Jiang Ye, Zhao Shangquan, Xiao Xinyu, Pi Jiaqi, Wang Youliang, Yi Nan, Zou Lijia, Xu Zixiao, Xiao Yanhe, Ao Xin, Ding Guangni, Zhou Weihua, Zhou Naigen, Xue Zhigang
Jiangxi Province Key Laboratory of Lithium-ion Battery Materials and Application, School of Physics and Material Science, Nanchang University, Nanchang, 330031, China.
School of Chemistry and Chemical Engineering, Nanchang University, Nanchang, 330031, China.
Angew Chem Int Ed Engl. 2025 Oct 13;64(42):e202510997. doi: 10.1002/anie.202510997. Epub 2025 Aug 27.
Gel polymer electrolyte (GPE) is a desirable candidate for high-safety lithium batteries but is still plagued by the dynamic fluctuations of liquid electrolyte components, which induce localized fluid aggregation or leakage, ultimately leading to performance instability or even degradation. Here, we develop a novel poly(benzoxazine-propylene-oxide)-based GPE, achieving superior electrochemical performance and high safety simultaneously. Through molecular architecture design, the strategic incorporation of long-chain propylene-oxide segments and amide functionalities into the benzoxazine backbone endows the polymer matrix with enhanced lithium-ion transport capability. Catalyst-free thermal curing triggers oxazine ring-opening polymerization, constructing three-dimensional chemically cross-linked network architecture, generating abundant hydrogen bonds. The synergistic interaction between chemical crosslinking and dynamic hydrogen-bonding enabled exceptional electrolyte uptake (600% w/w within 5 min) coupled with effective solvent immobilization. The incorporated long-chain propylene-oxide segments exhibited synergistic solvation effects with carbonate solvents, enabling superior ionic conductivity (9.62 mS cm at 20 °C). The Li||Li symmetric cells based on PBz-PO-GPE 2000 operated for 3000 h at 0.1 mA cm, and LiFePO||Li full cells delivered 140.7 mAh g initial discharge capacity at 2 C rate, near-unity coulombic efficiency, and 70.5% capacity retention after 1800 cycles. This multiscale design of GPE provides an effective strategy for electrolyte exploration in high-performance lithium metal batteries.
凝胶聚合物电解质（GPE）是高安全性锂电池的理想候选材料，但仍受液体电解质成分动态波动的困扰，这会导致局部流体聚集或泄漏，最终导致性能不稳定甚至退化。在此，我们开发了一种新型的基于聚（苯并恶嗪 - 环氧丙烷）的GPE，同时实现了优异的电化学性能和高安全性。通过分子结构设计，将长链环氧丙烷链段和酰胺官能团策略性地引入苯并恶嗪主链，赋予聚合物基体增强的锂离子传输能力。无催化剂热固化引发恶嗪开环聚合，构建三维化学交联网络结构，产生大量氢键。化学交联和动态氢键之间的协同相互作用实现了优异的电解质吸收（5分钟内达到600% w/w）以及有效的溶剂固定。引入的长链环氧丙烷链段与碳酸酯溶剂表现出协同溶剂化效应，在20°C时实现了优异的离子电导率（9.62 mS cm）。基于PBz-PO-GPE 2000的Li||Li对称电池在0.1 mA cm下运行3000小时，LiFePO||Li全电池在2 C倍率下初始放电容量为140.7 mAh g，库仑效率接近100%，1800次循环后容量保持率为70.5%。这种GPE的多尺度设计为高性能锂金属电池的电解质探索提供了一种有效策略。
