Stepwise Electrocatalysis as a Strategy against Polysulfide Shuttling in Li-S Batteries

Most issues with Li-S batteries are caused by the slowness of the multielectron sulfur electrochemical reaction resulting in the loss of sulfur as soluble polysulfides to the electrolyte and the redox shuttling of polysulfides between the cathode and anode during battery charge and discharge. The acceleration of the polysulfide conversion reaction to their end products via electrocatalysis has the appeal of a root-cause solution. However, the polysulfide electrocatalysts developed to date have rarely considered polysulfide conversion as a multistep reaction and, as such, were not optimized to target specific steps in the overall S₈ ↔ Li₂S ↔ Li₂S conversion. The targeting approach is however beneficial, as it can be used to design multicatalyst systems to reduce as many rate-limiting steps in the overall catalysis as effectively possible. This article demonstrates the concept and implementation of stepwise electrocatalysis in polysulfide conversion, using Fe-N and Co-N co-doped carbons to selectively catalyze the long-chain polysulfide conversion (S₈ ↔ Li₂S₄) and the short-chain polysulfide conversion reactions (Li₂S₄ ↔ Li₂S), respectively. The two electrocatalysts were deployed in the sulfur cathode as a dual layer, using an ordered spatial separation to synergize their catalytic effects. A sulfur electrode designed as such could utilize ∼90% of the sulfur theoretical specific capacity and support a high areal capacity of ∼8.3 mAh cm^-2 and a low electrolyte/sulfur ratio of 5 μL mg^-1.