Strategies to Explore and Develop Reversible Redox Reactions of Li–S in Electrode Architectures Using Silver-Polyoxometalate Clusters

Investigations of the Ag (I)-substituted Keggin K3[H3AgIPW11O39] as a bifunctional Lewis acidic and basic catalyst are reported that explore the stabilization of Li2Sn moieties so that reversible redox reactions in S-based electrodes would be possible. Spectroscopic investigations showed that the Li2Sn-moieties can be strongly adsorbed on the {AgIPW11O39} cluster, where the Ag(I) ion can act as a Lewis acid site to further enhance the adsorption of the S-moieties, and these interactions were investigated and rationalized using DFT. These results were used to construct an electrode for use in a Li–S battery with a very high S utilization of 94%, and a coulometric capacity of 1580 mAh g–1. This means, as a result of using the AgPOM, both a high active S content, as well as a high areal S mass loading, is achieved in the composite electrode giving a highly stable battery with cycling performance at high rates (1050 and 810 mAh g–1 at 1C and 2C over 100 to 300 cycles, respectively).