite materials introduced here for Na-S batteries. As a result, the optimized CoS2/N-doped carbon/S electrode showed excellent electrochemical performance with high reversible specific capacities of 488 mA h g-1 (962 mA h g(s)-1) after 100 cycles (0.1 A g-1) and 403 mA h g-1 after 1000 cycles (1 A g-1) with a superior rate performance (262 mA h g-1 at 5.0 A g-1).