Solvent Dynamics in Gel Polymer Electrolytes for Lithium–Sulfur Batteries

Gomes, Luisa; Dai, Huidong; Chambers, Daniel; Sanctis, Victor Ribeiro; Yang, Kevin; Dong, Ruizhi; Do, Anhtu; Ji, Tongtai; Mukerjee, Sanjeev

doi:10.1021/acsnano.5c01797

Solvent Dynamics in Gel Polymer Electrolytes for Lithium–Sulfur Batteries

Journal Article · Fri May 16 00:00:00 EDT 2025 · ACS Nano

DOI:https://doi.org/10.1021/acsnano.5c01797· OSTI ID:2566943

^[1]; ^[1]; ^[1]; Sanctis, Victor Ribeiro ^[1]; ^[1]; Dong, Ruizhi ^[1]; Do, Anhtu ^[1]; ^[1]; ^[1]

Northeastern Univ., Boston, MA (United States)

Li−sulfur (Li−S) batteries are promising as the next-generation energy storage technology but face challenges due to sluggish sulfur redox reaction (SRR) kinetics and a sulfur shuttling effect. While many studies have explored polycaprolactone (PCL)-based gel polymer electrolytes (GPEs) to address these issues, the influence of solvent properties, including dielectric constant (ϵ) and donor and acceptor numbers (DN and AN), remain unexplored despite their critical impact on performance and full-scale implementation. This study systematically compares three distinct electrolytes, dimethoxyethane (DME), dimethyl sulfoxide (DMSO), and tetraethylene glycol dimethyl ether (TEGDME)-paired with PCL, to correlate the varied solvent properties and their effects on the physical properties of the GPE, in terms of Li⁺ transport and solvation, and polysulfide’s confinement. Among them, the DME-based GPE, with an intermediate DN, exhibited the lowest crystallinity (2.31%), highest ionic conductivity (7.49 mS/cm), and high Li⁺ transference number (0.77). As a result, it achieved a specific capacity of 795 mAh/g sulfur and an average Coulombic efficiency of 97.5% after 120 cycles at C/5, outperforming its competitors. Operando Raman and UV−vis spectroscopy confirmed that PCL effectively confines long-chain polysulfides within its network, mitigating the shuttle effect and facilitating reversible polysulfide conversion. These findings demonstrate that GPEs with moderate DN values and balanced ϵ significantly enhance stability, extend cycle life, and improve rate performance for Li−S batteries. This work provides valuable insights into the design of advanced electrolyte systems for practical energy storage applications.

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Research Organization:: National Energy Technology Laboratory (NETL), Pittsburgh, PA, Morgantown, WV, and Albany, OR (United States)

Sponsoring Organization:: National Science Foundation (NSF); US Army Research Office (ARO); USDOE; USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Vehicle Technologies Office (VTO)

Grant/Contract Number:: EE0009646

OSTI ID:: 2566943

Alternate ID(s):: OSTI ID: 2569400

Journal Information:: ACS Nano, Journal Name: ACS Nano Journal Issue: 21 Vol. 19; ISSN 1936-086X; ISSN 1936-0851

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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