Summary
The electronic nonconductivity of S and shuttle effect of soluble polysulfides are two fundamental issues that limit the application of lithium‐sulfur (Li‐S) batteries. Regarding these issues, herein, a sponge‐like Ketjen black (KB)‐triphenylphosphine sulfide (TPS) multifunctional modification layer was proposed to coat the separator of the advanced Li‐S batteries. The layer was formed by an in situ spontaneous reaction between triphenylphosphine (TPP) of the conventional KB‐TPP layer and Li2S6 solution. This functional layer can ensure a high e− and Li+ conductivity while inhibiting the diffusion of soluble polysulfides. As a result, the redox activity, rate capability, and cycling stability of the batteries are significantly enhanced. Comparing with the discharge capacities at 2C for the PE separator, introducing the KB‐TPS functional layer was beneficial for the capacity retentions of the cells, since the capacity increased from 16.1% to 66.6% at the same C‐rate. A capacity degeneration rate of 0.045% per cycle was obtained for the cell with an S area density of 3.6 mg cm−2. This work is a step forward in the exploration of advanced Li‐S batteries, being a valuable reference for the study of related systems.