Insight into the Electrode Mechanism in Lithium‐Sulfur Batteries with Ordered Microporous Carbon Confined Sulfur as the Cathode

In lithium‐sulfur batteries, small S 2–4 molecules show very different electrochemical responses from the traditional S 8 material. Their exact lithiation/delitiation mechanism is not clear and how to select proper electrolytes for the S 2–4 cathodes is also ambiguous. Here, S 2–4 and S 8 /S 2–4 composites with highly ordered microporous carbon as a confining matrix are fabricated and the electrode mechanism of the S 2–4 cathode is investigated by comparing the electrochemical performances of the S 2–4 and S 2–4 /S 8 electrodes in various electrolytes combined with theoretical calculation. Experimental results show that the electrolyte and microstructure of carbon matrix play important roles in the electrochemical performance. If the micropores of carbon are small enough to prevent the penetration of the solvent molecules, the lithiation/delithiation for S 2–4 occurs as a solid‐solid process. The irreversible chemically reactions between the polysulfudes and carbonates, and the dissolution of the polysulfides into the ethers can be effectively avoided due to the steric hindrance. The confined S 2–4 show high adaptability to the electrolytes. The sulfur cathode based on this strategy exhibits excellent rate capability and cycling stability.