Prussian Blue Nanocubes with an Open Framework Structure Coated with PEDOT as High‐Capacity Cathodes for Lithium–Sulfur Batteries

It is shown that Prussian blue analogues (PBAs) can be a very competitive sulfur host for lithium-sulfur (Li-S) batteries. Sulfur stored in the large interstitial sites of a PBA host can take advantage of reversible and efficient insertion/extraction of both Li+ and electrons, due to the well-trapped mobile dielectron redox centers in the well-defined host. It is demonstrated that Na2 Fe[Fe(CN)6 ] has a large open framework, and as a cathode, it both stores sulfur and acts as a polysulfide diffusion inhibitor based on the Lewis acid-base bonding effect. The electrochemical testing shows that the S@Na2 Fe[Fe(CN)6 ]@poly(3,4-ethylenedioxythiophene) composite achieves excellent reversibility, good stability, and fast kinetics. Its outstanding electrochemical properties should be ascribed to the internal transport of Li+/e- , maximizing the utilization of sulfur. Moreover, the open metal centers serve as the Lewis acid sites with high affinity to the negatively charged polysulfide anions, reducing the diffusion of polysulfides out of the cathode and minimizing the shuttling effect. The fundamental basis of these exceptional performance characteristics is explored through a detailed analysis of the structural and electrochemical behavior of the material. It is believed that the PBAs will have a useful role in ensuring more effective and stable Li-S batteries.