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薄层致密MOFs复合固态电解质膜形貌调控促进Li+传导研究

作者：张诗晨，李易杭，何宇晨，杨雄斌，齐新鸿，姜晓滨，贺高红

单位：大连理工大学，精细化工全国重点实验室，膜科学与技术研究开发中心，大连 116024

关键词：复合固态电解质膜；金属有机骨架；形貌调控; 锂枝晶抑制

DOI号： 10.16159/j.cnki.issn1007-8924.2026.02.002

分类号： TQ028； TM911.3

出版年,卷(期):页码： 2026,46(2):13-23

摘要：

金属有机骨架(MOFs)具有可调控的孔结构、规则的通道及良好的热/电化学稳定性，因此作为固态电解质的填料受到广泛的关注，但其应用受限于离子电导率和抑制锂枝晶能力之间的权衡。针对这一瓶颈，本研究提出一种区别于传统共混或双侧修饰的界面生长策略，在聚偏氟乙烯六氟丙烯（PVDFHFP）基膜单侧可控构筑薄层致密ZIF67层，并结合原位聚合制备复合固态电解质膜。通过调控反应时间控制ZIF67层形貌和厚度，提升基膜对前驱液的浸润性，增强电解质/电极界面相容性；利用ZIF67的多孔结构和路易斯酸碱作用限域吸附阴离子促进锂盐的解离，同时致密薄层设计避免了锂离子传导阻力的增加，从而将离子电导率提升至2.93 mS/cm（30 ℃）。所组装的磷酸铁锂(LFP)|MOF0.5|Li固态锂金属电池具有良好的倍率性能和长循环稳定性，0.5 C下循环560圈容量保留率达81.4%，库仑效率接近100%，且具有更低的极化电压。本研究为提升MOFs基复合固态电解质膜的离子电导率和抑制锂枝晶能力提供了新思路。

Metal-organic frameworks (MOFs) have garnered significant attention as fillers for solid-state electrolytes due to their tunable pore structures, ordered channels, and favorable thermal and electrochemical stability. However, their application is constrained by the trade-off between ionic conductivity and the ability to suppress lithium dendrites. To address this bottleneck, this study proposed a unilateral interfacial growth strategy distinct from conventional blending or bilateral modification approaches, enabling the controlled construction of a thin, dense ZIF-67 layer on one side of a poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) based membrane, followed by in-situ polymerization to fabricate a composite solid electrolyte membrane. By adjusting the reaction time, the morphology and thickness of the ZIF-67 layer were regulated to enhance the wettability of the precursor solution on the membrane and improve the interfacial compatibility between the electrolyte and the electrodes. The porous structure and Lewis acid-base interactions of ZIF-67 confined and adsorbed anions, promoting the dissociation of lithium salts, while the design of a dense thin layer avoided an increase in lithium-ion transport resistance. Consequently, the ionic conductivity was increased to 2.93 mS/cm (30 ℃). The assembled LiFePO4 (LFP)|MOF-0.5|Li solid-state lithium metal battery exhibited excellent rate capability and long-term cycling stability, retaining 81.4% of its capacity after 560 cycles at 0.5 C with a coulombic efficiency approaching 100%, along with a lower polarization voltage. This work provides a new strategy for enhancing the ionic conductivity and lithium dendrite suppression capability of MOF-based composite solid electrolyte membranes.

基金项目：

国家自然科学基金(22308041, 22538002); 辽宁省自然科学基金(2025-BS-0044); 中央高校基本科研业务费(DUT25XQLP18)

作者简介：

张诗晨 (2000-)，男，浙江绍兴人，硕士研究生，主要研究方向为固态锂离子电池及固态电解质膜

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