The redox processes of Li2Sn false(6⩽n⩽12false) at a glassy carbon electrode in THF was studied by programmed cyclic voltammetry in the range of +1300 to −2000 mV (vs. polysulfide reference electrode) at sweep rates of 2–200 mV/s. One anodic and up to three cathodic peaks were detected. The anodic peak seems to result from the oxidation of all PS's through the same intermediate to elemental sulfur. The first cathodic peak is caused by the reduction of all PS false(n>6false) to Li2S6 in a diffusion controlled reaction. The second reduction peak most likely arises from the reduction of S62− to S52− . This is apparently preceded by a chemical step. The third reduction peak is caused by the reduction of S52− to S22− or S2− or a mixture of both in a diffusion‐controlled reaction. The high Tafel slope of the third peak apparently results from passivation of the electrode by the precipitation of Li2S and Li2S2 .

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ChemInform Abstract Cyclic voltammograms of Li2Sn(6 ≤ n ≤ 12), recorded in THF at a glassy carbon electrode in the range +1300 to -2000 mV at sweep rates of 2-200 mV/s, show one anodic and up to three cathodic peaks. The anodic peak is assigned to the xidation of all polysulfides (PS) to elemental sulfur via the same intermediate. The first cathodic peak is caused by the reduction of all PS (n > 6) to Li2S6 in a diffusion controlled reaction. The second cathodic peak is most probably due to reduction of S62-to S52-. The hird reduction peak results from the reduction of S52-to S22-or S2-in a diffusion-controlled reaction. The high Tafel slope of the third peak is explained by passivation of the electrode by precipitation of Li2S and Li2S2.

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