Regulating Polysulfide Diffusion and Deposition via Rational Design of Core−Shell Active Materials in Li−S Batteries

Polar host materials with strong adsorption capacity of polysulfides are designed to limit the shuttle effect in sulfur cathodes. However, a critical problem is to control diffusion and deposition of lithium polysulfides during cycling, which significantly impacts cycling stability and sulfur utilization. Here, we report using a sequential adsorption-guided self-assembly to design two types of core−shell sulfur particles with opposite polysulfide adsorption gradients to explore quantitatively the regulation of polysulfide diffusion and deposition. We show that a positive core−shell design of sulfur particles (PCSD@SP), i.e., polysulfide adsorption capability decreasing from the interior to the exterior of the host, is more effective in restricting polysulfide diffusion and regulating polysulfide deposition than the negative core−shell counterpart (NCSD@SP). As a result, the PCSD@SP electrode with a sulfur loading of 7 mg cm⁻² exhibits a stable areal capacity of 6 mAh cm⁻² over 130 cycles at 0.2C. At intermittent discharge/charge, the PCSD@SP electrode retains excellent stability compared with the NCSD@SP. We conclude that rational design of positive core−shell active materials can be used to regulate polysulfide diffusion and deposition to boost electrochemical reaction dynamics and performance. The reported findings will be of immediate benefit to a range of researchers in the design of high-performance lithium−sulfur batteries. © 2022 American Chemical Society.