Nonhomogeneous In Situ Polymerization of Poly(1,3-dioxolane) Electrolytes for High Stable Polymer Lithium Batteries

作者：Tian-kun Gao, Ke Fang, Meiqi Hu, Jianwei Ji, Ying Liu, Liping Zhou, Gang Zhang, Lianli Zou, Yin Yin, Mao‐xiang Jing · 发表于：ACS Sustainable Chemistry & Engineering · 年份：2025 · DOI：10.1021/acssuschemeng.5c09861 · 被引用次数：6 · 研究领域：Advanced Battery Materials and Technologies、Advancements in Battery Materials、Fiber-reinforced polymer composites

Homogeneous in situ polymerization is a green and common method to prepare polymer electrolytes and improve interfacial contact effectively. However, it is difficult to balance high mechanical properties, good interfacial flexible contact, and controlled polymerization processes under different initiator conditions. In this work, a nonhomogeneous in situ polymerization process was proposed to prepare a gradient structural poly(1,3-dioxolane) (PDOL) solid electrolyte. By preloading the aluminum trifluoromethanesulfonate (Al(OTf) 3 ) initiator on the porous skeleton, the polymerization rate is controlled to form a gel–solid–gel rigid–flexible composite structure. This nonhomogeneous design significantly reduces sensitivity to initiator dosage/activity, enabling controllable and easy-to-operate processes. Simultaneously, this gradient structure maintains high ionic conductivity while retaining high mechanical properties characteristic of solid electrolytes and favorable interfacial soft bonding properties typical of gel electrolytes. The prepared NPDOL-3 + 1 electrolyte possesses an electrochemical stabilization window of 5.5 V, an ionic conductivity of 3.29 × 10 –4 S·cm –1, and a high lithium-ion migration number of 0.71 with a tensile strength of 175 MPa. The Li/NPDOL/Li cell could be cycled for up to 1000 h at 0.3 mA cm –2 without significant changes, indicating the NPDOL-3 + 1 electrolyte possesses good interfacial stability with the lithium electrode. These features enable ...