Polysulfide Chemistry in Sodium–Sulfur Batteries and Related Systems— A Computational Study by G3X(MP2) and PCM Calculations

AbstractThe sodium–sulfur (NAS) battery is a candidate for energy storage and load leveling in power systems, by using the reversible reduction of elemental sulfur by sodium metal to give a liquid mixture of polysulfides (Na2Sn) at approximately 320 °C. We investigated a large number of reactions possibly occurring in such sodium polysulfide melts by using density functional calculations at the G3X(MP2)/B3LYP/6‐31+G(2df,p) level of theory including polarizable continuum model (PCM) corrections for two polarizable phases, to obtain geometric and, for the first time, thermodynamic data for the liquid sodium–sulfur system. Novel reaction sequences for the electrochemical reduction of elemental sulfur are proposed on the basis of their Gibbs reaction energies. We suggest that the primary reduction product of S8 is the radical anion ${{\rm S}{{{{\bullet}}- \hfill \atop 8\hfill}}}$, which decomposes at the operating temperature of NAS batteries exergonically to the radicals ${{\rm S}{{{{\bullet}}- \hfill \atop 2\hfill}}}$ and ${{\rm S}{{{{\bullet}}- \hfill \atop 3\hfill}}}$ together with the neutral species S6 and S5, respectively. In addition, ${{\rm S}{{{{\bullet}}- \hfill \atop 8\hfil