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LiFSI-Initiated In Situ Polymerization of Sulfur-Containing Allyl Thiirane: High-Conductivity; High-Voltage; and Interface-Stabilizing Electrolytes for Lithium-Ion Batteries
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DOI：10.1021/acsaem.6c00666.png)
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Abstract
En 中文
The development of safe, high-performance polymer electrolytes with fast lithium-ion transport, wide electrochemical stability, and durable interfaces remains a critical challenge for next−generation lithium-ion batteries. Herein, we report a sulfur-containing allyl thiirane monomer that undergoes LiFSI-initiated in situ cationic ring-opening polymerization to form an amorphous poly(allyl-mercapto-thiirane) (PAMT) gel polymer electrolyte. By integrating a sulfur-rich backbone with pendant allyl groups, the PAMT network simultaneously promotes weak Li+ coordination for rapid ion migration and built-in interphase-forming functionality. The optimized PAMT electrolyte exhibits a low glass transition temperature (around −44 °C) and delivers high ionic conductivity up to 8.5 × 10−3 S cm−1 at 80 °C, a low activation energy of 0.24 eV, and a high lithium-ion transference number of 0.80. Linear sweep voltammetry demonstrates oxidative stability above 5 V vs Li/Li+, enabling compatibility with high-voltage cathodes. The in situ polymerization process generates intimate and conformal electrode−electrolyte interfaces, producing uniform cathode−electrolyte interphases on LiFePO4 and dense, LiF-rich solid−electrolyte interphases on lithium metal. As a result, LiFePO4∥Li cells deliver an initial discharge capacity of ∼146 mAh g−1 at 0.1 C, retain ∼102 mAh g−1 at 1 C, and maintain stable cycling for over 200 cycles with Coulombic efficiencies exceeding 98%. Compared with representative gel and solid polymer electrolytes, the PAMT system achieves a rare combination of high conductivity, wide voltage tolerance, and interfacial durability. This work establishes LiFSI-triggered in situ polymerization of sulfur-containing thiirane monomers as an effective strategy for designing advanced polymer electrolytes for high-voltage and high-safety lithium batteries.
Keywords:
Batteries
Electrodes
Electrolytes
Lithium
solid polymer electrolytes
in situ polymerization
sulfur-containing monomers
lithium bis(fluorosulfonyl)imide (LiFSI)
high-voltage lithium-ion batteries
interphase engineering
Journal
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5.5
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1.1W
Citations:
4.5W
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Cited Papers