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Room-temperature sodium-sulfur (RT Na-S) batteries have attracted ever-increasing attention because of their enhanced energy density and low price. Although the performance of RT Na-S batteries is obtained in many other research, the basic mechanism and kinetics have not involved yet, especially in discharge product growth, which affects electrochemical performance. Meanwhile, designed additional redox activities (in the presence of oxygen) could simultaneously suppress sodium polysulfide shuttling and enhance energy density according to our group reported. However, the kinetic study of the intermediate has not been explored. In this work, we discussed the deposition of low-order sodium polysulfide (Na₂S_x, x ≤ 2) in different potentials and types of glyme-solvents in Na-S and Na/(O₂)-S system. The results show that the morphology of deposition Na₂S_x(x ≤ 2) is affected by interfacial energy barrier controlled by overpotentials and the radius of sodium ions, which produced the precipitation of particle shape rather than film. Potentiostatic experiments show the kinetics are elevated in the presence of oxygen. In addition, the exchange current density of different sodium polysulfides was studied. The high-order sodium polysulfide has a lower exchange current density than that of low-order sodium polysulfide in Na-S system, requiring greater driving force, while transformation of the intermediate from high-order oxy-sulfur to low-order oxy-sulfur species require less impulse in Na/(O₂)-S systems. This paper provides new understandings of the deposition mechanism and kinetics of Na₂S_x(x ≤ 2) Na-S and Na/(O₂)-S system in and to choose the appropriate solvent and potential.