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Morphology regulation of thin and dense MOFs-based composite solid electrolyte membranes to promote Li+ conduction

Authors： ZHANG Shichen, LI Yihang, HE Yuchen, YANG Xiongbin, QI Xinhong, JIANG Xiaobin, HE Gaohong

Units： State Key Laboratory of Fine Chemicals, Research and Development Center of Membrane Science and Technology, Dalian University of Technology, Dalian 116024, China

KeyWords： composite solid electrolyte membrane; metal organic framework; morphology regulation; lithium dendrite inhibition

ClassificationCode：TQ028； TM911.3

year,volume(issue):pagination： 2026,46(2):13-23

Abstract：

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.

Funds：

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)

AuthorIntro：

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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