Band Structure Engineering And Orbital Orientation Control Constructing Dual Active Sites For Efficient Sulfur Redox Reaction.

The kinetics difference among multi-step sulfur electrochemical processes leads to the accumulation of soluble polysulfides and thus shuttle effect in lithium-sulfur (Li-S) batteries. While the interaction between catalysts and representative species has been reported, the root of the kinetics difference, interaction change among redox reactions, remains unclear, which significantly impedes the rational design of catalysts for Li-S batteries. Here, we apply density functional theory to decipher the interaction change among electrocatalytic sulfur reactions, using tungsten disulfide (WS 2 ) a model system to demonstrate the efficiency of modifying electrocatalytic selectivity via dual-coordination design. Band structure engineering and orbital orientation control are combined to guide the design of WS 2 with boron dopants and sulfur vacancies (B-WS 2- x ), accurately modulating interaction with lithium and sulfur sites in polysulfide species for relatively higher interaction with short-chain polysulfides (Li 2 S 4 and Li 2 S 2 ). The modified interaction trend is experimentally confirmed by distinguishing the kinetics of each electrochemical reaction step, indicating the effectiveness of the designed strategy. An Ah-level pouch cell with B-WS 2- x delivers a gravimetric energy density of up to 417.6 Wh kg -1 with a low electrolyte/sulfur ratio of 3.6 μL mg -1 and negative/positive capacity ratio of approximately 1.2. This work presents a dual-coordination strategy for advancing evolutionarily catalytic activity, offering a rational strategy to develop effective catalysts for practical Li-S batteries . This article is protected by copyright. All rights reserved.