Mitigation of polysulfide shuttle effect in Li-S batteries through catalytic disproportionation reaction

Journal Article · Wed Jan 28 00:00:00 UTC 2026 · Electrochimica Acta

DOI: https://doi.org/10.1016/j.electacta.2026.148334 · OSTI ID:3018625

Qu, Huainan  ^[1]; Qiu, Dantong ^[1]; Zhang, Xiaoxiao ^[1]; Zheng, Dong  ^[1]; Yang, Xiao-Qing  ^[2]; Qu, Deyang  ^[1]

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1. Univ. of Wisconsin, Milwaukee, WI (United States)
2. Brookhaven National Laboratory (BNL), Upton, NY (United States)

Polysulfides are poorly retained within porous cathodes and readily diffuse into the electrolyte over time, leading to the well-known shuttle effect that undermines the reversibility of Li-S batteries. Here, in this study, we demonstrate that catalytic disproportionation of polysulfides provides an effective pathway to suppress this process by rapidly converting dissolved species into solid sulfur and sulfides, thereby preventing their migration into the electrolyte. Fundamentally, the sluggish kinetics of sulfur redox reactions are responsible for the accumulation and redistribution of soluble polysulfides in the bulk electrolyte. By accelerating these kinetics, catalyzed disproportionation not only confines sulfur within the conductive cathode matrix but also promotes the homogeneous precipitation of Li₂S₂/Li₂S, which enhances electrochemical reversibility and cycling stability. Using nitrogen-doped carbon (NC800) as a model catalyst, we reveal its ability to drive a pseudo-16-electron reduction pathway, leading to a single dominant Li₂S product and uniform deposition within the porous framework. In contrast, a non-catalytic carbon (KB) yields multiple polysulfide intermediates and heterogeneous deposition. The mechanistic insights provided here highlight the pivotal role of catalytic disproportionation in reshaping sulfur redox pathways and offer a rational strategy for mitigating polysulfide shuttling in practical Li-S pouch cells.

• Research Organization: Brookhaven National Laboratory (BNL), Upton, NY (United States)
• Sponsoring Organization: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (VTO). Advanced Battery Materials Research Program
• Grant/Contract Number: SC0012704
• OSTI ID: 3018625
• Report Number(s): BNL--229413-2026-JAAM
• Journal Information: Electrochimica Acta, Journal Name: Electrochimica Acta Vol. 554; ISSN 0013-4686
• Publisher: ElsevierCopyright Statement
• Country of Publication: United States
• Language: English